CN101339334B - Liquid crystal alignment agent and liquid crystal display unit - Google Patents
Liquid crystal alignment agent and liquid crystal display unit Download PDFInfo
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- CN101339334B CN101339334B CN2008101250973A CN200810125097A CN101339334B CN 101339334 B CN101339334 B CN 101339334B CN 2008101250973 A CN2008101250973 A CN 2008101250973A CN 200810125097 A CN200810125097 A CN 200810125097A CN 101339334 B CN101339334 B CN 101339334B
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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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- 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
Abstract
The present invention relates to an aligning agent for liquid crystal containing at least a polymer and solvent selected from polyamic acid and polyimide gained by dewatering closed-loop, the solvent contains: (A) a first solvent containing compound with formula (I); (B) a second solvent selected from at least one of N-methyl-2-pyrrolidone, gamma-butyrolactone, 1,3-dimethyl-2-imidazolone, N, N-dimethylformamide and N, N- dimethylacetylamide; and (C) a third solvent selected from at least one of butyl cellosolve, diacetone alcohol, carbonic sub-propyl ester, diethylene glycol diethyl aether and ethyl-3- oxethyl propionic ether. (In formula (I) the R respectively represents alkyl with 3 to 10 carbon atoms).
Description
Technical field
The present invention relates to aligning agent for liquid crystal and liquid crystal display cells.More specifically, particularly in the ink-jet application method coating good and can be used in the aligning agent for liquid crystal of the liquid crystal orientation film that all excellent performances such as liquid crystal aligning ability are provided and the liquid crystal display cells of display characteristic and reliability excellence.
Background technology
At present, as liquid crystal display cells, known have a so-called TN (twisted-nematic, TwistedNematic) the TN type liquid crystal display cells of type liquid crystal cell, described TN type liquid crystal cell obtains as following, promptly, comprise polyamic acid in the substrate surface formation that is provided with ITO nesa coatings such as (indium oxide-tin oxide), the liquid crystal orientation film of polyimide etc., and with it as the used for liquid crystal display element substrate, with this 2 plate base subtend configuration, formation has the nematic crystal layer of positive dielectric anisotropy in the crack betwixt, thereby makes the box of sandwich structure, and the major axis of above-mentioned liquid crystal molecule reverses 90 ° from a substrate continuously to another substrate.In addition, developed with TN type liquid crystal display cells and compared, contrast height, STN that view angle dependency is few (supertwist to row, SuperTwisted Nematic) type liquid crystal display cells.This STN type liquid crystal display cells uses and mixes material that the chirality agent as optically active substance forms as liquid crystal in nematic crystal, and the birefringence effect that utilizes the major axis by liquid crystal molecule to produce reversing the state more than 180 ° continuously between substrate.
And then in recent years, proposed to produce the electric field parallel, thereby the lateral electric-field type liquid crystal display cells of control liquid crystal molecule with real estate by 2 electrodes that are used to drive liquid crystal in the configuration of one-sided substrate upper comb shape ground.Known this element generally is referred to as plane conversion type (in planeswitching, IPS type), visual angle excellence, extensive.With IPS type element and optical compensating film and time spent, have following obvious characteristics especially, that is, can and then improve viewing angle characteristic, do not have gray inversion or tonal variation, can access the wide viewing angle that compares favourably with Braun tube.
In addition, a kind of MVA of being referred to as (multi-domain vertical alignment has been proposed, Multi-DomainVertical Alignment) (patterning is vertical orientated for mode or PVA, Patterned VerticalAlignment) vertical alignment-type liquid crystal display device of mode (is opened flat 11-258605 communique and " liquid crystal " with reference to the spy, Vol.3 (No.2), p117 (1999)), it is vertical orientated and form on substrate that described MVA mode or PVA mode make the liquid crystal molecule with negative dielectric anisotropic.Excellences such as the liquid crystal display cells visual angle of these vertical orientation modes, contrast are not carried out the advantage of milled processed etc., and are excellent aspect preparation section yet in the formation of liquid crystal orientation film.
But in recent years, LCD TV is progressively popularized, and the large-scale production line that is called " the 7th generation " is started working.The construction of more large-scale in addition " the 8th generation " production line is also in the works.The advantage that substrate is maximized as using large-scale production line, can enumerate can reduce be used for from a plate base take off the multi-disc panel activity time, reduce cost or these aspects that can adapt with the maximization of liquid crystal display cells self.On the contrary, as the shortcoming of the maximization of substrate, can be set forth in the homogeneity of the printing that is difficult to guarantee aligning agent for liquid crystal under the large-area scope.Especially, can enumerate, generation be arranged owing to the bad situation that causes the electrical characteristics that do not possess liquid crystal orientation film of the printing of aligning agent for liquid crystal when utilize the offset press that extensively adopts when the large tracts of land scope is carried out the film forming of liquid crystal orientation film all the time.
In order to address the above problem, carried out in the film forming of liquid crystal orientation film, utilizing the research of ink-jet application method.As the advantage of ink-jet application method, can enumerate, in press the aligning agent for liquid crystal of Shi Yonging equates in fact with the liquid measure of reality coating, thus the use amount of aligning agent for liquid crystal is expected to reduce; Owing to do not use galley, thus do not need the replacing of this galley or washing etc., thus can reduce needed time, labour and cost in maintenance; And then has a flexibility that can adapt with multiple panel size.
For the large substrate that utilizes large-scale production line to make,, require aligning agent for liquid crystal more more excellent than existing printing in the ink-jet application method in order to make liquid crystal display cells with high qualification rate.And then, become more strict for the requirement that improves display quality in recent years, especially for liquid crystal aligning or electrical characteristics, require to have the liquid crystal orientation film that surpasses existing characteristic.
Summary of the invention
The present invention is based on the above-mentioned fact and makes, its purpose is to provide aligning agent for liquid crystal and shows the high-quality display characteristic and the liquid crystal display cells of reliability excellence, described aligning agent for liquid crystal is the printing excellence in the ink-jet application method especially, can improve the product percent of pass in utilizing the preparation section of large-scale production line, and can be used in the liquid crystal orientation film of all excellent performances such as liquid crystal aligning ability, electrical characteristics are provided.
Of the present invention and then other purpose and advantage can be clear and definite by following explanation.
According to the present invention, above-mentioned purpose of the present invention and advantage are to pass through first aspect, a kind of aligning agent for liquid crystal is reached, described aligning agent for liquid crystal contains at least a kind polymkeric substance and the solvent that is selected from the polyimide that makes polyamic acid that the reaction of tetracarboxylic dianhydride and diamine compound obtains and its dehydration closed-loop is obtained
Solvent contains: first solvent, (B) that (A) comprise the compound of following formula (I) expression comprise and are selected from N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolacton, 1,3-dimethyl-2-imidazolone, N, at least a kind second solvent in dinethylformamide and the N,N-dimethylacetamide and (C) comprise at least a kind the 3rd solvent that is selected from butyl cellosolve, diacetone alcohol, propylene carbonate, diethylene glycol diethyl ether and ethyl-3-ethoxy-c acid esters.
(in the formula (I), R represents independently that respectively carbon number is 3～10 alkyl.)
Above-mentioned purpose of the present invention and advantage are by second aspect, have that the liquid crystal display cells of the liquid crystal orientation film that is obtained by above-mentioned aligning agent for liquid crystal reaches.
Embodiment
Below, be elaborated for the present invention.
Aligning agent for liquid crystal of the present invention contains at least a kind polymkeric substance and the solvent that is selected from the polyimide that makes polyamic acid that the reaction of tetracarboxylic dianhydride and diamine compound obtains and its dehydration open loop is obtained.
[tetracarboxylic dianhydride]
As being used for synthesizing the polyamic acid that contains at aligning agent for liquid crystal of the present invention or the tetracarboxylic dianhydride of polyimide, for example can enumerate, the compound of following formula (1) expression,
(in the formula (1), R
1Represent independently that respectively hydrogen atom, chlorine atom or carbon number are 1～6 alkyl.)、
The compound of following formula (2) expression
(in the formula (2), R
2Represent independently that respectively carbon number is 1～6 alkyl, n is 0～4 integer.)、
Butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 1,2,4-tricarboxylic basic ring amyl group acetate dianhydride, dicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 3,5,6-three carboxyls norbornane-2-acetate dianhydride, Fourth Ring [4.4.0.1
2.5.1
7,10] dodecane-3,4,8,9-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 5-(2, the 5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, dicyclo [2.2.2]-Xin-4-alkene-2,3,5,6-tetracarboxylic dianhydride, dicyclo [2.2.2]-Xin-7-alkene-2,3,5,6-tetracarboxylic dianhydride, following formula (II-1) and (II-2) aliphatics or the alicyclic tetracarboxylic dianhydride of the compound of expression etc. separately;
(in the following formula, R
3And R
5Be respectively divalent organic group with aromatic rings, R
4And R
6Be respectively that hydrogen atom or carbon number are 1～6 alkyl, the R of a plurality of existence
4And R
6Can be respectively identical, also can be different.)
Pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenylsulfone acid's dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-the diphenyl 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) diphenyl sulfide 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 phthalic acid dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) phenyl phosphine oxygen dianhydride, ethylene glycol-two (dehydration benzenetricarboxylic acid ester), propylene glycol-two (dehydration benzenetricarboxylic acid ester), 1,4-butylene glycol-two (dehydration benzenetricarboxylic acid ester), 1,6-hexanediol-two (dehydration benzenetricarboxylic acid ester), 1,8-ethohexadiol-two (dehydration benzenetricarboxylic acid ester), 2, two (4-hydroxy phenyl) propane-two of 2-(dehydration benzenetricarboxylic acid ester), aromatic tetracarboxylic acid's dianhydride of the compound that following formula (3)～(6) are represented separately etc. etc.
As the object lesson of the compound of following formula (1) expression, for example can enumerate 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-diethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-diethyl-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 etc., wherein preferred 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-diethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride or 1,3-diethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride.
As the object lesson of the compound of following formula (2) expression, for example can enumerate 1,3,3a, 4,5,9b-six hydrogen-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-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-ethyl-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-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-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-methyl-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-8-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-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1,3-diketone etc.
These tetracarboxylic dianhydrides can a kind use separately, perhaps also can use mixing more than 2 kinds.
Wherein, the preferred use contained the compound that is selected from following formula (1) expression, compound, the pyromellitic acid dianhydride, 1,2 of following formula (2) expression, 4-tricarboxylic basic ring amyl group acetate dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride and 1,2,4, the tetracarboxylic dianhydride of among the 5-cyclohexane tetracarboxylic dianhydride at least a kind (below be also referred to as " specific tetracarboxylic dianhydride ").
When the polymkeric substance that contains in aligning agent for liquid crystal of the present invention is polyamic acid, for the tetracarboxylic dianhydride who is used for synthesizing it, preferably the total amount with respect to the tetracarboxylic dianhydride contains 10 moles of specific tetracarboxylic dianhydrides more than the %, more preferably contain 20 moles more than the %, and then preferably contain 40 moles more than the %.Under this situation, the tetracarboxylic dianhydride as beyond the specific tetracarboxylic dianhydride preferably uses the ester ring type tetracarboxylic dianhydride.
On the other hand, when the polymkeric substance that contains in aligning agent for liquid crystal of the present invention is polyimide, for the tetracarboxylic dianhydride who is used for synthesizing it, preferably the total amount with respect to the tetracarboxylic dianhydride contains 50 moles of specific tetracarboxylic dianhydrides more than the %, more preferably contain 70 moles more than the %, and then preferably contain 80 moles more than the %.Under this situation, the tetracarboxylic dianhydride as beyond the specific tetracarboxylic dianhydride preferably uses the ester ring type tetracarboxylic dianhydride.
[diamine compound]
As being used for synthesizing the polyamic acid that contains at aligning agent for liquid crystal of the present invention or the diamine compound of polyimide, for example can enumerate following formula (III-1) and (III-2) compound of expression and other diamine compound separately.
(in the following formula, X
1Represent independently of each other singly-bound ,-O-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-,-S-, methylene, carbon number are 2～6 alkylidene or phenylene, R
7Be that carbon number is that 10～20 alkyl, carbon number are that 4～40 1 valency organic group with ester ring type skeleton or carbon number are 6～20 1 valency organic group with fluorine atom, R
8Be that carbon number is 4～40 the divalent organic group with ester ring type skeleton.)
In following formula (III-1), as using R
7The carbon number of expression is 10～20 alkyl, can enumerate for example positive decyl, dodecyl, n-pentadecane base, n-hexadecyl, n-octadecane base, n-eicosane base etc.As being the ester ring type skeleton that contains in 4～40 the 1 valency organic group at carbon number with ester ring type skeleton, for example can enumerate, be derived from the ester ring type skeleton of naphthenic hydrocarbon such as cyclo-butane, cyclopentane, cyclohexane, cyclodecane; The bridge joint ester ring type skeleton of norborene, diamantane etc.; Steride skeleton etc.
Here, the steride skeleton is meant the structure that comprises cyclopentanoperhydro-phenanthrene nuclear or one or two above skeletons that form two keys of its carbon-carbon bond.As R
71 valency organic group with steride skeleton, preferred carbon number is 17～40 group, more preferably carbon number is 17～29 group.As above-mentioned R with steride skeleton
7Object lesson, for example can enumerate cholestane-3-base, courage steroid-5-alkene-3-base, courage steroid-24-alkene-3-base, courage steroid-5,24-diene-3-base etc.
For R
71 valency organic group with ester ring type skeleton, part or all of its hydrogen atom also can use halogen atom, preferred fluorine atom to replace.It as carbon number 6～20 1 valency organic group with fluorine atom, for example can enumerate, the group that part or all of hydrogen atom in following organic group replaces with fluorine atom or fluoroalkyl etc., it is that the carbon number of 6～20 straight chain shape alkyl, cyclohexyl, ring octyl group etc. is that the carbon number of 6～20 ester ring type alkyl, phenyl, xenyl etc. is 6～20 aromatic hydrocarbyl etc., wherein R that described organic group has the carbon number of n-hexyl, n-octyl, positive decyl etc.
7Carbon number comprise the carbon of fluoroalkyl, be below 20.
As the X in the following formula (III-1)
1, preferred-O-,-CO-,-COO-or-OCO-.
Object lesson as the diamine compound of following formula (III-1) expression, for example can enumerate, dodecyloxy-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2, the compound that 4-diaminobenzene, following formula (7)～(22) are represented separately etc.
In following formula (III-2), as using R
8The carbon number of expression is the ester ring type skeleton that contains in 4～40 the divalent organic group with ester ring type skeleton, for example can enumerate, and is derived from the ester ring type skeleton of naphthenic hydrocarbon such as cyclo-butane, cyclopentane, cyclohexane, cyclodecane; The bridge joint ester ring type skeleton of norborene, diamantane etc.; Steride skeleton etc.
Here, steride skeleton and above-mentioned R
7In the steride skeleton identical.As R
8The divalent organic group with steride skeleton, preferred carbon number is 17～40 group, more preferably carbon number is 17～29 group.As R with steride skeleton
8Object lesson, for example can enumerate cholestane-3,3-two bases, cholestane-3,6-two bases, courage steroid-5-alkene-3,6-two bases, courage steroid-24-alkene-3,6-two bases, courage steroid-5,24-diene-3,6-two bases etc.
For R
8The divalent organic group with ester ring type skeleton, part or all of its hydrogen atom also can use halogen atom, preferred fluorine atom to replace.
As the object lesson of the diamine compound of following formula (III-2) expression, can enumerate the compound following formula (23)～(27) for example represented separately etc.
As above-mentioned other diamine compound, for example can enumerate, p-phenylenediamine (PPD), the 2-methyl isophthalic acid, the 4-phenylenediamine, 2-ethyl-1, the 4-phenylenediamine, 2,5-dimethyl-1, the 4-phenylenediamine, 2,5-diethyl-1, the 4-phenylenediamine, 2,3,5,6-tetramethyl-1, the 4-phenylenediamine, m-phenylene diamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 2,2 '-diethyl-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-two (trifluoromethyl)-4,4 '-benzidine, 3,3 '-diethyl-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) propane 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, 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-n-heptyl cyclohexyl) phenoxy group-2, the aromatic diamine of 4-diaminobenzene etc.;
1, two (amino methyl) benzene, 1 of 3-, the aliphatic diamine of 3-propane diamine, butanediamine, pentanediamine, hexane diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine 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-1,3,5-triazines, 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, the 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, 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) aniline etc. has the diamines of the nitrogen-atoms beyond 2 primary amine groups and this primary amine groups in molecule;
The compound that following formula (28)～(30) are represented separately etc.
(in the following formula, R
9Represent independently that respectively carbon number is 1～12 alkyl, p represents 1～3 integer respectively independently, and q is 1～20 integer, and y is 2～12 integer, and z is 1～5 integer.)
As above-mentioned other diamine compound, preferred p-phenylenediamine (PPD), the 2-methyl isophthalic acid, the 4-phenylenediamine, 2-ethyl-1, the 4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,5-diethyl-1, the 4-phenylenediamine, 2,3,5,6-tetramethyl-1, the 4-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 2,2 '-diethyl-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-diethyl-4,4 '-benzidine, 3,3 '-two (trifluoromethyl)-4,4 '-benzidine, 4,4 '-diamino-diphenyl ether, 4,4 '-diaminobenzophenone, 2, two (4-aminophenyl) propane of 2-, 2, two (4-aminophenyl) HFC-236fa of 2-, 2,6-diamino-pyridine or 3, the 4-diamino-pyridine.
Above-mentioned diamine compound can a kind uses separately, perhaps also can use mixing more than 2 kinds.
When using aligning agent for liquid crystal of the present invention as the aligning agent for liquid crystal of vertical orientating type, as being used for synthesizing the polyamic acid that contains at aligning agent for liquid crystal or the diamine compound of polyimide, preferred at least a kind the diamine compound that uses in the diamine compound that contains the diamine compound that is selected from following formula (III-1) expression and following formula (III-2) expression.Under this situation, the ratio that the diamine compound of following formula (III-1) or following formula (III-2) expression accounts for the diamine compound total amount is preferably 7 moles more than the %, more preferably 10 moles more than the %.
[synthesizing of polyamic acid]
The polyamic acid that aligning agent for liquid crystal of the present invention can contain can obtain by above-mentioned tetracarboxylic dianhydride and diamine compound are reacted.
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 of diamines, tetracarboxylic dianhydride's anhydride group is the ratio of 0.2～2.0 equivalent, more preferably the ratio of 0.8～1.2 equivalent.The synthetic reaction of polyamic acid be in preferred organic, preferred-20 ℃～150 ℃, more preferably under 0～100 ℃ the temperature conditions, with preferred 0.5～24 hour, more preferably 2～10 hours reaction time carries out.
As spendable organic solvent here, just be not particularly limited so long as can dissolve the solvent of the polyamic acid that is synthesized, can enumerate for example 1-Methyl-2-Pyrrolidone, 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 etc.The use amount of organic solvent (α) is preferably following amount: the total amount (β) that makes tetracarboxylic dianhydride and diamine compound is the amount of 0.1～30 weight % with respect to the total amount (alpha+beta) of reaction solution.
For above-mentioned organic solvent, can with the part of its use amount under the scope that the polyamic acid that generates is not separated out by using as displacements such as the alcohol of the poor solvent of polyamic acid, ketone, ester, ether, halogenated hydrocarbons, hydrocarbon.
Object lesson as above-mentioned poor solvent, can enumerate for example methyl alcohol, ethanol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4-methyl-2 pentanone, 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 etc.
When the part of organic solvent is replaced when using with poor solvent, the use amount of poor solvent is preferably below the 50 weight % with respect to the total amount of organic solvent.
As described above, obtain dissolving the reaction solution that polyamic acid forms.For this polyamic acid solution, it directly can be supplied with the dehydration closed-loop reaction of subsequent processing, resupply the dehydration closed-loop reaction after also the polyamic acid that contains can being separated in reaction solution, perhaps can also supply with the dehydration closed-loop reaction in the refining back of the polyamic acid that will separate.The separation of polyamic acid can utilize injects above-mentioned polyamic acid solution a large amount of poor solvents and obtains precipitate, and with the method for this precipitate drying under reduced pressure, is perhaps undertaken by the method for the polyamic acid solution decompression being heated up in a steamer with evaporator.In addition, can make with extra care polyamic acid by following method, described method has the polyamic acid that will obtain like this to be dissolved in once more in the organic solvent, then makes its method of separating out in poor solvent, perhaps carries out 1 time or the method for the operation of heating up in a steamer with the evaporator decompression for several times.
[synthesizing of polyimide]
The polyimide that aligning agent for liquid crystal of the present invention can contain can be by synthesizing above-mentioned polyamic acid dehydration closed-loop.The polyimide of Shi Yonging in the present invention, can be that whole amic acid structures that polyamic acid has are carried out the complete imidizate thing that imidizate forms, perhaps also can be the part imidizate thing that only part in the amic acid structure is carried out imidizate, makes amic acid structure and imide structure and deposit.When the polymkeric substance that contains in aligning agent for liquid crystal of the present invention was polyimide, its imidizate rate was preferably more than 40%.Here so-called " imidizate rate " be meant, with the imide structure number value that shared ratio is represented with percent in the sum of the amic acid structure of polymkeric substance and imide structure.The imidizate rate can be by measuring as following
1H-NMR tries to achieve by following numerical expression (i), and is described
1H-NMR is that the polyimide with abundant drying is dissolved in suitable deuterated solvent, for example deuterated dimethyl sulfoxide, is primary standard substance with the tetramethylsilane, at room temperature measure and.
(in numerical expression (i), A1 is from the peak area of NH matrix (near the 10ppm), and A2 is that (7～8ppm), α is that aromatic rings proton number in the polymer precursor (polyamic acid) is with respect to the ratio of sub 1 of NH matrix from the peak area of aromatic rings proton.)
The dehydration closed-loop of polyamic acid carries out by the following method: the method for (1) heating polyamic acid, perhaps (2) are dissolved in polyamic acid in the organic solvent, add dewatering agent and dehydration closed-loop catalyzer and the method that heats as required in this solution.
Temperature of reaction in the method for above-mentioned (1) heating polyamic acid is preferably 50～200 ℃, more preferably 60～170 ℃.When temperature of reaction was lower than 50 ℃, the dehydration closed-loop reaction can not fully be carried out, and when temperature of reaction surpassed 200 ℃, the molecular weight of gained polyimide can reduce sometimes.Reaction time is preferably 0.5～72 hour, more preferably 1～10 hour.
On the other hand, add in polyamic acid solution in the method for dewatering agent and dehydration closed-loop catalyzer above-mentioned (2), as dewatering agent, can use for example acid anhydrides such as acetic anhydride, propionic andydride, trifluoro-acetic anhydride.Though the use amount of dewatering agent also depends on the imidizate rate of expectation, preferably the amic acid structure that has with respect to polyamic acid is 0.01～20 mole for 1 mole.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.The use amount of above-mentioned dewatering agent, dehydration closed-loop agent is many more, can improve the imidizate rate more.As the organic solvent that is used for dehydration closed-loop reaction, can enumerate and be identical solvent as being used for the cited organic solvent of solvent that polyamic acid synthesizes.The temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 10～150 ℃.Reaction time is preferably 1～12 hour, more preferably 1～6 hour.
For the imide amination polymer that in said method (1), obtains, can directly it be supplied with the modulation of aligning agent for liquid crystal, perhaps also can supply with the modulation of aligning agent for liquid crystal in the refining back of the imide amination polymer that will obtain.On the other hand, in said method (2), can obtain containing the reaction solution of imide amination polymer.For this reaction solution, can directly it be supplied with the modulation of aligning agent for liquid crystal, also dewatering agent and dehydration closed-loop catalyzer can removed the modulation that aligning agent for liquid crystal is supplied with in the back from reaction solution, also imide amination polymer can be separated the modulation that aligning agent for liquid crystal is supplied with in the back, perhaps the refining back of the imide amination polymer that separates can also supplied with the modulation of aligning agent for liquid crystal.For dewatering agent and dehydration closed-loop catalyzer are removed from reaction solution, can application examples such as the method for solvent exchange etc.The separation of imide amination polymer, refining can carrying out with the separating of above-mentioned polyamic acid, operation that process for purification is same by carrying out.
The polymkeric substance of＜end modified type 〉
Polyamic acid of Shi Yonging or polyimide can be the end modified types that has carried out molecular-weight adjusting in the present invention.By using the polymkeric substance of end modified type, can under the situation of not damaging effect of the present invention, further improve the coating characteristics of aligning agent for liquid crystal etc.
The polymkeric substance of end modified type like this can synthesize by add suitable molecular weight regulators such as sour single acid anhydride, monoamine compound, monoisocyanates compound in reaction system when synthesizing polyamides is sour.Here, as the single acid anhydride of acid, 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.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.As the monoisocyanates compound, can enumerate for example phenyl isocyanate, naphthyl isocyanate etc.
As the usage ratio of molecular weight regulator, with respect to used tetracarboxylic dianhydride and the diamines when the synthesizing polyamides acid that adds up to 100 weight portions, the use amount of preferred molecular weight correctives is below 20 weight portions, more preferably below 10 weight portions.
Polyamic acid that obtains as described above or imide amination polymer when making concentration and be the solution of 10 weight %, preferably have the solution viscosity of 20～800mPas, more preferably have the solution viscosity of 30～500mPas.
The concentration that the solution viscosity of above-mentioned polymkeric substance (mPas) is to use E type rotational viscosimeter under 25 ℃ fine solvent (for example gamma-butyrolacton, the N-N-methyl-2-2-pyrrolidone N-etc.) modulation of using this polymkeric substance to be formed is the value that the polymer solution of 10 weight % is measured gained.
[adjuvant arbitrarily]
Aligning agent for liquid crystal of the present invention is as must composition containing at least a kind polymkeric substance in polyamic acid and the polyimide and the following solvent of being selected from as described above, in addition, under the scope of not damaging the object of the invention, as any adjuvant, also can contain epoxy compound or functional silanes compound.The liquid crystal orientation film that these compounds can form with further raising is that purpose is added for the adhesiveness of substrate surface.
As above-mentioned epoxy compound, for example can enumerate, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2, the 4-hexanediol, N, N, N ', N '-four glycidyl group P-xylene diamines, N, N, N ', N '-four glycidyl group m-xylene diamine, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N, N ', N '-four glycidyl group-4,4 '-diamino-diphenyl ether, N, N, N ', N '-four glycidyl group-2,2 '-dimethyl-4,4 '-benzidine, N, N, N ', N '-four glycidyl group-1, the 2-diamino-cyclohexane, N, N, N ', N '-four glycidyl group-1, the 3-diamino-cyclohexane, N, N, N ', N '-four glycidyl group-1, the 4-diamino-cyclohexane, two (N, N-diglycidyl-4-aminocyclohexyl) methane, two (N, N-diglycidyl-2-methyl-4-aminocyclohexyl) methane, two (N, N-diglycidyl-3-methyl-4-aminocyclohexyl) methane, 1, two (the N of 3-, N-diglycidyl amino methyl) cyclohexane, 1, two (N, the N-diglycidyl amino methyl) cyclohexanes of 4-, 1, two (the N of 3-, N-diglycidyl amino methyl) benzene, 1, two (N, the N-diglycidyl amino methyl) benzene of 4-, 1,3,5-three (N, N-diglycidyl amino methyl) cyclohexane, 1,3,5-three (N, N-diglycidyl amino methyl) benzene, the compound that following formula (31)～(35) are represented separately etc.The cooperation ratio of these epoxy compounds (is meant the polyamic acid that contains and the total amount of its imide amination polymer with respect to the total amount of 100 parts by weight polymer in aligning agent for liquid crystal.Below identical), be preferably below 40 weight portions, more preferably 0.1～30 weight portion.
As above-mentioned functional silanes compound, for example can enumerate, the 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-, 3-(N-allyl-N-glycidyl) TSL 8330,3-(N, N-diglycidyl) TSL 8330 etc.
The cooperation ratio of these functional silanes compounds is preferably below 2 weight portions, more preferably 0.2～1 weight portion with respect to the total amount of 100 parts by weight polymer.
[aligning agent for liquid crystal]
Aligning agent for liquid crystal of the present invention is that any adding ingredient that is selected from least a kind polymkeric substance in polyamic acid and the polyimide and uses as required that dissolving contains as described above in solvent constitutes.
The solvent that uses in aligning agent for liquid crystal of the present invention contains:
(A) comprise the compound of following formula (I) expression first solvent,
(B) comprise and be selected from N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolacton, 1,3-dimethyl-2-imidazolone, N, at least a kind second solvent in dinethylformamide and the N,N-dimethylacetamide and
(C) comprise at least a kind the 3rd solvent that is selected from butyl cellosolve, diacetone alcohol, propylene carbonate, diethylene glycol diethyl ether and ethyl-3-ethoxy-c acid esters.
Preferred its boiling point of the compound of following formula (I) expression is 140～200 ℃, and preferably its surface tension is 18～27mN/m.From the boiling point of the compound that makes following formula (I) expression and surface tension viewpoint in above-mentioned scope, R in the following formula (I) preferably carbon number is 4～8 alkyl, be more preferably carbon number and be 4～6 alkyl, can enumerate for example amyl group, isopentyl etc. specifically.
As the object lesson of the compound of following formula (I) expression, can enumerate for example diamyl ether, diisoamyl ether etc., preferably use at least a kind that is selected from them.
In aligning agent for liquid crystal of the present invention, with respect to above-mentioned (A) first solvent, (B) second solvent and (C) total of the 3rd solvent, (A) ratio of first solvent is preferably 0.5～20 weight %, more preferably 1～10 weight %.With respect to above-mentioned (A) first solvent, (B) second solvent and (C) total of the 3rd solvent, (B) ratio of second solvent is preferably 10～94.5 weight %, more preferably 30～89 weight %.With respect to above-mentioned (A) first solvent, (B) second solvent and (C) total of the 3rd solvent, (C) ratio of the 3rd solvent is preferably 5～70 weight %, more preferably 10～60 weight %.
In aligning agent for liquid crystal of the present invention, if above-mentioned (A) first solvent, (B) second solvent and (C) the 3rd solvent contain with preferred aforementioned proportion, then can preferably realize desired effects of the present invention, promptly special coating excellent in the ink-jet application method.Especially, when using boiling point and surface tension at compound conduct (A) first solvent that the following formula (I) of above-mentioned scope is represented, even, also can find purpose of the present invention to greatest extent for the less situation of ratio that contains of (A) first solvent, from but preferred.
Aligning agent for liquid crystal of the present invention can only use above-mentioned (A) first solvent, (B) second solvent and (C) the 3rd solvent also can be with other solvents and (A) first solvent, (B) second solvent and (C) the 3rd solvent merging use as solvent.As other solvents that can here use, for example can enumerate butyrolactam, 4-hydroxy-4-methyl-2 pentanone, glycol monoethyl ether, butyl lactate, methyl methoxy base propionic ester, ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diglycol monotertiary methyl ether, carbiphene, diglycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate etc.
As the solvent composition of aligning agent for liquid crystal of the present invention, be polymkeric substance and arbitrarily adjuvant in aligning agent for liquid crystal, do not separate out and the surface tension that makes aligning agent for liquid crystal at the such composition of 20～40mN/m scope.Consider from above-mentioned viewpoint, (A) first solvent in the aligning agent for liquid crystal of the present invention, (B) second solvent and (C) the total amount ratio shared of the 3rd solvent with respect to the total amount of solvent be preferably more than the 30 weight %, more preferably more than the 50 weight %, and then more than the preferred 70 weight %.
Solid component concentration in the aligning agent for liquid crystal of the present invention (the total weight of the composition in the aligning agent for liquid crystal beyond the solvent in the general assembly (TW) of aligning agent for liquid crystal shared ratio) 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 forms and becomes filming of liquid crystal orientation film by it being coated substrate surface, but when the solid component concentration of aligning agent for liquid crystal during less than 1 weight %, this thickness of filming is too small and be difficult to obtain good liquid crystal orientation film, on the other hand, and when solid component concentration surpasses 10 weight %, the thickness of filming is excessive and be difficult to obtain good liquid crystal orientation film, in addition, have the viscosity of aligning agent for liquid crystal to increase, coating characteristics is easy to the situation of variation.The scope of particularly preferred solid component concentration is 2～8 weight %, therefore, especially preferably makes the scope of the solution viscosity of aligning agent for liquid crystal at 3～15mPas.
Temperature when modulating aligning agent for liquid crystal of the present invention is preferably 0 ℃～60 ℃, more preferably 20 ℃～40 ℃.
[manufacture method of liquid crystal display cells]
Liquid crystal display cells of the present invention has the liquid crystal orientation film that is formed by aligning agent for liquid crystal of the present invention as described above.
Liquid crystal display cells of the present invention for example can be made by following method.
(1) at first be coated with liquid crystal orientation film of the present invention on a pair of substrate, remove and desolvate, formation is filmed.Here, when the display mode of the liquid crystal display cells that should make is the vertical electric field mode of TN type, STN type, VA type etc., 2 substrates that are provided with the nesa coating that has formed pattern on single face are used as a pair of substrate.On the other hand, when the display mode of the liquid crystal display cells that should make is the transverse electric field mode, will be provided with the substrate of nesa coating and have the substrate of nesa coating to use as a pair of substrate with pectination pattern.
For above-mentioned any situation, at (when substrate has nesa coating, on this side's with nesa coating of substrate the face) coating of liquid crystalline alignment agent on the substrate.Substrate can use glass such as for example comprising float glass, soda-lime glass; The transparency carrier of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, ester ring type polyolefin.Nesa coating as being arranged on the substrate one side can use for example 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.In addition, in order to obtain the nesa coating that these have formed pattern, can adopt after formation does not have the nesa coating of pattern, utilize photo-engraving process to form method of patterning and have the mask of expecting figure etc. by when nesa coating forms, using, directly form the method etc. of the nesa coating of pattern.
The coating of aligning agent for liquid crystal on substrate can be undertaken by suitable coating processes such as rolling method, spin-coating method, print process, ink-jet methods.When adopting ink jet printing method as coating process, aligning agent for liquid crystal of the present invention has the advantage that can bring into play good coating (printing) especially.
When the coating of liquid crystalline alignment agent,, can on applied of substrate, be coated with functional silanes compound, functionality titanium compound etc. in advance for the adhesiveness of further improving substrate surface and nesa coating and filming.
After the coating, 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 ℃.Preferred 10 seconds～20 minutes of preliminary drying time, more preferably 10 seconds～10 minutes.Then, solvent is removed fully etc., carry out sintering (back baking) operation as purpose.The purpose of this back baking except be solvent is removed from film fully, also be when the polymkeric substance that in aligning agent for liquid crystal of the present invention, contains be when having the polymkeric substance of amic acid structure, can further carry out the dehydration closed-loop of the amic acid structure of the polymkeric substance that in aligning agent for liquid crystal of the present invention, contains by heating, thereby further improve the imidizate rate of filming.Preferred 80～300 ℃ of back baking temperature, more preferably 120～250 ℃.Preferred 5～60 minutes of back baking time, more preferably 5～30 minutes.
Like this, can form and become filming of liquid crystal orientation film.Preferred 0.001～1 μ m of formed thickness of filming, more preferably 0.005～0.5 μ m.
When the liquid crystal display cells that is suitable for aligning agent for liquid crystal of the present invention is the liquid crystal display cells of VA type, for example also can as the spy open record and narrate in the 2002-327058 communique behind the fabrication that forms overshooting shape on the substrate coating of liquid crystalline alignment agent, seek the improvement of viewing angle characteristic.
(2) when the display mode of the liquid crystal display cells that should make is the VA type, filming of forming as described above can directly be used as liquid crystal orientation film, but also can carry out following milled processed as required.On the other hand, when vertical electric field mode beyond the display mode of the liquid crystal display cells that should make is the VA type and transverse electric field mode, carry out milled processed for the coated surface that forms.
Milled processed can comprise for example roller of the cloth of fibers such as nylon, rayon, cotton by having with circumvolution, carries out abrasive method in a certain direction and carries out.Thus, give the alignment capability of the liquid crystal molecule of filming, form liquid crystal orientation film.And then, carry out following such processing for filming after the milled processed, make liquid crystal orientation film have different liquid crystal aligning abilities in each zone, can improve the visual field characteristic of the liquid crystal display cells that obtains thus, described processing be for example in Japanese kokai publication hei 6-222366 communique or Japanese kokai publication hei 6-281937 communique, disclose such, make the processing of a part of regional tilt angle variation of liquid crystal orientation film by a part of irradiation ultraviolet radiation to liquid crystal orientation film, or in Japanese kokai publication hei 5-107544 communique, disclose such, after the part on liquid crystal orientation film surface forms resist film, with direction that formerly milled processed is different on carry out milled processed, the processing that above-mentioned resist film is removed then.
(3) as above prepare 2 substrates that form liquid crystal orientation film like that,, can make liquid crystal cell by between 2 plate bases of configuration relatively, disposing liquid crystal.Here, when carrying out milled processed for filming, two plate bases are so that the grinding direction of respectively filming is in the angle of regulation, for example vertical or antiparallel is carried out the subtend configuration like this.
For making liquid crystal cell, can enumerate two kinds of for example following methods.
First method is known all the time method.At first, so that liquid crystal orientation film separately is situated between 2 plate bases relatively like this by gap (box gap) configuration relatively, 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, with the filling orifice sealing, can prepare liquid crystal cell thus then.
Second method is the technology that is referred to as ODF (single filling, One Drop Fill) mode.Assigned position on the plate base in 2 plate bases that form liquid crystal orientation film is coated with for example encapsulant of ultraviolet light curable, and then after dripping liquid crystal on the liquid crystal orientation film, other the substrate so that liquid crystal orientation film is fitted relatively like this, follow whole irradiating ultraviolet light for substrate, with sealant cures, can prepare liquid crystal cell thus.
For the situation of any method, preferably to the liquid crystal cell made as described above and then be heated to and make used liquid crystal be the temperature of isotropic phase, slowly cool to room temperature then, the flow orientation when removing liquid crystal thus and injecting.
By making polarization plates be fitted in the outer surface of liquid crystal cell, can obtain liquid crystal display cells of the present invention.
Here, as sealant, can use and for example contain hardening agent and as epoxy resin of the alumina balls of sept (spacer) etc.
As above-mentioned liquid crystal, can use for example nematic crystal, smectic shape type liquid crystal etc., wherein preferred nematic crystal.For the situation of VA type liquid crystal cell, preferably have the nematic crystal of negative dielectric anisotropic, can use for example dicyanobenzenes class liquid crystal, pyridazine class liquid crystal, Schiff bases liquid crystal, azoxy class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal etc.Situation for TN type liquid crystal cell or STN type liquid crystal cell, the nematic crystal that preferably has positive dielectric anisotropy can use for example biphenyls liquid crystal, cyclohexylbenzene class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, bicyclooctane class liquid crystal, cubane (キ ユ バ Application) class liquid crystal etc.Also can be in these liquid crystal, so add cholesteryl liquid crystals such as cholest chlorine (コ レ ス チ Le Network ロ ラ イ De), cholesteryl nonanoate, cholesteryl carbonate for example, the chirality agent of selling with trade name C-15, CB-15 (メ Le Network corporate system), to the last of the ten Heavenly stems oxygen base benzal-to strong dielectricity liquid crystal such as amino-2-methyl butyl cinnamates wait and use.
As the polarization plates that is fitted in the liquid crystal cells outside surface, can list 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.
Embodiment
Below, by embodiment and then specifically describe the present invention, but the present invention is not limited to these embodiment.
Synthesis example 1
In the N-N-methyl-2-2-pyrrolidone N-, add compound, 70mmol p-phenylenediamine (PPD) and 20mmol 4 successively as 10mmol following formula (11) expression of diamine compound, 4 '-diaminodiphenyl-methane and as tetracarboxylic dianhydride's 100mmol 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, the total amount of making tetracarboxylic dianhydride and diamine compound is the solution of 20 weight % with respect to the total amount of solution, carries out 4 hours reaction under 60 ℃, obtains containing the solution of polyamic acid.
Contain in the solution of polyamic acid at this, the total amount (theoretical value) of adding with respect to the amic acid structure that contains in polyamic acid is the pyridine and the acetic anhydride of 2 times of moles, is heated to 110 ℃ of dehydration closed-loop reactions of carrying out 4 hours then.
The solution that obtains is joined in the excessive ether, obtain sediment,, and carry out drying under reduced pressure, can obtain the imidizate rate thus and be 78% polyimide (PI-1) its recovery.
Synthesis example 2
Will be as tetracarboxylic dianhydride's 110g (0.50 mole) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as 38g (0.35 mole) p-phenylenediamine (PPD), the 20g (0.1 mole) 4 of diamines, 4 '-diaminodiphenyl-methane and 26g (0.05 mole) 3-(3,5-diaminobenzoic acid base) cholestane is dissolved in the 800g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out 6 hours reaction, obtain containing the solution of polyamic acid.Take out the polyamic acid solution that obtains on a small quantity, add the N-N-methyl-2-2-pyrrolidone N-, make the solution that polyamic acid concentration is 10 weight %, the solution viscosity of measuring it is 60mPas.
Then, in the polyamic acid solution that obtains, add the N-N-methyl-2-2-pyrrolidone N-of 1800g, and add 80g pyridine and 100g acetic anhydride, under 110 ℃, carry out 4 hours dehydration closed-loop reaction.After the dehydration closed-loop reaction, (, pyridine and the acetic anhydride that uses in the dehydration closed-loop reaction can be removed to outside the system by this solvent exchange operation by the solvent in the system being carried out solvent exchange with new gamma-butyrolacton.Below identical), can obtain about 1100g and contain the solution that 15 weight % imidizate rates are about 80% imide amination polymer (PI-2).Take out a small amount of this imide amination polymer solution, add gamma-butyrolacton, make the solution that polyamic acid concentration is 10 weight %, the solution viscosity of measuring it is 87mPas.
Synthesis example 3
Will be as tetracarboxylic dianhydride's 110g (0.50 mole) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as 43g (0.40 mole) p-phenylenediamine (PPD) and 52g (0.10 mole) 3-(3 of diamines, 5-diaminobenzoic acid base) cholestane is dissolved in the 830g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out 6 hours reaction, obtain containing the solution of polyamic acid.Take out the polyamic acid solution that obtains on a small quantity, add the N-N-methyl-2-2-pyrrolidone N-, make the solution that polyamic acid concentration is 10 weight %, the solution viscosity of measuring it is 60mPas.
Then, in the polyamic acid solution that obtains, add the N-N-methyl-2-2-pyrrolidone N-of 1900g, and add 40g pyridine and 51g acetic anhydride, under 110 ℃, carry out 4 hours dehydration closed-loop reaction.After the dehydration closed-loop reaction,, can obtain about 1200g and contain the solution that 15 weight % imidizate rates are about 50% imide amination polymer (PI-3) by the solvent in the system being carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-.Take out a small amount of this imide amination polymer solution, add the N-N-methyl-2-2-pyrrolidone N-, make the solution that polyamic acid concentration is 10 weight %, the solution viscosity of measuring it is 47mPas.
Synthesis example 4
Will be as tetracarboxylic dianhydride's 110g (0.50 mole) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as 49g (0.45 mole) p-phenylenediamine (PPD) and 26g (0.05 mole) 3-(3 of diamines, 5-diaminobenzoic acid base) cholestane is dissolved in the 750g N-N-methyl-2-2-pyrrolidone N-, under 60 ℃, carry out 6 hours reaction, obtain containing the solution of polyamic acid.Take out the polyamic acid solution that obtains on a small quantity, add the N-N-methyl-2-2-pyrrolidone N-, make the solution that polyamic acid concentration is 10 weight %, the solution viscosity of measuring it is 58mPas.
Then, in the polyamic acid solution that obtains, add the N-N-methyl-2-2-pyrrolidone N-of 1800g, and add 40g pyridine and 51g acetic anhydride, under 110 ℃, carry out 4 hours dehydration closed-loop reaction.After the dehydration closed-loop reaction,, can obtain about 1100g and contain the solution that 15 weight % imidizate rates are about 50% imide amination polymer (PI-4) by the solvent in the system being carried out solvent exchange with new N-N-methyl-2-2-pyrrolidone N-.Take out a small amount of this imide amination polymer solution, add the N-N-methyl-2-2-pyrrolidone N-, make the solution that polyamic acid concentration is 10 weight %, the solution viscosity of measuring it is 85mPas.
Embodiment 1
The polyimide (PI-1) that will obtain in above-mentioned synthesis example 1 is dissolved in the mixed solvent (mixing ratio (weight ratio)=5: 30: 40: 25), obtain the aligning agent for liquid crystal that solution viscosity is 6mPas that comprises diisoamyl ether, gamma-butyrolacton, N-N-methyl-2-2-pyrrolidone N-and butyl cellosolve.It is utilized the aperture is that the filtrator of 0.2 μ m filters, and carries out following evaluation then.
The evaluation of＜ink-jet application 〉
Substrate as the coating of liquid crystalline alignment agent, use following such substrate, that is, the glass substrate that has transparency electrode that will comprise ITO heated 1 minute on 200 ℃ heating plate, then carrying out ultraviolet ray/ozone washing, is substrate after below 10 ° and just made the contact angle of the water of transparency electrode face.
Use ink-jet application machine (sesame Pu メ カ ト ロ ニ Network ス (strain) system) that the aligning agent for liquid crystal (filtering afterwards) of above-mentioned modulation is coated on the transparency electrode face of the above-mentioned glass substrate that has a transparency electrode.The coating condition enactment of this moment be 2500 times/2 of (nozzle minute), discharge rate 250mg/ per 10 seconds back and forth (amount to 4 times) and be coated with.After the coating, leave standstill after 1 minute and be heated to 80 ℃, forming average film thickness thus is filming of 0.1 μ m.For filming of obtaining, under interference fringe instrumentation lamp (sodium vapor lamp) irradiation, with the naked eye observe, to not find inhomogeneous and the two average evaluation of depression is ink-jet application " well ", to find that at least one the average evaluation in inhomogeneous and the depression is ink-jet application " bad ", the ink-jet application of the above-mentioned aligning agent for liquid crystal of result is " well ".
The preparation of＜liquid crystal cell 〉
As following, be used to estimate the preparation of the liquid crystal cell of liquid crystal orientation and voltage retention.In the preparation of following liquid crystal cell, the coating of aligning agent for liquid crystal utilizes spin-coating method to carry out, and this is in order to compare with the aftermentioned comparative example of ink-jet application difference.
Utilize spin-coating method that the aligning agent for liquid crystal (filtering the back) of above-mentioned modulation is coated on the transparency electrode face of the glass substrate that has transparency electrode that contains the ITO film, preliminary drying is 1 minute on 80 ℃ heating plate, then dried by the fire 10 minutes the back on 200 ℃ heating plate, and forming average film thickness thus is filming of 0.1 μ m.Repeat same operation, prepare a pair of (2) have liquid crystal orientation film on nesa coating substrate.
In each outer rim of above-mentioned a pair of substrate, 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 with liquid crystal orientation film.Then, by liquid crystal injecting port between a pair of substrate, fill nematic crystal (メ Le Network corporate system, MLC-6601) after, with the acrylic compounds light-curing adhesive liquid crystal injecting port is sealed, make liquid crystal cell thus.
The evaluation of＜liquid crystal aligning 〉
Liquid crystal cell for above-mentioned manufacturing, under the Nicol crossed polarized light, observe by range estimation, the average evaluation that will not have light to reveal is liquid crystal aligning " well ", with the average evaluation of observing the light leakage is liquid crystal aligning " bad ", and the liquid crystal aligning of the above-mentioned liquid crystal cell of result is " well ".
The evaluation of＜voltage retention 〉
For the above-mentioned liquid crystal cell that obtains, add the voltage of 5V with time that adds of 60 microseconds, 167 milliseconds interval after, measure from removing the voltage retention behind 167 milliseconds of the impressed voltages.Determinator uses (strain) Dongyang テ Network ニ カ system VHR-1.With this value is that average evaluation more than 95% is voltage retention " well ", will be voltage retention " bad " less than 95% average evaluation, the voltage retention of the above-mentioned liquid crystal cell of result " well ".
Embodiment 2
In the solution that contains imide amination polymer (PI-2) that above-mentioned synthesis example 2 obtains, add diisoamyl ether, gamma-butyrolacton, N-N-methyl-2-2-pyrrolidone N-and butyl cellosolve, solvent composition is a diisoamyl ether: gamma-butyrolacton: the N-N-methyl-2-2-pyrrolidone N-: butyl cellosolve=5: 30: 40: 25 (weight ratios) are modulated into the aligning agent for liquid crystal that solution viscosity is 6mPas.It is utilized the aperture is that the filtrator of 0.2 μ m filters, and carries out evaluation similarly to Example 1 then.Evaluation result is shown in table 1.
Embodiment 3
In the solution that contains imide amination polymer (PI-3) that above-mentioned synthesis example 3 obtains, add diisoamyl ether, N-N-methyl-2-2-pyrrolidone N-and butyl cellosolve, solvent composition is a diisoamyl ether: the N-N-methyl-2-2-pyrrolidone N-: butyl cellosolve=5: 50: 45 (weight ratio) is modulated into the aligning agent for liquid crystal that solution viscosity is 6mPas.It is utilized the aperture is that the filtrator of 0.2 μ m filters, and carries out evaluation similarly to Example 1 then.Evaluation result is shown in table 1.
Embodiment 4
In the solution that contains imide amination polymer (PI-4) that above-mentioned synthesis example 4 obtains, add diisoamyl ether, N-N-methyl-2-2-pyrrolidone N-and butyl cellosolve, solvent composition is a diisoamyl ether: the N-N-methyl-2-2-pyrrolidone N-: butyl cellosolve=5: 50: 45 (weight ratio) is modulated into the aligning agent for liquid crystal that solution viscosity is 6mPas.It is utilized the aperture is that the filtrator of 0.2 μ m filters, and carries out evaluation similarly to Example 1 then.Evaluation result is shown in table 1.
Comparative example 1
In the solution that contains imide amination polymer (PI-3) that above-mentioned synthesis example 3 obtains, add diisoamyl ether, N-N-methyl-2-2-pyrrolidone N-, solvent composition is a diisoamyl ether: N-N-methyl-2-2-pyrrolidone N-=5: 95 (weight ratio) is modulated into the aligning agent for liquid crystal that solution viscosity is 6mPas.It is utilized the aperture is that the filtrator of 0.2 μ m filters, and carries out evaluation similarly to Example 1 then.Evaluation result is shown in table 1.
Comparative example 2
In the solution that contains imide amination polymer (PI-2) that above-mentioned synthesis example 2 obtains, add butyrolactone, N-N-methyl-2-2-pyrrolidone N-and butyl cellosolve, solvent composition is a diisoamyl ether: the N-N-methyl-2-2-pyrrolidone N-: butyl cellosolve=40: 30: 30 is modulated into the aligning agent for liquid crystal that solution viscosity is 6mPas.It is utilized the aperture is that the filtrator of 0.2 μ m filters, and carries out evaluation similarly to Example 1 then.Evaluation result is shown in table 1.
The invention effect
Therefore coating excellence when aligning agent for liquid crystal of the present invention particularly uses in the ink-jet application method can improve the product percent of pass in utilizing the manufacturing process of large-scale production line.In addition, the liquid crystal orientation film that is obtained by aligning agent for liquid crystal of the present invention has all characteristics such as excellent liquid crystal aligning ability, electrical characteristics, is preferably applied to the liquid crystal display cells of vertical orientating type especially.
Liquid crystal display cells of the present invention with above-mentioned liquid crystal orientation film can be used as various devices, for example display device of desk-top computer, wrist-watch, desk clock, mobile phone, counting display board, spoken and written languages processor, personal computer, LCD TV etc. well.
Claims (5)
1. aligning agent for liquid crystal, it contains at least a kind polymkeric substance and the solvent that is selected from the polyimide that makes polyamic acid that tetracarboxylic dianhydride and diamine compound reaction obtain and its dehydration closed-loop is obtained, it is characterized in that,
Solvent contains:
(A) comprise the compound of following formula (I) expression first solvent,
In the formula (I), R represents independently that respectively carbon number is 3～10 alkyl,
(B) comprise and be selected from N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolacton, 1,3-dimethyl-2-imidazolone, N, at least a kind second solvent in dinethylformamide and the N,N-dimethylacetamide and
(C) comprise at least a kind the 3rd solvent that is selected from butyl cellosolve, diacetone alcohol, propylene carbonate, diethylene glycol diethyl ether and ethyl-3-ethoxy-c acid esters.
2. aligning agent for liquid crystal as claimed in claim 1, with respect to above-mentioned (A) first solvent, (B) second solvent and (C) total of the 3rd solvent, (A) ratio of first solvent is 0.5～20 weight %, (B) ratio of second solvent is 10～94.5 weight %, and (C) ratio of the 3rd solvent is 5～70 weight %.
3. aligning agent for liquid crystal as claimed in claim 1 or 2, the boiling point of the compound of following formula (I) expression is 140～200 ℃, surface tension is 18～27mN/m.
4. aligning agent for liquid crystal as claimed in claim 3, wherein, the compound of following formula (I) expression is at least a kind that is selected from diamyl ether and the isoamyl ether.
5. as each described aligning agent for liquid crystal in claim 1 or 2, wherein, the tetracarboxylic dianhydride comprises the compound that is selected from following formula (1) expression, compound, the pyromellitic acid dianhydride, 1 of following formula (2) expression, 2,4-tricarboxylic basic ring amyl group acetate dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride and 1,2,4, among the 5-cyclohexane tetracarboxylic dianhydride at least a kind
In the formula (1), R
1Represent independently that respectively hydrogen atom, chlorine atom or carbon number are 1～6 alkyl,
In the formula (2), R
2Represent independently that respectively carbon number is 1～6 alkyl, n is 0～4 integer.
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| JP5699543B2 (en) * | 2010-11-02 | 2015-04-15 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| CN103620488B (en) * | 2011-06-21 | 2016-02-24 | 日产化学工业株式会社 | Light orientation process method aligning agent for liquid crystal and use the liquid crystal orientation film of this aligning agent for liquid crystal |
| CN102408399B (en) * | 2011-08-12 | 2014-04-16 | 中国科学院化学研究所 | Alkyl substituent-containing alicyclic dianhydride compound and polyimide prepared by same |
| CN102517039A (en) * | 2011-10-25 | 2012-06-27 | 珠海彩珠实业有限公司 | Preparation methods of liquid crystal orientation agent, liquid crystal orientation membrane, and liquid crystal cells thereof |
| JP5990928B2 (en) * | 2012-02-24 | 2016-09-14 | Jsr株式会社 | Liquid crystal alignment agent |
| JP6146077B2 (en) * | 2012-06-29 | 2017-06-14 | Jsr株式会社 | Method for producing liquid crystal alignment film |
| JP6146135B2 (en) * | 2012-08-30 | 2017-06-14 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal aligning film, method for producing liquid crystal aligning film, and liquid crystal display element |
| CN102898407B (en) * | 2012-09-24 | 2015-08-05 | 中国科学院化学研究所 | A kind of fluorine-containing alicyclic dianhydride compound and preparation method thereof and application |
| TWI564283B (en) * | 2012-10-18 | 2017-01-01 | Nissan Chemical Ind Ltd | A liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device |
| WO2014061780A1 (en) * | 2012-10-18 | 2014-04-24 | 日産化学工業株式会社 | Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| KR102159410B1 (en) * | 2013-03-14 | 2020-09-23 | 제이엔씨 주식회사 | Liquid crystal aligning agents and liquid crystal display devices |
| JP6248784B2 (en) * | 2014-04-25 | 2017-12-20 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| WO2016063834A1 (en) * | 2014-10-20 | 2016-04-28 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element using same |
| CN107077031B (en) * | 2014-11-21 | 2020-11-06 | Jnc株式会社 | Liquid crystal aligning agent containing polyamic acid or derivative thereof, liquid crystal alignment film, and liquid crystal display element |
| JP2016138236A (en) * | 2014-12-26 | 2016-08-04 | Jsr株式会社 | Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| JP2017052877A (en) | 2015-09-09 | 2017-03-16 | 富士ゼロックス株式会社 | Polyimide precursor composition, manufacturing method of polyimide precursor composition and manufacturing method of polyimide molded body |
| JP6780259B2 (en) | 2016-02-22 | 2020-11-04 | 富士ゼロックス株式会社 | Polyimide precursor composition and method for producing polyimide precursor composition |
| WO2018062353A1 (en) * | 2016-09-29 | 2018-04-05 | 日産化学工業株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device |
| KR102619748B1 (en) * | 2017-03-31 | 2023-12-29 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display device |
| WO2018199087A1 (en) * | 2017-04-25 | 2018-11-01 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| JP6904216B2 (en) * | 2017-10-30 | 2021-07-14 | Jnc株式会社 | A liquid crystal alignment agent for forming a liquid crystal alignment film, a liquid crystal alignment film, and a liquid crystal display element using the same. |
| WO2019116702A1 (en) * | 2017-12-14 | 2019-06-20 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal element |
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