Branched ethylene-propylene compositions which have improved melt strength and shear thinning are provided. The weight average branching index gxe2x80x2 for the higher molecular weight region of the ethylene-propylene composition is less than 0.95. Additionally, a novel process is provided for efficiently producing a branched ethylene-propylene composition comprising:

The present invention relates to gel-free, diene-free, branched semi crystalline high-C3 ethylene-propylene polymer compositions and a method for the preparation of branched semi-crystalline high-C3 ethylene-propylene polymer compositions using single site catalyst compounds.
The class of rubbery ethylene-propylene copolymers, conventionally referred to as EPR polymers, is well known and has gained substantial commercial acceptance. The copolymers are known to have good properties such as weatherability, ozone resistance and thermal stability and the polymers have accepted utility in automotive applications, as construction materials and as wire and cable coatings, among others. However, conventional ethylene-propylene rubbery copolymers are often difficult to process unless compounded by relatively large amounts of other materials.
A number of proposals have been made to improve the processability of the ethylene-propylene rubbery copolymer. In Yamamoto et al, U.S. Pat. No. 4,125,699, there are disclosed ethylene-propylene copolymers having a relatively high ethylene content produced in the presence of vanadium-containing polymerization catalysts. The copolymers of Yamamoto et al. are said to have improved processability because of a relatively broad molecular weight distribution. Vanadium catalysts, however, are of relatively low activity and many, if not most, of the more recent commercial ethylene-propylene rubbery copolymers are produced with a titanium-based catalyst because of the higher catalytic activity available through the use of such catalysts.
Processability has been improved in other types of polymers due to the presence of long chain branching. For example, EP 190 889 A2 discloses high energy irradiation of polypropylene to create what is believed to be polypropylene having substantial free-end long branches of propylene units. EP 384 431 discloses the use of peroxide decomposition of polypropylene in the substantial absence of oxygen to obtain a similar product.
Other examples of long chain branched polypropylene include U.S. Pat. No. 5,541,236, which introduces long chain branching by bridging two PP backbones to form H-type polymers, and U.S. Pat. No. 5,514,761, which uses dienes incorporated in the backbones to achieve a similar effect. However, it is difficult to avoid cross-linking and gel formation in such processes.
Thus, there is still a need for ethylene-propylene copolymer compositions having improved processability.
The present invention meets that need by providing gel-free, diene-free, branched ethylene-propylene (EP) polymer compositions that have improved sprayability, elasticity, and molecular weight. The weight average branching index gxe2x80x2 for the higher molecular weight region of the ethylene-propylene polymer compositions is less than 0.95. Additionally, a novel process is provided for efficiently producing branched ethylene-propylene polymer compositions comprising:
a) contacting propylene monomers and ethylene monomers in a reactor with an inert hydrocarbon solvent or diluent and a catalyst composition comprising one or more single site catalyst compounds capable of producing an ethylene-propylene polymer at a temperature from about 50xc2x0 C. to about 180xc2x0 C., wherein the ratio in the reactor of the propylene and ethylene monomers to the inert hydrocarbon solvent or diluent is less than 2.0, and further, wherein the propylene and ethylene monomers and the inert hydrocarbon solvent or diluent comprise no more than 90 percent of the total contents of the reactor; and
b) recovering a branched ethylene-propylene polymer composition, wherein the weight average branching index gxe2x80x2 for the higher molecular weight region of the ethylene propylene polymer composition is less than 0.95.
The present invention provides a novel method for producing gel-free, diene-free, branched EP. In addition, the branched EP product of the present invention is novel. The weight average branching index gxe2x80x2 for the higher molecular weight region of the ethylene-propylene polymer composition is less than 0.95. In some embodiments, the weight average branching index for the higher molecular weight region of the ethylene-propylene polymer composition is less than the 0.90. In other embodiments, it is less than 0.85. These branching characteristics result in a polymer with improved rheological characteristics.
An unusual feature of the branched ethylene-propylene polymers of the present invention is the presence of a significant amount of branching in the higher molecular weight range of the polymer. This branching results in improved melt strength and shear thinning, as well as other unique physical properties. In this case, the amount of branching is determined using the weight average branching index gxe2x80x2 of the branched ethylene-propylene polymer. The weight average branching index gxe2x80x2 is defined as gxe2x80x2=[IV]br/[IV]lin|Mw wherein [IV]br is the intrinsic viscosity of a branched polymer sample and [IV]lin is the intrinsic viscosity of a linear polymer sample. It is well known in the art that as the gxe2x80x2 value decreases, branching increases. See B. H. Zimm and W. H. Stockmayer, J. Chem. Phys. 17, 1301 (1949).
With regard to the molecular weight distribution of the ethylene-propylene polymer composition of the present invention, the following definitions apply:
Lower molecular weight region: That portion of the polymer product which has a molecular weight which is less than Peak MW (Mp).
Higher molecular weight region: That portion of the polymer product which has a molecular weight which is more than Peak MW (Mp).
Preferably, the ethylene-propylene polymers of the present invention have a high propylene content, wherein a majority of the monomeric content of the polymer is propylene. In other words, the propylene content of the ethylene-propylene polymers is greater than 50%. More preferably, the propylene content of the ethylene-propylene polymers is in the range of 75 to 95%. Most preferably, the propylene content of the ethylene-propylene polymers is in the range of 80 to 90%.
Other comonomers can be included in the branched ethylene-propylene of the present invention. Examples of these other comonomers include C4-C20 xcex1-olefins, geminally disubstituted monomers, C5-C25 cyclic olefins, C8-C25 styrenic olefins, and lower carbon number (C3-C8) alkyl substituted analogs of the cyclic and styrenic olefins. Preferably, the other comonomers comprise from 3 to 25 mole percent of the ethylene-propylene composition. More preferably, they comprise from 5 to 20 mole percent of the ethylene-propylene composition.
In a preferred embodiment, the total comonomer content of the branched ethylene-propylene composition of the present invention is from 5 to 40 mole percent. More preferably, the total comonomer content is from 10 to 30 mole percent. Most preferably, the total comonomer content is from 15 to 25 mole percent.
Catalysts
Catalysts which are useful for producing the branched EP of the present invention include single-site catalysts which are capable of producing ethylene-propylene polymers. Single-site catalysts which are useful in the present invention include metallocene catalysts, as well as complexes such as those described in Johnson, Killian, and Brookhart, J. Am. Chem. Soc., 1995, 117, 6414; Small, Brookhart and Bennett, J. Am. Chem. Soc., 1998, 120, 4049-4050; Repo et al., Journal of Organometallic Chemistry, 1997, 549, 177-186; and Britovsek et al., Chem. Commun., 1998, 849-850. Other useful single-site catalysts include bridged bis(arylamido) Group 4 compounds such as those described by D. H. McConville, et al, in Organometallics 1995, 14, 5478-5480. Each of these documents is incorporated by reference for the purposes of U.S. patent practice.
In some embodiments, metallocene catalysts are used to produce the branched ethylene-propylene polymers of the present invention. As used herein, xe2x80x9cmetallocenexe2x80x9d refers generally to compounds represented by the formula CpmMRnXq, wherein CP is the cyclopentadienyl ring which may be substituted, or a derivative thereof that may be substituted, M is a Group-4, -5, or -6 transition metal, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten. R is a hydrocarbyl group or hydrocarboxy group having from 1 to 20 carbon atoms, X is a halogen, m=1-3, n=0-3, q=0-3, and the sum of m+n+q is equal to the oxidation state of the transition metal.
Methods for making and using metallocenes are well known in the art. For example, metallocenes are detailed in U.S. Pat. Nos. 4,530,914; 4,542,199; 4,808,561; 4,871,705; 4,892,851; 4,933,403; 4,937,299; 5,017,714; 5,057,475; 5,120,867; 5,132,381; 5,155,080; 5,198,401; 5,278,119; 5,304,614; 5,324,800; 5,350,723; and 5,391,790 each fully incorporated herein by reference.
Preferred metallocenes are those that are stereorigid and comprise a Group 4, 5, or 6 transition metal, biscyclopentadienyl derivative, preferably bis-indenyl metallocene components having the following general structure:
wherein M1 is a metal of Group 4, 5, or 6 of the Periodic Table, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, preferably, zirconium, hafnium and titanium, most preferably zirconium and hafnium;
R1 and R2 are identical or different, are one of a hydrogen atom, a C1-C10 alkyl group, preferably a C1-C3 alkyl group, a C1-C10 alkoxy group, preferably a C1-C3 alkoxy group, a C6-C10 aryl group, preferably a C6-C8 aryl group, a C6-C10 aryloxy group, preferably a C6-C8 aryloxy group, a C2-C10 alkenyl group, preferably a C2-C4 alkenyl group, a C7-C40 arylalkyl group, preferably a C7-C10 arylalkyl group, a C7-C40 alkylaryl group, preferably a C7-C12 alkylaryl group, a C8-C40 arylalkenyl group, preferably a C8-C12 arylalkenyl group, or a halogen atom, preferably chlorine;
R3 and R4 a re hydrogen atoms;
R5 and R6 are identical or different, preferably identical, are one of a hydrogen atom, halogen atom, preferably a fluorine, chlorine or bromine atom, a C1-C10 alkyl group, preferably a C1 -C4 alkyl group, which may be halogenated, a C6-C10 aryl group, which may be halogenated, preferably a C6-C8 aryl group, a C2-C10 alkenyl group, preferably a C2-C4 alkenyl group, a C7-C40 arylalkyl group, preferably a C7-C10 arylalkyl group, a C7-C40 alkylaryl group, preferably a C7-C12 alkylaryl group, a C8-C40 arylalkenyl group, preferably a C8-C12 arylalkenyl group, a xe2x80x94NR215, xe2x80x94SR15, xe2x80x94OR15, xe2x80x94OSiR315 or xe2x80x94PR215 radical, wherein R15 is one of a halogen atom, preferably a chlorine atom, a C1-C10 alkyl group, preferably a C1-C3 alkyl group, or a C6-C10 aryl group, preferably a C6-C9 aryl group;
xe2x80x83xe2x95x90BR11,xe2x95x90A1R11, xe2x80x94Gexe2x80x94, xe2x80x94Snxe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x95x90SO, xe2x95x90SO2, xe2x95x90NR11, xe2x95x90CO, PR11, or xe2x95x90P(O)R11;
wherein:
R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C20 alkyl group, preferably a C1-C10 alkyl group, a C1-C20 fluoroalkyl group, preferably a C1-C10 fluoroalkyl group, a C6-C30 aryl group, preferably a C6-C20 aryl group, a C6-C30 fluoroaryl group, preferably a C6-C20 fluoroaryl group, a C1-C20 alkoxy group, preferably a C1-C10 alkoxy group, a C2-C20 alkenyl group, preferably a C2-C10 alkenyl group, a C7-C40 arylalkyl group, preferably a C7-C20 arylalkyl group, a C8-C40 arylalkenyl group, preferably a C8-C22 arylalkenyl group, a C7-C40 alkylaryl group, preferably a C7-C20 alkylaryl group or R11 and R12, or R11 and R13, together with the atoms binding them, can form ring systems;
M2 is silicon, germanium or tin, preferably silicon or germanium, most preferably silicon;
R8 and R9 are identical or different and have the meanings stated for R11;
m and n are identical or different and are zero, 1 or 2, preferably zero or 1, m plus n being zero, 1 or 2, preferably zero or 1; and
the radicals R10 are identical or different and have the meanings stated for R11, R12 and R13. Two adjacent R10 radicals can be joined together to form a ring system, preferably a ring system containing from about 4-6 carbon atoms.
Alkyl refers to straight or branched chain substituents. Halogen (halogenated) is fluorine, chlorine, bromine or iodine atoms, preferably fluorine or chlorine.
Particularly preferred metallocenes are compounds of the structures:
wherein:
M1 is Zr or Hf, R1 and R2 are methyl or chlorine, and R5, R6 R8, R9,R10, R11 and R12 have the above-mentioned meanings.
The chiral metallocenes may be used as a racemate for the preparation of highly isotactic polypropylene polymers and copolymers. It is also possible to use the pure R or S form. An optically active polymer can be prepared with these pure stereoisomeric forms. Preferably the meso form of the metallocene is removed to ensure the center (i.e., the metal atom) provides stereoregular polymerization. Separation of the stereoisomers can be accomplished by known literature techniques. For special products it is also possible to use rac/meso mixtures.
Methods for preparing metallocenes of the present invention are fully described in the Journal of Organometallic Chem., volume 288, (1958), pages 63-67, and in EP-A-320762, for preparation of the metallocenes described, both of which are herein fully incorporated by reference.
Illustrative but non-limiting examples of some preferred metallocenes include: Dimethylsilanylbis (2-methyl4-phenyl-1-indenyl)ZrCl2 Dimethylsilanylbis(2-methyl-4,5-benzoindenyl)ZrCl2; Dimethylsilanylbis(2-methyl-4,6-diisopropylindenyl)ZrCl2; Dimethylsilanylbis(2-ethyl-4-phenyl-1-indenyl)ZrCl2; Dimethylsilanylbis(2-ethyl-4-naphthyl-1-indenyl)ZrCl2, Phenyl(Methyl)silanylbis(2-methyl-4-phenyl-1-indenyl)ZrCl2, Dimethylsilanylbis(2-methyl-4-(1-naphthyl)-1-indenyl)ZrCl2, Dimethylsilanylbis(2-methyl-4-(2-naphthyl)-1-indenyl)ZrCl2, Dimethylsilanylbis(2-methyl-indenyl)ZrCl2, Dimethylsilanylbis(2-methyl-4,5-diisopropyl-1-indenyl)ZrCl2, Dimethylsilanylbis(2,4,6-trimethyl-1-indenyl)ZrCl2, Phenyl(Methyl)silanylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl2, 1,2-Ethandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl2, 1,2-Butandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl2, Dimethylsilanylbis(2-methyl-4-ethyl-1-indenyl)ZrCl2, Dimethylsilanylbis(2-methyl-4-isopropyl-1-indenyl)ZrCl2, Dimethylsilanylbis(2-methyl-4-t-butyl-1-indenyl)ZrCl2, Phenyl(Methyl)silanylbis(2-methyl-4-isopropyl-1-indenyl)ZrCl2, Dimethylsilanylbis(2-ethyl-4-methyl-1-indenyl)ZrCl2, Dimethylsilanylbis(2,4-dimethyl-1-indenyl)ZrCl2, Dimethylsilanylbis(2-methyl-4-ethyl-1-indenyl)ZrCl2, Dimethylsilanylbis(2-methyl-xcex1-acenaphth-1-indenyl)ZrCl2, Phenyl(Methyl)silanylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl2, Phenyl(Methyl)silanylbis(2-methyl-4,5-(methylbenzo)-1-indenyl)ZrCl2, Phenyl(Methyl)silanylbis(2-methyl-4,5-(tetramethylbenzo)-1-indenyl)ZrCl2, Phenyl(Methyl)silanylbis(2-methyl-a-acenaphth-1-indenyl)ZrCl2, 1,2-Ethandiylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl2, 1,2-Butandiylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl2, Dimethylsilanylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl2, 1,2-Ethandiylbis(2,4,7-trimethyl-1-indenyl)ZrCl2, Dimethylsilanylbis(2-methyl-1-indenyl)ZrCl2, 1,2-Ethandiylbis(2-methyl-1-indenyl)ZrCl2, Phenyl(Methyl)silanylbis(2-methyl-1-indenyl)ZrCl2, Diphenylsilanylbis(2-methyl-1-indenyl)ZrCl2, 1,2-Butandiylbis(2-methyl-1-indenyl)ZrCl2, Dimethylsilanylbis(2-ethyl-1-indenyl)ZrCl2, Dimethylsilanylbis(2-methyl-5-isobutyl-1-indenyl)ZrCl2, Phenyl(Methyl)silanylbis(2-methyl-5-isobutyl-1-indenyl)ZrCl2, Dimethylsilanylbis(2-methyl-5-t-butyl-1-indenyl)ZrCl2, Dimethylsilanylbis(2,5,6-trimethyl-1-indenyl)ZrCl2, and the like.
Some preferred metallocene catalyst components are described in detail in U.S. Pat. Nos. 5,149,819, 5,243,001, 5,239,022, 5,296,434 and 5,276,208 all of which are herein fully incorporated by reference. In addition, the bis-amido and bis-arylamido transition metal catalysts of U.S. Pat. No. 5,318,935 and copending U.S. patent application Ser. No. 08/803,687, filed Feb. 24, 1997, can be useful in forming the branched ethylene-propylene polymers of the present invention.
Most preferably, the catalyst used to produce the branched ethylene-propylene of the present invention is a substituted bridged bis-indenyl zirconocene or hafnocene such as dimethylsilyl bis(2-methyl-indenyl)ZrCl2, dimethylsilyl bis(2-methyl-indenyl)ZrMe2, dimethylsilyl bis(2-methyl-4-phenyl-1-indenyl)ZrCl2, dimethylsilyl bis(2-methyl-4-(1-naphthyl)-1-indenyl)ZrCl2, or dimethylsilyl bis(indenyl)hafnium dimethyl.
The terms xe2x80x9ccocatalystxe2x80x9d and xe2x80x9cactivatorxe2x80x9d are used herein interchangeably and are defined to be any compound or component which can activate a bulky ligand transition metal compound or a metallocene, as defined above. Alumoxane may be used as an activator. There are a variety of methods for preparing alumoxane, non-limiting examples of which are described in U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and WO 94/10180, each of which is fully incorporated herein by reference. It may be preferable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution.
It is also within the scope of this invention to use ionizing activators, neutral or ionic, or compounds such as tri(n-butyl)ammonium tetrakis(pentaflurophenyl)boron, which ionize the neutral metallocene compound. Such ionizing compounds may contain an active proton, or some other cation associated with but not coordinated or only loosely coordinated to the remaining ion of the ionizing compound. Combinations of activators are also contemplated by the invention, for example, alumoxane and ionizing activators in combinations, see for example, WO 94/07928.
Descriptions of ionic catalysts for coordination polymerization comprised of metallocene cations activated by non-coordinating anions appear in the early work in EP-A-0 277 003, EP-A-0 277 004 and U.S. Pat. No. 5,198,401 and WO-A-92/00333 (incorporated herein by reference). These teach a preferred method of preparation wherein metallocenes (bisCp and monoCp) are protonated by an anion precursor such that an alkyl/hydride group is abstracted from a transition metal to make it both cationic and charge-balanced by the non-coordinating anion.
The term xe2x80x9cnoncoordinating anionxe2x80x9d means an anion which either does not coordinate to said cation or which is only weakly coordinated to said cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base. xe2x80x9cCompatiblexe2x80x9d noncoordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral four coordinate metallocene compound and a neutral by-product from the anion. Noncoordinating anions useful in accordance with this invention are those which are compatible, stabilize the metallocene cation in the sense of balancing its ionic charge in a +1 state, yet retain sufficient lability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization.
The use of ionizing ionic compounds not containing an active proton but capable of producing both the active metallocene cation and an noncoordinating anion is also known. See, EP-A-0 426 637 and EP-A-0 573 403 (incorporated herein by reference). An additional method of making the ionic catalysts uses ionizing anion pre-cursors which are initially neutral Lewis acids but form the cation and anion upon ionizing reaction with the metallocene compounds, for example the use of tris(pentafluorophenyl) boron. See EP-A-0 520 732 (incorporated herein by reference). Ionic catalysts for addition polymerization can also be prepared by oxidation of the metal centers of transition metal compounds by anion pre-cursors containing metallic oxidizing groups along with the anion groups, see EP-A-0 495 375 (incorporated herein by reference).
Where the metal ligands include halogen moieties (for example, bis-cyclopentadienyl zirconium dichloride) which are not capable of ionizing abstraction under standard conditions, they can be converted via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc. See EP-A-0 500 944 and EP-A1-0 570 982 (incorporated herein by reference) for in situ processes describing the reaction of alkyl aluminum compounds with dihalo-substituted metallocene compounds prior to or with the addition of activating anionic compounds.
Support Materials
The metallocenes described herein may be supported using a porous particulate material, such as for example, talc, inorganic oxides, inorganic chlorides and resinous materials such as polyolefin or polymeric compounds.
Preferred support materials are porous inorganic oxide materials, which include those from the Periodic Table of Elements of Groups 2, 3, 4, 5, 13 or 14 metal oxides. Silica, alumina, silica-alumina, and mixtures thereof are particularly preferred. Other inorganic oxides that may be employed either alone or in combination with the silica, alumina or silica-alumina are magnesia, titania, zirconia, and the like.
Preferably the support material is porous silica which has a surface area in the range of from about 10 to about 700 m2/g, a total pore volume in the range of from about 0.1 to about 4.0 cc/g and an average particle size in the range of from about 10 to about 500 xcexcm. More preferably, the surface area is in the range of from about 50 to about 500 m2/g, the pore volume is in the range of from about 0.5 to about 3.5 cc/g and the average particle size is in the range of from about 20 to about 200 xcexcm. Most preferably the surface area is in the range of from about 100 to about 400 m2/g, the pore volume is in the range of from about 0.8 to about 3.0 cc/g and the average particle size is in the range of from about 30 to about 100 xcexcm. The average pore size of typical porous support materials is xe2x89xa610 xc3x85. Preferably, a support material is used that has an average pore diameter of xe2x89xa650 xc3x85, and most preferably it is in the range of from about 75 to about 350 xc3x85. It may be particularly desirable to dehydrate the silica at a temperature of from about 100xc2x0 C. to about 800xc2x0 C. anywhere from about 3 to about 24 hours.
The metallocenes, activator and support material may be combined in any number of ways. Suitable support techniques are described in U.S. Pat. Nos. 4,808,561 and 4,701,432 (each fully incorporated herein by reference.) Preferably the metallocenes and activator are combined and their reaction product supported on the porous support material as described in U.S. Pat. No. 5,240,894 and WO 94/28034, WO 96/00243, and WO 96/00245 (each fully incorporated herein by reference.) Alternatively, the metallocenes may be preactivated separately and then combined with the support material either separately or together. If the metallocenes are separately supported, then preferably, they are dried then combined as a powder before use in polymerization.
Regardless of whether the metallocene and activator are separately precontacted or whether the metallocene and activator are combined at once, the total volume of reaction solution applied to porous support is preferably less than about 4 times the total pore volume of the porous support, more preferably less than about 3 times the total pore volume of the porous support and even more preferably in the range of from more than about 1 to less than about 2.5 times the total pore volume of the porous support. Procedures for measuring the total pore volume of porous support are well known in the art. The preferred method is described in Volume 1, Experimental Methods in Catalyst Research, Academic Press, 1968, pages 67-96.
Methods of supporting ionic catalysts comprising metallocene cations and noncoordinating anions are described in WO 91/09882, WO 94/03506, WO 96/04319 and U.S. Pat. No. 5,643,847 (incorporated herein by reference.) The methods generally comprise either physical adsorption on traditional polymeric or inorganic supports that have been largely dehydrated and dehydroxylated, or using neutral anion precursors that are sufficiently strong Lewis acids to activate retained hydroxy groups in silica containing inorganic oxide supports such that the Lewis acid becomes covalently bound and the hydrogen of the hydroxy group is available to protonate the metallocene compounds.
The supported catalyst system may be used directly in polymerization or the catalyst system may be prepolymerized using methods well known in the art. For details regarding prepolymerization, see U.S. Pat. Nos. 4,923,833 and 4,921,825, EP 0 279 863 and EP 0 354 893 each of which is fully incorporated herein by reference.
Polymerization Processes
Branched ethylene-propylene polymers of the present invention may be produced using the catalyst described above in any process including gas, slurry, suspension, or solution phase processes. Additionally, combinations of the above reactor types in multiple, series reactors, or multiple reaction conditions, or multiple catalyst configurations are explicitly intended.
In the preferred embodiment, this invention is directed toward the polymerization of ethylene and propylene in a slurry or solution phase polymerization process, particularly a solution polymerization process.
Typically in a gas phase polymerization process a continuous cycle is employed wherein one part of the cycle of a reactor, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization. The recycle stream usually contains one or more monomers continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. This heat is removed in another part of the cycle by a cooling system external to the reactor. The recycle stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and new or fresh monomer is added to replace the polymerized monomer. (See for example U.S. Pat. Nos. 4,543,399; 4,588,790; 5,028,670; 5,352,749; 5,405,922, and 5,436,304 all of which are fully incorporated herein by reference.)
A slurry polymerization process generally uses pressures in the range of from about 1 to about 500 atmospheres or even greater and temperatures in the range of from xe2x88x9260xc2x0 C. to about 280xc2x0 C. In a slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid or supercritical polymerization medium to which ethylene, propylene and comonomers and often hydrogen along with catalyst are added. The medium employed should be liquid under the conditions of polymerization and relatively inert. The liquid employed in the polymerization medium can be an inert hydrocarbon solvent or diluent. For example, an alkane or a cycloalkane such as hexane or isobutane can be used. In a preferred embodiment, hexane or propylene monomer serves as the polymerization diluent.
Preferably, the ethylene monomers, the propylene monomers and the inert hydrocarbon solvent or diluent comprise no more than 90 percent of the total contents of the reactor. More preferably, they comprise no more than 80 percent of the total contents of the reactor. Most preferably, the ethylene monomers, the propylene monomers and the inert hydrocarbon solvent or diluent comprise no more than 70 percent of the total contents of the reactor. In a preferred embodiment, the ethylene monomers, the propylene monomers and the inert hydrocarbon solvent or diluent comprise at least 50 percent of the total contents of the reactor.
Also, the ratio in the reactor of the ethylene and propylene monomers to the inert hydrocarbon solvent or diluent in the reactor feed is preferably less than 2.0. More preferably, the ratio is less than 1.0. Still more preferably, it is less than 0.8. Most preferably, the ratio in the reactor of the ethylene and propylene monomers to the inert hydrocarbon solvent or diluent in the reactor feed is less than 0.5.
Preferably, the polymerization is carried out using a pressure of from about 200 kPa to about 7,000 kPa at a temperature in the range of from about 50xc2x0 C. to about 180xc2x0 C.
More preferably, the polymerization is carried out at a temperature in the range of from about 50xc2x0 C. to about 130xc2x0 C. Most preferably, the polymerization is carried out at a temperature in the range of from 60xc2x0 C. to 110xc2x0 C.
The polymerization may be conducted in batch, semi-batch or continuous mode and the entire polymerization may take place in one reactor or the polymerization may be carried out in a series of reactors. Preferably, the polymerization is carried out in continuous mode.
The reaction time for the polymerization of the present invention will depend upon the catalyst system and reaction conditions.
The above-described temperatures, reaction times and other conditions are considered suitable ethylene-propylene polymerization conditions for the purposes of this invention.
Hydrogen may be added to the polymerization system as a molecular weight regulator in the first and/or subsequent reactors depending upon the particular properties of the product desired and the specific metallocenes used. When metallocenes having different hydrogen responses are used, the addition of hydrogen will affect the molecular weight distribution of the polymer product accordingly. Hydrogen may also affect the distribution of branching.
For preparation of the branched ethylene-propylene polymer, preactivation of the metallocene may be advantageous. For example, it is widely known in the art that preactivation of the metallocene with alumoxane before addition to a continuous solution-phase reactor yields higher activities than continuous addition of metallocene and activator in two separate streams. Furthermore, it may be advantageous to control precontacting time to maximize catalyst effectiveness, e.g., avoiding excessive aging of the activated catalyst composition.
Industrial Utility
The branched ethylene-propylene polymers of the present invention exhibit improved melt properties, such as shear thinning, elasticity, melt strength and low viscosity. The branched ethylene-propylene polymers of the present invention are useful in a variety of applications, including hot melt adhesives, elastic compositions, modifiers and molded products.
In order that the invention may be more readily understood, reference is made to the following examples, which are intended to illustrate the invention but not to limit the scope thereof.

Branched semi-crystalline high-C3 ethylene-propylene compositions

Abstract: b) recovering a branched ethylene-propylene composition, wherein the weight average branching index gxe2x80x2 for the higher molecular weight region of the ethylene-propylene composition is less than 0.95.


The present invention relates to a mobile communication terminal having an unmanned air vehicle, the mobile communication terminal being smart-phones, tablet-phones, or tablet-PCs which are carried by users and used for mobile communication, and the unmanned air vehicle being kept in the mobile communication terminal or in various mobile communication terminals that may be developed in the future, and being capable of navigating and performing various operations according to a control using the mobile communication terminal. The present invention provides a mobile communication terminal having an unmanned air vehicle, which includes: an unmanned air vehicle including a flying means, a wireless communication means and an image capturing means; and a mobile communication terminal part including: a hangar part in which the unmanned air vehicle is kept; an unmanned air vehicle control means controlling the unmanned air vehicle to navigate and capture images through wireless communication with the unmanned air vehicle; and a manipulation part through which a control command of a user is input to the unmanned air vehicle control means.

For a long time, unmanned air vehicles operated by using an radio control (RC) have been used for hobby and industrial or military services, and those unmanned air vehicles are controlled in close ranges by using an RC controller. Recently, unmanned aerial vehicles, called as drones, have been widely known for carrying out aerial photographing or air attack by remote control for military operations. Currently, the use of drones has been developed and has widely spread into use such as logistics delivery (delivery service), searching for missing persons and wildfire monitoring, tracking of vehicles used in crimes, observation of animals in danger of extinction, etc. In addition, in terms of the size of unmanned aerial vehicles, micro unmanned aerial vehicles called "nano drones" as well as large-sized drones that can be used for logistics delivery have been developed.
In addition, recently, these unmanned aerial vehicles have recently begun to attract a great deal of attention in commercial uses, along with techniques to control their operation by using mobile communication terminals such as feature-phones or smart-phones. Examples of related arts of controlling unmanned aerial vehicles by using feature-phones or smart-phones are disclosed in a patent document 1 and a patent document 2 of prior art documents. In other words, the patent document 1 (Korean Patent Application No. 10-2002-0070417, Publication Date: 9 Sep. 2002) discloses an radio control system for an unmanned aerial vehicle, the system using a mobile phone (cellular phone, PCS, IMT2000, etc.) including Bluetooth therein. In addition, in the patent document 2 (Korean Patent No. 10-1117207, Publication Date: 18 Jan. 2012), an unmanned aerial vehicle includes an electronic map, flight navigation points thereof are designated, and the unmanned aerial vehicle is controlled to automatically navigate along the flight navigation points. Herein, a communication system, a coordinate input system, and a manual/auto switching system are provided, so that a navigation track and a navigation state of the unmanned aerial vehicle are monitored by manually or automatically controlling the unmanned aerial vehicle through a smart-phone. As described above, the technique for controlling the unmanned aerial vehicle using a conventional feature-phone or smart-phone is widely known and commercialized.

Mobile communication terminal having unmanned air vehicle


In servicing a wellbore having casing cemented therein, an assembly deploys on tubing (coiled tubing or jointed pipe) downhole. Fluid is circulated down the tubing to the assembly, and a perforating gun on the assembly passes the circulated fluid through it. A tool downhole on the assembly is then operated with the circulated fluid passed through the perforating gun. For example, the tool can include a fluid-operated motor and milling tool. To allow the fluid to flow through the gun, an outer housing supports the load between the tubing and operable tool and has an inner flow tube disposed therein. Charges for perforating are supported in the space between the housing and flow tube. Once cleanup or other service is done with the tool, a detonation is initiated for the perforating the casing with one or more charges of the perforating gun. The detonation can be initiated by a deployed device or ball shifting a sleeve to drive a pin into a detonator. Detonating cord can connect the detonation to the charges.

Toe cleanout and initial perforating in a horizontal well require two complete trips to be run into the well for the separate operations and involve large costs. For example, a horizontal wellbore "toe prep" service is performed with a coil tubing operation. In this toe prep service, coil tubing deploys a fluid-activated motor downhole. The motor turns a mill to cleanout the lower section of the wellbore casing of residual cement and the like. Once cleanout is done and the equipment removed, a subsequent descent of Tubing Conveyed Perforating (TCP) equipment is then used to perforate the casing to allow for pumping into the reservoir rock. This ultimately allows operators to perform conventional plug and perforation operations.
Tubing Conveyed Perforating (TCP) equipment is the most common type of equipment used for performing toe preparation of the casing. In the perforating operation, TCP equipment consisting of one to ten guns is conveyed downhole to prepare the toe of the wellbore casing with perforations. The TCP equipment, which is nonelectric, then establishes the first perforations in the casing and can be conveyed on coil tubing or on pipe.
In the pipe-conveyed operation, multiple pressure-activated firing heads of the TCP equipment are fired at the same time and may or may not have time delays attached. Pipe tally is used to correlate the position of the TCP equipment downhole in the casing, and a packer may or may not be run to isolate the annulus. In general, such an operation can have a total trip time from about 8 to 12 hours.
In the coil tubing-conveyed operation, one pressure-activated firing head or ball-drop-differential firing head fires first in the TCP equipment. Then, time delays between gun activations can allow the coil tubing to move the TCP equipment to different zones to be perforated. In the end, the number of guns that can be run and the different zones that can be perforated may be limited by the lubricator and crane equipment at surface. The depth recorded from the clean-out run with the coil tubing can be used to correlate the position of the TCP equipment downhole to the zones to be perforated. Overall, such an operation can have a total trip time from about 6 to 10 hours.
Rather than using perforations to prepare the toe, a sliding sleeve can be attached to the casing just above the toe shoe and can be cemented in place with the casing. To establish initial fluid communication, operations can circulate a ball to shift the sliding sleeve open. At this point, opens ports on the sleeve are then in contact with the formation to allow for fluid communication used in fracturing operations and the like.
Use of such a sliding sleeve removes the need for running coil tubing or using workover rigs, and the run time of such operations can be avoided. Still, use of such a sliding sleeve produces a limited number of holes at the toe. Pressure pumping is required to open the sleeves, and the initial preparation may need to be followed by wireline pump-down perforation operations.
Importantly, if the sleeve does not operate properly or if operations are unable to establish a sufficient pump rate, operators must perform traditional TCP toe preparation anyway. Besides, cementing the sleeve offers its own challenges as operations must limit the cement sheath at the sleeve and risk over displacing the cement.
Because the first operation after cementing is normally the cleanout run on coil tubing, it would be advantageous to combine toe-prep perforating with the clean-out run. However, combining these runs is not possible with conventional explosive perforating guns and equipment. Instead, combined runs of cleanout and toe-prep perforation can be done when sand jet perforation is used. In this technique, a mill and motor are run in the casing to drill-up any residual fill and cement in the casing. Then, operations uses high-pressure jets to direct an abrasive fluid slurry to abrade holes into the casing.
Sand jet perforation may not always be useful or possible for a given implementation. If the sand jet perforating tool does not operate properly or if a sufficient pump rate cannot be established, operations must perform traditional tubing conveyed perforating (TCP) toe-prep anyway. Besides, sand jet perforation may create a limited number of holes so that wireline (WL) pump-down perforating operations may still need to be performed afterwards.
In an attempt to overcome the problems with the above techniques, a toe gun has been developed that is attached to the outside of the casing. An example of such an external toe gun is the EXternal Toe Gun (EXTG) available from Smart Completions, Ltd. The external toe gun has TCP guns mounted to the outside of the casing just above the toe shoe and are cemented in place. The guns are actuated by pressuring up the casing and bursting a rupture disc. Once activated, the gun fires in two directions—into the casing to make a flow path and away from the casing into the formation to complete the flow path.
As will be appreciated, having an external toe gun outside the casing requires a larger borehole, which carries additional drilling costs and problems. The guns must also be run at the same time as the casing. Accordingly, the guns must remain downhole longer and can become damaged.
In the end, even this technique can produce a limited number of holes so that subsequent wireline pump-down perforation may need to be done. Finally, if a gun does not fire, traditional TCP toe prep must be performed anyway.
Wellbore isolation and re-perforating in an existing well also typically require two complete trips to be run into the well for the separate operations and involve large costs. For example, a rigless workover and re-perforation service is performed with a coil tubing operation. In this rigless workover service, coil tubing deploys a fluid-activated inflatable plug. The plug fills with fluid transmitted through the tubing and seals against the completion liner or casing to isolate the lower section from the remaining wellbore. Once isolation is achieved and the equipment removed, a subsequent descent of Tubing Conveyed Perforating (TCP) equipment is then used to perforate the casing to allow for pumping into and treating and/or extraction from the reservoir rock. This ultimately allows operators to perform rigless workover, recompletion operations.
The subject matter of the present disclosure is directed to overcoming, or at least reducing the effects of, one or more of the problems set forth above.

Pump-through perforating gun combining perforation with other operation


A jewelry piece to hold the ends of a plurality of parallel beaded jewelry strings has two interdigitated U shaped bodies. Each body has a slot along at least one edge in which to slide the end pieces of each bead string. This jewelry piece can be used as a coupling for a necklace or bracelet or for an earring with hanging beaded strings.

1. Field of the Invention
This invention relates to a jewelry piece for holding the ends of a plurality of strings of ornamental objects such as strings of beads made of a valuable metal. The end bead of each such string is held in parallel side by side relation in the jewelry piece and can be readily disconnected therefrom or the jewelry piece can act as one member of a coupling for connecting a further series of bead strings together.
2. Description of the Prior Art
Jewelry is worn in a wide range of different styles and it is frequently the desire of the wearer to repeat a given pattern in a variety of jewelry items such as a necklace, bracelet, or earrings. A wearer may have a supply of a favorite item such as a beaded gold chain that she desires to use in different lengths in one or more of the aforementioned items.
The prior art has dealt with this problem in a variety of different ways, none of them being completely satisfactory. Miller U.S. design Pat. No. D57,180 discloses a bracelet made of a plurality of strings of beads held in parallel side by side relation but the strings are held in a permanent mount where removal or rearrangement is difficult. U.S. Pat. No. 1,646,999 to Goodridge discloses a spacer bar that can be closed over several rows of parallel beads to hold them in a desired spaced relation but again the bar, once clamped is difficult to pry open and change the relationship of the rows.
McFarland U.S. Pat. No. 2,644,992 teaches a bead chain clamp for jewelry with a pair of connectable end members, each having a plurality of individual slots for insertion of the end bead of a string of beads. Each end bead must be inserted in its own respective slot. U.S. Pat. No. 4,628,708 to Ivey discloses a jewelry chain organizer that clamps around parallel rows of bead chains that are already in a desired arrangement. Romano U.S. Pat. No. 6,014,871 teaches a jewelry system with a necklace that can be disassembled and reconfigured to form a single or double strand bracelet through a series of disconnectable elements.
This invention relates to a jewelry piece for holding the ends of a plurality of strings of ornamental objects such as beads made of a valuable metal. Such strings are held in parallel side by side relation in the jewelry piece and can be readily disconnected therefrom or the jewelry piece can act as one member of a coupling for connecting a further series of bead strings together. The jewelry piece is a flat U shaped body with a bight and a long leg and a short leg extending perpendicularly from the bight. When used as a coupling two U shaped jewelry pieces are interdigitated with the short leg of each jewelry piece being positioned between the legs of an adjacent jewelry piece. A slot is formed in the outer peripheral edge of each jewelry piece, at least along the edge of the long leg and an end bead of a chain of beads can be fitted into an end opening of the slot so that only the end bead is held in the slot and the remainder of the string can hang out from the slot and be supported by the jewelry piece. The end bead of each of a plurality bead strings can each be fitted side by side into the slot so that the strings will be supported from the piece in parallel side by side relation. When all of the bead strings are cut to the same length, a second jewelry piece can be similarly fitted to the second end. Then the two jewelry pieces can be interdigitated together to form a coupling for a bracelet or a necklace, ring, or belt. If the second end is left free, that is, without a jewelry piece being attached thereto, then a special pin can be a connected to the jewelry piece so it, with the bead strings hanging from the slot, the jewelry piece and beads can be used as a brooch, pin, tie clip, tie pin, cufflink or pendent. Alternatively the bead strings can be cut to different lengths for decorative effect. Of course a bracelet, a necklace, and a brooch can all be formed so that the wearer can have a matching ensemble of jewelry.


Data communications are provided in a computer system by accepting message information within a unified information exchange manager. The unified exchange manager is executed to select an appropriate application from a plurality of applications that are executable on the computer system. The unified exchange manager selects the appropriate application based on a data type of the message information. The message information from the unified information exchange manager is passed to the appropriate application program if said user accepts said message information.

The present invention relates to the field of computer operating systems software. In particular the present invention discloses a method of providing an immediate response computer communication system for both external and internal interprocess communication.
Modern computer operating systems support several application programs executing concurrently. To communicate with external hardware devices, the application programs call input/output routines in the operating system. To facilitate communication between applications, an operating system may provide a message passing system or a method of opening xe2x80x9csocketsxe2x80x9d between applications.
However, using two different methods for communicating information is unnecessarily complex. It would be desirable to have a simplified method of communicating information from and to application programs. Furthermore, it would be desirable to have a messaging system that allows dormant applications to be immediately activated upon receiving information that is destined for the dormant application.

Method and apparatus for unified external and interprocess communication


A light-emitting element including a first electrode, a second electrode, and an EL layer provided between the first and second electrodes is provided. The first electrode includes a conductive layer, a first transparent conductive layer in contact with the conductive layer, and a second transparent conductive layer in contact with the first transparent conductive layer. The first transparent conductive layer contains a first oxide. The second transparent conductive layer contains a second oxide. The conductive layer has a function of reflecting light. The first oxide contains In and M (M represents Al, Si, Ti, Ga, Y, Zr, La, Ce, Nd, or Hf). The second oxide contains In. The resistivity of the second transparent conductive layer is lower than that of the first transparent conductive layer. The thickness of the second transparent conductive layer is greater than or equal to that of the first transparent conductive layer.

1. Field of the Invention
One embodiment of the present invention relates to a light-emitting element, or a light-emitting device, a display device, an electronic device, and a lighting device each including the light-emitting element.
Note that one embodiment of the present invention is not limited to the above technical field. The technical field of one embodiment of the invention disclosed in this specification and the like relates to an object, a method, or a manufacturing method. In addition, one embodiment of the present invention relates to a process, a machine, manufacture, or a composition of matter. Specifically, examples of the technical field of one embodiment of the present invention disclosed in this specification include a semiconductor device, a display device, a liquid crystal display device, a light-emitting device, a lighting device, a power storage device, a memory device, a method for driving any of them, and a method for manufacturing any of them.
2. Description of the Related Art
In recent years, research and development have been extensively conducted on light-emitting elements using electroluminescence (EL). In a basic structure of such a light-emitting element, a layer containing a light-emitting substance (an EL layer) is interposed between a pair of electrodes. By applying a voltage between the pair of electrodes of this element, light emission from the light-emitting substance can be obtained.
Since the above light-emitting element is a self-luminous type, a light-emitting device using this light-emitting element has advantages such as high visibility, no necessity of a backlight, low power consumption, and the like. Further, the light-emitting device using the light-emitting element also has advantages in that it can be formed to be thin and lightweight, and has high response speed.
In the case where the above light-emitting element is used for a display panel, there are the following two methods: a method of providing subpixels in a pixel with EL layers having functions of emitting light of different colors (hereinafter referred to as a separate coloring method) and a method of providing subpixels in a pixel with, for example, a common EL layer having a function of emitting white light and color filters each having a function of transmitting light of a different color (hereinafter referred to as a white EL+color filter method, and it is noted that the emission color of the common EL layer is not limited to white).
One of the advantages of the white EL+color filter method is that the EL layer can be shared by all of the subpixels. Therefore, compared with the separate coloring method, loss of a material of the EL layer and cost of patterning for forming the EL layer can be reduced; thus, display devices can be manufactured at low cost with high productivity. In the separate coloring method, it is necessary to provide a space between the subpixels to prevent mixture of the materials of the EL layers in the subpixels. In contrast, the white EL+color filter method has another advantage in that the space is not necessary and therefore a high-resolution display device having higher pixel density can be achieved.
The light-emitting element can emit light of a variety of colors depending on the kind of light-emitting substance included in the EL layer. A light-emitting element which can emit white light or light of color close to white with high efficiency has been particularly required to be applied to a lighting and a display device utilizing the white EL+color filter method. In addition, a light-emitting element having low power consumption is required.
In order to improve the extraction efficiency of light from a light-emitting element, a method has been proposed, in which a micro optical resonator (microcavity) structure utilizing a resonant effect of light between a pair of electrodes is used to increase the intensity of light having a specific wavelength (e.g., see Patent Document 1).
Furthermore, in order to reduce power consumption of a light-emitting element, a method has been proposed, in which a metal oxide having a high work function is used for one of a pair of electrodes, through which light is not extracted, to reduce voltage loss due to the electrode and thus to reduce the drive voltage of a light-emitting element (e.g., see Patent Document 2).

Light-emitting element including EL layer, electrode which has high reflectance and a high work function, display device, electronic device, and lighting device

Semiconductor Energy Laboratory Co., Ltd.


An organic light-emitting display device including a TFT comprising an active layer, a gate electrode comprising a lower gate electrode and an upper gate electrode, and source and drain electrodes insulated from the gate electrode and contacting the active layer; an organic light-emitting device electrically connected to the TFT and comprising a pixel electrode formed in the same layer as where the lower gate electrode is formed; and a pad electrode electrically coupled to the TFT or the organic light emitting device and comprising a first pad electrode formed in the same layer as in which the lower gate electrode is formed, a second pad electrode formed in the same layer as in which the upper gate electrode is formed, and a third pad electrode comprising a transparent conductive oxide, the first, second, and third pad electrodes being sequentially stacked.

1. Field
The following description relates to an organic light-emitting display device and a method of manufacturing the organic light-emitting display device, and more particularly, to an organic light-emitting display device that is simple to manufacture and includes a pad portion with increased corrosion-resistance and reduced resistance, and a method of manufacturing the organic light-emitting display device.
2. Description of Related Art
Flat panel displays such as organic light-emitting display devices and liquid crystal displays (LCDs) are manufactured on a substrate on which a pattern including a thin film transistor (TFT), a capacitor, and wiring connecting the TFT to the capacitor is formed. In general, to form a fine pattern including the TFT and the like, the fine pattern is transferred to a substrate used to manufacture a flat panel display, by using a mask on which the fine pattern is drawn.
However, in a process of transferring a pattern by using a mask, a mask on which a necessary pattern is drawn is first prepared. Thus, as the number of processes using a mask increases, the manufacturing costs for preparing for the use of masks increases. Moreover, the manufacturing process is complicated due to the above-described complicated processes, and a manufacturing time is increased, leading to an increase in manufacturing costs.


Provided is an ink composition suitable for an ink jet system, which comprises a pigment or a dye, an aqueous medium, a water soluble resin having an oxazolyl group or a fine particle having an oxazolyl group adsorbed on its outer surface and a compound having at least one carbonyl group wherein the composition has a viscosity of not more than 15 cp at 25.degree. C.

1. Field of the Invention
The present invention relates to an ink suited for ink-jet printers, and also to an ink-jet recording process and apparatus that make a record on paper by causing ink to fly from orifices of a recording head by the action of energy, preferably heat energy. More particularly, it relates to an ink-jet recording process and apparatus that make a record on non-coated paper such as paper for copying, paper for reporting, notepaper, letter paper, bond paper and computer printout paper (continuous business forms) commonly used in offices and homes.
2. Related Background Art
Ink-jet recording systems have the advantages that they make less noise in the course of recording and a recorded image with a high resolution can be obtained at a high speed because of use of a highly integrated head. Inks used in such ink-jet recording systems are those prepared by dissolving various kinds of water-soluble dyes in water or in a mixed solution of water and an organic solvent.
When the water-soluble dyes are used, however, light fastness of recorded images is often questioned because such water-soluble dyes have poor light fastness by nature.
Water fastness of recorded images is also often questioned because the dye is water-soluble. More specifically, if recorded images become wet with rain, sweat, or water from food and drink, they may become blurred or disappear.
Meanwhile, light fastness and water fastness are similarly questioned also in writing utensils such as ball-point pens because water-soluble dyes are mainly used, and various water-based pigment inks for writing utensils have been proposed so that such problems can be settled. Examples of studies on dispersion stability, prevention of ink solidification at pen points and prevention of ball wear of ball-point pens for the purpose of putting water-based pigment inks into practical use are seen in Japanese Patent Application Laid-Open No. 58-80368, No. 61-200182, No. 61-247774, No. 61-272278, No. 62-568, No. 62-101671, No. 62-101672, No. 1-249869, No. 1-301760, etc. Recently, ball-point pens or markers making use of water-based pigment inks have become commercially available.
Also ink-jet recording inks making use of water-based pigment inks, pigment inks making use of specific water-soluble solvent and polymeric dispersant are proposed in Japanese Patent Application Laid-Open No. 56-147859 and No. 56-147860. Inks making use of a pigment and a dye in combination are also proposed in Japanese Patent Application Laid-Open No. 4-57859 and No. 4-57860.
In ink-jet recording, it is very important for non-volatile components in the ink to rapidly cohere after ejection onto the recording paper. When, however, the conventional water-based pigment inks are used in ink-jet recording, the non-volatile components which have cohered on recording paper are kept present on the recording paper as a solid material after the ink has been fixed thereon. Hence, there has been the problem that print surfaces stain when strongly rubbed or when traced with a highlighter pen (fluorescent-ink pen).
When conventional inks are used to make a record by ink-jet recording on plain paper on which no particular ink-receiving layer is formed, there also has been the problem that feathering may occur, though it differs more or less depending on composition. Accordingly, in order to prevent the feathering, it is proposed to add a highly viscous solvent to ink. The feathering can be prevented by increasing the ink viscosity. However, a highly viscous organic solvent must be added in a large quantity for such purpose, so that the ink comes to have an excessively high viscosity which brings about the problem that the ejection of ink may become unstable because of a decrease in ejection speed of the ink from nozzles or a decrease in surface tension. There still also has been the problem that the degree of print density or feathering may differ depending on the types of recording paper.
As an attempt to solve such problems, Japanese Patent Publication No. 60-500540 and Japanese Patent Application Laid-open No. 63-159485 disclose techniques in which iodine or the like is added to ink to improve the quality level of prints on a specific recording paper. The techniques disclosed in these publications, however, are not effective for a great variety of recording paper.

Ink, ink-jet recording process and apparatus making use of the same


A machine tool comprises a mounting member for attachment to a workpiece. The mounting member includes a bearing portion that has an external surface of circular cross section and is formed with an aperture in its external surface. A utility device has an internal peripheral surface that defines a cylindrical cavity for receiving the bearing portion of the mounting member in a manner that allows the utility device to move axially and rotationally relative to the mounting member. A clamp is actuable when the utility device is fitted to the bearing portion of the mounting member for releasably retaining the utility device against axial and rotational movement relative to the bearing portion. A spring-loaded detent member projects into the cylindrical cavity from the peripheral surface and is receivable in the aperture of the bearing portion for retaining the operating assembly against axial and rotational movement relative to the bearing portion in the event that the clamp is not actuated.

This invention relates to a portable machine tool.
The Model BB1149 Portable Boring Bar sold by Climax Portable Machine Tools, Inc. of Newberg, Oregon is a portable boring machine that is used for boring out a hole in a workpiece to a desired diameter and with its axis at a desired orientation. Referring to FIG. 1 of the drawings, spacer plates 4A and 4B are tack welded to opposite sides of the workpiece (not shown) and mounting brackets 8A and 8B are attached to the spacer plates respectively using screws. Each mounting bracket includes a ring portion that defines a circular aperture. The manner in which the mounting brackets are attached to the spacer plates allows movement of the mounting brackets relative to the spacer plates, and the mounting brackets are initially positioned so that the centers of the two circular apertures lie at least approximately on the desired central axis of the final bore. A mounting bearing 12 is attached to each mounting bracket in a manner allowing limited movement of the mounting bearing relative to the mounting bracket. The assembly of the mounting bearing and mounting bracket may be as shown in U.S. Pat. No. 4,990,037, the disclosure of which is hereby incorporated by reference herein. As shown in U.S. Pat. No. 4,990,037, the mounting bearing is generally cylindrical, having a central axis, and defines a passage through which an elongate boring bar extends with clearance. A collar defines a bore through which the boring bar extends with a snug fit allowing rotational and axial relative movement, and a spherical bearing is effective between the collar and the mounting bearing and allows the collar to pivot relative to the mounting bearing about a point that lies on the central axis of the mounting bearing. The mounting bearing has a spherical external bearing surface, and the center of curvature of the spherical bearing surface coincides with the center of pivotal movement of the collar relative to the mounting bearing.
Referring again to FIG. 1, the boring bar, which is designated 16 in FIG. 1, is fitted through the mounting bearings 12, and the positions of the mounting bearings are adjusted relative to the mounting brackets so that the central axis of the boring bar lies on the desired central axis of the final bore. A rotational drive assembly 22 is fitted on the boring bar. The rotational drive assembly includes a clamp ring 24 that defines a cylindrical mounting cavity. When the rotational drive assembly is fitted on the boring bar, the mounting bearing 12A is received in the cylindrical mounting cavity of the clamp ring 24, and the clamp ring 24 is then tightened. In this manner, the rotational drive assembly 22 is secured to the workpiece. The spherical configuration of the external bearing surface of the mounting bearing 12A allows the clamp ring to be tightened firmly against the bearing surface even if the central axis of the boring bar does not coincide with the central axis of the mounting bearing. The rotational drive assembly includes a motor 28 that is coupled through gearing (not shown) to a drive collet 32 that is fitted on the boring bar and is keyed thereto. Thus, when power is supplied to the motor, the boring bar is driven to rotate relative to the rotational drive assembly.
An axial feed assembly 40 is also fitted on the boring bar 16. The axial feed assembly includes a housing 44 that is coupled to the rotational drive assembly through a lead screw 48 that is parallel to the boring bar and holds the housing 44 against rotation relative to the rotational drive assembly. The housing 44 contains a feed collet 52 that is rotatable within the housing 44 but is held against axial movement relative to the housing. The feed collet 52 is clamped to the boring bar 16, whereby the housing 44 is held against axial movement relative to the boring bar and the feed collet is driven to rotate inside the housing 44. The feed collet is drivingly coupled to a lead nut that is in threaded engagement with the lead screw 48. As the feed collet is rotated, the lead nut rotates and the axial feed assembly is moved toward or away from the rotational drive assembly. Thus, the boring bar is moved axially relative to the workpiece.
Proper installation of the portable boring machine is a demanding task, and it is sometimes necessary that the machine be installed in a confined space. In these circumstances, it is possible that the operator will find it difficult or inconvenient to tighten the clamp ring 24 that secures the rotational drive assembly to the mounting bearing 12A while maintaining a firm grip on the rotational drive assembly.
When the Model BB1149 Portable Boring Bar is in use, there is a possibility that the operator will not be attentive and the axial feed of the boring bar will be such that the toolhead, which is mounted on the boring bar, passes beyond the workpiece and collides with the mounting bracket or other environmental structure. This may cause damage to the boring machine or other structures.


A portable bracket is removably attached to a structure, such as a tree, for the purpose of relieving the strain on a hunter who is holding and aiming their firearm. A bracket comprising a back plate and a horizontal plate is secured to a tree using a strap and binder arrangement. The firearm support is portable and lightweight and maybe useful for other purposes within a campsite, such as holding a lantern and a like.

Traditionally, in mooring watercraft to a dock, various types of devices have been developed whereby the most simplistic comprises a rope that is tied between the boat and dock. Unfortunately, such lines do not prevent damaging collisions between the boat and the dock. It is also common that weather conditions; such as rough water, turbulent winds, and tidal changes; or boat wakes can buffet the boat forcefully against the dock, or even another watercraft. This is apt to cause serious and expensive damage to the boat and/or the dock. Similar damage often results when two or more boats are tied together, commonly referrer to as rafting.
Thus, it is desirable to provide a rigid watercraft standoff which will permit vertical movement of the watercraft only, thereby accommodating the dynamics of the water while preventing damage to the watercraft by maintaining a fixed distance between the watercraft hull and the mooring.
Conventional devices for mooring a recreational watercraft include bumpers or fenders, which may be attached either to the boat or to a dock, to prevent the boat from being damaged by hitting against the dock due to the action of wind, waves, and wakes. However, these bumpers can rub and/or scuff the boat often causing moderate, but permanent, damage to the boat.
In many situations, it is necessary to moor watercraft to a floating dock, where the wave dynamics become intense as the water becomes turbulent with high winds to the point where the dock and the watercraft undulate relative to each, but not necessarily in unison. In such situations, the watercraft could be damaged in the event that the gunwale of the watercraft rises higher than the dock thereby dislocating fenders onto the surface of the dock or in the alternative the watercraft hull becomes lower than the dock, thereby defeating the purpose of the fenders all together and exposing the watercraft to direct contact with the dock.
Other conventional docking/mooring devices include fiberglass or stainless steel poles permanently affixed to docks, to rigid posts that hold watercraft off and away from docks to which the watercraft is secured. Typically, in the cases where a pair of rigid parallel members is attached between the dock and the watercraft, an additional crisscrossed mooring line serves to restrain the watercraft from moving in a direction parallel to the dock.
Therefore, it is desirable to provide a rigid mooring device using one or more rigid members to maintain a consistent horizontal position relative to the dock, without the use of the aforementioned crisscrossed mooring configuration or rigidly mounted members.
It is further desirable to provide a portable mooring device that will keep a boat at a fixed distance from a mooring dock, whether the dock is of the permanent or floating type, and which will allow movement of the boat in only the vertical direction as the watercraft reacts to wave action.
It is also desirable to provide a portable mooring device that can be used in attaching boats side by side, commonly referred to rafting-off.
Furthermore, it is desirable to provide a mooring apparatus that can be used effectively with various types of docks and watercraft, without requiring any alterations to either.
Moreover, it is desirable to provide a mooring apparatus that is portable and conveniently deployed and removed so that casting off a watercraft is readily and safely executed.
It is desirable to provide a mooring apparatus for boaters with very limited leased docking space.
It is also desirable to provide a mooring device for boats which is removable, and which can be used to secure a boat to a dock or another boat using the conventional cleats provided on docks and boats.
It is desirable to provide a multi-purpose pole to be used as a boat hook by a deck mate when navigating about a mooring, or another boat.
It is further desirable to provide a mooring device for boats which can be used to connect two boats stern to bow for towing.
It is desirable to provide a rigid mooring member system, which can be positioned to adapt to a range of lengths of watercrafts, and which can be used with a series of boat cleat configurations and sizes.


A header for an agricultural harvester. The header includes a connector adapted to be connected to a feeder of the agricultural harvester. The header further includes a cutter bar and a first lateral crop transporting mechanism to move crop material towards a first opening at the connector. The header further includes a second lateral crop transporting mechanism provided at a distance from the first lateral crop transporting mechanism. The second lateral crop transporting mechanism is provided to move crop material towards a second opening at the connector, the second opening being different from the first opening.

Intercropping, meaning that two different types of crop materials are planted alternating and/or mixed on a single field, is becoming more and more popular. Recent studies show that yields can be improved, manuring can be reduced and the necessity of using pesticides can be decreased. For example, U.S. Pat. No. 6,631,585 describes a process for intercropping corn and soy bean plants. Thereby, it is described that the corn and soy beans create a microclimate of humidity as well as a root system and ground cover which effectively resists drought and erosion. It appears therefore that, selecting specific combinations of plants, intercropping can result in one crop type having a positive effect on the other crop type and vice versa.
It is an object of the present invention to provide a header for an agricultural combine which allows to harvest intercropped materials in an improved manner.

Dual header for an agricultural harvester


A triangular ring laser gyroscope having a single anode, single cathode, and self-compensating discharge path which cancels gyro bias, bias drift, and noise. The discharge path extends from the anode through a cross channel in the center of the gyro block to the cathode. Counter-propagating laser beams traverse one segment of the discharge path in the direction of the Langmuir flow from anode to cathode, and another segment of the discharge path of equal length in a direction opposite to that flow. The Langmuir return flow from cathode to anode occurs along the walls of the gyro cavity, producing a more uniform gas flow velocity in the central region of the discharge path. Drag effects on the counter-propagating laser beams are equal but opposite, and the laser beams traverse a more uniform region of the Langmuir flow when thermally-induced changes in the gyro cause beam wandering. Gyro bias, bias drift, and noise are substantially cancelled.

This invention relates to triangular ring laser gyroscopes and to canceling gyro bias, bias drifts, and noise in such instruments.
In the early 19th century, Fresnel predicted that the speed of light propagating in a moving medium is a function of the velocity of the medium in the direction of propagation. This very small effect was first observed by Fizeau in 1851. Now known as the Fresnel-Fizeau drag effect, the phenomenon is very difficult to measure by interferometric means, but is easily measured using ring laser gyroscopes. Such gyroscopes are sensitive to the apparent frequency shifts produced in the propagating laser beams by the drag effects of gas flow in the laser's gain medium.
Podgorski and Aronowitz ("Langmuir Flow Effects in the Laser Gyro", IEEE J Quantum Electronics, QE-4, 11-18, 1968) have shown that the equilibrium gas flow in a direct current excited helium-neon laser is caused by a wall effect first explained by Langmuir in 1923. Langmuir established that, in a plasma filled gas discharge tube, the equilibrium gas flow profile is the super-position of two gas flow patterns: a flow along the walls from cathode to anode, and a backflow in the center of the discharge tube from anode to cathode.
The Fresnel-Fizeau drag and Langmuir flow effects discussed above degrade the performance of ring laser gyroscopes in two ways. First, the Fresnel-Fizeau drag effect produces an apparent difference, or bias, between the frequencies of laser beams counter-propagating around the gyro through the Langmuir gas flow regions. Second, the Langmuir flow produces a non-uniform gas flow velocity in the discharge region. As temperature changes cause mirror and cavity deformations, the laser beams move about, or wander, within the discharge region, and randomly traverse the non-linear gas flow regions. Fresnel-Fizeau drag effects on the wandering beams therefore produce drifts or variations in the gyro bias and noise.
A frequency bias and a non-uniform gas flow are not necessarily undesirable, as long as the laser beam path remains fixed relative to the gyro block. In fact, means for establishing a known frequency bias are ordinarily incorporated in ring laser gyro designs to avoid "lock in" effects, since a known bias can be compensated for in laser measurements. However, beam wandering in the non-uniform gas flow region of the discharge path is a source of unpredictable and uncompensable variations and drifts in gyro bias and noise which limit the measurement accuracy of the ring laser gyro.
Present-day triangular ring laser gyros compensate for gyro bias by utilizing symmetric split-discharge configurations in which two anodes are symmetrically located in opposite directions from a common cathode along the optical propagation path. Each of the gyro's counter-propagating laser beams successively encounters two regions of the discharge path, one in which the gas flows in the direction of propagation and another in which the gas flows in the opposite direction. As a result, each counter-propagating beam experiences equal but opposite drag effects which essentially cancel the bias effects.
The successful application of the split-discharge technique requires that the two discharge segments be geometrically equivalent and that the discharge currents in the two segments be equal. Maintaining the necessary precise equality in discharge currents is accomplished by sophisticated electronic control circuitry. Additionally, the split-discharge technique requires dual anodes and their associated seals and a large cathode. These required elements increase the manufacturing complexity and cost of the gyro and reduce its reliability.
Moreover, in conventional split-discharge triangular ring laser gyros, the equilibrium flow of lasing medium gas occurs by Langmuir flow within each segment of the split discharge path. Consequently, beam wandering produces undesirable gyro bias drift and noise even where the bias effects may be canceled by the discharge path configuration.
An alternative technique that achieves bias cancellation without the need for current-balancing circuitry and dual anodes, but for a ring laser gyro having a four-segment and non-coplanar optical path, is described in U.S. Pat. No. 4,397,027, to Zampiello et al. The technique includes a single discharge path such that each counter-propagating laser beam traverses one segment of the discharge path in the same direction as the gas flow and another segment in the opposite direction. The drag effects of the gas flow on laser beam frequency are equal and opposite so that the net bias effect is essentially canceled.
However, the approach of Zampiello et al. cannot be practiced in triangular ring laser gyroscopes, in which the optical path has only three segments and the optical path and the discharge path are inherently coplanar. Moreover, such an approach does not address the reduction of bias drift and noise caused by drag effects and beam wandering. The split-discharge approach of conventional triangular ring laser gyroscopes not only does not reduce bias drifts and noise, but also requires the dual-anode and current balancing circuitry discussed above.
Thus, there is a need in the art for a triangular ring laser gyroscope which cancels gyro bias, gyro bias drifts, and noise, and which eliminates the need for multiple anodes, their associated seals, and current balancing electronics. It is therefore an object of this invention to provide a triangular ring laser gyroscope having a self-compensating single discharge path which substantially cancels bias effects, gyro bias drift, and noise.

Pressure-equalized self-compensating discharge configuration for triangular ring laser gyroscopes


Programmable via devices and methods for the fabrication thereof are provided. In one aspect, a programmable via device is provided comprising a substrate; a dielectric layer on the substrate; a heater on at least a portion of a side of the dielectric layer opposite the substrate; a first oxide layer over the side of the dielectric layer opposite the substrate and surrounding at least a portion of the heater; a first capping layer over a side of the first oxide layer opposite the dielectric layer; at least one programmable via extending through the first capping layer and the first oxide layer and in contact with the heater, the programmable via comprising at least one phase change material; a second capping layer over the programmable via; a second oxide layer over a side of the first capping layer opposite the first oxide layer; a pair of first conductive vias, each extending through the first and second oxide layers and the first capping layer, and in contact with the heater; and a second conductive via, located between the pair of first conductive vias, extending through the second oxide layer and in contact with the second capping layer.

Reconfigurable circuits have been widely used in the semiconductor industry for field programmable gate arrays (FPGAs) and for repair of a defective memory element. The FPGA consists of a set of simple, configurable logic blocks in an array with interspersed switches that can rearrange interconnections between the logic blocks.
Reconfigurable circuits are also expected to play a significant role in three-dimensional integration technology that is being currently developed. Three-dimensional integration fabricates multilayer structures that can form a single chip combination with different functionalities. In these multilayer (and multifunctional) systems, reconfigurable circuit connection is typically needed to provide controllable logic functionality, memory repair, data encryption, as well as other functions.
A programmable via is an enabling technology for high-performance reconfigurable logic applications without the trade offs in low logic gate density and power. Phase change materials are an attractive option for this application, but to date, have drawn the most attention from semiconductor memory developers as a possible replacement to flash memory.
Programmable vias implementing phase change materials have been developed. One notable challenge that exists, however, with regard to the practical implementation of programmable vias in logic devices, is being able to scale the programmable via process technology to integrate with the current technology node. To date, programmable via process technology is not readily scalable.
Therefore, scalable programmable via technology would be desirable.

This patent is subject to a terminal disclaimer.

CMOS-process-compatible programmable via device

International Business Machines Corporation


Apparatus for opening an obstructed region of a patient blood vessel comprising a catheter and guidewire. The guidewire is of sufficient length to extend from a region outside the patient to the obstructed region. The catheter acts as a guide tube supporting the guidewire for free axial and rotary movement. A power assembly is positioned outside the patient and has an output shaft joined to the guidewire. The power assembly further includes plural motors drivingly interrelated to move the output shaft to impart simultaneous axial reciprocation and rotary reciprocation to guidewire.

The subject invention is directed to a catheter system and apparatus for opening a totally or partially occluded blood vessel.
In my prior U.S. Pat. Nos. 4,936,845, issued Jun. 26, 1990, for "Catheter System Having Distal Tip For opening Obstructions," and 5,116,350, issued May 26, 1992, under the same title, I have disclosed methods and apparatus for opening an occluded blood vessel through the use of a catheter with a drive shaft having a distal tip portion that is impinged against the occlusion with an axial or rotary reciprocatory motion. The patents disclose two separate devices, one capable of producing an axially reciprocated movement and the other capable of producing a rotary reciprocal movement.
There are numerous other arthrectomy devices for opening vascular obstructions such as the Kinsey catheter disclosed in U.S. Pat. No. 4,749,376. These other prior devices that use rotary rotation all have the common problem of "wrapping" or "twisting" tissue because of the unidirectional rotation. The reciprocal rotation of my device prevents this from happening.
In my prior U.S. Pat. No. 4,854,325, issued Aug. 8, 1989, for "Reciprocating Guidewire Method," I have disclosed the use of a conventional guidewire for use in forming a passageway through a vascular obstruction. This system utilizes a conventional guidewire and catheter which is already in the patient's vascular system, such as in a coronary artery. This patent discloses a system for reciprocating the guidewire back and forth.
It now appears that it would be most desirable if the drive shaft tip or the guidewire tip were subjected to both forms of reciprocation (i.e., axial and rotary) simultaneously. The combined motions seem to produce more efficient and effective opening of the occlusions than either motion performed by itself.

Combined rotary and axial reciprocating guide wire


A fingerprint sensor apparatus including a sampling unit, an image analysing unit and a processor is provided. The sampling unit senses a fingerprint image. The image analysing unit analyses an image parameter of the fingerprint image to obtain an image data, and compares the image data to a reference data to obtain a comparison result. The comparison result includes that the image data corresponds to one of a plurality of stages. The stages are determined based on the image parameter, and the different stages correspond to different pressure regions. The processor controls an electronic device to execute a predetermined operation according to the stage corresponding to the image data. In addition, a method for controlling the fingerprint sensor apparatus is also provided.

1. Field of the Invention
The invention generally relates to a sensor apparatus and a method for controlling the sensor apparatus, in particular, to a fingerprint sensor apparatus and a method for controlling the fingerprint sensor apparatus.
2. Description of Related Art
In current market, a touch fingerprint sensor apparatus senses a pressure value applied thereto in a manner of capacitive scheme or mechanical scheme. The touch fingerprint sensor apparatus determines a touch is valid while the pressure value applied to the touch fingerprint sensor apparatus is larger than a predetermined threshold, and an electronic device including the touch fingerprint sensor would execute a corresponding operation. The predetermined threshold is usually set to be constant. However, if the pressure value applied to the touch fingerprint sensor apparatus is not larger than the predetermined threshold, the electronic device would do nothing at all. The constant predetermined threshold would cause needless inconvenience to the user that touches the touch fingerprint sensor apparatus. For example, the electronic device can not execute a specific operation according to a pressure region, or the electronic device may do nothing at all due to a light touch.
Hence, how to provide a fingerprint sensor apparatus that has a good user experience and satisfactory sensing quality without causing needless inconvenience to the user is one of the most important topics in the pertinent field.

Fingerprint sensor apparatus and a method for controlling the fingerprint sensor apparatus


A substrate lift pin assembly includes a tubular support member connected to a bottom of a pedestal beneath a lift pin through-hole. The tubular support member has an interior cavity and an end closure with a cartridge through-hole extending through the end closure. A cartridge member includes a lift pin holder portion and a plunger portion. The lift pin holder portion is located inside of the interior cavity of the tubular support member. The plunger portion extends through the cartridge through-hole of the end closure of the tubular support member. A lift pin extends through the lift pin through-hole and connects to the lift pin holder portion of the cartridge member. A handle member connects to the plunger portion of the cartridge member at a location near a distal end of the plunger portion relative to the tubular support member. The handle member is configured to engage a lifting mechanism.

1. Field of the Invention
The present invention relates to semiconductor device fabrication.
2. Description of the Related Art
Some modern semiconductor chip fabrication processes include positioning a substrate on a pedestal and rotating the pedestal during the processing of the substrate. Positioning of the substrate on the pedestal and removing of the substrate from the pedestal is generally performed using robotically controlled movement of an end effector device, where the end effector device is configured to interface with a bottom surface of the substrate. To avoid damaging interaction between the end effector device and the pedestal, it is often necessary to provide a vertical displacement mechanism by which the substrate can be received from the end effector device at a location above the pedestal, and by which the substrate can be lowered onto the pedestal after removal of the end effector from beneath the substrate, and by which the substrate can be raised from the pedestal to allow for positioning of the end effector beneath the substrate. The vertical displacement mechanism should be operationally reliable in order to avoid damage of the substrate, the pedestal, and/or the end effector. Therefore, the vertical displacement mechanism should be configured to avoid sticking, particularly in the presence of processing materials that may lead to such sticking. It is within this context that the present invention arises.

Lift pin assembly and associated methods