CN101241274A - Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element - Google Patents
Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element Download PDFInfo
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- CN101241274A CN101241274A CNA2008100742294A CN200810074229A CN101241274A CN 101241274 A CN101241274 A CN 101241274A CN A2008100742294 A CNA2008100742294 A CN A2008100742294A CN 200810074229 A CN200810074229 A CN 200810074229A CN 101241274 A CN101241274 A CN 101241274A
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- liquid crystal
- tetracarboxylic dianhydride
- acid
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- dianhydride
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- 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
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
Abstract
The present invention provides a liquid crystal alignment agent, including 100 portions polymer by weight having an amido acid binding unit and an imide binding unit, and at least 5 portions by weight compound represented by following formula (I-3) having epoxy in its molecule. Wherein, R is an organic group with 2 valence. The ratio of the amido acid binding unit numbers to the totally binding unit numbers of the amido acid binding unit and an imide binding unit is 60-95%. The present invention provides the liquid crystal alignment agent having excellent sticking capability whatever the electrode kinds of the liquid crystal display unit, a liquid crystal alignment film is obtained by the liquid crystal alignment agent, and a liquid crystal display unit having the film is also obtained by the liquid crystal alignment agent.
Description
Technical field
The present invention relates to aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells.More specifically, relate to how the type of electrodes that constitutes liquid crystal display cells burns all good aligning agent for liquid crystal of attached characteristic (the baked I is paid the I characteristic), the liquid crystal orientation film that obtains by this aligning agent for liquid crystal and liquid crystal display cells with this film.
Background technology
In the past, known TN type liquid crystal display cells with TN (Twisted Nematic) type liquid crystal cell, described TN type liquid crystal cell is to be formed with between 2 plate bases of liquid crystal orientation film Jie on the surface by nesa coating, formation has the nematic crystal layer of positive dielectric anisotropy, thereby form the box of sandwich structure, and the major axis of above-mentioned liquid crystal molecule is turned round continuously to turn 90 degrees and is obtained to another substrate from a substrate.
In addition, also have STN (Super Twisted Nematic) type liquid crystal display cells, it is being turned round the state more than the turnback continuously and is utilizing consequent birefringence effect by the major axis that the agent of interpolation chirality forms this liquid crystal molecule between substrate.In addition, in recent years, also develop reflection type liquid crystal display element, it forms the nematic liquid crystal layer of the same recurrence state of orientation with negative dielectric anisotropic, screw axis becomes parastate with substrate normal cholesteric liquid crystal layers between opposing substrates, be added with the reflection type liquid crystal display element of the visitor-principal mode of pigment in these liquid crystal layers.Liquid crystal aligning in these liquid crystal display cells shows by the liquid crystal orientation film that imposes friction treatment usually.At this, as the material of the liquid crystal orientation film that constitutes liquid crystal display cells, known in the past polyimide, polyamide and polyester etc.Polyimide particularly because thermotolerance, with excellences such as the compatibility of liquid crystal, physical strength, so be used in many liquid crystal display cells.
Recently, constantly develop with the research of the raising of the display quality headed by the high-precision refinement of liquid crystal display cells, low consumption electrification etc., the scope of utilizing of liquid crystal display cells is also enlarging.Reflection-type or the semi-transmission type liquid crystal display cells that particularly can keep high display quality when outdoor application are used to carried terminal, so use various metal electrodes (hereinafter referred to as reflecting electrode) for the function that shows the reflection exterior light.Yet, for liquid crystal display cells, existing with permeation type liquid crystal display element in the past and compare the attached problem of burning that is easy to generate with reflecting electrode, requirement is higher than the attached characteristic of burning that in the past requires more than the level to liquid crystal orientation film.
Summary of the invention
The object of the present invention is to provide the type of electrodes that can obtain to constitute liquid crystal display cells how to burn all aligning agent for liquid crystal of excellent liquid crystal orientation film of attached characteristic.
The liquid crystal display cells that other purpose of the present invention is above-mentioned liquid crystal orientation film is provided and has this film.
Other purpose of the present invention and advantage can be clear and definite by following explanation.
According to the present invention, above-mentioned purpose of the present invention and advantage be by, the 1st, a kind of aligning agent for liquid crystal is reached, described aligning agent for liquid crystal is characterised in that, polymkeric substance 100 weight portions that contain the amic acid combining unit of the acid imide combining unit of (I-1) expression that has following formula and following formula (I-2) expression, and compound (hereinafter referred to as " specific epoxy compound ") at least 5 weight portions that contain following formula (I-3) expression of epoxy radicals at molecule, wherein, above-mentioned amic acid combining unit is 60～95 moles of % with respect to the ratio of the total binding unit number of above-mentioned acid imide combining unit and above-mentioned amic acid combining unit.
(at this, P
1Be 4 valency organic groups, Q
1It is the divalent organic group.)
(at this, P
2Be 4 valency organic groups, comprise at least 30 moles of % and derive from 4 valency organic groups of pyromellitic acid dianhydride and derive from and be selected from 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride and 1,2,4, the 4 valency organic groups of at least a tetracarboxylic dianhydride among the 5-cyclohexane tetracarboxylic dianhydride; Q
2It is the divalent organic group.)
(at this, R is the divalent organic group.)
According to the present invention, above-mentioned purpose of the present invention and advantage be by, the 2nd, the liquid crystal orientation film that is formed by aligning agent for liquid crystal of the present invention is reached.
According to the present invention, above-mentioned purpose of the present invention and advantage be by, the 3rd, have that the liquid crystal display cells of liquid crystal orientation film of the present invention reaches.
Embodiment
Below, be elaborated for the present invention.
Aligning agent for liquid crystal of the present invention contains and has the acid imide combining unit that formed by tetracarboxylic dianhydride and diamine reactant and the polymkeric substance of amic acid combining unit.Acid imide combining unit and amic acid combining unit can be included in the same polymkeric substance, also can be included in the different polymkeric substance.
Above-mentioned amic acid combining unit is 60～95 moles of % with respect to the ratio of the total binding unit number of above-mentioned acid imide combining unit and above-mentioned amic acid combining unit.When being less than 60 moles of %, it is poor to burn attached characteristic sometimes, and when surpassing 95 moles of %, liquid crystal aligning is poor sometimes.
The polyamic acid that contains the amic acid combining unit is by obtaining tetracarboxylic dianhydride and diamine compound ring opening polyaddition, and polyimide is usually by obtaining the polyamic acid dehydration closed-loop.The part imide amination polymer usually can by make amic acid prepolymer and imide prepolymer in conjunction with and the method for synthetic segmented copolymer obtains.
＜polyamic acid and polyimide 〉
[tetracarboxylic dianhydride]
P in the following formula (I-2)
2Comprising at least 30 moles of % derives from 4 valency organic groups of pyromellitic acid dianhydride and derives from and be selected from 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride and 1,2,4, the 4 valency organic groups of at least a tetracarboxylic dianhydride among the 5-cyclohexane tetracarboxylic dianhydride.
P in the following formula (I-2)
2Can also contain the 4 valency organic groups that derive from above-mentioned other tetracarboxylic dianhydride in addition.As other such tetracarboxylic dianhydride, can enumerate for example butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[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)-naphtho-[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)-naphtho-[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)-naphtho-[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)-naphtho-[1,2-c]-furans-1, the 3-diketone, 3,5,6-three carboxyls norbornane-2-acetate dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[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)-naphtho-[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)-naphtho-[1,2-c]-furans-1, the 3-diketone, 5-(2, the 5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid dianhydride, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8,10-tetraketone, following formula (I) and aliphatics and the ester ring type tetracarboxylic dianhydrides such as compound that (II) represent;
(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
4Can be the same or different separately.)
3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-biphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two phthalandione dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, two (phthalandione) phenyl phosphine oxide dianhydride, TOPOT 2,2 (triphenyl phthalandione) dianhydride, two (triphenyl phthalandione) dianhydrides of metaphenylene, two (triphenyl phthalandiones)-4,4 '-diphenyl ether dianhydride, two (triphenyl phthalandiones)-4,4 '-diphenyl methane dianhydride, ethylene glycol bis (trimellitic anhydride ester), propylene glycol two (trimellitic anhydride ester), 1,4-butylene glycol two (trimellitic anhydride ester), 1,6-hexanediol two (trimellitic anhydride ester), 1,8-ethohexadiol two (trimellitic anhydride ester), 2, two (4-hydroxy phenyl) propane-two (trimellitic anhydride ester) of 2-, following formula (1)～(4) represented aromatic tetracarboxylic acid's dianhydrides such as compound.These compounds can be used singly or in combination of two or more thereof.
Wherein, consider from the angle that can show good liquid crystal aligning, preferred butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 5-(2, the 5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid dianhydride, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8,10-tetraketone, 2,2 ', 3, the represented compound of following formula (8) in the compound that following formula (5)～(7) in the compound of 3 '-biphenyl tetracarboxylic dianhydride, following formula (I) expression are represented and the compound of following formula (II) expression.
Preferred P
2Comprise: 30～70 moles of % of 4 valency organic groups that derive from pyromellitic acid dianhydride, derive from and be selected from 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride and 1,2,3, the 4 valency organic groups of at least a tetracarboxylic dianhydride among the 4-cyclohexane tetracarboxylic dianhydride or derive from 30～70 moles of % of 4 valency organic groups of other tetracarboxylic dianhydride.
In addition, as the P that constitutes in the following formula (I-1)
1The tetracarboxylic dianhydride, different with the situation of polyamic acid, can be above for the described tetracarboxylic dianhydride of polyamic acid without any restrictedly using.
[diamine compound]
As the diamine compound that is used for synthesizing polyamides acid or polyimide, can enumerate for example p-phenylenediamine (PPD), m-phenylene diamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formailide, 4,4 '-diamino-diphenyl ether, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-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 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (4-aminophenyl) HFC-236fa of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] sulfones of 2-, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 9, two (4-the aminophenyl)-10-hydrogen anthracenes of 9-, 2, the 7-diamino-fluorene, 9,9-dimethyl-2, the 7-diamino-fluorene, 9, two (4-aminophenyl) fluorenes of 9-, 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 '-(to the phenylene isopropylidene) dianiline, 4,4 '-(metaphenylene isopropylidene) dianiline, 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, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3, aromatic diamines such as 5-diaminobenzoic acid ester;
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 dicyclopentadienyl diamines (テ ト ラ ヒ De ロ ジ シ Network ロ ペ Application ジ エ ニ レ Application ジ ア ミ Application), six hydrogen-4, the inferior indanyl dimethylene diamines (メ ノ イ Application ダ ニ レ Application ジ メ チ レ Application ジ ア ミ Application) of 7-methylene, three ring [6.2.1.0
2,7]-undecylene dimethyl diamines, 4,4 '-di-2-ethylhexylphosphine oxide (cyclo-hexylamine), 1, two (amino methyl) cyclohexanes, 1 of 3-, the aliphatics and the ester ring type diamines of two (amino methyl) cyclohexanes of 4-etc.;
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-2,4-dihydroxy-pyrimidine, 2,4-diamido-6-dimethylamino-1,3, the 5-triazine, 1, two (3-aminopropyl) piperazines of 4-, 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, the 5-triazine, 2,4-diamido-6-methyl-s-triazine, 2,4-diaminostilbene, 3, the 5-triazine, 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, 3,5-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) aniline, 3,6-diamido carbazole, N-methyl-3,6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole, N, N '-two (4-aminophenyl) biphenylamine, and the represented compound of following formula (III)～(VI) etc. has the diamines of the nitrogen-atoms beyond 2 primary amine groups and this primary amine groups in molecule;
(in the formula, R
5Expression has 1 valency organic group of the ring structure that contains nitrogen-atoms that is selected from pyridine, pyrimidine, triazine, piperidines and the piperazine, and X represents the divalent organic group.)
(in the formula, X represents to have the divalent organic group that is selected from the ring structure that contains nitrogen-atoms in pyridine, pyrimidine, triazine, piperidines and the piperazine, R
6Expression divalent organic group, the X of a plurality of existence can be the same or different.)
The single-substituted diamines 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-divalent organic group among the CO-, R
8It is 6～30 alkyl that expression has 1 valency organic group of the group that is selected from steride skeleton, trifluoromethyl and the fluorin radical or carbon number.)
(in the formula, R
9The expression carbon number is 1～12 alkyl, the R of a plurality of existence
9Can be the same or different, p is 1～3 integer, and q is 1～20 integer.)
The compound that following formula (9)～(13) are represented etc.These diamine compounds can be used alone or in combination of two or more kinds.
(in the formula, y is 2～12 integer, and z is 1～5 integer.)
Wherein, preferred p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl thioether, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 9, two (4-aminophenyl) fluorenes of 9-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (4-aminophenyl) HFC-236fa of 2-, 4,4 '-(to the phenylene diisopropylidene) dianiline, 4,4 '-(metaphenylene diisopropylidene) dianiline, 1, the 4-cyclohexane diamine, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexylamine), 1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 1, two (amino methyl) cyclohexanes of 3-, following formula (9)～(13) represented compound, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 3,6-diamido carbazole, N-methyl-3,6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole, N, N '-two (4-aminophenyl) biphenylamine, the compound of following formula (14) expression in the compound of following formula (III) expression, the compound of following formula (16)～(21) expression in the compound of following formula (15) expression in the compound of following formula (IV) expression and the compound of following formula (V) expression.
[synthetic reaction of polyamic acid]
The tetracarboxylic dianhydride of supply polyamic acid synthetic reaction and the usage ratio of diamine compound are as follows: preferably with respect to amino 1 equivalent that contains in the diamine compound, tetracarboxylic dianhydride's anhydride group is the ratio of 0.5～2 equivalent, more preferably the ratio of 0.7～1.2 equivalent.
The synthetic reaction of polyamic acid be in organic solvent, preferred-20～150 ℃, more preferably carry out under 0～100 ℃ the temperature conditions.At this, as organic solvent, just be not particularly limited so long as can dissolve the solvent of the polyamic acid that is synthesized, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, N, N-dimethyl acetamide, N, non-proton class polar solvents such as dinethylformamide, dimethyl sulfoxide, gamma-butyrolacton, tetramethylurea, hexamethyl phosphoric triamide; Phenol solvents such as metacresol, xylenol, phenol, halogenated phenol.In addition, the use amount of organic solvent (a) is preferably following amount: the total amount (b) that makes tetracarboxylic dianhydride and diamine compound is the amount of 0.1～30 weight % with respect to the total amount (a+b) of reaction solution.
[poor solvent]
In above-mentioned organic solvent, the scope that can not separate out at the polyamic acid that generates and the alcohol that is used as the poor solvent of polyamic acid, ketone, ester, ether, halogenated hydrocarbons, hydrocarbon etc.Concrete example as described 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, methyl methoxy base propionic ester, ethyl ethoxy-c acid esters, diethy-aceto oxalate, diethyl malonate, ether, Ethylene Glycol Methyl ether, glycol ethyl ether, the ethylene glycol n-propyl ether, the ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 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, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether etc.
As above obtain dissolving the reaction solution that polyamic acid forms.Then, this reaction solution is injected in a large amount of poor solvents, obtains precipitate, this precipitate under reduced pressure can be carried out drying or with evaporator with the reaction solution decompression distillation, can obtain polyamic acid thus.In addition,, then make its operation of separating out, perhaps use the operation of evaporator decompression distillation with poor solvent by carrying out 1 time or for several times this polyamic acid being dissolved in the organic solvent again, can the purifying polyamic acid.
[polyimide]
The polyimide that constitutes aligning agent for liquid crystal of the present invention can be as above by preparing the polyamic acid dehydration closed-loop.The polyimide of Shi Yonging in the present invention can be the imidizate rate less than 100%, through the material of partial dehydration closed loop.Being meant to have the ratio of repetitive in all repetitives of polymkeric substance of imide ring or different imide ring in this said " imidizate rate ", is the value of representing with percent.Contain the imidizate rate and be the alignment agent of 20～100% imide amination polymer, during especially for TFT type element, can obtain the high evaluation of voltage retention.The dehydration closed-loop of polyamic acid carries out by the following method: (i) method of heating polyamic acid, perhaps (ii) polyamic acid is dissolved in the organic solvent, and in this solution, add dewatering agent and dehydration closed-loop catalyzer, the method that heats as required.
Temperature of reaction in the method for above-mentioned (i) heating polyamic acid is preferably 50～200 ℃, more preferably 60～170 ℃.When temperature of reaction was lower than 50 ℃, the dehydration closed-loop reaction was difficult to fully carry out, and when temperature of reaction surpassed 200 ℃, the molecular weight of gained imide amination polymer can reduce sometimes.
On the other hand, in the above-mentioned method of (ii) in polyamic acid solution, adding dewatering agent and dehydration closed-loop catalyzer,, can use for example acid anhydrides such as acetic anhydride, propionic andydride, trifluoro-acetic anhydride as dewatering agent.The use amount of dewatering agent is 0.01～20 mole for 1 mole with respect to the repetitive of polyamic acid preferably.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 use amount of dehydration closed-loop catalyzer is 0.01～10 mole with respect to 1 mole of dewatering agent preferably.It should be noted that as the organic solvent that is used for the dehydration closed-loop reaction, can enumerate as being used for the organic solvent that the synthetic solvent of polyamic acid is enumerated.The temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 10～150 ℃.In addition,, carry out the operation same with the purification process of polyamic acid to the reaction solution that so obtains, thus can the purifying polyimide.
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 measures
1H-NMR can obtain the imidizate rate by the formula of following formula shown in (ii).
Imidizate rate (%)=(1-A
1/ A
2* α) * 100 (ii)
A
1: from the peak area (10ppm) of NH matrix
A
2: from the peak area of other proton
α: other proton number in the polymer precursor (polyamic acid) is with respect to the ratio of sub 1 of NH matrix
The polymkeric substance of＜end modified type 〉
Above-mentioned polyamic acid, polyimide and part imidizate block polymer can be the end modified type polymkeric substance that has carried out molecular-weight adjusting.By using this end modified type polymkeric substance, improve the coating characteristics of aligning agent for liquid crystal etc. with can can't harm effect of the present invention.End modified type polymkeric substance like this can add sour single acid anhydride, monoamine compound, monoisocyanates compound in synthesizing polyamides when acid and wait synthetic in reaction system.Wherein, as the single acid anhydride of acid, can enumerate for example maleic anhydride, anhydride phthalic acid, 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, naphthyl isocyanate etc.
＜solution viscosity 〉
The polymkeric substance that uses in the alignment agent of the present invention when making the solution of 10 weight %, preferably has the viscosity of 20～800mPas, more preferably has the viscosity of 30～500mPas.
The solution viscosity (mpas) that it should be noted that polymkeric substance is to use specified solvent, is that the solution of 10 weight %s measure to being diluted to solid component concentration with E type rotational viscosimeter under 25 ℃.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention normally is dissolved with above-mentioned polymkeric substance and interpolation arbitrarily in organic solvent other composition constitutes.Constitute the represented acid imide combining unit of following formula (I-1) in the polymkeric substance of aligning agent for liquid crystal of the present invention: the molar ratio of the amic acid combining unit that following formula (I-2) is represented is 40: 60～5: 95.
As the organic solvent that constitutes aligning agent for liquid crystal of the present invention, can enumerate as the cited solvent of solvent that in the synthetic reaction of polyamic acid, uses.In addition, also can suitably select as when the synthetic reaction of polyamic acid can and the cited poor solvent of the solvent of usefulness come and use.
As the particularly preferred organic solvent that uses in the aligning agent for liquid crystal of the present invention, can enumerate 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, methyl methoxy base propionic ester, ethyl ethoxy-c acid esters, Ethylene Glycol Methyl ether, glycol ethyl ether, the ethylene glycol n-propyl ether, the ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, TC, the diethylene glycol monomethyl ether acetic acid esters, the TC acetic acid esters, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether etc.These solvents can use separately or mix more than 2 kinds and use.Particularly preferred solvent composition be with the combination of above-mentioned solvent and composition, be polymkeric substance in alignment agent, do not separate out and the surface tension of alignment agent at the composition of 25～40mN/m scope.
Solid component concentration in the aligning agent for liquid crystal of the present invention is to consider viscosity, volatility etc. and select.Preferably in the scope of 1～10 weight %.Promptly, aligning agent for liquid crystal of the present invention is applied in substrate surface, formation becomes filming of liquid crystal orientation film, but solid component concentration is during less than 1 weight %, this thickness of filming is too small and be difficult to obtain good liquid crystal orientation film, when solid component concentration surpassed 10 weight %, the thickness of filming was excessive and be difficult to obtain good liquid crystal orientation film equally, and the viscosity of aligning agent for liquid crystal increases and coating characteristics is poor.
The method that the scope that it should be noted that particularly preferred solid component concentration is used during according to coating of liquid crystalline alignment agent on substrate and difference.For example, when using spin-coating method, the scope of preferred especially 1.5～4.5 weight %.When using print process, especially preferably make the scope of solid component concentration, make the scope of solution viscosity thus at 12～50mPas at 3～9 weight %.When using ink-jet method, especially preferably make the scope of solid component concentration, make the scope of solution viscosity thus at 3～15mPas at 1～5 weight %.
Temperature when preparing aligning agent for liquid crystal of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
In the aligning agent for liquid crystal that forms liquid crystal orientation film of the present invention, must contain specific epoxy compound.As specific epoxy compound, can enumerate for example N, N, N ', N '-four glycidyl group m-xylene diamine, 1, two (N, N-diglycidyl amino methyl) cyclohexanes of 3-etc.These cooperation ratios that contain the compound of epoxy radicals are more than 5 weight portions with respect to polymkeric substance 100 weight portions, are preferably 10～30 weight portions.
In addition, aligning agent for liquid crystal of the present invention can also contain the compound of functional silanes.As the described compound that contains functional silanes, can enumerate for example 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, two (oxidation ethylidene (oxyethylene))-3-TSL 8330s of N-, two (oxidation the ethylidene)-3-aminopropyltriethoxywerene werene of N-etc.
These cooperation ratios of compound that contain functional silanes are preferably below 2 weight portions, more preferably below 0.2 weight portion with respect to polymkeric substance 100 weight portions.
＜liquid crystal display cells 〉
The liquid crystal display cells that uses aligning agent for liquid crystal of the present invention to obtain for example can be made by the following method.
(1) in the one side of the substrate that is provided with the nesa coating that forms pattern, is coated with aligning agent for liquid crystal of the present invention, follows, form by the heating coated face and film by for example methods such as rolling method, spin-coating method, print process, ink-jet method.At this,, can use for example by glass such as float glass, soda-lime glass as substrate; The transparency carrier that plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, ester ring type polyolefin constitute.Nesa coating as being arranged on the substrate one side can use to comprise tin oxide (SnO
2) NESA film (U.S. PPG register of company trade mark), comprise indium oxide-tin oxide (In
2O
3-SnO
2) ITO film etc.The pattern of these nesa coatings forms can adopt photo-engraving process, use the method for mask in advance.During the coating of liquid crystalline alignment agent, in order further to improve substrate surface and nesa coating and the adhesiveness of filming, can be in advance on this surface of substrate coating contain functional silanes compound, contain the compound of functionality titanium etc.Behind the coating of liquid crystalline alignment agent, the alignment agent liquid that is coated with in order to prevent dirty (liquid hang down れ) etc. are preferably implemented preparation heating (preliminary drying).Preferred 30～200 ℃ of preliminary drying temperature, more preferably 40～150 ℃, preferred especially 40～100 ℃.Then, solvent is removed fully,, implemented sintering (back baking) operation for polyamic acid is carried out hot-imide.Preferred 80～300 ℃ of this sintering (back baking) temperature, more preferably 120～250 ℃.Like this, the aligning agent for liquid crystal of the present invention that contains polyamic acid is removed organic solvent after by coating and can be formed and become filming of liquid crystal orientation film, and then carries out dehydration closed-loop by heating, can form the liquid crystal orientation film of further imidizate.Preferred 0.001～1 μ m of the thickness of formed liquid crystal orientation film, more preferably 0.005～0.5 μ m.
(2) for formed coated surface, with circumvolution the roller of the cloth that is made of for example fibers such as nylon, rayon, cotton is arranged, carry out friction treatment in the certain orientation friction.Thus, give the liquid crystal molecular orientation ability of filming, form liquid crystal orientation film.
In addition, by the liquid crystal orientation film that is formed by aligning agent for liquid crystal of the present invention is imposed following processing, can improve the visual field characteristic of liquid crystal display cells; The processing that described processing for example discloses in Japanese kokai publication hei 6-222366 communique, Japanese kokai publication hei 6-281937 communique is such, tilt angle is changed by the part irradiation ultraviolet radiation, perhaps in Japanese kokai publication hei 5-107544 communique, disclose such, form resist film on the liquid crystal orientation film surface portion ground of implementing friction treatment, with direction that formerly friction treatment is different on carry out friction treatment after, remove above-mentioned resist film, make the processing of the liquid crystal aligning capacity variation of liquid crystal orientation film.
(3) as above make 2 substrates that form liquid crystal orientation film like that, 2 plate bases are situated between by gap (box gap) configuration relatively, make the frictional direction quadrature or the antiparallel of each liquid crystal orientation film, with the fit periphery of 2 plate bases of sealant, in the box gap that marks off by substrate surface and sealant, inject filling liquid crystal, filling orifice is sealed constitute liquid crystal cells.Then, at the outside surface of liquid crystal cells, promptly constitute the transparent substrate side configuration polarization plates of liquid crystal cell, obtain liquid crystal display cells thus.
At this,, can use and for example contain hardening agent and as epoxy resin of the alumina balls of sept (spacer) etc. as sealant.
As liquid crystal, can enumerate nematic crystal and smectic crystal, wherein preferred nematic crystal, for example, can use Schiff bases liquid crystal, azoxy class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, two alkanes liquid crystal, bicyclooctane class liquid crystal, cube alkanes liquid crystal etc.In addition, can in these liquid crystal, for example add cholesteryl liquid crystal such as cholest chlorine (コ レ ス チ Le Network ロ ラ イ De), cholesteryl nonanoate, cholesteryl carbonate or wait with the chirality agent that trade name " C-15 ", " CB-15 " (メ Le Network corporate system) are sold and to use.Further, can also use oxygen base benzal-in the last of the ten Heavenly stems strong dielectricity liquid crystal such as amino-2-methyl butyl cinnamate.
In addition, as the polarization plates that is fitted in the liquid crystal cells outside surface, can enumerate polarization plates that the polarizing coating that is called as " H film " that absorbs iodine when making the polyvinyl alcohol (PVA) stretch orientation with the clamping of cellulose acetate diaphragm forms or the polarization plates that contains H film itself etc.
As above, compare with alignment films in the past by the liquid crystal orientation film that aligning agent for liquid crystal of the present invention forms, burn attached excellent, can perform well in constituting various liquid crystal display cells such as TN type liquid crystal display cells, STN type liquid crystal display cells, reflection type liquid crystal display element and semi-transmission type liquid crystal display cells.
Liquid crystal display cells of the present invention can be used for various devices effectively, for example, can be used as the display device of desk-top computer, wrist-watch, platform table, mobile phone, counting display board, spoken and written languages processor, personal computer, LCD TV etc. well.
Embodiment
Below, be described more specifically the present invention by embodiment, but the present invention is not limited to these embodiment.Burning in embodiment and the comparative example is attached, the imidizate rate is estimated by the following method.
[burning attached]
Liquid crystal display cells is applied the DC voltage 20 hours of 5.0V, obtain the voltage that remains in after the firm cut-out DC voltage in the liquid crystal cell, try to achieve residual DC voltage thus by flicker null method (Off リ Star カ-elimination method).The value of residual DC voltage is following being judged as of 0.1V, other be bad.
[assay method of the imidizate rate 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 measures
1H-NMR obtains the imidizate rate by the formula of following formula shown in (ii).
Imidizate rate (%)=(1-A
1/ A
2* α) * 100 (ii)
A
1: from the peak area (10ppm) of NH matrix
A
2: from the peak area of other proton
α: other proton number in the polymer precursor (polyamic acid) is with respect to the ratio of sub 1 of NH matrix
[solution viscosity]
The solution viscosity of polymkeric substance (mPas) is to use specified solvent, is that the solution of 10 weight %s measure obtain to being diluted to solid component concentration with E type rotational viscosimeter under 25 ℃.
Synthesis example 1
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride 191g (0.85 mole) and 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl) naphtho-[1,2-c] furans-1,3-diketone 47g (0.15 mole) is as the p-phenylenediamine (PPD) 91g (0.85 mole) of diamine compound, two aminopropyl tetramethyl disiloxane 25g (0.10 mole) and 3, two (4-aminobenzoic acyl-oxygen base) the cholestane 25g (0.040 mole) of 6-, aniline 2.8g (0.030 mole) as monoamine is dissolved among the N-N-methyl-2-2-pyrrolidone N-4500g, reacts 6 hours down at 60 ℃.Then, gained polyamic acid 30g is dissolved among the N-N-methyl-2-2-pyrrolidone N-570g, adds pyridine 23g and acetic anhydride 18g, under 110 ℃, carried out dehydration closed-loop 4 hours.After the imidization reaction, with new gamma-butyrolacton the solvent in the system is carried out solvent exchange (by this operation with the pyridine that uses in the imidization reaction, acetic anhydride except that to system), the solution viscosity of (gamma-butyrolacton solution) is that 65mPas, imidizate rate are about 95% imide amination polymer (being referred to as " polyimide (A-1) ") the about 120g of solution when obtaining solid component concentration and being 10 weight %.
Synthesis example 2
Will be as tetracarboxylic dianhydride's pyromellitic acid dianhydride 109g (0.50 mole), 1,2,3,4-cyclo-butane tetracarboxylic dianhydride 98g (0.50 mole), as 4 of diamine compound, 4-diamino-diphenyl ether 200g (1.0 moles) is dissolved among N-N-methyl-2-2-pyrrolidone N-230g, the gamma-butyrolacton 2060g, after reacting 3 hours under 40 ℃, append gamma-butyrolacton 1350g, solution viscosity is polyamic acid (being referred to as " polyamic acid (B-1) ") the about 3590g of solution of 200mPas when obtaining solid component concentration and being 10 weight %.
Synthesis example 3
Will be as tetracarboxylic dianhydride's 1,2,3,4-cyclo-butane tetracarboxylic dianhydride 98g (0.50 mole), pyromellitic acid dianhydride 109g (0.50 mole), as 4 of diamine compound, 4 '-diaminodiphenyl-methane 198g (1.0 moles) is dissolved among N-N-methyl-2-2-pyrrolidone N-230g, the gamma-butyrolacton 2060g, after reacting 3 hours under 40 ℃, append gamma-butyrolacton 1350g, solution viscosity is polyamic acid (being referred to as " polyamic acid (B-2) ") the about 3600g of solution of 125mPas when obtaining solid component concentration and being 10 weight %.
Synthesis example 4
Will be as tetracarboxylic dianhydride's 1,2,3,4-cyclo-butane tetracarboxylic dianhydride 98g (0.50 mole), pyromellitic acid dianhydride 109g (0.50 mole), as 2 of diamine compound, 2 '-dimethyl-4,4 '-benzidine 212g (1.0 moles) is dissolved among N-N-methyl-2-2-pyrrolidone N-230g, the gamma-butyrolacton 2060g, after reacting 3 hours under 40 ℃, append gamma-butyrolacton 1350g, solution viscosity is polyamic acid (being referred to as " polyamic acid (B-3) ") the about 3600g of solution of 220mPas when obtaining solid component concentration and being 10 weight %.
Synthesis example 5
Will be as tetracarboxylic dianhydride's 1,2,3,4-cyclo-butane tetracarboxylic dianhydride 196g (1.0 moles), as 2 of diamine compound, 2 '-dimethyl-4,4 '-benzidine 212g (1.0 moles) is dissolved among N-N-methyl-2-2-pyrrolidone N-370g, the gamma-butyrolacton 3300g, reacts 3 hours down at 40 ℃, obtains the polyamic acid that solution viscosity is 160mPas (being referred to as " polyamic acid (B-4) ") the about 3700g of solution.
Embodiment 1
Polyimide (A-1) that will obtain in synthesis example 1 and the polyamic acid (B-1) that obtains in synthesis example 2 are dissolved in the mixed solvent (weight ratio 71/17/12) of gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/butyl cellosolve, make polyimide: polyamic acid=20: 80 (weight ratio), dissolve the N of 20 weight portions with respect to polymkeric substance 100 weight portions, N, N ', N '-four glycidyl group m-xylene diamine, make the solution that solid component concentration is 3.5 weight %, after fully stirring, filtrator with aperture 1 μ m filters this solution, makes aligning agent for liquid crystal of the present invention.The glass substrate one side of using spinner that above-mentioned aligning agent for liquid crystal is applied to be located at thick 1mm by (rotating speed: 2500rpm on the film formed nesa coating of ITO, the coating time: 1 minute), drying is 1 hour under 200 ℃, is the tunicle of 0.08 μ m thereby form dry film thickness.By having circumvolution the rubbing machine of the roller of rayon system cloth is arranged, this tunicle is imposed the friction treatment of following condition: the rotating speed 400rpm of roller, the translational speed 3cm/ second of platform, fine hair is pressed into length (the sufficient Ya Ru み Long さ of hair) 0.4mm.Then, ultrasonic washing is 1 minute in ultrapure water, and drying is 10 minutes in 100 ℃ cleaning oven.Then, each outer rim at the above-mentioned liquid crystal orientation film coated substrates of a pair of transparency electrode/transparent electrode substrate with liquid crystal orientation film, after coating is mixed with the epoxy adhesive of diameter 5.5 μ m alumina balls,, make adhesive cures with the overlapping pressing of the relative mode of liquid crystal aligning face.Then, by liquid crystal injecting port between substrate, fill nematic crystal (メ Le Network corporate system, MLC-6221) after, with the acrylic compounds light-curing adhesive liquid crystal injecting port is sealed, the two sides applying polarization plates in the substrate outside makes liquid crystal display cells.The burning of estimating the gained liquid crystal display cells is attached.The aligning agent for liquid crystal that obtains in the present invention, residual DC voltage shows the low value that 0.1V is following.
Embodiment 2～6 and comparative example 1～8
The polyimide (A-1) that will in synthesis example 1, obtain, polyamic acid (B-1)～(B-4) and the N that in synthesis example 2～5, obtains, N, N ', N '-four glycidyl group m-xylene diamine or 1, cyclohexane is dissolved in the gamma-butyrolacton 3-two (N, N-diglycidyl amino methyls) is in the mixed solvent of principal ingredient, obtains the solution that solid component concentration is 3.5 weight %, filtrator with aperture 1 μ m filters this solution, makes aligning agent for liquid crystal of the present invention thus.Use each aligning agent for liquid crystal that so makes, operation forms tunicle on substrate surface similarly to Example 1, uses the substrate manufacture liquid crystal display cells that is formed with this liquid crystal orientation film, and it is attached to estimate burning.To respectively the results are shown in table 1.
Table 1
| Embodiment/comparative example | Polyimide | Polyamic acid | Polyimide: polyamic acid mixing ratio (polyimide combining unit/polyamic acid combining unit) | Compound (use level) * that contains epoxy radicals | Burn attached |
| Embodiment 1 | A-1 | B-1 | 20/80(18.8/81.2) | N, N, N ', N '-four glycidyl group-m-xylene diamine (20) | Good |
| Embodiment 2 | A-1 | B-2 | 20/80(18.8/81.2) | N, N, N ', N '-four glycidyl group-m-xylene diamine (20) | Good |
| Embodiment 3 | A-1 | B-3 | 20/80(18.8/81.2) | N, N, N ', N '-four glycidyl group-m-xylene diamine (20) | Good |
| Embodiment 4 | A-1 | B-1 | 20/80(18.8/81.2) | 1, two (N, the N-diglycidyl amino methyl) cyclohexanes (20) of 3- | Good |
| Embodiment 5 | A-1 | B-2 | 20/80(18.8/81.2) | 1, two (N, the N-diglycidyl amino methyl) cyclohexanes (20) of 3- | Good |
| Embodiment 6 | A-1 | B-3 | 20/80(18.8/81.2) | 1, two (N, the N-diglycidyl amino methyl) cyclohexanes (20) of 3- | Good |
| Comparative example 1 | A-1 | B-4 | 20/80(18.8/81.2) | N, N, N ', N '-four glycidyl group-m-xylene diamine (20) | Bad |
| Comparative example 2 | A-1 | B-4 | 20/80(18.8/81.2) | 1, two (N, the N-diglycidyl amino methyl) cyclohexanes (20) of 3- | Bad |
| Comparative example 3 | A-1 | B-1 | 20/80(18.8/81.2) | N, N, N ', N '-four glycidyl group-m-xylene diamine (2) | Bad |
| Comparative example 4 | A-1 | B-2 | 20/80(18.8/81.2) | 1, two (N, the N-diglycidyl amino methyl) cyclohexanes (2) of 3- | Bad |
| Comparative example 5 | A-1 | B-3 | 20/80(18.8/81.2) | N, N, N ', N '-four glycidyl group-m-xylene diamine (2) | Bad |
| Comparative example 6 | A-1 | B-1 | 80/20(75.2/24.8) | N, N, N ', N '-four glycidyl group-m-xylene diamine (20) | Bad |
| Comparative example 7 | A-1 | B-3 | 80/20(75.2/24.8) | N, N, N ', N '-four glycidyl group-m-xylene diamine (20) | Bad |
| Comparative example 8 | A-1 | B-1 | 80/20(75.2/24.8) | 1, two (N, the N-diglycidyl amino methyl) cyclohexanes (2) of 3- | Bad |
* with respect to the use level (weight portion) of total weight 100 weight portions of polyimide and polyamic acid
Claims (3)
1. aligning agent for liquid crystal, it is characterized in that, contain polymkeric substance 100 weight portions of amic acid combining unit of the acid imide combining unit of (I-1) expression that has following formula and following formula (I-2) expression and compound at least 5 weight portions that contain following formula (I-3) expression of epoxy radicals at molecule, wherein, above-mentioned amic acid combining unit is 60～95 moles of % with respect to the ratio of the total binding unit number of above-mentioned acid imide combining unit and above-mentioned amic acid combining unit
At this, P
1Be 4 valency organic groups, Q
1It is the divalent organic group;
At this, P
2Be 4 valency organic groups, comprise at least 30 moles of % and derive from 4 valency organic groups of pyromellitic acid dianhydride and derive from and be selected from 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride and 1,2,4, the 4 valency organic groups of at least a tetracarboxylic dianhydride among the 5-cyclohexane tetracarboxylic dianhydride; Q
2It is the divalent organic group;
At this, R is the divalent organic group.
2. liquid crystal orientation film is formed by the described aligning agent for liquid crystal of claim 1.
3. liquid crystal display cells, it has the described liquid crystal orientation film of claim 2.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007026369 | 2007-02-06 | ||
| JP2007026369 | 2007-02-06 |
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| CN101241274A true CN101241274A (en) | 2008-08-13 |
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| JP (1) | JP2008216985A (en) |
| KR (1) | KR20080073664A (en) |
| CN (1) | CN101241274A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812304A (en) * | 2009-02-19 | 2010-08-25 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal display device and manufacture method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5556395B2 (en) | 2009-08-28 | 2014-07-23 | Ｊｓｒ株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element |
| JP5633677B2 (en) | 2009-09-04 | 2014-12-03 | Jsr株式会社 | Liquid crystal alignment agent |
| JP5699469B2 (en) | 2009-09-16 | 2015-04-08 | Jsr株式会社 | Liquid crystal alignment agent |
| JP5831674B2 (en) | 2010-02-03 | 2015-12-09 | Jsr株式会社 | Liquid crystal alignment agent |
-
2008
- 2008-01-24 JP JP2008013518A patent/JP2008216985A/en not_active Withdrawn
- 2008-02-01 TW TW097103972A patent/TW200846787A/en unknown
- 2008-02-05 KR KR1020080011711A patent/KR20080073664A/en not_active Application Discontinuation
- 2008-02-13 CN CNA2008100742294A patent/CN101241274A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812304A (en) * | 2009-02-19 | 2010-08-25 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal display device and manufacture method thereof |
| CN101812304B (en) * | 2009-02-19 | 2014-03-19 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal display device and fabricating method thereof |
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| Publication number | Publication date |
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| JP2008216985A (en) | 2008-09-18 |
| TW200846787A (en) | 2008-12-01 |
| KR20080073664A (en) | 2008-08-11 |
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Open date: 20080813 |