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The tubulysins are members of a new class of natural products isolated from myxobacterial species (F. Sasse, et al., J. Antibiot. 2000, 53, 879-885). As cytoskeleton interacting agents, the tubulysins are mitotic poisons that inhibit tubulin polymerization and lead to cell cycle arrest and apoptosis (H. Steinmetz, et al., Chem. Int. Ed. 2004, 43, 4888-4892; M. Khalil, et al., ChemBioChem. 2006, 7, 678-683; G. Kaur, et al., Biochem. J. 2006, 396, 235-242). Tubulysins are extremely potent cytotoxic molecules, and exceed the cell growth inhibition of many other clinically relevant traditional chemotherapeutics, including epothilones, paclitaxel, and vinblastine. Furthermore, they are potent against multidrug resistant cell lines (A. Domling, et al., Mol. Diversity 2005, 9, 141-147). These compounds show high cytotoxicity tested against a panel of cancer cell lines with IC50 values in the low picomolar range; thus, they are of interest as potential anticancer therapeutics. However, tubulysins have been reported to exhibit a narrow, or in some cases nonexistent, therapeutic window such that disease treatment with tubulysins is hampered by toxicity and other unwanted side effects. Accordingly, tubulysins have been conjugated with targeting agents to improve their therapeutic window. A total synthesis of tubulysin D possessing C-terminal tubuphenylalanine (RA═H) (H. Peltier, et al., J. Am. Chem. Soc. 2006, 128, 16018-16019) has been reported. Recently, a modified synthetic protocol toward the synthesis of tubulysin B (RA═OH) (O. Pando, et al., Org. Lett. 2009, 11, 5567-5569) has been reported. However, attempts to follow the published procedures to provide larger quantities of tubulysins were unsuccessful, being hampered in part by low yields, difficult to remove impurities, the need for expensive chromatographic steps, and/or the lack of reproducibility of several steps. The interest in using tubulysins for anticancer therapeutics accents the need for reliable and efficient processes for preparing tubulysins, and analogs and derivatives thereof. Therefore, there is a need for tubulysin derivatives, tubulysin analogs, and other tubulysin conjugate intermediates that are useful for preparing such targeted conjugates.
Tubulysin derivatives useful for preparing vitamin receptor binding tubulysin conjugates (also referred to herein as tubulysin linker derivatives) are described herein. Structurally, tubulysin linker derivatives include linear tetrapeptoid backbones, including illustrative compounds having the following formula
and salts thereof, wherein
Ar1 is optionally substituted aryl or optionally substituted heteroaryl;
Ar2 is optionally substituted aryl or optionally substituted heteroaryl;
L is selected from the group consisting of
where p is an integer from about 1 to about 3, m is an integer from about 1 to about 4, and * indicates the points of attachment;
Ra, Rb, and R are each independently selected in each instance from the group consisting of hydrogen and alkyl; or any two of Ra, Rb, and R are taken together with the attached carbon atom(s) to form a carbocyclic ring; RAr represents hydrogen, or 1 to 4 substituents each independently selected from the group consisting of amino or derivatives thereof, hydroxy or derivatives thereof, halo, thio or derivatives thereof, nitro, sulfonic acids and derivatives thereof, carboxylic acids and derivatives thereof, and alkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, heteroaryl, heteroarylalkyl, and heteroarylheteroalkyl, each of which is optionally substituted;
X is hydrogen; or X is alkyl or alkenyl, each of which is optionally substituted; or X is R16C(O)CH(R17)CH2; where R17 is C(O)R16, C(O)OR16, or CN; where R16 is independently in each instance alkyl, alkenyl, cycloalkyl, cycloalkenyl, heteroaryl, arylalkyl, or heteroarylalkyl, each of which is optionally substituted; or X is CH2QR18; where Q is N, O, or S; and R18 is alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, arylalkyl, heteroaryl, or heteroarylalkyl, each of which is optionally substituted, or R18 is acyl, sulfonyl, or phosphonic acid or a derivative thereof;
R4 is optionally substituted alkyl or optionally substituted cycloalkyl;
R3 is optionally substituted alkyl;
R5 and R6 are each independently selected from the group consisting of optionally substituted alkyl and optionally substituted cycloalkyl;
R7 is optionally substituted alkyl;
RAr represents hydrogen, or 1 to 4 substituents each independently selected from the group consisting of amino or derivatives thereof, hydroxy or derivatives thereof, halo, thio or derivatives thereof, nitro, sulfonic acids and derivatives thereof, carboxylic acids and derivatives thereof, and alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, heteroaryl, heteroarylalkyl, and heteroarylheteroalkyl; and n is 1, 2, 3, or 4.
In another embodiment, X is Y—CH2, where Y is R2C(O)O or R12O; R2 is selected from the group consisting of optionally substituted alkyl and optionally substituted cycloalkyl; and R12 is alkyl, alkenyl, alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl or heteroarylalkyl, each of which is optionally substituted.
In another embodiment, compounds of the formula
and salts thereof, are described. In another embodiment, the tubulysin linker derivative has formula T1
or a salt thereof. In another embodiment, the tubulysin linker derivative has formula T2
or a salt thereof.
In another embodiment, in any of the embodiments described herein Ar2 is optionally substituted aryl.
In another embodiment, in any of the embodiments described herein Ar2 is optionally substituted heteroaryl.
Another illustrative group of tubulysins described herein are more particularly comprised of one or more non-naturally occurring or hydrophobic amino acid segments, such as N-methyl pipecolic acid (Mep), isoleucine (Ile),
and analogs and derivative of each of the foregoing. Derivatives and analogs of tubuvaline include compounds of the following formula,
wherein R4, R5 and R6 are as described in any of the embodiments described herein. Derivatives and analogs of tubutyrosine or tubuphenylalanine include compounds having formula,
wherein R3 and Ar1 are as described in any of the embodiment described herein. A common feature in the molecular architecture of potent natural occurring tubulysins is the acid and/or base sensitive N-acyloxymethyl substituent (or a N,O-acetal of formaldehyde) represented by R2CO2CH2 in the formula (T1).
In another embodiment, the compounds described herein are NHNH—C(O)O-L-SS—Ar2 derivatives of naturally occurring tubulysins. An illustrative group of tubulysin derivatives described herein are those having formula 1.
Formula 1, Structures of several tubulysin derivativesTubulysinRAR2AOHCH2CH(CH3)2BOHCH2CH2CH3COHCH2CH3DHCH2CH(CH3)2EHCH2CH2CH3FHCH2CH3GOHCH═C(CH3)2HHCH3IOHCH3
Processes for preparing tubulysins, and analogs and derivatives thereof, are also described in WO 2012/019123, the disclosure of which is incorporated herein by reference in its entirety.
The formation of tubulysins conjugated to vitamin receptor binding moieties for targeted and/or selective delivery to cell populations expressing, overexpressing or selectively expressing cell surface vitamin receptors necessitates further modification of the highly toxic tubulysins. Described herein are improved processes for making natural tubulysins analogs or derivatives, which are useful for preparing vitamin receptor binding tubulysin conjugates including compounds of formula (T) and formula (I). Vitamin receptor binding conjugates of tubulysins are described in U.S. Patent Publication 2010/0048490, the disclosure of which is incorporated herein by reference in its entirety.
In one illustrative embodiment of the invention, processes for derivatives or analogs of natural tubulysins including compounds of formula (T). In another embodiment, vitamin receptor binding conjugates of tubulysins are described. The processes include one or more steps described herein. In another embodiment, a process is described for preparing a compound of formula B, wherein R5 and R6 are as described in the various embodiments herein, such as each being independently selected from optionally substituted alkyl or optionally substituted cycloalkyl; and R8 is C1-C6 n-alkyl; wherein the process comprises the step of treating a compound of formula A with a silylating agent, such as triethylsilyl chloride, and a base, such as imidazole in an aprotic solvent.
It is to be understood that R5 and R6 may each include conventional protection groups on the optional substituents.
In another embodiment, a process is described for preparing a compound of formula C, wherein R5 and R6 are as described in the various embodiments herein, such as each being independently selected from optionally substituted alkyl or optionally substituted cycloalkyl; R8 is C1-C6 n-alkyl; and R2 is as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; wherein the process comprises the step of treating a compound of formula B with a base and a compound of the formula ClCH2OC(O)R2 in an aprotic solvent at a temperature below ambient temperature, such as in the range from about −78° C. to about 0° C.; wherein the molar ratio of the compound of the formula ClCH2C(O)R2 to the compound of formula B is from about 1 to about 1.5.
It is to be understood that R2, R5 and R6 may each include conventional protection groups on the optional substituents.
In another embodiment, a process is described for preparing a compound of formula D, wherein R5 and R6 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; R8 is C1-C6 n-alkyl; R2 is as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; and R7 is optionally substituted alkyl; wherein the process comprises the steps of
a) preparing a compound of formula (E1) where X1 is a leaving group from a compound of formula E; and
b) treating a compound of formula C under reducing conditions in the presence of the compound of formula E1.
It is to be understood that R2, R5, R6, and R7 may each include conventional protection groups on the optional substituents.
In another embodiment, a process is described for preparing a compound of formula F, wherein R5 and R6 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; R2 is as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; and R7 is optionally substituted alkyl; wherein the process comprises the step of treating compound D with a hydrolase enzyme.
In another embodiment, a process is described for preparing a compound of formula F, wherein R5 and R6 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; R2 is as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; and R7 is optionally substituted alkyl; wherein the process comprises the step of treating compound D with a trialkyltin hydroxide (e.g. trimethyltin hydroxide). It is to be understood that R2, R5, R6, and R7 may each include conventional protection groups on the optional substituents.
In another embodiment, a process is described for preparing a compound of formula AF, wherein R5 and R6 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; R2 is as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; and R7 is optionally substituted alkyl; wherein the process comprises the step of contacting compound D with an alcohol, R12OH, where R12 is alkyl, alkenyl, alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl or heteroarylalkyl, each of which is optionally substituted; and a transesterification catalyst. In one embodiment the transesterification catalyst is trifluoroacetic acid (TFA). In another embodiment, the transesterification catalyst is selected from the group consisting of (R13)8Sn4O2(NCS)4, (R13)2Sn(OAc)2, (R13)2SnO, (R13)2SnCl2, (R13)2SnS, (R13)3SnOH, and (R13)3SnOSn(R13)3, where R13 is independently selected from alkyl, arylalkyl, aryl, or cycloalkyl, each of which is optionally substituted. In another embodiment, the transesterification catalyst is (R13)2SnO. Illustrative examples of R13 include methyl, n-butyl. n-octyl, phenyl, o-MeO-phenyl, p-MeO phenyl, phenethyl, and benzyl.
It is to be understood that R5, R6, R12, and R7 may each include conventional protection groups on the optional substituents.
In another embodiment, a process is described for preparing a transesterification product of each of the compounds of formula A and/or B, wherein R5, R6, and R8 are as described in the various embodiments herein, and where R12 is different from R9; wherein the process comprises the step of contacting compound B with an alcohol, R12OH, where R12 is alkyl, alkenyl, alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl or heteroarylalkyl, each of which is optionally substituted; and a transesterification catalyst. Illustratively, the transesterification catalyst is selected from the group consisting of (R13)8Sn4O2(NCS)4, (R13)2Sn(OAc)2, (R13)2SnO, (R13)2SnCl2, (R13)2SnS, (R13)3SnOH, and (R13)3SnOSn(R13)3, where R13 is independently selected from alkyl, arylalkyl, aryl, or cycloalkyl, each of which is optionally substituted. In another embodiment, the transesterification catalyst is (R13)2SnO. Illustrative examples of R13 include methyl, n-butyl. n-octyl, phenyl, o-MeO-phenyl, p-MeO phenyl, phenethyl, and benzyl.
It is to be understood that R5, R6, and R12 may each include conventional protection groups on the optional substituents.
In another embodiment, a process is described for preparing a compound of formula G, wherein R5 and R6 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; R2 is as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; and R7 is optionally substituted alkyl; wherein the process comprises the step of treating the silyl ether of compound F with a non-basic fluoride containing reagent.
It is to be understood that R2, R5, R6, and R7 may each include conventional protection groups on the optional substituents.
In another embodiment, a process is described for preparing a compound of formula AG, wherein R5 and R6 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; R2 is as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; and R7 is optionally substituted alkyl; wherein the process comprises the step of contacting compound F with an alcohol, R12OH, where R12 is alkyl, alkenyl, alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl or heteroarylalkyl, each of which is optionally substituted; and a transesterification catalyst. In one embodiment the transesterification catalyst is trifluoroacetic acid (TFA). In another embodiment, the transesterification catalyst is selected from the group consisting of (R13)8Sn4O2(NCS)4, (R13)2Sn(OAc)2, (R13)2SnO, (R13)2SnCl2, (R13)2SnS, (R13)3SnOH, and (R13)3SnOSn(R13)3, where R13 is independently selected from alkyl, arylalkyl, aryl, or cycloalkyl, each of which is optionally substituted. In another embodiment, the transesterification catalyst is (R13)2SnO. Illustrative examples of R13 are methyl, n-butyl. n-octyl, phenyl, o-MeO-phenyl, p-MeO phenyl, phenethyl, and benzyl.
It is to be understood that R2, R5, R6, R7, and R12 may each include conventional protection groups on the optional substituents.
In another embodiment, a process is described for preparing a compound of formula BG, wherein R5 and R6 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; R2 is as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; R12 is as described in the various embodiments herein, such as being selected from alkyl, alkenyl, alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl or heteroarylalkyl, each of which is optionally substituted; and R7 is optionally substituted alkyl; wherein the process comprises the step of contacting compound AF with a metal hydroxide or carbonate. Illustrative examples of a metal hydroxide or carbonate include LiOH, Li2CO3, NaOH, Na2CO3, KOH, K2CO3, Ca(OH)2, CaCO3, Mg(OH)2, MgCO3, and the like.
It is to be understood that R5, R6, R7, and R12 may each include conventional protection groups on the optional substituents.
In another embodiment, a process is described for preparing a compound of formula H, wherein R5 and R6 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; R2 and R4 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; and R7 is optionally substituted alkyl; wherein the process comprises the step of treating a compound of formula G with an acylating agent of formula R4C(O)X2, where X2 is a leaving group.
It is to be understood that R2, R4, R5, R6, and R7 may each include conventional protection groups on the optional substituents.
In another embodiment, a process is described for preparing a compound of formula AH, wherein R5 and R6 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; R2 and R4 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; R12 is as described in the various embodiments herein, such as being selected from alkyl, alkenyl, alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl or heteroarylalkyl, each of which is optionally substituted; and R7 is optionally substituted alkyl; wherein the process comprises the step of treating a compound of formula BG with an acylating agent of formula R4C(O)X2, where X2 is a leaving group.
It is to be understood that R4, R5, R6, and R7 may each include conventional protection groups on the optional substituents.
In another embodiment, a process is described for preparing a tubulysin linker derivative of formula (T1), wherein Ar1 is optionally substituted aryl; Ar2 is optionally substituted aryl or optionally substituted heteroaryl; L is selected from the group consisting of
where
p is an integer from about 1 to about 3, m is an integer from about 1 to about 4, and * indicates the points of attachment;
Ra, Rb, and R are each independently selected in each instance from the group consisting of hydrogen and alkyl; or any two of Ra, Rb, and R are taken together with the attached carbon atom(s) to form a carbocyclic ring;
RAr represents 0 to 4 substituents selected from the group consisting of amino, or derivatives thereof, hydroxy or derivatives thereof, halo, thio or derivatives thereof, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, heteroaryl, heteroarylalkyl, heteroarylheteroalkyl, nitro, sulfonic acids and derivatives thereof, carboxylic acids and derivatives thereof; R1 is hydrogen, optionally substituted alkyl, optionally substituted arylalkyl or a pro-drug forming group; R5 and R6 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; R3 is optionally substituted alkyl; R2 and R4 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; and R7 is optionally substituted alkyl;
wherein the process comprises the step of forming an active ester intermediate from a compound of formula H; and reacting the active ester intermediate with a compound of the formula I to give a compound of the formula T.
It is to be understood that Ar1, Ar2, R1, R2, R4, R5, R6, and R7 may each include conventional protection groups on the optional substituents.
In another embodiment, a process is described for preparing a tubulysin linker derivative of formula (T2), wherein Ar1 is optionally substituted aryl; Ar2 is optionally substituted aryl or optionally substituted heteroaryl; L is selected from the group consisting of
where
p is an integer from about 1 to about 3, m is an integer from about 1 to about 4, and * indicates the points of attachment;
Ra, Rb, and R are each independently selected in each instance from the group consisting of hydrogen and alkyl; or any two of Ra, Rb, and R are taken together with the attached carbon atom(s) to form a carbocyclic ring;
RAr represents 0 to 4 substituents selected from the group consisting of amino, or derivatives thereof, hydroxy or derivatives thereof, halo, thio or derivatives thereof, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, heteroaryl, heteroarylalkyl, heteroarylheteroalkyl, nitro, sulfonic acids and derivatives thereof, carboxylic acids and derivatives thereof;
R1 is hydrogen, optionally substituted alkyl, optionally substituted arylalkyl or a pro-drug forming group; R5 and R6 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; R3 is optionally substituted alkyl; R2 and R4 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; and R7 is optionally substituted alkyl;
wherein the process comprises the step of contacting compound T, with an alcohol, R12OH, where R12 is alkyl, alkenyl, alkynyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl or heteroarylalkyl, each of which is optionally substituted; and a transesterification catalyst.
In one embodiment the transesterification catalyst is trifluoroacetic acid (TFA). In another embodiment, the transesterification catalyst is selected from the group consisting of (R13)8Sn4O2(NCS)4, (R13)2Sn(OAc)2, (R13)2SnO, (R13)2SnCl2, (R13)2SnS, (R13)3SnOH, and (R13)3SnOSn(R13)3, where R13 is independently selected from alkyl, arylalkyl, aryl, or cycloalkyl, each of which is optionally substituted. In another embodiment, the transesterification catalyst is (R13)2SnO. Illustrative examples of R13 are methyl, n-butyl. n-octyl, phenyl, o-MeO-phenyl, p-MeO phenyl, phenethyl, and benzyl. It is to be understood that Ar1, Ar2, R1, R2, R4, R5, R6, R7, and R12 may each include conventional protection groups on the optional substituents.
In another embodiment, a process is described for preparing a tubulysin linker derivative of formula (T2), wherein Ar1 is optionally substituted aryl; Ar2 is optionally substituted aryl or optionally substituted heteroaryl; L is selected from the group consisting of
where
p is an integer from about 1 to about 3, m is an integer from about 1 to about 4, and * indicates the points of attachment;
Ra, Rb, and R are each independently selected in each instance from the group consisting of hydrogen and alkyl; or any two of Ra, Rb, and R are taken together with the attached carbon atom(s) to form a carbocyclic ring;
RAr represents 0 to 4 substituents selected from the group consisting of amino, or derivatives thereof, hydroxy or derivatives thereof, halo, thio or derivatives thereof, alkyl, haloalkyl, heteroalkyl, aryl, arylalkyl, arylheteroalkyl, heteroaryl, heteroarylalkyl, heteroarylheteroalkyl, nitro, sulfonic acids and derivatives thereof, carboxylic acids and derivatives thereof;
R1 is hydrogen, optionally substituted alkyl, optionally substituted arylalkyl or a pro-drug forming group; R5 and R6 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; R3 is optionally substituted alkyl; R2 and R4 are as described in the various embodiments herein, such as being selected from optionally substituted alkyl or optionally substituted cycloalkyl; and R7 is optionally substituted alkyl;
wherein the process comprises the step of forming an active ester intermediate from a compound of formula AH; and reacting the active ester intermediate with a compound of the formula I to give a compound of the formula T2.
It is to be understood that Ar1, Ar2, R1, R12, R3, R4, R5, R6, and R7 may each include conventional protection groups on the optional substituents.
It is to be understood that the acyloxymethyl group (R2—C(O)—CH2) present on any of compounds C, D, F, G, H, and T1 may be converted into the corresponding ether group (R12—O—CH2), or other group (X or Y—CH2) using the process of contacting the compound with trifluoroacetic acid (TFA), as described herein, and also as described in WO 2009/055562, the disclosure of which is incorporated herein by reference. Accordingly, the following compounds are also described herein
It is to be further understood that each of XC, XD, XF, XG, and XH can be used in the processes described herein in place of each of C, D, F, G, and H, respectively, to prepare the corresponding compound having an ether group (R12—O—CH2), or other group (X).
It is to be further understood that each of YC, YD, YF, YG, and YH can be used in the processes described herein in place of each of C, D, F, G, and H, respectively, to prepare the corresponding compound having an ether group (R12—O—CH2), or other group (Y—CH2).
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The invention relates to a SQUID arrangement for measuring a change in the magnetic field having a direct current SQUID, the change in the magnetic field being caused by a specimen that is arranged in a magnetization field. Moreover, the invention relates to a method for measuring such a change. Finally, the method relates to the use of such a SQUID arrangement or such a method for various applications.
If the change in the magnetization of a specimen is to be measured, this specimen must be disposed for this purpose in a constant magnetic field, the so-called exciter field or magnetization field. A change in the magnetization of the specimen can then be detected as a change in the magnetic field. A superconducting quantum interference detector (SQUID) can measure such a change in the magnetic field in the surroundings of the specimen. The SQUID is coupled to the specimen via a flux transformer. However, the flux transformer transfers only a portion of the magnetic flux and thus also only a portion of the signal energy to the SQUID. Or, in particular in the case of very small specimens, there is direct coupling in that the specimen is placed directly in the SQUID loop. This can reduce a loss in magnetic flux. Such an arrangement is known for instance in U.S. Pat. No. 4,588,947. In both cases, the magnetization field is produced by a separate superconducting coil into which a so-called exciter current or magnetizing current is injected.
One object of the present invention is to provide a simple design in which the losses in the magnetic flux are also simultaneously minimized.
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1. Technical Field of the Invention
The present invention relates to a mounting arrangement for a lens which permits adjustment during assembly of a camera. The invention is particularly, but not exclusively, applicable to the manufacture of small, inexpensive solid state cameras for use in products such as camera phones.
2. Description of Related Art
It is known to provide an image sensor or camera assembly comprising a solid state single chip image sensor and a lens, in which the lens can be adjusted in position during manufacture to achieve optimal focus of the image on the image sensor surface. Typically, the lens is mounted in a lens barrel which has a screw-threaded engagement with a lens mount, and an apparatus adjusts the focus by relative rotation until an optimal focus of a test image is achieved, as judged by an evaluation circuit. The lens barrel may then be locked relative to the chip holder, for example by bonding.
It has been found that after such adjustment a proportion of sensors suffer from unacceptable image quality because of artifacts in the output image. We have established that one cause of this arises from small particles being dislodged from the surfaces of the screw-threaded engagement and lodging on the image sensor surface, or on an optical element (for example, an infrared IR filter) overlying the image sensor surface. Any sensors or cameras suffering from this problem have to be discarded, with consequent increase in the average cost of acceptable sensors.
There is a need in the art to address this problem.
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{
"pile_set_name": "USPTO Backgrounds"
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Traditional transportation modes via water, land, rail and air revolutionized the movement and growth of our current culture. Adverse environmental, societal, and economic impacts of these traditional transportation models, however, initiated a movement to find alternative transportation modes that take advantage of the significant improvements in transportation technology and efficiently move people and materials between locations. High-speed transportation systems utilizing rails or other structural guidance components have been contemplated as a solution to existing transportation challenges while improving safety, decreasing the environmental impact of traditional transportation modes and reducing the overall time commuting between major metropolitan communities.
A high speed, high efficiency transportation system utilizes a low-pressure environment in order to reduce drag on a vehicle at high operating speeds, thus providing the dual benefit of allowing greater speed potential and lowering the energy costs associated with overcoming drag forces. In embodiments, these systems may use a near vacuum (e.g., low-pressure) environment within a tubular structure.
Tube structures for low-pressure environments, however, may have some drawbacks, including material and manufacturing costs. Thus, there exists a need for alternative structures to the tube for low-pressure environments.
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{
"pile_set_name": "USPTO Backgrounds"
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1. Field
The following description relates to a technique for processing an input/output (I/O) request in a solid state drive. More particularly, this description relates to a method of handling I/O request and solid state drive (SSD) using the method.
2. Description of the Related Art
An SSD commonly refers to an apparatus for storing information using a semiconductor device. Currently, research has been conducted to use and operate SSD devices in ways similar to a hard disk drive (HDD) but without mechanical operation.
An SSD can input or output data at a higher speed than an HDD and has very low mechanical delay and failure rate. An SSD also has low in power consumption and is light in weight.
Typically, an SSD includes a plurality of memory modules and a controller to control the memory modules. The controller may exchange data with a host through an interface.
The controller may receive an I/O request from a host and process the I/O request. When a storable address of each memory module is determined in advance and an I/O request size is not large, some memory modules may enter an idle state leaving only a few operating remaining memory modules. However, this lack of operating memory modules may become severe when a large quantity of small-size requests occur after a workload shows a random access pattern.
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In the microfiltration or ultrafiltration treatment of liquids such as chemicals and water, fine particle-removing performance, permeation flux for liquid, resistance to chemicals, pressure resistance, heat resistance, and the like are important selection factors for membrane filter. For this reason, porous membranes comprising high molecular weight polymers such as fluororesins including polytetrafluoroethylene (hereinafter, abbreviated as "PTFE") and the like, polyethylene, polypropylene, polyolefins, and the like have conventionally been selected.
However, membranes which have been rendered hydrophilic have become more and more necessary in recent years. That is, in the semiconductor industry, for example, washing of silicon wafers is being conducted using nitric acid, hydrofluoric acid, sulfuric acid, or the like, but when replacing the chemicals after circulating and washing, air flows into the cartridge filter for filtration by discharging the chemicals. Because of this, the surface of a hydrophobic membrane such as PTFE membrane or the like in the filter comes into contact with air and the effect that the membrane has been treated with an organic solvent or the like to render the membrane hydrophilic is lost and, hence, introduction of chemicals in the next operation results in a significantly reduced liquid permeation flux.
Therefore, there has been a problem that the membrane should again be rendered hydrophilic with a liquid having a low surface tension.
On the other hand, known methods for rendering a porous polymer membrane hydrophilic include, for example, surface treatment with a plasma or sputtering, exposure to radiation, and the like (Unexamined Published Japanese Patent Applications Nos. 59-186604 and 1-98640, and others). However, such methods have had a problem that the imparted hydrophilicity is insufficient, or if a membrane is to be rendered sufficiently hydrophilic, the membrane surface is modified excessively, causing to change the rejection performance the membrane originally possesses.
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Field of the Invention
This invention relates generally to aircraft and, more particularly, to an aircraft with a controlled flow of air over an airfoil, thereby permitting both vertical takeoffs and landings, as well as vertical and (normal) horizontal flight. The aircraft has passages for redirecting the air flowing over the airfoil to the front of the airfoil and to produce a force in a direction of the desired flight path.
Discussion of the Related Art
In recent years, the increase in the power and efficiency of engines along with the development of lightweight structural materials has provided increased interest and incentive for the practical development of low cost, lightweight personal aircraft. These aircraft have become more inexpensive and more readily available as the improved technology has been applied to the problem.
Notwithstanding the improvements in the newly developed aircraft, these vehicles have been subject to the traditional limitation that the aircraft must develop forward speed relative to air mass before the lifting properties of the airfoil can be utilized. To overcome this problem, aircraft, such as helicopters, have been developed in which the engine and a suitably-oriented propeller provide thrust from the engine literally to drag the aircraft into motion in a vertical direction. Similarly, vertical liftoff aircraft have utilized directed flow of the exhaust of jet engines to produce vertical motion.
However, in the cases of these types of vertical travel aircraft, the apparatus has been complex and expensive, and has attempted to solve the problem of vertical travel through the use of directed force rather than the attempt to utilize the properties of a lifting body. For example, U.S. Pat. No. 3,987,981, "Roll Control For Aircraft, Particularly Flying Barrels, Adapted to be Driven by Means of Ducted Fans," uses louvers or flaps to direct the flow of air from a ducted fan in the opposite direction from the direction of the directed flight pattern. A similar technique is shown for U.S. Pat. No. 2,610,005 "Propulsion Means for Vertical Rising Aircraft." In U.S. Pat. No. 3,901,463 "Lift and Propulsion Means for a Vertical Take-off and Landing Aerodyne" provides two propellers that can simultaneously force air into a partially enclosed chamber, and impart a force in direction opposite to an opening in the chamber. U.S. Pat. No. 2,623,712 "Airplane with Pivotally Mounted Sustaining Wing" provides a wing structure that can be pivoted on a fuselage to provide some measure of control over the flight path. U.S. Pat. No. 2,008,737 "Airplane", discloses a passage in the aircraft so that the force of air against the walls of the passage provide a lifting force for the aircraft. And U.S. Pat. No. 3,017,139, "Ring Airfoil Aircraft" uses flaps to direct the flow of air and provide a lifting force. In each of these examples, the directed air flow is the means of controlling a flight path.
A need has therefore been felt for a simple aircraft configuration that can conveniently and safely move in a vertical direction and that makes use of the properties of the lifting surfaces to provide the requisite vertical force.
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The present invention concerns devices for access and tracking of tracks on the surface of mobile data media readable and/or writable optically by a laser beam.
In the case of a medium in the form of a disk, which shall be taken as the example for the rest of the account, the data is recorded along tracks in the form of either a single spiral extending from the center to the edge of the disk, or a series of concentric circles.
During reading or recording, the disk is in motion. Its movement is rotational about an axis which is perpendicular to the surface of the disk and passes through its center.
Generally, a reading and/or recording device includes means which allow the laser beam to access the track which is to be read and/or written and means to assure the tracking. Tracking is carried out by monitoring and correcting firstly the focussing of the luminous spot that the laser beam makes on the surface of the disk and secondly the radial positioning error of this spot in relation to the axis of the track.
Thus, a classical device for access and tracking includes among other things an access carriage??, a focussing lens and a radial tracking mirror. These elements make up the optical head which is known as the "mobile head". When the device for reading and recording is in operation, the focussing lens and the radial tracking mirror follow a track, whatever the position of the optical head. When the optical head moves the radial tracking stops but the focussing continues. During an access, the access carriage allows firstly the focussing lens and the radial tracking mirror to be positioned above the track, and secondly, the radial tracking mirror is activated to adjust the tracking.
To carry out the access and radial tracking operations, a device in which the motor coil assures both access and radial tracking has been described in the French Patent N.degree. 82 03425.
According to this patent, the optical head is attached to and slides on a guide rail. Means for flexible links between the gliding elements and the optical head are provided in order to obtain a good operation. The use of simple gliding systems does not enable satisfactory tracking to be obtained. Furthermore, in the French Patent N.degree. 82 03425, the focussing lens and its associated coil are linked to the rest of the optical head, which also contains the radial tracking mirror and the access coil, by means of a flexible link in order to avoid the focussing operation being accompanied with a diaphragm effect.
Such a structure for a device for access and control increases the mass of the mobile head and therefore the mass of counterweight necessary to balance it, which has as the main disadvantage of increasing the weight of the head and thereby limiting the speed of access.
By carrying out studies on devices for access and control for an optical disk, the applicant noticed that by using a monobloc structure including the optical head and the two coils for the motor-devices it is possible as is described in French Patent N.degree. 89 08800 to eliminate the means of flexible linkage while maintaining a high level of precision and thus to lighten the mobile head and enable faster access to the tracks.
However, the fact that the optical head and the two coils for the motor-coils are solidly linked is a disadvantage in some cases. When the control device is activated in order to correct the focussing of the laser beam, its movement causes a slight decentering of the beam on the pupil of the focussing lens. For example, when the mobile data medium used has an insufficiently flat surface, this decentering results in deformation and enlargement of the focussing spot accompanied by a reduction in the density of the optical power of this spot. This enlargement may be enough to prevent the laser beam from correctly reading and/or writing data.
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Field of the Invention
The present invention relates to a communication apparatus, a method of controlling the same, and a non-transitory computer-readable storage medium.
Description of the Related Art
Conventionally, if a communication apparatus maintains continuous connection to a communication partner in order to perform communication of high immediacy, power consumption may be increased, and an operating time of a device may be decreased. It is therefore necessary to save power for communication processing when communication of high immediacy is performed.
As a technique capable of saving the power for the communication processing when communication of high immediacy is performed, a technique of establishing connection when a communication apparatus receives a trigger from a server is proposed in Japanese Patent Laid-Open No. 2014-146876. According to this technique, power savings can be achieved without requiring the communication apparatus to maintain continuous connection. There is also a technique such as BLE (Bluetooth® Low Energy) as a power saving technique or a WoL (Wake on LAN) as a technique of activating the communication apparatus from a sleep mode. Note that the sleep mode refers to a mode in which some functions of the communication apparatus are turned off, and power consumption is suppressed.
When the communication apparatus in the sleep mode is caused to receive a message (for example, a push notification) by activating it from a remote site, activation from the remote site cannot be performed in some cases. For example, since connection is cut off due to distance limitation in BLE, the communication apparatus shifted to the sleep mode cannot return from the sleep mode.
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The present invention is directed toward an insulin injection guide and more particularly toward a device which is adapted to be placed around a person's thigh to assist him in giving himself an insulin injection in the proper location.
Diabetes mellitus is a disease or disorder which is unfortunately shared by many people both young and old. The condition is characterized by an inadequate secretion or utilization of insulin which results in excessive amounts of sugar in the blood. In many cases, the condition can be controlled by observing a strict diet. Other, more serious cases, can only be controlled by regular injections of insulin.
Since an insulin injection must be received daily, it is impractical to so frequently visit a doctor or nurse and accordingly most people who must take insulin injections are taught to administer the injections themselves. In recent years, even relatively young children have been taught to administer their own insulin injections.
Insulin injections are normally given in the front portion of a person's thigh. This is done for both physiological reasons and for convenience since one cannot only see what they are doing but can utilize two hands during the injection process. In addition, since various adverse conditions can result by repeatedly injecting oneself in the same position, users of insulin are taught to inject themselves in a different spot on the thigh each day and to utilize both their right and left thighs. Unfortunately, many people and particularly the very young and the very old may forget where they gave themselves the last injection or may merely forget to vary the injection sight and may tend to continually give themselves injections in the same location.
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1. Field
A cooking device is disclosed herein.
2. Background
A cooking device is a device for cooking food using heat of a heating source. As an example of the cooking device, an oven range includes an oven chamber in which the food is cooked, and a burner which cooks the food in the oven chamber by burning a gas.
In Korean Patent Publication No. 10-2010-0013997 (published on Feb. 10, 2010) as a prior art document, there is disclosed an oven range.
In the oven range, a burner chamber is provided under a bottom surface thereof which forms an oven chamber, and a lower burner which convectively heats food in the oven chamber is installed in the burner chamber.
The oven range in the prior art document has the following problems.
First, as described above, to provide air heated by the lower burner from the burner chamber into the oven chamber, the oven chamber and the burner chamber are in communication with each other. However, since the burner chamber is provided under the oven chamber, a part of the bottom surface of the oven chamber should be open.
When a part of the bottom surface of the oven chamber is open, food leftovers or the like may be introduced into the burner chamber through an open portion of the oven chamber in communication with the burner chamber when the food is cooked in the oven chamber or the food is put into or taken out of the oven chamber. Therefore, a product may be contaminated by the food leftovers or the like.
Also, since a part of the bottom surface of the oven chamber is open, it is not easy to clean the oven chamber due to an opening of the bottom surface.
Also, since the lower burner is installed under the oven chamber, a cavity capacity is reduced by a burner installation space.
Also, in the case in which the lower burner is installed at an outer side of the oven chamber, when it is necessary to replace or check an ignition unit for igniting a mixed gas supplied to the lower burner, an outer case which surrounds the oven chamber should be separated therefrom, and thus an operation therefor is complicated, and much time is spent.
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The present invention relates to a trash collection, management and disposal system.
In office work areas, especially those work areas where substantial quantities of scrap paper and various other types of trash are generated, the collection, transportation and disposal of the trash is a task whose cost to the business may achieve significant proportions. Nevertheless, management rarely devotes significant attention to the handling of trash because it rarely appreciates that worthwhile cost savings can be realized with improved trash disposal systems. Management generally takes the view that engineering and product development personnel better spend their time in projects related more directly to the primary purpose of the enterprise. Trash disposal is viewed as an incidental activity capable of being carried out in the conventional manner. Hence, little if any thought is devoted to ways of collecting, transporting and disposing of trash in an efficient manner which takes into account the needs of all employees.
It is widely held that pleasant work surroundings increase employee morale and efficiency. The custodial staff is also an important element in a profitable business. Providing these employees with a waste management system that involves the entire work force lightens their work load, increases their morale and motivates them to work with greater efficiency.
Identified deficiencies in present trash handling systems include:
employment of open waste baskets whose short height and limited capacity are not compatible in offices where large quantities of trash are generated;
employmemt of open waste baskets which are unsightly and can be a source of contamination and unpleasant odors in the work area;
positioning of waste baskets adjacent to walls allows personnel to use the walls as back-stops against which trash can be thrown for deflection into the waste baskets resulting is soiled walls; and
inefficient modes of transferring the trash from the waste baskets and other collectors where it is originally deposited to the final dump site.
It is the general object of the present invention, therefore, to provide an integrated trash collection, management and disposal system.
It is another object of the present invention to provide a trash management system enabling a minimum number of trash transfers.
It is another object of the present invention to provide an improved trash collection container which is durable, mobile and easily handled by custodial personnel.
It is another object of the present invention to provide a trash collection container having an improved hinge assembly pivotally mounting a cover on the container.
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The iris surrounds the dark, inner pupil region of an eye and extends concentrically to the white sclera of the eye.
A. K. Jain, A. Ross, and S. Prabhakar, “An introduction to biometric recognition,” IEEE Trans. Circuits Syst. Video Technol., vol. 14, 2004 discloses that the iris of the eye is a near-ideal biometric.
For the purposes of iris based recognition, an image of a subject comprising an iris region is acquired with an imaging system, typically using infra-red (IR) illumination to bring out the main features of an underlying iris pattern.
Then, eye and/or iris detection is applied over the whole acquired image to identify a region of the image containing the iris pattern. Iris segmentation is performed on the detected region of the image in order to define an iris segment, and then feature extraction is performed on the iris segment. The extracted features can be used to generate an iris code for the subject of the acquired image and this can be used in conjunction with stored iris code(s) to identify, recognise or authenticate the subject of the image.
If there are certain requirements for the input image regarding the iris size and location, as in the case of BS ISO/IEC 19794-6:2005 compliant images, this can speed up the detection process.
Without such requirements, there can be a large variation in iris size and location within acquired images. For example, in the context of handheld devices, for example, smartphones, the range of distances between the eye and the device can vary from less than 15 cm out to 40 cm or more, depending on how close a user holds the device or the length of the user's arm—this can affect the size, location and quality of the iris region appearing in an acquired image.
Thus, the detection process can be slow and possibly lead to false candidates, since the initial processing step has to detect where the iris is located within the whole acquired image and determine the size of the iris.
As indicated, in an attempt to speed up processing, some systems perform relatively large-scale and so faster, eye detection before performing refined iris detection on the result of the eye detection. However, this can result in non-segmented or wrongly segmented iris images, especially in cases where the image is so closely acquired that only a portion of the eye is included therein. In these cases, since the full eye is not within the image, the eye detection can fail to correctly locate the eye, thus providing a poor quality or wrong result for the following image processing.
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There is often a need to perform garbage collection and other compactions operations to copy a word line of data from a source page to a destination page in memory. There are several ways in which the data can be moved. For example, an “off-chip copy” operation can be used, in which the word line of data is read from a source page and transferred over a bus to a controller and is then transferred back over the bus to the memory and written to a destination page. To avoid transferring data back and forth over the controller-memory bus, an “on-chip copy” operation can be used, in which a word line of data is read from a source page, written into data latches in the memory chip, and then written to a destination page. Although on-chip copy is faster than off-chip copy since it avoids toggling the data between the controller and the memory, there are some disadvantages associated with on-chip copy. For example, on-chip copy requires that data be programmed in the destination page in the same order/format as the data is stored in the source page. As another example, on-chip copy can be susceptible to the accumulation of program and sense errors, as moving data many times with an on-chip copy operation can cause decode errors. To address this issue, a hybrid off-chip/on-chip copy operation can be used, in which data read from the source page is both stored in data latches in the memory (as in an on-chip copy operation) and sent to the controller (as in an off-chip copy operation), which tests the integrity of the data. If the data is valid, the data stored in the data latches in the memory is simply programmed to the destination page without toggling the data back from the controller to the memory, thereby cutting the data toggle time in half compared to using a typical off-chip copy operation.
Overview
Embodiments of the present invention are defined by the claims, and nothing in this section should be taken as a limitation on those claims.
By way of introduction, the below embodiments relate to a storage module and method for on-chip copy gather. In one embodiment, a storage module is provided with a memory comprising a plurality of word lines and a plurality of data latches. The memory copies data from a first word line into a first data latch and copies data from a second word line into a second data latch. The memory then copies only some of the data from the first data latch and only some of the data from the second data latch into a third data latch. After that, the memory copies the data from the third data latch to a third word line.
In another embodiment, a storage module is provided comprising a memory and an on-chip copy gather module. The on-chip copy gather module is configured to use a plurality of data latches in the memory to gather data from portions of source word lines in the memory and copy the gathered data to a destination word line in the memory. In yet another embodiment, a storage module is provided comprising a memory and a controller. The controller is configured to gather data from portions of a plurality of source word lines in the memory and copy the gathered data to a destination word line while preventing accumulation of errors from bad columns in the memory.
Other embodiments are possible, and each of the embodiments can be used alone or together in combination. Accordingly, various embodiments will now be described with reference to the attached drawings.
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Hyperlipidemic conditions are often associated with elevated plasma concentrations of low density lipoprotein (LDL) cholesterol and very low density lipoprotein (VLDL) cholesterol. Such concentrations can be reduced by decreasing the absorption of bile acids from the intestine. One method by which this may be achieved is to inhibit the bile acid active uptake system in the terminal ileum. Such inhibition stimulates the conversion of cholesterol to bile acid by the liver and the resulting increase in demand for cholesterol produces a corresponding increase in the rate of clearance of LDL and VLDL cholesterol from the blood plasma or serum.
There has now been identified a novel class of heterocyclic compounds which reduce the plasma or serum concentrations of LDL and VLDL cholesterol and in consequence are particularly useful as hypolipidemic agents. By decreasing the concentrations of cholesterol and cholesterol ester in the plasma, the compounds of the present invention retard the build-up of atherosclerotic lesions and reduce the incidence of coronary heart disease-related events. The latter are defined as cardiac events associated with increased concentrations of cholesterol and cholesterol ester in the plasma or serum.
For the purposes of this specification, a hyperlipidemic condition is defined as any condition wherein the total cholesterol concentration (LDL+VLDL) in the plasma or serum is greater than 240 mg/dL (6.21 mmol/L) (J. Amer. Med. Assn., 256, 20, 2849-2858 (1986)). International Patent Application No. WO 96/05188 describes compounds of formula (0) ##STR2##
We have now discovered a group of compounds which have greater hypolipidemic activity in vivo than those specifically disclosed in International Patent Application No. WO 96105188. The compounds differ in the definition of group R.sup.7. Accordingly, the present invention provides compounds of the formula (I): ##STR3## wherein R.sup.1 is a straight chained C.sub.1-6 alkyl group;
R.sup.2 is a straight chained C.sub.1-6 alkyl group; PA1 R.sup.3 is hydrogen or a group OR.sup.11 in which R.sup.11 is hydrogen, optionally substituted C.sub.1-6 alkyl or a C.sub.1-6 alkylcarbonyl group; PA1 R.sup.4 is pyridyl or optionally substituted phenyl; PA1 R.sup.5, R.sup.6 and R.sup.8 are the same or different and each is selected from hydrogen, halogen, cyano, R.sup.15 -acetylide, OR.sup.15, optionally substituted C.sub.1-6 alkyl, COR.sup.15, CH(OH)R.sup.15, S(O).sub.n R.sup.15, P(O)(OR.sup.15).sub.2, OCOR.sup.15, OCF.sub.3, OCN, SCN, NHCN, CH.sub.2 OR.sup.15, CHO, (CH.sub.2).sub.p CN, CONR.sup.12 R.sup.13, (CH.sub.2).sub.p CO.sub.2 R.sup.15, (CH.sub.2).sub.p NR.sup.12 R.sup.13, CO.sub.2 R.sup.15, NHCOCF.sub.3, NHSO.sub.2 R.sup.15, OCH.sub.2 R.sup.15, OCH.dbd.CHR.sup.15, O(CH.sub.2 CH.sub.2 O).sub.n R.sup.15, O(CH.sub.2).sub.p SO.sub.3 R.sup.15, O(CH.sub.2).sub.p NR.sup.12 R.sup.13 and O(CH.sub.2).sub.p N.sup.+ R.sup.12 R.sup.13 R.sup.14 wherein PA1 p is an integer from 1-4, PA1 n is an integer from 0-3 and PA1 R.sup.12, R.sup.13, R.sup.14 and R.sup.15 are independently selected from hydrogen and optionally substituted C.sub.1-6 alkyl; PA1 R.sup.7 is a group of the formula ##STR4## wherein the hydroxyl groups may be substituted by acetyl, benzyl, or EQU --(C.sub.1 -C.sub.6)-alkyl-R.sup.17 PA1 wherein the alkyl group may be substituted with one or more hydroxyl groups; PA1 R.sup.16 is --COOH, --CH.sub.2 --OH, --CH.sub.2 --O-Acetyl, --COOMe, --COOEt; PA1 R.sup.17 is H, --OH, --NH.sub.2, --COOH or COOR.sup.18 ; PA1 R.sup.18 is (C.sub.1 -C.sub.4)-alkyl or --NH--(C.sub.1 -C.sub.4)-alkyl; PA1 X is --NH--or --O--; and PA1 R.sup.9 and R.sup.10 are the same or different and each is hydrogen or C.sub.1-6 alkyl; PA1 and salts, solvates, and physiologically functional derivatives thereof. PA1 (m) the compounds of Synthetic Example 1 to 5 as hereinafter disclosed. PA1 a) acylation of a compound of fomula (II) ##STR8## by standard procedures (e.g. with N,N-carbonyl-diimidazole) at the --X--H group or PA1 a) alkylation of a compound of fomula (II) by standard procedures at the --X--H group or PA1 a) glycosylation or glucuronidation a compound of fomula (II) at the --X--H group, especially using the imidate method and PA1 b) cleavage of protecting groups, especially of hydroxyl and amino functional groups, e.g. acetyl by hydrolysis, benzyl by hydrogenolysis.
When R.sup.4 is a substituted phenyl group, there may be one to five, preferably one or two substituents which are the same or different and are each selected from halogen, hydroxy, nitro, phenyl-C.sub.1-6 alkoxy, C.sub.1-6 alkoxy, optionally substituted C.sub.1-6 alkyl, S(O).sub.n R.sup.15, CO.sub.2 R.sup.15, O(CH.sub.2 CH.sub.2 O).sub.n R.sup.15, O(CH.sub.2).sub.p SO.sup.3 R.sup.15, O(CH.sub.2).sub.p NR.sup.12 R.sup.13 and O(CH.sub.2).sub.p N.sup.+ R.sup.12 R.sup.13 R.sup.14 wherein R.sup.12 to R.sup.15, n and p are as hereinbefore defined.
Preferred embodiments of the compounds of formula (I) include compounds of the formula (III), (IV) or (IVa) ##STR5## wherein R.sup.1 to R.sup.10 and X are as hereinbefore defined.
When one or more of R.sup.3 to R.sup.6, R.sup.8 or R.sup.11 to R.sup.14 is a substituted C.sub.1-6 alkyl group, or comprises a C.sub.1-6 alkyl group the substituents may be the same or different and each is selected from hydroxy, halogen, C.sub.1-6 alkyl, C.sub.1-6 alkoxy, COR.sup.20, nitrile, CO.sub.2 R.sup.20, SO.sub.3 R.sup.20, NR.sup.21 R.sup.22, N.sup.+ R.sup.21 R.sup.22 R.sup.23 wherein R.sup.20 to R.sup.23 are the same or different and each is selected from hydrogen or C.sub.1-6 alkyl.
Suitably R.sup.1 is methyl, ethyl or n-propyl and preferably R.sup.1 is ethyl. Suitably R.sup.2 is methyl, ethyl, n-propyl, n-butyl or n-pentyl. Preferably R.sup.2 is n-butyl.
Preferably R.sup.5 is hydrogen.
Suitably R.sup.7 is selected from ##STR6##
Suitably X is --O--.
Suitably R.sup.9 and R.sup.10 are hydrogen, methyl or ethyl, hydrogen. Preferably R.sup.9 and R.sup.10 are both hydrogen.
Suitably R.sup.4 is pyridyl or phenyl optionally substituted, preferably at the 4- and/or 3-position by halogen, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, hydroxy, carboxy or O(CH.sub.2).sub.3 SO.sub.3 H. Preferably R.sup.4 is unsubstituted phenyl.
In the compounds of the formula (III): suitably at least one and preferably all of R.sup.5, R.sup.6 and R.sup.8 are hydrogen. When R.sup.5, R.sup.6 and R.sup.8 are other than hydrogen then they are suitably C.sub.1-4 alkyl optionally substituted by fluorine, C.sub.1-4 alkoxy, halogen or hydroxy, most suitably methyl, methoxy, hydroxy, trifluoromethyl or chloro and preferably methoxy.
In the compounds of the formula (IV): suitably two or three of R.sup.5, R.sup.6 and R.sup.8 are hydrogen, the others being C.sub.1-4 alkyl optionally substituted by fluoro,C.sub.1-4 alkoxy, halogen or hydroxy and most suitably methyl, methoxy, hydroxy, trifluoromethyl or chloro and preferably methoxy.
In the compounds of formula (IVa): suitably at least one and preferably all of R.sup.5, R.sup.6 and R.sup.8 are hydrogen. When R.sup.5, R.sup.6 and R.sup.8 are other than hydrogen then they are suitably C.sub.1-4 alkyl optionally substituted by fluorine, C.sub.1-4 alkoxy, halogen or hydroxy, most suitably methyl, methoxy, hydroxy, trifluoromethyl or chloro and preferably methoxy. Most preferably, R.sup.1 is n-butyl, R.sup.2 is ethyl, R.sup.3, R.sup.5, R.sup.6, R.sup.8, R.sup.9 and R.sup.10 are hydrogen, R.sup.4 is phenyl and R.sup.7 is ##STR7##
Pharmaceutically acceptable salts are particularly suitable for medical applications because of their greater aqueous solubility relative to the parent, ie basic, compounds. Such salts must clearly have a pharmaceutically acceptable anion or cation. Suitable pharmaceutically acceptable acid addition salts of the compounds of the present invention include those derived from inorganic acids, such as hydrochloric, hydrobromic, phosphoric, metaphosphoric, nitric, sulphonic and sulphuric acids, and organic acids, such as acetic, benzenesulphonic, benzoic, citric, ethanesulphonic, fumaric, gluconic, glycollic, isothionic, lactic, lactobionic, maleic, malic, methanesulphonic, succinic, p-toluenesulphonic, tartaric and trifluoroacetic acids. The chloride salt is particularly preferred for medical purposes. Suitable pharmaceutically acceptable base salts include ammonium salts, alkali metal salts, such as sodium and potassium salts, and alkaline earth salts, such as magnesium and calcium salts.
Salts having a non-pharmaceutically acceptable anion are within the scope of the invention as useful intermediates for the preparation or purification of pharmaceutically acceptable salts and/or for use in non-therapeutic, for example, in vitro, applications.
The term "physiologically functional derivative" as used herein refers to any physiologically acceptable derivative of a compound of the present invention, for example, an ester, which upon administration to a mammal, such as a human, is capable of providing (directly or indirectly) such a compound or an active metabolite thereof.
A further aspect of the present invention is prodrugs of the compounds of the invention. Such prodrugs can be metabolised in vivo to give a compound according to the invention. These prodrugs may or may not be active in their own right.
The compounds of the present invention can also exist in different polymorphic forms, for example, amorphous and crystalline polymorphic forms. All polymorphic forms of the compounds of the present invention are within the scope of the invention and are a further aspect thereof.
The term "alkyl" as used herein refers, unless otherwise stated, to a monovalent straight or branched chain radical. Likewise, the term "alkoxy" refers to a monovalent straight or branched chain radical attached to the parent molecular moiety through an oxygen atom. The term "phenylalkoxy" refers to a monovalent phenyl group attached to a divalent C.sub.1-6 alkylene group which is itself attached to the parent molecular moiety through an oxygen atom.
The compounds of formula (I) exist in forms wherein the carbon centres --C(R.sup.1)(R.sup.2)-- and --CHR.sup.4 -- is/are chiral. The present invention includes within its scope each possible optical isomer substantially free, i.e. as associated with less than 5%, of any other optical isomer(s), and mixtures of one or more optical isomers in any proportions, including racemic mixtures.
For the purposes of this specification, the absolute chiralities of the aforementioned carbon centres are given in the order --C(R.sup.1)(R.sup.2), then --CHR.sup.4 --.
In those cases where the absolute stereochemistry at --C(R.sup.1)(R.sup.2)-- and --CHR.sup.4 -- has not been determined, the compounds of the invention are defined in terms of the relative positions of the R.sup.1 /R.sup.2 and H/R.sup.4 substituents. Thus those compounds wherein the bulkier of the R.sup.1 and R.sup.2 substituents, i.e. the substituent of higher mass, and the R.sup.4 substituent are both located on the same side of the thiazepine ring are referred to herein as "cis", and those compounds in which the bulkier of the R.sup.1 and R.sup.2 substituents are located on opposite sides of the ring are referred to as "trans" and are preferred. It will be evident to a skilled person that both "cis" and "trans" compounds of the invention can each exist in two enantiomeric forms which are individually designated "(+)-" or "(-)-" according to the direction of rotation of a plane of polarised light when passed through a sample of the compound. Cis or trans compounds of the invention in which the individual anantiomers have not been resolved are referred to herein using the prefix "(+)-".
According to further aspects of the invention, there are also provided:
(a) compounds of formula (I) and pharmaceutically acceptable salts, solvates and physiologically functional derivatives thereof for use as therapeutic agents, particularly in the prophylaxis and treatment of clinical conditions for which a bile acid uptake inhibitor is indicated, for example, a hyperlipidemic condition, such as atherosclerosis;
(b) pharmaceutical compositions comprising a compound of formula (I) or one of its pharmaceutically acceptable salts, solvates, or physiologically functional derivatives, at least one pharmaceutically acceptable carrier and, optionally, one or more other physiologically active agents;
(c) the use of a compound of formula (I) or of a pharmaceutically acceptable salt, solvate, or physiologically functional derivative thereof in the manufacture of a medicament for the prophylaxis or treatment of a clinical condition for which a bile acid uptake inhibitor is indicated, for example, a hyperlipidemic condition, such as atherosclerosis;
(d) a method of inhibiting the absorption of bile acids from the intestine of a mammal, such as a human, which comprises administering an effective bile acid absorption inhibiting amount of a compound of formula (I) or of a pharmaceutically acceptable salt, solvate, or physiologically functional derivative thereof to the mammal;
(e) a method of reducing the blood plasma or serum concentrations of LDL and VLDL cholesterol in a mammal, such as a human, which comprises administering an effective cholesterol reducing amount of a compound of formula (I) or of a pharmaceutically acceptable salt, solvate, or physiologically functional derivative thereof to the mammal;
(f) a method of reducing the concentrations of cholesterol and cholesterol ester in the blood plasma or serum of a mammal such as a human, which comprises administering an effective cholesterol and cholesterol ester reducing amount of a compound of formula (I) or of a pharmaceutically acceptable salt, solvate, or physiologically functional derivative thereof to the mammal;
(g) a method of increasing the fecal excretion of bile acids in a mammal, such as a human, which comprises administering an effective bile acid fecal excretion increasing amount of a compound of formula (I) or of a pharmaceutically acceptable salt, solvate, or physiologically functional derivative thereof to the mammal;
(h) a method for the prophylaxis or treatment of a clinical condition in a mammal, such as a human, for which a bile acid uptake inhibitor is indicated, for example, a hyperlipidemic condition, such as atherosclerosis, which comprises administering a therapeutically effective amount of a compound of the formula (I) or of a pharmaceutically acceptable salt, solvate, or physiologically functional derivative thereof to the mammal;
(i) a method of reducing the incidence of coronary heart disease-related events in a mammal, such as a human, which comprises administering an effective coronary heart disease-related events reducing amount of a compound of formula (I) or of a pharmaceutically acceptable salt, solvate, or physiologically functional derivative thereof;
(j) a method of reducing the concentration of cholesterol in the blood plasma or serum of a mammal, such as a human, which comprises administering an effective cholesterol reducing amount of a compound of formula (I);
(k) processes for the preparation of compounds of formula (I) (including salts, solvates and physiologically functional derivatives thereof as defined herein); and
(l) novel chemical intermediates in the preparation of compounds of formula (I).
Hereinafter all references to "compound(s) of formula (I)" refer to compound(s) of formula (I) as described above together with their salts, solvates and physiologically functional derivatives as defined herein.
The amount of a compound of formula (I) which is required to achieve the desired biological effect will, of course, depend on a number of factors, for example, the specific compound chosen, the use for which it is intended, the mode of administration and the clinical condition of the recipient. In general, a daily dose is the range of from 0.3 mg to 100 mg (typically from 3 mg to 50 mg) per day per kilogram bodyweight, for example, 3-10 mg/kg/day. An intravenous dose can, for example, be in the range of from 0.3 mg to 1.0 mg/kg, which can conveniently be administered as an infusion of from 10 ng to 100 ng per kilogram per minute. Infusion fluids suitable for this purpose can contain, for example, from 0.1 ng to 10 mg, typically from 1 ng to 10 mg, per millilitre. Unit doses can contain, for example, from 1 mg to 10 g of the active compound. Thus ampoules for injection can contain, for example, from 1 mg to 100 mg and orally administrable unit dose formulations, such as tablets or capsules, may contain, for example, from 1.0 to 1000 mg, typically from 10 to 600 mg. In the case of pharmaceutically acceptable salts, the weights indicated above refer to the weight of the benzothiazepine ion derived from the salt.
For the prophylaxis or treatment of the conditions referred to above, the compounds of formula (I) can be used as the compound per se, but are preferably presented with an acceptable carrier in the form of a pharmaceutical composition. The carrier must, of course, be acceptable in the sense of being compatible with the other ingredients of the composition and must not be deleterious to the recipient. The carrier can be a solid or a liquid, or both, and is preferably formulated with the compound as a unit-dose composition, for example, a tablet, which can contain from 0.05% to 95% by weight of the active compound. Other pharmacologically active substances can also be present including other compounds of formula (I). The pharmaceutical compositions of the invention can be prepared by any of the well known techniques of pharmacy consisting essentially of admixing the components.
Pharmaceutical compositions according to the present invention include those suitable for oral, rectal, topical, buccal (e.g. sub-lingual) and parenteral (e.g. subcutaneous, intramuscular, intradermal, or intravenous) administration, although the most suitable route in any given case will depend on the nature and severity of the condition being treated and on the nature of the particular compound of formula (I) which is being used. Enteric-coated and enteric-coated controlled release formulations are also within the scope of the invention. Preferred are acid and gastric juice resistant formulations. Suitable enteric coatings include cellulose acetate phthalate, polyvinylacetate phthalate, hydroxypropylmethylcellulose phthalate and anionic polymers of methacrylic acid and methacrylic acid methyl ester.
Pharmaceutical compositions suitable for oral administration can be presented in discrete units, such as capsules, cachets, lozenges, or tablets, each containing a predetermined amount of a compound of formula (I); as a powder or granules; as a solution or a suspension in an aqueous or non-aqueous liquid; or as an oil-in-water or water-in-oil emulsion. As indicated, such compositions can be prepared by any suitable method of pharmacy which includes the step of bringing into association the active compound and the carrier (which can constitute one or more accessory ingredients). In general, the compositions are prepared by uniformly and intimately admixing the active compound with a liquid or finely divided solid carrier, or both, and then, if necessary, shaping the product. For example, a tablet can be prepared by compressing or moulding a powder or granules of the compound, optionally with one or more accessory ingredients. Compressed tablets can be prepared by compressing, in a suitable machine, the compound in a free-flowing form, such as a powder or granules optionally mixed with a binder, lubricant, inert diluent and/or surface active/dispersing agent(s). Moulded tablets can be made by moulding, in a suitable machine, the powdered compound moistened with an inert liquid diluent.
Pharmaceutical compositions suitable for buccal (sub-lingual) administration include lozenges comprising a compound of formula (I) in a flavored base, usually sucrose and, acacia or tragacanth, and pastilles comprising the compound in an inert base such as gelatin and glycerin or sucrose and acacia.
Pharmaceutical compositions suitable for parenteral administration conveniently comprise sterile aqueous preparations of a compound of formula (I), preferably isotonic with the blood of the intended recipient. These preparations are preferably administered intravenously, although administration can also be effected by means of subcutaneous, intramuscular, or intradermal injection. Such preparations can conveniently be prepared by admixing the compound with water and rendering the resulting solution sterile and isotonic with the blood. Injectable compositions according to the invention will generally contain from 0.1 to 5% w/w of the active compound.
Pharmaceutical compositions suitable for rectal administration are preferably presented as unit-dose suppositories. These can be prepared by admixing a compound of formula (I) with one or more conventional solid carriers, for example, cocoa butter, and then shaping the resulting mixture.
Pharmaceutical compositions suitable for topical application to the skin preferably take the form of an ointment, cream, lotion, paste, get spray, aerosol, or oil. Carriers which can be used include vaseline, lanoline, polyethylene glycols, alcohols, and combinations of two or more thereof. The active compound is generally present at a concentration of from 0.1 to 15% w/w of the composition, for example, from 0.5 to 2%.
Transdermal administration is also possible. Pharmaceutical compositions suitable for transdermal administration can be presented as discrete patches adapted to remain in intimate contact with the epidermis of the recipient for a prolonged period of time. Such patches suitably contain the active compound in an optionally buffered, aqueous solution, dissolved and/or dispersed in an adhesive, or dispersed in a polymer. A suitable concentration of the active compound is about 1% to 35%, preferably about 3% to 15%. As one particular possibility, the active compound can be delivered from the patch by electrotransport or iontophoresis, for example, as described in Pharmaceutical Research, 2(6), 318 (1986).
The compounds of the invention can be prepared by conventional methods known to a skilled person or in an analogous manner to processes described in the art.
For example, compounds of the formula (I) can be prepared by a process which comprises
The compounds of formula (II) can be prepared according to the method of preparation disclosed in WO 96/05188.
The compounds of formula (I) substantially free, of other optical isomers can be obtained either by chiral synthesis, for example, by the use of the appropriate chiral starting material(s), such as the aziridine, or by resolution of the products obtained from achiral syntheses, for example, by chiral hplc or by classical resolution with chiral acids.
Optional conversion of a compound of formula (I), or a compound of formula (I) comprising a basic substituent, to a corresponding acid addition salt may be effected by reaction with a solution of the appropriate acid, for example, one of those recited earlier. Optional conversion of a compound of formula (I) comprising an acidic substituent to a corresponding base salt may be effected by reaction with a solution of the appropriate base, for example, sodium hydroxide. Optional conversion to a physiologically functional derivative, such as an ester, can be carried out by methods known to those skilled in the art or obtainable from the chemical literature.
In addition, compounds of the formula (I) may be converted to different compounds of the formula (I) by standard methods known or available from the literature to those skilled in the art, for example by alkylation of a hydroxy group.
Comparison of the hypolipidemic activity of of the compounds according to the invention with compound no. 11 of WO 96/05188:
In order to prove the greater hypolipidemic activity of the compounds according to the invention tests were carried out by means of three genetically modified cell lines. These were derivatives of the generally known "Chinese hamster ovary" (CHO) cell line, which on account of incorporated expression plasmids additionally produced sodium-dependent bile acid transporters. The first cell line (CHO/pRIBAT8) was in this case the ileal transporter of the rabbit (RIBAT), the second (CHO/pHIBAT8) the ileal transporter of the human (HIBAT) and the third (CHO/pHLBAT5) the hepatic transporter of the human. All plasmids were based on the standard plasmid pCDNA1neo, which as important elements has a cytomegaloviral promoter for the permanent expression of heterologous genes and a gene for the production of cell resistance against the substance G418.
The starting material for the production of the plasmid for the RIBAT-producing cell line (pRIBAT8) was total RNA of the terminal ileum of the rabbit. From this by means of an RT-PCR procedure (reverse transcriptase reaction, followed by a polymerase chain reaction) with the aid of the oligonucleotides 5'-gtcagaccagaagcttgggcttctgcagac-3'(SEQ ID NO:1) and 5'-atcttaataatattctagacagtttttctttg-3'(SEQ ID NO:2), a cDNA was synthesized which contained the total protein-coding region of the RIBAT, and also 41 base pairs on the 5'-adjacent and 31 base pairs on the 3'-adjacent untranslated region. This region was flanked by cleavage sites for the restriction enzymes Hind3 (at the 5'-end) and Xba1 (at the 3'-end). The obtained cDNA and DNA of plasmid pcDNA1 neo were digested using the two restriction enzymes mentioned and resulting fragments were combined by means of ligase to give the expression plasmid pRIBAT8.
The plasmid for the HIBAT-producing cell line (pHIBAT8) was prepared analogously to pRIBAT8. In this case, total RNA of human terminal ileum and the oligonucleotides 5'-taaaagttggatccggtagaagtaaacg-3'(SEQ ID NO:3) and 5'-tctgttttgtcctctagatgtctacttttc-3'(SEQ ID NO:4) served as starting material. Besides the total protein-coding region of HIBAT, the resulting cDNA also contained 97 base pairs on the 5'-adjacent and 5 base pairs on the 3'-adjacent untranslated region. This region was flanked by cleavage sites for the restriction enzymes BamH1 (at the 5'-end) and Xba1 (at the 3'-end). The obtained cDNA and DNA of plasmid pcDNA1 neo were digested using the two restriction enzymes mentioned and resulting fragments were combined by means of ligase to give the expression plasmid pRIBAT8.
A commercially available cDNA gene bank prepared from human liver served as starting material for the plasmid for the preparation of the HLBAT-producing cell line (pHLBAT5). From this by means of a PCR procedure (polymerase chain reaction) with the aid of the oligonucleotides 5'-ggagtggtcttccactggatcccaggaggatggagg-3'(SEQ ID NO:5) and 5'-ccagaatccaggccacctctagaagggctaggctgt-3'(SEQ ID NO:6), a cDNA was synthesized which contained the total protein-coding region of the HLBAT, and also 7 base pairs on the 5'-adjacent and 6 base pairs on the 3'-adjacent untranslated region. This region was flanked by cleavage sites for the restriction enzymes BamH1 (at the 5'-end) and Xba1 (at the 3'-end). The obtained cDNA and DNA of plasmid pcDNA1neo were digested using the two restriction enzymes mentioned and resulting fragments were combined by means of ligase to give the expression plasmid pHLBAT5.
For the preparation of the genetically modified cell lines, CHO cells were transfected with DNA from pRIBAT8, pHIBAT8 or pHLBAT5 and cells which developed resistance against the selection substance G418 were selectively additionally cultured by addition of the substance to the cell medium. The cells CHO/pRIBAT8, CHO/pHIBAT8 and CHO/pHLBAT5 were then isolated from the amount of G418-resistant cells and pure clonal lines were cultured therefrom. The tool used for following the isolation process was in this case a fluorescent bile acid derivative (3.beta.-NBD-NCT; N-[7-(4-nitrobenzo-2-oxa-1,3-diazol)]-3.beta.-amino-7a, 12a-dihydroxy -5.beta.-cholan-24-oyl)-2'-aminoethanesulfonate. Cells with intact bile acid transporters rapidly absorbed this substance from the cell medium and as a result became fluorescent. They could thereby be easily differentiated from cells without intact bile acid transporters with the aid of a fluorescence microscope.
All three cell lines transported radiolabelled taurocholic acid efficiently from the extracellular medium into the cell interior. This process was sodium-dependent. In contrast to this, CHO cells without intact bile acid transporters only absorbed very small amounts of taurocholic acid. Building on this knowledge, a characterization of test substances according to the invention was carried out as follows: cells of the type CHO/pRIBAT8, CHO/pHIBAT8 or CHO/pHLBAT5 were simultaneously exposed in culture dishes to radiolabelled taurocholic acid and a test substance and the absorption of radioactive material by the cells was measured. The test substance concentrations here were varied systematically from dish to dish and all other parameters were kept constant. To prepare them for experiment, the cells were routinely cultured in medium (minimum essential medium (MEM); 1% MEM non-essential amino acid solution; 10% foetal calf serum; 400 g/ml of G418) in culture flasks, if required removed from their environment by means of trypsin, inoculated in diluted form into culture dishes (diameter: 3.5 cm) and additionally cultured in medium. Shortly before reaching cell confluence, the medium was removed from the cells and the contents of each dish were washed with 2 times 1.5 ml of PBS (Dulbecco's phosphate-buffered saline solution). After removing the wash solution, 1 ml of a defined concentration of test substance in PBS was added to each dish and they were incubated at 21.degree. C. for 30 minutes. This preincubation solution was then replaced by a test solution which contained [24-.sup.14 C]- taurocholic acid in a concentration of 4.3 M and of a specific radioactivity of 7400 Bq/ml, but otherwise had the same volume and the same composition as the pre-incubation solution. The cells were exposed to the test solution at 21.degree. C. for 30 minutes and then washed with 5 times 1.5 ml of PBS per dish. To lyse the cells, 1 ml of an aqueous solution containing 0.1 mol/l of NaOH and 0.1% (weight/volume) of SDS was added to each dish, which was incubated for 30 minutes at 21.degree. C. and triturated. Finally, the contents of each dish were mixed with 10 ml of a commercially available scintillator solution and the radioactivity taken up by the cells was determined with the aid of a scintillation-measuring apparatus.
To assess the transport results, the radioactivity values were not plotted directly, but their % relationship to a control value in the case of which measurement had been carried out without inhibiting test substance. Half-maximal inhibition values (IC.sub.50) resulted from this graphically or arithmetically:
______________________________________ Example 3 IC.sub.50 (RIBAT) : 70 nm = 0,07 .mu.M Example 11 of WO 96/05188 IC.sub.50 (RIBAT) : 4.mu.M ______________________________________
An analogous investigation of the effect of the same substances on the transport of the cell line CHO/pHIBAT8 showed that here the corresponding IC.sub.50 value varied approximately within the same order of magnitude. In contrast to this, the IC.sub.50 value determined with the cell line CHO/pHLBAT5 was several powers of ten higher. This shows that compounds according to the invention can exert a comparable effect on orthologous sodium-dependent bile acid transporters of various species and, in contrast to this, the effect on paralogous transporters of other organs can be very much smaller.
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The determination of blood glucose is critical to diabetic patients. These patients must measure their blood glucose level several times daily in order to determine how much insulin their body requires. For diabetics with internally implantable or external insulin pumps, the ability to have a reliable glucose sensor that can continuously measure their blood glucose is essential for the realization of an artificial pancreas device.
Considerable efforts have been placed on the development of reliable methods for measuring blood glucose noninvasively. Although several sensors have been successfully developed for in vitro and in vivo applications, these sensors can be used only for intermittent measurements or short term monitoring. None of these devices are suitable for long-term in vivo applications utilizing noninvasive means.
The concentration of a limited number of analytes in blood can be measured noninvasively by spectroscopic means. For instance, by measuring the amount of optical radiation either absorbed by, transmitted through or reflected from biological tissues, it is possible to derive a quantitative measurement relative to the concentration of oxygen in blood. In contrast to invasive measurement, noninvasive measurements are clearly more attractive because they are safe, fast, convenient, painless and can be used to provide short-term and long-term continuous information on changing levels of blood analytes in the body. Therefore, noninvasive measurement of blood constituents is desirable, especially in children and older patients.
Several attempts have been made in the past to develop a reliable method for quantitative noninvasive measurement of glucose levels in biological tissues by irradiating the tissue with light at predetermined wavelengths and using the principle of absorption spectroscopy. Some methods are based on detecting the resonance absorption peaks in the infrared region of the electromagnetic spectrum, also known as the "fingerprints" region, which are caused by vibrational and rotational oscillations of the molecules and are characteristic for different molecules. Other techniques are based upon near-infrared spectroscopy to determine the sample's composition. Unlike the "fingerprint" region, which is valuable as a tool for obtaining structural information on the sample, structural measurements in the near infrared region of the spectra are obscured because of multiple and weak overtones yielding many overlapping peaks.
Regardless of which spectroscopic method is employed, there are four basic practical difficulties which limit the noninvasive detection of most biological substances including glucose: 1) The high intrinsic background absorption by water, 2) the relatively low concentration of most biological substances, 3) the number of weak and overlapping absorption peaks in the spectra, and 4) the highly scattering properties of biological tissues. Moreover, the large variations in the optical properties of skin among different individuals makes absolute measurements and calibrations very difficult and impractical.
Two methods are commonly utilized for obtaining spectral information from biological tissues for the purpose of measuring the concentration of various biochemical constituents noninvasively. One method is based on information derived from the absolute optical spectra of tissues containing blood. According to this concept, the tissue is illuminated with light at different preselected wavelengths and either the total or proportional amount of light which is transmitted through, reflected from, or transflected by the tissue is measured by a photodetector. This technique was utilized for example by Hewlett-Packard in their ear oximeter product (U.S. Pat. No. 3,638,640 by Shaw) and by Rosenthal et al. (U.S. Pat. No. 5,028,787). According to the other method, which is widely used in pulse oximetry, the tissue is illuminated by two different light sources. Typically, one wavelength around 660 nm and the other in the range between 815 nm and 960 nm are used. The change in optical absorption caused by the pulsation of arterial blood in the tissue is measured and analyzed to provide a quantitative measure of the amount of oxygen present in the arterial blood. According to this second technique, the ratio between the normalized pulsatile and nonpulsatile components of a single pair of red and infrared wavelengths transmitted through tissue is used to compute the amount of oxygen saturation in the arterial blood. Both of these methods are useful for measuring, for example, the oxygen saturation in blood but cannot be readily utilized for measuring the concentration of glucose or other low concentration substances in blood. The reasons are related to the fact that the optical absorption spectra of oxyhemoglobin, which corresponds to fully oxygenated blood, and deoxyhemoglobin, which corresponds to fully deoxygenated blood, are significantly different from each other. Furthermore, the optical absorption spectra of blood in the 660 to 9660 nm region of the spectrum is significantly stronger than the background optical absorption of the blood-less tissue. Lastly, the relative concentration of hemoglobin is normally about 150 times higher than that of glucose and hemoglobin has a much higher optical absorption compared to that of glucose.
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(1) Field of the Invention
This invention pertains to emulsifiers which give improved adhesion when used to prepare adhesive polymeric latices by emulsion polymerization. More particularly, it relates to emulsifiers which are more effective than conventional emulsifiers allowing reduced levels to be used to produce equivalent stability in a dispersed adhesive latex system.
(2) Description of the Prior Art
Emulsion polymers are often used in synthetic adhesives and coatings production. Preparation involves the initiation of polymerization of one or more ethylenically unsaturated monomers in the presence of an aqueous phase containing a suitable emulsifying agent or combination of agents. Emulsifying agents are generally anionic, but sometimes are nonionic or cationic in electrolytic charge of the organic fraction. Among the anionic emulsifying agents utilized for this application are water-soluble soaps, such as alkali metal oleates, stearates, or rosin acids, sulfates of higher alcohols, such as sodium lauryl sulfate, sulfonates of alkyl acyl hydrocarbons such as dodecylbenzene sulfonate, sulfonated alfa-olefins, polyether alcohols and a host of analogous and similar surface active emulsifying agents. U.S. Pat. No. 3,505,265 teaches certain divalent salts of alkylated diphenyl ether sulfonates as emulsion polymerization emulsifiers.
The total amount of the emulsifying agent in adhesive latices generally ranges from about 2 to 5 parts per 100 parts of monomer used in the polymerization. This amount is required so that the latex will remain stable to coagulation during handling and further processing. Much of the total emulsifier adsorbs to the individual latex particle surfaces and the higher the emulsifier level, the greater the extent to which the particle surfaces are covered. The emulsion polymer is generally formulated with pigments or extenders and other additives to a variety of coating compositions. Such ingredients compete with the emulsion polymer surface for emulsifier. Since uncoated particle surface is also needed for interaction with compounding ingredients such as thickeners, low emulsifier coverage contributes to minimum quantities of such ingredients being required. Further, excessive colloidal stability of the compounding system requires greater water removal before the emulsion polymer coagulates to adhere the coating components together and to the substrate. Thus, the minimum of emulsifying agent that provides adequate colloidal stability for handling and processing helps insure quick coagulation and fewer problems in drying the coating.
Therefore, it is the object of the present invention to provide emulsion polymerization emulsifiers which produce adhesive and coating compositions with improved adherence to the substrate material. It is a further object to provide emulsion polymerization emulsifiers which when employed in aqueous adhesive and coating compositions in reduced amounts produce adequate stability and yet provide rapid coagulation and improved drying.
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Although it is applicable to any micromechanical components, the present invention and its underlying problem will be explained below with reference to acceleration and rotation rate sensors.
German Patent Application No. DE 195 37 814 A1 describes a method for manufacturing micromechanical sensors, for example acceleration and rotation rate sensors. Movable silicon structures, whose motions are sensed quantitatively by determining capacitance changes, are generated. The movable silicon structures are generated in an etching step, trenches being generated with a high aspect ratio in the silicon layer. In a second step a sacrificial layer, for example an oxide layer, is removed from beneath the micromechanical functional layer made of silicon. In a subsequent process the movable silicon structures thereby obtained are hermetically closed off, for example with a cap wafer that is applied using a seal-glass soldering process. Depending on the application, a gas atmosphere having a desired or suitable pressure is enclosed inside the volume closed off by the cap wafer.
In rotation rate sensors, a very low pressure is typically enclosed, for example on the order of 1 mbar. The background for this is that in these rotation rate sensors, a portion of the movable structure is driven resonantly. At very low pressure, it is very easy to excite a desired vibration with relatively small electrical voltages, because of the very low damping.
In acceleration sensors, on the other hand, it is usually not desirable for the sensor to vibrate, which is possible when a corresponding external acceleration is applied. These acceleration sensors are therefore operated at higher pressures, for example at 500 mbar. In addition, the surfaces of such acceleration sensors are often also equipped with organic coatings that prevent adhesive bonding of the movable structures.
If the intention is to manufacture very small and economical combinations of rotation rate and acceleration sensors, this can be done by integrating both a rotation rate sensor and an acceleration sensor onto one chip. The two sensors are manufactured simultaneously on one substrate. Such sensor combinations are encapsulated at the substrate level by way of a cap wafer that provides two separate cavities per chip.
The different pressures that are required in the cavities of the rotation rate sensor and of the acceleration sensor can be achieved, for example, by using a getter. For this, a suitable getter is locally incorporated into the cavity of the rotation rate sensor. A high pressure is initially enclosed in both cavities. The getter is then activated by way of a temperature step, whereupon said getter then pumps or getters the cavity volume of the rotation sensor to a low pressure.
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1. Field of the Invention
The present invention relates to a fuel injection method and device for engines which receives fuel from a common rail and injects the fuel from injectors into combustion chambers.
2. Description of the Prior Art
As for the fuel injection control in engines such as diesel engines, a common-rail type fuel injection system has been known which provides a high injection pressure and performs optimum control on the injection characteristics, such as fuel injection timing and the amount of fuel injected, according to the operating condition of the engine. The common-rail type fuel injection system stores in the common rail a fuel pressurized to a predetermined pressure by a fuel pump and then injects the stored fuel from injectors into corresponding combustion chambers. A controller controls the fuel pressure in the common rail and the operation of control valves for the injectors so that the pressurized fuel will be injected from each injector under optimum injection conditions according to the engine operating conditions.
The conventional common-rail type fuel injection system is described by referring to FIG. 7. The fuel is supplied to individual injectors 1 from a common rail 2 through branch pipes 3 that form a part of the fuel passage. The fuel, which was pumped by a feed pump 6 from a fuel tank 4 through a filter 5 and pressurized to a predetermined intake pressure, is delivered to a fuel pump 8 through a fuel pipe 7. The fuel pump 8 is a plunger type which is driven by the engine to raise the fuel pressure to a high pressure determined by the operating condition of the engine and deliver the pressurized fuel through a fuel pipe 9 to the common rail 2. The fuel is then stored temporarily in the common rail 2 at the elevated pressure, from which it is supplied to individual injectors 1. As many injectors 1 as the number of cylinders are provided in the engine. These injectors 1 are controlled by a controller 12, an electronic control unit, to inject fuel supplied from the common rail 2 into the corresponding combustion chambers at optimum timings and in optimum amounts. Because the pressure at which the fuel is injected from the injectors 1 is almost equal to the pressure of the fuel stored in the common rail 2, the injection pressure is controlled by controlling the fuel pressure in the common rail 2.
The fuel released from the fuel pump 8 is returned to the fuel tank 4 through a return pipe 10. Of the fuel supplied from the branch pipes 3 to the injectors 1, the fuel that was not used for injection into the combustion chambers is returned to the fuel tank 4 through a return pipe 11. The controller 12 is supplied with signals from a variety of sensors for detecting the engine operating condition, which include: engine cylinder determination and crank angle sensors for detecting an engine revolution speed Ne; an accelerator opening sensor for detecting the amount of accelerator operation Acc; a water temperature sensor for detecting the cooling water temperature; and an intake pipe inner pressure sensor for detecting the inner pressure of the intake pipe. The controller 12, based on these signals, controls the fuel injection characteristics of the injectors 1, i.e., the fuel injection timing and the amount of fuel to be injected so that the engine output will become optimum for the current engine operating condition. The common rail 2 is provided with a pressure sensor 13 which detects the fuel pressure in the common rail 2 and sends the detection signal to the controller 12. The controller 12 controls the amount of fuel delivered from the fuel pump 8 so that the fuel pressure in the common rail 2 is restored to a predetermined pressure after the common rail pressure has fallen as a result of fuel consumption from the common rail 2 for injection from the injectors 1.
The conventional common-rail type fuel injection system controls the fuel injection pressure to a target value according to the engine operating state and at the same time calculates injection characteristics corresponding to the operating state, i.e., the amount of fuel to be injected (determined by the fuel injection pressure and the fuel injection period) and the fuel injection timing, and controls the operation of the injectors according to the calculated results, thereby realizing the fuel injection characteristics conforming to the engine operating state. The common rail pressure that determines the injection pressure is raised by the fuel pump and controlled to a predetermined injection pressure by a pressure control valve (see Japanese Patent Publication No. 60020/1985 for example).
In the common-rail type fuel injection device, the controller sends a command pulse as an injection command signal to each of the solenoid valves of the injectors, and a needle valve is lifted by a solenoid that is energized in response to the command pulse to open nozzle holes provided at the nozzle end of each injector to inject fuel. It should be noted, however, that there is normally a time lag from the instant that the controller issues a command pulse to the solenoid valve to the instant that the fuel actually starts to be injected from the nozzle holes of the injector. This time lag results from a response delay present in a drive circuit, i.e., a delay after the command pulse has been issued from the controller to the solenoid until the solenoid is actually energized, and a mechanical delay after the solenoid has been energized to lift the needle valve until the fuel is injected from the nozzle holes. Further, even if the timings at which to turn on the command pulses from the controller are the same, the fuel injection start timings may differ from one injector to another because of variations among individual injectors and among cylinders (e.g., difference in distance between the pressure sensor and the injector).
The conventional fuel injection device for engines deals with such a time lag by taking it to be a fixed delay and not considering variations of the time lag. Hence, changes over time of the time lag and variations among individual injectors combine to prevent optimum combustion of fuel, causing deterioration of the exhaust emission performance and also engine vibrations due to differences in the combustion timing among cylinders.
The method and device for detecting fuel injection timings, disclosed in Japanese Patent Laid-Open No. 210174/1996 and intended to determine precise fuel injection timings in a diesel engine, performs a sequence of steps which involve monitoring a pressure in the fuel pipe connecting a fuel injection pump of the diesel engine and the fuel injection nozzles, detecting a first fall in the monitored pressure of a magnitude greater than a predetermined value after the monitored pressure has reached a predetermined high pressure value, and then determining a pressure fall start timing to be a fuel injection start timing. The above-described method and device for detecting the fuel injection timing, however, concerns a fuel injection system using a distribution or column type pump that distributes fuel to the injectors, and is not intended for application to the common-rail type fuel injection system. That is, the type of the system for which the above method is intended differs from the common-rail type fuel injection system under consideration in this invention.
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The present invention relates to a headbox for a machine for the manufacture of fibrous webs made from stock suspensions, and more particularly for the manufacture of paper webs. The headbox is of the type having an outlet duct. The duct has lateral side walls which define a determined duct width The duct is further bordered by two duct walls, respectively located above and below, and converging in the direction of flow of suspension to form an outlet slot in the downstream region. One duct wall is movably and adjustably supported by a duct wall beam, and is preferably pivotally supported at its upstream end, so that the clear width of the outlet slot can be varied by means of a lifting appliance. The bearing force of that appliance acts against the pressure of the suspension which acts on the movable duct wall. A support beam extends across the width of the machine adjacent to the adjustable duct wall beam. The movable duct wall beam together with the support beam extends over the machine width and forms a beam unit. A pressure cushion, which acts against the suspension pressure that acts on the movable duct wall, is disposed between the movable duct wall beam and the support beam.
A headbox of this type is known from German Published Application 3,614,302, which corresponds to U.S Pat. No. 4,770,745. In this publication, the movable duct wall is part of a U-shaped, L-shaped or box-shaped duct wall beam. The support beam, which is different from the duct wall beam, may have an I-shaped or a triangular shaped cross section. In all cases, there is a pivotable connection between the duct wall beam and the support beam located at both ends of the duct wall beam This is known from an advertisement entitled, "Unsere Stufendiffusor-Stoff-Auflaufe sind Marketfuhrer" of Sulzer Escher Wyss, published in the November 1987 issue of "Wochenblatt for Papierfabrikation".
This German application also discloses that the structural unit, which consists of the duct wall beam and the support beam and is hereinafter known as the "beam unit", is connected to the headbox housing by means of a pivot bearing. At each end of the beam unit there is also a lifting appliance, e.g. a spindle, by means of which the movable duct wall can be swung up or down, to vary the clear width of the outlet slot. For this purpose, the movable duct wall is connected to the headbox housing by means of a hinge joint. The publication provides no guidance about how the lifting appliance is hingedly connected to the beam unit However, it is customary to provide a journal hinge at each end of the duct wall beam. See FIG. 4 herein.
A major problem with such headboxes is keeping the clear width, i.e. the space between the top and bottom duct walls, of the outlet slot constant with the greatest possible accuracy over the entire machine width. In practice, it has repeatedly been shown that local deviations in the desired outlet slot width impair the quality of the resulting paper web. Investigations have shown that a W-shaped or M-shaped profile of the cross section of the outlet slot is usually found, which produces a corresponding irregular "weight per unit area transverse cross section" (usually called "cross direction profile of the basis weight") of the paper web. It has also been shown that a certain error in the slot width of the outlet slot can cause a ten fold error in the basis weight of the paper web.
It has also been recognized that some of the problems were caused by the above mentioned articulation of the two lifting appliances located at the two ends of the duct wall beam, i.e. on the front side and the drive side of the paper making machine, by means of a journal hinge Previously, at each end of the movable duct wall itself, a journal extended at right angles to the machine direction and was hinged to the lifting appliance. A large portion of the forces originating from the pressure of the suspension from the movable duct wall must be transferred by the respective journal located on the movable duct wall to the stationary headbox housing. As a result, the journal transmits transverse force and a bending moment into the movable duct wall This has disadvantageous effects on the contours of the movable duct wall for the following reason. The loading of the movable duct wall which originates from the stock suspension is distributed substantially uniformly over the length of the wall, i.e. over the machine width. However, from the opposite direction, the loading of the movable duct wall is composed of a uniformly distributed load produced by the compressed air cushion and by the transverse forces and the bending moments produced by the lifting device. It has been shown that satisfactory results were not achieved under these conditions.
The same comment also applies for the headbox disclosed in Voith (the assignee hereof) publication p. 2503, page 4. For the reasons stated, repeated attempts have been made to improve the uniformity of the outlet slot width by additional measures. More particularly, at the outlet slot, a locally deformable component, e.g. a profile bar, was provided. This could be adjusted by means of a plurality of spindles uniformly distributed over the machine width However, the accuracy which can be achieved by this measure is frequently not sufficient to meet current requirements for paper quality.
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A DFE is used to try to equalize the frequency response of a received signal through a channel and increase the eye opening without amplifying noise. Some received signals are interfered by prolonged reflections of previously received signals, making it difficult for the DFE to equalize the frequency response.
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This application claims priority of European Application No. 00201327.4, filed on Apr. 12, 2000.
The present invention relates to a water borne two-component cross-linkable composition comprising an aqueous dispersion of an amino-functional polymer and a compound comprising at least two acetoacetate groups or acetoacetamide groups or a combination of the two groups.
The reaction mechanism by which cross-linking occurs is as follows:
The advantage of such a two-component composition is that curing can be achieved at low temperatures, for instance ambient temperature, or in a short time at elevated temperatures, for instance 30 to 60 minutes at 60xc2x0 C.
A disadvantage of such a two-component composition is a limited pot life due to premature reactions in the composition, causing a large increase in viscosity and subsequent gelation. More particularly, the reaction between a primary amino group and an acetoacetate or acetoacetamide group is much too fast for actual use in two-component systems.
In the past comparable two-component systems have been solvent borne, based on the combination of polyacetoacetates and polyketimines (ketone blocked amines), as described in U.S. Pat. No. 3,668,183, K. L. Hoy et al., Journal of Paint Technology, Vol. 46, No. 591, pp. 70-75 (1974), and C. H. Carder et al., Journal of Paint Technology, Vol. 46, No. 591, p. 76-80 (1974). These systems are in fact moisture curing systems, because the velocity determining step in this reaction is the deblocking of the ketimine into an amino group and a ketone by hydrolysis.
U.S. Pat. No. 5,227,414 discloses water borne two-component coating compositions based on an aqueous dispersion of an amino-functional polyurethane and an epoxy cross-linker. A disadvantage of these systems is that curing at ambient temperature is rather slow.
Heat curable water borne coating compositions based on an amino-functional polymer dispersion are described in U.S. Pat. No. 4,096,105. These aqueous amino-functional polymer dispersions are cross-linked by unsaturated carbonyl compounds such as acryloyl-functional compounds, and are used in cathodic electrocoating applications.
The present invention provides a water borne two-component cross-linkable composition based on an aqueous dispersion of an amino-functional epoxy derived polymer and a compound comprising at least two acetoacetate groups or acetoacetamide groups or a combination of the two groups. This composition provides coatings with high gloss, good water and solvent resistance, and high hardness. This composition also provides adhesives with high adhesion strength.
According to the invention, a water borne two-component cross-linkable composition is provided comprising:
A) an aqueous dispersion of an at least partially neutralized amino-functional epoxy derived polymer and
B) a compound comprising at least two acetoacetate groups or acetoacetamide groups or a combination of the two groups.
The amino-functional epoxy derived polymer may be prepared from:
a) at least one bisepoxide compound,
b) at least one amino-functional compound comprising at least one primary amine group selected from
1) an alkyl amine with 2 to 20 carbon atoms in the alkyl group,
2) a polyether amine with a Mn=500 to 3000,
3) N-alkyl amino alkyl amine, and/ or
4) N-hydroxy alkyl amino alkyl amine, and
c) at least one compound containing at least one xe2x80x94NHxe2x80x94 group and at least one ketimine group.
The bisepoxide compound (a) is preferably selected from diglycidyl ethers of Bisphenol A and F or their higher molecular weight homologues, such as Epikote(copyright) resins from Shell, i.e. Epikote(copyright) 828 and Epikote(copyright) 1001, the diglycidyl ether of hydrogenated Bisphenol A, such as Eponex(copyright) 1510 from Shell, various polyethylene glycol or polypropylene glycol diglycidyl ethers, and mixtures thereof.
Examples of alkyl amines (b1) also include alkyl amines with other functional groups such as ethanol amine. Preferably, the alkyl amine has 6 to 18 carbon atoms in the alkyl group. Typical examples thereof are octyl amine, dodecyl amine, tetradecyl amine, and mixtures thereof, such as Armeen(copyright) CD from Akzo Nobel Chemicals.
Preferably, the polyether amine (b2) is selected from C1-C4 alkoxy polyoxy ethylene/polyoxy propylene amine. Examples include methoxy polyoxy ethylene/polyoxy propylene amines, which are available from Texaco under the tradename Jeffamine(copyright), such as Jeffamine(copyright) M-1000 (PO/ EO=3/19; Mn=1176) and Jeffamine(copyright) M-2070 (PO/ EO=10/32; Mn=2200).
The use of N-alkyl amino alkyl amine (b3) and N-hydroxy alkyl amino alkyl amine (b4) leads to a branched structure, because these amines have a functionality of 3 towards the bisepoxide compound. Accordingly, an epoxy functionality higher than 2 is obtained. Preferred is a functionality of 2 to 3.5. With higher functionalities there is a risk of gelation during the synthesis.
One example of N-alkyl amino alkyl amine (b3) is N-ethyl ethylene diamine.
One example of N-hydroxy alkyl amino alkyl amine (b4) is 2-(2-amino ethyl amino) ethanol.
It has been found that incorporating a non-ionic polyether group into the amino-functional epoxy derived polymer provides a better colloidal stability, smaller particle size of the aqueous dispersions, and improvement in the emulsification of compound B in the amino-functional epoxy derived polymer dispersion. Accordingly, it is preferred that the amino-functional compound (b) comprising at least one primary amine group comprises a polyether amine (b2). Certain combinations of amino-functional compounds with a polyether amine (b2) are more preferred, such as a polyether amine (b2) combined with an alkyl amine (b1) with 2 to 20 carbon atoms in the alkyl group and a polyether amine (b2) with a N-hydroxy alkyl amino alkyl amine (b4).
Compounds containing at least one xe2x80x94NHxe2x80x94 group and at least one ketimine group (c) are prepared by reacting a compound bearing a primary amine and a secondary amino group with a ketone. Examples of a compound bearing a primary amine and a secondary amino group include diethylene triamine, dipropylene triamine, dihexylene triamine, triethylene tetramine, tripropylene tetramine, N-amino ethyl piperazine, N-methyl-1,3-propane diamine, 2-(2-amino ethyl amino) ethanol, and N-ethyl ethylene diamine. Suitable examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, dibutyl ketone, di-isobutyl ketone, ethyl amyl ketone, and methyl hexyl ketone.
The amino-functional epoxy derived polymers are preferably prepared in a first step by chain extension of the bisepoxides by the amino-functional compound comprising at least one primary amine group. The bisepoxides are used in excess, so that an epoxy terminated prepolymer is formed. In a second step the epoxy terminated prepolymer is further reacted with the ketimine compound also containing a NH group.
Depending on the molecular weight, the ketimine-functional epoxy derived polymer can be synthesised in the melt or in an organic solvent, such as a ketone, glycol ether, propylene glycol ether or a cyclic ether. Examples include methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, butyl glycol, 1-methoxy propanol, dioxane, and tetrahydrofuran. The reaction temperature ranges from 40 to 150xc2x0 C. and preferably is between 60 and 120xc2x0 C.
The so formed ketimine-functional epoxy derived polymer is dispersed in water with sufficient volatile organic acid to convert the ketimine groups into primary amino groups and ketones and to form an acid salt of 10 to 100% of the amino groups, preferably 20 to 75% of the amino groups, followed by removal of the ketone and the solvent by (azeotropic) distillation, optionally under reduced pressure, preferably under vacuum. Formation of acid salt groups means that 10 to 100%, preferably 20 to 75%, of the amino groups are neutralized.
Examples of useful volatile organic acids are formic acid, acetic acid, lactic acid, and propionic acid. In combination with these volatile organic acids also small amounts of other acids may be used such as sulphuric acid, hydrochloric acid, and phosphoric acid. Preferred are acetic acid and lactic acid and combinations thereof with phosphoric acid.
As the amino groups of the amino-functional epoxy derived aqueous polymer dispersions are at least partially protonated by a volatile organic acid, they effectively retard the cross-linking reaction, so that prolonged pot lives can be obtained.
A variety of dispersing techniques can be employed to disperse the ketimine-functional epoxy derived polymer in water. For example, the organic acid may be added to the ketimine-functional epoxy derived polymer solution together with a small amount of water to deblock the amino groups. This concentrated amino-functional epoxy derived polymer solution may subsequently be added to water under stirring (direct emulsification). Alternatively, after addition of the organic acid, water may be added slowly to the ketimine-functional epoxy derived polymer solution (inverse emulsification).
Said amino-functional epoxy derived polymer has an average molecular weight Mn of 500 to 10,000, preferably 1,000 to 8,000, more preferably 1,500 to 6,000, measured with Size Exclusion Chromatography using polymethyl methacrylate as standard, an amino number of 20 to 500 mg KOH/g, preferably 30 to 150 mg KOH/g, and, optionally, up to 20 wt. %, preferably 4 to 15 wt. %, of a polyether amine. The aqueous amino-functional epoxy derived polymer dispersion has a particle size of 10 to 500 nm, preferably between 15 and 300 nm, more preferably between 20 and 150 nm. Its solids content is between 20 and 50 wt. %, usually between 30 and 45 wt. %. The pH of the aqueous dispersion is between 7 and 10, preferably between 8 and 9.
The compound comprising at least two acetoacetate groups or acetoacetamide groups or a combination of the two groups (B) may be a polyacetoacetate-functional compound, a polyacetoacetamide-functional compound, or a compound comprising at least one acetoacetate group and at least one acetoacetamide group.
Preferably, the compound comprising at least two acetoacetate groups or acetoacetamide groups or a combination of the two groups (B) is an organic compound. An xe2x80x9corganic compoundxe2x80x9d in this context is defined as a hydrocarbon compound containing no metal atoms.
The compound comprising at least two acetoacetate groups or acetoacetamide groups or a combination of the two groups (B) preferably has a functionality of 2 to 5. They can be synthesised by various methods.
Polyacetoacetates can be prepared by trans-esterification of polyhydroxyl compounds with acetoacetic acid ester. Examples are 1,6-hexane diol diacetoacetate, 1,5-pentane diol diacetoacetate, trimethylol propane triacetoacetate, pentaerythritol tetra-acetoacetate, and di-trimethylol propane tetra-acetoacetate. An acetoacetate-functional compound may also be prepared by transesterification of the reaction product of diisopropanol amine and Eponex(copyright) 1510 with t.butyl acetoacetate.
Polyacetoacetamides may be prepared from a hydroxy-functional aceto-acetamide with a polyfunctional isocyanate. Examples include the reaction product of N-(2-hydroxyethyl) acetoacetamide and a tri-isocyanate such as 4-isocyanato methyl-1,8-octane diisocyanate or a polyisocyanate such as the isocyanurate or allophanate trimer of 1,6-hexamethylene diisocyanate.
Optionally up to 15 wt. %, preferably up to 10 wt. %, of a C1-4 alkoxy polyoxyalkylene group with a Mn of 500 to 3,000 is introduced into the compound comprising at least two acetoacetate groups or acetoacetamide groups or a combination of the two groups. Such modified compound comprising at least two acetoacetate groups or acetoacetamide groups or a combination of the two groups may be obtained by reacting the above-mentioned compounds with a small amount of a polyether amine, such as the previously mentioned Jeffamines(copyright), or a methoxy polyethylene glycol. Alternatively, a polyacetoacetate-functional resin may be prepared by reacting a polyisocyanate, an alkoxy polyethylene glycol, a diol, and t.butyl acetoacetate.
An especially useful polyacetoacetate-functional urethane has been prepared from the reaction product of 1 mole of glycerol carbonate and 1 mole of 3-amino propanol
esterified with 3 moles of t-butyl acetoacetate giving a tri-functional acetoacetate urethane. Substituting a small amount of 3-amino propanol with Jeffamine(copyright) M-1000 provides a modified acetoacetate-functional compound with polyether groups incorporated therein.
It has been found that incorporating a non-ionic polyether group into the compound comprising at least two acetoacetate groups or acetoacetamide groups or a combination of the two groups improves the emulsification of compound B in water and/or the amino-functional epoxy derived polymer dispersion.
Alternatively, the compound comprising at least two acetoacetate groups or acetoacetamide groups or a combination of the two groups may be acetoacetate- and/or acetoacetamide-functional resins, such as acetoacetate-and/or acetoacetamide-functional polyacrylates or polyurethanes.
The compound comprising at least two acetoacetate groups or acetoacetamide groups or a combination of the two groups may be used as such, as a concentrated solution in an organic solvent, as a concentrated solution in water or as an aqueous emulsion.
Said compound comprising at least two acetoacetate groups or acetoacetamide groups or a combination of the two groups has an acetoacetate and/or acetoacetamide number of 150 to 500 mg KOH/g, preferably 200 to 450 mg KOH/g, and, optionally, up to 15 wt. %, preferably up to 10 wt. %, of a polyether group.
The compound comprising at least two acetoacetate groups or acetoacetamide groups or a combination of the two groups and the aqueous amino-functional epoxy derived polymer dispersion should be mixed in such a ratio that the ratio of the acetoacetate and/or acetoacetamide groups to the amino groups lies in the range from 0.2-2:1, preferably 0.5-1.5:1.
Compound B may be mixed into compound A by any suitable technique. However, simple stirring is usually sufficient. The pot life may be a few hours to several weeks. In this respect the polyacetoacetamides show much longer pot lives than the polyacetoacetates.
Optionally, an epoxy-functional compound (C) may be added to the composition. Examples of such an epoxy-functional compound include mono-epoxy functional compounds such as Cardura(copyright) E10 ex Shell, 3-glycidyloxy propyl trimethoxy silane (e.g. Silquest(copyright) A-187 ex Witco, Dynasylan(copyright) Glymo ex Degussa Hxc3xcls AG, or Dow Corning(copyright) Z-6040 ex Dow Corning), and (3,4-epoxycyclohexyl) ethyl triethoxy silane (e.g. Coatosil(copyright) 1770 ex Witco), and polyepoxy-functional compounds such as Epikote(copyright) 828 ex Shell and Ancarez(copyright) AR550 ex Air Products. The epoxy-functional compound may be used in an amount of 10 to 40 eq. % epoxy groups on NH2 groups, preferably 20 to 35 eq. %.
The composition of the present invention consists essentially of water, being an aqueous composition. However, about 20 wt. % of liquid content of the composition may be an organic solvent. As suitable organic solvents may be mentioned hexylglycol, butoxyethanol, 1-methoxy-propanol-2, 1-ethoxy-propanol-2, 1-propoxy-propanol-2, 1-butoxy-propanol-2, 1-isobutoxy-propanol-2, dipropylene glycol monomethyl ether, methanol, ethanol, propanol, butanol, pentanol, hexanol, ethylene glycol, diethylene glycol, dimethyl dipropylene glycol, diacetone alcohol, methylether of diacetone alcohol, and ethoxy ethyl propionate. The VOC of the composition may range from 0 to 400 g/l, preferably from 0 to 200 g/l, most preferred is 0 to 100 g/l.
The composition may contain other compounds such as pigments, effect pigments, such as aluminium parts, UV absorbers, adhesion promotors, such as epoxy silane, HALS-type stabilisers, flow additives, fillers, dispersing agents, dyes, levelling agents, anti-cratering agents, and anti-foam agents.
The present compositions are of particular interest in coating compositions or adhesives. Preferably, a two-pack composition is used. Preferably, the first component of the two-pack coating or adhesive comprises compound A, while the second component of the composition comprises compound B. Optionally, compound C may be present in either or both components. Preferably, compound C is combined with compound B in the second component.
The composition according to the invention can be used on various substrates, in particular wood, plastics, and metal substrates such as aluminium, steel, galvanised steel, aluminium, copper, zinc, magnesium, and alloys thereof, for industrial applications of any kind.
The coating composition may be used, e.g., as a putty, primer, filler, base coat, top coat or clear coat. Preferably, the coating composition is a primer or filler. The composition is particularly advantageous for use as a coating for car repair, since it is easily sprayable and can be applied at ambient temperatures. The coating composition is also applicable in the automotive industry for the finishing of large transport vehicles, such as trains and buses, and can also be used on airplanes.
The composition can be applied using conventional spray equipment or high- and/or low volume low-pressure spray equipment, resulting in a high-quality finish. Other modes of application are roller coating, brushing, sprinkling, flow coating, dipping, electrostatic spraying or electrophoresis, spraying being preferred. Curing temperatures are preferably between 0 and 80xc2x0 C. The composition may be left to dry and cure at ambient temperature over one to several days or for a shorter time at elevated temperature, for instance 20 to 60 minutes at 40 to 80xc2x0 C.
The present invention is illustrated by, but not limited to the following examples.
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Wnt is a secreted protein that binds to surface receptors of neighboring cells to regulate the expression of various genes. The Wnt gene family was found ubiquitously in various types of tumors and was given a name “int” as the first cellular oncogene. Since then, it was found that a wingless gene implicated in the metamorphosis of Drosophila species is a homolog of the gene int-1 and therefore it was also suggested that the int gene will play a crucial role in the embryogenesis of Drosophila species. Accordingly, the name Wnt was coined as a combination of Wg (wingless) and Int.
The Wnt signaling pathway has been recognized as a key pathway responsible for oncogenesis. A member of the Wnt signaling pathway, such as adenomatous polyposis coli (APC), Axin, Axin2, βTrCP (E3 ligase), or the like, that binds to β-catenin to form an inactivated complex, may undergo mutagenesis incapable of degrading β-catenin and β-catenin may also be mutated to a non-degradable form, which leads to increased nuclear β-catenin accumulation, finally resulting in activation of the Wnt/β-catenin pathway. High nuclear accumulation of β-catenin leads to formation of a complex of β-catenin with T-cell factor/Lymphoid enhancing factor (TCF/LEF), which consequently results in induction of transcription of target genes.
Activation of the Wnt/β-catenin pathway is known to elicit regulated expression of numerous genes involved in carcinogenesis. The Wnt/β-catenin pathway induces expression of c-myc and cyclin D1 to thereby activate cell division, and also induces expression of a growth factor receptor, c-met and a growth factor, fibroblast growth factor 18 (FGF 18) to thereby increase cell proliferation. Further, it increases expression of anti-apoptotic proteins such as survivin protein as well as proteins necessary for cell proliferation, and induces expression of a vascular endothelial growth factor (VEGF) gene to stimulate tumor angiogenesis and provide a foundation for tumor growth and metastasis. In addition, for migration and metastasis of cancer cells, APC stimulated exchange factor (ASEF), matrix metalloproteinase (MMP) family, CD44 and the like, which are correlated with cell adhesion and extracellular matrix, function as target proteins of the Wnt/β-catenin pathway. A great deal of research and study has been actively attempted on development of an antitumor agent that is intended to target the Wnt/β-catenin pathway implicated in regulation of a variety of carcinogenesis-related proteins as described above. Unfortunately, most of such approaches made up to date are pathway inhibitors using chemical synthetic drugs which are designed based on a tertiary structure of individual proteins implicated in the Wnt/β-catenin pathway (Nick et al., Nature Reviews Drug Discovery, 5:997-1014, 2006).
RNA-mediated interference (RNAi) is a phenomenon wherein a 21-25 nucleotide-long double stranded siRNA specifically binds to a transcript (mRNA transcript) having a complementary sequence and degrades the corresponding transcript to thereby inhibit expression of a target protein of interest. As the RNA-mediated interference has recently suggested the solution to the problems encountered in development of conventional chemical synthetic drugs, many efforts have been made on development of various therapeutic agents, particularly antitumor agents, through selective inhibition of the expression of a certain protein at the transcript level. Production of target-directed small-molecule chemical drugs takes a long development period of time and tremendous development costs until they are optimized to certain protein targets, whereas the most pronounced advantage of siRNA drugs using the RNA-mediated interference phenomenon is in that it readily enables development of the optimized lead compounds for all the protein targets including non-druggable target substances. Protein or antibody drugs suffer from difficulties of production thereof due to complicated manufacturing processes, whereas siRNAs have significant advantages such as ease of synthesis, separation and purification, consequently relatively easy and convenient commercial-scale production, higher storage stability attributed to intrinsic nature of nucleic acid materials, as compared to protein drugs, and the like. Further, siRNA-based drugs are receiving a great deal of interest as a novel drug candidate group, based on a variety of strengths such as specific molecular target-directed antagonism, unlike conventional drugs (David et al., Nature Chemical Biology, 2:711-719, 2006).
The primary challenge associated with siRNA-based therapy is the identification of the optimum sequence where siRNA has the highest activity in the target base sequence. It is known that the efficiency of RNA-mediated interference is significantly affected by a specific binding site to the target transcript. Based on the database accumulated for the past several years, algorithms have been developed which are capable of designing a sequence position of siRNA substantially inhibiting expression of the target RNA, instead of simply binding to the transcript, and are currently available to users. However, it cannot be said that all of siRNAs determined by an in silico method using computer algorithms can effectively inhibit target RNAs in real cells and in vivo. Further, it is known that even when requirements necessary for complementary binding of siRNA to the target transcript are satisfied, the stability and intracellular location of RNAs and proteins, the state of proteins implicated in RNA-mediated interference, and a variety of other unknown factors are implicated in the determination of RNA-mediated interference efficiency. To this end, there is a need for development of a technique which will be carried out for a target protein by selecting several target sequence positions per transcript of one gene, preparing the corresponding siRNAs and screening an optimum position sequence having high expression-inhibitory activity from among such a candidate group (Derek et al., Annual Review of Biomedical Engineering, 8:377-402, 2006).
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There are many examples of functional structures or components that can provide, produce, or detect electromagnetic or electronic signals or other characteristics. One advantageous form for these structures is in the form of functional blocks, which can be discrete elements with a characteristic shape, such as a NanoBlock™ Integrated Circuit made by Alien Technology Inc. The functional blocks are typically objects, microstructures, or microelements with integrated circuits built therein or thereon. These functional blocks have many applications and uses. The functional components can be used as an array of display drivers in a display where many pixels or sub-pixels are formed with an array of electronic elements. For example, an active matrix liquid crystal display includes an array of many pixels or sub-pixels which are fabricated using amorphous silicon or polysilicon circuit elements. Additionally, a billboard display or a signage display such as store displays and airport signs are also among the many electronic devices employing these functional components.
Functional components have also been used to make other electronic devices. One example of such use is that of a radio frequency (RF) identification tag (RFID tag) which contains a functional block or several blocks each having a necessary circuit element. Information is recorded into these blocks, which is then transferred to a base station. Typically, this is accomplished as the RFID tag, in response to a coded RF signal received from the base station, functions to cause the RFID tag to modulate and reflect the incident RF carrier back to the base station thereby transferring the information.
Such RFID tags are being incorporated into many commercial items for uses such as tracking and authenticating the items.
Demand for functional components has expanded dramatically. Clearly, the functional components have been applied to make many electronic devices, for instance, the making of microprocessors, memories, power transistors, super capacitors, displays, x-ray detector panels, solar cell arrays, memory arrays, long wavelength detector arrays, phased array antennas, RFID tags, chemical sensors, electromagnetic radiation sensors, thermal sensors, pressure sensors, or the like. The growth for the use of functional components, however, has been inhibited by the high cost of assembling the functional components into substrates and fabricating final devices or end products that incorporate the functional components.
Often the assembling of these components requires complex and multiple processes thereby causing the price of the end product to be expensive. Furthermore, the manufacturing of these components is costly under current methods because of slow, inefficient, and wasteful uses of the technologies and the materials used to make these products.
For cost and form factor considerations, many electronic devices are being constructed with ever-smaller electronic components. In particular, devices like RFID transponders, electronic displays, active antennas, sensors, computational devices, memory, and a number of wireless devices rely on integrated circuits (ICs) as small a 1 mm on a side, with demand to decrease the size further. While the raw component cost of devices can decrease along with their size, assembly of the components into devices becomes more difficult and more costly as their size decreases. There is a need for technologies that enable the low-cost assembly of active components that are on the order of hundreds of microns on a side, or even smaller and making interconnections to these active components.
Technologies like Fluidic Self Assembly (described in previous patents, including U.S. Pat. No. 5,545,291) can be effective in placing small integrated circuits in precise locations on a substrate. Many electronic components, however, require further processing to be integrated into devices. In particular, making electrical contact to the integrated circuit is necessary in many cases. The integrated circuit may need to be electrically connected to other active or passive components, sensors, power sources, antennas, display elements, or other integrated circuits.
Presently, electrical interconnections can be formed using a variety of processes. As one example, lithographic processes can be used in which a conductive layer (such as a metal) are deposited across a device, and then etched back to form wires and interconnections. As another example, screen printing can be used to print wires and interconnects using conductive inks. While both processes can interconnect many devices at once, there are limitations. For example, both processes rely on precise knowledge of the location of the integrated circuit on the receiving substrate. If there is some uncertainty in the exact position of the devices, then misregistration of the wiring pattern may lead to devices that are not interconnected properly. This misregistration problem becomes more severe in cases where the devices are small, or if plastic webstock is used as the receiving substrate. In another example, in the case of printing methods like screen printing, ink bleed can lower yield by inadvertent connection between electrical traces. This problem becomes more severe as devices get smaller. Additionally, there may be limitations in the set of materials that are compatible with screen printing, so that some desirable conductive materials cannot be processed with screen printing.
There is thus a need for a processing technology that allows for the precise interconnection of small functional components on a variety of receiving substrate materials, whether these materials be plastic, metal foils, glass, paper, or fiber (cloth) materials. Alternatively, there is a need for electronic system designs that are tolerant of poorly-registered interconnections that readily enable the use of small functional components. There is a need for inventions that allow of the construction of electronic components and devices on a variety of different materials, in high volumes, and at low costs.
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1. Field of the Invention
This invention relates to a technique for driving a self-luminous display panel of the active matrix driving type.
More particularly, this invention relates to a self-luminous display panel driving method, a self-luminous display panel and an electronic apparatus of an active matrix driving type.
2. Description of the Related Art
An organic EL (Electro Luminescence) element has a characteristic called electroluminescence characteristic of re-emitting light in response to a voltage applied thereto. In recent years, a display device of the self-luminous type wherein such organic EL elements are disposed in a matrix has been and is proceeding.
A display panel which uses an organic EL element can be driven by an application voltage lower than 10 V. Therefore, the display panel of the type has a characteristic that the power consumption is low. Further, the display panel which uses an electronic EL element which is a self-luminous element has another characteristic that reduction in weight and reduction in film thickness are easy. In addition, the display panel which uses an organic EL element has a further characteristic that the response speed is as high as approximately several microseconds and an after image is less likely to appear upon display of moving pictures.
A passive matrix type driving system and an active matrix type driving system are available as a driving system for a display panel which uses an organic EL element. In recent years, development of a display panel of the active matrix type driving system wherein an active element such as a thin film transistor is disposed for each pixel is proceeding energetically.
A display panel of the active matrix type driving type is disclosed, for example, in Japanese Patent Laid-Open No. 2003-255856, No. 2003-271095, No. 2004-133240, No. 2004-029791, and No. 2004-093682.
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The technology described in this patent document relates generally to SRAM devices and more particularly to bit line pre-charge circuitry and methods of pre-charging a bit line in an SRAM device.
Static random access memory (SRAM) is commonly used in electronic devices. SRAM cells have the advantageous feature of holding data without a need for refreshing. SRAM cells may include different numbers of transistors, and are often accordingly referred to by the number of transistors, for example, six-transistor (6T) SRAM, eight-transistor (8T) SRAM, and the like. The transistors typically form a data latch for storing a data bit. Additional transistors may be added to control the access to the transistors. SRAM cells are typically arranged as an array having rows and columns. Typically, each row of the SRAM cells is connected to a word-line, which determines whether the current SRAM cell is selected or not. Each column of the SRAM cells is connected to a bit line (or a pair of bit lines), which is used for storing a data bit into a selected SRAM cell or reading a stored data bit from the selected SRAM cell.
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1. Field of the Invention
The present invention relates to water quality measurement for assessing an effect of water, which is fed to a water treatment membrane, on occlusion of the membrane.
2. Description of the Related Art
Various kinds of membranes are used to separate a component contained in water. There are two water filtration methods using the membrane. One of the methods is a dead-end filtration method or a method of passing an entire volume of feed water through a membrane. A component having failed to pass through the membrane is accumulated on the membranous surface. The other method is a cross flow filtration method, wherein water flows in parallel with the membranous surface and part of the water passes through the membrane. Among the membranes, a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, and a reverse osmosis membrane may be used for cross flow filtration. According to an ideal cross flow filtration method, a permeated water volume takes on a certain value determined with a water flow velocity but does not depend on an operation time. A component of raw water that does not permeate through a membrane is condensed and discharged. In contrast, according to the dead-end filtration method, a component of raw water that does not permeate through a membrane is accumulated. Therefore, a permeated water volume decreases along with the passage of an operation time. This phenomenon is called fouling. Even in the cross flow filtration method, since the component is adsorbed by the membrane, a phenomenon that the permeated water volume decreases is manifested. The phenomenon is also called fouling.
A related art will be described below by taking a reverse osmosis membrane, which is employed in advanced wastewater treatment, for instance. A semipermeable membrane is adopted as the surface of the reverse osmosis membrane, and the material thereof falls broadly into a cellulose triacetate series and an aromatic polyamide series. The membrane made of either of the materials allows only water to pass through by utilizing for filtration a difference in intensity of interaction between water molecules and dissolved components, and is used for the purpose of removing electrolytes in water.
The reverse osmosis membrane made of the aromatic polyamide series has high water permeability and exhibits excellent electrolyte removing performance, and is therefore widely used for industries. As for the structure of the reverse osmosis membrane, the structure of a complex membrane having a polyamide membrane, which has a thickness of 0.1 μm or less, formed on a microporous support whose thickness ranges from several tens of micrometers to several hundreds of micrometers is often adopted. The reverse osmosis membrane is used to remove dissolved organic substances or electrolytes during desalination of seawater, manufacture of pure water necessary to fabricate precision electronic devices such as semiconductors, advanced clean water treatment, or final treatment of wastewater or drainage.
For the final treatment of wastewater among the foregoing usages, water is generally fed to a reverse osmosis membrane through a treatment process described below. First, bulk trash and refuse contained in wastewater are removed through a screen. Thereafter, microscopic suspended substances including sand are settled in a sedimentation tank by applying, if necessary, a coagulant or the like and thus separated. Suspended solids and dissolved organic substances are contained in supernatant water, and are therefore biodegraded using microorganisms. Metabolites of the microorganisms are generated as sludge, and the sludge and water are separated from each other while being sedimented in the sedimentation tank or being passed through a microfiltration membrane. A primary effluent of the thus treated wastewater hardly contains suspended solids. In this state, disinfection or the like is performed in order to purify the effluent to such an extent that the water quality becomes high enough to sluice the effluent to a river. In Japan, in this state, treated wastewater is sluiced to a river, and water circulation is accomplished by utilizing natural purification. However, the Middle East, continental inland, or an island devoid of a river does not have a river or lake large enough to achieve the natural purification. Therefore, there is an increasing demand for reuse of the primary effluent of wastewater as drinkable water or industrial water by further purifying the effluent. The reverse osmosis membrane is used to remove dissolved organic substances or electrolytes from the primary effluent of wastewater during final treatment.
The primary effluent of wastewater contains organic substances that are measured as a total organic carbon (TOC) content ranging from 5 mg/L to 20 mg/L, though it varies depending on treatments performed in stages ending with a preceding stage. When the organic substances are separated from water using the reverse osmosis membrane, the organic substances can be reduced down to 1 mg/L or less. The TOC content is one of indices signifying water quality, indicates a total content of carbon in an organic compound among carbon compounds dissolved in water, and represents the total content of organic substances without identifying the components.
The reverse osmosis membrane employed in final wastewater treatment may be folded like a shape called a spiral or formed like a hollow fiber in order to increase a membranous surface area in a module. The spiral structure has a saclike reverse osmosis membrane fixed to the central core portion thereof and has it furled like an umbrella and stored in a cylinder. The mainstream of the module has a cylindrical shape having a diameter of 4 or 8 inches and a length of 1 m.
Adsorbates on a membranous surface include scales deposited due to a rise in the concentration of electrolytes in the vicinity of the membranous surface, a bio-fouling caused by microorganisms grown on the membranous surface, and an organic fouling caused by adsorption of organisms. The adsorbates are removed by regularly pouring cleansing water to the membranous surface or by utilizing a shearing stress. However, when organic substances are adsorbed by the membranous surface, they cannot be fully removed by the shearing stress but are gradually accumulated to make it necessary to replace the reverse osmosis membrane module with a new one. When the reverse osmosis membrane module is replaced with a new one, it is necessary to cease operation for a prolonged period of time. In addition, since the reverse osmosis membrane module cannot be recycled, the reverse osmosis membrane module has to be replaced with a new one. This leads to a cause of an increase in a running cost.
In the past, a fouling index (FI) value has been used as a water quality assessment method for predicting a fouling on a reverse osmosis membrane. The FI value may be called a silt density index (SDI) value. An FI value measurement method is stipulated in the JIS K 3802. Namely, water is passed through a filter, which has bores of 0.45 μm in diameter and has a diameter of 47 mm, at 206 kPa according to the dead-end filtration method, and a ratio of a time necessary to filter 500 ml in an initial stage to a time necessary thereto after the water is passed for fifteen min is calculated as the FI value. Manufacturers of the reverse osmosis membrane determine the upper limit of the FI values of feed water, and demand that the FI value should range from 3 to 4.
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The present invention relates to a display pallet which together with an object can be put on a transport pallet and transported with the latter.
Display pallets of the above-mentioned general types are known in the art. A known display pallet is a stable supporting member adapted to be placed on a transport means. The display pallet is connected with an object after its manufacture, transported with the same, and serves as a stable support for the object. The object may be a machine or a device to be examined or sold. The object may also be composed of several boxes with foodstuffs, sweets or canned food which in condition of self-service must be located at a well visible place for exhibition purpose. The display pallets with the objects which are put and mounted thereon must be transported to their predetermined place in a simple manner. For this purpose, several display pallets with the objects are placed on transport pallets and transported. Both the transport pallets and the display pallets must be held and transported by the same transporting means. This, however, encounters some difficulties inasmuch as the transport pallets have, as a rule, widths of 600 mm., and a maximum distance of the holding device of the transporting means amounts to 550 mm. Thereby, the maximum thickness of both side walls of the display pallet must not exceed 25 mm.
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Cloud-based computing systems are increasingly at risk of security breaches from brute force and other types of attacks designed to gain privileged access to the system. In a brute force attack, single client devices, or groups of client devices, are configured to repeatedly request access to the cloud-based system until access is granted. Each request may iterate through a sequence of possible values for login parameters such as user names and passwords. Because the total number of possible values is typically much larger than the number of registered or correct values for logging in to the system, brute force attacks typically involve a large number of incorrect requests for access before they succeed.
One way to try to stymie a brute force attack is to present the client device with a Turing challenge—for example, a Completely Automated Public Turing test to Tell Computers and Humans Apart (CAPTCHA). Turing challenges such as CAPTCHAs require a human user at the client device to answer a question or provide information in response to an inquiry, puzzle, or problem that is designed to be easy for a human but difficult for a computer program to provide a correct response. In such a system, only client devices that correctly provide a response to the Turing challenge will have their request for access (e.g., a request containing login information) processed, and an automated brute force attack will not be able to submit any of its requests for access. However, having to respond to a Turing challenge with every login can be irritating to human users. There is a need for approaches for protecting against brute force attacks while avoiding annoying human users with a Turing challenge. Such alternative systems and methods for protecting against brute force attacks are described herein.
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1. Field of the Invention
The present invention generally relates to a method, medium, and apparatus for reserving resources when a handover occurs in a mobile network. More particularly, the present invention pertains to a method, medium, and apparatus for reserving resources by searching for a candidate access router and a candidate crossover router for an area where a mobile node will potentially move, and pre-reserve or re-reserve the appropriate resources through a router found through the search.
2. Description of the Related Art
As information and globalization ages draw near, research into active wireless Internet systems has increased. Wireless Internet can be briefly classified into fixed wireless Internet and mobile wireless Internet. Fixed wireless Internet is limited in mobility, but has superior transmission capacity and speed. Systems for WLAN (Wireless Local Area Network), B-WLL (Broadband Wireless Local Loop), LMDS (Local Multipoint Distribution Service), and Bluetooth, belong to the wireless fixed Internet. By contrast, the mobile wireless Internet, which is implemented by different types of systems in notebook computers and PCs, according to the generations of the mobile communication network, secures the mobility superiority, but is limited in transmission capacity and speed.
With the development of mobile communication networks, the mobile wireless Internet has developed from an initial form, such as CDPD (Cellular Digital Packet Data) using the 1st generation AMPS (Advanced Mobile Phone Service) network, to a service form using wireless application protocols such as WAP (Wireless Application Protocol), ME (Mobile Explorer) and I-mode, based on the 2nd or 2.5-generation IS-95/GSM network. The standardization of ALL IP mobile networks based on IMT-2000, which is the 3rd-generation mobile communication system, has progressed in stages, and it is expected that the IP-based standardization will be gradually carried out from the fields of IP-based core networks to wireless access networks and terminals.
The present ALL IP mobile network is the next-generation mobile communication network which has become a matter of great concern all over the world, with standardization work having progressed in the 3GPP (3rd Generation Partnership Project) around Northern Europe and in the 3GPP2 (3rd Generation Partnership Project 2) around North America. From these projects, many technical issues have been brought to light in the academic world, through various kinds of forums and through the standardization and development of the ALL IP mobile network carried out through various kinds of consortiums made up by world-famous mobile communication network providers, manufacturers developing network constituent elements, Internet service providers providing new Internet services, and manufacturers of IP packet network constituent elements.
In order to support the mobility in the mobile wireless network where the ALL IP is implemented, an MIP (Mobile IP) and a QoS (Quality of Service), securing a reliable transmission of data and multimedia traffic, are required. The reliable transmission of the multimedia traffic is supported by a pre-reservation of network resources, for which an RSVP (Resource Reservation Protocol) has been mainly used. However, since the present RSVP was not designed to take into consideration the mobility of wireless networks, a proper resource reservation cannot be made when MIP is implemented.
After the appearance of MIP, research for a resource reservation for mobile networks has continuously progressed, and the representative protocols are MRSVP (Mobile RSVP), RSVP-MP (RSVP Mobility Proxy), and CORP (method of Concatenation and Optimization for resource Reservation Path).
FIG. 1 illustrates paths for pre-establishing resources, according to the conventional MRSVP. MRSVP classifies resource reservation states into a passive reservation state and an active reservation state. The passive reservation state is a state where a resource has been previously reserved, and not presently in use, and the active reservation state is a state where the reserved resource is in use. A proxy agent is provided in an access router to manage the transmission of a user's mobile terminal or mobile node 10 from the passive reservation state to the active reservation state. The mobile node can move within a mobile network and accordingly changes its network access position. The proxy agent manages cells adjacent to a cell where the mobile node is positioned, and preemptively takes part in a multicast RSVP session through special reservation schemes, wherein traffic is not actually transferred.
Referring to FIG. 1, the mobile node 10 establishes a communication session with a correspondent node 20 through a path 1. The correspondent node 20 communicates with the mobile node 10 by connecting with the access router CAR included in a core network.
In this state, if a handover of the mobile node 10 occurs, the mobile node 10 transmits a specification message to adjacent access routers AR2, AR3, . . . , and ARn. The specification message includes a flow specification, which is to be transmitted to a remote proxy agent by the mobile node and a flow ID (Identification). Between the access routers AR2, AR3, . . . , and ARn, where a communication session is not currently established, and the correspondent node 20, the passive reservation state is set. If the mobile node 10 moves, it can extend the reservation path by changing a corresponding passive reservation state to an active reservation state and by transferring traffic through the active reservation state.
Although this solved the problem of time delay of the QoS re-establishment, MRSVP pre-reserves resources of adjacent cells where the mobile terminal may move in the mobile network, which may be short of resources, thereby wasting resources in the access network. The mobile node should keep a mobility specification that includes position information for all of the neighbors of the mobile node while the mobile node moves and as it establishes a communication session with the correspondent node 20. Since an intermediate router manages all state information about passive reservation states, unnecessary overhead occurs, which emphasizes a corresponding problem of the mobile network having limited scalability. When the mobile node 10 moves, communication sessions between mobile node 10 and previous resources in a previous cell are not promptly released, thereby creating a double reservation being kept with respect to the same communication session, causing a waste of resources. As these handovers frequently occur, generating such double resource reservations, the resource availability of new communication sessions becomes disturbed.
FIG. 2 illustrates paths for establishing new resources through an address changing method, according to the conventional RSVP-MP. The RSVP-MP structure is mutually combined with hierarchical mobility management schemes of MIP, is provided with an RSVP-MP agent placed at MAP (Mobility Anchor Point) or in GFA (Gateway Foreign Agent), and performs an address change between an LCoA (Local Care-of-Address), which is an address of the access router, and an RCoA (Regional Care-of-Address), which is a global address of another address.
Referring to FIG. 2, the mobile node 10 establishes a communication session with a correspondent node 20 through path 1. If the mobile node 10 performs a handover from an area managed by AR1, which is currently connected to the mobile node 10, to an area managed by AR2, mobility 10 is allocated with CoA, a new temporary address, and requests a re-establishment of resource reservation according to the change of paths. If an end-to-end re-establishment of resources from the mobile node 10 to the correspondent node 20 is made, the resource re-establishment creates a time delay, preventing the mobile node 10 from being properly provided with QoS.
However, if the handover of the mobile terminal 10 occurs, the RSVP-MP structure performs communication by converting LCoA of the access network into RCoA that is a global address through an MP (Mobility Proxy) and using RCoA. Thus, according to the RSVP-MP structure, re-establishment of entire paths is not required, but only requires the path in a section between AR1 and MAP, in which LCoA is used, to be re-established. That is, RCoA is used from MAP to the correspondent node 20, and thus, even if a handover occurs, it is not required to re-establish the RSVP session from MAP to the correspondent node, but only requires the RSVP session to be re-established between the mobile node to MAP. Since RSVP-MP does not require the re-establishment of the end-to-end resource reservation, it can reduce time delays due to the limited required re-establishment of the RSVP-MP session.
Although RSVP-MP does not require the reestablishment of the end-to-end resource reservation, a time delay of as much as one round-trip time still occurs in order to establish the resource reservation, and a prompt release of the reservation state of the resources established through the old access router is not performed, thereby similarly again causing the double reservation of resources. If the handover frequently occurs, the handover still disturbs the resource use for new communication sessions due to the double resource maintenance. Since the RSVP-MP structure should be implemented in parallel to the hierarchical mobility management schemes of MIP, which have not yet been completed, it cannot be an independent protocol and, accordingly, may be changed as it is implemented.
FIG. 3 is a view illustrating a conventional CORP type RSVP path extending process through a hierarchical reservation path and path extending process using an optimized reservation path.
Referring to FIG. 3, the CORP type RSVP provides QoS by using a method of extending the existing RSVP path if a handover occurs. The CORP type RSVP uses a CRP (Concatenation for Reservation Path)r to extend the RSVP path.
The CRP type RSVP extends the RSVP path using PRPs (Pseudo Reservation Paths). The CRP type RSVP determines one representative BS (Base Station) among BSs (Base Stations) managed by one access router, and pre-reserves the resources for adjacent BSs.
Referring to FIG. 3, several access routers AR1, AR2, . . . , ARn, which belong to the access network, manage respective areas area 1 to area n. Each respective area includes several cells, and a BS manages the respective cells. If the mobile node 10 performs a handover in the area managed by one access router, the BS that manages the cell that the mobile node 10 accordingly has reached, transmits a CRP information message (that is, information message) for informing BSs, of the adjacent cells, of the arrival of the mobile node at BSs, and makes the adjacent cells pre-reserve their resources.
The continuous extension of the RSVP path by CRP makes an infinite path or a loop path, and in order to prevent this, an ORP (Optimization for Reservation Path) is used along with CORP. Specifically, if a handover occurs within an area managed by one access router AR1, the handover is processed according to CRP, while if a handover occurs due to the mobile node's movement to another access router AR2, the mobile node 10 establishes a new RSVP session with the correspondent node 20. Accordingly, in the case of the handover occurring in one access router, resources can be promptly secured, and thus previous problems caused by the path extension can be solved with QoS being secured.
As described above, since CORP pre-reserves the resources of adjacent cells to which the mobile node will move and simultaneously establishes the end-to-end RSVP session in a mobile network having insufficient resources, the inefficient waste of resources occurs in the access network. Since CORP uses a multicast method when establishing a new session by extending the path, and since there should also be a new RSVP session established from a new access router to the correspondent node 20 whenever the mobile node moves to another access router, trouble occurs in scalability of the network. Although CORP releases old resources, unlike MRSVP, the release of the existing resources according to CORP includes the release of the existing resources up to the correspondent node 20, and thus a prompt process is not achieved and a new session establishments for other terminals are disturbed.
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Sudden health problems such as sudden cardiac arrest and injuries caused by accidents kill thousands of people and cause permanent injury every year. Fast and competent care can be essential to positive outcomes in such situations. For example, it is said that the chance of surviving a sudden cardiac arrest falls by ten percent for every minute in delaying effective treatment.
Emergency events like sudden cardiac arrests and accidents are generally responded to by organized emergency response units, such as ambulance or fire crews, and by laypeople who are immediately around the events so that they personally witness or offer assistance for the events. Often, the laypeople in a victim's immediate vicinity are not trained to treat the victim, or are too overwhelmed to provide effective treatment. On the other hand, the organized emergency response units may be far away from the victim, so that they cannot arrive at the scene for a long time.
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In life in general there is frequently found the necessity for heating the contents of a barrel or tank or some other such object with a nonplaner surface. These objects may be located in a place subject to the ravages of the outdoors and the associated elements or they may be indoors and subject to cleaning spray or they may be in an area which contains or has a possibility of containing explosive gases. A practical and safe method to apply heat is to utilise a flexible electric heating pad fastened to the object. There are a number of such systems available and they do heat objects as required.
These systems in general include a heating element embedded between two flexible insulators, a ground shield to provide mechanical and grounding protection for the heater, a ground conductor connected to the ground shield and power conductors connected to the heating element, thermostatic control, a junction box in which terminations are made between the conductors and the power cord and a method by which the unit may be attached to the nonplaner surface.
Some of the systems have junction boxes which are bonded to the flexible heater and permanently seal the terminations between the conductors and the power cord and some have junction boxes which are mechanically attached to the flexible heater but do not provide a waterproof seal to the terminations and some have the junction box in a remote location from the connection between the ground conductor and the ground shield and the connection between the power conductors and the heating element. There follows a list of problems associated with these types of heating systems when utilized for heating objects subject to the ravages of the outdoors and the associated elements or indoors and subject to cleaning spray or in an area which contains or has a possibility of containing explosive gases.
For some industrial applications it is a requirement of certification agencies that electric heaters have a power cord which is replaceable in case of damage during use. In order to replace the power cord the termination between the power conductors and the power cord must not be permanently sealed and must be accessible thus necessitating the use of an accessible junction box. In addition the junction box must be sealed sufficiently or have inherent characteristics so as to prevent moisture or explosive gases from entering it. The problems include the difficulty of excluding moisture or explosive gases from the area of the connection between the ground shield and the ground conductor and between the heating element and the power conductors, the difficulty of preventing mechanical stress on the connection between the ground shield and the ground conductor and between the heating element and the power conductors, the difficulty of excluding moisture or explosive gases from the area of the termination between the conductors and the power cord, the difficulty of excluding moisture or explosive gases from the thermostat, the difficulty of maintaining access to the area of the termination between the conductors and the power cord, the difficulty of securing the junction box to the heater.
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Prior to the use of packet-based voice communications, telephone conferences were a service option available within standard non-packet-based telephone networks such as Pulse Code Modulation (PCM) telephone networks. As depicted in FIG. 1A, a standard telephone switch 15 is coupled to a plurality of telephone terminals 16 to be included within a conference session as well as a conference bridge 17. It is noted that these telephone terminals 16 are coupled to the telephone switch 15 via numerous other telephone switches (not shown). The telephone switch 15 forwards any voice communications received from the terminals 16 to the conference bridge 17, which then utilizes a standard algorithm to control the conference session.
One such algorithm used to control a conference session, referred to as a “party line” approach, comprises the steps of mixing the voice communications received from each telephone terminal 16 within the conference session and further distributing the result to each of the telephone terminals 16 for broadcasting. A problem with this algorithm is the amount of noise that is combined during the mixing step, this noise comprising a background noise source corresponding to each of the telephone terminals 16 within the conference session.
An improved algorithm for controlling a conference session is disclosed within U.S. patent application Ser. No. 08/987,216 entitled “Method of Providing Conferencing in Telephony” by Dal Farra et al, filed on Dec. 9, 1997, assigned to the assignee of the present invention, and herein incorporated by reference. This algorithm comprises the steps of selecting primary and secondary talkers, mixing the voice communications from these two talkers and forwarding the result of the mixing to all the participants within the conference session except for the primary and secondary talkers. The primary and secondary talkers receive the voice communications corresponding to the secondary and primary talkers respectively. The selection and mixing of only two talkers at any one time can reduce the background noise level within the conference session when compared to the “party line” approach described above.
In a standard PCM telephone network as is depicted in FIG. 1A, all of the voice communications are in PCM format when being received at the conference bridge 17 and when being sent to the individual telephone terminals 16. Hence, in this situation, the mixing of the voice communications corresponding to the primary and secondary talkers is relatively simple with no conversions of format required.
Currently, packet-based voice communications are being utilized more frequently as Voice-over-Internet Protocol (VoIP) becomes increasingly popular. In these standard VoIP communications, voice data in PCM form is being encapsulated with a header and footer to form voice data packets; the header in these packets has, among other things, a Real Time Protocol (RTP) header that contains a time stamp corresponding to when the packet was generated. One area that requires considerable improvement is the use of packet-based voice communications to perform telephone conferencing capabilities.
As depicted within FIG. 1B, a plurality of packet-based voice communication terminals, terminals A,B,C 22,24,26 in this case, are coupled to a packet-based network 20. Currently, in order for the users of these terminals 22,24,26 to communicate within a voice conference, a packet-based voice communication central bridge 28 must be coupled to the packet-based network 20. This conference bridge 28 has a number of problems. These problems include the latency inherently created within the conference bridge 28, the considerable amount of signal processing power required, the cost of the conference bridge, the limited input/output capacity of the conference bridge, and the maintenance and management of the conference bridge that is required. It should be noted that the high signalling power required is partially due to the conference bridge 28 having to compensate for a variety of problems that typically exist within current packet-based networks. These problems include possible variable delays, out-of-sequence packets, lost packets, and/or unbounded latency.
FIG. 2 is a logical block diagram of a well-known conference bridge design that could be implemented within the network of FIG. 1B. In this design, the conference bridge 28 comprises an inputting apparatus 30, an energy detection, talker selection and mixing block 32 and an outputting apparatus 34. Typically all three of these blocks are implemented in software.
The inputting apparatus 30 performs a number of functions on the packets that are received at the conference bridge 28 from the terminals within a voice conference. These functions include protocol stack, jitter buffer and decompression operations. During the protocol stack operation, the inputting apparatus 30 receives packets comprising compressed voice signals, hereinafter referred to as voice data packets, and strips off the packet overhead required for transmitting the voice data packets through the packet-based network 20. During the jitter buffer operation, the inputting apparatus 30 receives the compressed voice signals, ensures that the compressed voice signals are within the proper sequence (i.e. time ordering signals), buffers the compressed voice signals to ensure smooth playback and ideally implements packet loss concealment. During the decompression operation, the inputting apparatus 30 receives the buffered compressed voice signals, converts them into standard PCM format and outputs the resulting voice signals (that are in Pulse Code Modulation) to the energy detection, talker selection and mixing block 32.
The energy detection, talker selection and mixing block 32 performs almost identical functionality to the conference bridge 17 within FIG. 1A. The key to the design of a conference bridge 28 as depicted in FIG. 2 is the inputting block 30 transforming the packet-based voice communications into PCM voice communications so the well-known conferencing algorithms can be utilized within the block 32. As described previously, in one conferencing algorithm, primary and secondary talkers are selected for transmission to the participants in the conference session to reduce the background noise level from participants who are not talking and to simplify the mixing algorithm required. The selection of primary and secondary talkers is performed with an energy detection operation to determine the voice conference participants that are speaking, followed by a talker selection operation to choose the primary and secondary talkers and a mixing operation to mix the voice communications received from the primary and secondary talkers. The resulting output from the block 32 is a voice communication consisting of a mix between the voice communications received from the primary and secondary talkers. Further outputs from the block 32 include the unmixed voice communications of the primary and secondary talkers that are to be forwarded, as described previously, to the secondary and primary talkers respectively.
The outputting apparatus 34 performs a number of functions on the outputs from the block 32, these functions including compression and transmission operations. During the compression operation, the outputting apparatus 34 receives and compresses respective ones of the three outputs from the energy detection, talker selection and mixing block 32. During the transmission operation, the outputting apparatus 34 performs a protocol stack operation on the compressed voice signals, encapsulates the compressed voice signals within the packet-based format required for transmission on the packet-based network 20 and transmits voice data packets comprising the compressed voice signals to the appropriate terminals 22,24,26 within the conference session. It is noted that, in the case of the talker selection algorithm described above, the mixed voice signal is forwarded to all the terminals with the exception of the primary and secondary talkers while the primary and secondary talkers are sent the appropriate unmixed voice signals.
One problem with the setup depicted within FIG. 2 is the degradation of the voice signals as the voice signals are converted from PCM format to compressed format and vice versa within the conference bridge 28, these conversions together being referred to generally as transcoding. A further problem results from the considerable latency that the processing within the conference bridge 28. The latency of this processing can result in a significant delay between when the talker(s) speaks and when the other participants in the conference session hear the speech. This delay can be noticeable to the participants if it is beyond the perceived real-time limits of human hearing. This could result in participants talking while not realizing that another participant is speaking. Yet another key problem with the design depicted in FIG. 2 is the considerable amount of signal processing power that is required to implement the conference bridge 28. As stated previously, each of the components shown within FIG. 2 are normally simply software algorithms being run on DSP components(s). This considerable amount of required signal processing power is expensive. Even further, another key problem within current conference bridge designs is their limited input/output capacity. This limited capacity is not always significant but could be exceeded in cases where there are large numbers of participants within the conference session. As well, a large number of participants within a conference session could put a strain on the capacity of the packet-based network 20 itself due to the concentration of traffic that occurs with the use of packet-based conference bridges.
Hence, a new design within a packet-based voice communication network is required to implement voice conferencing functionality. In this new design, a reduction in transcoding, latency and/or required signal processing power within the conferencing network is needed.
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1. Field of the Invention
The present invention relates to a structure for detachably mounting a horizontal drill head on a drill head of a machine tool such as a wood working machine.
2. Description of Background Art
In a conventional mounting structure, the detachable horizontal drill head is mounted on the drill head of the machine tool by securing the driving shaft of the horizontal drill head to the spindle of the machine tool as well as by securing the guide pin slidably inserted into the pin bore formed in the head case of the machine tool to the horizontal drill head. That is, the horizontal drill head is secured to the machine tool by the driving shaft and the guide pin slidable in the pin bore formed in the head case of the drill head of the machine tool.
In such a manner, the detachable horizontal drill head can be mounted on the drill head of the machine tool when horizontal drill working is required and the mounted horizontal drill head can be vertically advanced toward and retracted from the work placed on the work table by the vertical actuation of the driving spindle of the machine tool.
However, since the pin bore for slidably receiving the guide pin is formed in the bead case of the drill head of the machine tool, it is very expensive to form the pin bore with the required high accuracy of parallelism to the direction of sliding motion of the driving shaft of the horizontal drill head.
Also in the conventional detachable horizontal drill head, since the pin bore is formed in the head case of the drill head, the size of the head case is necessarily increased and thus the overall size of the machine tool is increased.
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Drug resistance invariably develops over the course of continuing chemotherapy. Overcoming this problem is a major challenge in the treatment of cancer. Indeed, tumor cells utilize multiple mechanisms to increase their resistance to chemotherapeutic drugs. For example, tumor cells may overexpress the multiple drug resistant transporter and oncoprotein epidermal growth factor receptor genes, as well as induce the activity of NF-E2-related factor 2, a redoxsensing transcription factor that upregulates a wide spectrum of genes involved in glutathione metabolism and drug detoxification. See (Huang et al., 2005a; Makarovskiy et al., 2002; Wang et al., 2010); (Salzberg et al., 2007; Sirotnak et al., 2000); (Singh et al., 2010; Zhang et al., 2010); and (Huang and Sadee, 2003; Seruga et al., 2010). The Hedgehog pathway is another cell signaling pathway that is involved in chemoresitance. (DomingoDomenech et al., 2012).
To date, no single agent that was designed to target a specific mechanism of resistance has been found to be effective. However, one potential source of novel therapies for addressing drug resistance are traditional Chinese herbal medicines. Indeed, such medicines have been used for thousands of years to restore imbalances of body functions that result from a multitude of diseases. Treatment with herbal medicines usually involve ingestion of a herbal “extract” that contains multiple chemical components that can potentially act at different sites and pathways in the body. Thus, these medicines have the potential to target multiple cellular and molecular mechanisms that may offer a new opportunities in overcoming drug resistance, or simply improve the efficacy of drugs. See Chow & Huang 2010, Pon et al 2010. As described herein, an ethanol extract from one particular traditional Chinese medicinal herb, Triperygium wilfordii, which is also known by its Chinese (Mandarin) name, Lei Gong Teng, sensitizes cancer cells that have become resistant to chemotherapeutic drug therapy, so that the cancer once again becomes sensitive to the chemothearpeutic drug.
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1. Field of the Invention
The present invention relates to a data line drive circuit which drives a display panel of a matrix type, a liquid crystal display device using the data line drive circuit, and a method for driving data lines.
2. Description of Related Art
In a liquid crystal panel of the liquid crystal display device of a matrix type, the scanning lines and the data lines are extended in a row direction and in a column direction, and pixels are arranged at intersections of the scanning lines and the data lines. Each pixel has an active element (Thin Film Transistor (TFT)). The gate electrode of the active element is connected to the scanning line, and the drain electrode is connected to the data line. Moreover, a liquid crystal capacitance that is equivalent to a capacitive load is connected to the source electrode of the active element, and another side of the liquid crystal capacitance is connected to a common electrode line.
In the liquid crystal display device, in order to drive the scanning lines and the data lines of the liquid crystal panel, a scanning line drive circuit and a data line drive circuit are provided. The scanning line is scanned sequentially from the top to the bottom by the scanning line drive circuit. At this time, a voltage is applied to the liquid crystal capacitance from the data line drive circuit through the active element arranged at each pixel. In the liquid crystal display device, based on the voltage applied to the liquid crystal capacitance, alignment of the liquid crystal molecules changes and the transmissivity of light changes. This change of transmissivity enables color display having grayscale.
In the liquid crystal display device, there is known an alternating current drive method in which a polarity of a voltage (hereinafter referred to as a “pixel voltage”) applied to the liquid crystal capacitance from the data line through the TFT is inverted for every predetermined period. That is, the pixel is driven by an alternating current manner. Here, the polarity means a polarity of the pixel voltage based on a voltage (Vcom) of the common electrode line of the liquid crystal. This is because it is preferable for the pixels to be driven by the alternating current manner, since if a voltage with a fixed polarity is applied to the liquid crystal capacitance, physical characteristics of the liquid crystal molecules will degrade with a lapse of time. As a method for realizing such alternating current driving, there are known the dot inversion drive system where a polarity of the pixel voltage is inverted each time one scanning line is scanned, a two-line dot inversion drive system where a polarity of the pixel voltage is inverted each time two scanning lines are scanned and so on.
Since the voltage applied to the pixel in the inversion drive system is an alternating voltage centering to Vcom, a voltage range for driving is large. These voltages are supplied from the data line drive circuit, and the data line drive circuit consumes a large amount of electric power for driving the liquid crystal display device.
Moreover, along with upsizing of the liquid crystal panel and increasing number of outputs of the data line drive circuit, the data line drive circuit increases its power consumption remarkably.
In a typical data line drive circuit, the liquid crystal panel is driven with all the outputs therefrom being in the same timing. Then, currents concentrate on a same timing and a large current flows instantaneously. In this way, a large EMI (Electro-Magnetic Interference) noise occurs at a moment. In order to reduce this EMI noise, reducing concentration of the currents is needed.
We have now discovered the followings.
As a related art of reducing concentration of currents, a data line drive circuit is described in Japanese Laid-Open Patent Application JP-P 2003-233358A. Referring to FIG. 1, the data line drive circuit is provided with a multi-output amplifier circuit and a delay circuit. The multi-output amplifier circuit is divided into a left amplifier block and a right amplifier block. The operation timings of this data line drive circuit are shown in FIGS. 2A to 2C. When a line output signal shown in FIG. 2A is supplied, the left amplifier block is driven in synchronization with the line output signal as shown in FIG. 2B, and the right amplifier block is driven by a signal obtained by delaying the line output signal in the delay circuit. Thus, by shifting the operation timings of a plurality of amplifier blocks, the concentration of currents can be reduced and the EMI noise can be reduced.
However, since the amplifier blocks execute charging at respective different timings with a fixed time constant, when looking at the amplifier blocks at a certain timing, there is a case where a waveform is fully risen up in the left amplifier block having an early operation timing whereas a waveform is not fully risen up in the right amplifier block having a delayed operation timing. Such a case gives rise to a voltage difference between the right amplifier block and the left amplifier block, and display unevenness occurs as a result. Moreover, recently, there is a panel for a liquid crystal TV using 120-Hz driving. In this liquid crystal display device, since a period when the liquid crystal is charged from the amplifier block decreases to a half of the typical case, a trend of the device to easily generate display unevenness due to the above-mentioned difference of the charging timing becomes more remarkable.
Furthermore, in the liquid crystal display device, there is a case where collection of charges may be conducted in order to curtail power consumption. The collection of charges must be completed before the line output signal falls to a “L” level again after it rose to a “H” level. However, in a related technique, charging is conducted at the different timing and with the fixed time constant. Therefore, there is a case as follows: if the fixed time is secured in order to collect charges, the next period to drive the pixels starts; if the charge collection operation is started earlier, the outputs of the amplifiers may cause electrical shorting through the liquid crystal load. In order to prevent this, the charge collection period must be shortened, and as a result the amount of charges to charge the liquid crystal load increases, which leads to an increase of consumed electric current. This will be contrary to reduction of the EMI noise.
Moreover, an apparatus for driving a liquid crystal is disclosed in Japanese Laid-Open Patent Application JP-A-Heisei 11-85113. Referring to FIG. 3, in this related application, two kinds of switches S1 and S2 that are different in an ON-resistance value are provided at an output of an output circuit. The switches S1 and S2 are switched in response to signals C3 and C4 from the outside and a strobe signal STB. For this reason, even if the control is done with a maximum fineness, the control can be done only for each line, and this application has a same problem as the above-mentioned JP-P 2003-233358A.
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1. Field
Exemplary embodiments of the present invention relate to a semiconductor device and, more particularly, to a semiconductor device having a NoC (Network-on-Chip) structure and operating based on dynamic thermal management and a routing method thereof.
2. Description of the Related Art
A semiconductor device having a general NoC structure simultaneously restricts the performance of each node through throttling to perform its own thermal management. However, in such thermal management, the semiconductor device may not have communications through a node to which the throttling is applied, resulting in degradation of its overall performance.
In order to remove such concerns, various throttling methods are provided. Since a comprehensive solution has not been provided, performance degradation of the semiconductor device is still a big issue. For example, in an existing method, when throttling occurs during routing, the routing is reset from the beginning. In this case, due to the re-routing, routing reliability is also reduced.
The cited reference (U.S. Pat. No. 8,743,703) discloses a thermal management method using throttling, but does not disclose a solution for efficiently performing the thermal management of a semiconductor device having an NoC structure.
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MicroRNAs (miRNAs) are short RNA oligonucleotides of approximately 22 nucleotides that are involved in gene regulation. MicroRNAs regulate gene expression by targeting mRNAs for cleavage or translational repression. Although miRNAs are present in a wide range of species including C. elegans, Drosophila and humans, they have only recently been identified. More importantly, the role of miRNAs in the development and progression of disease has only recently become appreciated.
As a result of their small size, miRNAs have been difficult to identify using standard methodologies. A limited number of miRNAs have been identified by extracting large quantities of RNA. MiRNAs have also been identified that contribute to the presentation of visibly discernable phenotypes. Expression array data shows that miRNAs are expressed in different developmental stages or in different tissues. The restriction of miRNAs to certain tissues or at limited developmental stages indicates that the miRNAs identified to date are likely only a small fraction of the total miRNAs.
Computational approaches have recently been developed to identify the remainder of miRNAs in the genome. Tools such as MiRscan and MiRseeker have identified miRNAs that were later experimentally confirmed. Based on these computational tools, it has been estimated that the human genome contains 200-255 miRNA genes. These estimates are based on an assumption, however, that the miRNAs remaining to be identified will have the same properties as those miRNAs already identified. Based on the fundamental importance of miRNAs in mammalian biology and disease, the art needs to identify unknown miRNAs. The present invention satisfies this need and provides a significant number of miRNAs and uses therefore.
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{
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The present invention relates to a novel process for the preparation of soap articles containing dried shapes of soap.
In the prior art, a shaped piece of soap, a printed film or the like is filled into a cake of transparent soap in the following manner. The cake of soap is divided into halves. A shaped piece of soap or a printed film is placed upon one half which is then fused at its surface to be joined to another half with the application of water or heat. Finally, another half is joined to the thus fused surface of the said one half. However, an amount of (hot) water may enter the junction of both halves during use, resulting in their separation or formation of a whitened layer on that junction.
To solve this problem, it is proposed to use adhesives. It is found, however, that the use of adhesives offers a problem in connection with safety.
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{
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This disclosure relates generally to computer systems, and more specifically, to real-time pattern matching of database transactions and unstructured text.
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Over the last few years, safety concerns regarding football helmets and concussions have become a most pressing issue. Safety issues in football are now ubiquitous, ranging from increased safety measures in the NFL to academics rating the best football helmets. And now legislation is spreading across America aimed at treating student-athletes with concussions.
Football helmet manufacturers are very aware of this, which is why they have created the most innovative and advanced helmets the sport has ever seen. Helmets have radically transformed over the last 10 years into engineering marvels.
The drive to minimize head injuries in sports is stronger than ever, especially in football. The NFL, recognizing the importance, has put stricter player-safety rules and policies in place—but technology is catching up to offer preventive methods to combat the issue.
One way of minimizing head injuries and concussion is to predict the impact using wireless sensors. Wireless sensors estimates and calculate the distance, speed and direction of an external object before an impact happens. Therefore, before an impact happens certain pads can be activated to absorb portion of the force of impact and minimize the force applied to scalp. The pads also can reduce the head movement to avoid possible spine injury.
The drawings referred to in this description should be understood as not being drawn to scale except if specifically noted.
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This invention relates to electronic ignition systems for internal combustion engines.
Published European Application No. 0 071 910 A2 discloses an electronic ignition system having individual spark plug ignition devices as well as an additional ignition device common to all spark plugs. In that system, transistor ignition devices with current regulation are used as the individual spark plug ignition devices and the common ignition device contains a regulated direct-current converter connected, by way of diodes, to the secondary windings of the ignition coils of those ignition devices. Both types of ignition devices may be controlled or regulated as a function of parameters of the internal combustion engine, such as rpm, load and knocking.
A disadvantage of this prior art ignition system is that essentially only a single ignition pulse is supplied by the direct-current converter for each ignition process. As a result, difficulties may occur in ignition with a lean mixture, especially in operating modes of the internal combustion engine which are of interest in view of modern reduced emission objectives.
In this respect, more favorable behavior is provided by a programmable transistor ignition system, hereinafter called a "PTI", such as is disclosed in German Offenlegungsschrift No. 23 40 865. That PTI contains an electronic switch connecting a direct-current voltage source into an output transformer and having a switching frequency which is a multiple of the firing frequency of each spark plug. Like the conventional ignition device, the PTI is controllable according to operating and environmental parameters. A disadvantage of this known PTI is the requirement for a mechanical distributor, which is known to be relatively susceptible to trouble. In addition, the PTI does not supply very precisely timed ignition sparks.
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The present invention relates to an ink composition for inkjet recording (which may hereinafter be called xe2x80x9cinkjet recording ink compositionxe2x80x9d) capable of providing high-quality recorded images, excellent in discharge stability and also excellent in shelf life of the images thus formed.
With recent widespread use of computers, inkjet printers have come to be used not only at offices but also at home for printing images on paper, film or cloth.
Inkjet recording is conducted by the following method, for example, a method of discharging ink droplets by making use of a piezoelectric element to apply pressure to them; a method of discharging ink droplets by heating an ink to generate air bubbles therein; a method making use of ultrasonic wave; or a method of making use of static power for suction and discharge of ink droplets. Inks for such inkjet recording methods, aqueous inks, oil-based inks or solid (molten) inks are used. Of these, aqueous inks are most popularly employed in consideration of manufacturing ease, handling ease, odor and safety.
Colorants used for such inkjet recording inks are required to have high solubility in a solvent, permit high-density recording, provide good hue, have excellent fastness to light, heat, air, water and chemicals, have good fixing property to an image receiving material without cause bleeding easily, have excellent storage stability as an ink, have no toxicity, have high purity and be available at a low cost. It is however very difficult to find a colorant capable of satisfying the above-described requirements without lowering their levels. Particularly, there is a strong demand for a colorant having a good magenta hue and excellent light fastness.
A variety of dyes and pigments have already been proposed for use in inkjet recording and they are practically used. Colorants satisfying all of the above-described requirements have however not yet been found. It is difficult to attain satisfactory color hue and light fastness simultaneously by using conventionally well known dyes or pigments having a color index number assigned thereto.
In Japanese Patents Laid-Open Nos. 74761/1983 and 92369/1985, proposed is an ink comprising a dye, glycerin, and diethylene glycol or an ethylene-oxide adduct of an alcohol, while use of an ethylene-oxide adduct of a long-chain linear alcohol is proposed in Japanese Patent Laid-Open No. 265098/2000. These proposals are however accompanied with the drawback that the quality of an image formed using the above-described ink deteriorates during storage.
In Japanese Patents Laid-Open Nos. 88048/1994, 333532/1996 and 333533/1996, and U.S. Pat. Nos. 5,837,043 and 5,626,655, proposed are inks comprising an ethylene-oxide adduct of a higher alcohol and capable of lessening bleeding of a recorded image, but these inks also involve problems such as tendency to cause clogging and a change in color tone due to poor shelf life of an image after printing.
An object of the present invention is therefore to provide an inkjet recording ink composition having high discharge stability and being free from defects in hue, weather resistance, water resistance and image quality.
(1) An ink composition for inkjet recording obtained by dissolving or dispersing, in an aqueous medium, an azo dye having an aromatic nitrogen-containing 6-membered heterocycle as a coupling component, said composition further comprising a surfactant.
(2) An ink composition for inkjet recording as described above in (1), wherein the azo dye is represented by the following formula (A-1):
wherein,
A represents a residue of a 5-membered heterocyclic diazo component A-NH2,
B1 and B2 represent xe2x95x90CR1xe2x80x94 and xe2x80x94CR2xe2x95x90, respectively, or either one represents a nitrogen atom and the other one represents xe2x95x90CR1xe2x80x94 or xe2x80x94CR2xe2x95x90,
R5 and R6 each independently represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, aryloxycarbonyl group, a carbamoyl group, an alkyl- or aryl-sulfonyl group or a sulfamoyl group, which may each have a substituent, and
G, R1, and R2 each independently represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, an acyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a silyloxy group, an acyloxy group a carbamoyloxy group, a heterocyclic oxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group, an acylamino group, an ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl- or aryl-sulfonylamino group, a heterocyclic sulfonylamino group, a nitro group, an alkyl- or aryl-thio group, an alkyl- or aryl-sulfonyl group, a heterocyclic sulfonyl group, an alkyl- or aryl-sulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group, which may each have a substituent, or
a pair R1 and R5, or a pair R5 and R6 may be coupled to form a 5- or 6-membered ring.
(3) An ink composition for inkjet recording as described above in (1) or (2), wherein the surfactant is a nonionic surfactant.
(4) An ink composition for inkjet recording as described above in any one of (1) to (3), wherein the surfactant is represented by the formula (I) or (II):
R1Oxe2x80x94(CH2CH2O)m1xe2x80x94Hxe2x80x83xe2x80x83(I)
wherein, R1 represents a C5-40 alkyl group and m1 represents an average mole of ethylene oxide added, specifically, 2 to 40.
R2COOxe2x80x94(CH2CH2O)m2xe2x80x94Hxe2x80x83xe2x80x83(II)
wherein, R2 represents a C5-40 alkyl group and m2 represents an average mole of ethylene oxide added, specifically 2 to 40.
(5) An inkjet recording method, which comprises using an ink composition for inkjet recording as described above in any one (1) to (4).
(6) An inkjet recording method, which comprises discharging, according to a recording signal, ink droplets onto an image receiving material having, on a substrate thereof, an image receiving layer containing white inorganic pigment particles and recording an image onto the image receiving material, wherein the ink droplets are made of an ink composition for inkjet recording as described above in any one of (1) to (4).
The invention will hereinafter be described more specifically.
A dye to be used for the inkjet recording ink composition of the invention is an azo dye having as a coupling component an aromatic nitrogen-containing 6-membered heterocycle, of which that represented by the following formula (A-1) is preferred.
In the formula (A-1), A represents the residue of a 5-membered heterocyclic diazo component A-NH2. Examples of the hetero atom of the heterocycle include N, O and S. Preferred is a nitrogen-containing 5-membered heterocycle and the heterocycle may be condensed with an aliphatic ring, an aromatic ring or another heterocycle. Preferred examples of the heterocycle as A include pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazole ring, benzothiazole ring, benzoxazole ring and benzoisothiazole ring. Each of these heterocyclic groups may have a substituent further. Of these, the pyrazole ring, imidazole ring, isothiazole ring, thiadiazole ring and benzothiazole ring represented by the below-described formulas (a) to (f) are preferred.
In the above-described formulas (a) to (f), R7 to R20 represents substituents similar to those described in G, R1 and R2.
Of the formulas (a) to (f), preferred are pyrazole and isothiazole rings represented by the formulas (a) and (b), with the pyrazole ring of the formula (a) being most preferred.
B1 and B2 represent xe2x95x90CR1xe2x80x94 and xe2x80x94CR2xe2x95x90, respectively, or one of them represents a nitrogen atom and the other one represents xe2x95x90CR1xe2x80x94 or xe2x80x94CR2xe2x95x90, of which the former case is preferred.
R5 and R6 each independently represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl- or aryl-sulfonyl group or a sulfamoyl group, which may each have a substituent further. Preferred examples of the substituent represented by R5 or R6 include a hydrogen atom, aliphatic groups, aromatic groups, heterocyclic groups, acyl groups, and alkyl- or aryl-sulfonyl groups. Of these, a hydrogen atom, aromatic groups, heterocyclic groups, acyl groups, and alkyl- or aryl-sulfonyl groups are more preferred, with a hydrogen atom, aryl groups and heterocyclic groups being most preferred. R5 and R6 however do not represent a hydrogen atom simultaneously. Each of these groups may have a substituent further.
G, R1 and R2 each independently represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, an acyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a silyloxy group, an acyloxy group, a carbamoyloxy group, a heterocyclic oxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group, an acylamino group, an ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, a heterocyclic sulfonylamino group, an alkyl- or aryl-sulfonylamino group, a nitro group, an alkyl- or aryl-thio group, a heterocyclic thio group, an alkyl- or aryl-sulfonyl group, a heterocyclic sulfonyl group, an alkyl- or aryl-sulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group or a sulfo group, which may each have a substituent further.
Preferred examples of the substituent represented by G include a hydrogen atom, halogen atoms, aliphatic groups, aromatic groups, a hydroxyl group, alkoxy groups, aryloxy groups, acyloxy groups, heterocyclic oxy groups, an amino group, acylamino groups, an ureido group, a sulfamoylamino group, alkoxycarbonylamino groups, aryloxycarbonylamino groups, alkyl- or aryl-thio groups and heterocyclic thio groups, of which a hydrogen atom, halogen atoms, alkyl groups, a hydroxyl group, alkoxy groups, aryloxy groups, acyloxy groups, an amino group, and acylamino groups are preferred, with a hydrogen atom, arylamino groups and acylamino group being most preferred. Each of these groups may have a substituent further.
Preferred examples of the substituent represented by R1 or R2 include a hydrogen atom, halogen atoms, alkyl groups, alkoxycarbonyl groups, a carboxyl group, a carbamoyl group, a hydroxyl group, alkoxy groups and a cyano group. Each of these groups may have a substituent further.
A pair R1 and R5, or a pair R5 and R6 may be coupled to form a 5- or 6-membered ring.
When each of the substituents represented by A, R1, R2, R5, R6 and G has a substituent further, substituents similar to those described in G, R1 and R2 can be given as examples.
When the dye of the invention is a water soluble dye, it has, as a substituent, an ionic hydrophilic group on any one position of A, R1, R2, R5, R6 and G. Examples of the ionic hydrophilic group as a substituent include a sulfo group, carboxyl group, phosphono group, and quaternary ammonium groups. As the ionic hydrophilic group, carboxyl, phosphono and sulfo groups are preferred, with carboxyl and sulfo groups being especially preferred. The carboxyl, phosphono or sulfo group may be in the form of a salt. Examples of the counterion which forms its salt include ammonium ion, alkali metal ions (ex. lithium ion, sodium ion and potassium ion) and organic cations (ex. tetramethylammonium ion and tetramethylguanidium ion).
The term xe2x80x9caliphatic groupxe2x80x9d as used herein means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group and a substituted aralkyl group. The aliphatic group may be branched or alternatively, may form a ring. The aliphatic group preferably has 1 to 20, more preferably 1 to 16 carbon atoms. The aryl portion of the aralkyl or substituted aralkyl group is preferably phenyl or naphthyl, with phenyl being especially preferred. Examples of the aliphatic group include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl, cyclohexyl, benzyl, 2-phenethyl, vinyl and allyl.
The term xe2x80x9caromatic groupxe2x80x9d as used herein means an aryl group and a substituted aryl group. As the aryl group, a phenyl or naphthyl group is preferred, with a phenyl group being especially preferred. The aromatic group has preferably 6 to 20, more preferably 6 to 16 carbon atoms. Examples of the aromatic group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m-(3-sulfopropylamino)phenyl.
The term xe2x80x9cheterocyclic groupxe2x80x9d embraces a substituted heterocyclic group and an unsubstituted heterocyclic group. The heterocycle may be condensed with an aliphatic ring, an aromatic ring or another heterocycle. As the heterocyclic group, a 5- or 6-membered heterocyclic group is preferred. Examples of the substituent include aliphatic groups, halogen atoms, alkyl- and aryl-sulfonyl groups, acyl groups, acylamino groups, sulfamoyl group, carbamoyl group and ionic hydrophilic groups. Examples of the heterocyclic group include 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-benzothiazolyl, 2-benzoxazolyl and 2-furyl.
The term xe2x80x9calkyl- or aryl-sulfonyl groupxe2x80x9d embraces a substituted alkyl- or aryl-sulfonyl group, and an unsubstituted alkyl- or aryl-sulfonyl group. Examples of the alkyl- or aryl-sulfonyl group include methylsulfonyl group or phenylsulfonyl group, respectively.
The term xe2x80x9calkyl- or aryl-sulfinyl groupxe2x80x9d embraces a substituted alkyl- or aryl-sulfinyl group and an unsubstituted alkyl- or aryl-sulfinyl group. Examples of the alkyl- and aryl-sulfinyl groups include methylsulfinyl group and phenylsulfinyl group, respectively.
The term xe2x80x9cacyl groupxe2x80x9d embraces a substituted acyl group and an unsubstituted acyl group. The acyl group has preferably 1 to 12 carbon atoms. Examples of the substituent include ionic hydrophilic groups. Examples of the acyl group include acetyl and benzoyl.
Examples of the halogen atom include fluorine, chlorine and bromine atoms.
The term xe2x80x9camino groupxe2x80x9d embraces an amino group substituted with an alkyl group, aryl group and/or heterocyclic group. The alkyl group, aryl group and/or heterocyclic group may have a substituent further
As the alkylamino group, that having 1 to 6 carbon atoms is preferred. Examples of the substituent include ionic hydrophilic groups. Examples of the alkylamino groups include methylamino and diethylamino.
The term xe2x80x9carylamino groupxe2x80x9d embraces a substituted arylamino group and an unsubstituted arylamino group. As the arylamino group, that having 6 to 12 carbon atoms is preferred. Examples of the substituent include halogen atoms and ionic hydrophilic groups. Examples of the arylamino group include phenylamino and 2-chlorophenylamino.
The term xe2x80x9calkoxy groupxe2x80x9d embraces a substituted alkoxy group and an unsubstituted alkoxy group. As the alkoxy group, that having 1 to 12 carbon atoms is preferred. Examples of the substituent include alkoxy groups, hydroxyl group, and ionic hydrophilic groups. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.
The term xe2x80x9caryloxy groupxe2x80x9d embraces a substituted aryloxy group and an unsubstituted aryloxy group. As the aryloxy group, that having 6 to 12 carbon atoms is preferred. Examples of the substituent include alkoxy groups and ionic hydrophilic groups. Examples of the aryloxy group include phenoxy, p-methoxyphenoxy and o-methoxyphenoxy.
The term xe2x80x9cacylamino groupxe2x80x9d embraces a substituted acylamino group. The acylamino group has preferably 2 to 12 carbon atoms. Examples of the substituent include ionic hydrophilic groups. Examples of the acylamino group include acetylamino, propionylamino, benzoylamino, N-phenylacetylamino and 3,5-disulfobenzoylamino.
The term xe2x80x9cureido groupxe2x80x9d embraces a substituted ureido group and an unsubstituted ureido group. The ureido group has preferably 1 to 12 carbon atoms. Examples of the substituent include alkyl and aryl groups. Examples of the ureido group include 3-methylureido, 3,3-dimethylureido and 3-phenylureido.
The term xe2x80x9csulfamoylamino groupxe2x80x9d embraces a substituted sulfamoylamino group and an unsubstituted sulfamoylamino group. Examples of the substituent include alkyl groups. Examples of the sulfamoylamino group include N,N-dipropylsulfamoylamino.
The term xe2x80x9calkoxycarbonylamino groupxe2x80x9d embraces a substituted alkoxycarbonylamino group and an unsubstituted alkoxycarbonylamino group. The alkoxycarbonylamino group has preferably 2 to 12 carbon atoms. Examples of the substituent include ionic hydrophilic groups. Examples of the alkoxycarbonylamino group include ethoxycarbonylamino group.
The term xe2x80x9calkyl- or aryl-sulfonylamino groupxe2x80x9d embraces a substituted alkyl- or aryl-sulfonylamino group and an unsubstituted alkyl- or aryl-sulfonylamino group. The sulfonylamino group has preferably 1 to 12 carbon atoms. Examples of the substituent include ionic hydrophilic groups. Examples of the alkyl- or aryl-sulfonylamino group include methylsulfonylamino, N-phenylmethylsulfonylamino, phenylsulfonylamino and 3-carboxyphenylsulfonylamino.
The term xe2x80x9ccarbamoyl groupxe2x80x9d embraces a substituted carbamoyl group and an unsubstituted carbamoyl group. Examples of the substituent include alkyl groups. Examples of the carbamoyl group include methylcarbamoyl and dimethylcarbamoyl.
The term xe2x80x9csulfamoyl groupxe2x80x9d embraces a substituted sulfamoyl group and an unsubstituted sulfamoyl group. Examples of the substituent include alkyl groups. Examples of the sulfamoyl group include dimethylsulfamoyl and di-(2-hydroxyethyl)sulfamoyl.
The term xe2x80x9calkoxycarbonyl groupxe2x80x9d embraces a substituted alkoxycarbonyl group and an unsubstituted alkoxycarbonyl group. The alkoxycarbonyl group has preferably 2 to 12 carbon atoms. Examples of the substituent include ionic hydrophilic groups. Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl.
The term xe2x80x9cacyloxy groupxe2x80x9d embraces a substituted acyloxy group and an unsubstituted acyloxy group. The acyloxy group has preferably 1 to 12 carbon atoms. Examples of the substituent include ionic hydrophilic groups. Examples of the acyloxy group include acetoxy and benzoyloxy.
The term xe2x80x9ccarbamoyloxy groupxe2x80x9d embraces a substituted carbamoyloxy group and an unsubstituted carbamoyloxy group. Examples of the substituent include alkyl groups. Examples of the carbamoyloxy group include N-methylcarbamoyloxy group.
The term xe2x80x9caryloxycarbonyl groupxe2x80x9d embraces a substituted aryloxycarbonyl group and an unsubstituted aryloxycarbonyl group. The aryloxycarbonyl group has preferably 7 to 12 carbon atoms. Examples of the substituent include ionic hydrophilic groups. Examples of the aryloxycarbonyl group include phenoxycarbonyl.
The term xe2x80x9caryloxycarbonylamino groupxe2x80x9d embraces a substituted aryloxycarbonylamino group and an unsubstituted aryloxycarbonylamino group. The aryloxycarbonylamino group has preferably 7 to 12 carbon atoms. Examples of the substituent include ionic hydrophilic groups. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino.
The term xe2x80x9calkyl-, aryl- or heterocyclic-thio groupxe2x80x9d embraces a substituted alkyl-, aryl- or heterocyclic-thio group and an unsubstituted alkyl-, aryl- or heterocyclic-thio group. The alkyl-, aryl- or heterocyclic thio group has preferably 1 to 12 carbon atoms. Examples of the substituent include ionic hydrophilic groups. Examples of the alkyl-, aryl- or heterocyclic-thio group include methylthio, phenylthio and 2-pyridylthio groups.
As the silyloxy group, that substituted with a C1-12 aliphatic or aromatic group is preferred. Examples of the substituted silyloxy group include trimethylsilyloxy and diphenylmethylsilyloxy.
The term xe2x80x9cheterocyclic oxy groupxe2x80x9d embraces a substituted heterocyclic oxy group and an unsubstituted heterocyclic oxy group. The heterocyclic oxy group has preferably 2 to 12 carbon atoms. Examples of the substituent include alkyl, alkoxy and ionic hydroxyl groups. Examples of the heterocyclic oxy group include 3-pyridyloxy and 3-thienyloxy.
The term xe2x80x9calkoxycarbonyloxy groupxe2x80x9d embraces a substituted alkoxycarbonyloxy group or an unsubstituted alkoxycarbonyloxy group. The alkoxycarbonyloxy group has preferably 2 to 12 carbon atoms. Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy and isopropoxycarbonyloxy.
The term xe2x80x9caryloxycarbonyloxy groupxe2x80x9d embraces a substituted aryloxycarbonyloxy group and an unsubstituted aryloxycarbonyloxy group. The aryloxycarbonyloxy group has preferably 7 to 12 carbon atoms. Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy.
The term xe2x80x9cheterocyclic oxycarbonyl groupxe2x80x9d embraces a substituted heterocyclic oxycarbonyl group and an unsubstituted heterocyclic oxycarbonyl group. The heterocyclic oxycarbonyl group has preferably 2 to 12 carbon atoms. Examples of the substituent include ionic hydrophilic groups. Examples of the heterocyclic oxycarbonyl group include 2-pyridyloxycarbonyl.
The term xe2x80x9cheterocyclic sulfonylamino groupxe2x80x9d embraces a substituted heterocyclic sulfonylamino group and an unsubstituted heterocyclic sulfonylamino group. The heterocyclic sulfonylamino group has preferably 1 to 12 carbon atoms. Examples of the substituent include ionic hydrophilic groups. Examples of the heterocyclic sulfonylamino group include 2-thiophenesulfonylamino and 3-pyridinesulfonylamino.
The term xe2x80x9cheterocyclic sulfonyl groupxe2x80x9d embraces a substituted heterocyclic sulfonyl group and an unsubstituted heterocyclic sulfonyl group. The heterocyclic sulfonyl group has preferably 1 to 12 carbon atoms. Examples of the substituent include ionic hydrophilic groups. Examples of the heterocyclic sulfonyl group include 2-thiophenesulfonyl and 3-pyridinesulfonyl.
The term xe2x80x9cheterocyclic sulfinyl groupxe2x80x9d embraces a substituted heterocyclic sulfinyl group and an unsubstituted heterocyclic sulfinyl group. The heterocyclic sulfinyl group has preferably 1 to 12 carbon atoms. Examples of the heterocyclic sulfinyl group include 4-pyridinesulfinyl.
In the invention, a structure represented by the following formula (A-2) is especially preferred.
In the formula (A-2), Z1 represents an electron attractive group having a Hammett substituent constant xcex4p of 0.20 or greater. The electron attractive group represented by Z1 has preferably xcex4p of 0.30 or greater, more preferably 0.45 or greater, especially 0.60 or greater. The constant xcex4p is however desired not to exceed 1.0. Preferred specific examples of the substituent include electron attractive substituents which will be described later. Of these, preferred are C2-12 acyl groups, C2-12 alkyloxycarbonyl groups, nitro group, cyano group, C1-12 alkylsulfonyl groups, C6-18 arylsulfonyl groups, C1-12 carbamoyl groups, and C1-12 alkyl halide groups, of which cyano group, C1-12 alkylsulfonyl groups, C6-18 arylsulfonyl groups are especially preferred, with cyano group being most preferred.
R1, R2, R5 and R6 have the same meanings as described in the formula (A-1).
R3 and R4 each independently represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl- or aryl-sulfonyl group or a sulfamoyl group. Of these, a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, and an alkyl- or aryl-sulfonyl group are preferred, with a hydrogen atom, an aromatic group and a heterocyclic group being especially preferred.
Z2 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. As Q, a group made of a nonmetal atomic group necessary for forming a 5- to 8-membered ring is preferred. The 5- to 8-membered ring may be substituted, be saturated or have an unsaturated bond. An aromatic group and a heterocyclic group are especially preferred. Preferred examples of the nonmetal atom include nitrogen atom, oxygen atom, sulfur atom and carbon atom. Specific examples of such a cyclic structure include benzene, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclohexene, pyridine, pyrimidine, pyrazine, pyridazine, triazine, imidazole, benzimidazole, oxazole, benzoxazole, thiazole, benzothiazole, oxane, sulfolane and thiane rings.
The groups as described in the formula (A-2) may each have a substituent further. When they have a substituent, substituents similar to those described in the formula (A-1), those mentioned in G, R1, or R2 by way of example and ionic hydrophilic groups can be given as examples.
With regards to Z1, a Hammett substituent constant "sgr"p value as used herein will next be described. The Hammett rule is an empirical rule suggested by L. P. Hammett in 1935 in order to deal quantitatively with the influence of substituents on reactions or equilibria of benzene derivatives, and nowadays its validity is widely accepted. The substituent constants determined by the Hammett rule include "sgr"p values and "sgr"m values, many of which are described in general books and are described in detail, for example, in xe2x80x9cLange""s Handbook of Chemistry,xe2x80x9d 12th edition, ed. by J. A. Dean, published in 1979 (McGraw-Hill), and in xe2x80x9cJournal of Japanese Chemistryxe2x80x9d, Extra Number, No. 122, pages 96 to 103, 1979 (Nankodo Co., Ltd.) In the present invention, each substituent is stipulated by the Hammett substituent constant "sgr"p values. It is however needless to say that substituents are not limited by these values which are known and described in literature in these books but rather the present invention includes substituents whose Hammett substituent constant "sgr"p values are not known in the literature but when measured in accordance with the Hammett rule, fall within its range. The compounds represented by the formulas (A-1) and (A-2) of the invention are not always benzene derivatives, but "sgr"p values are used as a measure for indicating electron effects of the substituent irrespective of the position of the substituent. In the invention, "sgr"p values are used in this sense.
Examples of electron attractive groups having a Hammett substituent constant "sgr"p value of 0.60 or greater include cyano group, nitro group, and alkylsulfonyl groups (such as methylsulfonyl and arylsulfonyl (e.g., benzenesulfonyl)).
Examples of electron attractive groups having an Hammett substituent constant "sgr"p value of 0.45 or greater include, in addition to the above-described ones, acyl groups (such as acetyl), alkoxycarbonyl groups (such as dodecyloxycarbonyl), aryloxycarbonyl groups (such as m-chlorophenoxycarbonyl), alkylsulfinyl groups (such as n-propylsulfinyl), arylsulfinyl groups (ex. phenylsulfinyl), sulfamoyl groups (such as N-ethylsulfamoyl and N,N-dimethylsulfamoyl), and alkyl halilde groups (such as trifluoromethyl).
Examples of the electron attractive groups with a "sgr"p value of 0.30 or greater include, in addition to the above-described groups, acyloxy groups (such as acetoxy), carbamoyl groups (such as N-ethylcarbamoyl and N,N-dibutylcarbamoyl), halogenated alkoxy groups (such as trifluoromethyloxy), halogenated aryloxy groups (such as pentafluorophenyloxy), sulfonyloxy groups (ex. methylsulfonyloxy), halogenated alkylthio groups (such as difluoromethylthio), aryl groups substituted with at least two electron attractive groups having a "sgr"p value of 0.15 or greater (such as 2,4-dinitrophenyl and pentachlorophenyl) and heterocycles (such as 2-benzoxazolyl, 1-benzothiazolyl and 1-phenyl-2-benzimidazolyl). Specific examples of the electron attractive group having a "sgr"p value of 0.20 or greater include, in addition to the above-described ones, halogen atoms.
The following are particularly preferred combinations of substituents for azo dyes of the formula (A-1). As R5 and R6, preferred are a hydrogen atom, alkyl groups, aryl groups, heterocyclic groups, a sulfonyl group and acyl groups, of which a hydrogen atom, aryl groups, heterocyclic groups and a sulfonyl group are preferred, with a hydrogen atom, aryl groups and heterocyclic groups being most preferred. R5 and R6 however do not represent a hydrogen atom simultaneously.
As G, preferred are a hydrogen atom, halogen atoms, alkyl groups, a hydroxyl group, an amino group and an acylamino groups, of which a hydrogen atom, halogen atoms, an amino group and acylamino groups are more preferred, with a hydrogen atom, an amino group and acylamino groups being still more preferred.
As A, preferred are pyrazole, imidazole, isothiazole, thiadiazole and benzothiazole rings, of which pyrazole and isothiazole rings are more preferred, with pyrazole ring being most preferred.
B1 and B2 are xe2x95x90CR1xe2x80x94 and xe2x80x94CR2xe2x95x90, respectively, and, as each of R1 and R2, a hydrogen atom, halogen atoms, a cyano group, a carbamoyl group, a carboxyl group, alkyl groups, a hydroxyl group, alkoxy groups and alkoxycarbonyl groups, more preferably a hydrogen atom, alkyl groups, a carboxyl group, a cyano group and a carbamoyl group are preferred.
As the compound of the formula (A-1), those having, as at least one of various substituents, the above-described preferred group are preferred, of which those having more substituents selected from the above-described preferred groups are more preferred, with those having all the substituents selected from the above-described preferred groups being most preferred.
Specific examples of the azo dye of the formula (A-1) will be described below, but azo dyes usable in the invention are not limited thereto.
The inkjet recording ink compositions of the invention each contains the azo dye preferably in an amount of 0.2 to 20% by mass, more preferably 0.5 to 15% by mass.
A description will next be made of a surfactant contained in the inkjet recording ink composition of the present invention.
By incorporating a surfactant in the inkjet recording ink composition of the present invention, thereby controlling the physical properties of the ink solution, it is possible to bring about excellent effects for improving discharge stability of ink, improving water resistance of the recorded image and preventing bleeding of the printed ink.
Examples of the surfactant include anionic surfactants such as fatty acid salts, alkyl sulfates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkylsufosuccinates, alkyl phosphates, naphthalenesulfonic acid-formalin condensate, and polyoxyethylene alkyl sulfates; cationic surfactants such as fatty amine salts, quaternary ammonium salts and alkyl pyridinium salts; and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl amines, glycerin fatty acid esters, oxyethylene oxypropylene block copolymer, and acetylene-based polyoxyethylene oxide.
Nonionic surfactants are preferred in consideration of the above-described effects, and also discharge stability of ink and prevention of bleeding. Especially compounds represented by the following formula (I) or (II) are preferred.
R1Oxe2x80x94(CH2CH2O)m1xe2x80x94Hxe2x80x83xe2x80x83(I)
wherein, R1 represents a C5-40, preferably C8-18 alkyl group which may be linear or branched, or may be substituted.
Examples of the substituent for an alkyl group represented by R1 include aryl groups (such as phenyl, o-tolyl, p-tolyl and p-t-butylphenyl), alkoxy groups (such as methoxy, ethoxy and n-butoxy) and halogen atoms (such as chlorine and bromine atoms).
Specific examples of the alkyl group represented by R1 include n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl, n-octadecyl, 2-ethylhexyl, 1-ethylpentyl, 1-n-butylpentyl, 1-n-pentylhexyl, 1-n-hexylheptyl, 1-n-heptyloctyl, 1-n-octylnonyl, 6-methoxyhexyl, and 2-phenylethyl.
m1 represents an average mole of ethylene oxide added and, more specifically, 2 to 40, preferably 3 to 30, especially 3 to 20.
Of the compounds represented by the formula (I), those represented by the formula (I-1) are especially preferred in the present invention.
wherein, R11 and R12 each independently represents a C4-10 saturated hydrocarbon and they have 8 to 18 carbon atoms in total, m11 stands for 3 to 20. Examples of the C4-10 saturated hydrocarbon represented by R11 or R12 include n-butyl, i-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl and n-decyl. R11 and R12 have 8 to 18 carbon atoms in total, with 8 to 16 carbon atoms being more preferred. m11 stands for 3 to 20, more preferably 5 to 20, still more preferably 6 to 18.
Specific examples of the compound represented by the formula (I) will next be described, but the present invention is not limited thereto.
W1-1,2
(n)C8H17Oxe2x80x94(CH2CH2O)m1xe2x80x94H
W1-1: m1=5
W1-2: m1=10
W1-3,4
(n)C10H21Oxe2x80x94(CH2CH2O)m1xe2x80x94H
W1-3: m1=10
W1-4: m1=15
W1-5xcx9c7
(n)C12H25Oxe2x80x94(CH2CH2O)m1xe2x80x94H
W1-5: m1=10
W1-6: m1=15
W1-7: m1=20
W1-8
(n)C14H29Oxe2x80x94(CH2CH2O)15xe2x80x94H
W1-9
(n)C16H33Oxe2x80x94(CH2CH2O)15xe2x80x94H
W1-10, 11
C18H35Oxe2x80x94(CH2CH2O)m1xe2x80x94H
W1-10: m1=12
W1-11: m1=25
W1-12
C18H37Oxe2x80x94(CH2CH2O)20xe2x80x94H
Specific examples of the compound represented by the formula (I-1) will next be described, but the present invention is not limited thereto.
The compound represented by the formula (II) will next be described.
R2COOxe2x80x94(CH2CH2O)m2xe2x80x94Hxe2x80x83xe2x80x83(II)
wherein, R2 represents a C5-40, preferably C5-30 alkyl group which may be linear or branched, or may be substituted.
Examples of the substituent for the alkyl group represented by R2 include aryl groups (such as phenyl, o-tolyl, p-tolyl and p-t-butylphenyl), alkoxy groups (such as methoxy, ethoxy and n-butoxy) and halogen atoms (such as chlorine and bromine atoms) Specific examples of the alkyl group represented by R2 include n-pentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl, n-octadecyl, 2-ethylhexyl, 1-ethylpentyl, 1-n-butylheptyl, 1-n-hexylnonyl, 1-n-heptyldecyl, 1-n-octyldodecyl, 1-n-decyltatradecyl, 6- methoxyhexyl, and 2-phenylethyl.
m2 represents an average mole of ethylene oxide added and, more specifically, 2 to 40, preferably 3 to 30, especially 4 to 20.
Of the compounds represented by the formula (II), those represented by the formula (II-1) are especially preferred in the present invention.
wherein, R21 and R22 each independently represents a C2-20 saturated hydrocarbon group. The number of carbon atoms is preferably 4 to 13. Examples of the C2-20 saturated hydrocarbon group represented by R21 or R22 include ethyl, n-butyl, i-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl, n-hexadecyl and n-octadecyl. m21 represents an average moles of ethylene oxide added and more specifically 2 to 40, more preferably 3 to 30.
Specific examples of the compound represented by the formula (II) will next be described, but the present invention is not limited thereto.
W2-1,2
(n)C7H15COOxe2x80x94(CH2CH2O)m2xe2x80x94H
W2-1: m2=10
W2-2: m2=15
W2-3xcx9c5
(n)C11H23COOxe2x80x94(CH2CH2O)m2xe2x80x94H
W2-3: m2=10
W2-4: m2=15
W2-5: m2=20
W2-6xcx9c7
(n)C13H27COOxe2x80x94(CH2CH2O)m2xe2x80x94H
W2-6: m2=10
W2-7: m2=15
W2-8,9
(n)C15H31COOxe2x80x94(CH2CH2O)m2xe2x80x94H
W2-8: m2=10
W2-9: m2=15
W2-10,
C17H31COOxe2x80x94(CH2CH2O)20xe2x80x94H
W2-11
C17H33COOxe2x80x94(CH2CH2O)20xe2x80x94H
W2-12
C17H35COOxe2x80x94(CH2CH2O)15xe2x80x94H
Specific examples of the compound represented by the formula (II-1) will next be described, but the present invention is not limited thereto.
The compounds represented by the formulas (I) and (II) in the present invention can be synthesized in a known manner. They are available, for example, by the process as described in, for example, xe2x80x9cShin Kaimenkasseizai Nyumon (Introduction to Surfactants)xe2x80x9d (1992), p94 to p107, ed. by Takehiko Fujimoto. In the present invention, compounds of the formulas (I) and (II) may be used either singly or in combination.
The surfactant is incorporated in an amount of 0.001 to 15% by mass, preferably 0.005 to 10% by mass, more preferably 0.01 to 5% by mass based on the ink including the compound of the present invention represented by the formula (I) or (II).
The inkjet recording ink of the invention can be prepared by dissolving and/or dispersing, in an aqueous medium, the azo dye and the surfactant. The term xe2x80x9caqueous mediumxe2x80x9d as used herein means an aqueous medium obtained by adding an additive such as humectant, stabilizer and/or antiseptic as needed to water or a mixture of water and a small amount of a water miscible organic solvent.
Examples of the water miscible organic solvent usable in the invention include alcohols (such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol and benzyl alcohol), polyhydric alcohols (such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexane triol and thiodiglycol), glycol derivatives (such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethylether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and ethylene glycol monophenyl ether), amines (such as ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine and tetramethylpropylenediamine) and other polar solvents (ex. formamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile and acetone). At least two of these water miscible organic solvents can be used in combination.
When the azo dye is an oil soluble dye, it can be prepared by dissolving the oil soluble dye in a high-boiling-point organic solvent and then dispersing and emulsifying the resulting solution in an aqueous medium.
The high-boiling-point organic solvent to be used in the invention has a boiling point of 150xc2x0 C. or greater, preferably 170xc2x0 C. or greater.
Examples include phthalic acid esters (such as dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-tert-amylphenyl) isophthalate, and bis(1,1-diethylpropyl) phthalate), phosphoric acid or phosphonic acid esters (such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, dioctylbutyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, and di-2-ethylhexylphenyl phosphate), benzoic acid esters (such as 2-ethylhexyl benzoate, 2,4-dichlorobenzoate, dodecyl benzoate, and 2-ethylhexyl-p-hydroxy benzoate), amides (such as N,N-diethyldodecanamide and N,N-diethyllaurylamide), alcohols or phenols (such as isostearyl alcohol and 2,4-di-tert-amylphenol), aliphatic esters (such as dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate and trioctyl citrate), aniline derivatives (such as N,N-dibutyl-2-butoxy-5-tert-octylaniline), chlorinated paraffins (such as paraffins having a chlorine content of 10 to 80%), trimesic acid esters (such as tributyl trimesate), dodecyl benzene, diisopropyl naphthalene, phenols (such as 2,4-di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol and 4-(4-dodecyloxyphenylsulfonyl)phenol), carboxylic acids (such as 2-(2,4-di-tert-amylphenoxybutyric acid and 2-ethoxyoctanedacanoic acid), and alkylphosphoric acids (such as di-2(ethylhexyl)phosphoric acid and diphenylphosphoric acid). These high-boiling-point organic solvents may be used in an amount of 0.01 to 3 times the mass, preferably 0.01 to 1 time the mass of the oil soluble dye.
These high-boiling-point organic solvents may be used either singly or in combination of two or more [for example, tricresyl phosphate and dibutyl phthalate, trioctyl phosphate and di(2-ethylhexyl)sebacate, or dibutyl phthalate and poly(N-t-butyl acrylamide)].
Compounds other than the above-described high-boiling-point organic solvents but usable in the present invention and/or synthesizing processes thereof are described in, for example, U.S. Pat. Nos. 2,322,027, 2,533,514, 2,772,163, 2,835,579, 3,594,171, 3,676,137, 3,689,271, 3,700,454, 3,748,141, 3,764,336, 3,765,897, 3,912,515, 3,936,303, 4,004,928, 4,080,209, 4,127,413, 4,193,802, 4,207,393, 4,220,711, 4,239,851, 4,278,757, 4,353,979, 4,363,873, 4,430,421, 4,430,422, 4,464,464, 4,483,918, 4,540,657, 4,684,606, 4,728,599, 4,745,049, 4,935,321, or 5,013,639; European Patent No. 2,76,319A, 286,253A, 289,820A, 309,158A, 309,159A, 309,160A, 509,311A, or 510,576A; East German Patent No. 147,009, 157,147, 159,573, or 225,240A; British Patent No. 2,091,124A; Japanese Patent Laid-Open No. 47335/1973, 26530/1975, 25133/1976, 26036/1976, 27921/1976, 27922/1976, 149028/1976, 46816/1977, 1520/1978, 1521/1978, 15127/1978, 146622/1978, 91325/1979, 106228/1979, 118246/1979, 59464/1980, 64333/1981, 81836/1981, 204041/1984, 84641/1986, 118345/1987, 247364/1987, 167357/1988, 214744/1988, 301941/1988, 9452/1989, 9454/1989, 68745/1989, 101543/1989, 102454/1989, 792/1990, 4239/1990, 43541/1990, 29237/1992, 30165/1992, 232946/1992 or 346338/1992.
The above-described high-boiling-point organic solvents may be used in an amount of 0.01 to 3.0 times the mass, preferably 0.01 to 1.0 time the mass of the oil soluble dye.
In the invention, the oil soluble dye or high-boiling-point organic solvent is dispersed and emulsified in an aqueous medium. Upon emulsification and dispersion, a low-boiling-point organic solvent can be sometimes used from the viewpoint of emulsifying properties. The low-boiling-point organic solvent is an organic solvent having a boiling point of 30xc2x0 C. or greater but not greater than 150xc2x0 C. under normal pressure. Preferred examples include, but not limited to, esters (ethyl acetate, butyl acetate, ethyl propionate, xcex2-ethoxyethyl acetate and methyl cellosolve acetate), alcohols (such as isopropyl alcohol, n-butyl alcohol and secondary butyl alcohol), ketones (such as methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone), amides (such as dimethylformamide and N-methylpyrrolidone) and ethers (such as tetrahydrofuran and dioxane).
Emulsification and dispersion are conducted for the purpose of forming fine oil droplets of an oil phase by dispersing, in an aqueous phase composed mainly of water, an oil phase having a dye dissolved in a high-boiling-point organic solvent or, in some cases, in a mixed solvent thereof with a low-boiling-point organic solvent. At this time, to either one of the aqueous phase or oil phase or both of them, an additive such as surfactant, humectant, dye stabilizer, emulsion stabilizer, antiseptic and/or antifungal agent, which will be described later, may be added as needed.
Emulsification is usually conducted by adding an oil phase to an aqueous phase. Alternatively, so-called phase inversion emulsification wherein an aqueous phase is added dropwise to an oil phase can be preferably employed.
Various surfactants can be employed upon dispersion and emulsification in the invention. Preferred examples include anionic surfactants such as fatty acid salts, alkyl sulfates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphates, naphthalenesulfonic acid-formalin condensate, and polyoxyethylene alkyl sulfates; and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl amines, glycerin fatty acid esters, and oxyethylene oxypropylene block copolymers. As well as these surfactants, SURFYNOLS (trade name; product of Air Products and Chemicals) which are acetylene series polyoxyethylene oxide surfactants are preferred. Amine oxide type amphoteric surfactants such as N,N-dimethyl-N-alkylamine oxides are also preferred. Moreover, surfactants as described in Japanese Patent Laid-Open No. 157,636/1984, pp. (37)-(38), and Research Disclosure No. 308119 (1989) are also usable.
In order to stabilize the emulsion rightly after emulsification, a water soluble polymer can be added in combination with the surfactant. As the water soluble polymer, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, polyacrylic acid and polyacrylamide, and copolymers thereof are preferred. Natural water-soluble polymers such as polysaccharides, casein and gelatin are also preferred. In order to stabilize the dispersion of a dye, it is possible to use, in combination, polyvinyl, polyurethane, polyamide, polyurea or polycarbonate available by the polymerization of an acrylate ester, methacrylate ester, vinyl ester, acrylamide, methacrylamide, olefin, styrene, vinyl ether, or acrylonitrile, which polymer is substantially insoluble in an aqueous medium. These polymers preferably contain xe2x80x94SO2xe2x88x92 or xe2x80x94COOxe2x88x92. When such a polymer substantially insoluble in an aqueous medium is used in combination, it is used preferably in an amount not greater than 20% by mass, more preferably not greater than 10% by mass, based on the high-boiling-point organic solvent.
Upon preparation of an aqueous ink by dispersing and emulsifying an oil soluble dye or high-boiling-point organic solvent, control of its particle size is of particular importance. It is essential to minimize the average particle size in order to heighten color purity or density upon formation of an image by inkjet. The volume-average particle size is preferably 1 xcexcm or less, more preferably 5 to 100 nm.
The volume average particle size and particle distribution of the dispersed particles can be measured readily in a known manner, for example, the static light scattering method, dynamic light scattering method, centrifugal precipitation method or the method described on pages 417 to 418 of Jikken Kagaku Koza, 4th Edition. For example, a particle size can be measured easily by diluting an ink with distilled water to give the particle concentration in the ink of 0.1 to 1% by mass and measuring the resulting diluted ink by a commercially available volume-average particle size measuring instrument (for example, Microtrac UPA (trade name; product of Nikkiso Co., Ltd.). The dynamic light scattering method using Laser Doppler effect permits measurement of small particle size so that it is especially preferred.
The volume-average particle size is an average particle size based on the volume of the particles and it is found by multiplying the diameter of each particle by its volume and then dividing the sum of the products by the total volume of the particles. There is a description on page 119 of xe2x80x9cKobunshi Latex no Kagaku (Chemistry of High Molecular Latex)xe2x80x9d (written by Soichi Muroi, published by Kobunshi Kankokai).
It has been revealed that the existence of coarse particles plays an important role in printing performance. Described specifically, coarse particles cause clogging of a head nozzle or, if not so, form a stain and prevent discharge or cause irregular discharge of the ink, thereby having a serious influence on the printing performance. To prevent such phenomena, it is important to control the number of the particles having a particle size of 5 xcexcm or greater to 10 or less and the number of the particles having a particle size of 1 xcexcm or greater to 1000 or less, in 1 xcexcl of the resulting ink.
Such coarse particles can be removed by known centrifugal separation or precise filtration. Such separation may be conducted rightly after dispersion and emulsification, or after addition of various additives such as humectant and surfactant to the emulsified dispersion but rightly before filling a cartridge with the mixture.
A mechanical emulsifier can be employed as an effective means for decreasing the average particle size and removing coarse particles.
As the emulsifier, usable are known ones such as simple stirring system using a stirrer or impeller, inline stirring system, mill system using a colloid mill or ultrasonic wave system. A high pressure homogenizer is however especially preferred.
Mechanism of a high pressure homogenizer is described specifically in U.S. Pat. No. 4,522,354 or Japanese Patent Laid-Open No. 47264/1994. Examples of the commercially available one include Gaulin homogenizer (product of A.P.V GAULIN INC), microfluidizer (product of MICROFLUIDEX INC.) and Ultimaizer (product of Sugino Machine).
A recently developed high pressure homogenizer as described in U.S Pat. No. 5,720,551 having a mechanism for forming fine droplets in a ultrahigh pressure jet stream is particularly effective for emulsification and dispersion of the invention. xe2x80x9cDeBEE 2000xe2x80x9d (product of BEE INTERNATIONAL LTD.) is one of the emulsifiers adopting this ultrahigh pressure jet stream.
The pressure upon emulsification by a high pressure emulsifier is at least 50 MPa, preferably at least 60 MPa, still more preferably at least 180 MPa.
Use of at least two emulsifiers, for example, emulsification by a stirring emulsifier, followed by the use of a high pressure homogenizer is particularly preferred. It is also preferred to disperse and emulsify by such emulsifiers, add to the resulting emulsion an additive such as humectant and surfactant and subject the resulting mixture to high pressure homogenizer again while filling a cartridge with the resulting ink.
When both of a high boiling point organic solvent and a low boiling point organic solvent are incorporated, removal of the low boiling point solvent is preferred for stability, safety and sanitation of the emulsion. The low boiling point solvent can be removed in a known manner, for example, evaporation, vacuum evaporation or ultrafiltration, depending on the kind of the solvent. This removal of the low boiling point organic solvent is preferably conducted as soon as possible rightly after emulsification.
To the inkjet recording ink composition obtained by the invention, additives selected as needed from antidrying agent for preventing clogging at a jet orifice due to drying of an ink, penetration promoter to promote penetration of an ink into paper, ultraviolet absorber, antioxidant, viscosity regulator, surface tension regulator, dispersant, dispersion stabilizer, antifungal agent, rust preventive, pH regulator, antifoaming agent and chelating agent can be added.
As the antidrying agent to be used in the invention, water soluble organic solvents having a vapor pressure lower than that of water are preferred. Specific examples include polyhydric alcohols typified by ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivative, glycerin and trimethylolpropane; lower alkyl ethers of a polyvalent alcohol such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether and triethylene glycol monoethyl (or butyl) ether; heterocyclics such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and N-ethylmorpholine; sulfur-containing compounds such as sulfolane, dimethylsulfoxide and 3-sulfolene; polyfunctional compounds such as diacetone alcohol and diethanolamine; and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. The above-exemplified antidrying agents may be used either singly or in combination. The antidrying agent is preferably added in an amount of 10 to 50% by mass of the ink.
Examples of the penetration promoter usable in the invention include alcohols such as ethanol, isopropanol, butanol, di(tri)-ethylene glycol monobutyl ether, and 1,2-hexanediol and nonionic surfactants such as sodium lauryl sulfate and sodium oleate. Incorporation of it in an amount of 10 to 30% by mass in an ink brings about sufficient effects. It is preferably added in an amount within a range causing neither bleeding of print nor print-through.
Examples of the ultraviolet absorber to be used in the invention for improving the shelf life of images include benzotriazole compounds as described in Japanese Patent Laid-Open Nos. 185677/1983, 190537/1986, 782/1990, 197075/1993 and 34057/1997, benzophenone compounds as described in Japanese Patent Laid-Open Nos. 2784/1971 and 194483/1993 and U.S. Pat. No. 3,214,463, cinnamic acid compounds as described in Japanese Patent Publication No. 30492/1973 and 21141/1981 and Japanese Patent Laid-Open No. 88106/1998, triazine compounds as described in Japanese Patent Laid-Open No. 298503/1992, 53427/1996, 239368/1996 and 182621/1998 and International Patent Publication No. 501291/1996, and so-called fluorescent brightenersxe2x80x94compounds which emit fluorescence, absorbing ultraviolet raysxe2x80x94typified by the compounds as described in Research Disclosure No. 24239, and stilbene and benzoxazole compounds.
As the antioxidant for improving shelf life of a recorded image, various organic and metal complex type fading preventives can be used in the invention. Organic fading preventives include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, coumarones, alkoxyanilines and heterocycles, while metal complexes include nickel complexes and zinc complexes. More specifically, compounds as described in xe2x80x9cResearch Disclosure, No. 17643, VII, Section I or J, No. 15162, No. 18716, left column on page 650, No. 36544, page 527, No. 307105, page 872, and the patent cited in No. 15162, and compounds embraced in the formula of the typical compounds and compound examples described on pages 127 to 137 of Japanese Patent Laid-Open No. 215272/1987.
Examples of the antifungal agent usable in the invention include sodium dehydroacetate, sodium benzoate, sodium pyridinethion-1-oxide, ethyl p-hydroxybenzoate and 1,2-benzisothiazolin-3-one and salts thereof. It is preferably added in an amount of 0.02 to 5.00% by mass of the ink.
Details of the antifungal agent are described in xe2x80x9cDictionary of Antibacterial and Antifungal Agentsxe2x80x9d (ed. by The Society for Antibacterial and Antifungal Agents, Japan).
Examples of the rust inhibitor include acidic sulfites, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and benzotriazole. It is preferably added in an amount of 0.02 to 5.00% by mass in the ink.
The pH regulator to be used in the invention functions well for regulating pH of the ink, thereby imparting it with dispersion stability. The pH regulator is preferably added to adjust the pH of the ink to 4.5 to 10.0, more preferably to 6 to 10.0.
As basic pH regulators, organic bases and inorganic alkalis are usable while as acidic ones, organic acids and inorganic acids are usable
The organic bases include triethanolamine, diethanolamine, N-methyldiethanolamine and dimethylethanolamine. The inorganic alkalis include hydroxides of an alkali metal (ex. sodium hydroxide, lithium hydroxide and potassium hydroxide), carbonates (ex. sodium carbonate and sodium bicarbonate) and ammonia.
The organic acids include acetic acid, propionic acid, trifluoroacetic acid and alkylsulfonic acid. The inorganic acids include hydrochloric acid, sulfuric acid and phosphoric acid.
As the surface tension regulator, noionic, cationic and anionic surfactants other than those described above are usable in the invention. Examples of the anionic surfactants include fatty acid salts, alkyl sulfates, alkyl benzenesulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphates, naphthalenesulfonic acid formalin condensate, and polyoxyethylene alkyl sulfate esters; those of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, and oxyethylene oxypropylene block copolymers. SURFYNOLS (trade name; product of Air Products and Chemicals Inc.) which are acetylene type polyoxyethylene oxide surfactants are also preferably employed. Amine oxide type amphoteric surfactants such as N,N-dimethyl-N-alkylamine oxide are also preferred. Surfactants as described in Japanese Patent Laid-Open No. 157,636/1984, p(37) to p(38) and Research Disclosure No. 308119 (1989) are also usable.
The ink of the invention containing or not containing such a regulator is preferred to have a surface tension of 20 to 60 mN/m, more preferably 25 to 45 mN/m.
The ink usable in the invention has preferably a viscosity of 30 mPaxc2x7s or less. Since it has a viscosity of 20 mPaxc2x7s or less, a viscosity regulator is sometimes added to adjust its viscosity. Examples of the viscosity regulators include celluloses, water soluble polymers such as polyvinyl alcohol, and nonionic surfactants. More specific description about viscosity regulators can be found in Chapter 9 of xe2x80x9cViscosity Regulating Techniquexe2x80x9d (Information Technology Association, 1999) and pages 162 to 174 of xe2x80x9cChemicals for Inkjet Printers (Supplement, 98)xe2x80x94Researches on Development Trend and Prospect of Materialsxe2x80x94xe2x80x9d (CMC, 1997)).
In the invention, it is also possible to add, as needed, the above-described cationic, anionic or nonionic surfactant as a dispersant or dispersion stabilizer, and a fluorine or silicon compound, or a chelating agent typified by EDTA as an antifoaming agent.
Recording paper and recording film to be used in the image recording method of the invention will next be described. As recording paper and recording film, usable are those having, as a support, chemical pulp such as LBKP or NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP or CGP, or recycled pulp such as DIP, to which conventionally known additives such as pigment, binder, sizing agent, fixer, cationic agent and paper strength agent have been added as needed, and made using paper machine such as wire paper machine or cylinder paper machine. Alternatively, the support may be synthetic paper or plastic film sheet and it preferably has a thickness of 10 to 250 xcexcm and a basis weight of 10 to 250 g/m2.
The support may be used as a receiving material after disposing thereon an image receiving layer and back coat layer, or after disposing a size press or anchor coat layer by using starch or polyvinyl alcohol and then disposing thereon an image receiving layer and a back coat layer. The support may further be subjected to flattening treatment by a calendering machine such as machine calender, TG calender or soft calender.
In the invention, paper or a plastic film having both sides thereof laminated with polyolefin (ex. polyethylene, polystyrene, polyethylene terephthalate or polybutene, or copolymer thereof) is preferably employed as the support. Addition of a white pigment (ex. titanium oxide or zinc oxide) or a tinting dye (ex. cobalt blue, ultramarine or neodium oxide) to polyolefin is preferred.
In the image receiving layer disposed on the support, a porous material and an aqueous binder are incorporated. The image receiving layer preferably contains a pigment, preferably a white pigment. Examples of the white pigment include inorganic white pigments such as calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate and organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. As the white pigment, porous white inorganic pigment, particularly, synthetic amorphous silica having a large pore area is preferred. As the synthetic amorphous silica, silicic anhydride available by dry process and hydrated silicic acid available by wet process are usable, of which hydrated silicic acid is desired. These pigments may be used in combination.
Examples of the aqueous binder contained in the image receiving layer include water-soluble polymers such as polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationated starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyalkylene oxide and polyalkylene oxide derivatives and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. These aqueous binders may be used either singly or in combination. Of them, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferred from the viewpoints of adhesion to the pigment and peel resistance of the ink receptive layer.
The image receiving layer may contain, in addition to, the pigment and aqueous binder, a mordant, a water proofing agent, light resistance improver, surfactant, hardener and the like additives.
The mordant to be added to the image receiving layer is preferably immobilized. A polymeric mordant is preferably employed for this purpose.
Polymeric mordants are described in Japanese Patent Laid-Open Nos. 28325/1973, 74430/1979, 124726/1979, 22766/1980, 142339/1980, 23850/1985, 23851/1985, 23852/1985, 23853/1985, 57836/1985, 60643/1985, 118834/1985, 122940/1985, 122941/1985, 122942/1985, 235134/1985 and 161236/1989, and U.S. Pat. Nos. 2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124, 4,124,386, 4,193,800, 4,273,853, 4,282,305 and 4,450,224. Image receiving materials containing the polymer mordant as described on pages 212 to 215 of Japanese Patent Laid-Open 161236/1989 are particularly preferred. Use of these polymer mordants makes it possible to form an image having excellent image quality and improved light resistance.
A water proofing agent is effective for improving water resistance of a recorded image and as this agent, cationic resins are particularly desired. These cationic resins include polyamide polyamine epichlorohydrin, polyethyleneimine, polyaminesulfone, dimethyldiallyl ammonium chloride polymer, cation polyacrylamide and colloidal silica. Of these cationic resins, polyamide polyamine epichlorohydrin is particularly preferred. The cationic resin is preferably added in an amount of 1 to 15% by mass, particularly 3 to 10% by mass based on the whole solid content of the ink receiving layer.
Examples of the light resistance improver include zinc sulfate, zinc oxide, hindered amine antioxidants and benzophenone or benzotriazole ultraviolet absorbers, of which zinc sulfate is particularly preferred.
The surfactant functions as a coating aid, peeling improver, slip improver or antistatic agent. Description on the surfactant can be found in Japanese Patent Laid-Open Nos. 173463/1987 and 183457/1987.
Instead of the surfactant, organofluoro compounds may be employed. They are preferably hydrophobic. Examples include fluorine surfactants, oily fluorine compounds (ex. fluorine oil) and solid fluorine compound resins (ex. ethylene tetrafluoride resins). Organofluoro compounds are described in Japanese Patent Publication No. 9053/1982 (8th to 17th columns), and Japanese Patent Laid-Open Nos. 20994/1986 and 135826/1987.
As the hardener, materials as described on page 222 of Japanese Patent Laid-Open No. 161236/1989 are usable.
As other additives to the image receiving layer, pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent brighteners, antiseptics, pH regulators, matting agents and hardeners can be used. The ink receiving layer may be a single layer or a double layer.
The recording paper or recording film may have a back coat layer disposed thereon. To this layer, white pigments, aqueous binders and the other components can be added.
Examples of the white pigment to be incorporated in the back coat layer include white inorganic pigments such as light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, titan white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo boehmite, aluminum hydroxide, alumina, litopone, zeolite, hydrated halloysite, magnesium carbonate and magnesium hydroxide, and organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsules, urea resins and melamine resins.
As the aqueous binder to be incorporated in the back coat layer, usable are water soluble polymers such as styrene/maleate salt copolymers, styrene/acrylate salt copolymers, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationated starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose and polyvinylpyrrolidone, and water dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of the other component to be incorporated in the back coat layer include antifoaming agent, foaming inhibitor, dye, fluorescent brightener, antiseptic and water proofing agent.
To layers (including back layer) constituting the ink-jet recording paper or recording film, a fine particle dispersion of a polymer may be added. It is used in order to improve the physical properties of a film, for example, stabilizing size and preventing curling, adhesion and cracks. A description on the fine particle dispersion of a polymer can be found in Japanese Patent Laid-Open Nos. 245258/1987, 1316648/1987 and 110066/1987. Addition of a fine particle dispersion of a polymer having a low glass transition point (40xc2x0 C. or lower) to a mordant-containing layer enables to prevent occurrence of cracks or curing of the layer. Addition of a fine particle dispersion of a polymer having a high glass transition point also prevents occurrence of curling even when added to the back layer.
The ink composition of the invention can be used for any known inkjet recording method, for example, a charge control method of ejecting ink by making use of electrostatic induction power, drop-on-demand method (pressure pulse method) making use of oscillation pressure of a piezoelectric element, acoustic ink-jet method of exposing ink to acoustic beams converted from electric signals and utilizing a radiation pressure for discharging ink, and thermal ink-jet (bubble jet) method of heating ink to form bubbles and making use of the pressure thus generated.
Ink-jet recording methods include a method of jetting a number of photoinks, that is, small-volume inks having a low concentration, a method of improving image quality by using a plurality of inks having substantially the same hue but different concentrations and a method of using a colorless transparent ink.
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An elevator system is a moving means that conveniently carries passengers upstairs or downstairs. A common elevator system includes an elevator monitoring device capable of constantly monitoring elevators so as to safely carry the passengers to a target floor.
The elevator monitoring device receives operation information related to the current service floor, moving direction of the elevator, elevator moving status, hall/car call registered floor and the like, as well as control information related to movement to a specific floor, parking of the elevator and the like. Such information is received from a control unit of each elevator, thus enabling the elevators to be monitored in real time.
Generally, a plurality of elevators in the elevator system is classified into a plurality of elevator groups according to elevator characteristics for control and monitoring. Each elevator group includes at least one elevator. The conventional elevator monitoring device selects an arbitrary elevator group among the plurality of elevator groups and then displays various information on the elevators included in the selected elevator group through a monitoring screen.
When elevator-related information is displayed on the monitoring screen, the number of elevator groups that can be displayed is limited to one due to the limited size of the monitoring screen. Therefore, in order to monitor a specific elevator that is not included in the elevator group being currently displayed, the elevator group displayed on the monitoring screen must be switched to the elevator group, which includes that specific elevator.
If the elevator group displayed on the monitoring screen is changed, the elevators included in the previous elevator group cannot be monitored anymore. That is, it is impossible to monitor elevators of different elevator groups through one monitoring screen in the conventional elevator monitoring device.
Also, if setup values determining the service floors of each elevator are set differently from each other, there arises a problem in that the number of elevator groups must be set to as many as the number of elevators. Furthermore, in order to monitor each elevator, the monitoring screen must be changed as many times as the number of elevators.
In order to solve the above problems, a communication interface connecting each elevator group is employed to monitor elevators of different elevator groups through one monitoring screen. However, there is a problem in that an additional communication interface must be installed. Furthermore, since noise is generated due to the communication interface, it is difficult to obtain accurate elevator-related information.
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An important business process is the transportation of goods through a manufacturing process or supply chain/distribution network. During transportation through such channels, which may include several links and involve significant time periods (transport via land, sea and/or air, storage in one or more warehouses, etc.), products are susceptible to many potential harms. For example, goods may be misdirected, damaged, tampered with, and/or exposed to adverse environmental conditions. For certain goods, it is often useful, and in some cases critical, to know whether goods received at a destination location have been subjected to any such harms.
Conventional methods of determining whether goods have been exposed to these harms have relied on human intervention and other potentially time consuming and/or unreliable mechanisms. A need exists for improved methods and apparatuses for evaluating the pedigree and/or integrity of goods received at a destination.
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As an electrolyte material to be used as a polymer electrolyte membrane or a proton conductive polymer to be incorporated in a catalyst layer of an electrode constituting a polymer electrolyte fuel cell, it has been common to employ a polymer obtained by hydrolyzing a copolymer of tetrafluoroethylene (hereinafter referred to as “TFE”) with a perfluorovinyl ether of the formula (A), followed by treatment for conversion to an acid-form to convert —SO2F groups to —SO3H groups. In the formula (A), Y is a fluorine atom or a trifluoromethyl group, m is an integer of from 0 to 3, n is an integer of from 1 to 12, and p is 0 or 1, provided that (m+p)>0.CF2═CF(OCF2CFY)mOp(CF2)nSO2F (A)
Among such polymers, particularly preferably employed is one obtained by converting a polymer obtainable by copolymerization of TFE with a monomer represented by the formula (B) to (D), to an acid form. In the formulae (B) to (D), q is an integer of from 1 to 8, r is an integer of from 1 to 8, and s is 2 or 3.CF2═CFO(CF2)qSO2F (B)CF2═CFOCF2CF(CF3)O(CF2)rSO2F (C)CF2═CF(OCF2CF(CF3))sO(CF2)2SO2F (D)
However, although the above-mentioned conventional copolymer was excellent in such properties as an ion conductivity to accomplish a high cell output power and durability to make a long term operation possible, it had a problem that the production cost was high, and it could not be produced at low costs. As a large factor for such a high production cost of the conventional copolymer, it may be mentioned that, for example, in the case of a TFE/CF2═CFOCF2CF(CF3)OCF2CF2SO3H copolymer, it is produced by copolymerizing a vinyl ether monomer containing a —SO2F group synthesized by using, as an intermediate, expensive hexafluoropropylene oxide, with TFE.
Whereas, U.S. Pat. No. 4,273,729 discloses a copolymer of a monomer of the formula (2) (monomer (2)) synthesized without using hexafluoropropylene oxide, with TFE.CF2═CFCF2OCF2CF2SO2F (2)
However, the polymer synthesized for brine electrolysis in an Example (UTILITY EXAMPLE Q) of this patent publication, has an ion exchange capacity of 0.85 (meq/g dry resin) (equivalent weight: 1180), and thus, the ion exchange capacity is inadequate for a fuel cell, whereby it has a problem that the resistance is practically too high. Further, Journal of Applied Polymer Science, Vol. 47, 735-741 (1993) discloses a report on the results of a study of the synthesis of the monomer (2) and copolymerization of TFE with the monomer (2), wherein the relation between the charge composition comprising TFE and the monomer (2) and the obtainable polymer composition, is reported. However, also in this report, the highest ion exchange capacity among the obtained polymers is 0.77 (meq/g dry resin). And, it is stated that rather than the monomer (2), a conventional vinyl ether type monomer having a structure of CF2═CFO— is has a higher reactivity and is more advantageous for the copolymerization.
Namely, the monomer (2) has a lower copolymerization reactivity with TFE than the conventional vinyl ether type monomer, whereby a polymer having a high ion exchange capacity practically useful as an ion exchange membrane, has not heretofore been obtained. In the case of a copolymer using as starting materials a vinyl ether type monomer such as CF2═CFOCF2CF2SO2F or CF2═CFOCF2CF(CF3)OCF2CF2SO2F, and TFE, it is possible to obtain a polymer having an ion exchange capacity of at least 1.1 (meq/g dry resin) easily by means of 2,2′-azobisisobutyronitrile (AIBN), which is hydrocarbon, as the initiator, as disclosed e.g. in Examples of JP-A-60-243292. However, in the case of the monomer (2), polymerization will not substantially proceed by the polymerization by means of AIBN, as disclosed in Comparative Reference Example in this specification.
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Embodiments of the present invention generally relate to laser systems and, more specifically, to a chiller for use in a laser system.
High power laser systems have a broad range of applications throughout the scientific, industrial and medical fields. Laser systems generally include a pump source, a laser element and a laser resonator. The pump source may include laser diodes or bars that generate pump energy or a light input to the laser element. The laser element absorbs the pump energy and emits laser light responsive to the absorbed energy. The laser resonator operates to generate a harmonic of the laser light.
The laser element is generally tuned to absorb pump energy having a wavelength that is within a specified operating band. The wavelength of the pump energy varies with a temperature of the laser diodes and the current supplied to the laser diodes. As a result, it is important to maintain the pump source within an operating temperature range to ensure that the pump energy is within the operating band of the laser element.
Laser systems utilize a chiller that operates to cool the pump source and the laser element. The chiller generally circulates cooled liquid through heat exchangers coupled to the pump source and the laser element. The liquid absorbs heat from the heat exchangers to cool the pump source and the laser element. Conventional chillers generally maintain the pump source and the laser elements at the same temperature.
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The present invention relates to a high speed printer capable of printing information received from data handling apparatus, such as computers or calculators etc.
With the advent of computer technology and advances in the art of data processing, requirements for increased speed of handling information have become more stringent. One known type of rapid readout with permanent recordation incorporates a high speed printer that employs a character type ball bearing the characters to be printed on the outer surface of the ball. However, a type ball printer has the disadvantages that the printing speed is not sufficient and that a type ball is expensive.
The other prior high speed printer employs a type wheel having the characters to be printed at the outer periphery of respective spokes forming the wheel. The U.S. Pat. No. 3,356,199 is an example of a type wheel printer. However, said type wheel printer has the disadvantage that the number of type characters mounted on a single type wheel is limited. If we want to increase the number of type chatacters, the diameter of the type wheel or the length of the spokes must be increased, but the increase in the diameter of the wheel would increase the inertia of the wheel and reduce it's printing speed. Therefore the upper limit of the number of type characters available on said type wheel printer is only 60 or 70 characters.
In order to overcome the disadvantage of the prior type wheel printer, an improvement on the structure of the spokes of the wheel has already been proposed. In said improvement, a pair of type characters are mounted on a single spoke directly on the straight axis line of the spoke. However, said printer has the disadvantages that the type wheel must be shifted upward and/or downward during the high speed rotation of the wheel, in order to select the desired character from the pair of characters on each spoke, and the up/down shift operation of a wheel reduces substantially the operational speed of the printer. The operational speed of said printer is only 40 chatacters in each second.
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Projection systems such as those known and cited in the prior art shown above have contemplated a reversing of the deflection field of the television tube. None of the prior art known has provided protective circuitry to protect the television components from damage due to sparking or inductance leakage or capacative leakage from the deflection components of the television receiver, whether within the picture tube or disposed at the yoke area of the picture tube.
In order to provide ordinary use to the television receiver as well as provide projection of the pictures using the same television receiver in the projection mode, there is required means to protect the circuit elements as well as means to eliminate electrical reactants leaking from the circuit components, whether inductive or capacative in nature. It is contemplated that a switch means in a network inserted in the power line to the television receiver system for providing a holding state when projection is desired and a given or normal state when ordinary viewing of the television receiver is desired provides elimination of sparking, reactive circuit leakages and the like when a DP-DT switch is used in the deflection circuit.
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{
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Recently, an improvement in the fuel consumption of automobiles (namely, lowering of fuel consumption) has been desired by the request of the environmental protection. In the field of automobile tires, it is known that the fuel consumption of automobiles goes down by improving the viscoelastic property of vulcanized rubber used for tire production (see, “Rubber Technology Introduction”, p. 124 edited by The Society of Rubber Science and Technology, Japan, published by Maruzen Co., Ltd.).
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{
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1. Field of the Invention
The present invention relates to a rotary actuator having a rotor which is rotatable relative to a stator.
2. Discussion of Prior Art
A rotary actuator has been utilized in association with a diverter gate in the sorting of mail or other items traveling by a conveyor. The rotary actuator is effective to rotate the diverter gate from one position to another position within a matter of a few milliseconds, typically within about 0.020 seconds, so as to permit a rapid sorting process. The angle of rotation of the diverter gate is typically about 15° to 20° to move the item of mail from one conveyor path to another conveyor path.
The angle of rotation through which the diverter gate is moved is limited by rubber stop bumpers. The rubber stop bumpers are mounted external to the rotary actuator so as to allow precise adjustment and to minimize impact noise by the diverter gate. At the end of its operating stroke, the diverter gate may tend to rebound as it impacts against one of the rubber bumpers.
If the diverter gate can rebound back into the previous conveyor flow path, a missortment or jam may occur. To prevent a missortment or jam from occurring, the flow rate of mail or other items must be decreased to give time for the diverter gate to return to its fully actuated position. Alternatively, the rate of operation of the rotary actuator must be decreased to reduce the kinetic energy of the rotary actuator and diverter gate at an end of stroke position. Of course, both of these solutions to the problem of diverter gate rebound are counter to rapid sorting requirements.
The rotary actuator for the diverter gate must provide for both rapid movement of the diverter gate from an unactuated position to an actuated position and holding of the diverter gate at its actuated position upon impact of the diverter gate against a rubber bumper. In order to provide both functions adequately, the starting torque of the rotary actuator must be high to provide a high diverter gate acceleration rate. The ending torque of the rotary actuator must be high to counteract the rebound energy imparted by the rubber bumper to the diverter gate.
Known rotary actuators have previously utilized either one of two basic design approaches. The first basic design approach utilizes a pole configuration termed as “constant air gap” for the rotor and stator pole pieces. The second basic design approach utilizes a pole configuration termed as “diminishing air gap” for the rotor and stator pole pieces. The air gaps are the working air gaps across which magnetic flux is conducted between the rotor and stator pole pieces.
The “constant air gap” rotary actuator design is characterized by a high starting torque that decreases to a lower torque as the rotary actuator operates through its operating stroke (it being assumed that a constant current is applied to the coil of the rotary actuator). The high starting torque occurs when lobes of the rotor are only partially overlapping, or aligned with, corresponding stator lobes. Typically, there is a 3° overlap of the rotor lobes and stator lobes at the initial starting position of the rotor.
The maximum torque for the “constant air gap” rotary actuator design occurs between the initial position and an overlap position of about 10°. The torque then steadily drops off for the remainder of the stroke. For a rapid response, a high starting torque is essential to overcome inertia of components of the rotary actuator and diverter gate. However, a rotary actuator of the “constant air gap” design has a relatively low torque at the end of its operating stroke. This relatively low torque is insufficient to prevent rebound of a diverter gate upon impacting of the diverter gate against a rubber bumper.
The “diminishing air gap” rotary actuator design is characterized by a relatively low starting torque due to large initial air gaps between the rotor and stator pole pieces at the beginning of the operating stroke of the rotary actuator. As the rotor rotates, the air gaps decrease and the torque steadily rises toward a high ending torque. Therefore, for a given power level and loading conditions, the rotary actuators having a “constant air gap” design will produce a higher starting torque than the rotary actuators having a “diminishing air gap” design. However, the “diminishing air gap” rotary actuator design will have a higher end of stroke torque. Although the “diminishing air gap” rotary actuator design has potential to have a relatively high ending torque, small variations in the final position of the diminishing air gaps, being in a series magnetic circuit arrangement, can result in a large variation in the end of stroke torque of the “diminishing air gap” rotary actuator design.
In the foregoing discussion of the background of the present invention, the rotary actuators have been considered in association with a diverter for mail or other items that are traveling along a conveyor. It should be understood that rotary actuators have and, in all probability, will be used in many different environments. For example, rotary actuators have previously been utilized to actuate valves which control fluid flow.
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The present invention relates to a cube making and peeling machine for fruits, vegetables and the like, and in particular for tomatoes, which substantially comprises a first conveyor belt including a plurality of interexchangeable longitudinal equispaced parallel cables which, during the advancement motion of the first conveyor belt, will engage a cross top rotary extruder roller and a second bottom conveyor belt comprising a plurality of cross equispaced parallel blades.
The fruit slices, and in particular the preheated tomato slices, are deposited on the first conveyor belt and entrained toward the extruder roller.
As they are pressed between the extruder roller and cables of the first conveyor belt, the slices are downwardly pushed between the interspaces of said cables and are cut in longitudinal strips.
Simultaneously, the top end portions of the cross blades of the second bottom conveyor belt provide an upwardly directed pressure thereby forming on said strips cross cuts to reduce the strips into small cubes.
The skin and/or peel portion of the slices, during the operation, is engaged between the surface of the extruder roller and the cables forming the first conveyor belt, and are held engaged with these elements, to be successively detached and/or unloaded therefrom.
Through the interspaces included between the blades of the second bottom conveyor belt, the tomato and/or the like cubes are conveyed and discharged into a suitable collecting hopper.
The cubes are in a smooth or even condition and free of any skins.
As is known, in the food field and in particular in preparing vegetable products to be packaged in cans or the like, the vegetable products are preferably reduced to small pieces of cubes in order to facilitate all of the subsequent processing steps, in particular the preserving, cooking, mixing steps and so on.
In particular, tomatoes are conventionally processed by the above disclosed method in order to prepare tomato based food products, which find a broad use for preparing a lot of foods.
The qualities and advantages of these products, in addition to the basic vegetable characteristics of the used raw-materials, are evaluated depending on the amount of remaining peels or skins and depending on the maturing level of the used vegetables.
With a small remaining peel amount, and with a good maturing level, the quality of the product is considered very satisfactory.
Prior art methods of "cubing" and/or peeling the above mentioned products, use cubing and/or peeling machines which substantially comprise a square mesh net conveyor belt which is driven and held under tension by end rollers.
On this net there are discharged the products which are then conveyed under a plurality of rollers; the pressure provided by these rollers causes the products to be pushed through the net, thereby cutting the products into cubes having size substantially corresponding to the net mesh size.
Such a method, while it is satisfactory from a cube shape standpoint, is however affected by some limitations and drawbacks.
In particular, in this prior art method, hard parts can be introduced and/or processed together with the slices and portions of fruits or tomatoes to be cubed, these hard elements comprising, for example, not perfectly mature fruits, not perfectly cooked fruits or vegetables or wood pieces and the like.
As undesired hard portions are entrained between the end rollers and the net conveyor belt, the meshes of the latter can be deformed or broken, and these damages represent severe economical losses, since they require a full replacement of the conveyor belt, along stop of the system, and, accordingly, a consequent loss of yield.
Anyhow, the economic damage is a comparatively large one with respect to the single net of the conveyor belt: in fact, because of its configuration, the conveyor belt is very expensive.
Another drawback is that a central discharging of the products to be cubed and the construction of prior art cubing and peeling machines are not satisfactory: in fact, these prior art machines have a comparatively large size and their operation is not reliable.
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1. Field of the Invention
The present invention relates to a low voltage operation method of a plasma display panel and an apparatus thereof, and in particular to a low voltage operation method of a plasma display panel and an apparatus thereof which are capable of reducing a voltage supplied to an address by decreasing wall electric charge inside a cell in address discharge by applying a direct-current biasing voltage.
2. Description of the Prior Art
In a PDP (Plasma Display Panel), inside a discharge cell separated from bulkheads, red/green/blue colors fluorescent materials formed at the bulkheads are excited by ultraviolet rays generated in discharge of inert mixture of gas such as Hexe2x80x94Ne or Nexe2x80x94Xe, a character or a graphic is displayed by visible rays generated when the state of the fluorescent materials is changed from the excitation state to a ground state.
Because the PDP does not require an electron gun such as a cathode ray in order to display an image, it is thinner and lighter than a cathode ray tube and is favorable to high distinct and scale-up.
In addition, because the PDP includes electrodes, a dielectric layer, and discharge gas, etc. and is operated by charge and discharge, it has a function as a capacitor charging electric charge. Accordingly, the PDP consumes lots of energy in charging/discharging, the more the size of PDP increases, the more energy consumption of the PDP increases.
Accordingly, in order to consume energy more efficiently, three electrode AC surface discharge type PDP is used. In the three electrode AC surface discharge type PDP, because wall electric charge is accumulated at a surface, electrodes are prevented from sputtering occurred by discharge, therefore the three electrode AC surface discharge type PDP is favorable to a low voltage operation and having a long life span.
FIG. 1 is a perspective view illustrating a structure of the conventional surface discharge type PDP, and FIG. 2 is a sectional view illustrating a cell of the PDP as shown at FIG. 1. Herein, the conventional surface discharge type PDP includes an upper substrate 10, a scan electrode 20Y and a sustain electrode 20Z formed at the bottom surface of the upper substrate 10, an upper dielectric layer 30 accumulating wall electric charge generated in discharge of the PDP, a protecting layer 30 preventing the upper dielectric layer 30 from sputtering occurred in discharge of the PDP and heightening the discharge effect of secondary electron, a lower substrate 90, an address electrode 80X formed at the upper surface of the lower substrate 90, a lower dielectric layer 70 accumulating electric charge of the address electrodes 80X, a bulkhead 50 formed at the lower dielectric layer 70, and a fluorescent material 60 coated onto the bulkhead 50 and the lower dielectric layer 70.
The scan electrode 20Y and the sustain electrode 20Z respectively include transparent electrodes 22Y, 22Z and metal bus electrodes 21Y, 21Z. The metal bus electrodes 21Y, 21Z have a smaller line width than the transparent electrodes 22Y, 22Z, are formed at the edge of the transparent electrodes 22Y, 22Z and reduce voltage drop due to high resistance of the transparent electrodes 22Y, 22Z.
The upper dielectric layer 30 and the protecting later 40 are laminated onto the upper substrate 10 in which the scan electrode 20Y and the sustain electrode 20Z are formed. The upper dielectric layer 30 accumulates the wall electric charge generated in discharge of the PDP, the protecting layer 40 prevents the upper dielectric layer 30 from sputtering occurred in discharge of the PDP and improves the discharge efficiency of the secondary electron.
The lower dielectric layer 70 and the bulkhead 50 are laminated onto the lower substrate 90, and the fluorescent material 60 is coated onto the surface of the lower dielectric layer 70 and the bulkhead 50.
The address electrodes 80X formed at the lower substrate 90 are placed so as to be crossed with the scan electrode 20Y and the sustain electrode 20Z, and the bulkhead 50 is placed so as to be crossed with the address electrodes 80X in order to prevent ultraviolet and visible rays generated in discharge from leaking into an adjacent discharge cell.
Because the fluorescent material 60 is excited by ultraviolet rays generated in discharge of the PDP, one visible ray of red/green/blue is generated and inert mixture of gas such as Hexe2x80x94Ne or Hexe2x80x94Xe for discharge is injected into a discharge space of the discharge cell formed between the upper/lower substrates 10, 90 and the bulkhead 50.
The above-described three electrode AC surface discharge type PDP operates one frame by dividing it into several sub-fields having different luminous times in order to obtain gray level of a picture.
Each of the sub-fields is divided into a reset period for occurring discharge regularly, an address period for selecting a discharge cell and a sustain period for obtaining a gray level according to the discharge times.
For example, in order to display a picture with 256 gray level, a frame period (16.67 ms) corresponded to {fraction (1/60)} second is divided into eight sub-fields (SF1xcx9cSF8), the eight sub-fields (SF1xcx9cSF8) are divided into a reset period, an address period and a sustain period. The reset period and the address period of each sub-field are same, however the sustain period increases as a rate of 2n (n=0, 1, 2, 3, 4, 5, 6, 7). Because the sustain period is different in each sub-field, the gray level of the picture can be obtained.
In the above-described sub-field, an operation waveform supplied to the three electrode AC surface discharge type PDP will be described with reference to accompanying FIGS. 3A-3C.
FIGS. 3A-3C are waveform diagrams illustrating an operation waveform supplied to the three-way AC surface discharge type PDP in a sub-field according to the conventional art, the PDP operates one sub-field by dividing it into the reset period, the address period and the sustain period.
In the reset period, an ascending ramp waveform (ramp 1) and a descending ramp waveform (ramp 2) are supplied consecutively.
When the ascending ramp waveform (ramp 1) is supplied, weak discharge occurs between the scan electrode 20Y and the sustain electrode 20Z, and wall electric charge is accumulated at the upper dielectric layer 30. When the descending ramp waveform (ramp 2) is supplied, an operational margin of an operation circuit can be obtained sufficiently by removing the wall electric charge inside the cell appropriately.
By supplying the ramp waveform to the scan electrode 20Y for the reset period, a contrast ratio is increased by decreasing visible rays as many as possible for the reset period as a non-display period, and an operation voltage required for the address discharge is lowered by forming the wall electric charge at the whole panel uniformly.
For the address period, an electrode negative data pulse is supplied to the address electrode 80X, and an electrode positive scan pulse is sequentially supplied to the scan electrode 20Y in order to synchronize with the data pulse. The cell supplied the data pulse is address-discharged by being added the voltage corresponded to the voltage difference between the data pulse and the scan pulse and the internal wall voltage accumulated by the wall electric charge inside the cell.
For the sustain period, a sustain pulse is supplied to the scan electrode 20Y and the sustain electrode 20Z by turns, cells selected by the address discharge performs a sustain discharge whenever the sustain pulse is supplied. After all the sustain discharge according to a luminance relative ratio occurs, an erase signal having a chopping wave shape is supplied to the sustain electrode 20Z.
As described above, by discharging the wall electric charge inside the cell for the reset period, the voltage required for the address discharge is lowered.
However, in order to perform the address discharge, because a voltage not less than 60W is required, power for operating the PDP is consumed a lot. And, because parts suitable for the high voltage operation are expensive, a fabrication cost is increased.
In addition, because the number of wall electric charges is decreases in the high voltage, operation efficiency of the PDP is lowered.
It is an object of the present invention to provide a low voltage operation method of a plasma display panel and an apparatus thereof which are capable of lowering a voltage supplied from outside as an optimum level in address discharge by applying a DC biasing voltage to a PDP (Plasma Display Panel).
In order to achieve the above-mentioned object, a low voltage operation method of a plasma display panel in accordance with the present invention includes operating one frame by dividing it into several sub-fields in order to obtain a gray level of a PDP, dividing the sub-field into a reset period, an address period, a sustain period and supplying a ramp waveform in the reset period, and applying a DC biasing voltage in order to reduce wall electric charge discharged in descending of the ramp waveform.
In order to achieve the above-mentioned object, a low voltage operation apparatus of a plasma display panel in accordance with the present invention includes a plasma display panel, a maintenance operation unit being supplied a sustain voltage, a biasing voltage supplying unit supplying a DC biasing voltage, a first switch controlling a voltage applied from the biasing voltage supplying unit, a second switch controlling the operation of a reset voltage, a third switch controlling a voltage supplied from the first switch and the second switch, a fourth switch controlling supply of a scan voltage, and an operation intergrated circuit connected to a scan electrode.
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1. Technical Field
The invention relates to a manufacturing method for a semiconductor device embedded substrate in which a semiconductor device is embedded.
2. Related Art
Hitherto, a wiring substrate (hereinafter referred to as a semiconductor device embedded substrate), in which a semiconductor device is embedded, has been known. For example, the following method (see, e.g., Patent Document 1) has been known as a manufacturing method for a semiconductor device embedded substrate. That is, bumps serving as connection terminals to be electrically connected to a semiconductor integrated circuit which a semiconductor device has are formed in the semiconductor device. Then, the bumps are embedded in a wiring substrate. An insulating layer is applied around the semiconductor device. Subsequently, the bumps are exposed by drilling the insulating layer with a laser. Then, a wiring pattern (rewiring-wire) is formed on the exposed bumps.
In addition, another method (see, e.g., Patent Document 2) has been known, which includes a first step of forming bumps serving as connection terminals to be electrically connected to a semiconductor integrated circuit that a semiconductor device has, a second step of forming an insulating layer on bumps, a third step of drilling the insulating layer with laser to thereby form via-holes that reach the bumps, and a fourth step of forming a via wire, with which each via hole is filled, and a wiring pattern (rewiring-wire) to be connected to the via wire. This method uses the bumps as laser stopper layers when via-holes are formed.
[Patent Document 1] Japanese Patent No. 2842378
[Patent Document 2] JP-A-2005-332887
However, according to the conventional manufacturing methods for a semiconductor device, an insulating layer is formed on a semiconductor device to hide bumps serving as connection terminals which connect a wiring pattern (rewiring-wire) with a semiconductor integrated circuit that the semiconductor device has. Then, the semiconductor device is embedded in the substrate. In addition, the bumps are exposed by drilling the insulating layer with a laser. Thus, the conventional manufacturing methods have problems that it takes time to perform the step of drilling the insulating layer with a laser, and that the manufacturing cost of the semiconductor device embedded substrate is increased.
The conventional manufacturing methods have another problem that because laser beams having a predetermined spot diameter (the diameter is about, e.g., 70 μm) are irradiated, the interval of the bumps serving as connection terminals for electrically connecting the wiring pattern (rewiring-wire) to the semiconductor integrated circuit that the semiconductor device has is reduced only to about 150 μm.
In view of the above respects, the problem that the invention is to resolve is to provide a manufacturing method for a semiconductor device embedded substrate, which can suppress increase of the manufacturing cost thereof and extremely reduce the interval of connection terminals for electrically connecting a wiring pattern (rewiring-wire) to a semiconductor integrated circuit that the semiconductor device has.
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1. Field of the Invention
The invention relates generally to suspended grid ceiling systems which are used in supporting ceiling panels. More specifically, this invention covers an improved connection for assembling such grid systems.
2. Description of the Prior Art
Ceiling grid systems customarily comprise a plurality of parallel main runners and a plurality of parallel cross runners perpendicularly intersecting the main runners. The cross runners normally have locking connectors on each end insertable through openings in the main runners. Many of the early systems used locking connectors on the ends of the cross runners that were relatively easy to disassemble. However, these systems no longer meet many of the building codes. Building codes, to improve safety in seismic areas, have been revised to require ever higher locking tension requirements.
A new family of cross runner lock connections were designed to meet these high strength requirements as disclosed in U.S. Pat. Nos. 3,922,829; 4,108,563; 4,601,153 and 4,317,641. Their general construction entailed cross runners with like connector ends, each having a single detent and aperture. Although these connectors met the increased code requirements, these locks could not be disengaged without major distortion or destruction. This problem of trying to achieve high locking strength together with removability was addressed earlier, i.e., U.S. Pat. Nos. 4,621,474 and 4,648,230. Both of these lock designs have a removable sequence which is initiated by a lateral force. When lateral forces are applied to such cross tees, they can be withdrawn. This is a major flaw since a disengaging lateral force could be applied unintentionally when placing panels or light fixtures or by a seismic disturbance.
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Field
The present invention relates to a photovoltaic blind system.
Description of the Related Art
Photovoltaic power generation may be implemented in various forms because this type of power generation does neither entail noise, nor require special geographical features and a wide site, compared to other types of renewable energy generation. Of these various forms, technology for a building integrated photovoltaic (BIPV) system in which photovoltaic power generation panels are installed on a building has been developed.
A BIPV system may have a structure that is combined with a component of a building, such as a roof, a glass window, or the finishing material of an outer wall, because it utilizes places of a building on which solar light is incident. In particular, a structure that can be easily integrated with a building and allows its direction to be controlled by tracking the incident direction of solar light will be advantageous.
Accordingly, there has been proposed a photovoltaic blind system in which solar battery panels are combined with the slats of a blind system installed in order to block light from the outside to the inside or from the inside to the outside, thereby implementing both of blocking light and generating photovoltaic power.
It is expected that a photovoltaic blind system, constructed upon a large building whose outer walls are generally finished with glasses, can produce a considerable amount of renewable energy.
A photovoltaic blind system requires solar tracking ability for tracking the incident direction of solar light in order to maximize the amount of photovoltaic power generation. Previous studies suggest that a one-axis solar tracking technique capable of changing the angles of photovoltaic panels only in a horizontal direction or a vertical direction can improve performance by about 12 to 25%, and a two-axis solar tracking technique capable of changing the angles of photovoltaic panels in both horizontal and vertical directions can improve performance by about 30 to 45%, compared to a case without solar tracking ability.
Furthermore, although different photovoltaic blind systems could be classified either into one-axis solar tracking technique alike or into two-axis solar tracking technique, the different photovoltaic blind systems may exhibit different improvements in the amount of power generation according to their solar tracking algorithms. Accordingly, there is a need for a more effective solar tracking algorithm.
Solar tracking approaches may be classified into three types: optical sensor-based approach for detecting direction of the sun in the sky using optical sensors to face toward the sun; generated power output-based approach for finding direction in which the output of photovoltaic power generation maximizes so as to control the directions of photovoltaic panels; and location and time-based approach using the direction of the sun predicted based on location and time.
The optical sensor-based approach operates, for example, to determine direction of the sun based on direction of an optical sensor that measures the strongest solar light among optical sensors oriented toward various directions. Accordingly, the approach requires optical sensors and further a means for determining direction of the sun from the detected signals of the optical sensors, and thus higher costs.
However, due to the features of the blind system, orientation toward the sun does not necessarily ensure maximizing output of generated power. For example, if blind slats are adjusted for facing toward the sun when the sun stands at its meridian altitude in midsummer, the blind slats are disposed almost horizontally, only resulting a situation in which the photovoltaic panels are mostly shaded.
Furthermore, generally, the wavelength range in which optical sensors are most sensitive does not coincide with the wavelength range in which actual power production gets large, and thus the identified direction of the sun does not necessarily guarantee the largest power production. Moreover, with bad weather conditions, erroneous operation of optical sensors is inevitable. Accordingly,—effectiveness to cost thereof can be rather poor.
In contrast, the generated power output-based approach is an approach for producing a direction, to which predicted power output maximizes, based on recent power output data. Although this approach is inexpensive because optical sensors are not required and insensitive to weather conditions, this method suffers from being difficult for implementation.
The location and time-based approach is an approach for predicting direction of the sun simply using latitude, longitude, and orientation of installation. Although this location and time-based method is also inexpensive because optical sensors are not required and also insensitive to weather conditions, this method suffers from low accuracy.
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{
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1. Technical Field
Various embodiments of the present invention relate to a data storage device, and more particularly, to a data storage device with a multi-core controller.
2. Related Art
Recently, the paradigm for the computer environment has changed into a ubiquitous computing so that computer systems may be used anytime and anywhere. Thus, the use of portable electronic devices such as mobile phones, digital cameras, and notebook computers has rapidly increased. In general, such portable electronic devices employ a data storage device, which uses a memory device. The data storage device is used to store data to be used in a portable electronic device.
A data storage device using a memory device provides advantages in that, since there is no mechanical driving part, stability and durability are excellent, an information access speed is high and power consumption is small. Data storage devices having such advantages may include a universal serial bus (USB) memory device, a memory card having various interfaces, and a solid-state drive (SSD).
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Semiconductor device geometries have dramatically decreased in size since integrated circuits were first introduced several decades ago, and all indications are that this trend will continue on. Today's wafer fabrication plants are routinely producing devices having 0.25 μm and even 0.18 μm feature sizes, and the plants of the future will soon be producing devices having even smaller geometries.
As device sizes become smaller and integration density increases, one issue that has become an increasing concern to semiconductor manufacturers is that of inter-level “crosstalk.” Crosstalk is the undesired coupling of an electrical signal on one metal layer onto another metal layer, and arises when two or more layers of metal with intervening insulating or dielectric layers are formed on a substrate. Crosstalk can be reduced by moving the metal layers further apart, minimizing the areas of overlapping metal between metal layers, reducing the dielectric constant of the material between metal layers and combinations of these and other methods. Undesired coupling of electrical signals can also occur between adjacent conductive traces, or lines, within a conductive layer. As device geometries shrink, the conductive lines become closer together and it becomes more important to isolate them from each other.
Another issue that is becoming more of a concern with decreasing feature sizes is the “RC time constant ” of a particular trace. Each trace has a resistance, R, that is a product of its cross section and bulk resistivity, among other factors, and a capacitance, C, that is a product of the surface area of the trace and the dielectric constant of the material or the space surrounding the trace, among other factors. If a voltage is applied to one end of the conductive trace, charge does not immediately build up on the trace because of the RC time constant. Similarly, if a voltage is removed from a trace, the trace does not immediately drain to zero. Thus high RC time constants can slow down the operation of a circuit. Unfortunately, shrinking circuit geometries produce narrower traces, which results in higher resistivity. Therefore it is important to reduce the capacitance of the trace, such as by reducing the dielectric constant of the surrounding material between traces, to maintain or reduce the RC time constant.
Hence, in order to further reduce the size of devices on integrated circuits, it has become necessary to use insulators having a low dielectric constant. And as mentioned above, low dielectric constant films are particularly desirable for premetal dielectric (PMD) layers and intermetal dielectric (IMD) layers to reduce the RC time delay of the interconnect metallization, to prevent crosstalk between the different levels of metallization, and to reduce device power consumption.
The traditional insulator used in the fabrication of semiconductor devices has been undoped silicon oxide. Undoped silicon oxide films deposited using conventional CVD techniques may have a dielectric constant (k) as low as approximately 4.0 or 4.2. Many approaches have been proposed for obtaining insulating layers having a lower dielectric constant. Amongst these have been fluorine-doped silicon oxide films that may have a dielectric constant as low as 3.4 or 3.6. Another approach has been the development of carbon-doped silicon oxide (CDO) films. In some cases, CDO films are treated with e-beam radiation during and/or after growth in order to improve the film properties.
The use of electron beam (e-beam) radiation to treat materials is well known. For example, e-beams have been used for curing interlayer dielectrics for microelectronic devices, photoresist exposure, altering solubility characteristics of thin film layers, and the like. Often, the electron sources utilized in the past to generate e-beams for such electron beam treatments have been electron guns, which produce e-beams of narrow cross-section. For some applications, it is desirable to provide a large-area e-beam source which is controllable, uniform, insensitive to poor vacuum, and long lived. Thus, large area e-beam sources have been developed, some of which are suitable for use in semiconductor processing applications. An example of such a large-area e-beam source is described in U.S. Pat. No. 5,003,178, incorporated herein by reference in its entirety for all purposes.
When such a large area e-beam is used during a semiconductor fabrication process, charge buildup can occur in the materials present on the semiconductor substrate. For example, charge may buildup in dielectric layers deposited on the semiconductor substrate. Excessive charge buildup may result in unwanted electrical effects, including electrical breakdown across fragile structures such as MOS gate oxides, resulting in possible damage to the semiconductor devices.
Therefore, there is a need in the art for methods and structures which reduce the buildup of charge during electron beam treatment of semiconductor substrates.
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{
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1. Field of the Invention
The present invention relates generally to data processing, and more particularly to a computer implemented method, system, and computer usable program code for post-register allocation selective instruction scheduling.
2. Description of the Related Art
The processing speed of processors has increased at a dramatic rate over the last few years. With this increase in processing speed, there is a demand for more effective computer systems. The need for faster and more sophisticated compilers and compiling frameworks is essential to enable overall performance gains. A compiler translates code written in higher level programming languages into code executable by the computer system. Many modern compilers are dynamic compilers or Just-in-Time (JIT) compilers. A dynamic compiler translates a whole segment of code into a native code that is executable by a processor in the computer system. Machine code is an example of native code. Because dynamic compilers compile code at runtime, a program that takes a long time to compile reduces overall performance of a computer system. In addition, the program appears to execute slower to the end-user creating user dissatisfaction with the computing system and program.
Various techniques are used to reduce the performance effects of dynamic compiling. For example, instruction scheduling is a compiler or run-time technique that rearranges the execution order and functional resource allocation of the instructions compiled from a computer program so the instructions execute in the fastest and most efficient order possible. While the rearranged stream of instructions is semantically equivalent to the original stream, the instruction scheduler arranges and overlaps the execution of instructions so as to reduce overall execution time.
Unfortunately, even simple instruction scheduling requires significant compilation time as well as increasing memory and execution overhead. More complex models for instruction scheduling may further sacrifice compilation time to attain better performance in the compiled code.
Instruction scheduling may also cause conflicts with register allocation. Register allocation involves assigning variables to a limited number of hardware registers during program execution because variables in registers may be accessed more quickly than unassigned variables. Because there are far more variables than registers, multiple variables assigned to the same register may have conflicts. The goal of register allocation is to assign variables that do not conflict so as to minimize the use of non-register memory.
For example, if instruction scheduling occurs before register allocation, the rescheduled code tends to increase register motion including register spills and spill instructions which may break instruction groupings and introduce pipeline stalls and other compilation delays. Register spills occur when there are insufficient registers available for all of the variables that need to be stored and memory instead of registers must be used.
If register allocation precedes instruction scheduling, the assignment of a limited number of real registers to an indefinite number of virtual registers may create false constraints on dependencies between instructions. These dependencies may limit instructions from being moved or organized effectively, especially in systems with relatively small register sets. As a result, effective instruction scheduling has been limited because of problems balancing register allocation and performance limitations.
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It is desired that reference current of analog circuitry is generated without causing variation in its current value. However, in a conventional reference current generating circuitry, the current value of the reference current depends on the element values (e.g., resistance value, capacitance value, etc.) of passive elements. On-chip analog circuitry has a problem that the current value of the reference current varies depending on manufacturing variability of the passive elements, which are difficult to manufacture with high accuracy. Further, using off-chip passive elements, which can be manufactured with high accuracy, leads to a problem that the cost of the analog circuitry increases.
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1. Field of the Invention
The present invention relates to semiconductor devices and, in particular, to a semiconductor device containing a high-speed non-volatile memory which stores information in memory cells using phase change resistors.
2. Description of the Related Art
Aimed at a high-speed and highly integrated non-volatile memory, the development of phase change memories is now in progress as described in “2002 IEEE International Solid-State Circuits Conference, Digest of Technical Papers, pp. 202–203”. In the phase change memory, information is stored by utilizing a phase change material called a chalcogenide material which changes its resistivity depending on the state. Write operations to a phase change resistor are done by supplying a current thereto so that the resistor is heated to change the state. Lowering the resistivity, called a set operation, is done by keeping the resistor at relatively low temperature for enough long time, whereas raising the resistivity, called a reset operation, is done by heating it to relatively high temperature. In addition, a read operation from the phase change material is done by applying such a magnitude of current as not to change the state of the phase change resistor.
In “2002 IEEE International Electron Device Meetings, Technical Digest, pp. 923–926”, characteristics of phase change resistors are described. In “2003 Non-Volatile Semiconductor Memory Workshop, Digest of Technical Papers, pp. 91–92), a memory cell composed of a phase change resistor and a NMOS transistor is described.
These documents discuss the potentialities of the phase change memory not only as high-speed ROM (Read-Only Memory) but also as non-volatile RAM (Random Access Memory) which can be the unified memory having both ROM and RAM functions. FeRAM (Ferroelectric RAM) and MRAM (Magnetic RAM) are also under development as other high-speed non-volatile memories. However, it is difficult to reduce the area of the ferroelectric capacitor in FeRAM and therefore the area of the cell. MRAM has also a drawback that high-speed read is difficult since the magnitude of the readout signal is small due to the small change ratio of the magnetoresistance. On the other hand, the phase change memory allows easy scaling since reducing the electrode area of the phase change resistor decreases the power required to change the phase of the phase change resistor. In addition, since the resistance of the phase change resistor changes widely as compared with the magnetoresistance in MRAM, high-speed read operation can be realized. Due to these reasons, phase change resistor-used high speed non-volatile memory is expected to be implemented.
To use the phase change memory as a RAM, write time matters. To lower the resistivity of a phase change resistor, it is necessary to let current flow through the phase for an enough long period, for example, about 20 ns. In addition, after the resistivity is raised, it is necessary to wait for enough time, for example 20 ns, before a read operation is done from that memory cell so that the state of the phase change resistor settles.
To introduce a phase change memory as a non-volatile RAM chip, it is preferable to make the phase change memory compatible in specification with a low power RAM chip so as to minimize the system change. Recently, low power SRAM (Static RAM) chips are widely used as low power RAM chips. Merely replacing the internal memory array of a SRAM chip by a phase change memory array cannot conform to the operational specifications expected for ordinary SRAM chips. After the resistivity-lowering write operation is done, a sufficient amount of write time is required to access the same memory cell. After the resistivity-raising write operation is done, a large amount of time is also required to settle the state of the phase change resistor before the subsequent read access is done to the same memory cell. That is, it is difficult to raise the access speed to the level of low power SRAM chips.
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Although cellular phones are used primarily for making and receiving telephone calls, additional functionalities are being included in the cellular phones to allow users, for example, to take digital pictures, to listen to songs, to watch videos and/or to play games. These functionalities place a heavy demand on the cellular phone battery, which reduces the charged life of the battery. In a cellular phone, one of the most power-draining components is the power amplifier that transmits signals to the nearest cellular station. Therefore, the power-added efficiency (PAE) of a power amplifier, which is a measure of how much power is needed to achieve a given amount of amplification, is an important factor for the battery life of a cellular phone. With a higher PAE of the power amplifier, the amount of time that a user can talk on the cellular phone and/or operate other functionalities of the cellular phone can be increased.
In a power amplifier of a cellular phone, an impedance transformation network is used to reduce the impedance of the load (often 50 Ohms) to a more optimal output impedance for the amplifier so that the signal from the amplifier can properly be generated for the load. Although there are various impedance transformation networks, a conventional impedance transformation network of interest is an impedance transformation network that utilizes a set of stacked shunt ferroelectric varactors as a variable capacitor. Such an impedance transformation network is used in a power amplifier for cellular technologies that use variable transmission signal strength, such as Code Division Multiple Access (CDMA) technology, to achieve greater PAE for power levels other than the maximum power level. In contrast to semiconductor varactors, ferroelectric varactors have a higher Q factor, which makes these devices attractive for power amplifier applications.
However, the stacked shunt ferroelectric varactors of the conventional impedance transformation network are quite non-linear, and thus, the impedance transformation network requires a significant number of stacked shunt ferroelectric varactors to achieve an acceptable linearity. Unfortunately, as the number of stacked shunt ferroelectric varactors is increased, the series resistance is also increased, which degrades the total PAE of the power amplifier. Furthermore, the stacked shunt ferroelectric varactors must provide high capacitance for high power output levels, which means that the varactors must be operated at near zero DC voltage where the varactors are more non-linear. This necessitates additional stacked shunt ferroelectric varactors to achieve the desired linearity, resulting in greater series resistance.
In view of these concerns, what is needed is an impedance transformation network, power amplifier and method for efficiently transmitting an output signal in a power efficient manner.
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1. Field of the Invention
The present invention relates to a damper used in the power transmission route of automobiles or the like, and more particularly to a structure suited to a damper located between a stepless speed change gear and an engine flywheel, in a power transmission route having a belt type stepless speed change gear.
2. Description of the Prior Art
In the damper disc located before the stepless speed change gear as mentioned above, it is required that the relative torsional stiffness of the input part and output part of the damper be low in the driving direction (rotating direction), and in other words it is required that the input part be twisted largely with respect to the output part at a relatively small torque. In such a disk, moreover, it is needed to maintain such low torsional stiffness until the torsional torque increases to a relatively large value (that is, in a wide torsional angle range).
To achieve such high torsional angle and low torsional stiffness, conventionally, in some of the discs, plural compression coil springs were arranged in series as the spring mechanism to be incorporated therein. However, in such structure using series type springs, the position or posture of the springs may be unstable due to effects of centrifugal force, and the spring contacts with its adjacent member, and due to effects of such contact friction, the torsional characteristic becomes unstable as the entire disc.
To solve such problems, for example, as disclosed in the Japanese Laid-open Patent 61-223349, an intermediate member is placed between the output member and the input member, and the spring is maintained in a stable state by this intermediate member.
In this published structure, however, a total of four intermediate members in two different kinds are used, and the number of parts is increased, and the structure becomes complicated. That is, in this disclosed structure, in the torsional action in the normal direction, the input member is engaged with a pair of first intermediate members to move in the same direction, and in the torsional action in the reverse direction, the input member is engaged with the other (second) pair of intermediate members to move in the same direction. Thus, in this structure, one pair of intermediate members to be engaged with the input member in the normal direction, and another pair of intermediate members to be engaged with the input member in the reverse direction are needed, and the structure is complicated.
It is hence a primary object of the invention to present a structure capable of solving the above problems.
More specifically, in the damper disc disposed before the stepless speed change gear, a low torsional stiffness is required in a wide torsional angle range particularly in the driving direction, and the invention is intended to present a damper disc in a simple structure by making use of this characteristic.
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Awnings are often used to protect a user from various natural conditions, such as the sun or rain. Awnings can be used with vehicles, such as, for example, recreational vehicles, boats, or the like, and can even be used with structures, such as a building, or the like. Awnings can be adapted to move between an extended position and a stowed position. For example, the awning fabric can be adapted to roll about a roll tube between the extended and stowed positions. However, unless an extended edge of the awning fabric is substantially parallel to the central axis of the roll tube, one portion of the awning fabric may roll up differently than another portion. Thus, there is a need for an adjustment device for an awning that can overcome this problem.
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1. Field of the Invention
The invention relates to a scrubber apparatus. More particularly, the invention relates to a scrubber apparatus for gas abatement.
2. Description of the Related Art
Semiconductor manufacturing processes generate substantial waste gases that need to be abated before discharging in atmosphere. Conventionally, waste gases produced during semiconductor manufacturing processes, such as fluorocarbon or PFC, are processed in a scrubber installed after exhausting pumps. Fluorocarbon is taken as exemplary waste gas in the following description since it is substantially used in semiconductor processes.
With reference to FIG. 1, a schematic view describes a conventional scrubber apparatus. In FIG. 1, waste gases comprising fluorocarbon gases are to be treated by the scrubber apparatus 10. Fluorocarbon gases are delivered through waste gas inlets 12. To decompose fluorocarbon gases, high temperature condition is necessary. Accordingly, combustion with natural gas, such as propane, associated with oxygen, both delivered through respectively incineration gas inlet 16 and oxygen gas inlet 14, is generated inside a divergent cone 18. The gas with byproducts produced during the combustion flows out of the divergent cone 18 through openings 20 into the chamber 22. Cooling means 24, comprising a cooling circuit 26, cools down the gases that are treated in the scrubber 10. The cooling means 24, besides cooling down byproducts generated by the combustion, also enhances the removal of hazardous acid gases such as described hereafter. The byproducts produced during the combustion are processed according to two ways. Hazardous acids are neutralized through a scrubbing liquid 28, which can be typically an alkaline solution. The rest of gases pass up through a scrubber 30, are cooled by the cooling means 24, and pass through a mist eliminator 32 to be finally discharged into atmosphere.
Issues related to the conventional scrubber, such as described above, principally lie in an occurrence of incomplete combustion. Incomplete combustion happens when the scrubber functions in a deficiency mode or when abnormal events occur during the combustion, the deficiency mode can be defined as a non-optimal functioning of the scrubber, which results in a combustion that does not provide sufficient heat to decompose adequately the waste gases. Consequently, secondary pollution may be generated because the scrubber apparatus 10 does not process the byproducts that are produced by the incomplete combustion. Untreated hazardous gases may be thus released into atmosphere and cause environment pollution.
Another drawback of the conventional scrubber apparatus 10 is that a substantial amount of energy must be provided to decompose the fluorocarbon gas constituents. As a result, thermal waste is unfavorably generated during the combustion that, consequently, also necessitates a lot of coolant and refrigeration power to cool down the gases and byproducts issued from the combustion. In other words, the conventional scrubber excessively consumes energy. A solution is thus needed to improve the conventional scrubber and overcome at least the issues and drawbacks described above.
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The disclosure relates to thermal barrier coatings (TBCs). More particularly, the disclosure relates to TBCs applied to superalloy gas turbine engine components.
The application of TBCs, such as yttria-stabilized zirconia (YSZ) to external surfaces of air-cooled components, such as air-cooled turbine and combustor components is a well developed field. U.S. Pat. No. 4,405,659 to Strangman describes one such application. In Strangman, a thin, uniform metallic bonding layer, e.g., between about 1-10 mils, is provided onto the exterior surface of a metal component, such as a turbine blade fabricated from a superalloy. The bonding layer may be a MCrAlY alloy (where M identifies one or more of Fe, Ni, and Co), intermetallic aluminide, or other suitable material. A relatively thinner layer of alumina, on the order of about 0.01-0.1 mil (0.25-2.5 μm), is formed by oxidation on the bonding layer. Alternatively, the alumina layer may be formed directly on the alloy without utilizing a bond coat. The TBC is then applied to the alumina layer by vapor deposition or other suitable process in the form of individual columnar segments, each of which is firmly bonded to the alumina layer of the component, but not to one another. The underlying metal and the ceramic TBC typically have different coefficients of thermal expansion. Accordingly, the gaps between the columnar segments enable thermal expansion of the underlying metal without damaging the TBC.
U.S. Pat. No. 6,060,177 to Bornstein et al. (the disclosure of which is incorporated by reference herein as if set forth at length) describes use of an overcoat of chromia and alumina atop a yttria-stabilized zirconia (YSZ) TBC. Such an overcoat may protect against sulfidation attack and oxidation and may significantly extend the operational life of the component.
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Audio microphones are commonly used in a variety of consumer applications such as cellular telephones, digital audio recorders, personal computers and teleconferencing systems. In particular, lower-cost electret condenser microphones (ECM) are used in mass produced cost sensitive applications. An ECM microphone typically includes a film of electret material that is mounted in a small package having a sound port and electrical output terminals. The electret material is adhered to a diaphragm or makes up the diaphragm itself. Most ECM microphones also include a preamplifier that can be interfaced to an audio front-end amplifier within a target application such as a cell phone. Another type of microphone is a microelectro-mechanical Systems (MEMS) microphone, which can be implemented as a pressure sensitive diaphragm is etched directly onto an integrated circuit.
Environmental sound pressure levels span a very large dynamic range. For example, the threshold of human hearing is at about 0 dBSPL, conversational speech is at about 60 dBSPL, while the sound of a jet aircraft 50 m away is about 140 dBSPL. While the diaphragm of a microphone, such as a MEMS microphone, may be able to withstand high intensity acoustic signals and faithfully convert these high intensity acoustic signals into an electronic signal, dealing with such high-level signals poses some difficulties. For example, many amplifiers and preamplifiers for acoustic microphones are optimized for a particular dynamic range. As such, these systems may not be able to handle the full audio range without adding significant distortion.
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Rituximab is a chimeric monoclonal antibody that specifically recognizes a CD20 antigen specifically expressed in B-cell lymphocytes (Non-patent Documents 1 and 2). A CD20 antigen is widely expressed on B-cell malignant tumors, typically including such as follicular malignant lymphoma that develops relatively slow and diffuse malignant lymphoma that develops aggressively. Rituximab has been administered as a molecular targeting drug against a CD20 antigen in addition to chemotherapy for these B-cell malignancies expressing the CD20 antigen (Non-patent document 3 to 8). Although the CHOP chemotherapy has been utilized for B-cell lymphoma patients for more than 25 years, unfortunately, the cure rate of diseases has not been improved, even with a combination with other chemotherapies or change of a dosage. However, in recent reports, it has been confirmed that the cure and disease-free survival rates of the diseases are improved significantly by using rituximab for CD20 positive B-cell malignant lymphoma in combination with conventional chemotherapies based on CHOP (Non-patent Documents 3 to 8).
Although 5 years have passed since rituximab was started to be clinically used, the cure rate for CD20 positive malignant lymphomas is still unsatisfactory, and the considerable number of patients treated with rituximab have undergone the progression and transformation of a tumor that is unreative to rituximab (Non-patent Document 9 to 12). Recently, Terui et al reported that 5 out of 48 CD20 positive lymphoma patients showed rituximab resistance and genetic mutations in the CD20-coding sequence region in 10 out of 48 patients were confirmed (Non-patent document 10). A conformational change in the CD20 protein caused by genetic mutations has been speculated to contribute to one of mechanisms of rituximab resistance. However, the relationship between genetic mutations in the CD20-coding sequence region and rituximab resistance is not clearly indicated, which also suggested existence of mechanisms of rituximab resistance other than genetic mutations.
Recently, we had a patient of CD20 positive malignant B-cell lymphoma (diagnosis in onset) transformed to a tumor having a feature of rituximab resistance after repeated administration of rituximab. Disease progression of this patient worsened during the rituximab administration and CD20 expression in lymphoma cells was not observed in pathological findings and studies by flow cytometry (FCM) at the point. Non-patent Document 1: Cheson B D. Monoclocal antibody therapy for B-cell malignancies. Semin Oncol. April 2006; 33(2 Suppl 5): S2-14. Non-patent Document 2: Imai K, Takaoka A. Comparing antibody and small-molecule therapies for dancer. Nat Rev Cancer. September 2006; 6(9): 714-727. Non-patent Document 3: Coiffier B, Lepage E, Briere J, et al. CHOP chemotherapy plus rituximab compared with CHOP alone in elderly patients with diffuse large-B-cell lymphoma. N Engl J Med. Jan. 24, 2003; 346(4): 235-242. Non-patent Document 4: van Oers M H, Klasa R, Marcus R E, et al. Rituximab maintenance improves clinical outcome of relapsed/resistant follicular non-Hodgkin's lymphoma, both in patients with and without rituximab during induction: results of a prospective randomized phase III intergroup trial. Blood. Jul. 27, 2006. Non-patent Document 5: Habermann T M, Weller E A, Morrison V A, et al. Rotuximab-CHOP versus CHOP alone or with maintenance rituximab in order patients with diffuse large B-cell lymphoma. J Clin Oncol. Jul. 1, 2006; 24(19): 3121-3127. Non-patent Document 6: Pfreundschuh M, Trumper L, Osterborg A, et al. CHOP-like chemotherapy plus rituximab versus CHOP-like chemotherapy alone in young patients with good-prognosis diffuse large-B-cell lymphoma: a randomised controlled trial by the MabThera International Trial (MInT) Group. Lancet Oncol. May 2006; 7(5): 379-391. Non-patent Document 7: Hiddemann W, Kneba M, Dreyling M, et al. Frontline therapy with rituximab added to the combination of cyclophosphamide, doxorubicin, vincristine, and prednisone (CHOP) significantly improves the outcome for patients with advanced-stage follicular lymphoma compared with therapy with CHOP alone: results of a prospective randomized study of the German Low-Grade Lymphoma Study Group. Blood. Dec. 1, 2005; 106(12): 3725-3732. Non-patent Document 8: Czuczman M S, Weaver R, Alkuzweny B, Berlfein J, Grillo-Lopez A J. Prolonged clinical and molecular remission in patients with low-grade or follicular non-Hodgkin's lymphoma treated with rituximab plus CHOP chemotherapy: 9-year follow-up. J Clin Oncol. Dec. 1, 2004; 22(23): 4711-4716. Non-patent Document 9: Alvaro-Naranjo T, Jean-Martinez J, Guma-Padro J, Bosch-Princep R, Salvado-Usach M T. CD20-negative DLBCL transformation after rituximab treatment in follicular lymphoma: a new case report and review of the literature. Ann Hematol. September 2003; 2003; 82(9): 585-588. Non-patent Document 10: Yasuhito Terui T S, Yuji Mishima, Yuko Mishima, Natsuhiko Sugimura, Kiyotsugu Kojima, Masahiro Yokoyama, Kiyohiko Hatake. Identification of CD20 Mutations in Malignant Lymphoma: Can They Be Predictors of Response to Rituximab? Paper presented at: 47th American Society Of Hematology Annual Meeting; Dec. 12, 2005, 2005; Atlanta. Non-patent Document 11: Davis T A, Czerwinski D K, Levy R. Therapy of B-cell lymphoma with anti-CD20 antibodies can result in the loss of CD20 antigen expression. Clin Cancer Res. March 1999; 5(3): 611-615. Non-patent Document 12: Kinoshita T, Nagai H, Murate T, Saito H. CD20-negative relapse in B-cell lymphoma after treatment with Rituximab. J Clin Oncol. December 1998; 16(12): 3916. Non-patent Document 13: Crescenzi M, Seto M, Herzig G P, Weiss PD, Griffith R C, Korsmeyer S J. Thermostable DNA polymerase chain amplification of t(14;18) chromosome breakpoints and detection of minimal residual disease. Proc Natl Acad Sci USA. July 1988; 85(13): 4869-4873. Non-patent Document 14: Gribben J G, Freedman A, Woo S D, et al. All advanced stage non-Hodgkin's lymphomas with a polymerase chain reaction amplifiable breakpoint of bcl-2 have residual cells containing the bcl-2 rearrangement at evaluation and after treatment. Blood. Dec. 15, 1991; 78(12): 3275-3280. Non-patent Document 15: Maloney D G, Grillo-Lopez A J, White C A, et al. IDEC-C2B8(Rituximab) anti-CD20 monoclonal antibody therapy in patients with relapsed low-grade non-Hodgikin's lymphoma. Blood. Sep. 15, 1997; 90(6): 2188-2195. Non-patent Document 16: Maloney D G, Grillo-Lopez Aj, Bodkin D J, et al. IDEC-C2B8: results of a phase I multiple-dose trial in patients with relapsed non-Hodgkin's lymphoma. J Clin Oncol. October 1997; 15(10): 3266-3274. Non-patent Document 17: Egger G, Liang G, Aparicio A, Jones P A. Epigenetics in human disease and prospects for epigenetic therapy. Nature. May 27 2004; 429(6990): 457-463. Non-patent Document 18: Binder M, Otto F, Mertelsmann R, Veelken H, Trepel M. The epitope recognized by rituximab. Blood. May 16, 2006. Non-patent Document 19: Kiyoi H, Naoe T. Immunoglobulin variable region structure and B-cell malignancies. Int J Hematol. January 2001; 73(1): 47-53.
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The present invention relates to a printing apparatus for printing images based on image data.
Recently, so-called xe2x80x9cstand-alone printersxe2x80x9d capable of producing photographic images by itself without being connected to personal computer (personal computer will be referred to as xe2x80x9cPCxe2x80x9d hereinafter) have become commonplace. The stand-alone printers are constituted by reading apparatus and operation panels. The reading apparatus is employed so as to read auxiliary media adapted to communicate with such information processing systems as memory cards on which photographic image data are recorded. The operation panels are employed in order to set such printing conditions as print paper sizes for these photographic image data.
Since such stand-alone printers can print out without being connected to PC, users who have no such PC can print out photographic images on printing media, while these photographic images are photographed by digital cameras.
In accordance with general-purpose file systems for digital cameras, character data such as photographing data/time are stored as attribute information of image data into storage media. Such character data may be read out from the recording media in combination with the image data when the printing operation is carried out, and then, can be printed out in combination with these image data. For instance, in the case that image data are outputted in an album form, and in such a case that an index of images which are recorded on a recording medium is formed, such character data as photographing date/time which are printed out in combination with the images may constitute useful information for users.
However, image data, acquired in a file formed by executing an image edit application program is data acquired by a PC when the file is formed. Accordingly, the image data to be printed out cannot be acquired by the stand-alone printer when a printing operation is carried out without specifying the image data to be printed out when the file is formed. In other words, in accordance with the related image edit application program unless the image data to be printed out is specified, an output condition in a printing apparatus cannot be determined with respect to such unspecified image data. Namely, a printing position, either an enlarging ratio or a reduction ratio, or a filtering process operation cannot be designated with respect to image data acquired without specifying the image data to be printed out in the stand-alone printer. Unless the image data to be printed out is specified, the stand-alone printer cannot determine as to whether or not attribute information such as photographing date/time is printed out when the image data is outputted.
In a related printing apparatus, in a printing subject file in which an output condition such as a layout is determined with respect to image data, such image data to be printed out cannot be designated on the side of this related printing apparatus, or cannot be changed on the side of the related printing apparatus.
Generally, when a stand-alone printer has such a function capable of causing an operator to select as to whether or not character data such as photographing date/time is printed out, there is such a problem that an operation panel of this stand-alone printer owns a complex construction.
An object of the present invention is to provide a printing apparatus and a printing method, capable of previously setting an output condition such as a layout of image data designated when a printing operation is carried out before the printing operation is performed.
Another object of the present invention is to provide a printing apparatus and a printing method, capable of designating, or changing image data to be printed out in a printing subject file in which an output condition such as a layout is determined with respect to image data.
Another object of the present invention is to provide a printing apparatus and a printing method, capable of previously setting an output condition of character data belonging to image data which is designated during a printing operation, before image data to be outputted is designated.
Another object of the present invention is to provide a printing apparatus and a printing method, capable of designating, or changing image data to be printed out in a printing subject file in which an output condition of character data belonging to image data is determined.
In the beginning, implication of terminology used in this specification will now be explained.
A term xe2x80x9coutput subject identifierxe2x80x9d is a data for linking both image data acquired by a printing apparatus and such data used to define character data to an output setting value.
A term xe2x80x9cimage output setting valuexe2x80x9d is a value for determining a content of a process operation executed by the printing apparatus with respect to image data every such image data to be outputted. This process operation includes a process operation for determining a position of an image on a printing medium, a dimension of this image, and a shape of this image which is printed on the printing medium; a trimming process operation; a filtering process operation; a rotating process operation, and the like.
A term xe2x80x9cdrawing data regionxe2x80x9d is a region which is secured in an address space of the printing apparatus, for instance, a region of such an address space in which a data set of a list and a table, which are constituted by drawing data, is arranged.
A term xe2x80x9cwork areaxe2x80x9d is a region secured in an address space of the printing apparatus, namely such a region which temporarily stores data processed by executing a predetermined process by a processing apparatus.
A term xe2x80x9cprinting image dataxe2x80x9d is data which is produced by the processing apparatus based upon image data, namely the printing apparatus directly refers to data when the printing apparatus is mechanically operated so as to print out an image.
A term xe2x80x9cimage retrieve regionxe2x80x9d is a region which is secured in an address space of the printing apparatus, for instance, a region of such an address space in which a data set of a table, which are constituted by image data and an output subject identifier, is arranged.
A term xe2x80x9creference printing framexe2x80x9d is a frame which constitutes a reference used to determine as an output condition, a shape of an image printed out based on image data, a dimension of the image, and a position of the image on a printing medium. The reference printing frame may be made of any sorts of frames from which images are not projected on a printing medium. This reference printing frame need not owns the following condition. That is, a region on a printing medium, which is surrounded by this reference printing frame, is not completely made coincident with another region where a printed image occupies on the printing medium.
A term xe2x80x9ctrimming process operationxe2x80x9d corresponds to such a process operation capable of obtaining an image having a specific shape by deleting pixels which are distributed in a peripheral region of an image.
A term xe2x80x9cfiltering process operationxe2x80x9d corresponds to such an image processing operation as a density conversion, a sharpening process, and a smoothening process, which are executed with respect to image data.
A term xe2x80x9ccharacter output setting valuexe2x80x9d corresponds to such a value used to determine a sort of information which constitutes a printing subject contained in character data, or a value used to determine a font, a font size, a printing position of character data. For instance, the character output setting value corresponds to a value used to determine the following item based upon such character data indicative of a photographing year, a photographing month, photographing time, a shutter speed, an exposure value, which are recorded by a file system designed by a predetermined specification: xe2x80x9ca field value indicative of a shutter speed is read, and the field value is printed on a lower right portion of paper by the courier new font of 12 points.xe2x80x9d
A first printing apparatus of the present invention is provided with a drawing data storage unit, an input unit, an image data acquiring unit, an image processing unit, and a printing unit, which will be explained in the below-mentioned items (1) to (5):
(1) The drawing data storage unit acquires both an output setting value and an output subject identifier linked to the output setting value via an input interface, and produces drawing data containing both the output setting value and the output subject identifier to be stored in a drawing data region. The drawing data storage unit is constituted by a processing apparatus for executing a predetermined process.
Both the output setting value and the output subject identifier are acquired from, for example, an auxiliary recording apparatus connected to an input interface, and a computer connected via a communication cable to the input interface.
(2) The input unit inputs an identifier of image data which is recorded on an auxiliary recording medium and is mutually communicable between information processing systems in relation to the output subject identifier stored in the drawing data region. The input unit is constituted by, for example, a processing apparatus for executing a predetermined process, and an input apparatus such as a selection value inputting apparatus. For instance, the processing apparatus supplies identifiers of all of image data which are recorded on the auxiliary recording medium, and the selection value inputting apparatus causes a user to selectively input any one of the received identifiers, and then supplies the inputted identifier to the processing apparatus. Then, the processing apparatus defines the received identifier in relation to the output subject identifier.
(3) The image data acquiring unit acquires the drawing data from the drawing data region, in which image data which is specified while the identifier of the image data related to the output subject identifier is used as a retrieve key is transferred from the auxiliary recording medium via the input interface to a work area. The image data acquiring unit is arranged by, for instance, a reading apparatus of an auxiliary recording medium, and a processing apparatus for executing a predetermined process operation.
(4) The image processing unit produces printing image data from the image data of the work area by employing the output setting value of the drawing data derived from the drawing data region. The image processing unit is arranged by a processing apparatus for executing a predetermined process operation. The output setting value is applied to such a parameter to which the processing apparatus refers in the case that an image produced based upon image data is converted into another image which is expressed in a coordinate system allocated to a printing medium. For instance, the output setting value is applied to such a parameter to which the processing apparatus refers while this processing apparatus calculates the determine that a certain pixel is arranged at which position on a printing medium.
(5) The printing unit prints out an image on the printing medium based upon the printing image data. The printing unit is constituted by, for example, a printer engine equipped a paper transport mechanism, an ink jetting head, a head drive mechanism, a control board, and so on.
In accordance with the printing apparatus of the present invention, since the printing subject file in which the output condition such as the layout is determined is executed, the drawing data is produced from both the output setting value and the output subject identifier, which are contained by the printing subject file. As a result, the output condition such as the layout of the image data, which is designated during the printing operation, can be previously set before the printing operation is carried out. Also, since the image data stored in the auxiliary recording medium are defined in relation to the output subject identifiers, the image data to be printed out can be designated. Since the relationship between the output subject identifiers and the image data stored in the auxiliary recording medium are changed, the image data to be printed out can be changed in the printing subject file.
In accordance with the printing apparatus of the present invention, in the case that an output subject identifier which has not yet been stored in the drawing data region is newly acquired via the input interface, the data storage unit defines the output subject identifier not yet stored in the drawing data region in related to an identifier of predetermined image data, and stores the related output subject identifier into an image retrieve region. The input unit defines an identifier of image data recorded on the auxiliary recording medium in relation to the output identifier by rewriting the identifier of the image data stored in the image retrieve region.
In accordance with the printing apparatus of the present invention, the identifiers of the image data are defined in relation to the output subject identifiers by the image retrieve region. As a consequence, according to the printing apparatus of the present invention, since the image data related thereto by the image retrieve region can be acquired from the auxiliary recording medium, the repeated (duplicated) output subject identifier may be acquired, and then, a plurality of images may be printed out based upon one image data in accordance with the different output setting values which are related to the duplicated output subject identifier.
According to the printing apparatus of the present invention, the image processing apparatus applies the image output setting value of the drawing data to a parameter used to determine a position of a reference printing frame, a dimension thereof, and a shape thereof, so that the position, the dimension, and the shape on the printing medium for printing out the image can be previously set before the image to be printed out is specified.
According to the printing apparatus of the present invention, the image processing apparatus applies the image output setting value of the drawing data to a parameter used to enlarge, compress, or trim the image produced based upon the image data in order to allocate the image produced based upon image data of the work area to the reference printing frame. As a consequence, the position, the dimension, and the shape on the printing medium for printing out the image can be previously set before the image to be printed out is specified.
According to the printing apparatus of the present invention, the image processing apparatus applies the image output setting value of the drawing data to a parameter used to execute a filtering process operation with respect to the image data of the work area. As a result, the filtering process operation which is performed to the image during the printing operation can be previously set.
A second printing apparatus of the present invention is provided with a drawing data storage unit, an input unit, an image data acquiring unit, an image processing unit, and a printing unit, which will be explained in the below-mentioned items (1) to (5):
(1) The drawing data storage unit acquires an output subject identifier, and both an image output setting value and a character output setting value, which are defined in relation to the output subject identifier via an input interface, and produces drawing data which contains the output subject identifier, the image output setting value, and the character output setting value to be stored into a drawing data region. The drawing data storage unit is arranged by a processing apparatus for executing a predetermined process. Both the output setting value and the output subject identifier, and also the character output setting value are acquired from, for example, an auxiliary recording apparatus connected to an input interface, and a computer connected via a communication cable to the input interface. It should be understood that the output subject identifier, the image output identifier, and the character subject identifier may properly change expression formats of implication contents indicated by these values in the execution stages of the process operation in the printing apparatus.
(2) The input unit inputs an identifier of image data which is recorded on an auxiliary recording medium and is mutually communicable between information processing systems is inputted in relation to the output subject identifier stored in the drawing data region. The input unit is arranged by, for example, a processing apparatus for executing a predetermined process, and also a key input apparatus such as a selection value inputting apparatus. For instance, the processing apparatus supplies identifiers of all of image data which are recorded on the auxiliary recording medium, and the selection value inputting apparatus causes a user to selectively input any one of the received identifiers, and then supplies the inputted identifier to the processing apparatus. Then, the processing apparatus defines the received identifier in relation to the output subject identifier.
(3) The image data acquiring unit transfers both image data which is specified while the identifier of the image data related to the output subject identifier is used as a retrieve key, and also character data belonging to the image data from the auxiliary recording medium via the input interface to a work area. The image data acquiring unit is arranged by, for instance, a reading apparatus of an auxiliary recording medium, and a processing apparatus for executing a predetermined process operation.
(4) The image processing unit produces first printing image data from the image data of the work area by employing the image output setting value, and also produces second printing image data from the character data of the work area by employing a character output setting value. The image processing unit is arranged by a processing apparatus for executing a predetermined process operation. The image output setting value is applied to such a parameter to which the processing apparatus refers in the case that image data is converted into printing image data which is expressed in a coordinate system allocated to a printing medium. For instance, the image output setting value is applied to such a parameter to which the processing apparatus refers while this processing apparatus calculates to determine that a certain pixel is arranged at which position on a printing medium. In the case that the character data belonging to the image data is converted into the printing image data expressed in the coordinate system allocated to the printing medium, the character output setting value is applied to the parameter to which the processing apparatus refers. For example, the character output setting value is applied to such a parameter for indicating that any one of the field values of the character data belonging to the image data is derived to be printed out, or and also is applied to such a parameter for determining a font, a font size, and a printing position.
(5) The printing unit prints out an image on a printing medium based upon both the first printing image data and the second printing image data. The printing unit is constituted by, for example, a printer engine equipped a paper transport mechanism, an ink jetting head, a head drive mechanism, a control board, and so on.
In accordance with the printing apparatus of the present invention, since the printing subject file in which the output condition such as the layout is determined is executed, the drawing data is produced from the image output setting value and the output subject identifier and also the character output setting value, which are contained by the printing subject file. As a result, the output condition of the character data belonging to the image data, and also, the output condition such as the layout of the image data, which is designated during the printing operation, can be previously set before the printing operation is carried out. Also, since the image data stored in the auxiliary recording medium are defined in relation to the output subject identifiers, the image data to be printed out can be designated. Since the relationship between the output subject identifiers and the image data stored in the auxiliary recording medium are changed, the image data to be printed out can be changed in the printing subject file.
In accordance with the printing apparatus of the present invention, in the case that an output subject identifier which has not yet been stored in the drawing data region is newly acquired via the input interface, the data storage unit stores the output subject identifier not yet stored in the drawing data region into an image retrieve region. The input unit defines an identifier of image data recorded on the auxiliary recording medium in relation to the output identifier to input the identifier of the related image data.
In accordance with the printing apparatus of the present invention, the identifiers of the image data are defined in relation to the output subject identifiers by the image retrieve region. As a consequence, according to the printing apparatus of the present invention, since the image data related thereto by the image retrieve region can be acquired from the auxiliary recording medium, the repeated (duplicated) output subject identifier may be acquired, and then, a plurality of images may be printed out based upon one image data in accordance with the different output setting values which are related to the duplicated output subject identifier, and also the character data belonging to this image data.
According to the printing apparatus of the present invention, the image processing unit applies the character output setting value to a parameter used to determine a field of character data in which the second printing image data is produced. As a result, the image processing unit can previously set as to whether or not any one of the field values of the character data belonging to the image data is derived to be printed out, before the image data to be printed out is designated.
According to the printing apparatus of the present invention, the image processing unit applies the character output setting value to a parameter used to determine a font of the second printing image data. As a result, the image processing unit can previously set as to whether or not the character data belonging to the image data is printed out by employing which font, before the image data to be outputted is designated.
According to the printing apparatus of the present invention, the image processing unit applies the character output setting value to a parameter used to determine a font size of the second printing image data. As a result, the image processing unit can previously set as to whether or not the character data belonging to the image data is printed out by employing which font size, before the image data to be outputted is designated.
According to the printing apparatus of the present invention, the image processing unit applies the character output setting value to a parameter used to determine a printing position of the second printing image data. As a result, the image processing unit can previously set as to whether or not the character data belonging to the image data is printed out by on which position of the printing medium, before the image data to be outputted is designated.
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1. Field of the Invention
The present invention relates to a robot cleaner, and more particularly, to a robot cleaner which can execute a wireless charging.
2. Background of the Invention
Generally, a robot has been developed for an industrial use, and has managed some parts of factory automation. As the robot is applied to various fields recently, home robots as well as medical robots, space robots are being developed. A representative of the home robot is a robot cleaner, a kind of home electronic appliance capable of performing a cleaning operation by sucking peripheral dust or foreign materials with autonomously moving on a predetermined region. The robot cleaner can execute various functions as well as a home cleaning function using such an autonomous movement. For instance, the robot cleaner can autonomously move to a charging station when power of a battery thereof is used up, thereby executing a charging operation.
A mobile terminal is also provided with a battery for portability. Such a battery can be charged by a wired charging method and a wireless charging method. Recently, a wireless recharge technology is commercially used. The wireless charging method largely includes an electromagnetic induction method using an electromagnetic induction phenomenon, and a magnetic resonance method for transmitting power to transmitting and receiving terminals with the same frequency. However, both of the methods have the following disadvantages. Firstly, an additional charging device is needed to charge a battery of a mobile terminal by a wireless charging method. Secondly, a user has to directly move to a position of the charging device, and place the mobile terminal on the charging device. This results in a user's inconvenience.
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{
"pile_set_name": "USPTO Backgrounds"
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1. Field of the Invention
The present invention generally relates to electronic commerce (e-commerce) and, more particularly to electronically sharing technical information among suppliers, manufacturers and customers of a particular product development chain.
2. Background Description
In any large industry, such as the food industry, manufacturers purchase raw materials from suppliers, process the raw material to produce goods and, sell finished goods to customers. At each stage during production, volumes of data may be generated for different products, e.g., how to solve a particular manufacturing problem or, the best way to store the product. Specifications may be generated for finished products and advance sheets may be available for planned products. Since one manufacturer's finished product may be the next manufacturer's raw material, passing some or all information collected on the product may be important to both parties.
Further, audits may be required to be done on one product several times. Each audit may be at considerable expense to the party being audited. Typically, audit results are not generally available.
Currently, the food industry does not have a centralized repository that provides an all-encompassing platform for sharing technical information. This omission has created inefficiencies within the food industry because of redundancy and duplication of effort in the management and use of food-related technical information.
Thus, there is a need for providing suppliers, manufacturers and customers of a particular industry, such as the food industry, with a tool for managing and sharing specifications and other information in a standardized format.
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{
"pile_set_name": "USPTO Backgrounds"
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The invention relates to an electronic sewing machine and more particularly relates to a pattern elongation system of the sewing machine to produce a pattern of stitches enlarged or reduced in the fabric feeding direction with a constant feeding pitch such as the satin stitches. The sewing machine has an electronic memory storing stitch control data which are optionally read out to control the needle positions, so as to adjust the configuration of a pattern of stitches in a manner as mentioned.
According to the pattern elongation device of the sewing machine, the transmission mechanism from a pattern cam to the stitch forming instrumentalities is mechanically adjusted, and therefore the device is in general mechanically complex to produce various elongated patterns symmetrical or asymmetrical, and has been actually difficult to be reduced into practice. In fact, no pattern elongation device or system has been proposed in an electronic sewing machine having a memory storing the stitch control data.
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{
"pile_set_name": "USPTO Backgrounds"
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This invention relates to power line protection and more particularly to a novel method and apparatus for interrupting the flow of current in a three-wire, single-phase energy supply circuit in the event an open neutral line condition is created even when loads are not connected to the energized lines.
It is well known in the power distribution art that the neutral line of a three-wire, single-phase energy supply system may become an open circuit due to improper installation or physical damage. If unequal loads are connected between such open neutral line and each of the pair of energized lines, the load having the lower power requirement, and therefore the higher resistance, will have more than one half the total line-to-line voltage appearing across that load and may be damaged by the resulting additional voltage. Similarly, the higher wattage load will have less than half the line-to-line voltage appearing across that load and may be damaged by the resulting severe undervoltage. Additionally, many large home and commercial appliances operate from three-wire single-phase mains and utilize the neutral line as shock-protective means connected to the equipment case. An open neutral line to such installation creates a severe personnel shock hazard.
Open neutral line protection methods and circuits previously known to the art have either been complex or operable only if a load was connected between each energized line and the neutral line.
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{
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Light-emitting diodes (LEDs) are nowadays used in many cases for lighting purposes. Since LEDs typically generate narrowband, single-colored light having a quasi-monochromatic spectrum, a plurality of different-colored LEDs or one or a plurality of LEDs having an additional wavelength-converting dye have to be combined in order to generate white light.
A customary combination of LEDs for generating white light comprises quasi-monochromatic red LEDs having a peak wavelength in the range of approximately 600 to 700 nm, quasi-monochromatic green LEDs having a peak wavelength in the range of approximately 530 to 570 nm and quasi-monochromatic blue LEDs having a peak wavelength in the range of approximately 440 to 475 nm. If appropriate, LEDs having further colors can also be added to this so-called RGB combination.
Furthermore, it is also known, in a so-called RBW combination, to combine the abovementioned red and blue LEDs with one or a plurality of white-converted blue LEDs which generate blue light and have a dye that is excited by part of the blue light to emit light having longer wavelengths, which, in superimposition with the unconverted part of the blue light of the LED, produces white light.
By varying the light intensities respectively emitted by the individual LEDs, it is possible to generate different-colored mixed light, for example, also white light having different color temperatures. In this case, however, the individual LEDs are usually operated with low intensities depending on the mixed color to be obtained, as a result of which the total intensity of the mixed light is low. In order to achieve a certain luminous flux, it may be necessary as a result to use a larger number of LEDs, as a result of which the total costs for the LEDs increase.
It is also known to combine at least two or more white-converted LEDs each having a color locus lying on or near the white curve of a Planckian black-body radiator. In this case, the color loci and the white curve relate to the known CIE 1931 colorimetric diagram or CIE standard chromaticity diagram. In the case of such a combination with white-converted LEDs, however, it can happen that the superimposition of the white light respectively emitted itself does not lie on the white curve or at least regions on the white curve cannot be attained, particularly if only two different white-emitting LEDs or LED groups are used.
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{
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Aptamers are nucleic acid molecules having specific binding affinity to molecules through interactions other than classic Watson-Crick base pairing.
Aptamers, like peptides generated by phage display or monoclonal antibodies (“mAbs”), are capable of specifically binding to selected targets and modulating the target's activity or binding interactions, e.g., through binding aptamers may block their target's ability to function. Discovered by an in vitro selection process from pools of random sequence oligonucleotides, aptamers have been generated for over 130 proteins including growth factors, transcription factors, enzymes, immunoglobulins, and receptors. A typical aptamer is 10-15 kDa in size (20-45 nucleotides), binds its target with nanomolar to sub-nanomolar affinity, and discriminates against closely related targets (e.g., aptamers will typically not bind other proteins from the same gene family). A series of structural studies have shown that aptamers are capable of using the same types of binding interactions (e.g., hydrogen bonding, electrostatic complementarities, hydrophobic contacts, steric exclusion) that drive affinity and specificity in antibody-antigen complexes.
Aptamers have a number of desirable characteristics for use as therapeutics and diagnostics including high specificity and affinity, biological efficacy, and excellent pharmacokinetic properties. In addition, they offer specific competitive advantages over antibodies and other protein biologics, for example:
1) Speed and control. Aptamers are produced by an entirely in vitro process, allowing for the rapid generation of initial leads, including therapeutic leads. In vitro selection allows the specificity and affinity of the aptamer to be tightly controlled and allows the generation of leads, including leads against both toxic and non-immunogenic targets.
2) Toxicity and Immunogenicity. Aptamers as a class have demonstrated therapeutically acceptable toxicity and lack of immunogenicity. Whereas the efficacy of many monoclonal antibodies can be severely limited by immune response to antibodies themselves, it is extremely difficult to elicit antibodies to aptamers most likely because aptamers cannot be presented by T-cells via the MHC and the immune response is generally trained not to recognize nucleic acid fragments.
3) Administration. Whereas most currently approved antibody therapeutics are administered by intravenous infusion (typically over 2-4 hours), aptamers can be administered by subcutaneous injection (aptamer bioavailability via subcutaneous administration is >80% in monkey studies (Tucker et al., J. Chromatography B. 732: 203-212, 1999)). With good solubility (>150 mg/mL) and comparatively low molecular weight (aptamer: 10-50 kDa; antibody: 150 kDa), a weekly dose of aptamer may be delivered by injection in a volume of less than 0.5 mL. In addition, the small size of aptamers allows them to penetrate into areas of conformational constrictions that do not allow for antibodies or antibody fragments to penetrate, presenting yet another advantage of aptamer-based therapeutics or prophylaxis.
4) Scalability and cost. Therapeutic aptamers are chemically synthesized and consequently can be readily scaled as needed to meet production demand. Whereas difficulties in scaling production are currently limiting the availability of some biologics and the capital cost of a large-scale protein production plant is enormous, a single large-scale oligonucleotide synthesizer can produce upwards of 100 kg/year and requires a relatively modest initial investment. The current cost of goods for aptamer synthesis at the kilogram scale is estimated at $500/g, comparable to that for highly optimized antibodies. Continuing improvements in process development are expected to lower the cost of goods to <$100/g in five years.
5) Stability. Therapeutic aptamers are chemically robust. They are intrinsically adapted to regain activity following exposure to factors such as heat and denaturants and can be stored for extended periods (>1 yr) at room temperature as lyophilized powders.
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{
"pile_set_name": "USPTO Backgrounds"
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This invention relates to a coating material for golf balls and to a method of applying same; and more particularly relates to a novel and improved method and composition for increasing the distance of travel of propelled golf balls, in carry and roll.
Perhaps no more time and attention is devoted to any facet of sport than to improving golf club equipment to enable a golfer to hit the ball farther and straighter. Millions of dollars are spent each year to improve or modify the swing characteristics of a golf club whether by way of changing its composition, size, shaft length or stiffness. Similarly, golf balls are constantly being modified in terms of composition, number of dimples, impact resistance, etc. to somehow increase the distance or carry of the ball as well as minimize any tendency of the ball to hook or slice.
Previously, efforts have been made to alter the coefficient of friction of the golf club face so as to control its effect on the flight of the ball whether in terms of imparting more or less side spin or back spin. See U.S. Pat. No. 5,885,171. To the best of my knowledge however, no one has devised a simple effective method or means for lubricating the surface of a golf ball so as to improve its flight characteristics by increasing its distance or carry in response to a given impact or striking force, by reduction of the dynamic friction between the ball and the air. In this relation, it is desirable to enhance the ability of the ball to roll for greater distances along the ground and to minimize any tendency to hook or slice; and still further to make the ball far less susceptible to foreign elements, such as, the wind. Further, it is desirable to provide a composition and method of coating a golf ball which can be applied to the ball without applying to and affecting the golfer's hand in retaining a secure grip on the golf club when striking the ball or, in other words, will not be significantly transferred or removed from the surface of the ball when the ball is later handled in teeing the ball or in handling the ball on the green.
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{
"pile_set_name": "USPTO Backgrounds"
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The following relates to the fastener arts, nuclear reactor arts, nuclear power generation arts, nuclear fuel arts, and related arts.
In environments such as nuclear reactors, ultra-high vacuum (UHV) processing systems, and the like, installed components are not readily accessible. In such environments, a threaded fastener that works itself loose over time due to exposure to chronic vibration, thermal cycling, or other environmental factors presents a serious difficulty. Numerous fastener locking schemes are known for preventing a threaded fastener from working itself out. Some fastener locking schemes include additional locking hardware, such as a locking washer, cotter pin, lock wire, locking cup or lock plate to secure the fastener. Other fastener locking schemes require specialized modification of the surface of the flange or other component secured by the fastener. For example, some locking schemes rely on friction or deformation of the mating surfaces for the locking action while others require a modified opening (e.g., counter-sinked well) into which the fastener head is crimped to lock the fastener. Lock washers, pins, castellated nuts, and lock wire are problematic for securing components inside a nuclear reactor as these components are subjected to long term exposure (e.g., on the order of decades) to flow induced vibration, seismic loads, etc. Loosening or failure of a single fastener in an operating nuclear reactor can require reactor shutdown and unscheduled maintenance.
Similarly, in a UHV system, pump down to operating pressures of around 10−9 Torr or lower typically employs applying a sequence of different pumps (e.g., mechanical, cryogenic, diffusion, ion pumps) in a prescribed sequence over a period of days or weeks. A single fastener failure can require opening the UHV system and consequent unscheduled downtime for pump down on the order of weeks.
The following discloses improved locked fastener arrangements and fastening methods.
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{
"pile_set_name": "USPTO Backgrounds"
}
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1. Field of the Invention
The present invention relates to image display devices and modification methods performed by the same, and in particular to an image display device having a repairable pixel structure and a modification method performed by the same.
2. Description of the Related Art
Organic electro-luminescent (EL) displays including organic electro-luminescent elements (hereinafter referred to as organic EL elements) are known as image display devices including current-driven luminescent elements. The organic EL displays are attracting attention as a candidate for next-generation flat panel displays (FPDs) because they are viewable at wide angles and consume a small amount of power.
Usually, organic EL elements included in pixels are arranged in a matrix pattern. For example, in active-matrix organic EL displays, thin-film transistors (TFTs) are provided at intersections of scanning lines and data lines, and each TFT is connected with a capacitive element (capacitor) and the gate of a driving transistor. The TFT is turned on through a selected scanning line to allow a data signal to be provided to the driving transistor and the capacitive element through a corresponding data line so that the driving transistor and the capacitive element control the timing when the organic EL element produces luminescence. With this configuration of the pixel driving circuit, the active-matrix organic EL displays can cause the organic EL elements to keep producing luminescence until next scanning (selection), and thus there is no reduction in the display luminance even when the duty ratio increases. However, as typified by the active-matrix organic EL displays, when the complexity of the driving circuit configuration of the luminescent pixels increases or when the number of luminescent pixels increases, electrical troubles, such as a short circuit and/or an open circuit of circuit elements and wires, are more likely to occur during a manufacturing process which requires fine processing.
With organic EL panels, in particular, the capacitive elements included in the pixel driving circuits have a relatively wide element area. Consequently, the capacitive elements are susceptible to a particle or the like present between electrodes, thereby causing a higher percent defective of pixels through a short circuit.
Meanwhile, there is a method proposed for repairing a defective luminescent pixel after forming pixel driving circuit elements and wires. In order to repair a defective luminescent pixel which has become a bright point in a constant luminescent status due to a short circuit of a circuit element or the like, Patent Reference 1 (Japanese Unexamined Patent Application Publication No. 2008-203636) provides, in all the luminescent pixel regions, a non-overlapping portion connected to other conductive portions and wires with some distance therefrom. To repair a defective luminescent pixel, the non-overlapping portion is disconnected by laser irradiation. With this, transmission of electric signals to the defective luminescent pixel is blocked. Moreover, the defective luminescent pixel becomes a dark point with no damage from the laser irradiation.
Furthermore, in Patent Reference 2 (Japanese Unexamined Patent Application Publication No. 2007-66904), a pixel electrode formed in a luminescent region of each luminescent pixel is provided by connecting cells, so that by disconnecting a cell connection with a laser, only the defective luminescent cell is electrically insulated and becomes a dark point.
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{
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The present invention relates to a ski boot with a mechanism for securing a foot instep and heel.
As is known, in ski boots devices which perform the securing of the foot instep are currently employed; such devices are generally composed of a presser, on which presser, by means of pushing elements, cables or the like, a force is exerted which tends to exert a substantially vertical pressure with respect to the foot instep in order to perform the securing of the foot itself.
With such an embodiment, which is universally adopted, it turns out that the foot is not, in most cases, sufficiently restrained against the lateral movements, so that it is necessary to exert even high pressures in order to obtain an acceptable securing of the foot, with obvious discomfort to the user.
Another disadvantage which can be found in the prior art is furthermore represented by the fact that the securing action exerted on the foot unavoidably tends to shift the foot towards the rear part of the boot, where it is not always possible to create a securing force capable of conveniently securing the foot without causing discomfort to the user.
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{
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As well known in the arts, a precision motor is usually provided in a data reading apparatus, e.g. a compact disc player. In general, this motor, as shown in FIG. 1, includes rotor members and stator members. The rotor members include a shaft 10, a rotor 12 and the magnet 14 therein. During operation, above mentioned three members proceed the high speed rotation along the axis of the shaft 10. The stator members include the coils 16, a base plate 17, a circuit board 18, a bush 19, a rear cap 15 and a pivot plate 13.
During operation of the motor, to prevent the detachment of rotor from the stator, in general, a retaining ring 11 is provided at the end of the shaft 10. This retaining ring 11 may attach to the shaft 10 by press fit relationship. Or, alternatively, by an engagement approach, the retaining ring 11 is engaged with a corresponding groove on the shaft 10.
Typically, the aforementioned shaft 10, rotor 12, magnet 14, coils 16, base plate 17, circuit board 18, bush 19 are first assembled together. Afterwards, the retaining ring 11 is disposed at the end of the rotor. In succession, the rear cap 15 is assembled to the pivot plate 13 such that the rear cap 15 is in press-fit with the base plate 17.
The retaining ring 11 may be in form of "C" shape with a narrow slot thereon. Alternatively, the retaining ring 11 may be in form of a press-fit closed ring. Due to the existence of the retaining ring 11 touching against the bushing 19 as the shaft 10 is pulled by an external force, the shaft 10 will not be pulled out of the motor. However, the retaining ring 11 is in high speed rotation together with the shaft 10. Therefore, should a small amount of eccentric phenomenon with regard to the weight distribution of the retaining ring 11 exists, adverse effect is imposed over the high speed rotation of the shaft 10.
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{
"pile_set_name": "USPTO Backgrounds"
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1. Field of the Invention
The present invention relates to a semiconductor memory device such as a flash-type EEPROM (Electrically Erasable/Programmable Read Only Memory) and a method of manufacturing the same.
2. Description of the Related Art
A flash-type EEPROM conventionally used is configured as shown in FIGS. 14, 15, 16 and 17. FIG. 14 is a schematic plan view of the flash-type EEPROM, and FIGS. 15, 16 and 17 are sectional views taken along the lines XV--XV, XVI--XVI, and XVII--XVII of FIG. 14.
N.sup.+ -type drain diffusion regions 1 and N.sup.+ -type source diffusion regions 2 are formed in a P-type semiconductor substrate 10 with channel regions 3 defined between the diffusion regions 1 and 2. A floating gate 5 in an electrically floating state is formed on each of the channel regions 3 with a tunnel oxide film 4 interposed between them. A control gate 8 acting as a word line is superposed over the floating gate 5 with an insulating film 6 sandwiched between them. Either of the floating gate 5 and the control gate 8 is made of, for example, polycrystalline silicon film. Reference numeral 7 denotes low concentration impurity diffusion layers used for enhancing sustainable voltage of the source diffusion regions 1.
A layer insulating film 9 is formed over a surface of the substrate 10 on which the above-mentioned various components such as the control gate 8 are formed. Contact holes 11 are formed above the drain diffusion regions 1 in the layer insulating film 9. On a surface of the layer insulating film 9, aluminum wirings 12 serving as bit lines are formed in contact with the drain diffusion regions 1 in the contact hole 11. Reference numeral 13 designates field oxide films for isolating cells from one another.
Each drain diffusion region 1 and each source diffusion region 2 are shared with adjacent memory cells. The source diffusion regions 2 disposed along word lines (control gates 8) are interconnected by source lines 14. The source lines 14 are formed in the substrate 10 by impurity diffusion simultaneous with forming the source diffusion regions 2.
When writing voltage at a positive high level (e.g., 12 V) is applied to the control gate 8 and also positive high voltage (e.g., 7 V) is applied to the drain diffusion region 1, electrons are accelerated from the source diffusion region 2 toward the drain diffusion region 1. Simultaneously, a strong electric field caused in the boundary of each drain diffusion region 1 produces hot electrons, which pass through the tunnel oxide film 4 and are injected into the floating gate 5. In this way, writing is effected. When high voltage reverse in polarity to the voltage in the writing is applied between the control gate 8 and the substrate 10, electrons are pulled out of the floating gate 5. In this way, erasing is effected.
A threshold level of the voltage to be applied to the control gate 8 in order to electrically connect a source and a drain, takes two different values depending upon whether the electrons exist in the floating gate 5. Sense voltage which has an intermediate level between the two different threshold levels is applied and then connection/disconnection between the source and the drain is checked, and thus, reading information can be effected.
Because of the electrically floating state of the floating gate 5, the quantity of electric charge injected therein is not varied unless the writing voltage or the erasing voltage is applied thereto, and therefore, storing data can be effected in a non-volatile manner.
Such a flash-type EEPROM is made in a manner as described below. A field oxide film 13 is formed on a surface of the substrate 10 by a LOCOS (LOCal Oxidation of Silicon) method, and then, the tunnel oxide film 4 is formed over the entire surface of the substrate 10. In this situation, the floating gate 5 is formed by depositing polycrystalline silicon, adding phosphorus as impurity to gain conductivity, and then patterning it.
Then, the insulating film 6 is formed, and after deposition of polycrystalline silicon, addition of phosphorus, and patterning, the control gates 8 acting as word lines is formed. The source diffusion regions 2 and the source lines 14 are to be formed later by implanting ions in regions between the field oxide films 13. For that purpose, some components such as the control gates 8 must be formed in position without protruding into an area between the field oxide films 13. Hence, allowing for an accuracy of mask alignment and other factors, the components such as the control gates 8 are formed in positions a distance .DELTA.L receding from edges of the field oxide films 13, as shown in FIG. 17. If the control gates 8 are formed in a position protruding from the edges of the field oxide films 13, each of the source lines 14 is reduced in width to have an insufficient cross-sectional area, and this may cause a high resistance therein.
After the control gates 8 are formed, phosphorus ions are implanted to form the low concentration diffusion layers 7 surrounding the source diffusion regions 2. Then, arsenic ions are implanted with masks of the field oxide films 13 and the control gates 8, and thereby the N.sup.+ -type source diffusion regions 2, the N.sup.+ -type drain diffusion regions 1 and the source lines 14 are formed.
Then, the substrate 10 is covered with the layer insulating film 9, and the contact holes 11 are formed. After that, the aluminum wiring 12 acting as bit lines are formed and patterned.
In the above-mentioned flash-type EEPROM, however, degree of integration therein is restricted, and hence, there arises a disadvantage that miniaturization of the whole memory device is difficult. More specifically, the field oxide films 13 are used to isolate elements from each other in the abovementioned flash-type EEPROM. Hence, it is necessary to make the oxide films extend to a level deep enough from the surface of the substrate to perfectly isolate the elements, and this is why the oxide films 13 must be made thick. With the oxide films thickened, their width along the surface of the substrate 10 is necessarily increased, and naturally, a distance L1 between the bit lines (see FIG. 14) becomes large to some extent. This prevents an enhancement of integration in the memory device.
Moreover, as described above, since the source diffusion regions 2 and the source lines 14 are formed by ion implantation after the word lines (control gates 8) are formed, the word lines must be formed in positions receding from the edges of the field oxide films 13. In other words, in a configuration where the source lines 14 formed by the ion implantation extend in the semiconductor substrate 10 between the adjacent word lines (control gates 8), reduction of a distance L2 between the word lines is restricted. This also prevents an enhancement of integration in the memory device.
In addition to that, in a process of manufacturing the above flash-type EEPROM, although both the floating gate 5 and the control gate 8 are formed of polycrystalline silicon film, they are patterned individually. Hence, there arises another disadvantage that the manufacturing process is complicated.
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1. Field of the Invention
This invention relates to a new and improved chemical process for preparing a 1,1-dihalo-4-methyl-1,3-pentadiene, an intermediate in a known method for the production of certain pyrethroid insecticides.
2. Description of the Prior Art
Pyrethroids, naturally-occurring and synthetic derivatives of cyclopropanecarboxylic acid, have long been of interest as insecticides because they are active against a wide range of insect species, they display relatively low toxicity toward mammals, and they do not leave harmful residues. A notable recent technical advance in the pyrethroid art was the discovery of a dihalovinylcyclopropanecarboxylate, 3-phenoxybenzyl 2-(.beta.,.beta.-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylate, having an outstanding combination of insecticidal properties [Elliott et al., Nature, 244, 456 (1973); ibid., 246 169 (1973); South African 73/3528]. Since Elliott's discovery, a great deal of interest has been generated worldwide in economical processes for the production of this type of pyrethroid.
Several years before Elliott's discovery, a method for the production of ethyl 2-(.beta.,.beta.-dichlorovinyl)-3,3-dimethylcyclopropanecarboxylate was reported [Farkas et al., Coll. Czech. Chem. Comm., 24, 2230 (1959)]. This compound leads to the Elliott pyrethroid by ester interchange [Nature, 244, 456 (1973)]. According to the Farkas method, chloral may be condensed with either isobutenyl magnesium bromide or with isobutylene, using a free radical catalyst with the latter, to produce a mixture of pentenols, which then may be reacted as follows: ##STR1##
By this method the overall conversion of isobutylene to 1,1-dichloro-4-methyl-1,3-pentadiene, the key intermediate for the diazotization step, is reportedly less than 40%. Furthermore, for every kilogram of 1,1-dichloro-4-methyl-1,3-pentadiene produced, more than a kilogram of zinc dust is consumed. In a recent year, U.S. producers alone sold about 300 million kilograms of synthetic organic insecticides [Chemical and Engineering News, July 28, 1975, p. 19]. If the Elliott pyrethroid becomes a major agricultural commodity, commercial production of 1,1-dichloro-4-methyl-1,3-pentadiene by the Farkas method would seriously tax the world supply of zinc. Thus, other more practical and economical processes capable of yielding 1,1-dichloro-4-methyl-1,3-pentadiene from readily available starting materials have been sought.
As Farkas recognized, dienes of the type represented by 1,1-dichloro-4-methyl-1,3-pentadiene generally are prepared by the alkaline or pyrolytic dehydrohalogenation of 1,1,1,3-tetrachloroalkanes, which, in turn, are produced by the condensation of an alkene with carbon tetrachloride in the presence of a free radical catalyst [M. S. Kharasch et al., J. Amer. Chem. Soc., 69, 1100 (1947); ibid., 69, 1105 (1947)].
Following the general methods, Farkas attempted to make 1,1-dichloro-4-methyl-1,3-pentadiene by the dehydrohalogenation of 1,1,1,3-tetrachloro-4-methylpentane, but his efforts along this line were completely unsuccessful. Although the condensation between carbon tetrachloride and 3-methyl-1-butene proceeded in 38% yield, the treatment of 1,1,1,3-tetrachloro-4-methylpentane with base failed to produce a detectable amount of the desired 1,1,-dichloro-4-methyl-1,3-pentadiene. Furthermore, pyrolytic dehydrohalogenation of 1,1,1,3-tetrachloro-4-methylpentane "led only to dark colored tars" [Coll. Czech. Chem. Comm., 24, 2230 (1959)].
Thus, Farkas was compelled to adopt the costly, commercially unattractive method diagrammed above for the synthesis of the 1,1-dichloro-4-methyl-1,3-pentadiene required to produce the cyclopropanecarboxylate.
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This invention relates to an apparatus for detecting an in-focused condition of optical systems such, for example, as a camera and microscope or the like.
Various detecting apparatuses have heretofore been proposed which utilize two values of indices of performance each derived from the number of differences between illumination signals obtained per picture element. One of these conventional apparatuses comprises a first photosensitive element composed of a cadmium sulfide arranged in front of a focal plane of an optical system, a second photosensitive element arranged in the rear of the focal plane, a first analog-to-digital converter connected to the first photosensitive element, a second analog-to-digital converter connected to the second photosensitive element in order to obtain two digital values of indices of performance. In such apparatus, images are formed sequentially on each unit of photosensitive element by deflecting a mirror, so that the apparatus is large in size and requires complicate control operations.
In other conventional apparatus for detecting an in-focused condition of optical systems, two outputs delivered from photosensitive elements are compared with each other and during which the optical system is moved to and fro. As a result, it is difficult to precisely detect an in-focused condition. In addition, this apparatus can only detect a direction of deflection from an in-focused condition, but could not quantitatively detect its magnitude, so that the apparatus is troublesome in control and less responsive.
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{
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1. Field of the Invention
This invention relates generally to the field of data processing systems. More particularly, the invention relates to a system and method for managing configuration data for a plurality of sever nodes.
2. Description of the Related Art
Traditional client-server systems employ a two-tiered architecture such as that illustrated in FIG. 1a. Applications 102 executed on the client side 100 of the two-tiered architecture are comprised of a monolithic set of program code including a graphical user interface component, presentation logic, business logic and a network interface that enables the client 100 to communicate over a network 103 with one or more servers 101. A database 104 maintained on the server 101 provides non-volatile storage for the data accessed and/or processed by the application 102.
As is known in the art, the “business logic” component of the application represents the core of the application, i.e., the rules governing the underlying business process (or other functionality) provided by the application. The “presentation logic” describes the specific manner in which the results of the business logic are formatted for display on the user interface. The “database” 104 includes data access logic used by the business logic to store and retrieve data.
The limitations of the two-tiered architecture illustrated in FIG. 1a become apparent when employed within a large enterprise. For example, installing and maintaining up-to-date client-side applications on a large number of different clients is a difficult task, even with the aid of automated administration tools. Moreover, a tight coupling of business logic, presentation logic and the user interface logic makes the client-side code very brittle. Changing the client-side user interface of such applications is extremely hard without breaking the business logic, and vice versa. This problem is aggravated by the fact that, in a dynamic enterprise environment, the business logic may be changed frequently in response to changing business rules. Accordingly, the two-tiered architecture is an inefficient solution for enterprise systems.
In response to limitations associated with the two-tiered client-server architecture, a multi-tiered architecture has been developed, as illustrated in FIG. 1b. In the multi-tiered system, the presentation logic 121, business logic 122 and database 123 are logically separated from the user interface 120 of the application. These layers are moved off of the client 125 to one or more dedicated servers on the network 103. For example, the presentation logic 121, the business logic 122, and the database 123 may each be maintained on separate servers, 126, 127 and 128, respectively.
This separation of logic components and the user interface provides a more flexible and scalable architecture compared to that provided by the two-tier model. For example, the separation ensures that all clients 125 share a single implementation of business logic 122. If business rules change, changing the current implementation of business logic 122 to a new version may not require updating any client-side program code. In addition, presentation logic 121 may be provided which generates code for a variety of different user interfaces 120, which may be standard browsers such as Internet Explorer® or Netscape Navigator®.
The multi-tiered architecture illustrated in FIG. 1b may be implemented using a variety of different application technologies at each of the layers of the multi-tier architecture, including those based on the Java 2 Enterprise Edition™ (“J2EE”) standard, the Microsoft .NET standard and/or the Advanced Business Application Programming (“ABAP”) standard developed by SAP AG. For example, in a J2EE environment, the business layer 122, which handles the core business logic of the application, is comprised of Enterprise Java Bean (“EJB”) components with support for EJB containers. Within a J2EE environment, the presentation layer 121 is responsible for generating servlets and Java Server Pages (“JSP”) interpretable by different types of browsers at the user interface layer 120.
Although the multi-tiered system illustrated in FIG. 1b provides a more flexible and scalable architecture, it also results in significant additional complexity. For example, managing multiple clusters of presentation layer servers, business layer servers and databases, and the dependencies between them requires a significant amount of network administration overhead. Accordingly, new techniques which simplify the startup and management of multi-tiered enterprise systems are desirable.
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Tools for surgical preparations generally may include a sponge which is used by medical personnel to apply an antiseptic solution to a patient's skin. The sponge can be dipped into an antiseptic solution in a container and swabbed onto the patient's skin to prevent live bacteria from entering an incision or wound of the skin. Other devices have been developed that contain an antiseptic solution contained in the device for dispensing the solution from an applicator associated with the device. There is a continuing need for a dispensing device that can be configured for use to dispense a fluid, such as an antiseptic solution, to an applicator swab wherein required manipulation of the device prior to use may be minimized.
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The present invention relates to plastic package semiconductor devices and methods of making the devices, and more particularly to a ball grid array (BGA) package semiconductor device, a method of fixing and supporting the components of the device and a method of making the device.
Semiconductor package structures have advanced toward miniaturization and thinning to increase the density of components packaged therein. The quantity of information to be processed by one chip tends to increase. The number of input/output pins per package tends to increase. Since the size of the package cannot increase as much as one desires, however, the spacing between any adjacent lead pins tends to decrease greatly as the number of lead pins increases. Thus, the current situation is that a high technique is required for mounting devices on a circuit board or substrate. In order to facilitate the mounting of devices, packages have appeared having an external connection structure such as a pin grid array (PGA) and a BGA which are different in external connection form from the conventional ones. A face up type BGA package is disclosed in U.S. Pat. No. 5,216,278. A face down type is disclosed in U.S. Pat. No. 5,148,265.
The BGA structure similar to one disclosed in U.S. Pat. No. 5,216,278, for example, will next be outlined as an example of the face up type with reference to FIGS. 38-40.
FIG. 38 is a cross-sectional view of a BGA package. An IC chip 1 is bonded to a circuit board 2 by means of an adhesive or the like. The board 2 is made of an organic material such as a BT resin. The IC chip 1 is connected electrically by bonding wires 13 to pads 12 on the board 2.
FIG. 39 is a top plan view of the BGA package of FIG. 38. Wiring patterns each extending from a pad 12 on the board 2 are disposed on the board 2 to communicate with a terminal 3 on the back of the board 2.
FIG. 40 is a bottom view of the package of FIG. 38. The terminals 3 are disposed at crossing points of a grid and electrical wiring is completed by joining metal bumps 4 to the corresponding terminals 3. A protective package is finished by covering with resin 14 that surface of the board on which the IC chip 1 which is a constituent component is provided.
A plurality of cavities each for a BGA package are usually disposed within a mold and filled with resin in the molding process in view of productivity. Therefore, the BGA packages are difficult to position within the mold in such arrangement and a molded product removal process is very complicated. This increases the manufacturing cost.
A face down type BGA package structure similar to one disposed in U.S. Pat. No. 5,148,265, for example, will be described, with respect to FIGS. 41 and 42. FIG. 41 is a perspective view of a BGA package composed of inserts 32 of silicon rubber or the like placed on a circuit side surface of an IC chip 1 and a circuit film 31 having a circuit pattern placed on the inserts 32. The IC chip 1 and the circuit film 31 are connected by bonding wires 13.
FIG. 42 is an enlarged cross-sectional view of connections of FIG. 41. The protective package is completed by covering, with an elastic resin 14, the IC chip 1 and the package excluding the areas of the terminals 33 to complete a package. In this case, there are problems similar to those with the face up type package. Since, usually, a plurality of BGA packages is disposed within a mold and filled with resin in the molding process in view of productivity, the packages are difficult to position within the mold in such arrangement and a molded product removal process is very complicated. This would increase the manufacturing cost.
In the process of molding packages each including a circuit board, the circuit board is usually placed between an upper mold half and a lower mold half and resin is filled into cavities provided over the circuit board. Therefore, a runner and a gate which compose a flow path through which resin is fed over the board are required to be provided, which is a restriction to the design of an electric circuit. In addition, this might reduce the reliability of the package because there is a possibility of the circuit board being damaged in the process of removal of the runner and gate which become unnecessary after molding.
There are many known prior art molding methods which uses no runner and gate disposed on the circuit board which compose a flow path through which resin is filled onto the circuit board; for example, JP-B-61-46049 and JP-A-4-184944. JP-B-61-46049 discloses a molding process performed in an arrangement where a mold has a runner and a gate which compose a part of a flow path through which resin is fed into a cavity composed of plates (so-called "cavity plates") with the cavity and the circuit board being placed within the mold. In this process, there are no restrictions to the design of an electric circuit on the circuit board, but there is a possibility that when a thin package is to be produced, other problems will occur such as deformation of the cavity plates themselves or removal of resin burrs produced on the circuit board because the cavity plates are thin. In addition, each time molding is performed, the cavity plates are required to be replaced with new ones and hence automation of the molding process is difficult.
JP-A-4-184944 discloses a mold structure where a runner and a gate are incorporated in a mold to compose a flow path through which resin is fed into the mold. The engaged portions at the runner and gate are arranged to slide each other when the mold is opened. In this case, resin flows over the sliding parts, so that resin is likely to enter into a possible spacing between the sliding parts. Thus, resin burrs are likely to be produced to act as sliding resistance to the sliding element to thereby cause malfunction of same, undesirably. This malfunction can be a serious problem in the production of those packages.
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This section is intended to provide relevant contextual information to facilitate a better understanding of the various aspects of the described embodiments. Accordingly, it should be understood that these statements are to be read in this light and not as admissions of prior art.
A variety of treatment fluids can be used in subterranean formations during numerous types of process operations. Illustrative process operations can include, but are not limited to, drilling operations, perforating and/or fracturing operations, proppant packing operations, acidification operations, viscosity control operations, scale dissolution and removal operations, fluid loss operations, or sand control operations. Such treatment fluids can be used to increase hydrocarbon production from a subterranean formation, as well as the efficiency of such hydrocarbon production. Therefore, it will be appreciated that improvements are continually needed in the field of treatment fluids for use in subterranean formations.
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This application claims priority to Japanese Application No. 2000-353961, filed Nov. 21, 2000, the entire disclosure of which is hereby incorporated by reference herein.
1. Field of the Invention
The present invention relates to a personal watercraft. More particularly, the present invention relates to an improved exhaust system for a personal watercraft.
2. Description of the Related Art
Personal watercraft have become very popular in recent years. This type of watercraft is sporting in nature and typically is configured to carry a rider and possibly one to three passengers. A relatively small hull of the personal watercraft commonly defines a riders"" area and an engine compartment, which lies below the riders"" area. An internal combustion engine frequently powers a jet propulsion unit, which propels the watercraft. The engine lies within the engine compartment in front of a tunnel formed on the underside of the watercraft hull. The jet propulsion unit is located within the tunnel and is driven by a drive shaft. The drive shaft usually extends between the engine and the jet propulsion device, through a wall of the hull tunnel.
Recently, the use of personal watercraft has been restricted on some bodies of water. Some proponents of the restrictions cite operation noise. Primarily because of the small size of personal watercraft, a relatively simple exhaust system generally is used, which does not provide a significant degree of silencing. In addition, because the small personal watercraft can be used on quite small bodies of water, the perceived noise levels may be greater than larger watercraft having unmuffled exhaust systems but which do not operate on these small bodies of water.
An exhaust system of a typical personal watercraft discharges engine exhaust to the atmosphere either through or close to the body of water in which the watercraft is operating. In one arrangement, the exhaust is discharged through a discharge opening formed in a rearwardly opening pump chamber, which surrounds the jet propulsion unit and a rear portion of the tunnel. The exhaust passes from the opening to the body of water along side the jet propulsion unit. Although this discharge arrangement successfully reduces exhaust noise under some conditions, there are problems associated with this arrangement. For example, as the watercraft turns, water from the jet propulsion unit can be directed into the space between the pump chamber and the tunnel. This water can lead to choking in the exhaust system, which can adversely affect engine performance. In addition, when the watercraft is accelerated to planing speeds, the discharge opening can be exposed to atmosphere. This typically results in an increase in noise pollution.
A need therefore exists for an improved exhaust system for a personal watercraft, which reduces noise pollution from the watercraft without adversely effecting engine performance.
Therefore, one aspect of the present invention involves a small watercraft that comprises a hull having a longitudinal axis and an engine disposed within the hull. A tunnel is defined on an underside of the hull. A propulsion is driven by the engine and includes a jet pump unit disposed at least partially within the tunnel. An exhaust system communicates with the engine and extends to and terminates at an exhaust discharge outlet to discharge exhaust gases generated by the engine. The exhaust discharge outlet is located along the tunnel such that the exhaust gases are discharged into a space defined between the tunnel and the jet pump unit. An exhaust opening is located downstream of the exhaust discharge outlet and is defined between the tunnel and the jet pump unit. A barrier is located in the exhaust opening so as to form an exhaust sub-chamber in the tunnel upstream of the barrier.
Another aspect of the present invention involves a small watercraft that comprises a hull having a longitudinal axis and an internal combustion engine disposed within the hull. A tunnel is defined on an underside of the hull. A propulsion device is driven by the engine and includes a jet pump unit disposed at least partially within the tunnel. An exhaust system communicates with the engine and extends to and terminates at an exhaust discharge outlet to discharge exhaust gases generated by the engine. The exhaust discharge outlet is located on the tunnel such that the exhaust gases are discharged into a space defined between the tunnel and the jet pump unit. The watercraft further including means for forming an exhaust sub-chamber within the space to reduce exhaust gas noise.
Yet another aspect of the present invention involves a small watercraft that comprises a hull. A recess is formed in a lower surface of the hull. A propulsion unit is mounted within the recess. An engine drives the propulsion unit. An exhaust system extends between the engine and the recess. The recess extends rearward to an outlet. A barrier is disposed around a portion of the propulsion unit at a location in the recess that is upstream of the outlet.
It should also be noted that all of these aspects are intended to be within the scope of the invention herein disclosed. These and other aspects of the present invention will become readily apparent to those skilled in the art from the following detailed description of two preferred embodiments with reference to the attached figures, the invention not being limited to the particular preferred embodiments disclosed.
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In the anti-spam industry, spammers use various creative means for evading detection by spam filters. Accordingly, spam filter designers adopt a strategy of combining various detection techniques in their filters.
Current tools for message sender analysis include IP blacklists (e.g., real-time blacklists (RBLs)) and IP whitelists (e.g., real-time whitelists (RWLs)). Whitelists and blacklists add value to the spam classification process; however, whitelists and blacklists are inherently limited to providing a binary-type (YES/NO) response to each query. In contrast, a reputation system has the ability to express an opinion of a sender in terms of a scalar number in some defined range. Thus, where blacklists and whitelists are limited to “binary” responses, a reputation system can express “shades of gray” in its response.
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{
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1. Field of the Invention
The present invention relates to an optical scanning device which is used as an optical writing device of a digital image forming device using an electrophotographic method such as a laser printer, a digital copier, a facsimile machine or other such method. The present invention further relates to an optical scanning device and an image forming apparatus including the optical scanning device which has an intensity distribution transforming optical component for transforming the intensity distribution of a light flux, and the image forming apparatus can be used in a digital outputting apparatus, for example, a digital copier, a printer, a facsimile machine or other apparatus.
2. Description of the Related Art
A conventional optical scanning device includes a coupling lens which couples a light flux emitted by a light source to form a parallel light flux, a weakly convergent light flux, or a weakly divergent light flux. An optical deflector deflects the light flux received from the coupling lens at a uniform angular velocity. A scanning image-formation optical system converges the light flux deflected by the optical deflector to form a beam spot on a surface to be scanned, i.e. a photosensitive body, and, thus, the surface to be scanned is scanned with the beam spot. Such an optical scanning device is used as an optical writing device in a digital image forming apparatus using the electrophotographic method such as a laser printer, a digital copier, a facsimile machine or other apparatus.
In such an optical scanning device, in order to achieve high-density writing (more than 1200 dpi, for example), it is necessary to form a beam spot having a sufficiently small diameter.
In order to obtain a beam spot having such a small diameter, it is necessary to increase the NA of the optical system, of the optical scanning device. Further, in order to obtain a stable small-diameter beam spot, it is necessary that the optical system provides a large depth of focus which tolerates possible component allowance (the curvature radiuses, thicknesses, refractive indexes) for deviations of optical components of the optical system, mounting errors, and environment variations (temperature, humidity).
Assuming that the intensity distribution on the exit pupil of the optical system is a Gaussian distribution, the allowable degree of depth of focus 2d is in proportion to the second power of the beam spot diameter w, as shown in the following expression;
2d xe2x88x9dW2/xcexxe2x80x83xe2x80x83(1)
In the above expression, xcex represents the used wavelength. Thus, the allowable degree of depth of focus decreases sharply as the beam spot diameter is reduced. Therefore, when reduction of the beam spot diameter is attempted, the allowable degree of depth of focus decreases, and, as a result, it is not possible to obtain a stable small-diameter beam spot when the above mentioned component allowance deviations or environmental variations occur.
One solution to this problem is to generate the zero-order Bessel beam of the first kind and obtain a beam spot having a large allowable degree of depth of focus.
For example, Japanese Laid-Open Patent Application No. 9-304714 discloses an optical system providing a large allowable degree of depth of focus by arranging a shading member having a shading portion which shades a portion of a light flux on an optical path between a light source and an optical deflector.
Further, Japanese Laid-Open Patent Application No. 10-227992 discloses generation of a Bessel beam having an intensity distribution which is approximately in proportion to the second power of the zero-order Bessel function of the first kind, in a system in which a laser beam is incident on a diffraction optical component consisting of a binary optical component having an optical performance approximately equivalent to a conical prism.
However, in each of these systems, the intensity distribution of the beam is axially symmetric. Therefore, when the system is used as an optical system of an optical scanning device, it is difficult to independently set a beam spot in a main scanning direction (in which scanning is performed with a light flux) and in a subscanning direction (perpendicular to the main scanning direction).
In the above-mentioned system, a Bessel beam is obtained as a result of transforming the distribution of the amplitude term u1 (y1, z1) of the following equation (2) into an arbitrary amplitude distribution. The intensity distrubution thereof is expressed by the second power of the amplitude distribution. In the following equation (2), the direction of the optical axis is coincident with the x direction, the main scanning direction perpendicular to the optical axis is coincident with the y direction and the sub-scanning direction also perpendicular to the optical axis is coincident with the z direction. u 2 ( y 2 , z 2 ) = j xe2x80x83 ⅇ - ⅈ xe2x80x83 k ( x + y 2 2 + z 2 2 2 xe2x80x83 x ) λ xe2x80x83 x ∫ ∫ u 1 ( y 1 , z 1 ) ⅇ - xe2x80x83 ⅈ xe2x80x83 k 2 xe2x80x83 x ( y 1 y 2 + z 1 z 2 ) ⅆ y 1 ⅆ z 1 ( 2 )
The above equation (2) is expressed assuming that the intensity distribution u22 (y2, z2) of the beam spot on the image surface is approximately in accordance with the Fraunhofer diffraction.
In the above equation (2):
u2 (y2, z2): the amplitude distribution of the beam spot on the image surface;
u1 (y1, z1): amplitude distribution on the pupil;
xe2x88x92ik (y1y2+z1z2)/2x: phase difference on the pupil (k represents the wave number); and
j/xcex: Fresnel inclination coefficient (where xcex represents the used wavelength).
The expression of the Fraunhofer diffraction of the above equation (2) has the same meaning as that of Fourier transform expression, and the amplitude distribution u2 (y2, z2) on the image surface is equal to that obtained from Fourier transform being performed on the amplitude distribution u1 (y1, z1) on the pupil. Therefore, the expression of the Fraunhofer diffraction of the above equation (2) is referred to as a Fourier transformed image.
Further, in any method, when a Bessel beam is generated, side lobes develop. Therefore, when the sensitivity of the photosensitive body is high, image degradation such as resolution degradation and/or stain in background occurs.
FIGS. 1, 2A and 2B show an example of an optical scanning device according to the related art. FIG. 1 shows an optical arrangement of the optical scanning device. In FIGS. 2A and 2B, the optical scanning device is shown in a condition in which the optical scanning device is expanded along an optical path of a light flux extending from a light source to a surface to be scanned. FIG. 2A shows the sectional view of the optical scanning device taken along a deflection plane (including the plane formed as a result of the light flux scanning the surface to be scanned), and FIG. 2B shows the sectional view of the optical scanning device taken along the plane including the optical path of the light flux and perpendicular to the deflection plane.
As shown in FIGS. 1, 2A and 2B, the optical scanning device 30 includes a light source 1 which emits a laser light, a first optical system 2 for directing the laser light emitted by the light source 1 to an optical deflecting portion 3, the optical deflecting portion 3 which deflects the light flux from the first optical system 2, and a second optical system 4 for forming a beam spot on the surface 5 to be scanned using the thus-deflected light flux. The above-mentioned first optical system 2 includes a collimating lens 21, an aperture 22 and a cylindrical lens 23. The second optical system 4 includes a spherical lens 41 and an fxcex8 lens 42.
A process of optical scanning will now be described more specifically. The light flux emitted by the semiconductor laser 1, for example, is transformed into an approximately parallel light flux by the collimating lens 21, and passes through the aperture 22. It is also possible to use a coupling lens instead of the collimating lens 21, and to transform the light flux from the semiconductor laser 1 into a weakly divergent light flux or a weakly convergent light flux.
The light flux from the semiconductor laser 1 is transformed into the approximately parallel light flux, which is then converged into a line image elongated in the deflection direction by the cylindrical lens 23, and is directed to the deflection reflective surface of the polygon mirror 3. The light flux deflected by the polygon mirror 3 is incident on the scanning lens 41, and, the beam spot is formed on the surface 5 to be scanned. The characteristics of curvature of field and uniform-velocity characteristics of the scanning lens 41 are well corrected. Further, the light flux deflected by the polygon mirror 3 is first directed to a photodetection portion 6 by an optical-path changing mirror 8 via the scanning lens 41, and is used as a synchronization signal for detecting a position. from which an image is written.
Generally speaking, the intensity distribution of the light flux emitted from a laser light source is a Gaussian distribution. At this time, the depth of focus Z of the light flux which forms a beam spot having a diameter c,) on a surface to be scanned is expressed by the following expression;
Z=kxcfx892/xcexxe2x80x83xe2x80x83(a)
In the above equation (a), k represents a constant, and xcex represents the wavelength.
As can be clearly seen from the above equation (a), as the diameter xcfx89 of the beam spot is reduced, the depth of focus Z decreases at the rate of the second power of the diameter xcfx89 of the beam spot.
The diameter xcfx89 of the beam spot is expressed by the following equation:
xcfx89=Kxcex/NAxe2x80x83xe2x80x83(b)
In the above equation (b), K represents a constant, xcex represents the wavelength and NA represents the numerical aperture.
Recently, as the resolution of an image outputting apparatus which uses a laser as a light source such as a laser printer is increased and the quality of images obtained therefrom is increased, it is necessary to reduce the diameter of a beam spot on a surface to be scanned, that is, the surface of a photosensitive body in an example of a laser printer.
However, as shown in the equation (a), the depth of focus Z is determined to be in proportion to the second power of the diameter xcfx89 of a beam spot in the case of a Gaussian beam, reduction in the diameter xcfx89 of the beam spot results in decreases in the depth of focus Z, and, thereby, it is difficult to satisfy the allowable range for practical use.
In order to solve the problem, Japanese Laid-Open Patent Application No. 5-307151 discloses an optical scanning device in which a beam spot on a photosensitive body is formed by a Bessel beam.
The Bessel beam is a non-diffracting beam by using which it is possible to reduce the diameter of a beam spot and to increase the depth of focus in comparison to the above-described Gaussian beam. The Bessel beam has the Intensity distribution approximately in proportion to the second power of the zero-order Bessel function of the first kind. With regard to the Bessel beam, see xe2x80x9cExact Solutions For Non-diffracting Beamsxe2x80x9d, written by J. Durnin, Vol. 4, No. 4/April 1987/J. Opt. Soc. Am. A, page 651.
Methods of generating the Bessel beam include using a ring-shaped thin slit (see xe2x80x98Diffraction-Free Beamsxe2x80x99, written by J. Durnin et al., Physical Review Letters, Vol. 58, No. 15, Apr. 13, 1987, page 1499), and using an axicon prism (see xe2x80x98Long-Range Laser-Beam Spot Formation By An Axicon Prismxe2x80x99, written by Satoshi Kawata et al., Proceedings of Spring Lecture of Applied Physics Society (1990), page 829) and others.
The above-mentioned Japanese Laid-Open Patent Application No. 5-307151 discloses an optical scanning device which performs image formation on a surface of a photosensitive body using a Bessel beam having an intensity distribution approximately in proportion to the second power of the zero-order Bessel function of the first kind obtained from a laser light.
However, because the Bessel beam develops large side lobes, the image quality is degraded.
In order to reduce the side lobes, Japanese Laid-Open Patent No. 6-148545 discloses an optical scanning device which generates an eccentric Bessel beam, and cuts off the side lobes using a slit member. In this optical scanning device, the slit member having a slit in a direction which coincides with the deflection direction is arranged in proximity to a surface to be scanned.
However, it is difficult to adjust the position of this slit member properly. Further, by using the slit, the quantity of light is greatly reduced. There is another method in which an axicon prism is used for reducing the side lobes. However, in this method using the axicon prism, it is necessary to mount the axicon prism with high accuracy, and thereby, it is difficult to achieve mass production of optical scanning devices using the axicon prisms.
Japanese Laid-Open Patent Application No. 9-243945 discloses an optical scanning device in which stop means and shading means are provided between a collimating lens and a cylindrical lens. By using the simple means, the diameter of a beam spot is reduced, and the depth of focus is enlarged.
However, also in this method, a portion in the vicinity of the center of a light flux is cut off, and, thereby, the quantity of light is reduced.
Further, recently, consideration of environmental factors is required, and, recycling is being performed for OA equipment such as a copier. Accordingly, designing of structures and components which are suitable for recycling is becoming advanced, and, also, designing of components which can be used in common for various devices is being further developed.
To overcome the problems described above, preferred embodiments of the present invention provide an optical scanning device including an optical system which provides a large degree of depth of focus in order to obtain an excellent small-diameter beam spot even when component allowance (the curvature radiuses, thickness, refractive indexes) deviations of optical components of the optical system, mounting errors, environment variations (temperature, humidity), or other such problems occur.
Furthermore, preferred embodiments of the present invention provide an optical scanning device including an optical system through which the side lobes of the Bessel beam are minimized.
Another preferred embodiment of the present invention provides an optical scanning device which minimizes the diameter of a beam spot in a simple manner and without any adverse affects due to the side lobes and without causing reduction of the quantity of light.
Another preferred embodiment of the present invention provides an optical scanning device which is produced using components which can be used in common in various types of devices, and/or by recycling of a device in the related art.
In one specific preferred embodiment of the present invention, an optical scanning device includes a coupling lens which couples a light flux from a light source to form a parallel light flux, a convergent light flux or a divergent light flux, an optical deflector including a deflective reflection surface which deflects the light flux from the coupling lens at a uniform angular velocity, a scanning image-formation optical system which converges the deflected light flux from the optical deflector on a surface to be scanned to form a beam spot, wherein the device scans the surface to be scanned with the beam spot at a uniform velocity and the device further includes a depth increasing component, for increasing the depth of focus determined by the entire optical system of the device, on the optical path between the light source and the deflective reflection surface.
As a result of this novel combination of structural elements, it is possible to provide an optical scanning device which achieves a large allowable degree of depth of focus determined by the entire optical system of the device.
Accordingly, it is possible for the optical scanning device providing a large allowable degree of depth of focus to produce excellent small-diameter beam spots even when component allowance (the curvature radiuses, thickness, deviations of optical elements of mounting errors, and environment refractive Indexes) the optical system, variations (temperature, humidity) occur.
The depth increasing component may preferably include an intensity-distribution transforming component which transforms the intensity distribution of the light flux such that the intensity distribution on the exit pupil is changed so that the intensity at four corners thereof is higher than that at a central portion.
As a result of this unique structure, the optical scanning device achieves a large allowable degree of depth of focus determined by the entire optical system of the device.
The depth increasing component may also include a phase-distribution transforming component which transforms the phase distribution of the light flux such that the phase distribution on the exit pupil is arbitrarily changed.
As a result, the optical scanning device achieves a large allowable degree of depth of focus determined by the entire optical system of the device.
The depth increasing component may also include an intensity-distribution transforming component which transforms the intensity distribution of the light flux so that the intensity distribution on the exit pupil is changed, and a phase-distribution transforming component which transforms the phase distribution of the light flux such that the phase distribution on the exit pupil is changed.
As a result, the optical scanning device achieves a large allowable degree of depth of focus determined by the entire optical system of the device, and small side lobes.
The depth increasing component may also include an optical component obtained as a result of integrating an intensity-distribution transforming component which transforms the intensity distribution of the light flux such that the intensity distribution on the exit pupil is changed, and a phase-distribution transforming component which transforms the phase distribution of the light flux such that the phase distribution on the exit pupil is changed.
Thereby, the optical scanning device achieves a large allowable degree of depth of focus determined by the entire optical system of the device, and small side lobes, in a very compact configuration.
In another preferred embodiment of the present invention, an optical scanning device includes a light source which emits a light flux, an optical deflector which deflects the light flux, a first optical system which directs the light flux emitted from the light source to the optical deflector, and a second optical system which directs the light flux deflected by the optical deflector onto a surface to be scanned, wherein the first optical system includes an intensity-distribution transforming unit which has at least one intensity-distribution transforming lens and transforms the intensity distribution of the light flux emitted from the light source into an arbitrary intensity distribution.
As a result of this unique structure and arrangement thereof, the optical scanning device simply and reliably produces beam spots having a very small diameter, increases the depth of focus determined by the entire optical system of the device, and, at the same time, decreases the side lobes of the beam spot, without decreasing the quantity of light. Further, it is possible to use components of optical scanning devices in common and to recycle the optical scanning devices.
The first optical system may further include an optical coupling component which couples the light flux emitted from the light source and an optical converging component which converges, at least in the direction perpendicular to the deflection direction, the light flux in proximity to the optical deflector.
As a result of this structure which is relatively simple, i.e., the two optical components and the intensity-distribution transforming unit, the optical scanning device produces beam spots with minimal diameter, increases the depth of focus determined by the entire optical system of the device, and, at the same time, decreases the side lobes of the beams spot, without decreasing the quantity of light. Further, it is possible to use components of optical scanning devices in common and to recycle the optical scanning devices.
The first optical system may further include a collimating lens which transforms the light flux emitted from the light source into an approximately parallel light flux, and a cylindrical lens which has power in the sub-scanning direction and the intensity-distribution transforming unit may transform the intensity distribution of the light flux and emits the resulting light flux in a form of an approximately parallel light flux.
As a result, through a simple structure, i.e., the general-purpose collimating lens and cylindrical lens, and the intensity-distribution transforming unit, the designing of which for transforming an approximately parallel light flux into an approximately parallel light flux is relatively easy, the optical scanning device produces beam spots having a much smaller diameter, increases the depth of focus determined by the entire optical system of the device, and, at the same time, decreases the side lobes of the beam spot, without decreasing in the quantity of light. Further, it is possible to use components of optical scanning devices in common and to recycle the optical scanning devices.
The at least one intensity-distribution transforming lens may also include an axially symmetric aspherical lens.
Thereby, it is possible to miniaturize the device, and, because working of the axially symmetric aspherical lens is relatively easy, it is possible to reduce the cost of the device.
The intensity-distribution transforming unit may also include an axially symmetric aspherical lens in a form of a single lens.
Thereby, it is possible to miniaturize the device, and, because working the axially symmetric aspherical lens in a form of a single lens is relatively easy, it is possible to reduce the cost of the device.
The at least one intensity-distribution transforming lens may include a special toric lens.
Thereby, it is possible to change the intensity distribution of the light flux arbitrarily, and it is possible to increase the degree of freedom in the intensity-distribution transformation.
The intensity-distribution transforming unit may include a special toric lens in a form of a single lens.
Thereby, it is possible to change the intensity distribution of the light flux arbitrarily, and it is possible to increase the degree of freedom in the intensity-distribution transformation.
The light source may include a semiconductor laser which emits a light flux having an approximately Gaussian distribution and the light flux directed onto the surface to be scanned may have an intensity distribution which is a non-Gaussian distribution.
Thereby, it is possible to provide a less-expensive, small-sized optical scanning device.
The diameter of the beam spot of the light flux directed onto the surface to be scanned may be smaller than the diameter of the beam spot obtained when the intensity distribution of the light flux is not changed.
Thereby, through a simple arrangement, it is possible to obtain the high-resolution optical scanning device. Further, it is possible to obtain a small beam spot easily by combining the intensity-distribution transforming unit into the optical scanning device in the related art.
The intensity of the highest side lobe of the light flux directed onto the surface to be scanned may be smaller than 1/e2 of the peak intensity of the light flux.
Thereby, as a result of increasing the depth of focus determined by the entire optical system of the device and also reducing the intensity of the side lobes of the light flux through a very simple structure, the optical scanning device forms very high-quality images. Further, by combining the intensity-distribution transforming unit into the optical scanning device in the related art, it is possible to increase the depth of focus determined by the entire optical system of the device, and, also, at the same time, reduce the intensity of the side lobes of the light flux easily.
Further, by using any of the above-described optical scanning devices as an exposing unit of an image forming apparatus, it is possible to minimize the diameter of the beam spot, and, by increasing the depth of focus determined by the entire optical system of the device, and, also, at the same time, reducing the intensity of the side lobes of the light flux, it is possible to obtain high-resolution, high-quality images.
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The prevalence of airway diseases has increased in recent decades despite therapeutic advances. Among the airway diseases, asthma exacerbations and chronic obstructive pulmonary disease (COPD) are major causes of hospitalization. Both asthma and COPD involve chronic inflammation of the respiratory tract. Despite the presentation of similar symptoms, such as dyspnea, coughing, wheezing and expectoration, these airway diseases have different underlying pathophysiological processes. COPD is a term which refers to a large group of lung diseases characterized by obstruction of air flow that interferes with normal breathing. Emphysema and chronic bronchitis are the most important conditions that compose COPD. (Australian lung foundation, 2006). COPD involves chronic inflammation of the peripheral airways and lung parenchyma, which leads to progressive narrowing of the airways and shortness of breath. On the other hand Asthma is characterized by episodic airway obstruction symptoms and usually starts early in life. The inflammation differs markedly between asthma and COPD, with different cells, mediators, consequences and there is a difference in response to corticosteroids (Clinics (Sao Paulo). 2012; 67(11):1335-43). However, more recently it has become clear that severe asthma is much more similar to COPD, with similarities in the inflammation and sharing a poor response to corticosteroids (J Allergy Clin Immunol. 2013; 131(3):636-45). Interestingly, studies of molecular genetics are now showing that severe asthma and COPD share several gene polymorphisms (Comp Funct Genomics. 2012; 2012: 968267).
Chronic obstructive pulmonary disease (COPD) is a major global health problem that is becoming prevalent, particularly in developing countries. It is one of the most common diseases in the world, with a lifetime risk estimated to be as high as 25%, and now equally affects both men and women (Nature Reviews 2013; 12: 543-559).
Current forms of therapy for COPD are relatively ineffective, as there are no drugs available that considerably reduce disease progression or mortality or have a substantial effect on exacerbations, which are one of the most common causes of hospital admissions.
Long acting bronchodilators are the mainstay of current COPD therapy. There have been several advances in the development of β2-adrenergic receptor agonists and muscarinic receptor antagonists that only need to be administered once a day. Moreover, long acting β2-adrenergic receptor agonists (LABAs) and long-acting muscarinic acetylcholine receptor antagonists (LAMAs) have additive effects on bronchodilation and in the improvement of symptoms, which has led to the development of LABA-LAMA combination inhalers. However, although these drugs produce effective bronchodilation, they fail to treat the underlying inflammatory disease in patients with COPD.
Alternatively or additional to bronchodilators, oral or inhaled corticosteroids could also be used as COPD therapy. But corticosteroids have limitations as long term oral corticosteroid therapy is not recommended and inhaled corticosteroids are known to be associated with increased risk of pneumonia in patients. (www.bcguidelines.ca) Moreover, inhaled corticosteroids are found largely ineffective in significant number of COPD patients as an anti-inflammatory therapy in COPD (Ann Farn Med. 2006; 4(3):253-62). Recently, PDE-4 inhibitors have also been approved for treatment of severe COPD in adults; however, such PDE-4 inhibitors have shown dose limiting side effects (International Journal of COPD 2007; 2(2): 121-129).
With better understanding of the pathophysiology of COPD disease process and recognition of inflammation as an important feature, it is anticipated that disease modifying therapy for COPD targeting underlying inflammation will prove effective the way it has been successful in the treatment of other chronic inflammatory conditions like RA.
Many kinases are involved in the regulation of proinflammatory transcription factors and inflammatory genes. The mitogen-activated protein kinase (MAPK) family includes the p38 kinases, which consists of highly conserved proline-directed serine-threonine protein kinases that are activated in response to inflammatory signals. The p38 MAPK pathway, which is activated by cellular stress, regulates the expression of many inflammatory genes that are involved in COPD (Nature Reviews 2013; 12: 543-559). Proinflammatory cytokines/chemokines and environmental stress activates p38 mitogen activated protein kinase (MAPK) by phosphorylation, which in turn activates p38 MAPK signaling pathway. p38 is involved in the inflammatory responses induced by different stimuli through activation and release of proinflammatory cytokines/chemokines, posttranslational regulation of these genes, and activation of inflammatory cell migration. Therefore, p38 inhibitors present a potentially attractive treatment target for the chronic inflammatory conditions including COPD. Of the four isoforms known so far, p38 alpha is the most abundant in inflammatory cells and has been the most studied.
Over the past two decades, p38 MAPK has been the subject of intense multidisciplinary research. p38 MAPK inhibitors have been shown to be efficacious in several disease models, including rheumatoid arthritis, psoriasis, Crohn's disease, and stroke. Recent studies support a role for p38 MAPK in the development, maintenance, and/or exacerbation of a number of pulmonary diseases, such as asthma, cystic fibrosis, idiopathic pulmonary fibrosis, and chronic obstructive pulmonary disease. There is now an abundant literature which demonstrates that p38 MAPK is activated in chronic inflammatory conditions and that its activation results in the elaboration and release of further proinflammatory cytokines (Expert Opin. Investig. Drugs 2008; 17(10):1411-1425).
Though orally administered small molecule inhibitors targeted to p38 MAPK have proved to be effective in reducing various parameters of inflammation in cells and tissues obtained from patients with COPD in initial clinical studies, the major obstacle hindering the definition and exploitation of the potential utilities of p38 MAPK inhibitors in the treatment of human chronic inflammatory diseases has been the toxicity observed in patients. This has been sufficiently severe to result in the withdrawal from clinical development of many of the compounds progressed. Presently, none of them is yet approved anywhere in the world because of one or the other problems associated with selected molecules such as toxicity or selectivity (Expert Opin. Investig. Drugs 2008; 17(10):1411-1425 & Chest 2011; 139(6):1470-1479).
To overcome these problems of toxicity and selectivity of the target associated with known p38 MAPK inhibitors, some alternative strategies were designed. One of them was to design the treatment approaches wherein p38 kinase inhibitor is dosed directly to the inflamed organ.
Other strategies include developing newer generation p38 MAPK inhibitors with improved selectivity and lesser side effect profile.
There remains a need to identify and develop new p38 MAPK inhibitors which provides desired therapeutic potential along with improved pharmacokinetic profile and/or lesser side effects.
WO1998057937 discloses benzene derivatives as inhibitor of factor Xa with a neutral P1 specificity group.
WO200043384 discloses aromatic heterocyclic compounds for treating conditions involving inflammatory diseases. Disclosed compounds said to inhibit the release of inflammatory cytokines such as IL-1 and TNF.
WO2003072569 discloses 1,4-disubstituted benzofused cycloalkyl urea compounds in treating cytokine mediated disease.
US20080300281 discloses aryl and heteroaryl substituted heterocyclic ureas as p38 kinase inhibitor for the treatment of inflammatory or immunomodulatory diseases. Similarly, WO2008125014 also discloses urea derivatives as p38 kinase inhibitor.
Present invention provides novel indanyl urea derivatives as p38 MAPK inhibitors, which have demonstrated desired efficacy and safety profile.
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1. Field of the Invention
The present invention relates to a bearing mechanism for holding a shaft, a conveying apparatus in which such a bearing mechanism is applied to a conveying portion, and a recording apparatus in which such a conveying apparatus is used to convey a recording medium and an image is formed on the recording medium by a recording head.
2. Related Background Art
Recording apparatuses having a function as a printer, a copying machine or a facsimile, or recording apparatuses used as output devices for composite electronic equipments including a computer or a word processor or as output devices for work stations are designed that an image is on a sheet to be recorded (recording medium) such as a paper sheet or a plastic thin sheet based on image information.
Such recording apparatuses can be divided into an ink jet system, a wire dot system, a thermal system, a laser beam system and the like, in dependence upon a recording style.
In a serial type recording apparatus having a serial scanning system in which main scanning is effected along a direction transverse to a conveying direction (sub-scanning direction) of the sheet to be recorded, the entire image is recorded by recording means mounted on a carriage movable along the sheet to be recorded, by repeating one-line recording effected by the main scanning and a predetermined amount sheet feeding (pitch conveyance) alternately.
Among the above-mentioned recording apparatuses, the recording apparatus of ink jet type (ink jet recording apparatus) is designed to effecting the recording by discharging ink from recording means (a recording head) onto the sheet to be recorded. This recording apparatus has advantages that the recording means can easily be made compact, a fine image can be recorded at a high speed, the recording can be effected on a plain paper without special treatment, a running cost is inexpensive, noise can be suppressed due to non-impact recording and a color image can easily be recorded by using multi color inks.
Now, conveying means of a recording apparatus according to an earlier technology will be described with reference to FIGS. 13 to 18. FIG. 13 is a front view of such a recording apparatus and FIG. 14 is a sectional view of the recording apparatus.
A sheet feeding portion 503 is attached to a chassis 508 formed by bending a metal sheet. The sheet feeding portion 503 includes a conveying roller 536 for conveying a sheet Pxe2x80x2 and a PE sensor (sheet end detecting device) 532.
The conveying roller 536 is constituted by wounding an elastic material such as rubber around a surface of a metal shaft and is attached to the chassis 508 by mounting both ends of the metal shaft within conductive bearings 538, 539. A conveying roller tension spring 681 is disposed between the bearing 538 and the conveying roller 536 to apply load to the conveying roller 536 on rotating thereby to provide stable conveyance. Namely, by biasing the conveying roller 536 through the spring 681, predetermined load is applied.
The conveying roller 536 is attached as follows. First of all, one end of the metal shaft of the conveying roller 536 is inserted into the bearing 539 and then is attached to the chassis 508. Then, the other end of the metal shaft of the conveying roller 536 is passed through a cut out portion of the chassis 508. Then, the conveying roller tension spring 681 is attached and the bearing 538 is fitted into the chassis 508 while inserting the bearing 538 onto the shaft of the conveying roller 536 from outside. In this case, a pawl portion 686 of the bearing 538 enters into a groove portion 661 formed in the conveying roller 536, so that the conveying roller 536 is secured to the chassis 508. An assembled condition is shown in FIG. 15B.
A plurality of driven pinch rollers 537 abut against the conveying roller 536. The pinch rollers 537 are held by a pinch roller guide 530 pivotally mounted on a shaft 530a and are biased by a pinch roller spring 531 to urge the pinch rollers 537 against the conveying roller 536, thereby providing a conveying force for the sheet Pxe2x80x2.
The pinch rollers 537 are arranged so that they do not cover the entire area of the sheet Pxe2x80x2 but divided to hold only predetermined ranges of the sheet. In this case, the rotation shaft 530a of the pinch roller guide 530 is attached to bearings of an upper guide 533 for rotation.
Further, an inlet of the sheet feeding portion 503 to which the sheet Pxe2x80x2 is conveyed is provided with the upper guide 533 and a platen 534 which guide the sheet Pxe2x80x2. The upper guide 533 is provided with a PE sensor lever 535 for transmitting detection of leading and trailing ends of the sheet Pxe2x80x2 to the PE sensor 532.
The platen 534 is positioned by a bearing portion 642 fitted and slidable on the conveying roller 536 to be attached to the chassis 508, and an attachment shaft 643 directly attached to the chassis 508. Further, a sheet holding-down portion 544 for conveying a side edge of the sheet Pxe2x80x2 is provided at a sheet reference side of the platen 534.
With this arrangement, even if the side edge of the sheet Pxe2x80x2 is deformed or curled, the side edge of the sheet is prevented from floating to interfere with a carriage 550 or the recording head 507.
The recording head 507 for forming an image based on image information is disposed at a downstream side of the conveying roller 536 in a conveying direction of the sheet Pxe2x80x2.
In the above-mentioned arrangement, the sheet Pxe2x80x2 fed to the sheet feeding portion 503 is guided by the platen 534, pinch roller guide 530 and upper guide 533 to be sent to a pair of rollers (conveying roller 536 and pinch rollers 537).
In this case, the PE sensor lever 535 detects the leading end of the sheet Pxe2x80x2 being conveyed, thereby determining a printing position of the sheet Pxe2x80x2. Further, the sheet Pxe2x80x2 is conveyed on the platen 534 by rotating the pair of rollers 536, 537 by an LF motor (not shown).
Incidentally, the recording head 507 is an easy exchangeable ink jet recording head integrally formed with an ink tank. In this recording head 507, heat can be applied to ink by a heater or the like.
The ink is film-boiled by the heat to cause growth and contraction of a bubble to generate a change in pressure by which the ink is discharged from a nozzle 570 of the recording head 507, thereby forming the image on the sheet Pxe2x80x2.
In a sheet discharging portion 504, a transmitting roller 540 abuts against the conveying roller 536 and further abuts against a sheet discharging roller 541. Accordingly, a driving force of the conveying roller 536 is transmitted to the sheet discharging roller 541 through the transmitting roller 540. Further, a spur roller 542 abuts against the sheet discharging roller 541 to be driven by rotation of the sheet discharging roller 541.
The spur roller 542 is attached to a spur stay 641 of integral type provided on the platen 534.
By providing the spur stay 641 integral with the platen 534 in this way, since dimensions of the spur roller 542 and the sheet discharging roller 541 can be controlled within the same part, a dimensional relationship can be kept stably.
Further, the spur stay 641 has a partially cut-away portion 641a. When the head 507 is exchanged, the carriage 550 is moved up to the cut-away portion 641a to create a space through which a hook lever 553 for mounting and dismounting the head 507 can be manipulated.
With the above-mentioned arrangement, the sheet Pxe2x80x2 on which the image was formed in a carriage portion 505 is pinched by a nip between the sheet discharging roller 541 and the spur roller 542 to be conveyed and discharged onto a sheet discharging tray (not shown).
However, the above-mentioned technique has the following problems.
In the attachment of the conveying roller 536 to the chassis 508, as shown in FIGS. 5A and 15B, the groove portion 661 must be formed in the metal shaft of the conveying roller 536 and the pawl portion 686 must be provided on the bearing 538 corresponding to the groove 661 (FIG. 15A). Thus, the number of manufacturing steps is increased, thereby making the manufacturing cost more expensive. In addition, when the pawl 686 is disengaged, the pawl may be damaged, thereby causing a problem regarding operability.
Further, since the pinch rollers 537 do not hold down the entire area of the sheet Pxe2x80x2, as shown in FIG. 16, if the side edge of the sheet Pxe2x80x2 is warped, the sheet cannot enter below the sheet holding-down portion 644 but rides over the sheet holding-down portion 644, with the result that the side edge of the sheet Pxe2x80x2 may interfere with the carriage 550 or the recording head 507.
Furthermore, depending upon the kind of the sheet Pxe2x80x2 or surrounding environment such as temperature and humidity, a trailing end of the sheet Pxe2x80x2 may be floating after it was discharged. In such a case, if the trailing end of the sheet Pxe2x80x2 is pinched between the spur roller 542 and a spur roller cleaner 543 or a spur roller attaching portion 641 of the platen 534, poor sheet discharging will occur or the sheet Pxe2x80x2 will be damaged by the spur roller 542 (FIG. 17).
The present invention aims to eliminate the above-mentioned conventional drawbacks, and an object of the present invention is to provide a bearing mechanism in which a groove portion in a shaft and a pawl portion on a bearing corresponding to the groove portion are not required and which can improve production efficiency and operability, and a conveying apparatus which has such a bearing mechanism and in which, when a driven roller is not located at an entire area of a sheet to be conveyed, a side edge of the sheet to be conveyed can be directed correctly not to damage the sheet to be conveyed after the sheet was discharged, and a recording apparatus having such a conveying apparatus.
To achieve the above object, the present invention provides a bearing mechanism comprising a supporting plate having an aperture portion for holding a bearing, and the bearing including a fitting portion to be fitted into the aperture portion of the supporting plate and having a shaft bore into which a shaft is to be inserted and two pinching portions protruded outwardly and axially spaced apart from each other by a distance corresponding to a thickness of the supporting plate at the fitting portion, and wherein the supporting plate is provided, around the aperture portion thereof, with cut-away portions through which the pinching portions can pass, and the pinching portions has fixing means for fixing the rotation of the bearing at a rotated position where the supporting plate is pinched by the pinching portions from inside and outside, by pinching the supporting plate from inside and outside by moving the pinching portions from the cut-away portions by rotating the bearing after the fitting portion of the bearing was fitted into the aperture portion of the supporting plate.
The fixing means may comprise a protrusion provided one of the pinching portion of the bearing and the supporting plate, and depression or hole portion provided in the other of the pinching portion of the bearing and the supporting plate.
One of the two outwardly protruded pinching portions may have a configuration greater than a configuration of the opposed other pinching portion, and an opening greater than the configuration of the other pinching portion may be provided at the opposed position.
The bearing may have a handle portion.
Further, in a conveying apparatus having a conveying roller and bearing mechanisms disposed at both sides of the conveying roller, at least one of the bearing mechanisms may comprise the above-mentioned bearing mechanism.
Further, in a conveying apparatus having a conveying means comprising a conveying roller and a driven roller opposed to the conveying roller with the interposition of a conveying path and divided into a plurality of roller portions along an axial direction, a guide member for holding-down a side edge of a sheet to be conveyed may be disposed at a position where the driven roller is not located and the side edge of the sheet to be conveyed is passed.
The conveying means may have a driven roller holding portion for holding the driven roller and the guide member may be provided on the driven roller holding portion.
The guide member may have a radius same as that of the driven roller in a sectional configuration at a nip portion between the conveying roller and the driven roller and may have a tapered configuration smoothly spaced apart from the conveying path, from the nip portion toward an upstream side of the conveying path.
Further, in a conveying apparatus having a sheet discharging roller and a spur roller opposed to the sheet discharging roller with the interposition of a conveying path, protection member for preventing a sheet from being caught up may be disposed between the conveying path and the spur roller at a downstream side of the conveying path.
The protection members may be provided on a spur roller attaching portion and may be disposed at least outside of both outermost spurs of the spurs.
Further, in a recording apparatus having a recording head for forming an image on a recording medium as a sheet to be conveyed, a carriage for holding the recording head and capable of scanning in a main scanning direction, guide means for guiding the carriage in the main scanning of the carriage, and conveying means for conveying the recording medium in a sub-scanning direction, the above-mentioned conveying apparatus may be provided.
Further, in a recording apparatus having a recording head for forming an image on a recording medium as a sheet to be conveyed, a carriage for holding the recording head and capable of scanning in a main scanning direction, guide means for guiding the carriage in the main scanning of the carriage, and conveying means for conveying the recording medium in a sub-scanning direction, the conveying means may comprise a conveying roller, a driven roller opposed to the conveying roller and divided into a plurality of roller portions along an axial direction, a platen for defining a guide surface during recording, and a holding-down member provided on the platen and adapted to prevent a side edge of a recording medium from floating, and a guide member for holding-down the side edge of the recording medium may be disposed at a position where the driven roller is not located and the side edge of the sheet to be conveyed is passed, and the guide member may comprise the holding-down member.
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Field of the Invention
The present invention relates to methods of preventing and eliminating the formation of trisulfide bonds in proteins during protein production and purification procedures.
Background Art
Recombinant proteins, and in particular, monoclonal antibodies (mAbs), have become an important class of therapeutic compounds employed for the treatment of a broad range of diseases. Recent successes in the field of biotechnology have improved the capacity to produce large amounts of such proteins. However, extensive characterization of the products demonstrates that the proteins are subject to considerable heterogeneity. For example, molecular heterogeneity can result from chemically-induced modifications such as oxidation, deamidation, and glycation as well post-translational modifications such as proteolytic maturation, protein folding, glycosylation, phosphorylation, and disulfide bond formation. Molecular heterogeneity is undesirable because therapeutic products must be extensively characterized by an array of sophisticated analytical techniques and meet acceptable standards that ensure product quality and consistency.
Antibodies (or immunoglobulins) are particularly subject to such structural heterogeneity due to the fact that they are large, multi-chain molecules. For example, IgG antibodies are composed of four polypeptide chains: two light chain polypeptides (L) and two heavy chain polypeptides (H). The four chains are typically joined in a “Y” configuration by disulfide bonds that form between cysteine residues present in the heavy and light chains. These disulfide linkages govern the overall structure of the native H2L2 tetramer. Overall, IgG1 antibodies contain four interchain disulfide bonds, including two hinge region disulfides that link the H chains, and one disulfide bond between each heavy H and L chain. In addition, twelve intrachain disulfide linkages may involve each remaining cysteine residue present in the molecule. Incomplete disulfide bond formation, or bond breakage via oxidation or beta-elimination followed by disulfide scrambling, are all potential sources of antibody heterogeneity. In addition, a further type of modification, namely trisulfide (—CH2—S—S—S—CH2—) bond formation, was recently reported within the interchain, hinge region bonds of a human IgG2 antibody. See, Pristatsky et al., Anal. Chem. 81: 6148 (2009).
Trisulfide linkages have previously been detected in superoxide dismutase (Okado-Matsumoto et al., Free Radical Bio. Med. 41: 1837 (2006)), a truncated form of interleukin-6 (Breton et al., J. Chromatog. 709: 135 (1995)), and bacterially expressed human growth hormone (hGH) (Canova-Davis et al., Anal. Chem. 68: 4044 (1996)). In the case of hGH, it was speculated that trisulfide formation was promoted by H2S released during the fermentation process. See, International Published Patent Application No. WO 96/02570. Consistent with this hypothesis, the trisulfide content of hGH was increased by exposure to H2S in solution. See, U.S. Pat. No. 7,232,894. In addition, exposing bioreactor material or bacterial lysate to an inert gas inhibited trisulfide formation, apparently by stripping H2S from the system. See, International Published Patent Application No. WO 2006/069940.
Conditions that influence the level of trisulfide in hGH generated during purification from bacteria have previously been reported. For example, the presence of alkali metal salts has been reported to inhibit increases in trisulfide bonds during downstream protein processing. See, U.S. Pat. No. 7,232,894. Furthermore, treatment of hGH with reduction-oxidation (REDOX) compounds, including L-cysteine, in solution was found to convert trisulfide bonds to disulfide bonds. See, International Published Patent Application No. WO 94/24157. For example, treatment of purified IgG2 with a 20-fold molar ratio of L-cysteine in solution was found to convert hinge region trisulfide bonds to disulfides during sample preparation for analytical studies. See, Pristatsky et al., Anal. Chem. 81: 6148 (2009).
Unfortunately, removal of trisulfide bonds by exposure to cysteine in solution has several drawbacks, in particular for large scale processing. For example, large quantities of cysteine are required. This method also necessitates a separate step to remove cysteine from the sample after trisulfide bonds are removed. In addition, removal of trisulfide bonds by exposure to cysteine in solution can promote aggregation through the formation of undesirable disulfide linkages. Therefore, in order to address the limitations of previous methods for reducing trisulfide bonds, the methods described herein provide efficient and improved means for preventing and eliminating the formation of trisulfide bonds in proteins (such as, for example, in antibodies) during production and purification procedures used in the manufacture of such proteins.
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1. Field of the Invention
The present invention relates to a novel antitumor protein hybrid and a process for the preparation thereof. More particularly, the present invention relates to a novel protein hybrid, specifically useful as a remedy for malignant tumor, which has a moiety consisting of the antitumor immunoglobulin and a moiety substantially consisting of the fragment A of a diphtheria toxin, and a process for the preparation of the same.
2. Description of the Prior Art
Many drugs (anti-cancer agents) have hitherto been known to cure malignant tumor or cancer; however, since these drugs display considerable toxicity not only to tumor cells but also to normal cells, they can not be administered in doses large enough to perish tumor cells, which is their inherent demerit. To correct such demerit, several attempts have been made, wherein an anti-cancer agent or cytotoxic protein toxin is conjugated to a special carrier to make it attractive to tumor cells selectively. There exists an antitumor antibody (antitumor immunoglobulin), though very small in amount, in the blood or on the surface of tumor cells of a cancer patient. The antitumor antibody has hitherto been practically been obtained by first immunizing an animal with the cancer tissue and then absorbing the obtained antiserum with the normal tissue of a human being. Antitumor antibodies, whether autochthonous, allogenic, or xenogenic, do not necessarily display a cytotoxic effect against tumor cells; however, they have a common nature of binding to cancer cells with an extremely high selectivity. Antitumor antibodies have, therefore, been utilized as a carrier to make an anti-cancer agent or protein toxin bind to tumor cells selectively.
For instance, U.S. Pat. No. 4093607 discloses an antitumor drug comprising an antibody-drug conjugate in which an anti-cancer agent such as daunomycin, etc. is covalently bonded to the Fab' dimer of an antitumor immunoglobulin. This conjugate is a good one in respect of a fact that it binds the drug to a target tumor cell with some selectivity. But, in general, as the anti-cancer agent such as daunomycin, etc., when liberated from the conjugate prior to its entry to the cell, displays cytotoxicity not only against tumor cells but also against normal cells, it does not work satisfactorily in terms of efficacy to destroy tumor cells only. Moreover its cytotoxicity is not completely strong, either.
Studies have also been made as to the use of a diphtheria toxin, one of the protein toxins which are much stronger in cytotoxicity, in the place of an anti-cancer agent.
For instance, F. L. Moolten et al. report that they prepared a conjugate by conjugating a rabbit anti-SV40 antibody to a diphtheria toxin with glutaraldehyde as coupling agent and were able to protect hamsters challenged with SV40-transformed 3T3 cells by administering the conjugate to the hamsters (Journal of the National Cancer Institute, vol. 55, pp. 473-477, 1975).
P. E. Thorpe et al. report that a conjugate prepared by coupling a diphtheria toxin to an antilymphocytic antibody by means of chlorambucil greatly inhibited the protein synthesis of human lymphoblastoid cells, CLA4 (Nature, Vol. 271, pp. 752-754, 1978).
These studies show that a conjugate of diphtheria toxin and antibody displays toxicity against the tumor cells selectively. However, these conjugates, when used as an antitumor drug, are supposed to have some demerits as mentioned below. The first of the demerits is that the nonspecific toxicity of diphtheria toxin is not nullified. More particularly, the object of these methods is to concentrate diphtheria toxin on the surface of tumor cells by the aid of antitumor antibody; however, since the conjugate contains the whole molecule of diphtheria toxin in its composition, it is apt to bind to normal cell surface receptors for diphtheria toxin and display cytotoxicity against normal cells. The second of the demerits is found with the method of crosslinking the antibody with the diphtheria toxin. Many of the cross-linking agents such as glutaraldehyde, toluene diisocyanate, chlorambucil, etc. effect the cross-linking not only between the antibody and the toxin but also between the antibody and the antibody, and the toxin and the toxin, and moreover, they effect the formation of intramolecular bonds in the antibody and in the toxin molecule, thus causing the formation of undesirable products and decrease or loss of the antitumor activity.
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{
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In a computing system, the rate at which data is accessed from rotating media (e.g., hard disk drive, optical disk drive) (hereinafter “disk”) is generally slower than the rate at which a processor processes the same data. Thus, despite a processor's capability to process data at higher rates, the disk's performance often slows down the overall system performance, since the processor can only process data as fast as the data can be retrieved from the disk.
A cache system may be implemented to at least partially reduce the disk performance bottleneck by storing selected data in a high-speed memory location designated as the disk cache. Then, whenever data is requested, the system will look for the requested data in the cache before accessing the disk. This implementation improves system performance since data can be retrieved from the cache much faster than from the disk.
Certain access patterns, however, may decrease the efficiency of the cache system. For example, applications that repeatedly flush or overwrite the contents of the cache without using any of the cached data may render the cache system useless. When such access patterns arise, it may be better to circumvent the cache and access the disk directly.
Streams may be used to detect regular access patterns where it may be better to access the disk directly instead of first looking in the disk cache. A stream is a sequential, time-ordered set of read or write requests. Each stream is associated with a request size. A stream's request size is the amount of data to be read or written by the first request in the stream, though this request size may change over the life of the stream.
Currently, a stream's request size is used to determine whether a stream is suitable for direct disk access. For example, a stream having a small request size may not be suitable for direct disk access because small requests tend to involve data that is accessed frequently and is desirable to be cached. On the other hand, a stream having a large request size may be suitable for direct disk access because large requests tend to involve data that is not accessed frequently and is not desirable to be cached.
Despite of the above, some streams (e.g., streams generated by applications that access the entire disk or a large portion of the disk, such as backup, virus scan or desktop search software) have small request sizes but are not good candidates for caching, because when data accessed by said streams is cached, the cached data is flushed before it can be used, rendering the cache system useless.
Such result is obviously undesirable. Therefore, systems and methods are needed that can overcome the above shortcomings.
Features, elements, and aspects of the invention that are referenced by the same numerals in different figures represent the same equivalent, or similar features, elements, or aspects, in accordance with one or more embodiments.
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{
"pile_set_name": "USPTO Backgrounds"
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1. Field of the Invention
The present invention relates to an apparatus and method for reducing banding artifacts during ink jet printing, in particular, by modulating the swath boundaries of a printhead using variable interlacing percentages.
2. Description of the Related Art
Thermal ink jet printers apply ink to a print medium such as paper by ejecting ink drops from one or more printheads through a column or array of nozzles. The printheads are mounted on a carriage assembly that is movable in a lateral direction across the print medium and ink drops are selectively ejected from the nozzles at corresponding ink drop placement locations. Specifically, each nozzle is associated with a heater resistor that generates heat when sufficient current passes through it, with the generated heat causing ink within an associated ink reservoir to be ejected from the nozzle. The printheads are moved in a series of lateral passes or swaths across the print medium, and between printing passes, the print medium is advanced in a longitudinal or advance direction. Since the printhead moves in a direction that is perpendicular to the advance direction of the print medium, in each pass, each nozzle passes in a linear manner over the print medium. The line associated with each nozzle which overlies the print medium is commonly referred to as a raster or raster line. A plurality of raster lines extending across the image area of the print medium are disposed vertically adjacent to each other in the advance direction.
A printer controller determines which resistors will be “fired” and the proper firing sequence so that a desired image is printed. However, ink drop placement errors can occur due to a number of factors, including incorrect timing or variable ink drop flight time. Further, if the amount that the print medium is advanced between printing passes is not precisely equal to a theoretical advance amount, either adjacent printed lines can overlap, or be visibly distant from one another. These effects of incorrect line spacing are referred to as line continuation errors.
Known methods exist for ameliorating the effects of ink drop placement errors. One such method is known as shingling or interlaced printing. For a two pass shingling mode (i.e., 50% interlace level), approximately 50% of the ink drops are placed on any given printhead pass. The candidate dots in a first pass are selectively addressed according to a checkerboard pattern, with the remaining dots printed on the next pass, after the print medium is advanced. For a printhead with vertically disposed colors, and a raster which contains cyan, magenta and yellow dots, printing at a 50% interlace level requires that the printhead be passed at least six times across each raster line. Employing a shingling method generally improves print quality, while at the same time reducing the printing speed as compared to printing without shingling.
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{
"pile_set_name": "USPTO Backgrounds"
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Documents are commonly produced containing a plurality of images and such documents often have large file sizes. As such, computer systems used to process such large documents into displayable images require a substantial amount of processing time.
Downsampling is a technique used to decrease the size of a document by reducing the number of pixels in an image. Image downsampling is used to decrease extraneous image data. Downsampling techniques include, but are not limited to, subsampling, bicubic downsampling, and average downsampling. Decreasing the size of the document allows a document to be more easily and quickly, downloaded, transmitted and/or stored.
Image downsampling can be used to optimize, for example, Portable Document Format (PDF) files. Images are often compressed in PDF files in order to increase speed and functionality. The speed and functionality is increased because a compressed image is smaller and has less bytes. Due to the decreased number of bytes, a machine may process (i.e., upload, download, save and/or print) the image at a faster speed.
For example, Acrobat® 8 from Adobe Systems, Inc. deletes an image if that image occurs multiple times within an electronic document file. Acrobat® 8 deletes a redundant image if it is fully redundant or identical in all aspects. By downsampling the image, a smaller PDF file can be created because the image is stored only a single time in the document. References to the image are used when there are multiple instances of the image in the document.
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{
"pile_set_name": "USPTO Backgrounds"
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Materials with controlled size pore structures on the atomic dimension have been used as molecular sieves for sorption, catalysts, and ion exchange resins. The most well known of these materials are zeolites which is a name derived from the Greek, meaning boiling stones. The controlled pore structure of zeolites result from the chemical arrangement of (Al,Si)O.sub.4 tetrahedra which share all their oxygen vertices with nearby tetrahedra and are joined together to give rise to large cavities and controlled size windows into these cavities. The alumino-silicate framework forming the zolite usually has a negative charge which is balanced by alkalies and alkaline earths located outside the tetrahedra in the channels. These materials have proven to be useful in a variety of industrial applications because of the shape and chemistry of the pore structures formed by the linked alumino silicate tetrahedra. Pores in these materials can be monodisperse and small enough to act as molecular sieves so that different apparent surface areas are obtained according to the size of the absorbate molecules. The chemistry of the framework and the counter ions neutralizing electrical charge on the framework can have many catalytic applications. In particular, the controlled pore structure can produce shape selective effects in catalysis (see, e.g., N.Y. Chen, U.S. Pat. No. 3,630,966, Dec., 28, 1971).
In all zeolites, the chemical composition is intimately related to the size of the pore structure. Maximum pore size in zeolites is related to the geometric arrangement of the alumino-silicate tetrahedra and is always less than about 10 .ANG..
The present invention describes zeolite like materials made using physical fabrication techniques. Physical fabrication techniques such as etching, deposition and lithographic patterning have been extensively used for the production of microelectronics. Features with approximately one micron critical dimensions are routinely created using these methods for microelectronic circuitry; however, to produce porous materials capable of molecular sieving requires reducing the feature size by three orders of magnitude.
Reduction in feature size is obtained by using new methods for defining the pattern used with thin film etching and deposition techniques. By using physical fabrication techniques to produce controlled porosity on the molecular dimension, new degrees of freedom in constructing zeolite like materials are obtained. Physical fabrication techniques decouple the interrelationship between size and chemistry of the pore structures. Thus, the composition of zeolite like materials made with physical fabrication techniques is not limited to aluminosilicates. Using the physical fabrication techniques described herein it is possible to make zeolite-like materials from a wide variety of semiconductors, metals and insulators. Shape of pore structures made with physical fabrication techniques can be significantly different from those in natural and synthetic aluminosilicate zeolites. For example, the pore structure occuring in the physically fabricated etched superlattice structure described herewith is two dimensional rather than one dimensional as is the case for conventional zeolite materials. Precise control of pore size can be obtained using physical fabrication allowing for a choice of critical dimensions in the size range from approximately 10 to more than 10,000 .ANG.. This is a size range not readily accessible with conventional zeolite materials. With these broad ranges of flexibility of construction, etched superlattice zeolite-like materials made by physical fabrication techniques have a control over pore size and chemistry which is not available with conventional aluminosilicate zeolites. Since pore size and chemistry are the determining factors in use of zeolites for separations and catalysis, etched superlattice zeolite-like materials will have many inherent advantages in these areas. In particular, etched superlattices provide a new class of micro-porous shape selective materials that significantly expand the range of behavior spanned by conventional zeolites. The term "shape selective" or "shape selective activity" is taken throughout this patent to mean a material whose interaction with chemical molecules can be different depending on the molecular size or shape.
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{
"pile_set_name": "USPTO Backgrounds"
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It is known to provide one or more coded data structures on a surface that can be read and decoded by a suitable sensing device. Various embodiments of such a device incorporating an optical sensor are described in many of the documents incorporated into the present application by cross-reference.
The coded data structures disclosed in these documents include target features that enable the sensing device to identify the position of each structure. The relative positions of the features within each structure can also be interpreted to determine perspective distortion of the structure as sensed, enabling perspective correction to be performed on the sensed data. However, to enable the sensing device to decode the data in the structure, it is necessary that the rotational orientation of the structure be determined. Typically, this is achieved by providing at least one feature that is rotationally asymmetric in some way. For example, in one embodiment, a keyhole-shaped feature is provided that can be located with respect to the other features, and then recognised to ascertain the rotational orientation of the structure in relation to the sensing device. The actual data that is encoded in the data structure can then be decoded, since its position in the data structure can be inferred from the structure's position and rotational orientation.
Disadvantages with this arrangement include the need to dedicate space to one or more orientation features, and the difficulty of including redundancy in such features for the purposes of allowing rotational orientation determination in the presence of damage to the features. It is desirable, therefore, to encode orientation information both more space-efficiently and in an error-detectable and/or error-correctable fashion.
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{
"pile_set_name": "USPTO Backgrounds"
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The invention relates to a clock and data recovery circuit, and in particular to a clock and data recovery circuit employed in communication systems.
In a typical communication system, a transmitter generates data signals according to its clock and transmits the data signals to a receiver through channels. To correctly interpret the data signals, the receiver reads the data signals according to a clock synchronized with the transmitter's clock. The receiver thus requires a clock recovery system to recover the data signal from the transmitter. At least two clock recovery techniques are currently used. First, the transmitter's clock may be transmitted to the receiver on a channel parallel with the channel carrying the data signals. The receiver can then estimate the phase of the data signals from the phase of transmitter's clock. This technique however, is disadvantageous in that it requires an additional channel. Alternately, the phase of the data signals may be recovered directly from information carried in the data signals themselves.
FIG. 1 shows a conventional clock and data recovery circuit. The clock and data recovery circuit 1 comprises a control unit 10, a gated voltage controlled oscillator (GVCO) 11, a D flip-flop 12, and a phase locked loop (PLL) 13. The PLL 13 comprises a phase/frequency detector 130, a charge pump 131, a filter 132, and a GVCO 133. The control unit 10 controls the GVCO 11 to receive a data signal D1. The phase/frequency detector 130 of the PLL 13 receives a reference clock Cf1, and the filter 132 controls the GVCOs 11 and 133. The GVCOs 11 and 133 respectively output oscillated clocks CK1 and CK2 corresponding to the data signal D1. The D flip-flop 12 reads the data signal D1 according to the clock CK1, thus estimating the phase of the data signal D1 correctly.
In ideal conditions, the clock CK1 synchronizes with the clock CK2. However, since the processes of the GVCOs 11 and 133 may not match, difference between the phases of the locks CK1 and CK2 is increased with time, such that the D flip-flop 12 may incorrectly trigger the data signal D1.
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{
"pile_set_name": "USPTO Backgrounds"
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