CN104126148B

CN104126148B - Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal display cells and compound using the liquid crystal orientation film

Info

Publication number: CN104126148B
Application number: CN201280070183.3A
Authority: CN
Inventors: 小田拓郎; 筒井皇晶
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2011-12-21
Filing date: 2012-12-18
Publication date: 2017-05-31
Anticipated expiration: 2032-12-18
Also published as: WO2013094618A1; JP6146576B2; TWI478959B; KR101986397B1; KR20140107509A; CN104126148A; JPWO2013094618A1; TW201343720A

Abstract

The present invention relates to a kind of aligning agent for liquid crystal, containing the compound represented by following formula [1] and selected from polyimide precursor and at least a kind polymer of polyimides.[changing 1](in formula [1], R₁Represent hydrogen atom or methyl, R₂Represent phenyl ring, R₃Hydrogen atom or phenyl ring are represented, X represents singly-bound or oxygen atom).

Description

Aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal using the liquid crystal orientation film Show element and compound

Technical field

The present invention relates to the liquid crystal for making the aligning agent for liquid crystal used during liquid crystal orientation film and use the inorganic agent Display element.

Background technology

At present, the liquid crystal aligning of so-called polyimide is mainly used as the liquid crystal orientation film of liquid crystal display cells Film, liquid crystal of the film by coating with the solution of the polyimide precursors such as polyamic acid or soluble polyimide as main component Aligning agent and burn till and obtain.Liquid crystal orientation film is used for the purpose of the state of orientation for controlling liquid crystal.

As the characteristic required by liquid crystal orientation film, can enumerate can control the orientation of liquid crystal, voltage retention it is excellent, because straight The mitigation of stream voltage and the electric charge accumulated is fast, the ionic weight in liquid crystal cell is few etc..In addition, in recent years, with liquid crystal display cells Maximization, increasingly require to develop the liquid crystal display cells that are resistant to long-term use.In order to be able to long-term use, it is desirable to even if Light of the long-term irradiation from back light unit or the sun light characteristic comprising ultraviolet will not also change.Therefore, increasingly require to open Send the aligning agent for liquid crystal that display characteristic will not significantly change by backlight light or ultraviolet irradiation.

On top of these properties, in the manufacture craft of liquid crystal display cells in recent years, also increasingly require to introduce to shine Ultraviolet is penetrated to make the technique (referring for example to non-patent literature 1) of liquid crystal aligning.Additionally, liquid crystal display cells in recent years make In technique, by liquid crystal drop laxative remedy (ODF) or PSA (Polymer Sustained Alignment：Polymer stabilizing is orientated) place Reason etc. has introduced the technique of irradiation ultraviolet radiation, increasingly requires to develop the material for having tolerance to ultraviolet (referring for example to non- Patent document 2).

As the sunproof means for improving liquid crystal display cells, such as carried out in liquid crystal aligning in patent document 1,2 Benzotriazole Ultraviolet Stabilizer or Benzophenones ultra-violet absorber is added in agent to extend the trial in the life-span of liquid crystal.This Outward, carried out further adding in Benzotriazole Ultraviolet Stabilizer or Benzophenones ultra-violet absorber in patent document 3 Plus antioxidant extends the trial in the life-span of liquid crystal.Additionally, reported in patent document 4 adding BTA in alignment agent Class ultra-violet absorber, Benzophenones ultra-violet absorber, dialkyldithiocarbamacompositions slaine can make internal blas electricity It is pressed in below 100mV.In addition, reporting addition benzotriazole compound or the hindered amine in alignment agent in patent document 5,6 Compound is come the method that manufactures the excellent liquid crystal panel of light resistance.

But these compounds, although have and suppress to decline because of the voltage retention (hereinafter also referred to VHR) that UV irradiations cause Effect, but have the problem that the VHR for being made the initial stage due to addition declined.Additionally, in the case where firing temperature is high, due to these Compound can distil or thermally decompose, therefore there is a problem of its decreased effectiveness.

In order to solve these problems, it is proposed that the diamines (patent document 7) with triazine skeleton.

Prior art literature

Patent document

Patent document 1：Japanese Patent Laid-Open No. Sho 56-116012 publications

Patent document 2：Japanese Patent Laid-Open No. Sho 57-84429 publications

Patent document 3：Japanese Patent Laid-Open No. Sho 57-108828 publications

Patent document 4：Japanese Patent Laid-Open 10-148835 publications

Patent document 5：Japanese Patent Laid-Open 2003-215592 publications

Patent document 6：Japanese Patent Laid-Open 2004-53685 publications

Patent document 7：Japanese Patent Laid-Open 2011-128597 publications

Non-patent literature

Non-patent literature 1：Liquid crystal brief guide, Wan Shan Co., Ltd., liquid crystal brief guide editorial board compile, page 233

Non-patent literature 2：Liquid crystal, volume 14, No. 3,2010,175 (27)

The content of the invention

The technical problems to be solved by the invention

But, in the case of using the diamines of patent document 7, although the VHR after UV irradiations is uprised, but with triazine bone The diamines of frame is poor with the reactivity of acid dianhydride, it is impossible to increase import volume.In the case of a large amount of importings, although VHR reductions are suppressed, But HMW body cannot be obtained, the problem for producing rub to be deteriorated.

It is good it is an object of the invention to provide a kind of rub and light resistance is high, can form voltage in view of above-mentioned condition The aligning agent for liquid crystal of conservation rate liquid crystal orientation film high, liquid crystal orientation film and liquid crystal display cells and noval chemical compound.

Solve the technical scheme that technical problem is used

It is that the present inventor is conscientiously studied to achieve these goals as a result, find with the addition of containing triazine skeleton and The aligning agent for liquid crystal of the noval chemical compound (hereinafter also referred to as special additive) of polymeric matrix can realize above-mentioned purpose, So as to complete the present invention.That is, the present invention has following technology contents.

1. a kind of aligning agent for liquid crystal, it is characterised in that containing the compound represented by following formula [1] and selected from polyamides At least a kind polymer of imines precursor and polyimides.

[changing 1]

(in formula [1], R₁Represent hydrogen atom or methyl, R₂Represent phenyl ring, R₃Represent hydrogen atom or phenyl ring, X represent singly-bound or Oxygen atom.)

2. the aligning agent for liquid crystal as described in 1, it is characterised in that relative to the polymer of 100 mass parts, contain Compound represented by the formula [1] of 0.1~10 mass parts.

3. the aligning agent for liquid crystal as described in 1 or 2, it is characterised in that the polymer has double bond in its structure.

4. the aligning agent for liquid crystal as any one of 1~3, it is characterised in that the polymer is selected from polyamides Imines precursor and at least a kind by polyimides obtained by its imidizate, the polyimide precursor is by containing being selected from down The reaction of the diamine component and tetracarboxylic dianhydride's composition of the diamine compound of formula and obtain.

[changing 2]

(in formula, n is 1 to 20 integer, R₄It is hydrogen atom or methyl.)

5. a kind of liquid crystal orientation film, it is characterised in that aligning agent for liquid crystal as any one of 1~4 and obtain.

6. a kind of liquid crystal display cells, it is characterised in that possess the liquid crystal orientation film described in 5.

7. a kind of compound, it is characterised in that represented with following formula [1].

[changing 3]

8. the compound as described in 7, it is characterised in that any one with following formula is represented.

[changing 4]

Invention effect

If using the present invention, it is possible to provide can obtain that rub is good and high to the patience of light, voltage retention (VHR) The aligning agent for liquid crystal of liquid crystal orientation film high.Additionally, spy contained in the aligning agent for liquid crystal provided in the present invention Additive is determined for noval chemical compound.

Specific embodiment

Hereinafter, the present invention is described in detail.

Aligning agent for liquid crystal of the invention is containing special additive and selected from polyimide precursor and polyimides At least a kind inorganic agent of polymer.

Contained special additive is the compound represented by following formula [1] in aligning agent for liquid crystal of the invention.

[changing 5]

R₂Or R₃Phenyl ring, i.e. R₂Phenylene or R₃Phenyl, have the distillation of the special additive for suppressing film when burning till And the effect decomposed.Additionally, acrylic or methylpropenyl, due to the mutual reaction of special additive when film burns till, or With the polymer reaction of polyimide precursor or polyimides etc., therefore be have suppress specific compound distillation and decomposition effect The group of fruit.

Special additive is selected from polyimide precursor to the addition in aligning agent for liquid crystal relative to 100 mass parts With at least a kind total amount of polymer of polyimides, more preferably preferably 0.1~10 mass parts, 1~5 mass parts.Here, although Common additive can bring harmful effect in aligning agent for liquid crystal with addition to liquid crystal aligning, but of the invention specific add Plus agent is as described in the following examples, even if in aligning agent for liquid crystal also liquid crystal aligning will not deteriorate for addition.

Special additive is not particularly limited to the adding method in aligning agent for liquid crystal, can be to aligning agent for liquid crystal In be directly added into special additive, stirring dissolves it, or adds in advance the specific of 0.5wt%~10wt% or so Plus agent is dissolved in organic solvent, then by solution addition aligning agent for liquid crystal.

The synthetic method of special additive can be synthesized by the way that the technology in Synthetic Organic Chemistry is combined, without spy Do not limit.Can for example be synthesized with following methods.

Represented by formula [1] and linking group X is the special additive of singly-bound, can be by synthetic schemes described as follows (A) Shown, compound (i) and 2-hydroxyethyl methacrylate or acrylic acid 2- hydroxy methacrylates are reacted to synthesize.

[changing 6]

The compound represented by formula (i) in synthetic schemes (A), can make trimerization by synthetic schemes (B) as described below Grignard reagent represented by chlorine cyanogen and formula (ii) is reacted to synthesize.

[changing 7]

Additionally, represented by formula [1] and linking group X is the special additive of oxygen atom, can be by synthesis described as follows Shown in scheme (C), compound is synthesized with Cyanuric Chloride in 2-hydroxyethyl methacrylate or acrylic acid 2- hydroxy methacrylates (iii) after, synthesize with compound (iv) reaction.

[changing 8]

The raw material that the synthetic schemes of above-mentioned synthetic schemes (A)~(C) is used, can use commercially available chemical combination as needed Thing, it is also possible to which synthesis in addition is used.

In aligning agent for liquid crystal of the invention contained polyimide precursor refer to polyamic acid (Ployamic acid, Also referred to as Polyamide acid) and poly amic acid ester.Polyimide precursor is anti-by diamine component and tetracarboxylic dianhydride's composition Answer and obtain.Specifically, polyamic acid is to be reacted to obtain by diamine component and tetracarboxylic dianhydride.Poly amic acid ester is by diamines Composition is reacted or by tetracarboxylic acid acid diesters and diamine component in appropriate contracting in the presence of a base with tetracarboxylic acid acid diesters diacid chloride Carry out reacting acquisition in the presence of mixture, alkali.The polyimides contained in aligning agent for liquid crystal of the invention can be by making The polyamic acid be dehydrated so that its closed loop or poly amic acid ester is heated so that its closed loop obtain.As being used for The polymer of liquid crystal orientation film is obtained, any one in the polyamic acid, poly amic acid ester and polyimides is useful.

The diamine component for using is not particularly limited.It is as follows if enumerating its specific example.

As the example of alicyclic diamine class, can enumerate Isosorbide-5-Nitrae-DACH, 1,3- DACHs, 4,4 '- Diamino-dicyclohexyl methane, 4,4 '-diaminourea -3,3 '-dimethyidicyclohexyl amine, IPD etc..

As the example of aromatic diamines, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 2,4- diaminourea first can be enumerated Benzene, 2,5- diaminotoluenes, 3,5- diaminotoluenes, 1,4- diaminourea -2- methoxybenzenes, 2,5- diaminourea paraxylene, 1, 3- diaminourea -4- chlorobenzenes, 3,5- diaminobenzoic acids, 1,4- diaminourea -2,5- dichloro-benzenes, 4,4 '-diaminostilbene, 2- diphenyl Ethane, 4,4 '-diaminourea -2,2 '-dimethyl bibenzyl, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diaminourea -3,3 '-dimethyl diphenylmethane, 2,2 '-diaminourea Stilbene, 4,4 '-two Amino Stilbene, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diamino diphenyl sulfide, 4,4 '-two Double (3- amino-benzene oxygens) benzene of ADP base sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diaminobenzophenone, 1,3-, Double (4- amino-benzene oxygens) benzene of 1,3-, double (4- amino-benzene oxygens) benzene of 1,4-, 3,5- double (4- amino-benzene oxygens) benzoic acid, 4, Double [(4- amino-benzene oxygens) methyl] propane of 4 '-bis- (4- amino-benzene oxygens) bibenzyls, 2,2-, double [4- (the 4- aminobenzene oxygen of 2,2- Base) phenyl] HFC-236fa, double [4- (4- amino-benzene oxygens) phenyl] propane of 2,2-, double [4- (3- amino-benzene oxygens) phenyl] sulfones, Double [4- (4- amino-benzene oxygens) phenyl] sulfones, 1,1- couple of (4- aminophenyls) hexamethylene, α, α '-bis- (4- aminophenyls) -1,4- Double (4- aminophenyls) fluorenes of diisopropyl benzene, 9,9-, double (3- aminophenyls) HFC-236fas of 2,2-, 2,2- are double (4- aminophenyls) HFC-236fa, 4,4 '-diamino-diphenyl amine, 2,4- diamino-diphenyls amine, 1,8- diaminonaphthalenes, 1,5- diaminonaphthalenes, 1, Double (the 4- ammonia of 5- diamino-anthraquinones, 1,3- diaminourea pyrene, 1,6- diaminourea pyrene, 1,8- diaminourea pyrene, 2,7 diamin of luorene, 1,3- Base phenyl) tetramethyl disiloxane, benzidine, 2,2 '-dimethylbenzidine, double (4- aminophenyls) ethane of 1,2-, 1,3- be double Double (4- aminophenyls) butane of (4- aminophenyls) propane, 1,4-, double (4- aminophenyls) pentanes of 1,5-, double (the 4- amino of 1,6- Phenyl) hexane, double (4- aminophenyls) heptane of 1,7-, double (4- aminophenyls) octanes of 1,8-, double (4- aminophenyls) nonyls of 1,9- Double (4- amino-benzene oxygens) propane of double (4- aminophenyls) decane of alkane, 1,10-, 1,3-, double (4- amino-benzene oxygens) butane of 1,4-, Double (4- amino-benzene oxygens) pentanes of 1,5-, double (4- amino-benzene oxygens) hexanes of 1,6-, 1,7- double (4- amino-benzene oxygens) heptane, 1, Double (4- amino-benzene oxygens) octanes of 8-, double (4- amino-benzene oxygens) nonanes of 1,9-, 1,10- double (4- amino-benzene oxygens) decane, two (4- aminophenyls) 1,3- malonates, two (4- aminophenyls) 1,4- succinates, two (4- aminophenyls) 1,5- glutaric acids Ester, two (4- aminophenyls) 1,6- adipate esters, two (4- aminophenyls) 1,7- pimelates, two (4- aminophenyls) 1,8- are pungent Double [4- (the 4- ammonia of two acid esters, two (4- aminophenyls) 1,9- azelates, two (4- aminophenyls) 1,10- sebacates, 1,3- Phenoxyl) phenoxy group] propane, double [4- (4- amino-benzene oxygens) phenoxy group] butane of 1,4-, double [4- (the 4- aminobenzene oxygen of 1,5- Base) phenoxy group] pentane, double [4- (4- amino-benzene oxygens) phenoxy group] hexanes of 1,6-, double [4- (4- amino-benzene oxygens) the benzene oxygen of 1,7- Base] heptane, double [4- (4- amino-benzene oxygens) phenoxy group] octanes of 1,8-, double [4- (4- amino-benzene oxygens) phenoxy group] nonyls of 1,9- Double [4- (4- amino-benzene oxygens) phenoxy group] decane of alkane, 1,10- etc..

As the example of aromatic-aliphatic diamines, 3- aminobenzenes methyl amine, 4- aminobenzenes methyl amine, 3- ammonia can be enumerated Base-N- methylbenzylamines, 4- Amino-N-methyl benzyls amine, 3- aminophenethyls amine, 4- aminophenethyls amine, 3- amino- N- methylphenethylamines, 4- Amino-N-methyl phenethyls amine, 3- (3- aminopropyls) aniline, 4- (3- aminopropyls) aniline, 3- (3- dimethylaminopropyls) aniline, 4- (3- dimethylaminopropyls) aniline, 3- (4- aminobutyls) aniline, 4- (4- aminobutyls) Aniline, 3- (4- methylaminos butyl) aniline, 4- (4- methylaminos butyl) aniline, 3- (5- Aminopentyls) aniline, 4- (5- ammonia Base amyl group) aniline, 3- (5- methylamino-pentyls) aniline, 4- (5- methylamino-pentyls) aniline, 2- (6- amino naphthyl) methyl Amine, 3- (6- amino naphthyl) methyl amine, 2- (6- amino naphthyl) ethylamine, 3- (6- amino naphthyl) ethylamine etc..

As the example of hetero ring type Diamines, DAP, 2,4- diamino-pyridines, 2,4- diaminos can be enumerated Base -1,3,5- triazines, 2,7 diaminodibenz of uran, 3,6- diaminocarbazoles, 2,4- diaminourea -6- isopropyls -1,3,5- Double (4- the aminophenyls) -1,3,4- of triazine, 2,5-Diazole etc..

As the example of aliphatic diamine class, EDA, 1,3- diaminopropanes, Isosorbide-5-Nitrae-diaminourea can be enumerated Butane, 1,5- 1,5-DAPs, 1,6- diamino hexanes, 1,7- diaminoheptanes, 1,8- diamino-octanes, 1,9- diaminourea nonyls Alkane, 1,10- diamino decanes, 1,3- diaminourea -2,2- dimethylpropanes, 1,6- diaminourea -2,5- dimethylhexanes, 1,7- bis- Amino -2,5- dimethyl heptanes, 1,7- diaminourea -4,4- dimethyl heptanes, 1,7- diaminourea -3- methyl heptanes, 1,9- diaminos Double (3- amino propoxyl group) ethane of base -5- methyl heptanes, 1,12- diamino dodecanes, 1,18- diaminourea octadecane, 1,2- etc..

If importing double bond in the polymer contained in aligning agent for liquid crystal of the invention, by special when burning till The double bond position determined in additive and polymer is reacted, and the effect for suppressing distillation and the decomposition of special additive is further carried Height, by the cross-linking reaction between polymer, the rub of liquid crystal orientation film is also improved, thus preferably.

Method as double bond is imported in the polymer contained in aligning agent for liquid crystal of the invention, can enumerate and use The method of the diamine compound or tetracarboxylic dianhydride of double bond is imported.Wherein, from the simplicity of synthesis, work is preferably used The diamine compound of double bond has been imported in side chain for diamine component.As the specific example of such diamine compound, can example Show diamine compound as described below.

[changing 9]

(in formula, n is 1 to 20 integer, R₃It is hydrogen atom or methyl.)

As the preferred content of such diamine compound, 1~60wt% of preferably whole diamine components, more preferably 5~ 50wt%, further preferred 10~40wt%.

Additionally, as diamine component can also and with side chain have alkyl, containing fluoroalkyl, aromatic rings, aliphatic ring, The diamine compound of heterocycle and the big ring-type substituent being made up of them.Specifically, can illustrate with following formula [DA-1]~formula Diamines shown in [DA-26].

[changing 10]

(in formula [DA-1]~formula [DA-5], R₆For the alkyl of charcoal prime number 1~22 or containing fluoroalkyl.)

[changing 11]

(in formula [DA6]~formula [DA9], S₅Represent-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂- ,-O- ,-CO- or- NH-, R₆Represent the alkyl of carbon number 1~22 or containing fluoroalkyl.)

[changing 12]

(in formula [DA-10] and formula [DA-11], S₆Represent-O- ,-OCH₂-、-CH₂O-、-COOCH₂- or-CH₂OCO-, R₇ For the alkyl of carbon number 1~22, alkoxy, containing fluoroalkyl or fluoroalkoxy.)

[changing 13]

(in formula [DA-12]~formula [DA-14], S₇Represent-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、- CH₂OCO-、-CH₂O-、-OCH₂- or-CH₂-, R₈For the alkyl of carbon number 1~22, alkoxy, containing fluoroalkyl or fluoroalkoxy.)

[changing 14]

(in formula [DA15] and formula [DA16], S₈Represent-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、- CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂- ,-O- or-NH-, R₉It is fluorine-based, cyano group, trifluoromethyl, nitro, azo group, formyl Base, acetyl group, acetoxyl group or hydroxyl.)

[changing 15]

[changing 16]

(in formula [DA-17]~formula [DA-20], R₁₀It is the alkyl of carbon number 3~12, the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene It is respectively trans.)

[changing 17]

[changing 18]

[changing 19]

Additionally, as diamine component, also can simultaneously with following diamines.

[changing 20]

(in formula [DA-30], m is 0~3 integer；In formula [DA-33], n is 1~5 integer.)

The voltage retention (also referred to as VHR) of liquid crystal display cells, [DA- are can further improve by importing [DA-27] 28]~[DA-33] is reduced the effect of the accumulated charge of liquid crystal display cells, thus preferably.

In addition, as diamine component, it is also possible to enumerate with diamino radical siloxane shown in following formula [DA-34] etc..

[changing 21]

(in formula [DA-34], m is 1~10 integer.)

These diamine components can according to as liquid crystal orientation film when liquid crystal aligning, voltage retention performance, accumulation electricity The characteristics such as lotus, are used in mixed way using a kind or by two or more.

In order to obtain contained polyamic acid in aligning agent for liquid crystal of the invention, for being reacted with diamine component Tetracarboxylic dianhydride is not particularly limited.Its specific example is enumerated below.

As the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure, 1,2,3,4- cyclobutane tetrabasic carboxylic acids can be enumerated Dianhydride, 1,2- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2,3,4- tetramethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 2,3,4,5- tetrahydrochysenes Furans tetracarboxylic dianhydride, 1,2,4,5- cyclopentanetetracarboxylics dianhydride, 3,4- dicarboxyl -1- cyclohexyl ambers acid dianhydride, 3,4- bis- Carboxyl -1,2,3,4- tetrahydrochysene -1- naphthalene succinics dianhydride, 1,2,3,4- butane tetracarboxylics acid dianhydride, two rings [3,3,0] octane -2,4, 6,8- tetracarboxylic dianhydrides, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride, cis- 3, 7- dibutyl ring octyl- 1,5- diene -1,2,5,6- tetracarboxylic dianhydrides, three ring [4.2.1.0^2,5] nonane -3,4,7,8- tetrabasic carboxylic acids - 3,4:7,8- dianhydrides, six ring [6.6.0.1^2,7.0^3,6.1^9,14.0^10,13] hexadecane -4,5,11,12- tetrabasic carboxylic acids -4,5:11,12- Dianhydride, 4- (2,5- dioxotetrahydro furans -3- bases) -1,2,3,4-tetralin -1,2- dicarboxylic anhydrides etc..

Further, if also using aromatic series four outside the above-mentioned tetracarboxylic dianhydride with alicyclic structure or aliphatic structure Carboxylic acid dianhydride, then liquid crystal aligning is improved, and can reduce the accumulated charge of liquid crystal cell, thus preferably.As aromatic series four Carboxylic acid dianhydride, can enumerate pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid two Acid anhydride, 2,3,3 ', 4- biphenyl tetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4- benzophenone tetrabasic carboxylic acid two Acid anhydride, double (3,4- dicarboxyphenyis) ether dianhydrides, double (3,4- dicarboxyphenyis) sulfone dianhydrides, 1,2,5,6- naphthalene tetracarboxylic acids dianhydride, 2, 3,6,7- naphthalene tetracarboxylic acid dianhydrides etc..

Tetracarboxylic dianhydride can be according to liquid crystal aligning, voltage retentivity, the accumulated charge etc. when forming liquid crystal orientation film Characteristic, using a kind or and uses two or more.

For in order to obtain contained poly amic acid ester in aligning agent for liquid crystal of the invention and anti-with diamine component The tetracarboxylic acid acid dialkyl ester answered is not particularly limited.Its specific example is enumerated below.

As the specific example of aliphatic tetracarboxylic acid acid diesters, 1,2,3,4- cyclobutane tetracarboxylic acid acid dialkyl esters, 1 can be enumerated, 2- dimethyl -1,2,3,4- cyclobutane tetracarboxylic acids acid dialkyl ester, 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic acid acid dialkyls Ester, 1,2,3,4- tetramethyl -1,2,3,4- cyclobutane tetracarboxylic acids acid dialkyl ester, 1,2,3,4- pentamethylene tetracarboxylic acids acid dialkyl ester, 2,3,4,5- tetrahydrofuran tetracarboxylic acids acid dialkyl ester, 1,2,4,5- cyclopentanetetracarboxylics dialkyl ester, 3,4- dicarboxyl -1- hexamethylenes Base dialkyl succinate, 3,4- dicarboxyl -1,2,3,4- tetrahydrochysene -1- naphthalene succinics dialkyl ester, 1,2,3,4- butane tetracarboxylics Acid dialkyl ester, two rings [3,3,0] octane -2,4,6,8- tetracarboxylic acids acid dialkyl ester, 3,3 ', 4,4 ' dicyclohexyl tetrabasic carboxylic acid dioxanes Base ester, 2,3,5- tricarboxylic cyclopentyls dialkyl acetates, cis- 3,7- dibutyl ring octyl- 1,5- diene -1,2,5,6- tetrabasic carboxylic acids Dialkyl ester, three ring [4.2.1.0^2,5] nonane -3,4,7,8- tetrabasic carboxylic acids -3,4:7,8- dialkyl esters, six ring [6.6.0.1^2, ⁷.0^3,6.1^9,14.0^10,13] hexadecane -4,5,11,12- tetrabasic carboxylic acids -4,5:11,12- dialkyl esters, 4- (2,5- dioxotetrahydros Furans -3- bases) -1,2,3,4-tetralin -1,2- dicarboxylic acid dialkyl esters etc..

As aromatic tetracarboxylic acid's dialkyl ester, Pyromellitic Acid dialkyl ester, 3,3 ', 4,4 '-biphenyl tetracarboxylic acid can be enumerated Acid dialkyl ester, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid dialkyl ester, 2,3,3 ', 4- biphenyltetracarboxyacid acids dialkyl ester, 3,3 ', 4, 4 '-benzophenone tetracarboxylic acid acid dialkyl ester, 2,3,3 ', 4- benzophenone tetracarboxylic acids acid dialkyl ester, double (3,4- dicarboxyphenyis) ethers two Arrcostab, double (3,4- dicarboxyphenyis) sulfone dialkyl esters, 1,2,5,6- naphthalene tetracarboxylic acids dialkyl ester, 2,3,6,7- naphthalene tetracarboxylic acids Dialkyl ester etc..

It is contained in reaction acquisition aligning agent for liquid crystal of the invention by tetracarboxylic dianhydride and diamine component to gather During amic acid, can be using known synthetic method.Tetracarboxylic dianhydride and diamine component is typically set to react in organic solvent Method.The reaction of tetracarboxylic dianhydride and diamine component is easier to carry out in organic solvent, and do not generate accessory substance this It is favourable on a bit.

As the organic solvent for tetracarboxylic dianhydride and the reaction of diamines, as long as can dissolve the polyamic acid of generation Solvent is not particularly limited.Its specific example is enumerated below.

N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N- ethyl -2- pyrroles can be enumerated Pyrrolidone, N- methyl caprolactams, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolacton, isopropyl Alcohol, methoxy amylalcohol, cinene, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl are different Propyl group ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, second Base carbitol, ethylene glycol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propane diols, propane diols Monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, DPGME, diethylene glycol, diethylene glycol list second Acid esters, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, DPG list second Base ether, dipropylene glycol monoacetate list ethylether, DPG list propyl ether, dipropylene glycol monoacetate list propyl ether, 3- first Base -3- methoxybutyls acetic acid esters, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanols, diisopropyl ether, ethyl isobutyl base Ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, DIBK, methylcyclohexene, propyl ether, two hexyl ethers, twoAlkane, N-hexane, normal heptane, normal octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, second Sour methyl esters, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethylether, methyl pyruvate, ethyl pyruvate, 3- methoxies Base methyl propionate, 3- ethoxy-propionic acids methyl ethyl ester, 3- methoxypropionates, 3- ethoxy-propionic acids, 3- methoxypropionic acids, 3- first Epoxide propyl propionate, 3- methoxy propyls acid butyl ester, diethylene glycol dimethyl ether, 4- hydroxy-4-methyl-2-pentanones, 3- methoxyl groups-N, N- Dimethylpropionamide, 3- ethyoxyls-N, N- dimethylpropionamide, 3- butoxy-N, N- dimethylpropionamide etc..These solvents can To be used alone, but also also mix together.Even additionally, the solvent of insoluble polyamic acid, as long as in the polyamides of generation In the range of amino acid will not be separated out, it is also possible to be used in mixed way with above-mentioned solvent.

Additionally, the moisture in organic solvent hinders polymerisation, and can hydrolyze the polyamic acid of generation, thus it is organic Solvent preferably uses the organic solvent after dehydrating as far as possible.

When tetracarboxylic dianhydride and diamine component is reacted in organic solvent, following methods can be enumerated：Stirring make diamines into Be dispersed or dissolved in solution obtained by organic solvent, then directly addition tetracarboxylic dianhydride or make tetracarboxylic dianhydride disperse or It is dissolved in the method added again after organic solvent；On the contrary tetracarboxylic dianhydride is dispersed or dissolved in it is molten obtained by organic solvent The method that diamine component is added in liquid；Alternately add method of tetracarboxylic dianhydride and diamine component etc., it is also possible to using therein Any one method.In addition, when tetracarboxylic dianhydride or diamine component are made up of multiple compounds, can be in the state of being pre-mixed React it, it is also possible to it is reacted successively respectively, then low-molecular weight hybrid reaction obtained by making to react respectively and obtain height Molecular weight body.

Polymerization temperature now can select -20 DEG C~150 DEG C of arbitrary temp, preferably -5 DEG C~100 DEG C of scope. Though additionally, reaction can be carried out with arbitrary concentration, but if concentration is too low, it is difficult to obtain the polymer of HMW, if dense Spending the viscosity of then reaction solution high becomes too high and is difficult to uniform stirring, therefore tetracarboxylic dianhydride and diamine component are anti- Answer total concentration preferably 1~50 mass %, more preferably 5~30 mass % in solution.Initial reaction stage is carried out in higher concentrations, afterwards Organic solvent can be added.

In the polymerisation of polyamic acid, the ratio between the total mole number of tetracarboxylic dianhydride and the total mole number of diamine component are preferably 0.8~1.2.Identical with common polycondensation reaction, the mol ratio is closer to 1.0, and the molecular weight of the polyamic acid of generation is bigger.

Contained polyimides is to make above-mentioned polyamic acid dehydration closed-loop and obtain in aligning agent for liquid crystal of the invention Polyimides, be useful as obtaining the polymer of liquid crystal orientation film.In addition, aligning agent for liquid crystal of the invention In the polyimides that contains can be dissolved in the solvent contained in aligning agent for liquid crystal, i.e. be sub- solvent soluble polyamides Amine.

In aligning agent for liquid crystal of the invention in contained polyimides, (acyl is sub- for the dehydration closed-loop rate of acid amides acidic group Amination rate) do not need one to be set to 100%, can arbitrarily be adjusted according to purposes or purpose.

Method as polyamic acid imidizate is made, can enumerate the hot acid imide of the solution for directly heating polyamic acid Change, in the solution of polyamic acid add catalyst catalysis imidizate.

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

The catalysis imidizate of polyamic acid can by polyamic acid solution add base catalyst and acid anhydrides, At -20~250 DEG C, stirred preferably at 0~180 DEG C and carried out.The amount of base catalyst is 0.5~30 mole of acid amides acidic group Times, preferably 2~20 moles times, the amount of acid anhydrides is 1~50 mole times of acid amides acidic group, preferably 3~30 moles times.Urged as alkalescence Agent, can enumerate pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc., and wherein pyridine has for carrying out reaction The alkalescence of appropriateness, thus preferably.As acid anhydrides, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc. can be enumerated, wherein using It is easy to carry out reacting the purifying after terminating during acetic anhydride, thus preferably.Acid imide rate using catalysis imidizate can lead to Cross adjustment catalytic amount and reaction temperature, reaction time control.

As the synthetic method of poly amic acid ester, can be obtained by tetracarboxylic acid acid diesters diacid chloride and diamine reactant, also can be by four Carboxylic acid diesters and diamines react in the presence of appropriate condensing agent and alkali and obtain as the polyamide of one of polyimide precursor Acid esters.Or, it is also possible to prior polymeric polyamide acid, obtain the carboxylic esterification in amic acid using high molecular weight reactive.

Specifically, can by making tetracarboxylic acid acid diesters diacid chloride and diamines in the presence of alkali and organic solvent, in -20~ 150 DEG C, preferably 0~50 DEG C are reacted 30 minutes~24 hours, preferably 1~4 hour to synthesize.

The alkali can be used pyridine, triethylamine, 4-dimethylaminopyridine etc., in order that reaction gently carries out preferred pyrrole Pyridine.From for the easy amount for removing and being readily available from the viewpoint of HMW body, the addition of alkali is relative to tetracarboxylic acid acid diesters two Acyl chlorides is preferably 2~4 times moles.

When polycondensation reaction is carried out in the presence of condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1- can be used Ethyl -3- (3- dimethylamino-propyls) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy -1,3,5- triazine methyl Morpholine, O- (BTA -1- bases)-N, N, N ', N '-tetramethylurea (TMU) tetrafluoro boric acid ester, O- (BTA -1- bases)-N, N, N ', N '-tetramethylurea (TMU) hexafluorophosphoric acid ester, the (thio -3- benzos of 2,3- dihydros -2-Azoles) phosphonic acid diphenyl ester, 4- (4,6- dimethoxy -1, 3,5- triazine -2- bases) 4- methoxyl group morpholine hydrochloride n hydrates etc..

Additionally, in the method using above-mentioned condensing agent, additive is used as by adding lewis acid, reaction can be efficiently Carry out.As lewis acid, the preferably lithium halide such as lithium chloride, lithium bromide.Lewis acidic addition relative to above-mentioned condensing agent, It is preferred that 0.1~1.0 times of mole.

As the solvent used in above-mentioned reaction, can be used what is used during with the polymeric polyamide acid shown above-mentioned Solvent, considers, preferably METHYLPYRROLIDONE, gamma-butyrolacton from the dissolubility of monomer and polymer, can be by them 1 kind or two or more is used in mixed way.From the precipitation for being not susceptible to polymer and it is readily available the viewpoint of HMW body and examines Consider, concentration preferably 1~30 mass %, more preferably 5~20 mass % during synthesis.Additionally, in order to prevent the acyl of tetracarboxylic acid acid diesters two Chlorine water solution, the solvent for the synthesis of poly amic acid ester is dehydrated as far as possible, preferably in nitrogen atmosphere, prevents foreign gas It is mixed into.

Polyamic acid, the polyamide of generation are being reclaimed from polyamic acid, poly amic acid ester, the reaction solution of polyimides In the case of acid esters, polyimides, reaction solution is preferably put into poor solvent and it is precipitated.As for precipitation Poor solvent, can enumerate methyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, first Benzene, benzene, water etc..The polymer put into poor solvent and precipitated can be after being recovered by filtration, under normal or reduced pressure It is dried in normal temperature or heating.If additionally, the polymer for repeating to reclaim 2~10 times precipitation be re-dissolved in it is organic The operation that solvent and reprecipitation are reclaimed, then can reduce the impurity in polymer.As poor solvent now, for example, can enumerate Alcohols, ketone, hydrocarbon etc., if using the poor solvent of more than 3 kinds selected from these solvents, because purification efficiency is further carried It is high and it is preferred that.

The molecular weight of contained polyimide precursor or polyimides in aligning agent for liquid crystal of the invention, is considering In the case of operability, the uniformity of film when being formed to thus obtained painting film strength and film, using GPC (Gel Permeation Chromatography；Gel permeation chromatography) method determine weight average molecular weight be preferably 5000~1000000, More preferably 10000~150000.

Aligning agent for liquid crystal of the invention is the coating fluid for forming liquid crystal orientation film, and being will be above-mentioned sub- selected from polyamides At least one polymer and special additive of amine precursor and polyimides are dissolved in solution obtained by organic solvent.It is of the invention Solid component concentration in aligning agent for liquid crystal can suitably be changed according to the setting of the liquid crystal aligning film thickness to be formed, preferably 0.5~10 mass %, more preferably 1~8 mass %.Solid component concentration is then difficult to be formed uniform and do not had less than 0.5 mass % The film of defect, the storage stability of solution is deteriorated sometimes if more than 10 mass %.Solid constituent mentioned here be from The composition after solvent is removed in aligning agent for liquid crystal, refers to above-mentioned selected from polyimide precursor and at least one of polyimides Polymer, special additive and above-mentioned various additives.

There is no particular limitation for the manufacture method of aligning agent for liquid crystal of the invention.Generally by by above-mentioned polyamic acid The solution of solution, the solution of above-mentioned soluble polyimide or the solution of soluble polyimide and polyamic acid carry out Mix to manufacture.In the case of polyamic acid, the polyamic acid reaction solution of polycondensation acquisition can be used directly, or In the case of obtaining polyamic acid, it can again be dissolved in organic solvent, be used as polyamic acid solution.Polyamide Acid solution is used after being diluted to required concentration.

On the other hand, in the case of for soluble polyimide, soluble poly obtained by imidizate can be used directly Imide reaction solution, or in the case where polyimide powder has been obtained, it can be again dissolved in organic solvent It is middle to be used as polyimide solution.Polyimide solution is used after being diluted to required concentration.

As long as the organic solvent contained in aligning agent for liquid crystal of the invention can dissolve above-mentioned polymer and formula [1] institute The organic solvent of the compound of expression, is not particularly limited.Its concrete example is enumerated below.

N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N- methyl can be enumerated in oneself Acid amides, 2-Pyrrolidone, N- ethyl pyrrolidones, NVP, dimethyl sulfoxide, tetramethylurea, pyridine, diformazan Sulfone, pregnancy sulfoxide, gamma-butyrolacton, 3- methoxyl groups-N, N- dimethylpropionamide, 3- ethyoxyls-N, N- dimethylpropionamide, 3- Butoxy-N, N- dimethylpropionamide, 1,3- dimethyl-2-imidazolidinones, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, Methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4- hydroxyls -4- Methyl -2 pentanone etc..These solvents can be used alone, it is also possible to be used in mixed way.

Aligning agent for liquid crystal of the invention can contain composition other than the above.As its specific example, painting is improved The solvent or compound of film thickness uniformity or surface smoothness during cloth aligning agent for liquid crystal, raising liquid crystal orientation film and substrate The compound of adaptation etc..

As the concrete example of the solvent (poor solvent) of the uniformity or surface smoothness for improving thickness, following thing can be enumerated Matter.

For example, isopropanol, methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, first can be enumerated Base cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, second two Alcohol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propane diols, Propylene glycol monoacetate, the third two Alcohol monomethyl ether, propylene glycol t-butyl ether, DPGME, diethylene glycol, diethylene glycol monoacetate, diethylene glycol Dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, DPG list Acetic acid esters list ethylether, DPG list propyl 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, acetic acid Pentyl ester, butyl butyrate, butyl ether, DIBK, methylcyclohexene, propyl ether, two hexyl ethers, 1- hexanols, n-hexane, pentane, just Octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethyl Ether, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionates, 3- ethoxy-propionic acid Methylethyls ester, 3- methoxypropionic acids Ethyl ester, 3- ethoxy-propionic acids, 3- methoxypropionic acids, 3- methoxy propyls propyl propionate, 3- methoxy propyls acid butyl ester, 1- methoxyl groups -2- Propyl alcohol, 1- ethyoxyl -2- propyl alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propane diols two Acetic acid esters, propane diols -1- monomethyl ether -2- acetic acid esters, propane diols -1- list ethylether -2- acetic acid esters, DPG, 2- (2- second Epoxide propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate or isoamyl lactate etc. have low table Solvent of face tension force etc..

These poor solvents can use a kind, or be used in mixed way various.In the situation using solvent as described above Under, 5~80 mass % of the solvent total amount for preferably containing in aligning agent for liquid crystal, more preferably 20~60 mass %.

As the compound for improving film thickness uniformity or surface smoothness, fluorine class surfactant, type siloxane can be enumerated Surfactant, nonionic surface active agent etc..

More specifically, エ Off トップ EF301, EF303, EF352 (Tuo Kaimu products Co., Ltd. (トー can for example be enumerated ケ system プロダクツ societies) system), メガ Off ァッ Network F171, F173, R-30 ((big Japan of Dainippon Ink and Chemicals, Inc 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 strain formula meeting Society (Asahi Glass society) makes) etc..The use ratio of these surfactants is relative to the polymer included in aligning agent for liquid crystal 100 mass parts, preferably 0.01~2 mass parts, more preferably 0.01~1 mass parts.

As the concrete example of the compound of the adaptation for improving liquid crystal orientation film and substrate, can enumerate as shown below containing official Compound, the compound containing epoxy radicals of energy property silane etc..

For example, 3- TSL 8330s, APTES, 2- aminopropyls three can be enumerated Methoxy silane, 2- aminopropyltriethoxywerene werenes, N- (2- amino-ethyls) -3- TSL 8330s, N- (2- Amino-ethyl) -3- amino propyl methyls dimethoxysilane, 3- ureido-propyl trimethoxy silanes, the ethoxy of 3- ureido-propyls three Base silane, N- ethoxy carbonyl -3- TSL 8330s, N- ethoxy carbonyl -3- aminopropyl triethoxysilicanes Alkane, N- triethoxysilylpropyltetrasulfides diethylenetriamine, N- trimethoxy-silylpropyls diethylenetriamine, 10- The azepine decane of trimethoxysilyl -1,4,7- three, the azepine decane of 10- triethoxysilyls -1,4,7- three, 9- front threes Epoxide silicyl -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- aminopropyls three Double (the oxyethylene group) -3- aminopropyl trimethoxy silicon of methoxy silane, N- phenyl-APTES, N- Double (the oxyethylene group)-APTESs of alkane, N-, ethylene glycol diglycidylether, polyethylene glycol diglycidyl are sweet Oily ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol two Glycidol ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- dibromoneopentyl glycol 2-glycidyls Ether, 1,3,5,6- four glycidyl group -2,4- hexylene glycols, N, N, N ', N ',-four glycidyl group-m-xylene diamine, 1,3- Double (N, N- diglycidyl amino methyl) hexamethylenes, N, N, N ', N ',-four glycidyl group -4,4 '-diamino-diphenyl Methane etc..

Aligning agent for liquid crystal of the invention, filters preferably before substrate is coated, and coats on substrate afterwards, according to need After being dried, film is can be made into by burning till, the orientation process such as the rubbed treatment of the film coated surface or illumination, as this hair Bright liquid crystal orientation film is used.

At this moment, as long as the substrate transparency used substrate high, limits, it is possible to use glass base without special Plastic bases such as plate, acrylic acid substrate or polycarbonate substrate etc., from the angle for simplifying production technology, preferably use shape Into the substrate of ITO (tin indium oxide (Indium Tin Oxide)) electrode having for liquid crystal drive etc..In addition, reflective liquid crystal In display element, it is possible to use the opaque substrate such as silicon wafer, but unilateral substrate is only limitted to, electrode now can also make With reflectorized materials such as aluminium.

As the coating method of aligning agent for liquid crystal, spin-coating method, print process, ink-jet method etc. can be enumerated, but from productivity From the aspect of, industrial circle widely uses flexographic printing process, and the method can be also suitably used for aligning agent for liquid crystal of the invention.

Although drying process after coating of liquid crystalline aligning agent be not required in that, but after coating to before burning till In the case that this period is not fixed and do not burnt till immediately after being coated with for each piece of substrate, drying is preferably comprised Operation.The drying can evaporate solvent under the degree that film shape will not deform by carrying of substrate etc., to drying means There is no particular limitation.If enumerating concrete example, having makes it be dried in 50~150 DEG C, preferably 80~120 DEG C of heating plate 0.5~30 minute, the method for preferably 1~5 minute.

Being coated with burning till for the substrate of aligning agent for liquid crystal can be carried out under the arbitrary temp in 100~350 DEG C, but It is preferred that 150~300 DEG C, more preferably 180 DEG C~250 DEG C.The polyamic acid contained in aligning agent for liquid crystal due to this burn till from And amic acid is varied to the conversion ratio that acid imide is converted, but polyamic acid is without 100% imidizate.Wherein, preferably with More than 10 DEG C higher than the heat treatment temperature of necessary sealant cures etc. in liquid crystal cell manufacturing engineering of temperature is burnt till.

It is unfavorable in terms of the power consumption of liquid crystal display cells if the thickness of the film after burning till is blocked up；If excessively thin, Sometimes the reliability reduction of liquid crystal display cells, therefore preferably 10~200nm, more preferably 50~100nm.

The friction treatment of the coated surface being formed on substrate as described above can use existing rubbing device.Rubbing at this moment The material of wiper can enumerate cotton, artificial silk, nylon etc..Because the liquid crystal formed using aligning agent for liquid crystal of the invention is taken Rub to film is good, and the generation or the stripping of film scratched in the friction treatment are all difficult to produce.

Liquid crystal display cells of the invention are to obtain band liquid crystal by aligning agent for liquid crystal of the invention by the above method After the substrate of alignment films, the liquid crystal display cells for liquid crystal cell being manufactured by known method and being formed.

If of manufacture liquid crystal cell is enumerated, typically using following method：The one of liquid crystal orientation film will be formed with To substrate folder across preferably 1~30 μm, more preferably 2~10 μm of sept, according to making frictional direction into appointing in 0~270 ° The requirement of angle of anticipating is set, with sealant that periphery is fixed, is sealed after injection liquid crystal.To enclosing the method for liquid crystal without special Limitation, can enumerate what is sealed after vacuum method, the liquid crystal that drips of injection liquid crystal after being depressurized in obtained liquid crystal cell Method of dripping etc..

The liquid crystal aligning of so obtained liquid crystal display cells is good, further, since the rub of liquid crystal orientation film Well, it is difficult to produce the display of the stripping of the scuffing or film of the liquid crystal orientation film occurred during with friction treatment bad.Then, by It is high to the patience of light in liquid crystal orientation film, alleviate and shone with the ultraviolet of backlight illumination, the exposure of sunshine or manufacturing process The decline of the electrical characteristics penetrated, further, since voltage retention is high, can be used as reliability liquid crystal display device high.

Embodiment

The present invention will be described in more detail for embodiment shown below, but the present invention is not limited by this.

The synthesis example of special additive in the present invention is shown.Each assay method and analytical equipment for using are as described below.

Compound is dissolved in deuterochloroform, uses 400MHz's¹H NMR (Varian Associates, Inc. (US) 611 Hansen Way, Palo Alto, California 94303, U.S.A., バリア Application society, Varian, Inc) it is measured.

The synthesis of (synthesis example 1) special additive (M1)

Cyanuric Chloride 15.0g, 2-hydroxyethyl methacrylate 12.7g, tetrahydrofuran are added in 500mL four-hole boiling flasks 150g, ice bath cooling.At 0 DEG C of temperature, sodium hydride 3.9g is added, be stirred at room temperature 3 hours.Further add 4- phenyl benzene Phenol 12.5g, NaOH 2.9g, tetrahydrofuran 23g, the aqueous solution of water 30g.Afterwards, 15wt% aqueous ammonium chloride solutions are added, is used Ethyl acetate is extracted.Anhydrous magnesium sulfate is added in organic layer, after filtering, solvent is evaporated off with rotary evaporator.Will be residual Slag is purified by recrystallization, obtains white solid 21.7g.The result for determining the white solid with NMR is as follows.By this Results verification, the white solid for obtaining is the midbody compound represented by following formula (L1).

¹H-NMR(400MHz,CDCl₃)：δ7.67-7.55(m,4H),7.47-7.33(m,3H),7.27-7.21(m,2H), 6.14-6.09(m,1H),5.62-5.57(m,1H),4.68-4.62(m,2H),4.48-4.44(m,2H),1.96-1.90(m, 3H)

[changing 22]

In 500mL four-hole boiling flasks, midbody compound (L1) 21.4g, acetone 170g are added, backflow is lower to be added dropwise 4- phenyl Phenol 9.3g, NaOH 2.2g, acetone 43g, the aqueous solution of water 43g.Then, 15wt% aqueous ammonium chloride solutions, filtering are added The crystallization of generation, is purified by recrystallization, obtains white solid.The result for determining the white solid with NMR is as follows. By the results verification, the white solid for obtaining is the compound represented by following formula (M1).

¹H-NMR(400MHz,CDCl₃)：δ7.62-7.52(m,8H),7.46-7.39(m,4H),7.39―7.33(m, 2H),7.26-7.21(m,4H),6.13-6.10(m,1H),5.62-5.56(m,1H),4.65-4.58(m,2H),4.48-4.42 (m,2H),1.95-1.92(m,3H)

[changing 23]

The synthesis of (synthesis example 2) special additive (M2)

Cyanuric Chloride 15.0g, 2-hydroxyethyl methacrylate 12.7g, tetrahydrofuran are added in 500mL four-hole boiling flasks 150g, ice bath cooling.At 0 degree of temperature, sodium hydride 3.9g is added, be stirred at room temperature 3 hours.Further add phenol 14.9g, The aqueous solution of NaOH 6.3g, water 60g, is heated to temperature 50 C, stirs 2 hours.Afterwards, room temperature is cooled to, is added 15wt% aqueous ammonium chloride solutions, are extracted with ethyl acetate.Anhydrous magnesium sulfate is added in organic layer, after filtering, rotary evaporation is used Device is evaporated off to solvent.Residue silica gel column chromatography is purified, white solid 20.5g is obtained.It is solid the white to be determined with NMR The result of body is as follows.By the results verification, the white solid for obtaining is the compound represented by following formula (M2).

¹H-NMR(400MHz,CDCl₃)：δ7.43-7.34(m,4H),7.28-7.22(m,2H),7.19―7.12(m, 4H),6.14-6.08(m,1H),5.60-5.55(m,1H),4.58-4.52(m,2H),4.42-4.37(m,2H),1.94-1.90 (m,3H)

[changing 24]

The synthesis of (synthesis example 3) special additive (M3)

In 1L four-hole boiling flasks, Cyanuric Chloride 38.5g, tetrahydrofuran 385g, ice bath cooling are added.At 0 degree of temperature, it is added dropwise The tetrahydrofuran solution 240mL of 2 moles/L phenyl-magnesium-chlorides, is stirred at room temperature 15 hours.1 equivalent is added in reaction solution Hydrochloric acid 300mL, makes to be extracted with ethyl acetate.Saturated sodium bicarbonate aqueous solution is added in organic layer, organic layer is extracted.Organic Anhydrous magnesium sulfate is added in layer, after filtering, solvent is evaporated off with rotary evaporator.Residue is pure with silica gel column chromatography Change, obtain the midbody compound 42.8g represented by (L2).

[changing 25]

By in midbody compound (L2) 10.0g addition 300mL four-hole boiling flasks, tetrahydrofuran 100g is added simultaneously to dissolve.Will Solution is cooled to 0 DEG C of temperature, adds sodium hydride 1.8g, is added dropwise 2-hydroxyethyl methacrylate 5.3g's and tetrahydrofuran 80g Solution, stirs 30 minutes.15wt% aqueous ammonium chloride solutions are added in reaction solution, is extracted with ethyl acetate.Add in organic layer Enter anhydrous magnesium sulfate, after filtering, solvent is evaporated off with rotary evaporator.Residue silica gel column chromatography is purified, is obtained White solid 9.7g.The result for determining the white solid with NMR is as follows.By the results verification, the white solid for obtaining is Compound represented by following formula (M3).

¹H-NMR(400MHz,CDCl₃)：δ8.66-8.61(m,4H),7.64-7.50(m,6H),6.15-6.12(m,1H), 5.57-5.53(m,1H),4.94-4.89(m,2H),4.66-4.61(m,2H),1.94-1.90(m,3H)

[changing 26]

The synthesis example of polymer and polymer solution is shown.The explanation of the abbreviation for using, each assay method for using and point Analysis apparatus are as described below.

The explanation of the abbreviation for using

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

PMDA：Pyromellitic acid anhydride

TCA：2,3,5- tricarboxylic cyclopentyls acetic acid -1,4:2,3- dianhydrides

p-PDA：P-phenylenediamine

DDM：4,4 '-diaminodiphenyl-methane

2,4-DAA：2,4- diamino-Ns, N- diallylamines

4-ABA：4- amino-benzylamines

C12DAB：4- dodecyloxy -1,3- diaminobenzenes

DTT：2,4- diaminourea -6- phenyl -1,3,5- triazines

DABEMA：3,5- diaminourea ethyl benzoate methacrylates

NMP：METHYLPYRROLIDONE

γ-BL：Gamma-butyrolacton

BS：Butyl cellosolve

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

GPC devices：Showa Denko K. K ((strain) Shodex societies) makes (GPC-101)

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

Column temperature：50℃

Eluent：DMF is (as additive, lithium bromide-hydrate (LiBrH₂O) it is 30 mmoles That/L, phosphoric anhydride crystallization (o- phosphoric acid) are 30 mMs/L, tetrahydrofuran (THF) is 10ml/L)

Flow velocity：1.0mL/ minutes

Calibration curve making standard sample：(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 is poly- Ethylene glycol (molecular weight about 12000,4000,1000).

The acid imide rate of polyimides is calculated as follows：The polyimides is dissolved in d6-DMSO (dimethyl sulfoxide-d6), Determine 400MHz's¹H NMR (Varian Associates, Inc. (US) 611 Hansen Way, Palo Alto, California 94303, U.S.A. (バリア Application society, Varian, Inc)), are tried to achieve by the ratio of the integrated value of proton peak The ratio of non-imidizate and the acid amides acidic group of remaining, so as to calculate acid imide rate.

(synthesis example 4) polymer solution P-1

γ-the BL of NMP, 222g of DDM, 222g of 39.6g are added in 500ml four-hole boiling flasks and is dissolved, add 19.6g CBDA, 19.2g PMDA.In a nitrogen atmosphere, react 5 hours at room temperature, prepare the solution of polyamic acid.The polyamide The number-average molecular weight of acid is 10900, and weight average molecular weight is 27300.Add 450g's in the polyamic acid solution 400g for obtaining The BS of γ-BL, 150g, is stirred at room temperature 2 hours, obtains polymer solution P-1.

(synthesis example 5) polymer solution P-2

C12DAB, 813g of 4-ABA, 43.9g of 2,4-DAA, 18.4g of 40.6g are added in the removable flask of 1L NMP and dissolve, add 67.7g CBDA, 32.7g PMDA.In a nitrogen atmosphere, react 22 hours at room temperature, prepare The solution of polyamic acid.

In the solution 192g of the polyamic acid for obtaining, add the NMP of 345g to be diluted, add the acetic anhydride of 28.4g With the pyridine of 12.1g, reaction carries out imidizate in 3 hours at 50 DEG C.After the reaction solution is cooled into room temperature, input Into 2000ml methyl alcohol, the solid matter of precipitation is reclaimed.Then, after the solid matter is cleaned for several times with methyl alcohol, at 100 DEG C Drying under reduced pressure, obtains white powder (polyimides).The number-average molecular weight of the polyimides is 12500, and weight average molecular weight is 34100.Additionally, acid imide rate is 90%.

Then, the gained white powder of 6g is stirred 24 in the γ-BL, the mixed solution of the BS of 20g of 74g at 50 DEG C Hour simultaneously dissolves, and obtains the polymer solution P-2 that polymer concentration is 6wt%.

(synthesis example 6) polymer solution P-3

The NMP of DABEMA, 410g of p-PDA, 10.6g of 17.3g is added in 500ml four-hole boiling flasks and is dissolved, added The TCA of 44.4g.In a nitrogen atmosphere, react 24 hours at room temperature, prepare the solution of polyamic acid.The number of the polyamic acid Average molecular weight is 11500, and weight average molecular weight is 32200.In the solution 400g of the polyamic acid for obtaining add 400g NMP, The BS of 200g, is stirred at room temperature 2 hours, obtains polymer solution P-3.

[evaluation of special additive]

Determine special additive (M1)~(M3's) of synthesis using Shimadzu Seisakusho Ltd. (SHIMADZU societies) UV3100PC processed Molar absorption coefficient.

(embodiment 1)

(M1) 4.14mg manufactured in synthesis example 1 is dissolved in Wako Pure Chemical Industries, Ltd. (and light Pure medicines industry society) In optical voidness chloroform processed, it is diluted using measuring bottle, prepares 0.0000152mmol/cm³Solution.Determine the solution of preparation Molar absorption coefficient, is 0cm under 400nm²It is 0cm under/mmol, 375nm²It is 0cm under/mmol, 350nm²Under/mmol, 325nm It is 0cm²It is 145cm under/mmol, 300nm²It is 16130cm under/mmol, 275nm²It is 38006cm under/mmol, 250nm²/ It is 11814cm under mmol, 225nm²It is 119349cm under/mmol, 200nm²/mmol.From the data, special additive (M1) ultraviolet that wavelength is longer than 325nm is hardly picked up.

(embodiment 2)

(M2) 4.65mg manufactured in synthesis example 2 is dissolved in Wako Pure Chemical Industries, Ltd.'s optical voidness chloroform, It is diluted using measuring bottle, prepares 0.0000152mmol/cm³Solution.The molar absorption coefficient of the solution for preparing is determined, It is 0cm under 400nm²It is 0cm under/mmol, 375nm²It is 0cm under/mmol, 350nm²It is 0cm under/mmol, 325nm²/ mmol, It is 0cm under 300nm²It is 0cm under/mmol, 275nm²It is 1760cm under/mmol, 250nm²It is 10376cm under/mmol, 225nm²/ It is 57202cm under mmol, 200nm²/mmol.From the data, special additive (M2) hardly picks up wavelength and is longer than The ultraviolet of 275nm.

(embodiment 3)

(M3) 4.95mg manufactured in synthesis example 3 is dissolved in Wako Pure Chemical Industries, Ltd.'s optical voidness chloroform, It is diluted using measuring bottle, prepares 0.0000273mmol/cm³Solution.The molar absorption coefficient of the solution for preparing is determined, It is 0cm under 400nm²It is 0cm under/mmol, 375nm²It is 0cm under/mmol, 350nm²It is 238cm under/mmol, 325nm²/ mmol, It is 7220cm under 300nm²It is 29850cm under/mmol, 275nm²It is 23890cm under/mmol, 250nm²It is under/mmol, 225nm 12425cm²It is 65761cm under/mmol, 200nm²/mmol.From the data, special additive (M3) hardly picks up wavelength It is longer than the ultraviolet of 350nm.

(embodiment 4)

In polymer solution P-1, relative to the polymer of the polymer solution P-1 of 100 mass parts, synthesis example 1 is added (M1) of middle manufacture reaches 2 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Taken using the liquid crystal To inorganic agent, liquid crystal cell is made as follows, the liquid crystal cell of the liquid crystal aligning for obtaining showing good.In addition, with Visually observe liquid crystal aligning.For the VHR at the initial stage of the liquid crystal cell, when determining the VHR after UV irradiations, and without formula [1] The aligning agent for liquid crystal (comparative example 1) of represented compound (special additive) is compared, and the VHR at initial stage is high, additionally, understanding VHR after to UV irradiations is high, and light resistance is high.In addition in the substrate with liquid crystal orientation film after observing friction, it is not observed Friction abrasive dust or frictionally damage.Result is shown in table 1.

[table 1]

Aligning agent for liquid crystal is spun on the glass substrate with transparency electrode, is dried 70 seconds in 80 DEG C of heating plate Afterwards, carry out burning till for 10 minutes in 250 DEG C of heating plate, form the film that thickness is 100nm.With the friction of roll neck 120mm Device is under conditions of roller rotating speed 1000rpm, roller gait of march 50mm/ seconds, intrusion 0.3mm with rayon cloth to the coated surface Rubbed, obtained the substrate with liquid crystal orientation film.Prepare 2 substrates with liquid crystal orientation film, a piece of liquid crystal takes wherein To spreading 6 μm of sept on face, then printing and sealing agent thereon makes liquid crystal aligning face relative and frictional direction hangs down After another plate base is fitted under conditions of straight, make sealant cures, sylphon has been obtained.By the injection method that depressurizes in the sylphon Injection liquid crystal MLC-2003 (C080) (Merck ＆ Co., Inc. (メルク societies) system), seals inlet, obtains twisted nematic liquid crystals box.

On by twisted nematic liquid crystals box obtained in the above method, the voltage 60 that 4V is applied at a temperature of 23 DEG C is micro- Second, determine 16.67 milliseconds after voltage, be possible to keep voltage number as initial voltage conservation rate.Additionally, voltage is protected The measure of holdup use (East Yang テ Network ニカ societies of Toyo Corp.) system VHR-1 voltage retentions determine dress Put.

Will be above-mentioned<The making of liquid crystal cell>Described in the Twisted Nematic liquid crystal box that is made of method, use SEN special light sources The desk-top UV solidification equipments HCT3B28HEX-1 of company (セ Application special light sources Co., Ltd.) system carries out the light irradiation of 83 seconds.Now Illumination using illumination photometer (CRC companies (CRC societies) UV Light MEASUREMODEL UV-M02 processed) and UV-35 sensors survey Fixed, as a result illumination is 60.0mW/cm²。

To using above-mentioned<UV irradiates>Method treatment twisted nematic liquid crystal box at a temperature of 23 DEG C, apply 4V electricity Press 60 microseconds, determine the voltage after 16.67 milliseconds, the voltage for being possible to keep number irradiated as UV after voltage keep Rate.Additionally, the measure of voltage retention determines device using the VHR-1 voltage retentions of Toyo Corp..

[evaluation of rub resistance]

Above-mentioned<The making of liquid crystal cell>In obtain the substrate with liquid crystal orientation film stage in, it is aobvious with confocal laser Micro mirror and naked eyes are observed the surface of liquid crystal orientation film, are evaluated with following benchmark.Result is shown in table 1.

○：With the naked eye and with laser microscope friction abrasive dust or frictionally damage are not all observed.

△：Friction abrasive dust or frictionally damage is with the naked eye not observed, but friction abrasive dust is observed with laser microscope Or frictionally damage.

×：Film has stripping or with the naked eye and with laser microscope all observed friction abrasive dust or frictionally damage.

(embodiment 5)

In polymer solution P-1, relative to the polymer of the polymer solution P-1 of 100 mass parts, synthesis example 1 is added (M1) of middle manufacture reaches 5 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Taken using the liquid crystal To inorganic agent, liquid crystal cell is made according to method same as Example 4, the liquid crystal of the liquid crystal aligning for obtaining showing good Box.It is purple with without the compound represented by formula [1] when determining the VHR after UV irradiations for the VHR at the initial stage of the liquid crystal cell The aligning agent for liquid crystal (comparative example 1) of ultraviolet absorbers is compared, and the VHR at initial stage is high, moreover, it is understood that the VHR after UV irradiations Height, light resistance is high.In addition in the substrate with liquid crystal orientation film after observing friction, friction abrasive dust is not observed or friction is damaged Wound.Result is shown in table 1.

(embodiment 6)

In polymer solution P-1, relative to the polymer of the polymer solution P-1 of 100 mass parts, synthesis example 1 is added (M1) of middle manufacture reaches 10 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Use the liquid crystal Aligning agent, liquid crystal cell is made according to method same as Example 4, the liquid crystal of the liquid crystal aligning for obtaining showing good Box.For the VHR at the initial stage of the liquid crystal cell, when determining the VHR after UV irradiations, and without the compound represented by formula [1] Aligning agent for liquid crystal (comparative example 1) is compared, and the VHR at initial stage is high, moreover, it is understood that the VHR after UV irradiations is high, light resistance is high. In addition in the substrate with liquid crystal orientation film after observing friction, friction abrasive dust or frictionally damage is not observed.Result is shown in Table 1.

(embodiment 7)

In polymer solution P-1, relative to the polymer of the polymer solution P-1 of 100 mass parts, synthesis example 2 is added (M2) of middle manufacture reaches 2 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Taken using the liquid crystal To inorganic agent, liquid crystal cell is made according to method same as Example 4, the liquid crystal of the liquid crystal aligning for obtaining showing good Box.For the VHR at the initial stage of the liquid crystal cell, when determining the VHR after UV irradiations, and without the compound represented by formula [1] Aligning agent for liquid crystal (comparative example 1) is compared, and the VHR at initial stage is high, moreover, it is understood that the VHR after UV irradiations is high, light resistance is high. In addition in the substrate with liquid crystal orientation film after observing friction, friction abrasive dust or frictionally damage is not observed.Result is shown in Table 1.

(embodiment 8)

In polymer solution P-1, relative to the polymer of the polymer solution P-1 of 100 mass parts, synthesis example 2 is added (M2) of middle manufacture reaches 5 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Taken using the liquid crystal To inorganic agent, liquid crystal cell is made according to method same as Example 4, the liquid crystal of the liquid crystal aligning for obtaining showing good Box.For the VHR at the initial stage of the liquid crystal cell, when determining the VHR after UV irradiations, and without the compound represented by formula [1] Aligning agent for liquid crystal (comparative example 1) is compared, and the VHR at initial stage is high, moreover, it is understood that the VHR after UV irradiations is high, light resistance is high. In addition in the substrate with liquid crystal orientation film after observing friction, friction abrasive dust or frictionally damage is not observed.Result is shown in Table 1.

(embodiment 9)

In polymer solution P-1, relative to the polymer of the polymer solution P-1 of 100 mass parts, synthesis example 2 is added (M2) of middle manufacture reaches 10 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Use the liquid crystal Aligning agent, liquid crystal cell is made according to method same as Example 4, the liquid crystal of the liquid crystal aligning for obtaining showing good Box.For the VHR at the initial stage of the liquid crystal cell, when determining the VHR after UV irradiations, and without the compound represented by formula [1] Aligning agent for liquid crystal (comparative example 1) is compared, and the VHR at initial stage is high, moreover, it is understood that the VHR after UV irradiations is high, light resistance is high. In addition in the substrate with liquid crystal orientation film after observing friction, friction abrasive dust or frictionally damage is not observed.Result is shown in Table 1.

(embodiment 10)

In polymer solution P-1, relative to the polymer of the polymer solution P-1 of 100 mass parts, synthesis example 3 is added (M3) of middle manufacture reaches 2 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Taken using the liquid crystal To inorganic agent, liquid crystal cell is made according to method same as Example 4, the liquid crystal of the liquid crystal aligning for obtaining showing good Box.For the VHR at the initial stage of the liquid crystal cell, when determining the VHR after UV irradiations, and without the compound represented by formula [1] Aligning agent for liquid crystal (comparative example 1) is compared, and the VHR at initial stage is high, moreover, it is understood that the VHR after UV irradiations is high, light resistance is high. In addition in the substrate with liquid crystal orientation film after observing friction, friction abrasive dust or frictionally damage is not observed.Result is shown in Table 1.

(embodiment 11)

In polymer solution P-1, relative to the polymer of the polymer solution P-1 of 100 mass parts, synthesis example 3 is added (M3) of middle manufacture reaches 5 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Taken using the liquid crystal To inorganic agent, liquid crystal cell is made according to method same as Example 4, the liquid crystal of the liquid crystal aligning for obtaining showing good Box.For the VHR at the initial stage of the liquid crystal cell, when determining the VHR after UV irradiations, and without the compound represented by formula [1] Aligning agent for liquid crystal (comparative example 1) is compared, and the VHR at initial stage is high, moreover, it is understood that the VHR after UV irradiations is high, light resistance is high. In addition in the substrate with liquid crystal orientation film after observing friction, friction abrasive dust or frictionally damage is not observed.Result is shown in Table 1.

(embodiment 12)

In polymer solution P-1, relative to the polymer of the polymer solution P-1 of 100 mass parts, synthesis example 3 is added (M3) of middle manufacture reaches 10 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Use the liquid crystal Aligning agent, liquid crystal cell is made according to method same as Example 4, the liquid crystal of the liquid crystal aligning for obtaining showing good Box.For the VHR at the initial stage of the liquid crystal cell, when determining the VHR after UV irradiations, and without the compound represented by formula [1] Aligning agent for liquid crystal (comparative example 1) is compared, and the VHR at initial stage is high, moreover, it is understood that the VHR after UV irradiations is high, light resistance is high. In addition in the substrate with liquid crystal orientation film after observing friction, friction abrasive dust or frictionally damage is not observed.Result is shown in Table 1.

(embodiment 13)

In polymer solution P-2, relative to the polymer of the polymer solution P-2 of 100 mass parts, synthesis example 1 is added (M1) of middle manufacture reaches 2 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Taken using the liquid crystal To inorganic agent, liquid crystal cell is made according to method same as Example 4, the liquid crystal of the liquid crystal aligning for obtaining showing good Box.For the VHR at the initial stage of the liquid crystal cell, when determining the VHR after UV irradiations, and without the compound represented by formula [1] Aligning agent for liquid crystal (comparative example 1) is compared, and the VHR at initial stage is high, moreover, it is understood that the VHR after UV irradiations is high, light resistance is high. In addition in the substrate with liquid crystal orientation film after observing friction, friction abrasive dust or frictionally damage is not observed.Result is shown in Table 1.

(embodiment 14)

In polymer solution P-2, relative to the polymer of the polymer solution P-2 of 100 mass parts, synthesis example 2 is added (M2) of middle manufacture reaches 2 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Taken using the liquid crystal To inorganic agent, liquid crystal cell is made according to method same as Example 4, the liquid crystal of the liquid crystal aligning for obtaining showing good Box.For the VHR at the initial stage of the liquid crystal cell, when determining the VHR after UV irradiations, and without the compound represented by formula [1] Aligning agent for liquid crystal (comparative example 1) is compared, and the VHR at initial stage is high, moreover, it is understood that the VHR after UV irradiations is high, light resistance is high. In addition in the substrate with liquid crystal orientation film after observing friction, friction abrasive dust or frictionally damage is not observed.Result is shown in Table 1.

(embodiment 15)

In polymer solution P-2, relative to the polymer of the polymer solution P-2 of 100 mass parts, synthesis example 3 is added (M3) of middle manufacture reaches 2 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Taken using the liquid crystal To inorganic agent, liquid crystal cell is made according to method same as Example 4, the liquid crystal of the liquid crystal aligning for obtaining showing good Box.For the VHR at the initial stage of the liquid crystal cell, when determining the VHR after UV irradiations, and without the compound represented by formula [1] Aligning agent for liquid crystal (comparative example 1) is compared, and the VHR at initial stage is high, moreover, it is understood that the VHR after UV irradiations is high, light resistance is high. In addition in the substrate with liquid crystal orientation film after observing friction, friction abrasive dust or frictionally damage is not observed.Result is shown in Table 1.

(embodiment 16)

In polymer solution P-3, relative to the polymer of the polymer solution P-3 of 100 mass parts, synthesis example 1 is added (M1) of middle manufacture reaches 1 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Taken using the liquid crystal To inorganic agent, liquid crystal cell is made according to method same as Example 4, the liquid crystal of the liquid crystal aligning for obtaining showing good Box.For the VHR at the initial stage of the liquid crystal cell, when determining the VHR after UV irradiations, and without the compound represented by formula [1] Aligning agent for liquid crystal (comparative example 1) is compared, and the VHR at initial stage is high, moreover, it is understood that the VHR after UV irradiations is high, light resistance is high. In addition in the substrate with liquid crystal orientation film after observing friction, friction abrasive dust or frictionally damage is not observed.Result is shown in Table 1.

(embodiment 17)

In polymer solution P-3, relative to the polymer of the polymer solution P-3 of 100 mass parts, synthesis example 3 is added (M2) of middle manufacture reaches 1 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Taken using the liquid crystal To inorganic agent, liquid crystal cell is made according to method same as Example 4, the liquid crystal of the liquid crystal aligning for obtaining showing good Box.For the VHR at the initial stage of the liquid crystal cell, when determining the VHR after UV irradiations, and without the compound represented by formula [1] Aligning agent for liquid crystal (comparative example 1) is compared, and the VHR at initial stage is high, moreover, it is understood that the VHR after UV irradiations is high, light resistance is high. In addition in the substrate with liquid crystal orientation film after observing friction, friction abrasive dust or frictionally damage is not observed.Result is shown in Table 1.

(embodiment 18)

In polymer solution P-3, relative to the polymer of the polymer solution P-3 of 100 mass parts, synthesis example 3 is added (M3) of middle manufacture reaches 1 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Taken using the liquid crystal To inorganic agent, liquid crystal cell is made according to method same as Example 4, the liquid crystal of the liquid crystal aligning for obtaining showing good Box.For the VHR at the initial stage of the liquid crystal cell, when determining the VHR after UV irradiations, and without the compound represented by formula [1] Aligning agent for liquid crystal (comparative example 1) is compared, and the VHR at initial stage is high, moreover, it is understood that the VHR after UV irradiations is high, light resistance is high. In addition in the substrate with liquid crystal orientation film after observing friction, friction abrasive dust or frictionally damage is not observed.Result is shown in Table 1.

(comparative example 1)

Replace aligning agent for liquid crystal using polymer solution P-1, according to method same as Example 4 to rub resistance Property, VHR, UV irradiation after VHR evaluated.Result is shown in table 1.The substrate with liquid crystal orientation film after to friction is seen Examine, observed damage, friction abrasive dust.Additionally, the series of VHR and the compound represented by the formula that with the addition of [1] after UV irradiations It is in a ratio of relatively low level.

(comparative example 2)

In polymer solution P-1, relative to the polymer of the polymer solution P-1 of 100 mass parts, adding has triazine The compound benzoguanamine of skeleton reaches 5 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Use The aligning agent for liquid crystal, evaluates the VHR after rub resistance, VHR, UV irradiation according to method same as Example 4. Result is shown in table 1.It is visible compared with comparative example 1 to have an improvement, but with contain the compound represented by formula of the invention [1] Aligning agent for liquid crystal compare, observed friction abrasive dust, the VHR after UV irradiations is low, and UV patience is low.

(comparative example 3)

In polymer solution P-1, relative to the polymer of the polymer solution P-1 of 100 mass parts, north of the city chemistry is added Industrial Co., Ltd (north of the city chemical industry society) Benzotriazole Ultraviolet Stabilizer JF-83 processed, makes adding for ultra-violet absorber Dosage reaches 5 mass parts, is stirred at room temperature 1 hour, obtains aligning agent for liquid crystal.Using the aligning agent for liquid crystal, press VHR after rub resistance, VHR, UV irradiation is evaluated according to method same as Example 4.Result is shown in table 1.It was observed that Friction abrasive dust, the VHR after initial stage VHR, UV irradiation is low.

The possibility utilized in industry

Aligning agent for liquid crystal of the invention is good due to rub and light resistance, the TN to carrying out friction treatment (Twisted Nematic, twisted nematic) element, STN (Super-twisted nematic display, super twisted nematic Type) element, TFT (Thin Film Transistor, thin film transistor (TFT)) liquid crystal cell, the liquid crystal cell (IPS of lateral electric-field type (In-Plane Switching, plane conversion), FFS (Fringe Field Switching, fringe field conversion) etc.) have With.Light resistance is additionally, since well, for forming the liquid crystal display cells of the vertical orientating type for not carrying out friction treatment or making Liquid crystal orientation film in liquid crystal display cells with light orientation etc. is also useful.

Claims

1. a kind of aligning agent for liquid crystal, it is characterised in that containing the compound represented by following formula [1] and selected from polyimides At least a kind polymer of precursor and polyimides；

In formula [1], R₁Represent hydrogen atom or methyl, R₂Represent phenyl ring, R₃Hydrogen atom or phenyl ring are represented, X represents that singly-bound or oxygen are former Son.

2. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that relative to the polymer of 100 mass parts, Compound represented by formula [1] containing 0.1~10 mass parts.

3. aligning agent for liquid crystal as claimed in claim 1 or 2, it is characterised in that the polymer has in its structure Unsaturated double-bond.

4. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that the polymer is selected from polyimide precursor With by least a kind of polyimides obtained by its imidizate, the polyimide precursor is by containing the diamines selected from following formula The reaction of the diamine component and tetracarboxylic dianhydride's composition of compound and obtain；

In formula, n is 1 to 20 integer, R₄It is hydrogen atom or methyl.

5. a kind of liquid crystal orientation film, it is characterised in that aligning agent for liquid crystal as any one of Claims 1 to 4 and .

6. a kind of liquid crystal display cells, it is characterised in that possess the liquid crystal orientation film described in claim 5.

7. a kind of compound, it is characterised in that represented with following formula [1]；

In formula [1], R₁Represent hydrogen atom or methyl, R₂Represent phenyl ring, R₃Hydrogen atom or phenyl ring are represented, X represents singly-bound.

8. compound as claimed in claim 7, it is characterised in that represented with following formula