CN101082741A - Liquid crystal tropism agent and liquid crystal display element - Google Patents

Liquid crystal tropism agent and liquid crystal display element Download PDF

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CN101082741A
CN101082741A CNA2007101107148A CN200710110714A CN101082741A CN 101082741 A CN101082741 A CN 101082741A CN A2007101107148 A CNA2007101107148 A CN A2007101107148A CN 200710110714 A CN200710110714 A CN 200710110714A CN 101082741 A CN101082741 A CN 101082741A
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liquid crystal
dicarboxylic anhydride
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aligning agent
polyamic acid
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安田博幸
林英治
西川通则
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

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Abstract

The present invention relates to an aligning agent for liquid crystal and a liquid crystal display element. It is a liquid crystal aligning agent which will not produce air bubble when provides coating and the screening character of which is good. The liquid crystal aligning agent includes the polymer which uses amic acid structure and/or acid imide structure as repetitive unit and the epoxy-based compound represented by the formula (II). (R1 is n valence organic group, and n is the whole number chosen from 1 to 30).

Description

Aligning agent for liquid crystal and liquid crystal display cells
Technical field
The present invention relates to aligning agent for liquid crystal and liquid crystal display cells.More particularly, relate to the good aligning agent for liquid crystal of printing and by its liquid crystal display cells that makes.
Background technology
At present, as liquid crystal display cells, known TN type liquid crystal display cells with so-called TN type (Twisted Nematic) liquid crystal cell, it is being provided with the liquid crystal orientation film that forms on the substrate surface of nesa coating by making such as polyamic acid, polyimide, with its substrate as used for liquid crystal display element, these 2 substrates are oppositely arranged, form nematic crystal layer betwixt in the crack with positive dielectric anisotropy, constitute the box of sandwich construction, the major axis of liquid crystal molecule is turned round continuously to another piece substrate from a substrate and is turn 90 degrees.And, also developed and compared little IPS (In-PlaneSwitching) the type liquid crystal display cells of STN (SuperTwisted Nematic) the type liquid crystal display cells that can realize high-contrast and view angle dependency, VA (Vertical Allignment) type liquid crystal display cells, the video pictures high-speed response was good when view angle dependency was little optical compensation curved (OCB) type liquid crystal display cells with TN type liquid crystal display cells.
As the liquid crystal aligning membrane material of these liquid crystal display cells, former known polyimide, polyamide and polyester etc., particularly polyimide, its thermotolerance, good with the compatibility of liquid crystal, physical strength etc. is used in most liquid crystal display cells.The liquid crystal orientation film of being made by polyimide normally will be coated on the substrate as the polyamic acid of polyimide precursor or as the aligning agent for liquid crystal of the organic solvent solution of soluble polyimide, carry out imidizate by heating again and make.In this aligning agent for liquid crystal,, add silane coupling agent sometimes in order to improve equalization purpose to substrate.
But, added the aligning agent for liquid crystal of silane coupling agent,, be easy to generate bubble during coating though improved equalization to substrate, this bubble becomes the reason that liquid crystal orientation film produces pore, thereby produces the problem of liquid crystal aligning and the decline of gained liquid crystal display cells electrical property.
Summary of the invention
The purpose of this invention is to provide and to coating of substrates the time, can not produce bubble, aligning agent for liquid crystal that screening characteristics is good.
Another object of the present invention provide have pore-free, the liquid crystal display cells of liquid crystal orientation film that liquid crystal aligning and electrical property are good.
Other purpose of the present invention and advantage can be found out by the following description.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 1st, reach by a kind of aligning agent for liquid crystal, it is characterized in that containing: (A) have the repetitive of following formula (I-1) expression and/or following formula (I-2) expression repetitive polymkeric substance and
(B) formula (II) expression contains epoxy compounds.
Figure A20071011071400041
(in the formula, P 1Be the organic group of 4 valencys, Q 1Organic group for divalent).
(in the formula, P 2Be the organic group of 4 valencys, Q 2Organic group for divalent).
(in the formula, n is 1～30 integer, R 1Organic group for the n valency).
According to the present invention, above-mentioned purpose of the present invention and advantage, the 2nd, reach by a kind of liquid crystal display cells, it is characterized in that having the liquid crystal orientation film that makes by aligning agent for liquid crystal of the present invention.
According to aligning agent for liquid crystal of the present invention, can make the good liquid crystal orientation film of printing that does not have printing spot, pore when printing applies on substrate.
Liquid crystal display cells of the present invention is except can being suitable for TN type and STN type liquid crystal display cells, can also be applicable to SH (SuperHomeotropic) type, IPS (In-Plane Switching) type, optical compensation curved (OCB) type, ferroelectricity and anti-ferroelectricity liquid crystal display cells etc. by selecting used liquid crystal.
And liquid crystal display cells of the present invention can be used for various devices effectively, for example can be used for display device such as desk-top calculator, wrist-watch, table clock, counting display board, word processor, personal computer, liquid crystal TV set.
Embodiment
Below the present invention is carried out specific description.
(A) polymkeric substance
Used polymkeric substance has the repetitive of above-mentioned formula (I-1) expression and/or the repetitive of above-mentioned formula (I-2) expression among the present invention.For example, can enumerate polyamic acid and/or have imide amination polymer with this polyamic acid dehydration closed-loop (imidizate) resulting structures.In addition, for " imide amination polymer " among the present invention, comprise the polymkeric substance of the whole imidizates of its repetitive, perhaps the polymkeric substance of part imidizate.And the part of imide ring also can be different imide ring.
Preferred polymkeric substance is to have the repetitive of above-mentioned formula (I-1) expression and the polymkeric substance of the repetitive that above-mentioned formula (I-2) is represented among the present invention.As aligning agent for liquid crystal, can enumerate the polymkeric substance of for example following (1)～(3) with this polymkeric substance.
(1) contains the aligning agent for liquid crystal of polyamic acid and imide amination polymer.
(2) contain the aligning agent for liquid crystal of the segmented copolymer that makes by prepolymer with amic acid structure and the prepolymer with imide structure.
(3) contain aligning agent for liquid crystal by the imide amination polymer of polyamic acid partial dehydration closed loop gained.
Wherein, preferred (1) and (2), preferred (1) especially.
Polyamic acid
Used polyamic acid makes by making tetrabasic carboxylic acid dicarboxylic anhydride and diamine reactant among the present invention.
[tetrabasic carboxylic acid dicarboxylic anhydride]
As above-mentioned polyamic acid synthetic in used tetrabasic carboxylic acid dicarboxylic anhydride, for example, can enumerate the BTCA dicarboxylic anhydride, 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 3,5,6-three carboxyls norbornane-2-acetic acid dicarboxylic anhydride, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acid dicarboxylic anhydride, 1,3,3 a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 5-(2,5-dioxo tetrahydrofuran methylene)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dicarboxylic anhydride, dicyclo [2,2,2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, following formula (I) and aliphatics and the ester ring type tetrabasic carboxylic acid dicarboxylic anhydrides such as compound (II) represented separately;
Figure A20071011071400071
(in the formula, R 1And R 3Expression has the divalent organic group of aromatic rings, R 2And R 4Expression hydrogen atom or alkyl, the R of a plurality of existence 2And R 4Separately can be identical, also can be different);
The pyromellitic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-tetraphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-furans tetrabasic carboxylic acid dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dicarboxylic anhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two phthalic acid dicarboxylic anhydrides, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, two (phthalic acid) phosphniline oxide dicarboxylic anhydride, right-phenylene-two (triphenyl phthalic acid) dicarboxylic anhydride, between-phenylene-two (triphenyl phthalic acid) dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl ether dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl methane dicarboxylic anhydride, ethylene glycol-two (dehydration trimellitate), propylene glycol-two (dehydration trimellitate), 1,4-butylene glycol-two (dehydration trimellitate), 1,6-hexanediol-two (dehydration trimellitate), 1,8-ethohexadiol-two (dehydration trimellitate), 2,2-two (4-hydroxyphenyl) propane-two (dehydration trimellitate), aromatic tetracarboxylic acid's dicarboxylic anhydrides such as compound of following formula (1)～(4) expression.They can a kind separately or be used in combination more than 2 kinds.
Figure A20071011071400081
Figure A20071011071400091
Wherein, from showing the angle of good liquid crystal aligning, preferred BTCA dicarboxylic anhydride, 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrochysene-3-furyl)-and 3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrofuran methylene)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c] furans-1, the 3-diketone, dicyclo [2,2,2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, the pyromellitic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride, the compound of following formula (8) expression in the compound of following formula (5)～(7) expression in the compound of above-mentioned formula (I) expression and the compound of above-mentioned formula (II) expression.As preferred especially, can enumerate 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c] furans-1,3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c] furans-1, the compound of 3-diketone, pyromellitic acid dicarboxylic anhydride and following formula (5) expression.
Figure A20071011071400101
[diamines]
As above-mentioned polyamic acid synthetic in used diamines, can enumerate for example p-phenylenediamine, between-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamido diphenylethane, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formailide, 4,4 '-diaminodiphenyl ether, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 3,3 '-two (trifluoromethyl)-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamido benzophenone, 3,4 '-diamido benzophenone, 4,4 '-diamido benzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two [4-aminophenyl] HFC-236fa, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogen anthracene, 2, the 7-diamino-fluorene, 9,9-two (4-aminophenyl) fluorenes, 4,4 '-methylene-two (2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamido-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 1,4,4 '-(right-the phenylene isopropylidene) diphenylamine, 4,4 '-(-the phenylene isopropylidene) diphenylamine, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl, N, N '-two (4-aminophenyl)-benzidine, N, N '-two (4-aminophenyl)-N, N '-aromatic diamines such as dimethyl-benzidine;
1,1-m-xylene diamine, 1,3-propane diamine, butanediamine, pentanediamine, hexane diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 4,4-diamido heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene bicyclopentadiene diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0 2,7]-undecylene two methanediamines, 4,4 '-methylene two aliphatics and ester ring type diamines such as (cyclohexylamine);
2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamido-2,3-dicyano pyrazine, 5,6-diamido-2, the 4-dihydroxy-pyrimidine, 2,4-diamido-6-dimethylamino-1,3, the 5-triazine, 1,4-two (3-aminopropyl) piperazine, 2,4-diamido-6-isopropoxy-1,3, the 5-triazine, 2,4-diamido-6-methoxyl-1,3, the 5-triazine, 2,4-diamido-6-phenyl-1,3,5-triazines, 2,4-diamido-6-methyl-s-triazine, 2, the 4-diamino-1,3,5-triazines, 4,6-diamido-2-vinyl-s-triazine, 2,4-diamido-5-phenyl thiazole, 2, the 6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3, the 5-diaminostilbene, 2, the 4-triazole, 6,9-diamido-2-ethoxy acridine lactate, 3,8-diamido-6-phenylphenanthridineand, 1,4-diamido piperazine, 3, the 6-proflavin, two (4-aminophenyl) phenyl amine and 3,6-diamido carbazole, N-methyl-3,6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole, the diamines that has 2 primary amino radicals and this primary amino radical nitrogen-atoms in addition in the compound equimolecular that following formula (III)～(VI) is represented separately;
Figure A20071011071400121
(in the formula, R 5Expression is selected from the 1 valency organic group with nitrogen atom ring texture of pyridine, pyrimidine, triazine, piperidines and piperazine, and X represents the divalent organic group).
Figure A20071011071400122
(in the formula, R 6Expression is selected from the divalent organic group with nitrogen atom ring texture of pyridine, pyrimidine, triazine, piperidines and piperazine, and X represents the divalent organic group, and the X of a plurality of existence can be the same or different);
Single-substituted two amines of following formula (V) expression; The diamido organosiloxane of following formula (VI) expression;
(in the formula, R 7Expression is selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R 8It is 6～30 alkyl that expression has the 1 valency organic group of group of the steroid backbone of being selected from, trifluoromethyl and fluorine or carbon number).
(in the formula, R 9The expression carbon number is 1～12 alkyl, the R of a plurality of existence 9Separately can be identical, also can be different, p is 1～3 integer, q is 1～20 integer).
The compound of the following formula of can giving an example (9)～(13) expression etc.These diamines can be used in combination separately or more than 2 kinds.
Figure A20071011071400131
(in the formula, y is 2～12 integer, and z is 1～5 integer).
Wherein, preferred p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(right-the phenylene diisopropylidene) diphenylamine, 4,4 '-(-the phenylene diisopropylidene) diphenylamine, 1, the 4-cyclohexane diamine, 4,4 '-methylene two (cyclohexylamine), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, the compound of above-mentioned formula (9)～(13) expression, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, the compound of following formula (14) expression in the compound of above-mentioned formula (III) expression, dodecyloxy-2 in the compound of following formula (15) expression in the compound of above-mentioned formula (IV) expression and the compound of above-mentioned formula (V) expression, the 4-diaminobenzene, pentadecane oxygen base-2, the 4-diaminobenzene, hexadecane oxygen base-2, the 4-diaminobenzene, 1-octadecane oxygen base-2, the 4-diaminobenzene, dodecyloxy-2, the 5-diaminobenzene, pentadecane oxygen base-2, the 5-diaminobenzene, hexadecane oxygen base-2, the 5-diaminobenzene, octadecane oxygen base-2, the 5-diaminobenzene, N, N '-two (4-aminophenyl)-benzidine, N, N '-two (4-aminophenyl)-N, N '-dimethyl-benzidine, the compound of following formula (16)～(23) expression.
Figure A20071011071400141
[synthesizing of polyamic acid]
Supply with the tetrabasic carboxylic acid dicarboxylic anhydride of polyamic acid synthetic reaction and the usage rate of diamine compound, preferably with respect to contained amino in the 1 equivalent diamine compound, the anhydride group that makes the tetrabasic carboxylic acid dicarboxylic anhydride is the ratio of 0.2～2 equivalent, more preferably is the ratio of 0.3～1.2 equivalent.
The synthetic reaction of polyamic acid is preferable over-20～150 ℃, more preferably carries out under 0～100 ℃ temperature conditions in organic solvent.Here, as organic solvent, as long as can dissolve synthetic polyamic acid, then it is had no particular limits, can illustration for example N-N-methyl-2-2-pyrrolidone N-, N, N-dimethyl acetamide, N, aprotic polar solvents such as dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, HMPA; Between phenol solvent such as sylvan, xylenols, phenol, halogenated phenol.In addition, to be preferably the total amount (b) that makes tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound be the amount of 0.1～30 weight % with respect to the total amount (a+b) of reaction solution to the consumption of organic solvent (a).
In addition, in the scope that the polyamic acid that does not make generation is separated out, the poor solvent alcohols of all right coupling polyamic acid, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc. in the above-mentioned organic solvent.Object lesson as this poor solvent, can enumerate for example methyl alcohol, ethanol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1, the 4-butylene glycol, triethylene glycol, glycol monoethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, diethy-aceto oxalate, diethyl malonate, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, the ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic acid esters, the diethylene glycol monoethyl ether acetic acid esters, tetrahydrofuran, methylene chloride, 1, the 2-ethylene dichloride, 1, the 4-dichloroetane, trichloroethanes, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene etc.
As mentioned above, obtained dissolving the reaction solution of polyamic acid.Then, this reaction solution is put in a large amount of poor solvents, obtained precipitate, by this precipitate of drying under reduced pressure or with evaporator the reaction solution decompression is distillated and to obtain polyamic acid.Again, the operation of be dissolved in this polyamic acid in the organic solvent once more, separating out with poor solvent then or carry out once or for several times, can make with extra care polyamic acid thus with the operation that the evaporator decompression distillates.
Imide amination polymer
Imide amination polymer used among the present invention makes by the polyamic acid dehydration closed-loop that makes tetrabasic carboxylic acid dicarboxylic anhydride and diamine reactant gained.
[tetrabasic carboxylic acid dicarboxylic anhydride]
As above-mentioned imide amination polymer synthetic in used tetrabasic carboxylic acid dicarboxylic anhydride, can enumerate and the used identical compound of tetrabasic carboxylic acid dicarboxylic anhydride during above-mentioned polyamic acid is synthetic.
The used preferred ester ring type tetrabasic carboxylic acid of tetrabasic carboxylic acid dicarboxylic anhydride dicarboxylic anhydride during imide amination polymer of the present invention is synthetic.As particularly preferred object lesson, can enumerate 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c] furans-1,3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c] furans-1, the 3-diketone.In addition, can also be with ester ring type tetrabasic carboxylic acid dicarboxylic anhydride and other tetrabasic carboxylic acid dicarboxylic anhydride coupling.
[diamines]
As above-mentioned imide amination polymer synthetic in used diamines, can enumerate and the used identical diamines of diamines during above-mentioned polyamic acid is synthetic.
The diamines of the used preferred above-mentioned formula of diamines (V) expression during imide amination polymer of the present invention is synthetic.As preferred object lesson, and in the compound of above-mentioned formula (V) expression, can enumerate dodecyloxy-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, hexadecane oxygen base-2,4-diaminobenzene, 1-octadecane oxygen base-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2, the compound of 5-diaminobenzene, above-mentioned formula (16)～(23) expression.
In addition, in the imide amination polymer of the present invention, diamines and other diamines of all right above-mentioned formula of coupling (V) expression.As preferred compound in other diamines, can enumerate right-Ya phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(right-the phenylene diisopropylidene) diphenylamine, 4,4 '-(-the phenylene diisopropylidene) diphenylamine, 1, the 4-cyclohexane diamine, 4,4 '-methylene two (cyclohexylamine), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, the compound of above-mentioned formula (9)～(13) expression, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, N, N '-two (4-aminophenyl)-benzidine, N, N '-two (4-aminophenyl)-N, N '-dimethyl-benzidine, the compound of above-mentioned formula (14) expression in the compound of above-mentioned formula (III) expression, the compound of above-mentioned formula (15) expression in the compound of above-mentioned formula (IV) expression etc.
In imide amination polymer of the present invention, the diamines of above-mentioned formula (V) expression is preferably more than the 0.5 weight % of whole diamines, is preferably especially more than the 1 weight %.
[synthesizing of imide amination polymer]
The imide amination polymer that constitutes aligning agent for liquid crystal of the present invention is made by above-mentioned polyamic acid dehydration closed-loop.The dehydration closed-loop of polyamic acid can (i) by the method for heating polyamic acid, perhaps (ii) polyamic acid is dissolved in the organic solvent, the method that adds dewatering agent and dehydration closed-loop catalyzer and heating as required in this solution is carried out.
In the method for the heating polyamic acid of above-mentioned (i), temperature of reaction is preferably 50～200 ℃, more preferably 60～170 ℃.When 50 ℃ of temperature of reaction less thaies, then the dehydration closed-loop reaction can not be carried out fully, if temperature of reaction surpasses 200 ℃, the situation of the molecular weight and molecular weight of gained imide amination polymer then can occur.
On the other hand, in the above-mentioned method of in polyamic acid solution, adding dewatering agent and dehydration closed-loop catalyzer (ii),, can use for example acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride as dewatering agent.The consumption of dewatering agent with respect to the repetitive of 1 mole of polyamic acid, is preferably 0.01～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, collidine, lutidines, triethylamine.But, be not limited to these.The dehydration closed-loop catalyst consumption with respect to 1 mole of used dewatering agent, is preferably 0.01～10 mole.In addition, as the organic solvent that uses in the dehydration closed-loop reaction, can enumerate illustrative organic solvent with synthesize middle solvent for use as polyamic acid.And the temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 10～150 ℃.In addition, by the reaction solution that so obtains is carried out the operation same with the polyamic acid process for purification, can make with extra care imide amination polymer.
Used imide amination polymer among the present invention can also be the low polymkeric substance of imidizate rate of partial dehydration closed loop.The imidizate rate of used imide amination polymer is preferably more than 80% among the present invention, more preferably more than 85%.Here so-called " imidizate rate " is meant the sum with respect to polymer repeat unit, the value that the quantity ratios of the repetitive of formation imide ring is represented with %.At this moment, the part of imide ring can also be different imide ring.The imidizate rate can be obtained by following method.
[the imidizate rate assay method of imide amination polymer]
Imide amination polymer at room temperature behind the drying under reduced pressure, is dissolved in the deuterated dimethyl sulfoxide, is primary standard substance with the tetramethylsilane, at room temperature carries out 1H-NMR measures.Try to achieve with the following (ii) formula of expression.
Imidizate rate (%)=(1-A 1/ A 2* α) * 100------is (ii)
A 1: the peak area (10ppm) that derives from the proton of NH base
A 2: the peak area that derives from other proton
α: other the number ratio of proton of the proton of NH base in the precursor of relative 1 polymkeric substance (polyamic acid)
End modified type polymkeric substance
Above-mentioned polyamic acid and imide amination polymer can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting.This end modified type polymkeric substance can be by when polyamic acid synthetic, adds monobasic acid anhydrides, monoamine compound, monoisocyanates compound etc. and synthesize in reaction system.Wherein, as the monobasic acid anhydrides, can enumerate for example maleic anhydride, phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinic anhydride, n-tetradecane base succinic anhydride, n-hexadecyl succinic anhydride etc.In addition, as monoamine compound, can enumerate for example aniline, cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, n-pentadecane amine, n-hexadecane amine, n-heptadecane amine, n-octadecane amine, n-eicosane amine etc.In addition, as the monoisocyanates compound, can enumerate for example phenyl isocyanate, isocyanic acid naphthyl ester etc.
[solution viscosity]
The value of the solution viscosity in the synthesis example (mPas) adopts N-N-methyl-2-2-pyrrolidone N-or gamma-butyrolacton as solvent, for the solution that is diluted to regulation solid portion concentration, adopts E type rotational viscosimeter to carry out the mensuration of viscosity under 25 ℃.
(B) epoxy compounds
Used epoxy compounds can be enumerated the compound of following formula (II) expression among the present invention.
(in the formula, n is 1～30 integer, R 1Organic group for the n valency).
As the R in the above-mentioned formula (II) 1The n valency organic group of expression can be enumerated R 2, R 3(CO) 2, R 4OR 5Deng, wherein, as R 2, R 3, R 4, R 5Can enumerate carbon number separately and be 1～50 alkyl, carbon number and be the aliphatic alkyl, phenyl, phenylene of aliphatic alkyl, 4 valencys of 1～50 alkylidene, 3 valencys etc., its part hydrogen is optional can be replaced by hydroxyl, halogen, glycidyl oxygen base, cycloalkylidene.In addition, these organic groups can be branches, also can not have branch.And, R 1Can also constitute by a plurality of above-mentioned organic groups.
Particularly, can enumerate the compound of following formula (24)～(51) expression.
Figure A20071011071400201
Figure A20071011071400211
Commercially available product as the epoxy compounds that can use in the present invention, can enumerate the デ Na コ one Le EX611 that Na ガ セ ケ system テ Star Network ス produces, EX612, EX614, EX622, EX512, EX621, EX411, EX421, EX313, EX314, EX321, EX201, EX211, EX212, EX252, EX911, EX941, EX920, EX931, EX111, EX121, EX141, EX146, EX192, EX721, EX203, EX711, EX147, EX221, EM150, デ Na レ Star Network ス R45EPT, EX810, EX811, EX850, EX851, EX821, EX830, EX832, EX841, EX861, EX145, EX171 etc., but the present invention is not limited to these examples.
Among the present invention, the epoxy compounds of preferred above-mentioned formula (24), (27), (36), (43), (45), (47) and (51) expression.The above-mentioned epoxy compounds that contains can be used in combination separately or more than 2 kinds.
(B) epoxy compounds molecular weight used among the present invention is preferably 100～10000, and more preferably 200～5000.
The mixture ratio of (B) epoxy compounds in the aligning agent for liquid crystal of the present invention with respect to 100 weight portions (A) polymkeric substance, is generally 0.01～2 weight portion, is preferably 0.02～1 weight portion, more preferably 0.03～0.5 weight portion.If the imperfect situation of printing improvement effect then can appear in less than 0.01 weight portion, if surpass 2 weight portions, the situation of tackify can appear then.
Aligning agent for liquid crystal
Aligning agent for liquid crystal of the present invention usually by with above-mentioned (A) polymkeric substance with (B) contain epoxy compounds and dissolve to be contained in the organic solvent and constitute.
Temperature when modulating aligning agent for liquid crystal of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
As the organic solvent that constitutes aligning agent for liquid crystal of the present invention, can enumerate as the illustrated solvent of the solvent that uses in the polyamic acid synthetic reaction.In addition, can also suitably select as can coupling when the polyamic acid synthetic reaction and illustrative poor solvent carries out coupling.
Solids content concn is considered viscosity, volatility etc. and is selected in the aligning agent for liquid crystal of the present invention, is preferably the scope of 1～10 weight %.That is to say that aligning agent for liquid crystal of the present invention is coated on substrate surface, formation is filmed as liquid crystal orientation film, and when solids content concn less than 1 weight %, the thickness that will cause this to film is too small, thereby is difficult to obtain good liquid crystal orientation film; When solids content concn surpasses 10 weight %, will cause coating thickness blocked up, be difficult to obtain good liquid crystal orientation film equally, and the viscosity of aligning agent for liquid crystal increases, coating characteristic variation.
Organic solvent as aligning agent for liquid crystal use of the present invention, can exemplify the N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolacton, butyrolactam, N, dinethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2 pentanone, glycol monoethyl ether, butyl lactate, butyl acetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-just-propyl ether, ethylene glycol-different-propyl ether, ethylene glycol-just-butyl ether (butyl cellosolve), glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic acid esters, the diethylene glycol monoethyl ether acetic acid esters, diisobutyl ketone (DIBK), isoamyl propionate, isoamyl isobutyrate, isoamyl ether etc.These can use separately, or mix more than 2 kinds and use.
From improving the fusible angle of substrate surface is considered, can also be contained the compound of epoxy radicals in the aligning agent for liquid crystal of the present invention.As this epoxy compounds that contains, can enumerate for example preferred 1,3,5,6-four glycidyl group-2,4-hexanediol, N, N, N ', N '-four glycidyl group-m-xylenedimaine, 1,3-two (N, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-amino methyl cyclohexane etc.They and the mixture ratio that contains epoxy compounds with respect to 100 parts by weight polymer, are generally below 40 weight portions.
Liquid crystal display cells
Liquid crystal display cells of the present invention can be by for example following method manufacturing.
(1) aligning agent for liquid crystal of the present invention preferably is coated on the substrate one side that is provided with the nesa coating that forms pattern by methods such as print processes, then, films by applicator surface is added thermosetting.Here, as substrate, can use for example glass such as float glass, soda-lime glass; Plastics system transparency carriers such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate.Simultaneously go up set nesa coating as substrate, can use tin oxide (SnO 2) system NESA film (U.S. PPG register of company trade mark), indium oxide-tin oxide (In 2O 3-SnO 2) the ITO film etc. of system.The formation pattern of these nesa coatings adopts photoetch method or uses the method for mask in advance.When the coating of aligning agent for liquid crystal, for the cohesive of further improving substrate surface and nesa coating and filming, can also be on this surface of substrate coating in advance contain functional silanes compound, contain the compound of functionality titanium etc.Heating-up temperature after the aligning agent for liquid crystal coating is preferably 80～300 ℃, more preferably 120～250 ℃.In addition, contain the aligning agent for liquid crystal of the present invention of polyamic acid, by removing organic solvent after the coating, formation is filmed as alignment films, can also make its dehydration closed-loop by further heating, forms filming of further imidizate.The thickness of filming that forms is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) roller of fibrous cloth such as nylon, regenerated fiber, cotton carries out grinding process with certain direction friction with for example being tied with to formed coated surface.Like this, be formed in produced on filming liquid crystal molecular orientation can liquid crystal orientation film.
In addition; to the liquid crystal orientation film that forms by aligning agent for liquid crystal of the present invention; for example; carry out opening flat 6-222366 communique or the special processing of opening the part irradiation ultraviolet radiation as shown in the flat 6-281937 communique and tilt angle being changed as the spy; perhaps carrying out opening the liquid crystal orientation film upper surface after implementing grinding process as shown in the flat 5-107544 communique as the spy divides ground to form diaphragm; after carrying out grinding process with the direction different with previous grinding process; remove diaphragm; the processing that the liquid crystal aligning of liquid crystal orientation film can be changed can improve the visual field characteristic of liquid crystal display cells like this.
(3) make 2 substrates that as above form liquid crystal orientation film, 2 substrates are staggered relatively by gap (box gap), make the vertical mutually or antiparallel of polishing direction of liquid crystal orientation film separately, fitted with sealant in 2 substrate periphery positions, in the box gap that is partitioned into by substrate surface and sealant, annotate topping up crystalline substance, sealing filling orifice, constitute liquid crystal cell.Then, at the outside surface of liquid crystal cell, promptly constitute the polaroid of fitting on the another side of each substrate of liquid crystal cell, it is consistent or vertical to make its polarization direction and this substrate simultaneously go up the polishing direction of the liquid crystal orientation film that forms, and makes liquid crystal display cells.
Here, as sealant, for example can use epoxy resin as the salic ball of hardening agent and separator etc.
As liquid crystal, can enumerate nematic crystal and dish shape type liquid crystal, wherein preferred nematic crystal can use for example schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.In addition, can also add cholesteryl liquid crystal such as for example cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal and the chirality agent of selling with trade name " C-15 ", " CB-15 " (メ Le Network corporate system) etc. and using.And, can also use right-last of the ten Heavenly stems oxygen base benzylidene-right-ferroelectric liquid crystals such as amino-2-methyl butyl cinnamate.
In addition, as the polaroid of fitting on the liquid crystal cell outside surface, can enumerate polyvinyl alcohol (PVA) is extended that the polarizing coating that is referred to as the H film that orientation absorbs the iodine gained simultaneously is clipped in the acetate fiber diaphragm and the polaroid that polaroid of making or H film self are made.
[embodiment]
Below, by embodiment the present invention is carried out more specific description, but the present invention is not limited to these embodiment.
Synthesis example 1
Will be as the pyromellitic acid dicarboxylic anhydride 109.06g (0.5 mole), 1 of tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride 98.06g (0.5 mole), as 4 of diamine compound, 4-diamino-diphenyl ether 200.2g (1.0 moles) is dissolved in 230g N-N-methyl-2-2-pyrrolidone N-, the 2060g gamma-butyrolacton, and it was reacted 3 hours down at 40 ℃.Then, gamma-butyrolacton is appended 1350g, obtain the polyamic acid that the solution viscosity of about 3590g under solid portion concentration 10% is 200mPas (it is as " polyamic acid (A-1) ") solution.
Synthesis example 2
Will be as 1 of tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride 98.06g (0.50 mole), pyromellitic acid dicarboxylic anhydride 109.06g (0.5 mole), as 4 of diamine compound, 4 '-diaminodiphenyl-methane 198.27g (1.0 moles) is dissolved in 230g N-N-methyl-2-2-pyrrolidone N-, the 2060g gamma-butyrolacton, and it was reacted 3 hours down at 40 ℃.Then, gamma-butyrolacton is appended 1350g, obtain the polyamic acid that the solution viscosity of about 3600g under solid portion concentration 10% is 125mPas (it is as " polyamic acid (A-2) ") solution.
Synthesis example 3
Will be as 1 of tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride 196.12g (1.0 moles), as 4 of diamine compound, 4 '-diamino-diphenyl ether 200.2g (1.0 moles) is dissolved in 225g N-N-methyl-2-2-pyrrolidone N-, the 2021g gamma-butyrolacton, and it was reacted 4 hours down at 40 ℃.Then, gamma-butyrolacton is appended 1321g, obtain the polyamic acid that the solution viscosity of about 3600g under solid portion concentration 10% is 210mPas (it is as " polyamic acid (A-3) ") solution.
Synthesis example 4
Will be as 1 of tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride 196.12g (1.0 moles), as 2 of diamine compound, 2 '-dimethyl-4,4 '-benzidine 212.3g (1.0 moles) is dissolved in 370g N-N-methyl-2-2-pyrrolidone N-, the 3300g gamma-butyrolacton, and obtaining about 3700g solution viscosities of 3 hours of reaction under 40 ℃ is polyamic acid (it is as " polyamic acid (A-4) ") solution of 160mPas.
Synthesis example 5
Will be as 2 of tetrabasic carboxylic acid dicarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride 224.17g (1 mole), as 4 of diamine compound, 4 '-diamino-diphenyl ether 200.2g (1.0 moles) is dissolved in 240g N-N-methyl-2-2-pyrrolidone N-, the 2164g gamma-butyrolacton, and obtaining about 3700g solution viscosities of 4 hours of reaction under 40 ℃ is polyamic acid (it is as " polyamic acid (A-5) ") solution of 180mPas.
Synthesis example 6
Will be as 2 of tetrabasic carboxylic acid dicarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride 112.1g (0.5 mole), 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1,3-diketone 157.14g (0.5 mole), p-phenylenediamine 94.62g (0.875 mole) as diamine compound, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine 32.02g (0.1 mole), 3,6-two (4-aminobenzoic acyl-oxygen base) cholesterol (compound of above-mentioned formula (9) expression, down together) 6.43g (0.01 mole), octadecane oxygen base-2,5-diaminobenzene 5.65g (0.015 mole) is dissolved in the 960g N-N-methyl-2-2-pyrrolidone N-, and it was reacted 9 hours down at 60 ℃.The polyamic acid solution branch that obtains is taken a morsel, add NMP, measure viscosity under the solution of solid portion concentration 10%, solution viscosity is 58mPas.In the gained polyamic acid solution, add 2740g N-N-methyl-2-2-pyrrolidone N-, 396g pyridine and 409g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours.After the imidization reaction, solvent in system carries out solvent exchange (in this operation with new gamma-butyrolacton, outside system, remove the pyridine, the acetic anhydride that use in the imidization reaction), the solution viscosity of (gamma-butyrolacton solution) is imide amination polymer (it is as " imide amination polymer (B-1) ") solution of 31.0mPas, imidizate rate about 95% when obtaining about 2500g solid component concentration 15.0wt%, solid component concentration 8.0%.
Synthesis example 7
Will be as 2 of tetrabasic carboxylic acid dicarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride 112.08g (0.5 mole), 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone 157.14g (0.5 mole), p-phenylenediamine 95.71g (0.865 mole) as diamine compound, diamido propyl group tetramethyl disiloxane 24.85g (0.1 mole), and 3,6-two (4-aminobenzoic acyl-oxygen base) cholesterol 12.86g (0.02 mole), N-octadecylamine 8.09g (0.03 mole) as monoamine is dissolved in the 960.0g N-N-methyl-2-2-pyrrolidone N-, and it was reacted 6 hours down at 60 ℃.The polyamic acid solution branch that obtains is taken a morsel, add NMP, under the solution of solid portion concentration 10%, measure viscosity, be 60mPas.Then, in the gained polyamic acid solution, add 2700g N-N-methyl-2-2-pyrrolidone N-, 396.0g pyridine and 409.0g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours.After the imidization reaction, solvent in system carries out solvent exchange (in this operation with new gamma-butyrolacton, outside system, remove the pyridine, the acetic anhydride that use in the imidization reaction), the solution viscosity of (gamma-butyrolacton solution) is imide amination polymer (it is as " imide amination polymer (B-2) ") solution of 16.0mPas, imidizate rate about 95% when obtaining about 2000g solid component concentration 15.0wt%, solid component concentration 6.0%.
Synthesis example 8
Will be as 2 of tetrabasic carboxylic acid dicarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride 224.17g (1 mole), as the p-phenylenediamine 107.06g (0.99 mole), 3 of diamine compound, 6-two (4-aminobenzoic acyl-oxygen base) cholesterol 6.43g (0.0 1 moles) is dissolved in the 3039g N-N-methyl-2-2-pyrrolidone N-, it was reacted 6 hours down at 60 ℃, obtain the polyamic acid solution that solution viscosity is about 260mPas.Then, in the gained polyamic acid solution, append 2700g N-N-methyl-2-2-pyrrolidone N-, 396.0g pyridine and 306.0g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours.After the imidization reaction, solvent in system carries out solvent exchange (in this operation with new gamma-butyrolacton, outside system, remove the pyridine, the acetic anhydride that use in the imidization reaction), the solution viscosity of (gamma-butyrolacton solution) is imide amination polymer (it is as " imide amination polymer (B-3) ") solution of 72.0mPas, imidizate rate about 89% when obtaining the about 9.0wt% of about 3000g solid component concentration, solid component concentration 5.0%.
Synthesis example 9
Will be as 2 of tetrabasic carboxylic acid dicarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride 112.1g (0.5 mole), 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1,3-diketone 157.14g (0.5 mole), p-phenylenediamine 89.21g (0.825 mole) as diamine compound, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine 32.02g (0.1 mole), 1-(3,5-diaminobenzene formyloxy)-4-(4-trifluoromethyl benzoyloxy)-cyclohexane (compound of above-mentioned formula (20) expression, down together) 25.34g (0.06 mole), octadecane oxygen base-2,5-diaminobenzene 5.65g (0.015 mole) is dissolved in the 2175g N-N-methyl-2-2-pyrrolidone N-, and it was reacted 6 hours down at 60 ℃.The polyamic acid solution branch that obtains is taken a morsel, add NMP, measure viscosity under the solution of solid portion concentration 10%, solution viscosity is 110mPas.Then, in 1500g gained polyamic acid solution, append 3000g N-N-methyl-2-2-pyrrolidone N-, 221.0g pyridine and 228.0g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours.After the imidization reaction, solvent in system carries out solvent exchange (in this operation with new gamma-butyrolacton, outside system, remove the pyridine, the acetic anhydride that use in the imidization reaction), the solution viscosity of (gamma-butyrolacton solution) is about imide amination polymer (it is as " imide amination polymer (B-4) ") solution of 26.0mPas, imidizate rate about 92% when obtaining the about 10.0wt% of about 2000g solid component concentration, solid component concentration 4.5%.
Embodiment 1
Imide amination polymer (B-1) 100 weight portions that make in the synthesis example 6 and the EX-171 that contains epoxy compounds (Na ガ セ ケ system テ Star Network ス (strain) production) 0.05 weight portion of representing as above-mentioned formula (II) are dissolved in gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/butyl cellosolve (71/17/12 (weight ratio)) mixed solvent, make the solution that solids content concn is 4 weight %, is the filter filtration of 1 μ m with this solution with the aperture, makes aligning agent for liquid crystal of the present invention.Above-mentioned aligning agent for liquid crystal is coated on the transparency electrode face of the glass substrate that has ITO film system transparency electrode with liquid crystal orientation film printing machine (Japan's description printing machine (strain) is made), after on 80 ℃ the heating plate dry 1 minute, on 200 ℃ heating plate dry 10 minutes again, forming average film thickness was the overlay film of 600 dusts.With of the microscopic examination of this substrate with 20 times of multiplying powers, do not find the irregular and pore of printing, printing is good.
The sander of the roller that twines nylon type cloth is equipped with in employing, and with roller rotating speed 500rpm, operator's console translational speed 3cm/ second, fine hair is clamp-oned the condition that length is 0.4mm, and this overlay film is carried out grinding process, forms liquid crystal orientation film.Then, the substrate of above-mentioned formation liquid crystal orientation film flooded 1 minute in isopropyl alcohol after, on 100 ℃ heating plate dry 5 minutes.Then, on each outer rim with liquid crystal orientation film of a pair of aforesaid substrate, it is the epoxy adhesive of the alumina balls of 5.5 μ m that coating has added diameter, then, the liquid crystal aligning face is relatively overlapped and pressing, and bonding agent is solidified.Then, by liquid crystal injecting port between a pair of substrate, fill nematic crystal (メ Le Network society produces, MLC-6221) after, with propylene class Photocurable adhesive liquid crystal injecting port is sealed, the polaroid of fitting on the two sides in the substrate outside is made liquid crystal display cells of the present invention.
The gained liquid crystal display cells is applied 30Hz, the 3.0V square wave 500 hours of superposeed 6.0V alternating current (peak-peak) under 70 ℃ environment temperature, the visual observations element does not find that the demonstration of liquid crystal display cells is bad.
Embodiment 2～23, comparative example 1～2
Except adopting the polyamic acid and the imide amination polymer of synthesis example 1～9 gained, and beyond the baking temperature that contains the kind of epoxy compounds and addition and liquid crystal orientation film changes, modulate aligning agent for liquid crystal similarly to Example 1, on substrate, form overlay film, observation has or not the irregular and pore of printing, further make liquid crystal display cells, observation has or not demonstration bad.In addition, in embodiment 5～23, comparative example 1～2, polyamic acid and imide amination polymer are with polyamic acid: the ratio of imide amination polymer=4: 1 (weight portion) uses.One be listed in table 1 as a result.
Table 1
Polymkeric substance Contain epoxy compounds (weight portion) Printing Show bad
Embodiment 2 B-2 C-1(0.05) Well Do not have
Embodiment 3 B-3 C-1(0.05) Well Do not have
Embodiment 4 B-4 C-1(0.05) Well Do not have
Embodiment 5 A-1，B-1 C-1(0.05) Well Do not have
Embodiment 6 A-2，B-1 C-1(0.05) Well Do not have
Embodiment 7 A-3，B-1 C-1(0.05) Well Do not have
Embodiment 8 A-4，B-1 C-1(0.03) Well Do not have
Embodiment 9 A-5，B-1 C-1(0.03) Well Do not have
Embodiment 10 A-1，B-2 C-1(0.03) Well Do not have
Embodiment 11 A-2，B-2 C-1(0.03) Well Do not have
Embodiment 12 A-3，B-2 C-1(0.03) Well Do not have
Embodiment 13 A-4，B-2 C-1(0.05) Well Do not have
Embodiment 14 A-5，B-2 C-1(0.05) Well Do not have
Embodiment 15 A-1，B-3 C-1(0.05) Well Do not have
Embodiment 16 A-2，B-3 C-1(0.05) Well Do not have
Embodiment 17 A-3，B-3 C-1(0.05) Well Do not have
Embodiment 18 A-4，B-3 C-1(0.05) Well Do not have
Embodiment 19 A-5，B-3 C-1(0.05) Well Do not have
Embodiment 20 A-3，B-4 C-1(0.05) Well Do not have
Embodiment 21 A-4，B-4 C-1(0.05) Well Do not have
Embodiment 22 A-1，B-1 C-2(0.05) Well Do not have
Embodiment 23 A-4，B-4 C-2(0.05) Well Do not have
Comparative example 1 A-1，B-1 - Produce irregular Do not have
Comparative example 2 A-3，B-2 - Produce irregular Do not have
C-1:EX-171 (Na ガ セ ケ system テ Star Network ス (strain) produces, the compound of formula (47) expression)
C-2:EX-145 (Na ガ セ ケ system テ Star Network ス (strain) produces, the compound of formula (45) expression).

Claims (3)

1. aligning agent for liquid crystal is characterized in that containing: (A) have the repetitive of following formula (I-1) expression and/or following formula (I-2) expression repetitive polymkeric substance and
(B) epoxy compounds of following formula (II) expression,
Figure A2007101107140002C1
In the formula, P 1Be the organic group of 4 valencys, Q 1Be the organic group of divalent,
In the formula, P 2Be the organic group of 4 valencys, Q 2Be the organic group of divalent,
Figure A2007101107140002C3
In the formula, n is 1～30 integer, R 1Organic group for the n valency.
2. the described aligning agent for liquid crystal of claim 1, wherein (A) polymkeric substance is the polymkeric substance of the repetitive of repetitive with above-mentioned formula (I-1) expression and above-mentioned formula (I-2) expression.
3. a liquid crystal display cells is characterized in that having the liquid crystal orientation film that is made by the described aligning agent for liquid crystal of claim 1.
CNA2007101107148A 2006-06-02 2007-06-01 Liquid crystal tropism agent and liquid crystal display element Pending CN101082741A (en)

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