CN104704421B

CN104704421B - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells

Info

Publication number: CN104704421B
Application number: CN201380053008.8A
Authority: CN
Inventors: 根木隆之; 樱井宏之; 筒井皇晶
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2012-08-10
Filing date: 2013-08-06
Publication date: 2018-01-16
Anticipated expiration: 2033-08-06
Also published as: KR20150043359A; TWI485201B; WO2014024892A1; JP6319581B2; JPWO2014024892A1; CN104704421A; KR102096126B1; TW201425471A

Abstract

The present invention is a kind of aligning agent for liquid crystal, and it is included selected from the tetracarboxylic dianhydride and polyamic acid and at least one polymer and solvent by polyimides obtained by the polyamic acid imidizate obtained by diamine component progress polymerisation for making following formula (1) expression.[changing 1]

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells

Technical field

The present invention relates to the aligning agent for liquid crystal used when making liquid crystal orientation film, use the liquid crystal aligning of the aligning agent for liquid crystal Film and liquid crystal display cells.

Background technology

The liquid crystal display cells used in LCD TV, liquid crystal display etc. are as realizing slim and light weight display Part, nowadays it is widely used.As the liquid crystal orientation film for making liquid crystal aligning, mainly using the liquid of so-called polyimide Brilliant alignment films, the liquid crystal orientation film on glass substrate etc. by being coated with polyamic acid (also referred to as polyamic acid (polyamide acid)), the solution of the polyimide precursor such as poly amic acid ester or polyimides takes as the liquid crystal of principal component To agent, burnt till and obtained.

In order to improve the display characteristic of this liquid crystal display cells, by changing polyamic acid, poly amic acid ester and polyamides The structure of imines, the different polyamic acid of blending rating, poly amic acid ester and polyimides, or the method for adding additive etc., To carry out the improvement of liquid crystal aligning and electrical characteristics etc., control of pre-tilt angle etc. (with reference to patent document 1 etc.).

Prior art literature

Patent document

Patent document 1：Japanese Patent Laid-Open 2011-100099 publications

The content of the invention

The technical problems to be solved by the invention

However, with the development of the high performance of liquid crystal display cells, large area, the power saving of display device etc., liquid Characteristic required by brilliant alignment films is also increasingly stricter, also requires that liquid crystal display cells have patience for UV light exposure.Specifically For, for example, in liquid crystal injection, sealing to be added dropwise in the case that injection method carries out, to the irradiation of the encapsulant of sealing During ultraviolet, ultraviolet also is irradiated to the liquid crystal orientation film of image forming area sometimes.In addition, liquid crystal aligning is made by light irradiation In the case that film is orientated, ultraviolet (UV) is irradiated to liquid crystal orientation film in orientation process process.Moreover, at vertical orientated (VA) In liquid crystal display cells as mode, include applying voltage to liquid crystal molecule while irradiating sometimes in its manufacturing process The process of ultraviolet.In addition, when in use, liquid crystal display cells are also exposed under external ultraviolet sometimes.Liquid crystal orientation film In the case of the no patience of exposure for these ultraviolets, the problem of electrical characteristics such as voltage retention deteriorate can be produced.

The problem of the present invention is solve above-mentioned problem of the prior art, there is provided can obtain the excellent liquid crystal of ultraviolet resistance Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal display cells of alignment films.

Technical scheme used by solution technical problem

Present inventor has performed conscientiously studying, as a result find comprising the polyamides using the tetracarboxylic dianhydride of specific structure as raw material The aligning agent for liquid crystal of amino acid or polyimides and solvent is extremely effective in terms of above-mentioned problem is reached, so as to complete this hair It is bright.

That is, the present invention has following main points.

A kind of 1. aligning agent for liquid crystal, it is characterised in that comprising selected from make tetracarboxylic dianhydride and diamines that following formula (1) represents into Divide and carry out polyamic acid obtained by polymerisation and gather at least one of polyimides obtained by the polyamic acid imidizate Compound and solvent；

[changing 1]

Aligning agent for liquid crystal described in 2.1, it is characterised in that the polymer is polyimides.

3. a kind of liquid crystal orientation film, it is characterised in that obtained using the aligning agent for liquid crystal described in 1 or 2.

4. a kind of liquid crystal display cells, it is characterised in that possess the liquid crystal orientation film described in 3.

The effect of invention

It is excellent for the patience of ultraviolet using liquid crystal orientation film obtained by the aligning agent for liquid crystal of the present invention.Therefore, even if The liquid crystal orientation film of liquid crystal display cells as the process for for example including irradiation ultraviolet in the fabrication process, in manufacturing process The deterioration of the electrical characteristics such as middle voltage retention is also inhibited, it is possible to provide has the liquid crystal display cells of good electrical characteristics.This Outside, even if as the liquid crystal orientation film in the liquid crystal display cells used in the environment of ultraviolet, voltage retention etc. The deterioration of electrical characteristics is also inhibited, and turns into the liquid crystal display cells with good electrical characteristics.

Embodiment

Hereinafter, the present invention is described in detail.

The aligning agent for liquid crystal of the present invention includes to be polymerize selected from the tetracarboxylic dianhydride for representing above formula (1) with diamine component Polyamic acid obtained by reaction and by least one polymer of polyimides obtained by the polyamic acid imidizate and molten Agent.Aligning agent for liquid crystal refers to the solution for making liquid crystal orientation film；Liquid crystal orientation film refers to be used to make liquid crystal side as defined in To the film of orientation.

In formula (1) ,-NH- being bonded with phenyl ring is preferably present in contraposition or meta each other.

By making the tetracarboxylic dianhydride that the formula (1) represents carry out polymerisation with diamine component, polyamic acid can be obtained.This Outside, as the polyamic acid imidizate by obtained by, polyimides can be obtained.

Carried out moreover, the aligning agent for liquid crystal of the present invention includes the tetracarboxylic dianhydride for representing these formulas (1) with diamine component Polyamic acid obtained by polymerisation or by polyimides and solvent obtained by the polyamic acid imidizate.By using such as It is upper described comprising using the tetracarboxylic dianhydride that formula (1) represents as the polyamic acid or polyimides of raw material and the liquid crystal aligning of solvent Agent, as shown in following embodiments, can obtain ultraviolet (UV) patience it is excellent, caused by UV exposure voltage retention Etc. (VHR) liquid crystal orientation film that the deterioration of electrical characteristics is inhibited.Therefore, even if irradiating UV in the fabrication process, or sudden and violent It is exposed in the environment of UV and uses, the deterioration of the electrical characteristics such as voltage retention is also inhibited, it is possible to provide has excellent electrical characteristics Liquid crystal display cells.

In addition, comprising using the tetracarboxylic dianhydride that formula (1) represents as the polyimides of raw material and the aligning agent for liquid crystal of solvent Coating of liquid crystalline alignment agent when film homogeneity it is high, i.e. be not susceptible to produce the agglutinator of polymer in the end of coated surface Phenomenon (also referred to as albefaction aggegation).Obviously, comprising using the tetracarboxylic dianhydride that formula (1) represents as the polyamic acid of raw material and The aligning agent for liquid crystal of solvent is not easy to that the albefaction aggegation occurs.In addition, using the tetracarboxylic dianhydride that formula (1) represents as the poly- of raw material Dissolubility of the acid imide in the solvent that METHYLPYRROLIDONE or butoxy ethanol etc. are used for aligning agent for liquid crystal is high, i.e., Making for a long time to place aligning agent for liquid crystal will not also separate out, and storage stability is high.

In addition, the manufacture method for the tetracarboxylic dianhydride that formula (1) represents is not particularly limited, such as can be by making 1,2,4- hexamethylenes Alkane tricarboxylic acids -1,2- acid anhydride 4- acyl chlorides is reacted with phenylenediamine to manufacture.Japanese Patent Laid-Open 2012-72121 public affairs can specifically be enumerated Manufacture method described in report.

In addition it is also possible to the tetracarboxylic dianhydride beyond the tetracarboxylic dianhydride of formula (1) expression is set (to be also denoted as other tetracarboxylic acids below Acid dianhydride) and formula (1) represent tetracarboxylic dianhydride together with diamine component react.Now, formula (1) represent tetracarboxylic dianhydride compared with It is that 60~95 moles of % of the tetracarboxylic dianhydride's composition total amount used in the synthesis with polyamic acid amount uses well, more preferably four 70~90 moles of % of carboxylic acid dianhydride composition are the tetracarboxylic dianhydrides that formula (1) represents.By the tetracarboxylic dianhydride of formula (1) expression and its Its tetracarboxylic dianhydride and referred to as tetracarboxylic dianhydride's composition.

As other tetracarboxylic dianhydrides, the tetracarboxylic dianhydride that following formula (2) represents can be enumerated.

[changing 2]

(in formula (2), Z₁It is 4 valency organic groups of the carbon number 4~13 of the non-aromatic cyclic hydrocarbon base containing carbon number 4~6.)

In formula (2), as Z₁Concrete example, the 4 valency organic groups that following formula (2a)~formula (2j) represents can be enumerated.

[changing 3]

(in formula (2a), Z₂~Z₅It is hydrogen atom, methyl, chlorine atom or phenyl ring, they can be the same or different each other； In formula (2g), Z₆And Z₇It is hydrogen atom or methyl, they can be the same or different each other.)

In formula (2), from the viewpoint of polymerisation reactivity and the complexity of synthesis, Z₁Particularly preferred structure be formula (2a), formula (2c), formula (2d), formula (2e), formula (2f) or formula (2g).Wherein, preferred formula (2a), formula (2e), formula (2f) or formula (2g)。

In addition, the tetracarboxylic dianhydride that formula (2) represents is not particularly limited relative to the ratio of tetracarboxylic dianhydride's composition total amount, example Such as be preferably tetracarboxylic dianhydride's composition total amount 5~40 moles of % be above formula (2) represent tetracarboxylic dianhydride, more preferably 10~30 Mole %.

Other tetracarboxylic dianhydrides beyond the tetracarboxylic dianhydride represented as above formula (2), can enumerate Pyromellitic Acid, 2, and 3, 6,7- naphthalenetetracarbacidic acidics, 1,2,5,6- naphthalenetetracarbacidic acidics, 1,4,5,8 naphthalenetetracarboxylic acid, 2,3,6,7- anthracenes tetracarboxylic acid, 1,2,5,6- anthracenes four Formic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic, 2,3,3 ', 4- bibenzene tetracarboxylics, double (3,4- dicarboxyphenyis) ethers, 3,3 ', 4,4 '- Double (the 3,4- dicarboxyl benzene of benzophenone tetracarboxylic, double (3,4- dicarboxyphenyis) sulfones, double (3,4- dicarboxyphenyis) methane, 2,2- Base) propane, 1,1,1,3,3,3- hexafluoros -2,2- double (3,4- dicarboxyphenyis) propane, double (3,4- dicarboxyphenyis) dimethyl Double (3,4- dicarboxyphenyis) pyrroles of silane, double (3,4- dicarboxyphenyis) diphenyl silanes, 2,3,4,5- pyridines tetracarboxylic acid, 2,6- Pyridine, 3,3 ', 4,4 '-diphenyl sulfone tetraformic acid, 3,4,9,10- tetracarboxylic acids or 1,3- diphenyl -1,2,3,4- cyclobutanetetracarboxylics Dianhydride.

In addition, the tetracarboxylic dianhydride of above formula (1) expression of the raw material as polyamic acid or polyimides, other tetrabasic carboxylic acids Dianhydride can be a kind of or two or more respectively.

The diamine component of tetracarboxylic dianhydride's compositions such as the tetracarboxylic dianhydride represented with formula (1) reaction is not particularly limited, and can be made With the diamines commonly used in aligning agent for liquid crystal.As in general diamines, general diamines can be enumerated, there is the side for making liquid crystal vertical-tropism The diamines of chain, liquid crystal is set to show the diamines of high pre-tilt angle, the diamines with photoreactive group etc..

As general diamines, such as p-phenylenediamine, 2 can be enumerated, 3,5,6- tetramethyl-para-phenylene diamines, 2,5- dimethyl are to benzene Diamines, m-phenylene diamine (MPD), 2,4- dimethyl-m-phenylenediamines, 2,5- diaminotoluenes, 2,6- diaminotoluenes, 2,5- diaminobenzenes Phenol, 2,4- diaminophenols, 3,5- diaminophenols, 3,5- diaminourea benzylalcohol, 2,4- diaminourea benzylalcohol, 4,6- diaminourea isophthalic Diphenol, 4,4 '-benzidine, 3,3 '-dimethyl -4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-diaminourea connection Benzene, 3,3 '-dihydroxy -4,4 '-benzidine, 3,3 '-dicarboxyl -4,4 '-benzidine, 3,3 '-two fluoro- 4,4 '-connection Benzene, 3,3 '-trifluoromethyl -4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-diaminourea Biphenyl, 2,3 '-benzidine, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminourea Diphenyl methane, 2,2 '-diaminodiphenyl-methane, 2,3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 3, 3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 2,2 '-diamino-diphenyl ether, 2,3 '-diamino-diphenyl Ether, 4,4 '-sulfonyldianiline, 3,3 '-sulfonyldianiline, double (4- aminophenyls) silane, double (3- aminophenyls) silane, diformazan Base-bis- (4- aminophenyls) silane, dimethyl-bis- (3- aminophenyls) silane, 4,4 '-diaminodiphenyl sulfide, 3,3 '-diamino Base diphenyl sulfide, 4,4 '-diamino-diphenylamine, 3,3 '-diamino-diphenylamine, 3,4 '-diamino-diphenylamine, 2,2 '-diaminourea Diphenylamines, 2,3 '-diamino-diphenylamine, N- methyl (4,4 '-diamino-diphenyl) amine, N- methyl (3,3 '-diaminourea hexichol Base) amine, N- methyl (3,4 '-diamino-diphenyl) amine, N- methyl (2,2 '-diamino-diphenyl) amine, N- methyl (2,3 '-two Aminodiphenyl base) amine, 4,4 '-diaminourea benzophenone, 3,3 '-diaminourea benzophenone, 3,4 '-diaminourea benzophenone, 1,4- diaminos Base naphthalene, 2,2 '-diaminourea benzophenone, 2,3 '-diaminourea benzophenone, 1,5- diaminonaphthalenes, 1,6- diaminonaphthalenes, 1,7- diaminourea Double (the 4- of naphthalene, 1,8- diaminonaphthalenes, 2,5- diaminonaphthalenes, 2,6 diaminonaphthalenes, 2,7- diaminonaphthalenes, 2,8- diaminonaphthalenes, 1,2- Aminophenyl) ethane, double (3- aminophenyls) ethane of 1,2-, double (4- aminophenyls) propane of 1,3-, double (the 3- aminobenzenes of 1,3- Base) propane, double (4- aminophenyls) butane of 1,4-, 1,4- double (3- aminophenyls) butane, double (3,5- diethyl -4- aminobenzenes Base) methane, double (4- amino-benzene oxygens) benzene of 1,4-, double (4- amino-benzene oxygens) benzene of 1,3-, 1,4- double (4- aminophenyls) benzene, 1, Double (4- aminophenyls) benzene of 3-, double (the 4- aminobenzenes methyl) benzene of 1,4-, double (4- amino-benzene oxygens) benzene of 1,3-, 4,4 '-[1,4- Asias Phenyl is double (methylene)] diphenylamines, 4,4 '-[1,3- phenylenes are double (methylene)] diphenylamines, 3,4 '-[1,4- phenylenes are double (sub- Methyl)] diphenylamines, 3,4 '-[1,3- phenylenes double (methylene)] diphenylamines, 3,3 '-[1,4- phenylenes are double (methylene)] two Aniline, 3,3 '-[1,3- phenylenes are double (methylene)] diphenylamines, 1,4- phenylenes double [(4- aminophenyls) ketones], 1,4- are sub- Phenyl double [(3- aminophenyls) ketones], 1,3- phenylenes double [(4- aminophenyls) ketones], double [(the 3- amino of 1,3- phenylenes Phenyl) ketone], 1,4- phenylenes double (PABA esters), 1,4- phenylenes double (3- Aminobenzoates), 1,3- Asias benzene Base double (PABA ester), 1,3- phenylenes double (3- Aminobenzoates), double (4- aminophenyls) terephthalates, Double (3- aminophenyls) terephthalates, double (4- aminophenyls) isophthalic acid esters, double (3- aminophenyls) isophthalic diformazans Acid esters, N, N '-(1,4- phenylenes) double (4- aminobenzamides), N, N '-(1,3- phenylenes) double (4- aminobenzamides), N, N '-(1,4- phenylenes) double (3-ABs), N, N '-(1,3- phenylenes) double (3-ABs), N, N '- Double (4- aminophenyls) terephthalamides, N, N '-bis- (3- aminophenyls) terephthalamide, N, N '-bis- (4- aminobenzenes Base) isophtalamide, N, N '-bis- (3- aminophenyls) isophtalamide, double (4- aminophenyls) anthracenes of 9,10-, 4,4 '-it is bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS), 2,2 '-bis- [4- (4- amino-benzene oxygens) phenyl] propane, 2,2 '-bis- [4- (4- aminobenzene oxygen Base) phenyl] HFC-236fa, 2,2 '-bis- (4- aminophenyls) HFC-236fas, 2,2 '-bis- (3- aminophenyls) HFC-236fas, 2, 2 '-bis- (3- amino -4- aminomethyl phenyls) HFC-236fas, 2,2 '-bis- (4- aminophenyls) propane, 2,2 '-bis- (3- aminophenyls) Propane, 2,2 '-bis- (3- amino -4- aminomethyl phenyls) propane, 3,5- diaminobenzoic acids, 2,5- diaminobenzoic acids, 1,3- are double Double (3- amino-benzene oxygens) propane of (4- amino-benzene oxygens) propane, 1,3-, double (4- amino-benzene oxygens) butane of 1,4-, 1,4- are double Double (4- amino-benzene oxygens) pentanes of (3- amino-benzene oxygens) butane, 1,5-, double (3- amino-benzene oxygens) pentanes of 1,5-, 1,6- are double Double (3- amino-benzene oxygens) hexanes of (4- amino-benzene oxygens) hexane, 1,6-, 1,7- double (4- amino-benzene oxygens) heptane, 1,7- (3- Amino-benzene oxygen) heptane, double (4- amino-benzene oxygens) octanes of 1,8-, double (3- amino-benzene oxygens) octanes of 1,8-, double (the 4- ammonia of 1,9- Phenoxyl) nonane, 1,9- double (3- amino-benzene oxygens) nonane, 1,10- (4- amino-benzene oxygens) decane, 1,10- (3- aminobenzenes Epoxide) decane, 1,11- (4- amino-benzene oxygens) hendecane, 1,11- (3- amino-benzene oxygens) hendecane, 1,12- (4- aminobenzenes Epoxide) aromatic diamine such as dodecane, 1,12- (3- amino-benzene oxygens) dodecane, double (4- aminocyclohexyls) methane, double (4- Amino -3- methylcyclohexyls) alicyclic diamine such as methane, 1,3- diaminopropanes, 1,4-Diaminobutane, 1,5- diaminourea penta Alkane, 1,6- diamino hexanes, 1,7- diaminoheptanes, 1,8- diamino-octanes, 1,9- diamino nonanes, the 1,10- diaminourea last of the ten Heavenly stems The aliphatic diamines such as alkane, 1,11- diamino undecanes, 1,12- diamino dodecanes.

This general diamines is preferably 50~95 moles of % of the diamine component to be used in the synthesis of polyamic acid amount Use, more preferably the 70~90 of diamine component mole %.

As the diamines with the side chain for making liquid crystal vertical-tropism, liquid crystal is shown the diamines of high pre-tilt angle, can enumerate With chain alkyl, in the midway circular structure of chain alkyl or group, steroid radical, the hydrogen by these groups of branched structure Atomic component or diamines of the group as side chain for being all substituted by fluorine atom.Can specifically enumerate for example following formula (3), (4), (5), (6) diamines represented, but it is not limited to this.

[changing 4]

(in formula (3), l, m and n separately represent 0 or 1 integer, R³Represent the alkylidene of carbon number 2~6 ,-O- ,- COO- ,-OCO- ,-NHCO-, the alkylidene ether of-CONH- or carbon number 1~3, R⁴、R⁵And R⁶Separately represent phenylene or Cycloalkylidene, R⁷Represent hydrogen atom, the alkyl of carbon number 2~24 or containing fluoroalkyl, monovalence aromatic rings, univalent aliphatic series ring, monovalence Heterocycle or the big ring-type substitution body of the monovalence being made up of them.)

In addition, from the viewpoint of the complexity of synthesis, the R in above formula (3)³It is preferred that-O- ,-COO- ,-CONH-, carbon The alkylidene ether of number 1~3.

In addition, from the complexity of synthesis and from the viewpoint of making the ability of liquid crystal vertical-tropism, the R in formula (3)⁴、R⁵With R⁶It is preferred that l, m, n, R shown in table 1 below⁴、R⁵And R⁶Combination.

[table 1]

l	m	n	R⁴	R⁵	R⁶
						1	1	1	Phenylene	Phenylene	Cyclohexylidene
1	1	1	Phenylene	Cyclohexylidene	Cyclohexylidene
						1	1	1	Cyclohexylidene	Cyclohexylidene	Cyclohexylidene
1	1	0	Phenylene	Phenylene	-
						1	1	0	Phenylene	Cyclohexylidene	-
1	1	0	Cyclohexylidene	Cyclohexylidene	-

Moreover, l, m, n it is at least one be 1 in the case of, the R in formula (3)⁷It is preferred that hydrogen atom or carbon number 2~14 Alkyl or containing fluoroalkyl, the more preferably alkyl of hydrogen atom or carbon number 2~12 or containing fluoroalkyl.In addition, l, m, n are 0 feelings Under condition, R⁷It is preferred that the alkyl of carbon number 12~22 or containing fluoroalkyl, monovalence aromatic rings, univalent aliphatic series ring, monovalence heterocycle, by them The big ring-type substitution body of the monovalence of composition, the more preferably alkyl of carbon number 12~20 or containing fluoroalkyl.

In addition, the polymer with the side chain for making liquid crystal vertical-tropism makes the ability of liquid crystal vertical-tropism according to making liquid crystal hang down The structure for the side chain being directly orientated and it is different, but in general, if making the amount of the side chain of liquid crystal vertical-tropism more, i.e. diamine component In the contained diamine contents with the side chain for making liquid crystal vertical-tropism it is more, then improve the ability of liquid crystal vertical-tropism, if Above-mentioned amount is few, then aforementioned capabilities reduce.If in addition, having cyclic structure, compared with the situation without cyclic structure, deposit Make the high tendency of the ability of liquid crystal vertical-tropism.

[changing 5]

(in formula (4) and formula (5), A₁₀Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂- ,-O- ,-CO- or-NH-, A₁₁Represent singly-bound or phenylene, a expressions-R³-(R⁴)_l-(R⁵)_m-(R⁶)_n-R⁷(R³、R⁴、R⁵、R⁶、R⁷, in l, m, n and above formula (3) Definition it is identical), a ' represents to remove the divalent group of the structure after the elements such as hydrogen from above-mentioned a identicals structure.)

[changing 6]

(in formula (6), A₁₄It is the alkyl for the carbon number 3~20 that can be replaced by fluorine atoms, A₁₅It is 1,4- cyclohexylidenes or 1, 4- phenylenes, A₁₆It is that oxygen atom or-COO-* (here, indicate the key and A of " * "₁₅With reference to), A₁₇It is oxygen atom or-COO-* (these In, indicate the key of " * " and (CH₂)a₂With reference to).In addition, a₁For 0 or 1, a₂For 2~10 integer, a₃For 0 or 1.)

To two amino (- NH in formula (3)₂) binding site do not limit.It can specifically enumerate：Relative to side chain (- R³- (R⁴)_l-(R⁵)_m-(R⁶)_n-R⁷), 2,3,2,4,2,5,2,6,3,4,3,5 on phenyl ring.Wherein, it is poly- from synthesis From the viewpoint of reactivity during amic acid, preferably 2,4,2,5 or 3,5.If further contemplate difficulty or ease during synthesis diamines Degree, then more preferably 2,4 or 3,5.

As the concrete structure of formula (3), the diamines that following formula [A-1]~formula [A-24] represents can be enumerated, but be not limited to this.

[changing 7]

(in formula [A-1]~formula [A-5], A₁It is the alkyl of carbon number 2~24 or containing fluoroalkyl.)

[changing 8]

(in formula [A-6] and formula [A-7], A₂Expression-O- ,-OCH₂-、-CH₂O-、-COOCH₂- or-CH₂OCO-, A₃It is carbon number 1~22 alkyl, alkoxy, containing fluoroalkyl or fluoroalkoxy.)

[changing 9]

(in formula [A-8]~formula [A-10], A₄Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、- CH₂OCO-、-CH₂O-、-OCH₂- or-CH₂-, A₅It is the alkyl of carbon number 1~22, alkoxy, containing fluoroalkyl or fluoroalkoxy.)

[changing 10]

(in formula [A-11] and formula [A-12], A₆Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、- CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂- ,-O- or-NH-, A₇It is fluorine-based, cyano group, trifluoromethyl, nitro, azo group, formyl Base, acetyl group, acetoxyl group or hydroxyl.)

[changing 11]

(in formula [A-13] and formula [A-14], A₈It is the alkyl of carbon number 3~12, the cis-trans isomerism of Isosorbide-5-Nitrae-cyclohexylidene is divided Wei not transisomer.)

[changing 12]

(in formula [A-15] and formula [A-16], A₉It is the alkyl of carbon number 3~12, the cis-trans isomerism of Isosorbide-5-Nitrae-cyclohexylidene is divided Wei not transisomer.)

[changing 13]

The concrete example of the diamines represented as formula (4), the diamines that following formula [A-25]~formula [A-30] represents can be enumerated, but not It is defined in this.

[changing 14]

(in formula [A-25]~formula [A-30], A₁₂Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂-、-O-、-CO- Or-NH-, A₁₃Represent the alkyl of carbon number 1~22 or containing fluoroalkyl.)

The concrete example of the diamines represented as formula (5), the diamines that following formula [A-31]~formula [A-32] represents can be enumerated, but not It is defined in this.

[changing 15]

Wherein, from the viewpoint of the ability of liquid crystal vertical-tropism, the response speed of liquid crystal is made, preferably [A-1], [A-2], [A-3], [A-4], [A-5], [A-25], [A-26], [A-27], [A-28], [A-29], the diamines of [A-30].

It is this that there is the diamines for the side chain for making liquid crystal vertical-tropism and the diamines that makes liquid crystal show high pre-tilt angle to be preferably Used with 0~50 mole of % of the diamine component used in the synthesis of polyamic acid amount, more preferably the 10~40 of diamine component Mole %.

As the diamines with photoreactive group, can enumerate with vinyl, acryloyl group, methylacryloyl, alkene The photoreactive groups such as propyl group, styryl, cinnamoyl, chalcone base, cumarin base, dimaleoyl imino are as side chain Diamines, such as the diamines that following formulas (7) represent, but it is not limited to this.

[changing 16]

(in formula (7), R⁸Represent singly-bound or-CH₂-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂O-、- N(CH₃)-、-CON(CH₃)-、-N(CH₃Any of) CO-, R⁹Represent singly-bound or carbon that is non-substituted or being replaced by fluorine atoms The alkylidene of number 1~the 20 ,-CH of alkylidene₂- can be by-CF₂- or-CH=CH- arbitrarily substitute, any base exemplified below In the case that group is not adjacent to each other, it can also be substituted by these groups：-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、 Divalence carbocyclic ring, bivalent heterocyclic.R¹⁰Represent vinyl, acryloyl group, methylacryloyl, pi-allyl, styryl ,-N (CH₂CHCH₂)₂Or the structure that following formula represents.)

[changing 17]

In addition, the R in above formula (7)⁸Although it can be formed by the organic synthesis technology of routine, from the difficulty or ease journey of synthesis From the viewpoint of degree, preferably-CH₂-、-O-、-COO-、-NHCO-、-NH-、-CH₂O-。

In addition, as substitution R⁹Arbitrary-CH₂- divalence carbocyclic ring or bivalent heterocyclic carbocyclic ring or heterocycle, specifically can example Following structure is lifted, but is not limited to this.

[changing 18]

From the viewpoint of photoreactivity, R¹⁰Preferred vinyl, acryloyl group, methylacryloyl, pi-allyl, styrene Base ,-N (CH₂CHCH₂)₂Or the structure that following formula represents.

[changing 19]

In addition,-the R of above formula (7)⁸-R⁹-R¹⁰More preferably following structures.

[changing 20]

To two amino (- NH in formula (7)₂) binding site do not limit.It can specifically enumerate：Relative to side chain (- R⁸- R⁹-R¹⁰), 2,3,2,4,2,5,2,6,3,4,3,5 on phenyl ring.Wherein, from synthesizing polyamides acid when it is anti- From the viewpoint of answering property, preferably 2,4,2,5 or 3,5.If complexity during synthesis diamines is further contemplated, more preferably 2,4 or 3,5.

As the diamines with photoreactive group, following compound can be specifically enumerated, but be not limited to this.

[changing 21]

(in formula, X represent singly-bound or selected from-O- ,-COO- ,-NHCO- ,-NH- conjugated group, Y represent singly-bound or non- The alkylidene of carbon number 1~20 for substituting or being replaced by fluorine atoms.)

In addition, this diamines with photoreactive group is preferably the diamine component to be used in the synthesis of polyamic acid 0~70 mole of % amount use, more preferably 0~60 mole of %.

Above-mentioned diamines can be according to liquid crystal aligning when being made liquid crystal orientation film, pre-tilt angle, voltage retention performance, accumulation The characteristics such as electric charge, the response speed of liquid crystal when being made liquid crystal display cells, are used alone, or mixing two or more.

The polymerisation of diamine component and tetracarboxylic dianhydride's composition is generally carried out in organic solvent.As what is now used Organic solvent, as long as the polyamic acid of generation can be dissolved, it is not particularly limited.As concrete example, N, N- diformazans can be enumerated Base formamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N- methyl caprolactams, dimethyl sulfoxide, tetramethylurea, Pyridine, dimethyl sulfone, gamma-butyrolacton, isopropanol, methoxy amylalcohol, cinene, ethyl pentyl group ketone, methyl nonyl ketone, first Base ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, second Base cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, Ethylene glycol monobutyl ether, propane diols, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, DPG list Methyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, two Propylene glycol monomethyl ether, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethylether, DPG list propyl ether, two Propylene glycol monoacetate list propyl ether, 3- methyl -3- methoxybutyls acetic acid esters, tripropylene glycol methyl ether, 3- methyl -3- methoxies Base butanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, DIBK, methyl Cyclohexene, propyl ether, two hexyl ether, dioxanes, n-hexane, normal heptane, normal octane, diethyl ether, cyclohexanone, ethylene carbonate, carbonic acid Sub- propyl ester, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethylether, third Ketone acid methyl esters, ethyl pyruvate, 3- methoxy methyl propionates, 3- ethoxy-propionic acids methyl ethyl ester, 3- methoxypropionates, 3- second Epoxide propionic acid, 3- methoxypropionic acids, 3- methoxy propyls propyl propionate, 3- methoxy propyls acid butyl ester, diethylene glycol dimethyl ether or 4- hydroxyls- 4-methyl-2 pentanone etc..These organic solvents can be used alone, and can also be used in mixed way.Even also, it can not dissolve poly- The solvent of amic acid, in the range of the polyamic acid of generation does not separate out, it may be combined in above-mentioned solvent and use.In addition, have Moisture in solvent hinders polymerisation, and can hydrolyze the polyamic acid of generation, therefore organic solvent is preferably using warp The organic solvent dehydrated.

When diamine component and the tetracarboxylic dianhydride's composition is reacted in organic solvent, following methods can be enumerated：Stirring makes two Amine component is dispersed or dissolved in solution obtained by organic solvent, then directly adds tetracarboxylic dianhydride's composition or makes tetrabasic carboxylic acid two Anhydride component is dispersed or dissolved in the method added again after organic solvent；It is dispersed or dissolved in tetracarboxylic dianhydride's composition on the contrary The method that diamine component is added in solution obtained by organic solvent；The alternately method of addition tetracarboxylic dianhydride's composition and diamine component Deng any method therein can be used.In addition, carried out instead using a variety of respectively in diamine component or tetracarboxylic dianhydride's composition In the case of answering, it can be made to be reacted in the state of being pre-mixed, it can also be made to react successively respectively, difference can also be made Low-molecular weight hybrid reaction obtained by reaction.Polymerization temperature now can select -20 DEG C~150 DEG C of arbitrary temp, excellent The scope of -5 DEG C~100 DEG C of choosing.In addition, reaction can be carried out with arbitrary concentration, but if concentration is too low, it is difficult to obtain high score The polyamic acid (and polyimides) of son amount, the viscosity of reaction solution is too high if excessive concentration, it is difficult to is uniformly stirred Mix.Therefore, the concentration of the total amount of diamine component and tetracarboxylic dianhydride's composition is preferably 1~50 mass %, more excellent in reaction solution Select 5~30 mass %.It can be carried out in initial reaction stage with high concentration, then add organic solvent again.

In the polymerisation of polyamic acid, the ratio between the total mole number of diamine component and the total mole number of tetracarboxylic dianhydride's composition Preferably 0.8~1.2.Identical with common polycondensation reaction, the mol ratio is closer to 1.0, the molecule of the polyamic acid of generation Amount is bigger.

Thus polyamic acid obtained by polymerization, the polymer of the repeat unit e.g. represented with following formula [a].

[changing 22]

(in formula [a], R₁₁It is derived from tetracarboxylic dianhydride's compositions such as the tetracarboxylic dianhydride of above formula (1) expression as raw material 4 valency organic groups, R₁₂It is derived from the diamine component H as raw material₂N-R₁₂-NH₂Divalent organic group, j represent it is just whole Number.)

Above formula [a] can be R₁₁And R₁₂Polymer respectively a kind of, with same repeat unit, or can also be R₁₁Or R₁₂For the polymer of repeat units a variety of, that there is different structure.

Then, by making such polyamic acid dehydration closed-loop, polyimides can be obtained.

As the method for making polyamic acid imidizate, the hot acid imide for the solution for directly heating polyamic acid can be enumerated Change or added in the solution of polyamic acid the catalysis imidizate of catalyst.

Temperature when making polyamic acid hot-imide in the solution is 100~400 DEG C, preferably 120~250 DEG C, preferably The method that imidizate is carried out while outside system using the water generated by imidization reaction is expelled to.

The catalysis imidizate of polyamic acid can by adding base catalyst and acid anhydrides in polyamic acid solution, At -20~250 DEG C, preferably stir and carry out at 0~180 DEG C.The amount of base catalyst is 0.5~30 mole of acid amides acidic group Times, preferably 2~20 moles times, acid anhydrides amount is 1~50 mole times of acid amides acidic group, and preferably 3~30 moles are again.As alkalescence Catalyst, can enumerate pyridine, triethylamine, trimethylamine, tri-n-butylamine or trioctylamine etc., wherein pyridine have for carrying out reaction and The alkalescence of appropriateness is sayed, therefore preferably.As acid anhydrides, acetic anhydride, trimellitic anhydride or pyromellitic dianhydride etc. can be enumerated, wherein, It is easy to carry out the purifying after reaction terminates during using acetic anhydride, therefore preferably.Acid imide rate based on catalysis imidizate can To be controlled by adjusting catalytic amount and reaction temperature, reaction time.

The polymer of generation is reclaimed from the reaction solution of polymer (polyimides or polyamic acid), and (polyimides is poly- Amic acid) when, reaction solution, which is put into solvent, precipitates it.As the solvent for precipitation, methanol, third can be enumerated Ketone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene or water etc..Put into solvent In and precipitate polymer can be dried under normal or reduced pressure, under normal temperature or heating after being recovered by filtration.This Outside, if repeating the operation that 2~10 polymer for reclaiming precipitation are re-dissolved in organic solvent and reprecipitation recovery, The impurity in polymer can be reduced.As solvent now, it can enumerate such as alcohols, ketone or hydro carbons, if using choosing From more than 3 kinds of solvent of above-mentioned solvent, then purification efficiency further improves, therefore preferably.

The dehydration closed-loop rate (acid imide rate) of the acid amides acidic group of polyimides contained by the aligning agent for liquid crystal of the present invention is no 100% necessarily is necessary for, can arbitrarily be selected according to purposes and purpose in the range of 0% to 100%, preferably 50%~ 90%, more preferably 70%~86%.

In addition, for polyamic acid or the molecular weight of polyimides, it is contemplated that the polymer envelope (liquid crystal aligning of gained Film) intensity, polymer envelope formation when operability, the uniformity of polymer envelope, with using GPC (gel permeation chromatography) The Weight-average molecular gauge that method measures is preferably 5000~1000000, and more preferably 10000~150000.

In addition, as long as the solvent contained by the aligning agent for liquid crystal of the present invention can dissolve above-mentioned polyimides or polyamic acid and be Can, it is not particularly limited, DMF, DMA, METHYLPYRROLIDONE, N- first can be enumerated Base caprolactam, 2-Pyrrolidone, N- ethyl-2-pyrrolidones, NVP, dimethyl sulfoxide, tetramethylurea, pyrrole Pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 1,3- dimethyl-2-imidazolidinones, ethyl pentyl group ketone, methyl nonyl ketone, first Base ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether And the organic solvent such as 4- hydroxy-4-methyl-2-pentanones.These organic solvents can be used alone, and can also be used in mixed way.

For the solvent in the aligning agent for liquid crystal of the present invention, examined from the viewpoint that uniform polymer envelope is formed by coating Consider, the content of solvent is preferably 70~99 mass %.Its content can suitably be changed according to the thickness of Object LC alignment films.

The present invention aligning agent for liquid crystal component of polymer can only be selected from make above formula (1) represent tetracarboxylic dianhydride with Diamine component carry out polymerisation obtained by polyamic acid and by polyimides obtained by the polyamic acid imidizate at least A kind of polymer, the tetracarboxylic dianhydride that will can also be selected from represents above formula (1) are carried out obtained by polymerisation with diamine component Polyamic acid and at least one polymer of polyimides obtained by the polyamic acid imidizate is other with addition Mixed with polymers.Now, obtained relative to selected from making the tetracarboxylic dianhydride of above formula (1) expression carry out polymerisation with diamine component Polyamic acid and the total amount by least one polymer of polyimides obtained by the polyamic acid imidizate, in addition The contents of other polymer be 0.5~15 mass %, preferably 1.0~10 mass %.As other polymer in addition, The polyamic acid obtained by the tetracarboxylic dianhydride's composition and diamine component of the tetracarboxylic dianhydride represented not comprising above formula (1) can be enumerated Or polyimides.Further, as the polymer beyond polyamic acid and polyimides, specifically, can enumerate poly amic acid ester, Acrylate copolymer, methacrylate polymer, polystyrene or polyamide etc..

In the aligning agent for liquid crystal of the present invention, in the range of the effect of the present invention is not damaged, can contain can improve coating The organic solvent of the film thickness uniformity of polymer envelope during aligning agent for liquid crystal and surface smoothness (also referred to as poor solvent) or Compound.Can also contain can improve compound of adaptation of liquid crystal orientation film and substrate etc..

As the concrete example for the poor solvent for improving film thickness uniformity and surface smoothness, such as isopropanol, first can be enumerated Epoxide methyl anyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetic acid Ester, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol acetate, ethylene glycol list isopropyl Base ether, ethylene glycol monobutyl ether, propane diols, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, dipropyl Glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl Ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethylether, DPG list propyl group Ether, dipropylene glycol monoacetate list propyl ether, 3- methyl -3- methoxybutyls acetic acid esters, tripropylene glycol methyl ether, 3- methyl - 3- methoxybutanols, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl Ketone, methylcyclohexene, propyl ether, two hexyl ethers, n-hexane, pentane, normal octane, diethyl ether, methyl lactate, ethyl lactate, acetic acid Methyl esters, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethylether, methyl pyruvate, ethyl pyruvate, 3- methoxyl groups Methyl propionate, 3- ethoxy-propionic acids methyl ethyl ester, 3- methoxypropionates, 3- ethoxy-propionic acids, 3- methoxypropionic acids, 3- methoxies Base propyl propionate, 3- methoxy propyls acid butyl ester, 1- methoxy-2-propanols, 1- ethyoxyl -2- propyl alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propane diols -1- monomethyl ether -2- acetic acid esters, the third two Alcohol -1- list ethylether -2- acetic acid esters, DPG, 2- (2- ethoxy-cs epoxide) propyl alcohol, methyl lactate, ethyl lactate, lactic acid N-propyl, n-butyl lactate or isoamyl lactate etc. have organic solvent of low surface tension etc..

These poor solvents can use one kind, a variety of can also be used in mixed way.During using poor solvent as described above, Preferably account for 5~80 mass %, more preferably 20~60 mass % of organic solvent total amount contained in aligning agent for liquid crystal.

As the compound for improving film thickness uniformity and surface smoothness, fluorine class surfactant, type siloxane can be enumerated Surfactant, nonionic surface active agent etc..More specifically, such as エ Off トップ EF301, EF303, EF352 can be enumerated (illuminating product Co., Ltd. (トーケ system プロダクツ societies) system), メガ Off ァッ Network F171, F173, R-30 (big Japan's oil Black Co., Ltd. (big Japanese イ Application キ societies) system), Off ロラー De FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo スリーエ system society) system), アサヒガー De AG710, サー Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd (Asahi Glass society) system) etc..The use ratio of these surfactants is relative to aligning agent for liquid crystal In the mass parts of component of polymer 100 that contain, preferably 0.01~2 mass parts, more preferably 0.01~1 mass parts.

As the compound for the adaptation for improving liquid crystal orientation film and substrate, can enumerate compound containing functional silanes or Compound containing epoxy radicals, such as 3- TSL 8330s, APTES, 2- ammonia can be enumerated Base propyl trimethoxy silicane, 2- aminopropyltriethoxywerene werenes, N- (2- amino-ethyls) -3- aminopropyl trimethoxy silicon Alkane, N- (2- amino-ethyls) -3- amino propyl methyls dimethoxysilane, 3- ureido-propyl trimethoxy silanes, 3- urea groups third Ethyl triethoxy silicane alkane, N- ethoxy carbonyl -3- TSL 8330s, N- ethoxy carbonyl -3- aminopropyls three Ethoxysilane, N- triethoxysilylpropyltetrasulfides diethylenetriamine, N- trimethoxy-silylpropyl triethylenes Triamine, the azepine decane of 10- trimethoxysilyls -1,4,7- three, the azepine last of the ten Heavenly stems of 10- triethoxysilyls -1,4,7- three Alkane, 9- trimethoxysilyl -3,6- diaza nonyls acetic acid esters, 9- triethoxysilyl -3,6- diaza nonyls Acetic acid esters, N- benzyl -3- TSL 8330s, N- benzyls-APTES, N- phenyl -3- Double (the oxyethylene group) -3- aminopropyls of TSL 8330, N- phenyl-APTES, N- Trimethoxy silane, N- double (oxyethylene group)-APTES, ethylene glycol diglycidylether, poly- second two Alcohol diglycidyl ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentylglycol diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- dibromoneopentyl glycols Diglycidyl ether, 1,3,5,6- four glycidyl group -2,4- hexylene glycols, N, N, N ', N ',-four glycidyl group-meta-xylene Diamines, 1,3- double (N, N- diglycidyl amino methyl) hexamethylene, N, N, N ', N ',-four glycidyl group -4,4 '-diamino Base diphenyl methane etc..

During using these raisings and the compound of the adaptation of substrate, relative to polymer contained in aligning agent for liquid crystal into Divide 100 mass parts, its content is preferably 0.1~30 mass parts, more preferably 1~20 mass parts.If less than 0.1 mass parts, The effect that adaptation improves can not be expected, if being more than 30 mass parts, the orientation of liquid crystal is deteriorated sometimes.

In the aligning agent for liquid crystal of the present invention in addition to above-mentioned poor solvent and compound, as long as do not damaging the present invention Effect in the range of, then can add the mesh for changing the electrical characteristics such as the dielectric constant of liquid crystal orientation film, electric conductivity for reaching Dielectric and conductive materials.

The aligning agent for liquid crystal of the present invention can carry out friction treatment or light irradiation etc. and take after being coated on substrate and burning till To processing, so as to be used as liquid crystal orientation film.In addition, during for vertical orientated purposes etc., even if can also without orientation process As liquid crystal orientation film.As substrate now used, as long as the substrate that the transparency is high, is not particularly limited, except glass Outside substrate, plastic bases such as acrylic acid substrate and polycarbonate substrate etc. can also be used.It is excellent from the viewpoint of technique simplification Choosing uses the substrate formed with ITO (tin indium oxide (Indium Tin Oxide)) electrode for liquid crystal drive etc..It is in addition, anti- In emitting liquid crystal display cells, the opaque substrates such as silicon wafer can also be used, but be only limitted to the substrate of one side, electricity now Pole can also use the material of the reflected lights such as aluminium.

The coating method of aligning agent for liquid crystal is not particularly limited, industrial generally use passes through silk-screen printing, graph The method that brush, flexographic printing or ink-jet method etc. are coated.As other coating methods, there are infusion process, rolling method, slot coated Method, spin-coating method or spraying process etc., these methods can be used according to purpose.The albefaction of the above-mentioned aligning agent for liquid crystal of the present invention is coagulated Collection is inhibited, therefore standing time after it can be made even if being coated on substrate is long, uniformity and the transparency are also good Good liquid crystal orientation film.

Although drying process after aligning agent for liquid crystal is coated on substrate is not required in that, but after coating to burning till This period it is unfixed for each piece of substrate or in the case of not burning till immediately after being coated with, preferably comprising dry Drying process.As long as the drying removes solvent the degree that will not be deformed to film shape by reasons such as the transports of substrate, The drying means is not particularly limited.For example, it can enumerate in the heating plate of 40 DEG C~150 DEG C, preferably 60 DEG C~100 DEG C of temperature Dry 0.5~30 minute, the method for preferably 1~5 minute.

By being burnt till to the film that coating of liquid crystalline alignment agent is formed in aforementioned manners, liquid crystal orientation film can be made into (polymer envelope).Now, firing temperature can be 100 DEG C~350 DEG C of arbitrary temp, preferably 140 DEG C~300 DEG C, more excellent Select 150 DEG C~230 DEG C, more preferred 160 DEG C~220 DEG C.As firing time, when can be 5 minutes~240 minutes any Between.It is preferred that 10~90 minutes, more preferably 20~80 minutes.Heating can use conventional known method, such as heating plate, thermal cycle Formula stove or IR (infrared ray) types stove, band oven etc..If the thickness of the liquid crystal orientation film after burning till is blocked up, in liquid crystal display member Unfavorable in terms of the power consumption of part, if excessively thin, the reliability of liquid crystal display cells reduces sometimes, therefore preferably 5~300nm, more It is preferred that 10~100nm.Liquid crystal is set to be horizontally oriented or during tilted alignment, after being irradiated etc. by friction or polarized UV rays to burning till Liquid crystal orientation film implementation is handled.Even if in the case of irradiating implementation processing by polarized UV rays like this, use the present invention's The UV patience of liquid crystal orientation film obtained by aligning agent for liquid crystal is also excellent, therefore voltage is kept caused by polarized UV rays are irradiated The deterioration of the electrical characteristics such as rate is inhibited, and has good electrical characteristics.

The liquid crystal display cells of the present invention are to obtain band liquid crystal aligning by the aligning agent for liquid crystal of the present invention by the above method After the substrate of film, the liquid crystal display cells that form of liquid crystal cell are manufactured by known method.It is to enumerate one, then of the invention Liquid crystal display cells be the liquid crystal display cells for possessing following liquid crystal cells, the liquid crystal cell includes the two pieces of bases configured in opposite directions Plate, the liquid crystal layer that is arranged between substrate and the aligning agent for liquid crystal by the present invention that is arranged between substrate and liquid crystal layer are formed Above-mentioned liquid crystal orientation film.As such liquid crystal display cells of the invention, twisted-nematic (TN can be enumerated:Twisted Nematic) mode, vertical orientated (VA:Vertical Alignment) mode, horizontal alignment (IPS:In-Plane Switching) mode, OCB orientations (OCB:Optically Compensated Bend) etc. various liquid crystal display cells.

As the manufacture method of liquid crystal cell, following method can be illustrated：Prepare a pair formed with above-mentioned liquid crystal orientation film Substrate, sept is spread on the liquid crystal orientation film of one piece of substrate, by another piece in a manner of liquid crystal aligning film surface is in inner side Substrate is bonded, decompression injection liquid crystal and the method sealed；Or liquid crystal is added dropwise on the liquid crystal aligning film surface for being scattered with sept Afterwards, method for substrate being bonded and being sealed etc..

In addition, manufacture makes the mode responded relative to the vertical orientated liquid crystal molecule of substrate in the presence of electric field (vertically It is aligned) liquid crystal display cells in, in advance in liquid-crystal composition add photopolymerizable compound PSA (Polymer Sustained Alignment) type liquid crystal display or the addition optical polymerism in the liquid crystal orientation film (aligning agent for liquid crystal) During the SC-PVA type liquid crystal displays of compound, liquid crystal etc. can be injected simultaneously between a pair of substrates formed with above-mentioned liquid crystal orientation film After sealing, while to liquid crystal orientation film and liquid crystal applied voltages while ultraviolet is irradiated, so that polymerizable compound polymerize.I.e. Make, in the case where irradiating ultraviolet like this, to use the UV patience of liquid crystal orientation film obtained by the aligning agent for liquid crystal of the present invention It is excellent, therefore the deterioration of the electrical characteristics such as voltage retention is inhibited caused by ultraviolet irradiates, and has good electricity special Property.

As liquid crystal, the positive type liquid crystal or each with negative dielectric constant with positive dielectric constant anisotropy can be used The negative type liquid crystal of anisotropy, specifically, such as MLC-2003, MLC-6608 of usable Merck ＆ Co., Inc. (メルク societies) system, MLC-6609 etc..

As described above, liquid crystal display cells are due to excellent with ultraviolet resistance made of the aligning agent for liquid crystal of the present invention Liquid crystal orientation film, therefore even if as the liquid crystal aligning in the liquid crystal display cells used in the environment of ultraviolet The deterioration of the electrical characteristics such as film, voltage retention is also inhibited, and has good electrical characteristics, excellent in reliability.

[embodiment]

Hereinafter, enumerate embodiment and more specific description is carried out to the present invention.In addition, the present invention should not be construed as being limited to This.Abbreviation used in embodiment and comparative example is as described below.

PPHT：The N that following formula represents, N '-bis- (1,2- cyclohexane dicarboxylic acid acid anhydride -4- bases) carbonyl -1,4- phenylenediamines

PSHT：The N that following formula represents, N '-bis- (1,2- cyclohexane dicarboxylic acid acid anhydride -4- bases) carbonyl -3,3 '-diaminodiphenylsulfone

CBDA：1,2,3,4- cyclobutane tetracarboxylic dianhydrides

TDA：3,4- dicarboxyl -1,2,3,4- tetrahydrochysene -1- naphthalene succinic dianhydrides

[changing 23]

BAPU：Double (4- aminophenethyls) ureas of 1,3-

DDM：4,4 '-diaminodiphenyl-methane

DADA：N, N- diallyl -2,4- diaminourea aniline

APC16：1,3- diaminourea -4- hexadecane epoxide benzene

APC18：1,3- diaminourea -4- octadecane epoxide benzene

p-PDA：P-phenylenediamine

NMP：METHYLPYRROLIDONE

BCS：Butoxy ethanol

The assay method implemented in the present embodiment described below.

The molecular weight of polyamic acid and polyimides is to determine the polyamide by GPC (normal temperature gel permeation chromatography) device Acid or polyimides, number-average molecular weight and weight average molecular weight are calculated as polyethylene glycol, PEO scaled value.

GPC devices：Shodex (Showa Denko K. K) company system (GPC-101)

Post：Showa Denko K. K's system (KD803, KD805 series connection)

Column temperature：50℃

Eluent：N, N'- dimethylformamide are (as additive, lithium bromide-hydrate (LiBrH₂O) it is 30 mmoles That/L, phosphoric acid anhydrous crystal (o- phosphoric acid) are 30 mMs/L, tetrahydrofuran (THF) is 10mL/L)

Flow velocity：1.0ml/ minute

Calibration curve making standard specimen：(East ソー societies of TOSOH Co., Ltd) TSK standards PEO (molecule processed Amount about 900000,150000,100000,30000) and Polymer Laboratory company (Port リマーラボラトリー societies) system it is poly- Ethylene glycol (molecular weight about 12000,4000,1000).

The acid imide rate of polyimides determines as follows.

20mg polyimide powder is added to NMR probe tubes, addition deuterated dimethyl sulfoxide (DMSO-d₆, 0.05% TMS (tetramethylsilane) mixture) 0.53ml, it is completely dissolved it.For the solution, with data Co., Ltd. of JEOL The NMR analyzers (JNM-ECA500) of (Japanese Electricity データ system society) system determine 500MHz proton NMR.Acid imide rate Try to achieve as follows：The proton for coming from unconverted structure before and after imidizate is set to standard proton, uses the peak of the proton to accumulate The proton peak integrated value of score value and the NH bases from polyamic acid occurred near 9.5ppm~10.0ppm is asked by following formula .

Acid imide rate (%)=(1- α x/y) × 100

In above formula, x is the proton peak integrated value of the NH bases from polyamic acid, and y is the peak integrated value of standard proton, and α is The number ratio of the reference proton of NH matrix relative to polyamic acid during polyamic acid (acid imide rate is 0%) Example.

(synthesis example 1)

Using 1.33g PPHT as tetracarboxylic dianhydride's composition, using 0.32g p-PDA as diamine component, In 14.93g NMP, at room temperature react 18 hours, obtain polyamic acid (PAA-1) solid component concentration 10wt% it is molten Liquid.

(synthesis example 2~10)

In addition to using the composition shown in table 2, synthesis example 2~10 is obtained using the method same with above-mentioned synthesis example 1 Polyamic acid (PAA-2~PAA-10) solution.

[table 2]

(synthesis example 11)

The NMP that 12.59g is added in the solution 15.1g of the polyamic acid (PAA-1) obtained in synthesis example 1 is diluted, It is modulated into solid component concentration 6wt% polyamic acid solution.Acetic anhydride 2.95g and pyridine are added in the polyamic acid solution 1.37g, reacted 3 hours at 50 DEG C, carry out imidizate.After obtained polyimide solution is cooled into room temperature, throw Enter into 150g methanol, reclaim the solid matter of precipitation.Further, after cleaning the solid matter 2 times with methanol, subtract in 100 DEG C Press dry dry, obtain polyimides (SPI-1) khaki powder.Determine polyimides (SPI-1) acid imide rate, as a result for 79%.

(synthesis example 12~18)

In addition to using the composition shown in table 3, using the method same with above-mentioned synthesis example 11 obtain synthesis example 12~ The powder of 18 polyimides (SPI-2~SPI-8).

[table 3]

(embodiment 1)

Add 3.25g's in the solution 3.25g of the polymer (polyamic acid PAA-1) obtained in above-mentioned synthesis example 1 NMP, it is stirred at room temperature 3 hours.Polyamic acid is completely dissolved at the end of stirring.Further add 1.63g's in the solution BCS, it is stirred at room temperature 1 hour, obtains the polymer solution (A1) that solid component concentration is 4.0wt%.The polymer is molten Liquid is directly as the aligning agent for liquid crystal for forming liquid crystal orientation film.

(embodiment 2~7, comparative example 1~2)

In addition to using the composition shown in table 4, the polymerization of embodiment 2~7 is obtained using method similarly to Example 1 The polymer solution (B1~B2) of thing solution (A2~A7) and comparative example 1~2.

[table 4]

Note 1：Bottom is the weight of polymer solution used.

(embodiment 8)

7.53g NMP is added in polymer (polyimides SPI-1) 0.50g obtained in above-mentioned synthesis example 11, in room The lower stirring of temperature 3 hours.Polyimides is completely dissolved at the end of stirring.2.01g BCS is further added in the solution, in room The lower stirring of temperature 1 hour, obtains the polymer solution (A8) that solid component concentration is 5.0wt%.The polymer solution is directly made For the aligning agent for liquid crystal for forming liquid crystal orientation film.

(embodiment 9~13, comparative example 3~4)

In addition to using the composition shown in table 5, the poly- of embodiment 9~13 is obtained using method similarly to Example 8 The polymer solution (B3~B4) of polymer solution (A9~A13) and comparative example 3~4.In addition, each embodiment 9~13 also with reality It is same to apply example 8, polyimides is completely dissolved at the end of stirring.

[table 5]

[making of liquid crystal cell]

After the polymer solution (A1) obtained in embodiment 1, i.e. aligning agent for liquid crystal (A1) is filtered with 1.0 μm of filters, rotation It is applied on the glass substrate with transparency electrode, after being dried 80 seconds in 80 DEG C of heating plate, burns till 10 minutes, obtain in 230 DEG C To thickness 100nm film (polyimide film).The polyimide film is rubbed (roll neck 120mm, rotating speed with rayon cloth 1000rpm, translational speed 50mm/sec, intrusion 0.3mm) after, the ultrasonic irradiation of 1 minute is carried out in pure water, in 80 DEG C Dry 10 minutes, form liquid crystal orientation film.Prepare two pieces of substrates for carrying above-mentioned liquid crystal orientation film, taken in the liquid crystal of one piece of substrate After setting 6 μm of sept on to film surface, with the orthogonal condition of the frictional direction of two pieces of substrates by two pieces of substrate in combination, by week Sealing is enclosed, but leaves liquid crystal injecting port, the negative crystal born of the same parents that structure cell interval (cell gap) is 6 μm are made.In normal temperature in the structure cell Lower vacuum injection liquid crystal (MLC-2003 (C080), Merck Japanese firm (メ Le Network ジャパ Application society) system), seals inlet, Obtain the liquid crystal cell of 90 degree of orientations of liquid crystal torsion.

In addition, on the liquid obtained in the aligning agent for liquid crystal (A2~A13) and comparative example 1~4 that are obtained in embodiment 2~13 Brilliant alignment agent (B1~B4), liquid crystal cell is also manufactured using the same method of the aligning agent for liquid crystal (A1) with being obtained in embodiment 1.

[voltage retention (VHR) evaluation]

The evaluation of voltage retention is to apply the 4V μ s of voltage 60 at a temperature of 90 DEG C to the liquid crystal cell of gained, measure Voltage after 16.67ms, calculate voltage can keep it is how many, i.e. relative to the change of initial value, as voltage retention. In addition, the measure of voltage retention uses (East Yang テ Network ニカ societies of Toyo Corp.) system voltage retention survey Determine device VHR-1.The evaluation result (being denoted as in table 6 " initial ") is shown in table 6.

Then, 1J 365nm ultraviolet is irradiated to liquid crystal cell, the VHR after being irradiated to ultraviolet is equally evaluated. The evaluation result (being denoted as in table 6 " UV1J ") is shown in table 6.

[evaluation of pre-tilt angle]

After being heated 1 hour at 120 DEG C to the liquid crystal cell of gained, the measure of pre-tilt angle is carried out.Pre-tilt angle Axo Metrix companies " Axo Scan " using Muller matrix method determine.As a result it is shown in table 6.

[evaluation of albefaction aggegation characteristic]

Be added dropwise respectively on Cr substrates about 0.1ml embodiment 1~13 and comparative example 1~4 in obtained each liquid crystal aligning Agent (polymer solution), placed in the environment of 23 DEG C of temperature, humidity 55%.The every 10 minutes ends with the micro- sem observation drop Near portion.In addition, observation is carried out with 100 times of multiplying power.Produce time being evaluated as below 10 minutes of agglutinator ×, exceed 10 minutes and △ was evaluated as less than 1 hour, is evaluated as zero more than 1 hour and less than 3 hours, commenting more than 3 hours Valency is ◎.Evaluation result is shown in table 6.

[table 6]

As shown in table 6, it is known that using containing sub- as the polyamic acid or polyamides of raw material using the tetracarboxylic dianhydride that formula (1) represents In the case of the aligning agent for liquid crystal (polymer solution) of the embodiment 1~13 of amine, compared with comparative example 1~4, ultraviolet pre-irradiation The change of voltage retention afterwards is small, and performance degradation substantially reduces caused by ultraviolet irradiates.

In addition, understand containing the implementation using the tetracarboxylic dianhydride that formula (1) represents as the polyamic acid or polyimides of raw material The aligning agent for liquid crystal (polymer solution) of example 1~13 is also complete even if placing more than 3 hours in the evaluation of albefaction aggegation characteristic Agglutinator is not produced entirely, and there is excellent albefaction aggegation characteristic.In addition, also confirm that the aligning agent for liquid crystal of embodiment 1~13 leads to Crossing orientation process realizes the good orientation (pre-tilt angle) of liquid crystal.

Claims

1. a kind of aligning agent for liquid crystal, it is characterised in that carried out comprising the tetracarboxylic dianhydride that following formula (1) represents will be made with diamine component Polyimides and solvent obtained by polyamic acid imidizate obtained by polymerisation；

[changing 1]

The diamine component includes the diamines with the side chain for making liquid crystal vertical-tropism, and the diamines is with following formula (4), (5), (6) table Show：

[changing 2]

In formula (4) and formula (5), A₁₀Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂- ,-O- ,-CO- or-NH-, A₁₁Table Show singly-bound or phenylene, a expressions-R³-(R⁴)_l-(R⁵)_m-(R⁶)_n-R⁷, here, l, m and n separately represent 0 or 1 it is whole Number, R³Represent the alkylene ether of the alkylidene of carbon number 2~6 ,-O- ,-COO- ,-OCO- ,-NHCO- ,-CONH- or carbon number 1~3 Base, R⁴、R⁵And R⁶Separately represent phenylene or cycloalkylidene, R⁷Represent hydrogen atom, the alkyl or fluorine-containing of carbon number 2~24 Alkyl, monovalence aromatic rings, univalent aliphatic series ring, monovalence heterocycle or the big ring-type substitution body of monovalence being made up of them, a ' are represented The divalent group of the structure after a protium is removed from above-mentioned a identicals structure；

[changing 3]

In formula (6), A₁₄It is the alkyl for the carbon number 3~20 that can be replaced by fluorine atoms, A₁₅It is 1,4- cyclohexylidenes or 1,4- Asias benzene Base, A₁₆It is oxygen atom or-COO-*, here, indicates the key and A of " * "₁₅With reference to A₁₇It is oxygen atom or-COO-*, here, indicates The key of " * " and (CH₂)a₂With reference to；In addition, a₁For 0 or 1, a₂For 2~10 integer, a₃For 0 or 1.

2. a kind of liquid crystal orientation film, it is characterised in that usage right requires the aligning agent for liquid crystal described in 1 and obtained.

3. a kind of liquid crystal display cells, it is characterised in that possess the liquid crystal orientation film described in claim 2.