Catalyst system suitable for polymerizing unsaturated monomers and comprising active constituents obtainable by reacting

The present invention relates to a catalyst system suitable for polymerizing unsaturated monomers and comprising active constituents obtainable by reacting
A) a transition metal compound with
B) aluminum trifluoride,
C) a cation-forming compound and, if desired,
D) further components.
The present invention also relates to the use of aluminum trifluoride as activator in a catalyst system, to a process for preparing a catalyst system, to a process for preparing polymers based on monomers having Cxe2x80x94C double bond and/or Cxe2x80x94C triple bond, and to the use of a catalyst system for forming carbon-carbon covalent bonds or carbon-heteroatom covalent bonds.
It is known that the following reactions, for example, can be performed in preparing metal compounds that are active in polymerization, such as metallocenium ion catalysts:
a) metallocenedialkyl+strong cation-forming compound (Lewis acid), X. Yang, C. L. Stern. T. F. Marks, J. Am. Chem. Soc. 1991, 113, 3623-5
b) metallocenedialkyl+Brxc3x6nsted acid with non-nucleophilic anion, EP 0 591 756 (Idemitsu Kosan)
c) metallocene compound+aluminoxane EP 0 035 242 (BASF AG)
Reactions a) and b) have the common feature that they are severely restricted in terms of the choice of activator; that is, of the strong cation-forming compound and of the Brxc3x6nsted acid with non-nucleophilic anion. Only very specific, preferably perfluoroaromatic, boron compounds lead to a usable activator. Reaction c) requires large amounts of expensive aluminoxane, which is a disruptive factor in the resulting polymer.
There is therefore a desire to prepare active catalysts based on inexpensive, readily available and widely applicable activators. R. Taube in DD 265 150 A1 describes the polymerization of 1,3-butadiene in the presence of a mixture of nickel cyclodecatriene or nickel acetylacetonate with aluminum triethyl and aluminum trifluoride. The polymerization of other monomers, especially alkenes or styrene and its derivatives, and other catalysts, comprising aluminum trifluoride plus a cation-forming compound, are not mentioned.
It is an object of the present invention to provide a catalyst system which is not severely restricted in terms of the choice of activator. This means that even customary cation-forming compounds commonly employed in preparative organic chemistry, such as hexafluoroantimonic acid HSbF6, antimony pentafluoride SbF5, and trifluoromethanesulfonic acid CF3SO3H, could be used to generate transition metal catalysts. In addition, the catalyst system ought to be able to function per se as a supported catalyst or to be convertible to such a catalyst.
We have found that this object is achieved by the catalyst system defined at the outset, by the use of aluminum trifluoride in the catalyst system defined at the outset, by a process for preparing the catalyst system defined at the outset, by a process for preparing polymers using the catalyst system defined at the outset, and by the use of the catalyst system defined at the outset for forming carbon-carbon covalent bonds or carbon-heteroatom covalent bonds.
Suitable transition metal compounds A) are in principle all those which react with components B), C) and, if used, D) chemically to form an active catalyst.
Examples of highly suitable transition metal compounds A) are transition metal complexes with a ligand of the formulae F-I to F-IV
where the transition metal is selected from the elements Ti, Zr, Hf, Sc, V, Nb, Ta, Cr, Mo, W, Fe, CO, Ni, Pd and Pt or from an element of the rare earth metals. Preference is given here to compounds of nickel and palladium as the central metal.
E is an element from group 15 of the Periodic Table of the Elements (5th main group), preferably N or P and, with particular preference, N. The two atoms E in a molecule can be the same or different.
The radicals R1A to R18A, which can be the same or different, are as follows:
R1A and R4A are independently of one another hydrocarbon radicals or substituted hydrocarbon radicals, preferably those where the carbon adjacent to the element E is attached to at least two carbon atoms.
R2A and R3A are independently of one another hydrogen, hydrocarbon or substituted hydrocarbon radicals or else together form a ring system which may also include one or more heteroatoms.
R6A is hydrocarbon or substituted hydrocarbon radicals,
R5A is hydrogen, hydrocarbon or substituted hydrocarbon radicals,
R6A and R5A may also together form a ring system.
R8A is hydrocarbon or substituted hydrocarbon radicals,
R9A is hydrogen, hydrocarbon or substituted hydrocarbon radicals,
R8A and R9A may also together form a ring system.
R7A each independently of the others is hydrogen, hydrocarbon or substituted hydrocarbon radicals, it also being possible for two radicals R7A to form a ring system. n is an integer between 1 and 4, preferably 2 or 3.
R10A and R14A independently of one another are hydrogen, hydrocarbon or substituted hydrocarbon radicals.
R11A, R12A and R13A independently of one another are hydrogen, hydrocarbon or substituted hydrocarbon radicals, where two or more radicals R11A, R12A and R13A may also together form a ring system.
R15A and R18A independently of one another are hydrogen, hydrocarbon or substituted hydrocarbon radicals.
R16A and R17A independently of one another are hydrogen, hydrocarbon or substituted hydrocarbon radicals.
Examples of particularly suitable compounds F-I to F-IV are:
Di(2,6-di-i-propylphenyl)-2,3-dimethyldiazabutadienepalladium dichloride Di(di-i-propylphenyl)-2,3-dimethyldiazabutadienenickel dichloride Di(2,6-di-i-propylphenyl)-dimethyldiazabutadienepalladium dimethyl Di(2,6-di-i-propylphenyl)-2,3-dimethyldiazabutadienenickel dimethyl Di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienepalladium dichloride Di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienenickel dichloride Di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienepalladium dimethyl Di(2,6-dimethylphenyl)-2,3-dimethyldiazabutadienenickel dimethyl Di(2-methylphenyl)-2,3-dimethyldiazabutadienepalladium dichloride Di(2-methylphenyl)-2,3-dimethyldiazabutadienenickel dichloride Di(2-methylphenyl)-2,3-dimethyldiazabutadienepalladium dimethyl Di(2-methylphenyl)-2,3-dimethyldiazabutadienenickel dimethyl Diphenyl-2,3-dimethyl-diazabutadienepalladium dichloride Diphenyl-2,3-dimethyl-diazabutadienenickel dichloride Diphenyl-2,3-dimethyl-diazabutadienepalladium dimethyl Diphenyl-2,3-dimethyl-diazabutadienenickel dimethyl Di(2,6-dimethylphenyl)-azanaphthenepalladium dichloride Di(2,6-dimethylphenyl)-azanaphthenenickel dichloride Di(2,6-dimethylphenyl)-azanaphthenepalladium dimethyl Di(2,6-dimethylphenyl)-azanaphthenenickel dimethyl 1,1xe2x80x2-Dipyridylpalladium dichloride 1,1xe2x80x2-Dipyridylnickel dichloride 1,1xe2x80x2-Dipyridylpalladium dimethyl 1,1xe2x80x2-Dipyridylnickel dimethyl
Further particularly suitable transition metal compounds A) are those having at least one cyclopentadienyl-type ligand, which are commonly known as metallocene complexes (two or more cyclopentadienyl-type ligands) or half-sandwich complexes (one cyclopentadienyl-type ligand).
Particularly suitable metallocene complexes are those of the formula
where
M is titanium, zirconium, hafnium, vanadium, niobium or tantalum or an element from subgroup III of the Periodic Table or from the lanthanoids,
X is fluorine, chlorine, bromine, iodine, hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl having 1 to 10 carbons in the alkyl radical and 6 to 20 carbons in the aryl radical, xe2x80x94OR6 or xe2x80x94NR6R7,
n is an integer between 1 and 3, n corresponding to the valence of M minus 2,
and where
R6 and R7 are C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl having in each case 1 to 10 carbons in the alkyl radical and 6 to 20 carbons in the aryl radical,
R1 to R5 are hydrogen, C1-C10-alkyl, 5-7 membered cycloalkyl which can in turn carry a C1-C10-alkyl as substituent, C6-C15-aryl or arylalkyl, where two adjacent radicals may if desired together be saturated or unsaturated cyclic groups having 4 to 15 carbons, or are Si(R8)3 where
R8 is C1-C10-alkyl, C3-C10-cycloalkyl or C6-C15-aryl,
and where the radicals
R9 to R13 are hydrogen, C1-C10-alkyl, 5-7-membered cycloalkyl which can in turn carry a C1-C10-alkyl substituent, C6-C15-aryl or arylalkyl and where two adjacent radicals may if desired together be saturated or unsaturated cyclic groups having 4 to 15 carbons, or are Si(R14)3 where
R14 is C1-C10-alkyl, C6-C15-aryl or C3-C10-cycloalkyl,
or where the radicals R4 and Z together form a group xe2x80x94R15xe2x80x94Axe2x80x94 in which
xe2x95x90BR16, xe2x95x90AlR16, xe2x80x94Gexe2x80x94, xe2x80x94Snxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x95x90SO, xe2x95x90SO2, xe2x95x90NR16, xe2x95x90CO, xe2x95x90PR16 or xe2x95x90P(O)R16,
where
R16, R17 and R18 are the same or different and are hydrogen, halogen, C1-C10-alkyl, C1-C10-fluoroalkyl, C6-C10-fluoroaryl, C6-C10-aryl, C1-C10-alkoxy, C2-C10-alkenyl, C7-C40-arylalkyl, C8-C40-arylalkenyl or C7-C40-alkylaryl, or where two adjacent radicals in each case form a ring with the atoms linking them, and
M2 is silicon, germanium or tin,
R19 is C1-C10-alkyl, C6-C15-aryl, C3-C10-cycloalkyl, alkylaryl or Si(R20)3,
R20 is hydrogen, C1-C10-alkyl, C6-C15-aryl which may in turn be substituted by C1-C4-alkyls, or is C3-C10-cycloalkyl
or where the radicals R4 and R12 together form a group xe2x80x94R15xe2x80x94.
Preference among the metallocene complexes of the formula I is given to
The radicals X can be the same or different, but preferably are the same.
Of the compounds of the formula Ia, particular preference is given to those in which
M is titanium, zirconium or hafnium,
X is chlorine, C1-C4-alkyl or phenyl,
n is 2 and
R1 to R5 are hydrogen or C1-C4-alkyl.
Of the compounds of the formula Ib, preference is given to those in which
M is titanium, zirconium or hafnium,
X is chlorine, C1-C4-alkyl or phenyl,
n is 2,
R1 to R5 are hydrogen, C1-C4-alkyl or Si(R8)3, and
R9 to R13 are hydrogen, C1-C4-alkyl or Si(R14)3,
Particularly suitable compounds of formula Ib are those in which the cyclopentadienyl radicals are the same.
Examples of particularly suitable compounds include:
bis(cyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium dichloride, bis(ethylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride and bis(trimethylsilylcyclopentadienyl)zirconium dichloride and the corresponding dimethylzirconium compounds.
Particularly suitable compounds of the formula Ic are those in which
R1 and R9 are the same and are hydrogen or C1-C10-alkyls,
R5 and R13 are the same and are hydrogen, methyl, ethyl, isopropyl or tert-butyl,
R2, R3, R10 and R11 are such that R3 and R11 are C1-C4-alkyl R2 and R10 are hydrogen or else two adjacent radicals R2 and R3 and also R10 and R11 are together cyclic groups having 4 to 12 carbons,
M is titanium, zirconium or hafnium and
M2 is silicon
X is chlorine, C1-C4-alkyl or phenyl.
Examples of particularly suitable complex compounds Ic include:
Dimethylsilanediylbis(cyclopentadienyl)zirconium dichloride, dimethylsilanediylbis(indenyl)zirconium dichloride, dimethylsilanediylbis(tetrahydroindenyl)zirconium dichloride, ethylenebis(cyclopentadienyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, ethylenebis(tetrahydroindenyl)zirconium dichloride, tetramethylethylene-9-fluorenylcyclopentadienylzirconium diechloride, dimethylsilanediylbis(3-tert-butyl-5-methylcyclopentadienyl)-zirconium dichloride, dimethylsilanediylbis(3-tert-butyl-5-ethylcyclopentadienyl)-zirconium dichloride, dimethylsilanediylbis(2-methylindenyl)zirconium dichloride, dimethylsilanediylbis(2-isopropylindenyl)zirconium dichloride, dimethylsilanediylbis(2-tert-butylindenyl)zirconium dichloride, diethylsilanediylbis(2-methylindenyl)zirconium dibromide, dimethylsilanediylbis(3-methyl-5-methylcyclopentadienyl)-zirconium dichloride, dimethylsilanediylbis(3-ethyl-5-isopropylcyclopentadienyl)-zirconium dichloride, dimethylsilanediylbis (2-ethylindenyl)zirconium dichloride, dimethylsilanediylbis(2-methylbenzindenyl)zirconium dichloride dimethylsilanediylbis(2-ethylbenzindenyl)zirconium dichloride, ethylphenylsilanediylbis(2-ethylbenzindenyl)zirconium dichloride, ethylphenylsilanediylbis(2-methylbenzindenyl)zirconium dichloride, diphenylsilanediylbis(2-methylbenzindenyl)zirconium dichloride, diphenylsilanediylbis(2-ethylbenzindenyl)zirconium dichloride, and diphenylsilanediylbis(2-methylindenyl)hafnium dichloride and also the corresponding dimethylzirconium compounds.
Further examples of suitable complex compounds Ic include:
Dimethylsilanediylbis(2-methyl-4-phenylindenyl)zirconium dichloride, dimethylsilanediylbis(2-methyl-4-[1-naphthylindenyl])zirconium dichloride, Dimethylsilanediylbis(2-methyl-4-isopropylindenyl)zirconium dichloride, Dimethylsilanediylbis(2-methyl-4,6-diisopropylindenyl)zirconium dichloride, dimethylsilanediylbis(2-ethyl-4-phenylindenyl)zirconium dichloride, Dimethylsilanediylbis(2-methyl-4-(para-4-butyl)phenylindenyl) zirconium dichloride, and also the corresponding dimethylzirconium compounds.
Particularly suitable compounds of the formula Id are those in which
M is titanium or zirconium
X is chlorine, C1-C4-alkyl or phenyl.
and
R1 to R3 and R5 are hydrogen, C1-C10-alkyl, C3-C10-cycloalkyl, C6-C15-aryl or Si(R8)3 or where two adjacent radicals are cyclic groups having 4 to 12 carbons.
The synthesis of complex compounds of this kind can be carried out in accordance with methods known per se, preference being given to the reaction of the correspondingly substituted cyclic hydrocarbon anions with halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum.
Examples of appropriate preparation techniques are described, inter alia, in Journal of Organometallic Chemistry, 369 (1989), 359-370.
It is also possible to employ mixtures of different metallocene complexes.
Component B) is aluminum trifluoride. This is a known compound which is described, for example, in Holleman-Wiberg, Lehrbuch d. Anorgan. Chemie, 101st Ed. 1995, p. 1073 ff, Walter de Gruyter (Berlin, N.Y.). It can be in either crystalline or, preferably, amorphous form. A very suitable process for preparing amorphous aluminum trifluoride is the reaction of aluminum triorganyls with, for example, boron trifluoride etherate, as described in R. Taube, Macromol. Chem. 194 (1993), 1273-1288. the aluminum trifluoride B) can be isolated preparatively or prepared in situ for use.
The molar ratio of aluminum trifluoride B) to metal complex A) is from 10,000:1 to 1:1, preferably from 100:1 to 1:1 and, with particular preference, from 50:1 to 1:1.
The cation-forming compound C) is generally a Lewis acid (electrically neutral or positively charged) or a Brxc3x6nsted acid. Suitable neutral Lewis acids are preferably those which form a non-nucleophilic anion after reaction with the transition metal component A). Suitable positively charged Lewis acids, and suitable Brxc3x6nsted acids, are preferably those having a conjugated anion with little or virtually no nucleophilicity.
One of the features of the invention is that both moderate and strong Lewis acids, and anions of little to virtually no nucleophilicity, can be used to generate a catalyst.
Suitable cation-forming compounds C) from the class of the moderate neutral and positively charged Lewis acids are compounds of elements of Groups 13 to 15 of the Periodic Table of the Elements, of the formula MetRxe2x80x2n, where Met is an element from groups 13 to 15 of the Periodic Table of the Elements, Rxe2x80x2 is inorganic or organic radicals which can be the same or different, and n is an integer from 3 to 5 and represents the valence of Met.
Preference is given in this context to compounds comprising elements of groups 13 and 15 with only halogen atoms as substituents. Particular preference is given to boron trifluoride and antimony pentafluoride.
Positively charged Lewis acids can be selected, for example, from compounds of the formulae [MetRxe2x80x2n+1]⊕[An]xe2x8ax96 or [MetRxe2x80x2nxe2x88x921]⊕[An]xe2x8ax96, where Met is an element from groups 13 to 16 of the Periodic Table of the Elements, Rxe2x80x2 is inorganic or organic radicals which can be the same or different, and n is an integer from 2 to 5 which represents the valence of Met. The nature of the corresponding anion [An]xe2x8ax96 is not critical per se, with anions such as boron tetrafluoride and antimony hexafluoride, for example, having proven suitable. Positively charged Lewis acids with exclusively organic substituents are preferred. Particular preference is given to compounds such as C(C6H5)3⊕BF4xe2x8ax96 or O(CH3)3⊕BF4xe2x8ax96, for example.
Suitable compounds from the class of the Brxc3x6nsted acids with an anion of low nucleophilicity (b) are those in which the anion is of the formula MetRxe2x80x2n+1xe2x8ax96 where Met is an element from groups 13 to 15 of the Periodic Table of the Elements, Rxe2x80x2 is inorganic or organic radicals which can be the same or different, and n is an integer from 3 to 5 and represents the valence of Met. Preference is given to anions carrying exclusively halogen substituents on the central element. Compounds such as HBF4 and HSbF6 are particularly preferred. These compounds can also be in the form of etherates.
A further class of anions of low nucleophilicity which can be used is derived from the formula Rxe2x80x2SO3⊕. In this formula Rxe2x80x2 is an inorganic or organic radical, preferably an organic C1-C10-alkyl or C6-C20-aryl radical, where preferably at least some of the hydrogen atoms can be substituted by halogen atoms, preferably by fluorine atoms. Examples of particularly preferred compounds of this class are acids Rxe2x80x2SO3-H, such as fluorosulfonic, phenylsulfonic, trifluoromethylsulfonic and pentafluorophenylsulfonic acid.
Strong, neutral Lewis acids as component C) are compounds of the formula (II)
M3X1X2X3xe2x80x83xe2x80x83II
where
M3 is an element from main group III of the Periodic Table, especially B, Al or Ga, preferably B,
X1, X2 and X3 are hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl each having 1 to 10 carbons in the alkyl radical and 6 to 20 carbons in the aryl radical, or are fluorine, chlorine, bromine or iodine, and in particular are haloaryls, preferably pentafluorophenyl.
Particular preference is given to compounds of the formula II in which X1, X2 and X3 are the same, preferably tris(pentafluorophenyl)borane.
Ionic compounds as component C), having strong Lewis-acid cations, are compounds of the formula III
[(Ya+)Q1Q2 . . . Qz]d+xe2x80x83xe2x80x83III
where
Y is an element of main groups I to VI or of subgroups I to VIII of the Periodic Table,
Q1 to Qz are radicals bearing a single negative charge, such as C1-C28-alkyl, C6-C15-aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having 6 to 20 carbons in the aryl and 1 to 28 carbons in the alkyl radical, C3-C10-cycloalkyl, which can be unsubstituted or substituted by C1-C10-alkyl groups, or are halogen, C1-C28-alkoxy, C6-C15-aryloxy, silyl or mercaptyl,
a is an integer from 1 to 6 and
z is an integer from 0 to 5,
d being the difference a-z but being greater than or equal to 1.
Carbonium cations, oxonium cations and sulfonium cations, and also cationic transition metal complexes, are particular suitable. Mention may be made in particular of the triphenylmethyl cation, the silver cation and the 1,1xe2x80x2-dimethylferrocenyl cation. They preferably have noncoordinating counterions, especially boron compounds as are also mentioned in WO 91/09882, preferably tetrakis(pentafluorophenyl)borate.
Ionic compounds as component C) with Brxc3x6nsted acids as cations and preferably likewise noncoordinating counterions are mentioned in WO 91/09882; a preferred cation is N,N-dimethylanilinium.
The amount of metallocenium ion-forming compound is preferably from 0.1 to 10 equivalents based on the transition metal component A).
Component C) can also consist of or comprise an aluminoxane.
Compounds particularly suitable as the cation-forming component C) are open-chain or cyclic alumoxane compounds of the formula V or VI
where R24 is a C1-C4-alkyl, preferably methyl or ethyl, and m is an integer from 5 to 30, preferably from 10 to 25.
These oligomeric alumoxane compounds are customarily prepared by reacting a solution of trialkylaluminum with water as is described, inter alia, in EP-A 284 708 and U.S. Pat. No. 4,794,096.
In general, the resulting oligomeric alumoxane compounds are in the form of mixtures of both linear and cyclic chain molecules of various length, so that m should be regarded as an average value. The alumoxane compounds can also be present in a mixture with other metal alkyls, preferably with aluminum alkyls.
As component C) it is additionally possible to employ aryloxyalumoxanes as described in U.S. Pat. No. 5,391,793, aminoaluminoxanes as described in U.S. Pat. No. 5,371,260, aminoaluminoxane hydrochlorides as described in EP-A 633 264, siloxyaluminoxanes as described in EP-A 621 279, or mixtures thereof.
It has been found advantageous to use the transition metal compound A) and the oligomeric alumoxane compound in amounts such that the atomic ratio between aluminum from the oligomeric alumoxane compound and the transition metal from the transition metal compound A is from 1:1 to 106:1, preferably from 1:1 to 104:1, and, in particular, from 1:1 to 10:1.
As component D), the catalyst system of the invention may also include, if desired, an organometallic compound, preferably a metal compound of the formula IV
M1(R21)r(R22)s(R23)txe2x80x83xe2x80x83IV
where
M1 is an alkali metal, an alkaline earth metal or a metal from main group III of the Periodic Table, i.e., boron, aluminum, gallium, indium or thallium,
R21 is hydrogen, C1-C10-alkyl, C6-C15-aryl, alkylaryl or arylalkyl having in each case 1 to 10 carbons in the alkyl radical and 6 to 20 carbons in the aryl radical,
R22 and R23 are hydrogen, halogen, C1-C10-alkyl, C6-C5-aryl, alkylaryl, arylalkyl or alkoxy having in each case 1 to 10 carbons in the alkyl radical and 6 to 20 carbons in the aryl radical,
r is an integer from 1 to 3
and
s and t are integers from 0 to 2, the sum r+s+t corresponding to the valence of M1.
Where component D) is present together with A) and/or C), it is not the same as components A) and, especially, C).
Among the metal compounds of formula IV preference is given to those in which
M1 is lithium, magnesium or aluminum and
R21 to R23 are C1-C10-alkyl.
Particularly preferred metal compounds of the formula IV are n-butyllithium, n-butyl-n-octylmagnesium, n-butyl-n-heptyl-magnesium, tri-n-hexylaluminum, tri-isobutylaluminum, triethylaluminum and trimethylaluminum.
If component D) is employed it is present in the catalyst system in an amount of preferably from 800:1 to 1:1, in particular from 500:1 to 50:1 (molar proportion of M1 from IV to transition metal M from I).
In addition to A), B), C) and, if used, D), the catalyst system may comprise a support substance.
Examples of suitable support substances are organic polymers, but preferably porous inorganic materials.
The support materials employed are preferably finely divided supports having a particle diameter in the range from 0.1 to 1000 xcexcn preferably from 10 to 300 xcexcm, and, in particular, from 30 to 70 xcexcm. Examples of suitable organic supports are finely divided polymers, such as finely divided polyethylene or polypropylene. Examples of suitable inorganic supports are aluminum trioxide, silicon dioxide, titanium dioxide or mixed oxides thereof, aluminum phosphate or magnesium chloride. It is preferred to employ silica gels of the formula SiO2.a Al2O3, in which a is a number from 0 to 2, preferably from 0 to 0.5. The support particles can be used in granular form and also spray-dried in microscopic form. Products of this kind are obtainable commercially, examples being Silica Gel 332 from Grace or ES 70xc3x97to from Crosfield.
Preferred inorganic support materials are acidic, inorganic metal oxides or semimetal oxides of very high porosity, which are described, for example, in the prior German Patent Application 197 20 980.7, especially on page 3, line 45 to page 5, line 11.
The support materials may have been pretreated thermally or chemically (with metal alkyl compounds, for example) in order to obtain a certain profile of properties of the support (for example, water content and/or hydroxyl content).
The catalyst system of the invention is generally obtained by reacting aluminum fluoride with a transition metal compound A) which has been brought into contact beforehand with a cation former C). This reaction can be conducted in homogeneous liquid phase or else in the presence of a support material, generally with the use of organic solvents as suspension media. The resulting compound can be employed as a catalyst directly, in suspension. An alternative possibility is to isolate the compound and to employ it per se as a catalyst in, for example, gas-phase processes; otherwise, it can be resuspended after isolation and then employed as a catalyst.
The aluminum fluoride B) can also be prepared in situ (for example, by reacting an aluminum alkyl compound with boron trifluoride) and then brought into contact, in the presence or absence of a support material, with the product of reaction of transition metal compound A) and cation former C). The reaction of the transition metal compound A) with the cation former C) can also be conducted in the presence of aluminum fluoride B) and in the presence or absence of a support material.
The catalyst system of the invention is employed to polymerize monomers having a Cxe2x80x94C double bond or a Cxe2x80x94C triple bond. Said Cxe2x80x94C double or Cxe2x80x94C triple bond, or both, can be arranged either at the ends of or within the module, either exocyclically or endocyclically. Preferred monomers with Cxe2x80x94C triple bond are C2-C10-alk-1-ynes, such as ethyne, propyne, 1-butyne, 1-hexyne, and also phenylacetylene. Preferred monomers with a Cxe2x80x94C double bond are C2-C20-alk-1-enes and C8-C20 vinylaromatic compounds. The polymerization process of the Invention is preferably employed to polymerize or copolymerize C2-C12-alk-1-enes. Preferred C2-C12-alk-1-enes are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1heptene or 1-octene, and vinylaromatic monomers, such as styrene, p-methylstyrene or 2,4-dimethylstyrene, or mixtures of these C2-C12-alk-1-enes. Particular preference is given to homopolymers or copolymers of ethylene or of propylene, the proportion of ethylene or-propylene in the copolymers being at least 50 mol %. In the case of ethylene copolymers preference is given to those comprising propylene, 1-butene, 1-hexene, or 1-octene, or mixtures thereof, as further monomers. In the case of propylene copolymers, the copolymers concerned are in particular those comprising ethylene or 1-butene, or mixtures of these, as further monomers.
Preference is given to using the polymerization process of the invention to prepare polymers which comprise from 50 to 100 mol % of ethylene and from 0 to 50 mol %, in particular from 0 to 30 mol %, of C3-C12-alk-1-enes.
Preference is also given to those polymers which comprise from 50 to 100 mol % of propylene, from 0 to 50 mol %, in particular from 0 to 30 mol %, of ethylene and from 0 to 20 mol %, in particular from 0 to 10 mol %, of C4-C12-alk-1-enes.
The sum of the molar percentages is always 100.
The polymerization can be conducted by the techniques customary for polymerizing olefins, such as solution, suspension, stirred gas-phase or gas-phase fluidized-bed techniques, continuously or batchwise. As solvents or suspension media it is possible to use inert hydrocarbons, such as isobutane, or else the monomers themselves. Particularly suitable techniques for preparing the polymers are the suspension technique and the gas-phase technique (stirred gas phase, gas-phase fluidized bed).
Suitable reactors include continuously operated stirred vessels, loop reactors or fluidized-bed reactors, it also being possible if desired to use two or more reactors connected one after another in a row (reactor cascade).
The polymerization by means of the process of the invention is generally carried out at temperatures in the range from xe2x88x9250 to 300xc2x0 C., preferably from 0 to 150xc2x0 C., and under pressures of generally from 0.5 to 3000 bar, preferably from 1 to 80 bar. In the polymerization process of the invention it is advantageous to establish residence times of the respective reaction mixtures of from 0.5 to 5 hours, in particular from 0.7 to 3.5 hours. In the course of the polymerization it is also possible to use, inter alia, antistats and molecular mass regulators, an example being hydrogen.
Apart from for polymerization, the catalyst system of the invention can also be used for stoichiometric or catalytic, nonrepetitive carbon-carbon linkage, and for reducing carbonyl groups  greater than Cxe2x95x90O or imino groups  greater than Cxe2x95x90NH with carbon radicals, hydrides or amides, and also in the Diels-Alder reaction and in the hydrogenation of unsaturated carbon-carbon, carbon-heteroatom and heteroatom-heteroatom bonds with hydrogen and/or hydrides.
In general, these reactions proceed in the low molecular mass range and they generally lead to products having a molecular weight of less than about 1000.

Catalyst system with aluminum fluoride activator

Abstract: A) a transition metal compound with

Abstract: B) aluminum trifluoride,

Abstract: D) further components.


A sensing system for sensing the condition of an object comprises a transducer arranged to generate pressure waves directed at the object and detection means, such as a pressure wave detector, arranged to detect cavitation or other processes in the object. The system further comprises processing means arranged to receive detection signals from the detection means, to process the detection signals to measure a signal parameter of the detection signals that varies with a parameter of the object, and may generate a sensor output that varies in response to changes in the signal parameter.

Therapeutic ultrasound in general, and High-Intensity Focussed Ultrasound (HIFU) in particular, is rapidly emerging as a promising tool for non-invasive ablation of cancerous, diseased or fat tissue, and as a means of inducing localized heating for the purpose of hyperthermia-enhanced drug release.
For all of the above applications, a major factor limiting the use of therapeutic ultrasound is the lack of a technique that makes it possible to monitor changes in tissue properties at the ultrasound focus non-invasively.
When ultrasound is used to induce mild hyperthermia, the major effect at the ultrasound focus will be a mild increase in tissue temperature. When ultrasound is used to induce ablation, the primary effect will be a dramatic change in the viscoelastic properties of tissue (in a manner similar to cooking a steak).
Clinically available monitoring techniques include the use of B-mode pulse-echo ultrasound, which is only sensitive to changes in the acoustic impedance, speed of sound and attenuation of tissue; a major limitation of this technique is that it cannot be used during ultrasound exposure, because the signal from the therapy transducer will saturate that from the diagnostic transducer. Performing the procedure inside an MRI scanner is another clinically available alternative: MRI is capable of providing temperature measurements, albeit with poor spatio-temporal resolution, and is primarily prohibitive by virtue of its cost. Importantly for tissue ablation applications, it should be noted that temperature is an indirect indicator of tissue damage, and a more direct indicator is therefore desirable.
Under the right conditions, an ultrasound wave propagating through tissue will excite micron-sized bubbles, a phenomenon known as acoustic cavitation. These bubbles can either be spontaneously nucleated by the ultrasound, by making use of gas dissolved in the surrounding tissue, or injected intravenously, such as by using ultrasound contrast agents.


A chloroprene rubber latex for an adhesive containing a chloroprene rubber polymer which forms a copolymer with a chloroprene monomer and carboxyl-group containing vinyl monomer and which, when dissolved in chloroform to a concentration of 10% by weight, provides a solution free from organic solvent insolubles and having a solution viscosity of 100 mpa.multidot.s to 6000 mpa.multidot.s, a process for production thereof, and an adhesive composition using the same.

1. Field of the Invention
The present invention relates to chloroprene rubber latex for an adhesive containing, as an ingredient, a chloroprene rubber polymer. More specifically, it relates to a chloroprene rubber latex for an adhesive containing a polymer which, when dissolved in chloroform to a concentration of 10% by weight, provides a solution which does not contain organic solvent insolubles and which has a solution viscosity of 100 mpa.multidot.s to 6000 mpa.multidot.s, having an excellent room temperature bonding strength, high temperature bonding strength, water resistance, and other bonding properties and latex stability, and having these bonding properties balanced at a high level.
2. Description of the Related Art
Processes for the production of chloroprene rubber polymer latexes comprised of chloroprene and a carboxyl-group containing vinyl monomer such as acrylic acid or methacrylic acid are known from Japanese Unexamined Patent Publication (Kokai) No. 61-12710, Japanese Unexamined Patent Publication (Kokai) No. 62-257918, etc. Further, processes for production of latexes for adhesives using a water-soluble polymer such as a polyvinyl alcohol as an emulsifying and dispersing agent and adhesives using the same are known in Japanese Examined Patent Publication (Kokoku) No. 52-13983, Japanese Examined Patent Publication (Kokoku) No. 61-29968, etc.
However, there have been the following problems when using a chloroprene rubber latex produced by these processes.
(1) In the conventional latexes for adhesives, when increasing the molecular weight to improve the heat resistance, the tack retention (or adhesion retention) and room temperature bond strength were decreased and it was not possible to obtain physical properties sufficient for an adhesive. Further, attempts were made to improve the heat resistance by cross-linking the carboxyl-group containing vinyl monomer etc. with a metal oxide. However, it was not possible to achieve the physical properties expected due to the protective colloidal nature of the emulsifying agent used.
(2) When using an emulsifying agent having an excellent latex stability in the high pH region such as an alkaline metal salt of a rosin acid for the production, the rubber precipitates due to the slight changes in the pH when adding the tackifier, metal oxide, and other secondary components required for a chloroprene adhesive, and therefore, it is necessary to control the pH extremely carefully, which makes the procedure complicated. Further, when using a water-soluble polymer such as a polyvinyl alcohol for the production, a superior latex stability is exhibited due to the protective colloidal nature. However, since the polymer is water-soluble, the water resistance is remarkably degraded when used as an adhesive.

Chloroprene rubber latex for adhesive, process of production thereof, and adhesive composition using the same


A lighted heat dissipating panel made of sustainable renewable materials such as recycled aluminum and soy-based urethane, for use in architectural or shelving applications. The panel may be flat, rectangular, curvilinear, or of varying cross section so as to include any three-dimensional shape as desired. Lightweight materials such as carbon fiber, fiberglass, resin, soy-based urethane, and similar materials are used in combination with thermally conductive structural materials, such as expanded aluminum honeycomb, preferably fabricated from recycled aluminum, to provide a stiff, lightweight, machinable, moldable, and thermally conductive panel for use with lighting elements. Lighting elements are housed within the panel, providing illumination as desired. Heat is transferred from the lighting elements through the panel to the supporting structure and radiated from the panel itself, providing cooling effect for the lighting elements, reducing the temperature in the immediate vicinity of the lighting elements and providing for longer lighting element life.

1. Field of the Invention
The present invention generally relates to a lighted heat dissipating panel comprised of embedded light sources providing illumination as desired by a uses; more specifically, the present invention relates in at least one embodiment in which the heat dissipating panel is comprised of sustainable materials such as recycled expanded aluminum embedded in glass-carbon composite and in which the light emitting element is a Light Emitting Diode (LED), or a plurality of LEDs, which are in thermal contact with the light emitting surface whereby heat is transferred from the LEDs to the heat dissipating surface. The LEDs are thus cooled and are able to operate at a higher lumen output and with greater reliability than would otherwise be permitted in a non-cooled condition.
2. Background Art
Illuminated panels, for example illuminated shelving and illuminated panels used in architectural applications, have been used for many years and are generally well known in the relevant arts. Illuminated panels have many uses in architectural settings, merchandising settings, and the like. Such panels have generally depended upon either incandescent light elements or fluorescent light elements as the source of illumination embedded within the panel. However, recent advancements in LED technology have given rise to the production of cost efficient LED light elements that produce enough output power that they may be considered as light elements for architectural uses, area illumination, portable lighting such as flashlights, illuminated shelving applications, pool lighting and virtually any other lighting application that was formerly an incandescent or fluorescent lighting application. Such LED lighting has special benefits such as longevity of the light element itself, control over the spectrum of transmitted light, control over the intensity of the transmitted light, and energy efficiency as compared to the afore mentioned traditional light elements. It is thus desirable that LED light elements be utilized as a light element for illuminated panel applications.
As an example of the old art of illuminated panels based upon legacy lighting systems, see the apparatus disclosed in U.S. Pat. No. 6,364,273 BI which is directed towards merchandise shelving, in which is disclosed a shelf having a light rail extending along a front edge of the shelf which comprises a cover adapted to reflect light onto displayed merchandise while permitting light to pass through selected window portions to illuminate product and pricing information printed on transparent or translucent signage. Signage may also be supported on a sign strip behind the light rails, and along the front edge of the shelfboard. In the preferred embodiment wire management is provided by a raceway formed between a cover support and a backing strip for the fluorescent tube. A receptacle in communication with the wiring within the raceway is adapted to receive a connector from the ballust transformer, so that all permanent wiring for the fluorescent tube is concealed within the raceway. The ballust transformer can be unplugged from the wall receptacle and from the raceway receptacle, to thus completely remove the ballust transformer from the shelf for repair or replacement. The apparatus of U.S. Pat. No. 6,364,273 BI discloses fluorescent lighting.
Other exemplary legacy systems are also disclosed in U.S. Pat. No. 6,283,608 BI (disclosing a light fixture for shelving) and U.S. Pat. No. 6,755,547 B2 (disclosing a transparent panel illuminated by embedded light sources). Some illuminated panels utilizing LED light sources have recently been conceived; see, for example, U.S. Pat. No. 7,201,487 B2 (disclosing a transparent panel primarily for use in refrigerators in which the panel is illuminated from the side by embedded light sources, said panel further comprising prismatic shapes within said panel such that light is directed through the top or bottom surfaces of said panel).
LED light sources are also well known in the art. LEDs are light sources based upon a semiconductor structure, specifically a diode structure, which emit incoherent light (which may be in the ultraviolet, visible, or infrared spectrum) when electrical current is passed through the semiconductor junction. The original uses of LED light sources were in low-power applications such as indicator lights on instrumentation panels and the like. However, recent developments in LED technology have increased the output power and efficiency of LED sources so that it is now feasible to utilize them in traditional lighting applications previously reserved for incandescent, fluorescent, sodium, and similar lighting technologies. Commercially available LED light sources surpassed incandescent light source in terms of efficiency in or around 2002. More recently, LED light sources have become commercially available which exceed fluorescent light sources in efficiency. Fluorescent light sources typically exhibit around 100 lumens per Watt (lm/W) efficiency; however LED light sources have been recently developed which exhibit 130 lm/W, and there are other LED light sources available and currently in development which exhibit even greater efficiency.
As the output power of commercially available LED light sources has continued to improve, it has become necessary to develop methodologies and structures for removing the heat generated by the LED from the LED semiconductor junction. Typical problems caused by heating of the semiconductor junction and surrounding structure are: 1) failures brought on by such occurrences as non-homogenous distribution of the current density over the junction ("current crowding"), which causes a local hot spot in the diode junction leading to early failure due to thermal runaway; 2) nucleation and growth of dislocations in the active region of the diode in which the radiative recombination occurs due to the existence of an existing defect in the semiconductor crystalline structure and which is accelerated by heat; 3) degradation of materials utilized in the LED, such as phosphor, causing loss of efficiency and changes in output color; and 4) electromigration of metal atoms at the metallization layers of the diode causing growth of conductive "whiskers" and early failure. This is not a complete list of the undesired effects brought on by elevated temperatures; it is provided herein simply as a list of exemplary effects.
As an example of an LED that may be used in illuminated panel applications see the LED part number CL-L822 from Citizen Electronics Co, LTD. This surface mount LED is characterized by data sheets providing information for these products at a temperature of 25° C., or approximately room temperature. It is therefore desirable to operate these products and those like them as close to room temperature as possible. A heat conduction/dissipation apparatus is therefore required in such applications in order to remove heat from the LED in an effort to operate the LED as close to the data sheet temperature as practicable.
Attempts have been made to provide structure for removing the heat from the semiconductor junction of an LED. See, for example, U.S. Pat. No. 6,639,356 B2 (disclosing a heat dissipating base for an LED, and which further states the heat problem created by the use of LEDs in various applications, namely that " . . . Heat generated by LED (sic) becomes the largest drawback in LED manufacturing industry, which causes different malfunctions to the circuitry." U.S. Pat. No. 6,639,356 B2, col. 1. The invention of U.S. Pat. No. 6,639,356 B2 is an attempt to better conduct the heat away from the LED semiconductor junction so as to overcome the problems created by an overheated junction; namely reduced lifetime and output power. However, the invention of U.S. Pat. No. 6,639,356 B2 is directed to a package LED and simply providing a thermally conductive path out of the LED package. It does nothing to address the larger issue of dissipating heat away from the package.
Furthermore, advances in the availability and quality of enviro-friendly materials, including recycled materials such as recycled metals, for example recycled aluminum, and also including organic based resins, for example soy-based urethane, have now made it not only possible but also economically feasible to produce consumer products that are constructed from sustainable resources and at the same time reduce harmful emissions and reduce the carbon footprint.
Soy-based urethanes, for example, may now be used in place of ester-based resins and other urethanes for manufacture of commercial products. Such soy-based urethanes exhibit increased strength to weight ratio, are fabricated from renewable and sustainable resources, specifically soybean oil, require less or even no glass matt and may result in thinner cross sections in the final product, enable faster processing times and therefore higher throughput in production, and produce no Volatile Organic Compounds (VOC) emissions, specifically harmful styrene, during the production process. Furthermore the use of soybean oil based products is advantageous in that it reduces dependence upon foreign source of oil and petroleum products and serves to help insulate from the volatile and increasing price of such petroleum products.
It is therefore desirable that lighted panels should make use of the currently available LED light source technology due to the significant benefits such light sources provide such as extremely long life, ability to control output power and spectrum, and significant reduction in the amount of electrical energy consumed for comparable light output power as compared to traditional light sources. It is also desirable that such panels be sustainably constructed; in other words, be fabricated from renewable and sustainable resources such as materials that are recycled or organically produced materials, or both, so as to require a minimum of new raw materials and thus preserve limited natural resources. It is also desirable that the materials used in the construction of the product be of a nature to assist reducing the carbon footprint by reducing harmful VOC emissions as compared to material traditionally utilized in the production of commercial products.
However, utilizing LED light sources in illuminated panel applications gives rise to the significant challenge of removing the heat from the LED semiconductor junction and surrounding structure. It is thus desirable, and not currently known in the art, that a sustainably constructed heat dissipating apparatus or combination, preferably, but not necessarily, be fabricated at least in part from recycled materials that are a sustainable resource in order to be environmentally friendly, be lightweight, be physically stable and exhibit stiffness and bend resistance so as to be able to bear weight as shelving and to be utilized in architecture, and be conceived and constructed so as to enable the use of LED light sources in illuminated panel applications. It is also desirable that such an apparatus should not be limited to a flat panel shape; in other words, it is desired that it be moldable to a desired shape including three dimensional shapes, curves, and generally non-linear shapes so as to provide the product designer with a great number of options regarding the size and shape of the apparatus.

Sustainably constructed heat dissipating integrated lighting surface


The present disclosure relates to a synergistic mixture of betamethasone valerate and tranilast combined with a transdermal gel using skin permeation enhancement for application in scars for reducing or preventing the abnormal scar formation, specially keloids and hypertrophic scars. The disclosed synergistic mixture may exhibit permeation enhancing properties. The transdermal gel may include a mixture of silicone, phosphatidylcholine, pracaxi oil, and seje oil; one or more oils having essential fatty acids, behenic acid, oleic acid; one or more skin lipids; a butter having linoleic acid and linolenic acid; and solvents as transdermal penetration enhancers.

1. Field of the Disclosure
The present disclosure relates in general to pharmaceutical treatments, and more particularly, to permeable enhanced compositions to treat scars.
2. Background Information
Cuts, wounds, and surgical incisions are repaired due to the skin's constant ability to shed old cells and create new ones. Nevertheless, this process also results in the production of scars. While a visible scar may be the necessary and inevitable end to the healing process, the results vary with the individual. Some visible scars fade and improve in appearance, while others provide evidence of injury for decades to come. A physical injury to the body causes disruption in body structure. The wound may be present only under the skin, may affect only the skin surface, or may involve both.
Transdermal treatments have received increased attention. One limitation of the use of medication, such as Tranilast, in topical treatments is the permeability and its ability to reach the target area, passing through the stratum corneum which is responsible for providing a protective barrier against environmental damage, as the outermost layer of the epidermis consisting principally of dead epithelial cells that are filled with the protein keratin that waterproofs and toughens the skin. This characteristic of the skin may provide a difficulty for topical treatment to permeate through the skin in order to get to the inner layers of the skin, causing active pharmaceutical ingredients (API) not being easily permeated through the skin when employed in cosmetic products or pharmaceutical formulations that are topically or transdermally delivered.
There is still a need for transdermal formulations which include permeation enhancers that may increase skin permeability of API to reduce the abnormal scar formation in a short period of time, specially hypertrophic scars and keloids.

Mixture of betamethasone and tranilast with a transdermal gel for scar treatment

PROFESSIONAL COMPOUNDING CENTERS OF AMERICA (PCCA)


A method of injection molding contact lens molds for cast molding contact lenses having a rotationally asymmetric lens surface, and apparatus for carrying out the method, are disclosed.

This invention relates to a method of injection molding contact lens molds for cast molding contact lenses having a rotationally asymmetric lens surface, and apparatus for carrying out the method.
One method in practice for making contact lenses is cast molding. Cast molding of contact lenses involves depositing a curable mixture of polymerizable monomers in a mold cavity formed by two mold sections, curing the monomer mixture, and disassembling the mold assembly and removing the lens. Other processing steps, for example, hydration in the case of hydrogel lenses, may also be employed. One mold section forms the anterior lens surface (anterior mold section), and the other mold section forms the posterior lens surface (posterior mold section). Prior to the cast molding of the contact lens, each of the mold sections is formed by injection molding a resin in the cavity of an injection molding apparatus. Mounted in the injection molding apparatus are tools for forming the optical surfaces on the mold sections. Whereas the mold sections are typically used only once for casting a lens, the injection molding tools are used to make hundreds of molds.
Several known cast molding methods have the potential to mold a finished contact lens, for example, U.S. Pat. No. 5,271,875 (Appleton et al.). Since these methods avoid time-consuming and labor-intensive operations such as lathing, the methods have been found to offer the potential to reduce production time and cost for the manufacture of spherical contact lenses.
However, various problems have been encountered in employing cast molding technology for manufacturing other types of contact lenses, especially contact lenses that have at least one rotationally asymmetric surface. As one example, toric contact lenses (i.e., contact lenses having a toric optical zone that are used to correct refractive abnormalities of the eye associated with astigmatism) have at least one surface that is not rotationally symmetric. The problems encountered may be due to several factors. First, the toric optical zone is not spherical. Second, toric contact lenses include some type of ballast (such as prism ballast or slab-off zones) to inhibit rotation of the lens on the eye so that the cylindrical axis of the toric zone remains generally aligned with the axis of the astigmatism; in order to provide such ballast, the edge thickness of the lens is not uniform about the entire circumference of the lens. As another example of such lenses, many mulitfocal designs are not rotationally symmetric.
Applicant found that, in forming contact lens molds for molding lenses having a rotationally asymmetric lens surface, problems were encountered in consistently obtaining contact lens molds having the same geometries. Such inconsistencies in the contact lens mold geometries translated to inconsistencies in cast molding contact lenses in the molds. The present invention solves this problem.

Injection molding process for rotationally asymmetric contact lens surfaces


An improved release mechanism for use in combination with an industrial door, which includes an extension member extending across the doorway opening when the door is in its doorway-blocking positions, the releasing mechanism including a roller mounted for movement with the extension member, and a track including a guideway for receiving the roller and guiding it during normal door operation, the roller and track being movable relative to each other upon application of a breakaway force to the extension member, thereby allowing the roller to escape from the track when a breakaway force is applied to the extension member, the breakaway force being defined as a force that has a component perpendicular to the plane of the door above a certain magnitude.

A wide variety of doors are used in industrial settings. Such industrial doors include conventional sectional doors, comprising a series of panels hinged together to form the door. Typically, such a sectional door is movable between doorway-blocking positions and overhead-storing positions. For this purpose, a curved guide track is disposed on either side of the doorway, with one leg (adjacent to the doorway opening) extending vertically along the doorway, and the second leg (projecting back from the doorway opening) disposed above and behind the doorway. A curved track section joins the two legs. Sectional doors may also be vertically stored, that is they may have straight tracks and be movable in a continuous plane between doorway-blocking and doorway-opening positions. Typically, the panels comprising such a sectional door are formed of either metal or wood.
In other types of industrial doors, the door itself may be formed of fabric. One such type of fabric industrial door is a roll-up door, in which the door is a curtain of fabric rolled on a roller tube typically disposed above the doorway opening. To close the door, the curtain is drawn off of the roller, and the roller is reversed to roll the curtain up on the roller for the purpose of opening the door. Another type of fabric industrial door is a so-called "concertina" door. In a concertina door, the door typically also comprises a fabric curtain and a roller is disposed above the doorway opening. Straps are wound onto and off of the roller, and are connected typically to a leading edge of the curtain for the purpose of drawing the curtain up out of the way of the door opening, and allowing the curtain to fall and unfold to cover the door opening. The curtain itself does not wind on the tube, however, and rather is gathered in folds at the top of the door. A still further type of fabric industrial door is a sheet of fabric that is maintained in a flat orientation, and is moved between a doorway-blocking and a doorway-opening position. The doorway opening position may either be above the doorway or overhead, similar to an overhead-style sectional door. Further, while all of these doors have been described as moving vertically, they may also be modified such that their movement between door opening and door closing positions is in a horizontal or other direction, as opposed to a vertical direction. Roll-up doors comprising metal or chain sections are also known.
All of the industrial doors just described typically share a common feature of having a member extending across the doorway opening when the doorway is either in the closed or any of a variety of doorway-blocking positions. Such structure will be referred to herein as an "extension member." In sectional doors, the extension members are the door panels themselves. Fabric doors typically include either a relatively rigid bottom bar extending across the leading edge of the door, and/or other relatively rigid bars extending across the width of the door at locations other than at the leading edge (these are often referred to as "wind bars" as they assist in adding stability to the door and preventing it from billowing under wind load conditions).
A common problem associated with such doors as a result of the presence of these extension members extending across the doorway is unintentional impact. In an industrial or warehouse setting, such impact may occur by virtue of a fork lift or other material handling equipment (or a load carried thereon) being driven into the door and the impact is thus directly or indirectly transmitted to the extension members. In situations where such doors are used in automated factories, conveyors or other devices may cause objects being conveyed to accidentally impact the doors. Given the fact that such impacts are bound to occur, certain types of industrial doors can be designed to withstand such impacts. For example, the panels comprising a sectional door, and the associated track and hardware can be reinforced to withstand such impacts. Of course, this adds significant expense to the door. Further, fabric-type industrial doors typically do not have this option as the door itself is formed of fabric which is more easily damaged than the metal or wood typically comprising sectional doors.
Accordingly, another solution to allowing industrial doors to withstand impact is to allow them to have a controlled breakaway under such an impact. That is, the door is designed for certain components to separate upon an unintentional impact, thus protecting the remainder of the door. One example of such a structure is shown in U.S. Pat. No. 4,676,293, assigned to the assignee of the present invention. In that patent, a sectional door is disclosed that includes a bottom panel having significant flexibility, thus allowing it to absorb impact. However, if the impact is above a predetermined magnitude, the door is designed to allow the roller associated with the bottom-most panel to disengage from the panel, thus allowing the panel to swing free relative to the rest of the door. This action protects the bottom panel from damage.
The various breakaway mechanisms disclosed in the prior art may adequately perform the desired function, but may be limited in use to certain environments or types of doors. In other circumstances, the disclosed breakaway mechanisms may not adequately function. Even when they do function properly, however, reassembly or repair of such doors following breakaway may be a cumbersome or time-consuming process. Spare parts may need to be maintained on hand, and trained technicians may need to be called to reassemble the door following breakaway. Complex breakaway mechanisms may also significantly increase the costs associated with a given door.


Photographic images of local area events are efficiently provided. Each of a plurality of laboratories obtains photographic images of events in their local areas and uploads the images to a management server. The management server stores the images, correlated with area specifying data that specifies the location of the laboratory which has uploaded them. A user transmits the zip code of an area in which an event for which he desires photographic images was held, via an Internet television set. The management server searches for images uploaded by a laboratory in an area that matches the transmitted zip code, and transmits the images to the Internet television set. The user selects desired images. Then, the management server generates and transmits an output command that causes a laboratory to print the images selected by the user.

1. Field of the Invention
The present invention relates to a photographic image service. Particularly, the present invention relates to a photographic image service system that provides photographic images of local area events to users.
2. Description of the Related Art
Accompanying the spread of the Internet, it has become a widespread practice to place orders online. These orders include accessing a server on the Internet using a personal computer (hereinafter, referred to as "PC") while at home to shop, as well as performing bank transactions. In addition, portable terminals such as cellular telephones have also become rapidly widespread. It is an everyday occurrence to access servers on the Internet by using the portable terminals in the same manner as a PC. Further, with the recent introduction of Internet Television, systems for providing various services utilizing a specific channel of the television are also being realized.
Among these systems, there are those that provide services related to photographic images. For example, known systems include those that digitize photographic images obtained by a user then store the digitized image data in an image server; provide the digitized image data to the user, recorded on a recording medium such as a CD-R; and enable users to order prints of photographic images stored in the image server, via a network. There are known systems in which a user stores their own image data on a server on a network, and is enabled to place printing orders on the stored image data. For example, in the photographic image service system disclosed in U.S. Patent Laid-Open No. 20020093680, a user transmits their own image data to a server provided by a service provider, via a network such as the Internet. The server stores the image data transmitted thereto from the user, and also provides a printing order reception service wherein printing orders are received for the image data which are stored therein. In these systems, the contents of the printing order received by the server (the image or images to be printed, the print size, etc.) are transmitted to a laboratory that actually performs the printing. Note that there are cases in which the same service provider provides both the laboratory that actually performs printing and the server that stores and receives printing orders for image data, and cases in which the laboratory and the server are provided by different service providers.
Meanwhile, there are cases in which it is difficult for a user to obtain photographs for him or herself, due to geographical or time constraints. In response to these situations, systems exist in which photographic images, for example, of World Cup Soccer games, are exhibited on the Internet. Users order desired photographic images in the form of prints, or as data recorded in a recording medium, from among those exhibited on the Internet. By utilizing such systems, users are enabled to obtain photographic images which would be difficult to obtain by themselves. In addition, photographic images provided in these systems are photographed by professional photographers. Therefore, users are able to obtain photographic images of a higher quality than those that they would be able to photograph themselves.
However, systems for providing professionally photographed, high quality photographic images of events to users have as their targets large scale events of national to international importance. In the case of small scale events of importance only to a limited geographic area, such as a school athletic event or a town festival, photography is generally performed by those involved with the participants (parents, groups of friends, etc.). In this case, not only is securing photography locations troublesome, but as the photography is performed by amateurs, it is difficult to obtain high quality photographic images. Therefore, organizers of an event, for example, may commission a local photo studio to perform photography at the event. The photo studio prints out the photographic images for viewing by the participants, who order additional prints for photographic images that they desire. In this method, there is a problem that only participants in the event can obtain photographic images thereof. Only the photo studio which has been commissioned can perform photography and printing. Therefore, there is no competition among photo studios, and there is a problem that the users have limited freedom of choice regarding the photo studio.
In the case that a user desires photographs of their grandchild's elementary school athletic event, and the grandchild lives far away, the user must rely on photographs sent to them from their children, which is inconvenient. Photographs of small scale events, which are of importance only to a limited community such as that described above, are sometimes exhibited on personal web sites. However, these web sites are difficult to search for, and there is no guarantee regarding the quality of the photographic images. A method wherein the local photo studio exhibits the photographic images on the Internet to receive orders therethrough is unrealistic, because the burden on the photo studio is great from the viewpoint of costs in system construction and maintenance.


A liquid crystal display device with a multi-timing controller that generates a timing signal according to an individual display standard from a control signal according to various display standards to drive the liquid crystal display device. In the device, a liquid crystal display panel has a display standard corresponding to an arranged pixel. An interface receives a data inputted from the exterior thereof and a control signal corresponding to the display standard. A timing controller latches and outputs a data inputted from the interface, and generates and outputs timing signals for driving the liquid crystal display panel from the control signal. A driving circuit receives the timing signals from the timing controller to display a picture corresponding to the data on the liquid crystal display panel. In the timing controller, a display standard set part sets one display standard in response to a plurality of display standards and generates a setting signal corresponding to the display standard. A selector has each timing generation information according the plurality of timing standards and outputs a timing information corresponding to the set signal. A timing generator receives the timing information to generate and output the timing signals from the control signal.

1. Field of the Invention
This invention relates to a liquid crystal display device, and more particularly to a liquid crystal display device including a multi-timing controller that produces a timing signal according to each display standard from a control signal according to various standards to drive the liquid crystal display device.
2. Description of the Related Art
Generally, a liquid crystal display device has an inherent resolution corresponding to the number of integrated pixels, and has a higher resolution as its dimension becomes larger. In order to display a high quality of picture, makers of the liquid crystal display device increases a pixel integration ratio within a liquid crystal panel between liquid crystal display devices with same dimension to differentiate the resolution.
The standards of the image signal and the control signals under circumstance of a personal computer, etc. including the liquid crystal display device along with the resolution are set by the Video Electronics Standard Association (VESA) on February, 1989.
The typical standards of displays being commercially available in the current display industry include DOS Mode(640×350, 640×400, 720×400), VGA(640×400), SVGA(800×600), XGA(1024×768), SXGA(1280×1024) and UXGA(1600×1200) Modes, etc.
The LCD has a resolution fixed by the number of arranged pixels and hence requires image signals corresponding to a resolution of the liquid crystal display panel and control signals thereof from the system. Accordingly, the system converts image signals and control signals corresponding to various display standards into image signals and controls signals complying with a resolution and a display standard of the LCD using a scaler chip and the like to apply the same to the LCD.
FIG. 1 is a block diagram showing a configuration of the conventional LCD. In FIG. 1, an interface part 10 receives a data (RGB data) and control signals (e.g., an input clock, a horizontal synchronizing signal, a vertical synchronizing signal and a data enable signal) to apply them to a timing controller 12. A low voltage differential signal (LVDS) interface and a transistor transistor logic (TTL) interface are largely used for a data and control signal transmission to the driving system. Such interfaces are integrated into a single chip along with the timing controller 12 by collecting each function of them.
The timing controller 12 takes advantages of a control signal inputted via the interface part 10 to produce control signals for driving a data driver 18 consisting of a plurality of drive IC's (not shown) and a gate driver consisting of a plurality of gate drive IC's (not shown). Also, the timing controller 12 transfers data inputted from the interface part 10 to the data driver 18. A reference voltage generator 16 generates reference voltages of a digital to analog converter (DAC) used in the data driver 18, which are established by a producer on a basis of a transmissivity to voltage characteristic of the panel. The data driver 18 selects reference voltages in accordance with an input data in response to control signals from the timing controller 12 to convert the same into an analog image signal and apply the converted signal to a liquid crystal panel 22. The gate driver 20 makes an on/off control, one line by one line, of gate terminals of thin film transistors (TFT's) arranged on the liquid crystal panel 22 in response to the control signals inputted from the timing controller 12. Also, the gate driver 20 allows the analog image signals from the data driver 18 to be applied to each pixel connected to each TFT. A power voltage generator 14 supplies an operation voltage to each element, and generates a common electrode voltage and applies it to the liquid crystal panel 22.
In the configuration as mentioned above, the timing controller 12 produces desired control signals for a driving of the LCD in response to the input control signals. In this case, the timing controller 12 generally counts a clock on a basis of the edge of a horizontal synchronizing signal Hsync or a data enable (DE) signal to generate a control signal. The output signals of the timing controller 12 have a difference from each other depending on types of data drive IC and gate drive IC.
Hereinafter, types and timing of control signals used commonly except for signals required specially will be described. First, control signals required for the data driver includes source sampling clock (SSC), source output enable (SOE), source start pulse (SSP), liquid crystal polarity reverse (POL), a data polarity selection or data reverse (REV) and odd/even pixel data signals, etc. The SSC signal is used as a sampling clock for latching a data in the data driver, and which determines a drive frequency of the data drive IC. The SOE signal transfer data latched by the SSC signal to the liquid crystal panel. The SSP signal is a signal notifying a latch or sampling initiation of the data during one horizontal synchronous period. The POL signal is a signal notifying the positive or negative polarity of the liquid crystal for the purpose of making an inversion driving of the liquid crystal. The REV signal is a signal selecting the polarity of the transferred data. The odd/even pixel data signal is a signal representing an odd data of odd-numbered pixels and an even data of even-numbered pixel.
An operation of the data driver receiving the above-mentioned control signals is shown in FIG. 2. Referring to FIG. 2, first, if the data driver recognizes a "high" input of the SSP at the rising or falling edge of the SSC, then it latches a data inputted in response to the SSC. Next, the latched data is decoded into an analog output voltage in response to the SOE and supplies it to the liquid crystal panel. At this time, a positive decoder output voltage higher than the common electrode voltage is selected when the POL signal is a "high" state; while a negative decoder output voltage lower than the common electrode voltage when the POL signal is a "low" state, thereby making an inversion drive of the liquid crystal panel into a positive/negative polarity.
Control signals required for the gate driver includes gate shift clock (GSC), gate output enable (GOE) and gate start pulse (GSP) signals, etc. The GSC signal is a signal determining a time when a gate of the TFT is turned on or off. The GOE signal is a signal controlling an output of the gate driver. The GSP signal is a signal notifying a first drive line of the field in one vertical synchronizing signal.
An operation of the gate driver receiving the above-mentioned control signals is shown in FIG. 3. Referring to FIG. 3, the gate driver recognizes a "high" state of the GSP signal at the rising or falling edge of the GSC signal to output a gate signal maintaining a "high" state during a time interval equal to one period of the GSC signal. At this time, the GOE signal is combined with the gate signal output to disable an output equal to a "high" width of the GOE signal.
As described above, such a LCD requires individual controllers generating the control signals for controlling the data driver and the gate driver from the image signals and the control signals inputted in response to its inherent resolution. However, since the LCD uses various display formats from the VGA mode until the UXGA mode, it requires various timing controllers according to each resolution thereof. For this reason, the conventional LCD has a problem of a cost rise according to a development of the timing controller. In addition, the conventional LCD has a problem in that one developed timing controller can not be used for a liquid crystal display device according to a different display standard.

Liquid crystal display device with multi-timing controller


A new and distinct cultivar of Petunia plant named xe2x80x98Colorsplashxe2x80x99, characterized by its low-growing, mounded and outwardly spreading plant habit; green and pale yellow variegated leaves; and single flowers that are bright pink in color.

Petuniaxc3x97hybrida cultivar Colorsplash.
The present Invention relates to a new and distinct cultivar of Petunia plant, botanically known as Petuniaxc3x97hybrida, and hereinafter referred to by the cultivar name Colorsplash.
The new cultivar was discovered by the Inventor in a controlled environment in Chamblee, Ga. as a naturally-occurring branch mutation of the Petuniaxc3x97hybrida cultivar Pink Wave, not patented. The new Petunia was observed on a plant within a population of plants of xe2x80x98Pink Wavexe2x80x99 in May, 1999. This branch mutation was selected on the basis of its unique leaf variegation.
Asexual reproduction of the new cultivar by terminal vegetative cuttings taken in Chamblee, Ga. since November, 2000, has shown that the unique features of this new Petunia are stable and reproduced true to type in successive generations.
Plants of the cultivar Colorsplash have not been observed under all possible environmental conditions. The phenotype may vary somewhat with variations in environment such as temperature and light intensity without, however, any variance in genotype.
The following traits have been repeatedly observed and are determined to be the unique characteristics of xe2x80x98Colorsplashxe2x80x99. These characteristics in combination distinguish xe2x80x98Colorsplashxe2x80x99 as a new and distinct cultivar:
1. Low-growing, mounded and outwardly spreading plant habit.
2. Green and pale yellow variegated leaves.
3. Single flowers that are bright pink in color.
Plants of the new Petunia are most similar to plants of the parent cultivar. Plants of the new Petunia differ from plants of the cultivar Pink Wave primarily in foliage color as plants of the cultivar Pink Wave do not have variegated leaves. In addition, plants of the new Petunia grow slower than plants of the cultivar Pink Wave.


Impact is attenuated by a hollow resilient elongated one-piece body formed by a substantially flat reinforced rear wall, a top wall and front, side and bottom walls defining a cavity which is filled with water. A plurality of apertures are provided in the top wall, each of which apertures is defined by resilient walls and is closed by at least one resiliently deformable flap member adjacent to and covering the aperture. In response to a strong impact against the front wall of the body, a series of physical steps occur which result in deflection of the flap members from, followed by water from the cavity upwardly through, the apertures. The flap members return to a position adjacent to and covering the apertures after impact.

1. Field of the Invention
This invention relates generally to a shock attenuating apparatus, and more specifically to an improved automatic closure device for a liquid shock attenuating apparatus.
2. Description of the Prior Art
This invention is related to and an improvement of the invention described in U.S. Pat. No. 3,572,465 issued Mar. 3, 1971 to William Carl Olson for a Liquid Shock Attenuating and Preventing Device, the disclosure of which is incorporated by reference herein. That patent taught a shock attenuating device that may be adapted for use on, or in connection with automobile bumpers, roadway guardrails and the like. U.S. Pat. No. 3,572,465 described a device in which impact is attenuated by a hollow resilient elongated one-piece body formed by a substantially flat reinforced rear wall, a top wall and front, side and bottom walls defining a cavity which is filled with water. A plurality of apertures are provided in the top wall, each of which apertures is defined by resilient walls and is closed by a resiliently deformable plug in frictional engagement with the aperture walls. In response to a strong impact against the front wall of the body, a series of physical steps occur which result in ejecting the plugs from, followed by water from the cavity upwardly through, the apertures.
However, in this arrangement, the plugs are left outside the apertures after ejection. This is not only aesthetically unsightly, but also leaves the plugs exposed to damage or removal. Furthermore, the apertures are left open, thereby obviating the systems ability to attenuate a subsequent impact (as in a chain-reaction accident).

Automatic closure for shock attenuating apparatus


The invention is directed towards an efficient and ozone free ion generator in which the ion emitter is open to the surrounding space while the collector is provided by electrical ground remote and away from the ion emitter. In the case of a household generator, the ground is the electrical ground of the house. In the case of a car generator, the ground is the car frame. A safety circuit is arranged to turn the high voltage off if a hand or other body member (or pet) comes near or touches the exposed emitter to prevent electrical shock.

It is well known that a high voltage, in the range of a few thousand volts, applied to a sharp point produces ions in the surrounding air. A lot of negative ion generators based on this principle exist in the marketplace. They generally consist of a high voltage power supply of which its negative terminal is connected to a sharp point, usually that of a needle, and its positive terminal is connected to an electrode, typically a ring (collector), in front of the needle. Sometimes this is duplicated a few times in a typical unit. Many negative ion generators of which I am aware, mainly for car use, are of this type.
Having the positive electrode, a ring, in front of the negative needle, a short path is made from the needle(s) to the ring(s). This causes two major problems. First, the ions coming out of the needle(s) get readily absorbed by the ring(s) (collectors) and much less ions get through the ring(s) to be of benefit, resulting in inefficient ion generation. Second, the proximity of the opposite collector electrode (ring(s)) to the emitter(s) creates a high differential voltage gradient which, due to the high velocity of the ions bombarding the oxygen molecules of the air between the electrodes, produces ozone.

Ion generator with open emitter and safety feature


A method and computer program product for testing a system logger. Randomized input is provided into a logging facility and automated testing of the logging facility is performed in a multi-processing environment. Self-verification of data retrieved from the logging facility is performed to ensure no data loss occurs due to external system events or failures driven by a test tool. Real-time analysis of results received is performed by the test tool based on the randomized input into the logging facility. First failure data is captured and self-verification of results of a data recovery operation of the logging facility is performed in a disaster recovery scenario. Self-verification includes writing log blocks of random sizes to the log stream, iteratively forcing log data to be offloaded from primary storage to secondary storage, iteratively updating log stream attributes, and iteratively swapping duplexing modes.

1. Field of the Invention
The embodiments of the invention relate to a method and computer program product for verification of the operation and functionality of a data logging facility in a multiple system distributed computing environment.
2. Description of the Related Art
The IBM z/OS System Logger is a function provided by an operating system to exploiters running on z/OS. The number of exploiters of this component is increasing, as is its importance in relation to system performance and availability.
System Logger is a z/OS Multiple Virtual Storage (MVS) component that allows an application to log data from a sysplex. A sysplex can be thought of as a group of computer systems that act as a single entity by communicating with each other at the operating system level. Applications can log data from one system or multiple systems across the sysplex.
The advantage of using a System Logger is that the responsibility for tasks such as saving the log data (with the requested persistence), retrieving the data (potentially from any system in the sysplex), archiving the data, and expiring the data is removed from the creator of the log records. In addition, System Logger provides the ability to have a single, merged log, containing log data from multiple instances of an application within the sysplex.
During both functional and system verification testing of a z/OS System Logger, there is an ongoing problem of how to dynamically and persistently drive all functions of z/OS System Logger in a multiple system environment using a single method. There are many different test tools and applications that drive individual parts of z/OS System Logger, but there are no known tools or methods that have been derived for putting all of the pieces together in a single application.

Testing of a system logging facility using randomized input and iteratively changed log parameters

International Business Machines Corporation


With a view to providing an X-ray irradiator superior in workability in mounting a collimator box to an X-ray tube, the X-ray irradiator includes: a ring provided on an entry plate of the collimator box so as to surround an X-ray incidence window, the ring receiving therein a flange of the X-ray tube and having plural slots formed radially through the ring; plural tongue pieces inserted through the slots from outside to inside of the ring and holding down the back side of the flange; and a pair of half-rings which holds the plural tongue pieces at positions outside the ring and which, when one ends and opposite ends thereof are respectively opposed to each other, surrounds the ring with the plural tongue pieces inserted respectively into the plural slots.

The present invention relates to an X-ray irradiator and an X-ray imaging apparatus. Particularly, the present invention is concerned with an X-ray irradiator and an X-ray imaging apparatus in which X-rays from an X-ray tube are radiated to a subject through a collimator.
In an X-ray imaging apparatus, X-rays are radiated to a subject while limiting an irradiation field by a collimator. The collimator is accommodated within a collimator box which is secured to an X-ray tube (see, for example, Patent Literature 1).
[Patent Literature 1] Japanese Unexamined Patent Publication No. 2003-61941 (page 3, FIG. 1)
The mounting of a collimator box to an X-ray tube is performed using screws, but at least three screws are required. The load of the collimator box is imposed on those screws, so when mounting the collimator box to the X-ray tube, a tightening torque must be adjusted precisely with respect to all of the screws. Thus, the workability in manufacture and maintenance is poor, and if the tightening of the screws is not proper, there is a fear of fall-off of the collimator box.

X-ray irradiator and X-ray imaging apparatus

GE Medical Systems Global Technology Company, LLC


A computer-implemented robot pickup method including receiving a request from a user to pick up an article at a first location. A robot having a closeable transport container is navigated to the first location. The robot opens the closeable transport container and moves the article inside the closeable transport container at the first location, and navigates over an outdoor transportation network from the first location to the second location to deliver the article to the second location.

Methods and systems have been provided for delivering articles over roads and sidewalks to a location. Such systems have used wheeled vehicles. Recently disclosed systems utilize mixed autonomous wheeled vehicles.
What is needed is a method, system and robot that can permit autonomous delivery of articles, including goods and products, over a variety of outdoor transportation networks.


Among game elements, such as a character and an item, use status of a game element of a specific type or property (comprehensively “specific item”) is monitored. For example, the use status is monitored with respect to various monitoring parameters related to a transaction between users, a fusion, use in a game, or the like, of the game element. Then, when one or more of the monitoring parameters satisfy a predetermined adjustment support condition, an adjustment support control to increase a use quantity of the specific item of a monitoring target is performed. The use quantity of the specific item includes, for example, an available quantity of the specific item in the game or a total number of specific items that can be possessed and acquired by players.

In many games, a user or a player can own items acquired in relation to the games, and selectively use them. For example, in a Roll Playing Game (RPG), the player can equip a player character with a stronger item so as to make the player character stronger while clearing game stages, which is an important factor to enjoy the game.
The same can be said of, for example, a character selectively used as the player character, as well as the so-called item. Specifically, an important factor to enjoy a competition game including organizing a deck with characters is to acquire and own stronger characters through a competition result, a "gacha" lottery system, an online shop, a character fusion, and the like, so as to organize a stronger deck.
Accordingly, attractiveness of the game depends on how and how much to provide the user with game elements such as the item and the character which are owned and selectively used by each user. Thus, game makers have been making efforts to devise a method for dealing with these elements so as to enhance attractiveness of their game titles.
For example, Japanese Unexamined Patent Application Publication No. 2017-12424 discloses a technique to eliminate a loss of an opportunity for acquiring an item or the like related to a skipped game progress management unit in a game of a stage clear type in which a player sequentially plays a game and progresses the game progress management unit such as a stage, a map, a chapter and the like.
Unfortunately, there is no technique in computer control to control a "use quantity in a game" of the item or the character of each user playing the game. If any, there are some systems in which a winning probability of a so-called "gacha" lottery is changed or in which a limited item and a limited character are given to the player on some kind of conditions. However, both of the systems are manually set by game administrators. Moreover, the purpose of these systems is often to liven up the game (for example, to cause the number of login to increase). The winning probability of the gacha is not changed based on the "use quantity in the game" of the game element such as the item or the character possessed or used by each user.
The item and the character possessed or used by the user are basically given to the user on a predetermined fixed condition or fixed probability in most of the systems. Unfortunately, such systems require to manually determine and set, at a suitable timing in an appropriate way, how to change the winning probability of the gacha (lottery) and what kind of the limited item or the limited character can be given, depending on various stages such as an initial stage where the game has been just released and the number of users are small, a stage where the game starts gaining popularity and the number of users is drastically increasing, a stage where more than a certain number of skilled users with advanced play level exist, and the like. A loss of timing due to wrong determination may soon lead to a loss in popularity. In addition, since there is no concept of the "use quantity in the game", giving the item or the character does not always increase the "use quantity in the game".
It is preferable that a giving control of the item or the character be performed in such a manner that all users, regardless of beginners or skilled users, can maintain or enhance motivation to play the game. The giving control of the item and the character that can maintain or enhance the motivation to play the game naturally leads to an increase (or no decrease) in the "use quantity in the game" of the item or the character.


A clock reproduction circuit for reproducing a data clock from a data signal is disclosed. The clock reproduction circuit includes a voltage controlled oscillator, a phase detector, a frequency error detection circuit and a charge pump whose output is controlled by the outputs of the phase detector and the frequency error detection circuit. A VCO clock output from the voltage controlled oscillator is synchronized with the data clock by the beedback loop consisting of these elements. The frequency error detection circuit detects a frequency error between the VCO clock and the data clock by detecting changes in the phases of the VCO clock at the transition edges of the data signal. Analog and digital frequency error detection circuits are disclosed. Further, improved circuit elements in the clock reproduction circuit are disclosed.

An arrangement using a DLL (Delayed-Locked Loop) of the kind shown in FIG. 18 is known as a circuit that generates a signal having a prescribed phase with respect to an input signal. With regard to the arrangement shown in FIG. 18, see Reference 1 (ISSCC 1997 pp. 332–333, S. Sidiropoulos and Mark Horowitz et al., "A Semi-Digital DLL with Unlimited Phase Shift Capability and 0.08–400 MHz Operating Range").
As shown in FIG. 18, the DLL has an input buffer 11, a voltage-controlled delay line 14, a phase comparator 12 for detecting a phase difference between an output signal of the voltage-controlled delay line 14 and an output signal of the input buffer 11, and a filter 13 for smoothing a phase-difference detection signal output from the phase comparator 12. The voltage-controlled delay line 14 comprises a plurality of cascade-connected buffers. The phase comparator 12 is constituted by, e.g., a D-type flip-flop. The voltage-controlled delay line 14 is supplied with a voltage obtained by integrating the output signal of the phase comparator 12 by the filter 13, which includes a charge pump and an RC filter for converting the output signal of the phase comparator 12 to a voltage signal. The delay time in the voltage-controlled delay line 14 is variably set and feedback control is performed in such a manner that the phase of the output of input buffer 11 and the phase of the output of voltage-controlled delay line 14 will coincide (i.e., so that the phase difference between them will become zero). The multiple buffers of the voltage-controlled delay line 14 produce output clocks of equally spaced phase differences.
FIG. 19 illustrates a clock control circuit that produces a multi-phase clock by replacing the voltage-controlled delay line 14 of FIG. 18 with a variable oscillator circuit 15 such as a VCO (Voltage-Controlled Oscillator). With regard to the arrangement shown in FIG. 19, see Reference 2 (ISSC 1993 pp. 160–161, Mark Horowitz et al., "PLL Design for a 500 MB/s Interface"). FIG. 19 schematically illustrates one part of the main loop of a PLL circuit described in Reference 2. The variable oscillator circuit 15 such as a VCO produces a plurality of clock outputs (e.g., a plurality of clock outputs of equally spaced phase differences) and supplies these to transmit and receive fine loops (not shown) so that the phase of the internal clocks undergoes fine adjustment.
The arrangements shown in FIGS. 18 and 19 have a feedback loop constituted by a DLL or PLL and exhibit phase jitter ascribable to the feedback loop. This makes it difficult to generate correctly a signal of a desired phase. The present invention has been devised in view this problem.

This patent is subject to a terminal disclaimer.


When a gate voltage having a rectangular-shaped pulse is supplied, the voltage of a pixel electrode is pulled down and fluctuated by a fall of the gate voltage due to a parasitic capacitor formed between a gate line and the pixel electrode, i.e. a so-called drop voltage is generated. As the drop voltage depends on a time constant of a change in the gate voltage, it can be diminished by smoothing the falling edge of the gate voltage. This is achieved by, for example, providing a current discharging transistor of a gate driver 8 with a small channel width to decrease the maximum current value. By utilizing such a gate voltage, a liquid crystal display device with a small drop voltage can be provided, even when the capacitance of the parasitic capacitor is great.

1. Field of the Invention
The present invention relates to a display device of an active matrix type provided with a plurality of pixel electrodes arranged in a matrix and each connected to a thin film transistor (hereinafter referred to as a "TFT") as a switching element, and more particularly to a liquid crystal display (LCD) having an improved gate line driver.
2. Description of the Related Art
FIG. 1 shows an equivalent circuit diagram for one pixel in an LCD. A pixel TFT 5 connected to a gate line 2 and a data line 4 is connected to a pixel electrode 6. The pixel electrode 6 forms a capacitor CLC with an opposite electrode Vcom with liquid crystal 11 interposed therebetween. A storage capacitor CSC is provided in parallel to the liquid crystal capacitor CLC to maintain a voltage applied to the pixel electrode 6. While it is intended that the circuit have the above-described configuration, a parasitic capacitor CGS is generated between the gate and the source (the pixel electrode 6) of the TFT and increase in capacitance of the parasitic capacitor CGS results in problems, such as fluctuation in potential of the pixel electrode 6 due to the effects of a gate voltage applied to the gate line 2. In conventional devices, the effects of the parasitic capacitor CGS are reduced by providing a storage capacitor CSC with sufficient capacitance to account for that of the parasitic capacitor CGS.
In recent years, LCDs have come to be widely used for display devices in portable electronic devices, such as, for example, for viewfinders in digital still cameras and digital video cameras. LCDs for such portable devices must be made fine with a reduced display size while maintaining the number of pixels.
When a display size is reduced, the area of the pixel electrode is reduced, as is the electrode for forming the storage capacitor CSC. As a result, the capacitances of the liquid crystal capacitor CLC and the storage capacitor CSC are decreased. On the other hand, because the processible minimum line width is fixed, it is difficult to reduce the capacitance of the parasitic capacitor CGS beyond a certain level. Thus, when the LCD is made fine, the parasitic capacitor CGS has a relatively greater capacitance as compared to the liquid crystal capacitor CLC and the storage capacitor CSC.
Such an increase in capacitance of the parasitic capacitor CGS gives rise to an increase of a so-called drop voltage ΔV, i.e. the potential of the pixel electrode fluctuates because it is pulled down by a fall of the gate voltage. When the drop voltage ΔV is increased, various problems occur, such as generation of a difference in luminance between columns when liquid crystal is driven by an alternating voltage, and deviation of a central value Vc of a voltage applied to the pixel electrode from the potential Vcom of the opposite electrode.