CN110352382A

CN110352382A - Liquid crystal cell and its manufacturing method

Info

Publication number: CN110352382A
Application number: CN201880014550.5A
Authority: CN
Inventors: 加藤孝人; 樫下幸志
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2017-03-17
Filing date: 2018-02-27
Publication date: 2019-10-18
Also published as: TW201835163A; WO2018168440A1

Abstract

Liquid crystal display element 10 includes the 1st substrate 11 and the 1st the 2nd substrate 12 configured in opposite directions of substrate 11 and the liquid crystal layer 13 being configured between the 1st substrate 11 and the 2nd substrate 12.At least one of 1st substrate 11 and the 2nd substrate 12 are to wrap resiniferous substrate.Liquid crystal display element 10 includes: common electrode 14, is set on the 1st substrate 11；Pixel electrode 16, the isolation velum 15 that is situated between in common electrode 14 in the 1st substrate 11 configure；And liquid crystal orientation film, it is formed on the surface of at least one of the 1st substrate 11 and the 2nd substrate 12, and adjacent with liquid crystal layer 13.

Description

Liquid crystal cell and its manufacturing method

Cross-reference to related applications

The application is winner based on the Japanese publication number 2017-52456 that on March 17th, 2017 files an application, Its contents is quoted in the application.

Technical field

This disclosure relates to a kind of liquid crystal cell and its manufacturing method.

Background technique

In recent years, liquid crystal cell can be from mobile phone, smart phone, tablet personal computer (Personal Computer, PC) etc. until midget plants to the liquid crystal display element of the big picture such as LCD TV widely with using on the way.Make For liquid crystal cell, in addition to twisted nematic (Twisted Nematic, TN) type, STN Super TN (Super Twisted Nematic, STN) the vertical Electric Field Mode such as type, vertical orientation (Vertical Alignment, VA) type with liquid crystal cells Other than liquid crystal display element, it is known to which in-plane switching (In-Plane Switching, IPS) type, fringing field switch (Fringe Field Switching, FFS) lateral electric field types such as type liquid crystal display element (for example, referring to patent document 1).

In the liquid crystal cell of lateral electric field type, electrode is provided on a substrate in a pair of of substrate to (shared electricity Pole and pixel electrode).In the liquid crystal cell of lateral electric field type, by forming electric field between common electrode and pixel electrode, The liquid crystal molecule being orientated in the horizontal direction rotates in the horizontal direction.The transmission of incident light is controlled as a result,.Therefore, with it is vertical The liquid crystal cell of Electric Field Mode is compared, and the liquid crystal cell of lateral electric field type has wider array of angle of visibility characteristic, and can realize high product The display of matter.

The FFS type liquid crystal cell of one of liquid crystal cell as lateral electric field type is by parallel (homogeneous) The liquid crystal molecule of orientation applies fringe field and controls the liquid crystal cell of the mode of the transmission of light.In FFS type liquid crystal cell, One substrate surface is provided with common electrode, and on the surface of the common electrode, Jie completely cuts off velum and is provided with pixel electrode.If Electric field (fringe field) is formed between common electrode and pixel electrode, then it is electric towards sharing in the two sides electric field of pixel electrode Pole, the liquid crystal molecule being not only present on the liquid crystal molecule and pixel electrode between pixel electrode can rotate.Therefore, according to FFS Type liquid crystal cell, has the following advantages: wider array of angle of visibility and high contrast can be achieved.

Existing technical literature

Patent document

Patent document 1: Japanese Patent Laid-Open 2016-142945 bulletin

Summary of the invention

Problem to be solved by the invention

As liquid crystal cell, along with its multipurpose, and wishes that flexible, impact resistance can be improved and realize lightweight And slimming.Especially, it may be said that if can improve in the FFS type liquid crystal cell that wide view angle and high contrast can be achieved flexible Property etc. characteristics, then also bring along liquid crystal cell further purposes expand, quality improve.

The disclosure is formed in view of the project, and main purpose is to provide a kind of flexible and impact resistance well simultaneously And light weight and slim, the good FFS type liquid crystal cell of liquid crystal aligning.

Technical means to solve problem

The disclosure uses following means in order to solve the problem.

[1] a kind of liquid crystal cell comprising the 1st substrate, the 2nd substrate configured in opposite directions with the 1st substrate and configuration Liquid crystal layer between the 1st substrate and the 2nd substrate, at least one of the 1st substrate and the 2nd substrate are Resiniferous substrate is wrapped, and the liquid crystal cell includes: common electrode, is set on the 1st substrate；Pixel electrode, in institute The isolation velum that is situated between in the common electrode in the 1st substrate is stated to configure；And liquid crystal orientation film, it is formed in the 1st base On at least one of material and the 2nd substrate, and it is adjacent with the liquid crystal layer.

[2] a kind of manufacturing method of liquid crystal cell, wherein the liquid crystal cell include the 1st substrate, with the 1st substrate phase The 2nd substrate to configuration and the liquid crystal layer that is configured between the pair of substrate, and in the 1st substrate and the 2nd substrate At least one to wrap resiniferous substrate, on the 1st substrate be provided with common electrode and in the common electrode Be situated between the pixel electrode for completely cutting off velum and configuring, and the manufacturing method of the liquid crystal cell includes: in the 1st substrate and the described 2nd At least one of substrate coating of liquid crystalline alignment agent and the step of form liquid crystal orientation film；And forming the liquid crystal orientation film Afterwards, it is situated between every the 1st substrate and the 2nd substrate are configured in opposite directions and construct liquid crystal cells by the liquid crystal layer the step of.

The effect of invention

According to the composition, at least one of the 1st substrate and the 2nd substrate are set as to wrap resiniferous substrate, therefore can Obtain good flexible and impact resistance, light weight and the good FFS type liquid crystal cell of slim and liquid crystal aligning.

Detailed description of the invention

[Fig. 1] Fig. 1 is the sectional view for indicating the schematic configuration of FFS type liquid crystal display element.

[Fig. 2] Fig. 2 is the sectional view for indicating the schematic configuration of FFS type liquid crystal display element of the 2nd embodiment.

[Fig. 3] Fig. 3 is the floor map of pixel electrode.

[Fig. 4] Fig. 4 is the floor map of pixel electrode.

Specific embodiment

(the 1st embodiment)

< liquid crystal cell >

Hereinafter, referring to attached drawing, the 1st embodiment is illustrated.Furthermore each other about each embodiment below, for The same symbol is enclosed in mutually the same or impartial part in figure, quotes the explanation for the part of the same symbol.

In present embodiment, liquid crystal cell is embodied as to the liquid crystal display element 10 of FFS type.Liquid crystal display element 10 is such as Include a pair of of substrate comprising the 1st substrate 11 and the 2nd substrate 12 shown in Fig. 1 and is configured at the 1st substrate 11 and the 2nd substrate 12 Between liquid crystal layer 13.

1st substrate 11 and the 2nd substrate 12 are transparent substrate, at least one of the 1st substrate 11 and the 2nd substrate 12 be comprising The film base material of resin.In present embodiment, the 1st substrate 11 is glass baseplate, and the 2nd substrate 12 is to wrap resiniferous film base material.Institute In the case of stating, so that it may obtain the effect of lightweight and slimming and realize liquid crystal protection aspect for preferably.As composition The resin of film base material, such as can enumerate: silicon, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, poly- carbon Acid esters, polypropylene, polyvinyl chloride, aromatic polyamide, polyamidoimide, polyimides, tri acetyl cellulose The materials such as (Triacetyl Cellulose, TAC), polymethyl methacrylate.

Scan line, public wiring (common wiring) and signal wire (attached drawing summary) are provided on the 1st substrate 11, Common electrode 14 as the face electrode for being connected to public wiring is provided with by the region that scan line and public wiring divide.Separately Outside, in the 1st substrate 11, it is situated between in common electrode 14 and completely cuts off velum 15 and the pixel electrode 16 configured with comb teeth-shaped.By sharing Electrode 14 and pixel electrode 16 and construct electrode pair.Common electrode 14 and pixel electrode 16 are, for example, comprising tin oxide (SnO₂) Nesa (NESA) film (PPG register of company, U.S. trade mark) includes indium oxide-tin oxide (In₂O₃-SnO₂) tin indium oxide (Indium Tin Oxid, ITO) film or the transparent conductive film comprising carbon material.In the position that scan line and signal wire are reported to the leadship after accomplishing a task Nearby configured with the thin film transistor (TFT) (Thin Film Transistor, TFT) (attached drawing summary) as switching element, pass through TFT Driving the voltage of common electrode 14 and pixel electrode 16 is applied and is released to control.

Colored filter 17 and protective film 18 are provided on the 2nd substrate 12.Pixel electrode 16 in the 1st substrate 11, It is formed with liquid crystal orientation film 21 on the surface of slit 19 between pixel electrode 16, the table of the protective film 18 in the 2nd substrate 12 Liquid crystal orientation film 22 is formed on face.Liquid crystal orientation film 21, liquid crystal orientation film 22 are the liquid crystal molecules in regulation liquid crystal layer 13 The organic film of orientation is using the polymer composition comprising the polymer with light orientation base in present embodiment And the optical alignment film formed.

1st substrate 11 and the 2nd substrate 12 be situated between every spacer (not shown) and separate defined gap (cell gap) and It is configured.As spacer, column spacer, pearl spacer etc. can be enumerated.In addition, as spacer, just to substrate It, can also be using spacer structures (Fig. 1 or the Fig. 2 recorded in Japan Patent Patent 2016-196723 for the viewpoint of adhesion Dual (dual) spacer of middle record).1st substrate 11 and the 2nd substrate 12 are that mutual peripheral part is bonded via sealing material. Liquid crystal layer is formed with and to the space filling liquid crystal composition surrounded by these the 1st substrates 11, the 2nd substrate 12 and sealing material 13。

Polarizer 23, polarizer 24 are configured in the respective outside of the 1st substrate 11 and the 2nd substrate 12.In the 1st substrate 11 Outer edge be provided with terminal area, by being connected with the driver IC to drive liquid crystal in terminal area (integrated circuit, IC) etc., liquid crystal display element 10 is driven.

< aligning agent for liquid crystal >

Secondly, aligning agent for liquid crystal used in formation to liquid crystal orientation film 21, liquid crystal orientation film 22 is illustrated.Liquid crystal Component of polymer contained in alignment agent is not particularly limited, such as can be enumerated: the monomer with polyunsaturated bond gathers It closes object (hereinafter also referred to as " polymer P Ac "), polysiloxanes, polyamic acid, polyimides, poly amic acid ester, polyamide, gather Ester, cellulose derivative, polyacetals, polystyrene derivative, poly- (styrene-phenyl maleimide) derivative etc..These In, for liquid crystal aligning and the good aspect of rub resistance, preferably comprising being selected from by polymer P Ac, polyamic acid, gathering At least one of group composed by acid imide and poly amic acid ester.

As the component of polymer of aligning agent for liquid crystal, in these, so that it may sufficiently improve and press hydraulic fluid with finger or stylus etc. Patience (hereinafter also referred to as " resistance to finger pressing ") when the picture of crystal display element 10 even if aspect and toast after making For temperature is the aspect that also can get the liquid crystal orientation film excellent to the screening characteristics of substrate in the case where low temperature, preferably include Polymer P Ac., it can be achieved that more thin and light device and taking in the case where the substrate applications film base material of liquid crystal display element 10 Band property is excellent, and the flexibility of display area increases but then, resistance to finger pressing property decline.In terms of described, by making Use polymer P Ac as liquid crystal orientation film 21, the component of polymer of liquid crystal orientation film 22, can get ensures liquid crystal aligning and resistance to The good liquid crystal display element 10 of finger pressing property.

(polymer P Ac)

It as polyunsaturated bond possessed by the monomer for constituting polymer P Ac, such as can enumerate: (methyl) acryloyl Base, vinyl, styryl (ethenylphenyl), dimaleoyl imino etc..As the list with these polyunsaturated bonds The concrete example of body, such as can enumerate: (methyl) acrylic acid such as unsaturated carboxylic acid, esters of unsaturated carboxylic acids, unsaturated polybasic acid anhydride Based compound；The aromatic ethenyl compounds such as styrene, methyl styrene, divinylbenzene；1,3- butadiene, 2- methyl- 1,3- butadiene equiconjugate diolefin compound；N- methylmaleimido, N- N-cyclohexylmaleimide, N- benzyl maleimide Maleimide compounds such as amine etc..Furthermore a kind of or combination that can be used alone of the monomer with polymerism base unsaturated bond makes With two or more.

As polymer P Ac, just to the good aspect of the screening characteristics of film base material and can get show good liquid crystal It preferably at least include the polymer of the monomer of (methyl) acrylic compounds for the aspect of the liquid crystal cell of orientation (hereinafter also referred to as " poly- (methyl) acrylate ").According to poly- (methyl) acrylate, for example, with polyimides system resins phase Than, it is high to the dissolubility of low boiling point solvent, film thickness unevenness, coating unevenness, pin hole thus can be reduced in resulting film, can be obtained The liquid crystal orientation film for obtaining homogeneous, for the aspect preferably.In addition, film formation when can low temperature calcination, even if using contaminate Material also can control discoloration as in the case where colored filter colorant, can apply dyestuff, for the aspect preferably. Furthermore in the present specification, " poly- (methyl) acrylate " refers to comprising polyacrylate and polymethacrylates.

Poly- (methyl) acrylate can be the polymer for only including (methyl) acrylic compounds, can also be to include (first Base) acrylic compounds and other monomers polymer.Poly- (methyl) acrylate preferably has 20 mass % or more Structural unit from (methyl) acrylic compounds more preferably has 30 mass % or more, and then preferably has 40 Quality % or more particularly preferably has 50 mass % or more.

(methyl) acrylic compounds used when the polymerization of poly- (methyl) acrylate are not particularly limited.As it Concrete example, unsaturated carboxylic acid can for example enumerate (methyl) acrylic acid, acrylic acid α-ethyl ester, maleic acid, fumaric acid, itaconic acid, benzene Vinyl formate etc.；

Esters of unsaturated carboxylic acids can for example enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid Propyl ester, (methyl) butyl acrylate, (methyl) allyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid tricyclic [5.2.1.0^2,6] decyl- 8- base, (methyl) dicyclopentanyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid-2-ethyl Own ester, (methyl) lauryl acrylate, (methyl) acrylic acid trimethoxy silane base propyl ester, (methyl) acrylic acid 2,2,2- trifluoro Ethyl ester, five fluorine propyl ester of (methyl) acrylic acid 2,2,3,3,3-, (methyl) methoxyethyl acrylate, (methyl) acrylic acid-N, N- Dimethylamino ethyl ester, (methyl) methoxyethyl polyethylene glycol, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid 2- Hydroxy methacrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4- expoxycyclohexyl methyl esters, (methyl) acrylic acid 3,4- epoxy group butyl ester, acrylic acid 4- hydroxybutyl glycidol ether etc.；

Unsaturated polybasic acid anhydride can for example enumerate maleic anhydride, itaconic anhydride, cis- 1,2,3,4- tetrahydrophthalic acid Acid anhydride etc..Furthermore (methyl) acrylic compounds can be used alone these one kind or be applied in combination two or more.

Just make resulting liquid crystal cell liquid crystal aligning and electrical characteristics and liquid crystal orientation film it is good to the followability of substrate For good viewpoint, (methyl) acrylic compounds used in polymerization include preferably (methyl) propylene with epoxy group Sour based compound.The ratio of (methyl) acrylic compounds with epoxy group is preferably relative to monomer used in polymerization Entire amount and be set as 1 mass % or more, be more preferably set as 5 mass % or more, and then be preferably set as 10 mass % or more.

In the polymerization of poly- (methyl) acrylate, it is possible to use monomer other than (methyl) acrylic compounds (with Under, also referred to as " other monomers ").It as other monomers, can enumerate: conjugated diene compound, aromatic ethenyl compound, horse Carry out imide compound etc..In these, for the aspect of resistance to finger pressing property for substantially ensuring resulting liquid crystal cell, preferably To use aromatic ethenyl compound as other monomers.By polymer P Ac be set as (methyl) acrylic compounds with In the case where the copolymer of aromatic ethenyl compound, the use ratio of aromatic ethenyl compound is preferably relative to poly- The entire amount of monomer used in the synthesis of (methyl) acrylate and be set as the 1 mass % of mass %~80, be more preferably set as 2 The mass % of quality %~70, and then preferably it is set as 5 mass of mass %~60 %.

The polymerization reaction of (methyl) acrylic compounds is used to carry out preferably by free radical polymerization.As institute The polymerization initiator used when stating polymerization reaction, such as can enumerate: 2,2'- azos bis- (isobutyronitriles), 2,2'- azo bis- (2,4- Methyl pentane nitrile), the azo-compounds such as 2,2'- azo bis- (4- methoxyl group -2,4- methyl pentane nitriles)；Benzoyl peroxide base, The organic peroxies such as bis- (tert-butyl hydroperoxide) hexamethylenes of lauroyl peroxide base, the peroxidating trimethylace tonitric tert-butyl ester, 1,1'- Object；Hydrogen peroxide；Include these peroxide and the redox type initiator of reducing agent etc..In these, preferably azo Compound.Polymerization initiator can be used alone these one kind or be applied in combination two or more.The use ratio of polymerization initiator Relative to total 100 mass parts of monomer used in reaction, preferably 0.01 mass parts~50 mass parts, more preferably 0.1 Mass parts~40 mass parts.

The polymerization reaction of (methyl) acrylic compounds preferably carries out in organic solvent.As making in the reaction Organic solvent, such as can enumerate: alcohol, ether, ketone, amide, ester, hydrocarbon compound etc..In these, it is preferable to use selected from by alcohol And at least one of group composed by ether, more preferably use the part ether of polyalcohol.As its preferred concrete example, example It can such as enumerate: diethylene glycol Methyl ether, propylene glycol methyl ether acetate.Furthermore it, can be by these individually as organic solvent Using one kind or it is applied in combination two or more.

In the polymerization reaction of (methyl) acrylic compounds, reaction temperature is preferably set as 30 DEG C~120 DEG C, more excellent It is selected as being set as 60 DEG C~110 DEG C.Reaction time is preferably set as 1 hour~36 hours, and it is small to be more preferably set as 2 hours~24 When.In addition, the total amount (b) that the usage amount (a) of organic solvent is preferably set as monomer used in reaction is molten relative to reaction The entire amount (a+b) of liquid becomes the amount of 0.1 mass of mass %~50 %.Reaction solution containing poly- (methyl) acrylate can be straight The preparation for aligning agent for liquid crystal is connect, is taken after (methyl) acrylate poly- contained in reaction solution can also being isolated for liquid crystal To the preparation of agent.

About poly- (methyl) acrylate, just makes the liquid crystal aligning for being formed by liquid crystal orientation film good and ensure its liquid For the viewpoint of the ageing stability of brilliant orientation, gel permeation chromatography (Gel Permeation is utilized Chromatography, GPC) be measured obtained by the number average molecular weight (Mn) that converts of polystyrene be preferably 250~ 500,000, more preferably 500~100,000, and then preferably 1,000~50,000.

For the viewpoint for sufficiently obtaining the improvement of resistance to finger pressing property of resulting liquid crystal cell, relative to liquid crystal The content ratio of the total amount of the component of polymer of alignment agent, poly- (methyl) acrylate in aligning agent for liquid crystal is preferably 3 matter Measure % or more.About the lower limit of the content ratio, more preferably 5 mass % or more, and then preferably 20 mass % or more, it is special It You Xuanwei not 50 mass % or more.In addition, obtaining the various of the polymer different from poly- (methyl) acrylate about the upper limit In the case where the improvement of characteristic, preferably 99 mass % hereinafter, more preferably 95 mass % hereinafter, in turn be preferably 90 matter Measure % or less.Furthermore poly- (methyl) acrylate can be used alone one kind, also can be used in combination two or more.

(polyamic acid, poly amic acid ester and polyimides)

Polyamic acid, poly amic acid ester and polyimides can be synthesized according to conventionally known method.For example, polyamic acid can It is obtained and making tetracarboxylic dianhydride with diamine reactant.Poly amic acid ester for example can by make polyamic acid and esterifying agent (such as Methanol, ethyl alcohol, N,N-dimethylformamide diethyl acetal etc.) reaction method etc. and obtain.Polyimides can for example pass through Dehydration closed-loop is carried out to polyamic acid and carries out imidizate and obtains.Polyimides be preferably its acid imide rate be 20%~ 95%, more preferably 30%~90%.The acid imide rate be imide ring structure expressed as a percentage quantity relative to The quantity of the quantity and imide ring structure of the amic acid structure of polyimides it is total for shared ratio.

It as tetrabasic carboxylic acid used in polymerization, such as can enumerate: the rouge such as butane tetracarboxylic acid dianhydride, ethylenediamine tetra-acetic acid dianhydride Fat race tetracarboxylic dianhydride；1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride, 5- (2,5- dioxotetrahydro furans -3- base) -3a, 4,5,9b- naphthane [1,2- C] furans -1,3- diketone, 5- (2,5- dioxotetrahydro furans -3- base) -8- methyl -3a, 4,5,9b- naphthane [1,2-c] furan Bicyclic [3.3.0] octane -2:4,6:8- dianhydride of -1,3- diketone, the 2,4,6,8- tetracarboxylic of muttering, pentamethylene tetracarboxylic dianhydride, hexamethylene The ester ring types tetracarboxylic dianhydride such as alkane tetracarboxylic dianhydride；Pyromellitic acid anhydride, two phthalic acid of 4,4'- (hexafluoroisopropyli,ene) Acid anhydride, TOPOT 2,2′ p phenylenebis (trimellitic acid monoesters acid anhydride), ethylene glycol bis- (trimellitic anhydrides), 1,3- propylene glycol are bis- (trimellitic anhydride) Etc. aromatic tetracarboxylic dianhydrides etc. the tetracarboxylic acid recorded in Japanese Patent Laid-Open 2010-97188 bulletin can be used in addition to this Acid dianhydride.

It as diamines used in the polymerization, such as can enumerate: the aliphatic diamines such as ethylenediamine, tetra-methylenedimine； To ester ring types diamines such as cyclohexane diamine, 4,4' methylene bis (cyclo-hexylamine)；Six decyloxy diaminobenzenes, cholesteric alkyl oxygen Base diaminobenzene, diaminobenzoic acid cholesteric Arrcostab, diaminobenzoic acid cholesterol base ester, diaminobenzoic acid lanostane Bis- (the 4- amino benzoyl oxygroup) cholestane of base ester, 3,6-, bis- (4- amino-benzene oxygen) cholestane of 3,6-, the bis- (4- of 1,1- ((aminophenyl) methyl) phenyl) -4- butyl cyclohexane, 2,5- diamino-N, the fragrance of the side chain types such as N- diallyl aniline Race's diamines；P-phenylenediamine, 4,4'- diaminodiphenyl-methane, 4,4'- diamino-diphenyl amine, 4- aminophenyl -4'- amino Bis- (4- amino-benzene oxygen) pentanes of benzoic ether, 4,4'- chrysoidine, 3,5- diaminobenzoic acid, 1,5-, bis- [2- (4- Aminophenyl) ethyl] adipic acid, bis- (4- aminophenyl) amine, N, N- bis- (4- aminophenyl) methyl amines, N, bis- (the 4- amino of N'- Phenyl)-benzidine, 2,2'- dimethyl -4,4'- benzidine base, bis- (the trifluoromethyl) -4,4'- benzidines of 2,2'- Bis- [4- (4- amino-benzene oxygen) phenyl] propane of base, 4,4'- diamino-diphenyl ether, 2,2-, 4,4'- (the sub- isopropyl of phenylene two Base) dianil, bis- (4- amino-benzene oxygen) benzene of 1,4-, 4- (4- amino-benzene oxygen carbonyl) -1- (4- aminophenyl) piperidines, 4, The aromatic diamine of the non-side chain types such as 4'- [4,4'- propane -1,3- diyl is bis- (piperidines -1,4- diyl)] diphenylamines；1,3- is bis- Japanese Patent Laid-Open can be used in addition to this in diamino organosiloxanes such as (3- aminopropyl)-tetramethyl disiloxane etc. The diamines recorded in 2010-97188 bulletin.

About the polyamic acid, poly amic acid ester and polyimides contained in aligning agent for liquid crystal, the polyphenyl measured by GPC The weight average molecular weight (Mw) of ethylene conversion is preferably 1,000~500,000, more preferably 2,000~300,000.Molecule Amount distribution (Mw/Mn) is preferably 7 hereinafter, more preferably 5 or less.Furthermore polyamic acid, polyamide contained in aligning agent for liquid crystal Acid esters and polyimides can be only one kind, or combine two or more.

(silicon-containing compound)

It is achieved with and do not undermine liquid crystal aligning, press the screening characteristics of film base material, resistance to finger property and liquid that weatherability is high For the aspect of crystal display element 10, liquid crystal orientation film 21, liquid crystal orientation film 22 formation used in aligning agent for liquid crystal it is preferred For containing selected from least one of the group as composed by silane compound and polysiloxanes compound (hereinafter also referred to as " containing Silicon compound ").In these, even if it is higher with regard to the improvement of the weatherability of liquid crystal display element 10 and after realization toast temperature It particularly preferably include poly- silicon oxygen for can also making the good aspect of liquid crystal aligning in the case where the further low temperature of degree Alkane, so that it may make preferably to contain silane compound for the higher aspect of the adhesion of substrate.

(polysiloxanes)

Polysiloxanes can for example be obtained and condensation is hydrolyzed to water-disintegrable silane compound.As water-disintegrable Silane compound, such as can enumerate: the tetraalkoxysilane compounds such as tetramethoxy-silicane, tetraethoxysilane；Three second of methyl Oxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyl diethoxysilane etc. are containing alkyl or aryl Alkoxysilane compound containing trialkylsilyl group in molecular structure；

The alkoxysilane compound containing trialkylsilyl group in molecular structure of the sulfur-bearings such as 3- Mercaptopropyltriethoxysilane, mercapto methyl triethoxysilane；

Glycidoxypropyl methyltrimethoxysilane, glycidoxypropyl methyltriethoxysilane, 2- glycidol Oxygroup ethyl trimethoxy silane, 2- glycidoxypropyl ethyl triethoxysilane, 3- glycidoxypropyl trimethoxy Base silane, 3- glycidoxypropyl triethoxysilane, 3- glycidoxypropyl dimethoxysilane, 2- The alkoxysilane compound containing trialkylsilyl group in molecular structure containing epoxy group such as (3,4- expoxycyclohexyl) ethyl triethoxysilane；

3- (methyl) acryloyloxypropyltrimethoxysilane, 3- (methyl) acryloxypropyl dimethoxy Silane, 3- (methyl) acryloyloxy propyl methyl diethoxysilane, vinyltriethoxysilane etc. are containing unsaturated bond Alkoxysilane compound containing trialkylsilyl group in molecular structure；

3- TSL 8330,3-aminopropyltriethoxysilane, 2- TSL 8330, 2- aminopropyltriethoxywerene werene, N- (2- amino-ethyl) -3- TSL 8330, N- (2- amino-ethyl) - 3- aminopropylmethyldimethoxysilane, 3- ureido-propyl trimethoxy silane, 3- ureidopropyltriethoxysilane, N- first Base carbonyloxy group ethyl-N'- trimethoxysilylpropyl ethylenediamine, N- ethoxy carbonyl -3- TSL 8330 Etc. nitrogenous alkoxysilane compound containing trialkylsilyl group in molecular structure；

The alkoxysilane compound containing trialkylsilyl group in molecular structure etc. containing anhydride group such as trimethoxysilylpropyl succinic anhydride.Hydrolysable silanes Close object can be used alone these one kind or be applied in combination two or more.Furthermore " (methyl) acryloyl group " refers to comprising " propylene Acyl group " and " methylacryloyl ".

The hydrolysis-condensation reaction by make hydrolysable silanes compound as described above one or more with Water is preferably reacted in the presence of catalyst appropriate and organic solvent and is carried out.In reaction, the use ratio of water is opposite In 1 mole of hydrolysable silanes compound (total amount) and preferably 1 mole~30 moles.As used catalyst, such as It can enumerate: acid, alkali metal compound, organic base, titanium compound, zirconium compounds etc..The usage amount of catalyst is according to catalyst The differences such as the reaction conditions such as type, temperature should be suitable for setting, such as relative to the total amount of silane compound, preferably 0.01 Times mole~3 times moles.As used organic solvent, such as hydrocarbon, ketone, ester, ether, alcohol can be enumerated etc., in these, preferably Use water-insoluble or difficult water-soluble organic solvent.The use ratio of organic solvent is relative to silane chemical combination used in reaction Total 100 mass parts of object, preferably 10 mass parts~10,000 mass parts.

The hydrolysis-condensation reaction is for example heated preferably by oil bath etc. to implement.At this point, heating temperature is excellent It is selected as being set as 130 DEG C hereinafter, heating time is preferably to be set as 0.5 hour~12 hours.After the completion of reaction, by autoreaction liquid Solvent is removed after dividing the organic solvent layer taken to be optionally dried using desiccant, thus can get the poly- silicon oxygen as target Alkane.Furthermore the synthetic method of polysiloxanes is not limited to the hydrolysis-condensation reaction, such as can also be used in ethanedioic acid and alcohol In the presence of react hydrolysable silanes compound method etc. and carry out.

Can also make to contain in aligning agent for liquid crystal in side chain there is light orientation base or pre-tilt angle to assign the functional base such as base Polysiloxanes.Polysiloxanes with functional base can for example obtain in the following way, that is, for example at least the one of raw material Polymerization of the part by using the hydrolysable silanes compound containing epoxy group, polysiloxanes of the synthesis side chain with epoxy group, after And make the carboxylic acid reaction that there is the polysiloxanes of epoxy group with there is functional base.Alternatively, can also be used will have functional base Method of the hydrolysable silanes compound for the polymerization in monomer.

Polysiloxanes containing epoxy group preferably carries out in the presence of catalyst and organic solvent with reacting for carboxylic acid.Carboxylic The use ratio of acid preferably 5 moles of % or more relative to epoxy group possessed by the polysiloxanes containing epoxy group, more preferably For 10 moles of %~80 mole %.As the catalyst, such as the reaction as organic base, promotion epoxide can be used So-called hardening accelerator and well known compound etc..The use ratio of catalyst is relative to the polysiloxanes containing epoxy group 100 mass parts and preferably 100 below the mass.

As the preferred concrete example of used organic solvent, can enumerate: 2- butanone, methyl-n-butyl ketone, methyl iso-butyl ketone (MIBK), Cyclopentanone, cyclohexanone and butyl acetate etc..Organic solvent is preferably with solid component concentration as 5 mass of mass %~50 %'s Ratio uses.Reaction temperature in the reaction is preferably 0 DEG C~200 DEG C, and the reaction time is preferably 0.1 hour~50 hours. After the completion of reaction, after the organic solvent layer that autoreaction liquid point takes optionally being dried using desiccant, solvent is removed, by This can get the polysiloxanes with functional base.

About polysiloxanes, the weight of the conversion of polystyrene obtained by being measured using gel permeation chromatography (GPC) Average molecular weight is preferably 500~1,000,000, more preferably 1,000~100,000, and then preferably 1,000~50, 000.Furthermore polysiloxanes can be used alone one kind, also can be used in combination two or more.

(silane compound)

Silane compound contained in aligning agent for liquid crystal is that have carbon-silicon key organo-silicon compound, can be enumerated as poly- Silane compound used in the synthesis of siloxanes and the hydrolysable silanes compound etc. illustrated.The silane compound is preferably With alkoxysilane group, more preferably there is at least one in the group as composed by epoxy group, amino and mercapto The alkoxysilane compound containing trialkylsilyl group in molecular structure of kind functional group, particularly preferably containing the alkoxysilane compound containing trialkylsilyl group in molecular structure of epoxy group.Furthermore silane chemical combination Object can be used alone one kind, also can be used in combination two or more.

Silicon-containing compound in aligning agent for liquid crystal can be suitable for selection according to used compound.For example, containing poly- silicon In the case that oxygen alkane is as silicon-containing compound, for sufficiently improving the viewpoint of weatherability of resulting liquid crystal display element 10, The content ratio of polysiloxanes in aligning agent for liquid crystal is preferably the total amount relative to the component of polymer in aligning agent for liquid crystal And it is set as 1 mass % or more, 2 mass % or more are more preferably set as, and then be preferably set as 5 mass % or more.In addition, just pressing down For the viewpoint of the decline of resistance to finger pressing property in liquid crystal display element 10 processed, the upper limit value of the content ratio of polysiloxanes is excellent It is selected as being set as 97 mass % hereinafter, being more preferably set as 90 mass % or less.

In addition, may refrain from resistance to hand in the case where deploying silane compound as silicon-containing compound in aligning agent for liquid crystal Refer to the decline of pressing property and sufficiently obtains the sight of the improvement of the weatherability to the adhesion and liquid crystal display element 10 of substrate For point, the allotment ratio of silane compound be preferably total 100 mass parts relative to polymer and be set as 0.5 mass parts with On, more preferably it is set as 1 mass parts~30 mass parts.Furthermore as silicon-containing compound, polysiloxanes can be used only, it can also be only Using silane compound, polysiloxanes and silane compound can also be used in combination.

For the initial stage of liquid crystal is orientated the high aspect of undesirable inhibitory effect, liquid crystal orientation film 21, liquid crystal orientation film 22 Component of polymer to be preferably selected from least one of group as composed by poly- (methyl) acrylate and polysiloxanes poly- It closes object (hereinafter also referred to as " polymer Q ").Polymer Q for example shows the material with film base material compared with polyimides system resins Expect commonly used cyclic olefin polymer (hereinafter also referred to as " COP ") or tri acetyl cellulose (hereinafter also referred to as " TAC ") the close linear expansion coefficient of resin (ratio when length of object or volume increase due to temperature rises).Therefore, Heating when rear baking when by the manufacture of liquid crystal cell, the initial stage orientation that also can inhibit liquid crystal are bad and preferred.

The content ratio of polymer Q is preferably the total amount relative to component of polymer contained in aligning agent for liquid crystal and sets For 10 mass % or more, 20 mass % or more are more preferably set as, and then are preferably set as 30 mass % or more.Furthermore it polymerize Object Q, which can be used alone, one kind or to be applied in combination two or more.

(polymer with light orientation base)

Liquid crystal orientation film 21, liquid crystal orientation film 22 formation used in aligning agent for liquid crystal preferably contain with light orientation The polymer of property base.In the case where substrate is set as film base material, rub to the film for using aligning agent for liquid crystal and being formed Erasure is easy to produce friction grinding when managing, there is the anxiety of the decline of liquid crystal aligning or the decline of product yield.In view of the mentioned aspects, Liquid crystal orientation film 21, liquid crystal orientation film 22 are preferably set as optical alignment film, and realize that inhibition liquid crystal aligning is bad and product is good Rate.

Herein, so-called " light orientation base " refers to anti-by the caused photoisomerization reaction of light irradiation or photodimerizationization Answer, photolysis reactions, light Fries rearrangement reaction and assign anisotropic functional group to film.As the specific of light orientation base Example, such as can enumerate: comprising azobenzene or derivatives thereof as basic framework the base containing azobenzene, comprising cinnamic acid or its spread out Biology contains chalcone as basic framework as the base containing cinnamic acid structure of basic framework, comprising chalcone or derivatives thereof Base, comprising benzophenone or derivatives thereof as the base containing benzophenone of basic framework, comprising cumarin or derivatives thereof The base containing cumarin as basic framework, the structure containing cyclobutane comprising cyclobutane or derivatives thereof as basic framework Deng.In these, for the sensitive aspect for light, preferably containing the base of cinnamic acid structure, such as it can enumerate and have The base etc. of part-structure represented by following formula (1).

[changing 1]

(in formula (1), R is the alkyl of carbon number 1~10, the alkoxy of carbon number 1~10, at least one hydrogen atom through fluorine atom The fluoroalkoxy for the carbon number 1~10 of substituted carbon number 1~10 replaced containing fluoroalkyl, at least one hydrogen atom through fluorine atom or Fluorine atom.The integer that a is 0~4.In the case where a is 2 or more, multiple R be may be the same or different." * " indicates bond key)

In the part-structure represented by the formula (1), one of two bond keys " * " are preferably bonded to following formula (4) base represented by.In the situation, the liquid crystal aligning of resulting liquid crystal cell can be improved and it is preferred that.

[changing 2]

H-R¹¹-R¹²-* (4)

(in formula (4), R¹¹It, can also be in ring for phenylene, biphenylene, sub- terphenyl base, cyclohexylidene or bicyclohexylene There is the alkyl of carbon number 1~20, the alkoxy of carbon number 1~20, at least one hydrogen atom to replace through fluorine atom or cyano for part The substituted alkoxy of the carbon number 1~20 for replacing alkyl, at least one hydrogen atom to replace through fluorine atom or cyano of carbon number 1~20, Fluorine atom or cyano.R¹²It is singly-bound, the alkane diyl of carbon number 1~3, oxygen atom, sulphur in the case where phenyl ring in the formula that is bonded to (1) Atom ,-CH=CH- ,-NH- ,-COO- or-OCO-, carbonyl in the formula that is bonded to (1) in the case where are singly-bound, carbon number 1~3 Alkane diyl, oxygen atom, sulphur atom or-NH-." * " indicates bond key)

About light orientation base, can be had by polymer P Ac, can also be had by the polymer different from polymer P Ac.Make It for the main framing of the polymer, such as can enumerate: polyamic acid, poly amic acid ester, polyimides, polysiloxanes, polyamide Deng.For ensuring the reliability of liquid crystal display element 10 and the viewpoint of weatherability, it is preferable to use polysiloxanes as tool There is the polymer of light orientation base.

There is no particular restriction for the method for polymer of the synthesis with light orientation base, as long as suitable according to the main framing of polymer Preferably select.As concrete example, the method that can enumerate (1) using the monomer with light orientation base to be polymerize, (2) are closed At the polymer in side chain with the 1st functional group's (such as epoxy group etc.), then make with can be reacted with the 1st functional group the 2nd The side of the reactive compounds and the polymer reaction with the 1st functional group of functional group's (such as carboxyl etc.) and light orientation base Method etc..In the case where the polymer with light orientation base is polysiloxanes, just to the importing high-efficient aspect of side chain and Speech preferably utilizes the method for (2).

The case where aligning agent for liquid crystal contains the polymer with light orientation base and polymer without light orientation base Under, for assigning the viewpoint of sufficient alignment capability to the film for using aligning agent for liquid crystal to be formed by radioactive ray irradiation, The content ratio of polymer with light orientation base is preferably the total amount relative to the component of polymer in aligning agent for liquid crystal And it is set as 1 mass % or more, more preferably it is set as 5 mass of mass %~99 %.

(crosslinking agent)

Aligning agent for liquid crystal preferably contains the compound with bridging property base (hereinafter also referred to as crosslinking agent).Bridging property base It is that can form the base of covalent bond between same or different molecular by light or heat, such as can enumerate: (methyl) acryloyl group, tool There is the base (alkenyl, ethenylphenyl etc.) of vinyl, acetenyl, epoxy group (oxiranyl, oxetanylmethoxy), carboxyl, (protect Shield) isocyanate group etc..In these, for aspect with high reactivity, particularly preferably (methyl) acryloyl group.Crosslinking agent institute The quantity for the bridging property base having can be one, can also be multiple.For sufficiently improving the aspect of reliability of liquid crystal cell, It is preferably more than two, more preferably 2~6.

It as the concrete example of crosslinking agent, such as can enumerate: the compound containing allyl such as diallyl phthalate；

Ethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylic acid Ester, 1,6-hexylene glycols two (methyl) acrylate, pentaerythrite three (methyl) acrylate, two-trimethylolpropanes, four (first Base) acrylate, pentaerythrite four (methyl) acrylate, trimethylolpropane (methyl) acrylate, three hydroxyl of ethoxylation Methylpropane three (methyl) acrylate, ethylene glycol three (methyl) acrylate, gathers at dipentaerythritol six (methyl) acrylate Ether (methyl) acrylate, Ethoxylated bisphenol A bis- (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylic acid Ester, 2- methyl-1, (methyl) acrylic compounds such as 8- ethohexadiol two (methyl) acrylate；

Maleic acid, itaconic acid, trimellitic acid, tetrabasic carboxylic acid, cis- 1,2,3,4- tetrahydrophthalic acid, ethylene glycol are double partially The carboxylic acids such as benzenetricarboxylic acid, propylene glycol double trimellitic acid, two phthalic acid of 4,4'- oxygroup, trimellitic anhydrides；

Ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropylene glycol two Glycidol ether, polypropylene glycol diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- Bis- (4- hydroxy phenyl) propane diglycidyl ethers, trihydroxymethylpropanyltri diglycidyl ether, N, N, N', tetra- glycidol of N'- Base-m-xylene diamine, 1,3- bis- (N, N- diglycidyl amino methyl) hexamethylenes, N, N, N', N'- four glycidyl group- 4,4'- diaminodiphenyl-methane, N, N- diglycidyl-benzyl amine, N, N- diglycidyl-amino methyl hexamethylene Alkane, N, the epoxides such as N- diglycidyl-cyclo-hexylamine；

By the multivalence isocyanide such as toluene di-isocyanate(TDI), hexamethylene diisocyanate, diphenylmethylene diisocyanate (protection) isocyanate compound etc. that acid esters is protected through protecting group.It is preferably multifunctional (methyl) in these as crosslinking agent Acrylate compounds.

For the aspect that the improvement of liquid crystal aligning and resistance to finger pressing property can sufficiently be obtained, the allotment of crosslinking agent 100 mass parts of component of polymer used in preparation of the ratio relative to aligning agent for liquid crystal and it is more than preferably 0.5 mass parts, more Preferably 1 mass parts~40 mass parts, and then preferably 5 mass parts~30 mass parts.Furthermore crosslinking agent can be used alone one Kind, it also can be used in combination two or more.

As ingredient contained in aligning agent for liquid crystal, other than described, such as can enumerate: antioxidant, metal-chelating Compounds, hardening accelerator, surfactant, filler, dispersing agent, light sensitizer etc..The allotment ratio of these ingredients can It is suitable for selection according to each compound in the range of not undermining the effect of the disclosure.

(solvent)

The other compositions that aligning agent for liquid crystal is used with component of polymer and optionally are preferably dissolved in appropriate organic molten It is prepared by the form of liquid composition made of in matchmaker.It as used organic solvent, such as can enumerate: N- methyl -2- Pyrrolidones, N- ethyl-2-pyrrolidone, 1,2- dimethyl-2-imidazolinone, gamma-butyrolacton, butyrolactam, N, N- bis- Methylformamide, DMAC N,N' dimethyl acetamide, 4- hydroxy-4-methyl-2-pentanone, glycol monoethyl ether, butyl lactate, acetic acid fourth Ester, methyl methoxypropionate, ethyl ethoxy-c acid esters, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, second two Alcohol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol two Methyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid esters, diethyl two Alcohol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, diisobutyl ketone, isopentyl propionic ester, isopentyl Isobutyrate, isoamyl ether, ethylene carbonate, propylene carbonate etc..These can be used alone or be used in mixed way two or more.

Used organic solvent is preferably total amount relative to solvent contained in aligning agent for liquid crystal, in aligning agent for liquid crystal At least one in the group as composed by n-methyl-2-pyrrolidone, gamma-butyrolacton and N- ethyl-2-pyrrolidone The content ratio of kind solvent is 40 mass % or less.By being set as the range, liquid crystal just is formed on wrapping resiniferous substrate It can make for the aspect of the further low temperature of rear baking temperature when alignment films preferably.The content ratio is more preferably 35 mass % Hereinafter, being in turn preferably 30 mass % hereinafter, particularly preferably 1 mass of mass %~30 %.

As solvent composition, it is preferable to use the compound institute represented by being selected from by following formula (E-1)~formula (E-5) difference Boiling point under at least one of group of composition and 1 air pressure is 180 DEG C of solvents below (hereinafter also referred to as " specific molten Agent ").By using these specific solvents, even if the case where carrying out heating when film formation under low temperature (such as 180 DEG C or less) Lower screening characteristics is also good, can get liquid crystal aligning and resistance to finger presses the excellent liquid crystal cell of property, excellent for the aspect Choosing.

[changing 3]

(in formula (E-1), R⁴¹For the alkyl or CH of carbon number 1~4₃CO-, R⁴²For the alkane diyl or-(R of carbon number 1~4⁴⁷-O) r-R⁴⁸(wherein, R⁴⁷And R⁴⁸Separately it is the alkane diyl of carbon number 2 or 3, the integer that r is 1~4), R⁴³For hydrogen atom or carbon The alkyl of number 1~4)

[changing 4]

(in formula (E-2), R⁴⁴For the alkane diyl of carbon number 1~4)

[changing 5]

(in formula (E-3), R⁴⁵And R⁴⁶It is separately the alkyl of carbon number 1~8)

[changing 6]

R⁴⁹-R⁵⁰-OH (E-4)

(in formula (E-4), R⁴⁹For hydrogen atom or hydroxyl, in R⁴⁹In the case where hydrogen atom, R⁵⁰For the alkyl of carbon number 1~9, In R⁴⁹In the case where hydroxyl, R⁵⁰With the bilvalent radical of oxygen atom between the bivalent hydrocarbon radical or the carbon-carbon bond of carbon number 1~9)

[changing 7]

R⁵¹-COO-R⁵² (E-5)

(in formula (E-5), R⁵¹And R⁵²Separately there is between the monovalent hydrocarbon or the carbon-carbon bond of carbon number 1~6 oxygen The monad radical of atom)

As the concrete example of specific solvent, compound represented by the formula (E-1) can for example enumerate propylene glycol monomethyl ether, Propylene glycol methyl ether acetate, diethylene glycol Methyl ether, 3- methoxyl group-n-butyl alcohol, glycol monoethyl ether, ethylene glycol list second Ether, ethylene glycol ether, ethylene glycol-n-butyl ether (butyl cellosolve), glycol dimethyl ether, ethyl cellosolve acetate, diethyl Glycol dimethyl ether etc.；

Compound represented by the formula (E-2) can for example enumerate cyclobutanone, cyclopentanone, cyclohexanone；

Compound represented by the formula (E-3) can for example enumerate acetone, methyl ethyl ketone, methyl-n-propyl ketone, first Base-normal-butyl ketone, metacetone, methyl-isobutyl ketone, methyl-n-amyl ketone, ethyl-normal-butyl ketone, methyl-n-hexyl ketone, Di-Isobutyl ketone, trimethyl nonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methyl cyclohexanone, 2,4- pentanedione, acetone Benzylacetone, diisobutyl ketone etc.；

Compound represented by the formula (E-4) can for example enumerate methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, 3- methoxyl group Butanol, hexanol, enanthol, octanol, furfuryl alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5- cyclonol, benzyl alcohol, two The polyalcohols such as the single methanols such as pyruvic alcohol or ethylene glycol, 1,2- propylene glycol, 1,3 butylene glycol, 2,4-PD；

Compound represented by the formula (E-5) can for example enumerate part ester (such as the glycol monoethyl ether, second of polyalcohol The mono- 2- ethyl butyl ether of glycol monobutyl ether, ethylene glycol monohexylether, ethylene glycol, diethylene glycol monomethyl ether, Diethylene glycol monopropyl ether, two Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol list third The part ester of the polyalcohols such as ether), methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, the tertiary fourth of acetic acid Ester, acetic acid 3- methoxybutyl, acetic acid 2- ethylhexyl, methyl acetoacetate, ethyl acetoacetate, glycol monoethyl ether acetic acid Ester, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, propylene glycol methyl ether acetate, dihydroxypropane single-ether Acetic acid esters, propylene glycol monopropyl ether acetic acid esters, dipropylene glycol monomethyl ether acetic acid esters, oxalic acid glycol, acetic acid methoxy triglycol, third Acetoacetic ester, n-butyl propionate, two-N-butyl of ethanedioic acid, methyl lactate, ethyl lactate, n-butyl lactate, N_amyl lactate, third Diethyl adipate, repefral etc..Furthermore as specific solvent, can be used alone one kind, it also can be used in combination two Kind or more.

The use ratio of the total amount of solvent used in preparation relative to aligning agent for liquid crystal, specific solvent is preferably set For 30 mass % or more, 50 mass % or more are more preferably set as, and then are preferably set as 70 mass % or more, particularly preferably It is set as 80 mass % or more.

Wherein, organic solvent used in the preparation of aligning agent for liquid crystal is preferably the total amount relative to solvent and includes 40 Quality %'s or more is 150 DEG C of compounds below under 1 air pressure of boiling point, more preferably includes 50 mass % or more, Jin Eryou It is selected as comprising 70 mass % or more.

(total quality of the ingredient other than the solvent of aligning agent for liquid crystal accounts for liquid crystal to solid component concentration in aligning agent for liquid crystal The ratio of the gross mass of alignment agent) consider viscosity, volatility etc. and be suitable for selecting, the preferably model of 1 mass of mass %~10 % It encloses.In the case where solid component concentration less than 1 mass %, the film thickness of film becomes too small and is difficult to obtain good liquid crystal to take To film.On the other hand, in the case where solid component concentration is more than 10 mass %, become excessive there are the film thickness of film and be difficult to Good liquid crystal orientation film is obtained, in addition the viscosity of aligning agent for liquid crystal increases and the tendency of coating decline.

The manufacturing method > of < liquid crystal cell

Secondly, the manufacturing method to liquid crystal cell is illustrated.Liquid crystal cell (liquid crystal display element 10) passes through such as lower section Method manufacture, which comprises form liquid in the respective surface coating liquid crystalline substance alignment agent of the 1st substrate 11 and the 2nd substrate 12 The step A of brilliant alignment films 21, liquid crystal orientation film 22；By be formed with liquid crystal orientation film 21, liquid crystal orientation film 22 the 1st substrate 11 and 2nd substrate 12 is configured in the opposite mode of liquid crystal orientation film 21, liquid crystal orientation film 22 via liquid crystal layer 13 and constructs liquid crystal The step B of unit.

(step A)

The coating of aligning agent for liquid crystal is that the respective surface of the 1st substrate 11 and the 2nd substrate 12 is for example printed by plate Coating method well known to brush method, flexographic printing process, spin-coating method, roll coater method, ink-jet method, bar coater method etc. carries out.It is being coated with After aligning agent for liquid crystal, for the purpose of dropping liquid for preventing be coated with aligning agent for liquid crystal etc., preferably implement preheating (prebake conditions). Prebake conditions temperature is set according to the type of substrate, is preferably set as 140 DEG C hereinafter, being more preferably set as 120 DEG C hereinafter, excellent in turn It is selected as being set as 100 DEG C or less.The lower limit of prebake conditions temperature is preferably set as 30 DEG C or more, is more preferably set as 40 DEG C or more.In advance Baking time is preferably 0.25 minute~10 minutes.

Thereafter, for the purpose of completely removing solvent and optionally promotion cross-linking reaction, preferably implement calcining (rear baking) Step.In order to realize the Thermal protection for wrapping resiniferous substrate, calcination temperature (rear baking temperature) at this time is preferably set as 150 DEG C Hereinafter, being more preferably set as 140 DEG C hereinafter, being particularly preferably set as 110 DEG C or less.At this point, passing through gathering aligning agent for liquid crystal At least part of polymer component is set as poly- (methyl) acrylate, even if 150 DEG C of low temperature below of baking temperature after making In the case where, it also can get the alignment films of homogeneous, it is ensured that the liquid crystal aligning of liquid crystal cell and resistance to finger pressing property, it is just described For aspect preferably.Post-bake times are preferably 5 minutes~200 minutes, more preferably 10 minutes~120 minutes.For glass Substrate can also carry out film by high-temperature technology and be formed.In the situation, rear baking temperature is preferably set as 150 DEG C~300 DEG C, more preferably it is set as 170 DEG C~250 DEG C.Post-bake times are preferably 5 minutes~200 minutes, more preferably 10 minutes~ 100 minutes.

In the case where liquid crystal cell is color liquid crystal display device, as colored filter colorant, public affairs can be used Pigment, the dyestuff known.Herein, dyestuff is hot weaker, in the case where baking temperature high temperature after needing to make, the use of dyestuff There are limitations.In terms of described, by the way that at least part of the component of polymer of aligning agent for liquid crystal is set as poly- (methyl) third Olefin(e) acid ester can improve the dissolubility in low boiling point solvent, the low temperature of baking temperature after thus can realizing.In addition, after passing through The low temperature of baking temperature can apply dyestuff as colored filter colorant, with regard to the wide aspect of the selection width of material Speech it is also preferred that.

As film base material, for the viewpoint that the contrast and angle of visibility that may refrain from liquid crystal cell change, it is preferable to use Postpone small resin film.The value of delay (Δ nd) (wherein, Δ n is that the rate of curving is poor, d is film thickness) be preferably 20nm hereinafter, More preferably 10nm or less.In addition, in the case where the delay of film base material is high (In- in unit can also be used in film base material side Cell) polarizer.

Liquid crystal aligning ability is assigned to the film for using aligning agent for liquid crystal to be formed by orientation process.Present embodiment In, carry out the light orientation processing that the radioactive ray of polarisation or non-polarized are irradiated to film.

In light orientation processing, the light irradiation of film for example can be used the purple of the light of the wavelength comprising 150nm~800nm The radioactive ray such as outside line and luminous ray.Radioactive ray can be that polarisation is also non-polarized, or can also irradiate these combinations.It exposes There is no particular restriction for light method, such as can enumerate: irradiating linear polarization from the direction vertical with substrate surface or inclined direction Method, from method of oblique direction non-polarized etc..

As used light source, such as it can be used Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halid lamp, argon total Shake lamp, xenon lamp, excimer laser etc..The ultraviolet light of preferred wavelength region can by with such as optical filter, diffraction grating etc. Mechanism etc. and obtain light source.The exposure of radioactive ray is preferably 10J/m²~50,000J/m², more preferably 20J/m²~ 10,000J/m²。

Light irradiation for light orientation processing can wait progresss by the following method, and the method is after to rear baking procedure Method that film is irradiated, the method that the film after pre-bake step and before rear baking procedure is irradiated, in prebake conditions The method that film is irradiated during heating in either step in step and rear baking procedure.To assign orientation After the light irradiation of ability, it can also carry out using such as water, organic solvent (such as methanol, isopropanol, 1- methoxy-2-propanol second Acid esters, butyl cellosolve, ethyl lactate etc.) or these mixture processing that substrate surface is cleaned or to substrate The processing heated.

(step B)

In step B, prepare the 1st substrate 11 and the 2nd substrate 12 that are respectively formed with liquid crystal orientation film, with mutual liquid crystal Liquid crystal layer 13 is configured between two plate substrates that the opposite mode of alignment films 21, liquid crystal orientation film 22 configures in opposite directions and manufactures liquid crystal list Member.Specifically, can enumerate: being bonded the 1st substrate 11 and by base with the respective peripheral portion of the 2nd substrate 12 by sealant In the cell gap that material surface and sealant divide after injection filling liquid crystal composition, by the method for injection hole sealing；Wherein The peripheral portion of the liquid crystal orientation film side of one substrate is coated with sealant, so in liquid crystal alignment film surface as defined in several positions After liquid-crystal composition is added dropwise, another substrate is bonded and by liquid crystal in the entire surface of substrate in the opposite mode of liquid crystal orientation film Expansion, thereafter by method of sealant hardening (formula of dripping injects (One Drop Filling, ODF) mode) etc..As sealing Agent, such as the epoxy resin etc. of the alumina balls containing curing agent and as spacer can be used.As liquid crystal, nematic can be enumerated Liquid crystal and disc-like liquid crystal, wherein preferably nematic liquid crystal.

Then, liquid crystal display element 10 is made in the outer surface that polarizer is optionally fitted in liquid crystal cells.As inclined Tabula rasa can be enumerated using polarizer made of the cellulose acetate protective film clamping referred to as light polarizing film of " H film " or comprising H film certainly The polarizer of body, " the H film " are that iodine and winner are absorbed when making polyvinyl alcohol extend orientation.

Liquid crystal display element 10 can be effectively applied in various uses, such as can be used for clock and watch, portable game machine, text Word processor, notes type personal computer, auto-navigation system, video camera, personal digital assistant (Personal Digital Assistant, PDA), digital camera, mobile phone, smart phone, various monitors, LCD TV, information display etc. it is each Kind display device.In addition, liquid crystal cell can be used not only as liquid crystal display element 10, such as it also is used as light modulation film or phase difference Film.

(the 2nd embodiment)

Secondly, being illustrated centered on the difference of the 1st embodiment about the 2nd embodiment.By this embodiment party The liquid crystal display element 10 of formula is shown in Figure 2.In liquid crystal display element 10, configured with common electrode 14 and pixel electrode 16 1 substrate 11 is to wrap resiniferous substrate, and the 2nd substrate 12 configured with colored filter 17 is glass baseplate.In the composition In liquid crystal display element 10, it can be ensured that resistance to finger pressing property, and realize the lightweight of liquid crystal display element 10.

(the 3rd embodiment)

Secondly, being illustrated centered on the difference of the 1st embodiment about the 3rd embodiment.3rd embodiment party In the liquid crystal display element 10 of formula, the liquid crystal orientation film 22 of 12 side of liquid crystal orientation film 21 and the 2nd substrate of 11 side of the 1st substrate is used It forms aligning agent for liquid crystal different from each other and is formed.

1st alignment agent and 12 side of the 2nd substrate used in the formation of liquid crystal orientation film 21 as 11 side of the 1st substrate Liquid crystal orientation film 22 formation used in the 2nd alignment agent, such as the scheme of (1) below~(3) can be enumerated.

(1) main framing of the polymer contained as component of polymer it is identical with the 2nd alignment agent in the 1st alignment agent and The different scheme of the side-chain structure of polymer.

(2) the 1st alignment agents and the 2nd alignment agent contain polymer A and polymer B as component of polymer and these polymer Scheme A different in the 1st alignment agent and the 2nd alignment agent from the allotment ratio of polymer B.

(3) main framing of the polymer contained as component of polymer is different from the 2nd alignment agent in the 1st alignment agent Scheme.

In these, for glass baseplate, high-temperature technology is applied in film formation, on the other hand, for film base material, sufficiently really Screening characteristics and resistance to finger pressing property are protected, and can be preferably set as the viewpoint using low temperature process in film formation (3).As the concrete example of (3), preferably following scheme: aligning agent for liquid crystal (this reality on the surface of glass baseplate will be formed in Apply in mode as the 1st alignment agent) it is set as comprising in the group as composed by polyamic acid, poly amic acid ester and polyimides At least one polymer composition as component of polymer, will be formed on the surface of film base material aligning agent for liquid crystal (this It is the 2nd alignment agent in embodiment) it is set as polymer composition comprising polymer P Ac as component of polymer.Passing through height In the case that warm technique carries out film formation, rear baking temperature is preferably 80 DEG C~300 DEG C, more preferably 120 DEG C~250 DEG C.Afterwards Baking time is preferably 5 minutes~200 minutes, more preferably 10 minutes~100 minutes.In the situation, in the liquid crystal of Fig. 1 Show in element 10, the liquid crystal orientation film 21 being formed on the 1st substrate 11 as glass baseplate includes to be selected from by polyamic acid, gather At least one of group composed by amic acid esters and polyimides is used as component of polymer, is formed in as resin film base material The 2nd substrate 12 on liquid crystal orientation film 22 include polymer P Ac as component of polymer.

(other embodiments)

In the embodiment, liquid crystal orientation film 21, liquid crystal orientation film 22 are set as optical alignment film, such as can also pass through The friction treatment to be rubbed in a certain direction to film using the roller for being wound with the cloth comprising fibers such as nylon, artificial silk, cottons To assign liquid crystal aligning ability.

In the embodiment, it is set as one of the 1st substrate 11 and the 2nd substrate 12 to wrap resiniferous substrate, it can also It is set as both the 1st substrate 11 and the 2nd substrate 12 to wrap resiniferous substrate.

In the embodiment, liquid crystal orientation film is formed on the 1st substrate 11 and 12 the two of the 2nd substrate, but can also set For the composition for only forming liquid crystal orientation film in any one of the 1st substrate 11 and the 2nd substrate 12.

As film base material, for the phase difference by film base material realizes the viewpoint of view angle compensation, it is possible to use Postpone big resin film (for example, Δ nd > 20).

Embodiment

Hereinafter, by embodiment further progress specific description, but the disclosure is not limited to these embodiments.

In example below, weight average molecular weight Mw, the number average molecular weight of polymer are measured by the following method The solution viscosity of Mn and epoxide equivalent and polymer solution.Raw material compound and polymer used in following example must Measuring the synthesis carried out under synthesis scale shown in following synthesis examples by optionally repeat ensures.

[the weight average molecular weight Mw and number average molecular weight Mn of polymer]

Mw and Mn is by polystyrene scaled value obtained by the GPC measurement under the conditions of below.

Tubing string: Tosoh (stock) manufacture, TSKgelGRCXLII

Solvent: tetrahydrofuran or the N,N-dimethylformamide solution containing lithium bromide and phosphoric acid

Temperature: 40 DEG C

Pressure: 68kgf/cm²

[epoxide equivalent]

Epoxy list amount is by Japanese Industrial Standards (Japanese Industrial Standards, JIS) C2105 The hydrochloric acid of record-methyl ethyl ketone method is measured.

[solution viscosity of polymer solution]

The solution viscosity (mPas) of polymer solution is measured at 25 DEG C using E type rotational viscometer.

The abbreviation of compound used in example below and the relationship of structural formula are as described below.Furthermore below in order to It is convenient, " compound represented by formula (X) " is represented simply as " compound (X) ".

(carboxylic acid)

[changing 8]

(additive)

[changing 9]

The synthesis > of < polyamic acid

[synthesis example 1-1]

By as the 1,2,3,4- cyclobutane tetracarboxylic dianhydride 136.7g of tetracarboxylic dianhydride (relative to used in synthesis two 100 molar part of amine and be 90 molar parts) and 2,2'- dimethyl -4,4'- benzidine base 163.3g as diamines it is molten Solution carries out reacting for 3 hours at 40 DEG C in NMP1700g.Then, reaction mixture is injected into excessive methanol, Precipitate reaction product.After cleaning the sediment recycled using methanol, carry out doing for 15 hours under reduced pressure, at 40 DEG C It is dry, thus to obtain 290g polyamic acid (hereinafter, being set as polymer (PAA-1)).With by resulting polymer (PAA-1) in NMP In prepared as the mode of 10 mass %, measure the viscosity of the solution, result 80mPas.In addition, by described poly- Polymer solution stands 3 at 20 DEG C, as a result gelation does not occur and storage stability is good.

[synthesis example 1-2]

By as the 1,2,3,4- cyclobutane tetracarboxylic dianhydride 23.7g of tetracarboxylic dianhydride (relative to used in synthesis two 100 molar part of amine and be 46.5 molar parts) and pyromellitic acid anhydride 26.4g (relative to 100 moles of diamines used in synthesis Part and be 46.5 molar parts) and bis- [2- (4- aminophenyl) ethyl] adipic acid 99.9g as diamines be dissolved in propylene glycol In monomethyl ether 850g, reacted 6 hours at 40 DEG C.Thus to obtain polyamic acid (hereinafter, being set as polymer (PAA-2)) solution. The viscosity of resulting polymer (PAA-2) solution is measured, result 370mPas.In addition, by the polymer solution 3 are stood at 20 DEG C, as a result gelation does not occur and storage stability is good.

The synthesis > of < poly amic acid ester

[synthesis example 2]

Firstly, synthesizing following formula (DE- according to the method recorded in International Publication No. 2010/092989 embodiment 4 1) compound represented by, and according to the method recorded in International Publication No. 2010/092989 embodiment 47, under synthesis State compound represented by formula (DC-1).

[changing 10]

Then, in the 50mL three-necked flask for having nitrogen ingress pipe and thermometer, 1.08g (10.0mmol) is added to benzene Diamines, 16.0gNMP are cooled to about 10 DEG C, and prepare diamine solution.Being added wherein makes 3.12g (9.6mmol) compound (DC-1) it is dissolved in the solution of acid chloride being prepared in 1.90g (21.6mmol) pyridine and 16.0g gamma-butyrolacton in advance, in nitrogen Under air-flow, at room temperature react 4 hours.Resulting polymeric solution is diluted by gamma-butyrolacton, the one side in deionized water One side is stirred gently to inject and solidify.The solid for recycling precipitating, repeats 2 stirring and washings in isopropanol, It is dried in vacuo at 60 DEG C, and obtains the poly amic acid ester (PAE-1) of white powder.The quantity mean molecule of the polymer Measuring Mn is 19,000, molecular weight distribution mw/mn 1.5.

The synthesis > of polysiloxanes of the < containing epoxy group

[synthesis example 3]

2- (3,4- epoxy group is packed into the reaction vessel for having blender, thermometer, addition funnel and the cooling tube that flows back Cyclohexyl) ethyl trimethoxy silane 70.5g, tetraethoxysilane 14.9g, ethyl alcohol 85.4g and triethylamine 8.8g, in room temperature Lower mixing.Then, it after spending 30 minutes dropwise addition deionized water 70.5g from addition funnel, is stirred under reflux and at 80 DEG C Lower reaction 2 hours.Reaction solution is concentrated, is diluted using butyl acetate, the operation is repeated twice, is thus steamed It evaporates except triethylamine and water, obtains the polymer solution comprising the polysiloxane (SEp-1) containing epoxy group.Carry out 1H-NMR analysis, as a result confirmed the side reaction for not causing epoxy group during the reaction.The polysiloxane (SEp-1) Mw be 11,000, epoxide equivalent be 200g/ moles.

[synthesis example 4]

2- (3,4- epoxy group is packed into the reaction vessel for having blender, thermometer, addition funnel and the cooling tube that flows back Cyclohexyl) ethyl trimethoxy silane 100.0g, methyl iso-butyl ketone (MIBK) 500g and triethylamine 10.0g, it mixes at room temperature.After And after spending 30 minutes dropwise addition deionized water 100g from addition funnel, carry out under reflux mixing and at 80 DEG C reaction it is 6 small When.After the completion of reaction, organic layer is taken out, is become by the water that 0.2 mass % aqueous ammonium nitrate solution is cleaned to cleaning After until neutrality, distillation removes solvent and water under reduced pressure, thus to obtain polysiloxane (SEp-2) conduct containing epoxy group The viscous transparency liquid adjusted.1H-NMR analysis has been carried out to the polysiloxane (SEp-2), as a result confirmed in reaction process In do not cause the side reaction of epoxy group.The weight average molecular weight (Mw) of polysiloxane obtained in synthesis example 4 (SEp-2) It is 2,200, epoxide equivalent is 186g/ moles.

< has the synthesis > of the polysiloxanes of functional base

[synthesis example 5]

The polysiloxane (SEp-1) containing epoxy group obtained in synthesis example 3 is packed into the three-necked flask of 100mL 11.3g, n-butyl acetate 13.3g, cinnamic acid derivative 1.7g represented by the formula (CA-1) are (relative to polysiloxane (SEp-1) 100 molar part of epoxy group possessed by and be 32 molar parts), the carboxylic acid (Aronix (Aronix) containing acryloyl group M-5300, East Asia synthesis (stock) manufacture) 0.54g is (relative to 100 moles of epoxy group possessed by polysiloxane (SEp-1) Part and be 8 molar parts) and tetrabutylammonium bromide 0.9g, stirred 12 hours at 80 DEG C.After the completion of reaction, and then 20g is added N-butyl acetate carries out after washing three times the solution, and then additional 20g n-butyl acetate, is become with solid component concentration The mode of 10 weight % distills removal solvent.It is obtained as a result, containing the polymer (S-1) as light orientation polysiloxane 10 mass % of solid component concentration n-butyl acetate solution.The weight average molecular weight Mw of polymer (S-1) is 18,000.

[synthesis example 6]

The polysiloxane (SEp-2) containing epoxy group obtained in synthesis example 4 is packed into the three-necked flask of 100mL 8g, cyclopentanone 27.5g, cinnamic acid derivative 2.5g (is relative to 100 molar part of epoxy group represented by the formula (CA-2) 60 molar parts) and tetrabutylammonium bromide 0.1g, it is stirred 12 hours at 100 DEG C.After the completion of reaction, additional cyclohexanone 30g, leads to It crosses after 6 liquid separations cleaning washes the solution, and then additional 100gN- N-methyl-2-2-pyrrolidone N, it is dense with solid component Degree distills removal solvent as the mode of 10 mass %.It is obtained as a result, containing the polymer (S-2) as polysiloxane The nmp solution of 10 mass % of solid component concentration.The weight average molecular weight Mw of polymer (S-2) is 12,000.

The synthesis > of poly- (methyl) acrylate of <

[synthesis example 7]

Bis- (isobutyronitriles) 1 of 2,2'- azo of polymerization initiator are loaded as in the flask for having cooling tube and blender Mass parts and 180 mass parts of diethylene glycol Methyl ether as solvent.Then, methacrylic acid 3,4- epoxycyclohexyethylSiOi is added 20 mass parts of 80 mass parts of base methyl esters and methacrylic acid 3- methyl -3- oxetanylmethoxy methyl esters, after carrying out nitrogen displacement, slowly Ground starts to stir.Solution temperature is being risen to 80 DEG C, the temperature is being kept for 5 hours, and is being obtained comprising as containing epoxy group Polymethacrylates polymer (PAc-0) polymer solution.Furthermore according to the solid component concentration of polymer solution The monomer consumption rate (reaction conversion (conversion)) after reaction that calculates of measurement result be 99%.In addition, gained Polymer Mn be 16,000.

[synthesis example 8]

It is packed into 100 mass parts of polymethacrylates (PAc-0) obtained in synthesis example 7 containing epoxy group, contains acryloyl Carboxylic acid (Aronix (Aronix) M-5300, East Asia synthesis (stock) manufacture) 30 mass parts, the tetrabutyl as catalyst of base 10 mass parts of ammonium bromide, 150 mass parts of propylene glycol methyl ether acetate as solvent, are stirred in a nitrogen environment, at 90 DEG C 12 hours.After the completion of reaction, it is diluted using 100 mass parts of propylene glycol methyl ether acetate, and is washed three times.It is right The solution is concentrated, and is diluted using butyl acetate, and the operation is repeated twice, and is obtained comprising as containing propylene The polymer solution of the polymer (Pac-1) of the polymethacrylates of acyl group.The Mn of resulting polymer is 20,000.

[synthesis example 9]

In the flask for having cooling tube and blender, it is packed into 2,2'- azo pair -1.2 mass parts of isobutyronitrile and propylene glycol - 200 mass parts of 1- monomethyl ether -2- acetic acid esters.Then 80 mass parts of glycidyl methacrylate and 20 mass of styrene are packed into Part, after carrying out nitrogen displacement, slowly start to stir.So that solution temperature is risen to 95 DEG C, the temperature kept for 5 hours, And obtain the polymer solution comprising polymer (Pac-2).Furthermore according to the measurement knot of the solid component concentration of polymer solution Fruit and the monomer consumption rate (reaction conversions) after reaction that calculates is 99%.

The preparation > of < aligning agent for liquid crystal

[preparation example 1]

As component of polymer, the solution of polymer (S-1) will be contained obtained in synthesis example 5 to be scaled polymer (S-1) solution being equivalent to obtained in the amount and synthesis example 8 of 20 mass parts containing polymer (Pac-1) is poly- to be scaled It closes object (Pac-1) and is equivalent to the amount and the mixing of 5 mass parts of compound (add-1) of 80 mass parts, be added thereto as molten N-butyl acetate (BA), methyl ethyl ketone (MEK) and the propylene glycol methyl ether acetate (PGMEA) of matchmaker simultaneously dissolve, with solid at Point concentration is 4.0 mass %, the mass ratio of each solvent is prepared as the mode of BA:MEK:PGMEA=60:25:15.Utilize aperture 0.2 μm of filter is filtered the solution, thus prepares aligning agent for liquid crystal (A-1).

[2~preparation example of preparation example 7]

In addition to by the type of used polymer, crosslinking agent and solvent and blending amount such as recorded in following table 1 into Other than row change, aligning agent for liquid crystal (A-2)~aligning agent for liquid crystal (A-7) is prepared respectively in the same manner as preparation example 1.

[table 1]

Furthermore the numerical value of the blending amount of polymer and additive in table 1 indicates each compound relative to aligning agent for liquid crystal Preparation used in component of polymer total 100 mass parts allotment ratio (mass parts).The numerical value of the blending amount of solvent Indicate the allotment ratio (mass ratio) of the entire amount of solvent used in preparation of each compound relative to aligning agent for liquid crystal.Table 1 In, contracted notation is as described below.

(additive)

Add-1: trimellitic anhydride (compound represented by the formula (Add-1))

Add-2: compound represented by the formula (Add-2)

Add-3:3- glycidoxypropyltrimewasxysilane (compound represented by the formula (Add-3))

Add-4:N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine

(solvent)

PGME: propylene glycol monomethyl ether

PGMEA: propylene glycol methyl ether acetate

NMP:N- N-methyl-2-2-pyrrolidone N

BC: butyl cellosolve

BA: n-butyl acetate

MEK: methyl ethyl ketone

GBL: gamma-butyrolacton

[embodiment 1: utilizing the FFS type liquid crystal display element of light orientation]

1. the evaluation of the screening characteristics of pair film base material

The aligning agent for liquid crystal (A-1) of the preparation is coated on COP film base material using slit coater, at 120 DEG C Heating 2 minutes, is consequently formed 0.1 μm of average film thickness of film.Visually and 10 times of multiplying power microscope to the film into Thus the presence or absence of coating unevenness and defect (pin hole) of film coated surface are investigated in row observation.Evaluation is not observe by visual observation and Coating to coated surfaces is uneven and does not also observe every 1cm by microscope²The situation of defect be set as " excellent ", will pass through Every 1cm that the coating of coated surfaces is uneven but observes by microscope is not observed visually and²Defect number be 1 with Upper and 4 situations below are set as " good ", will not observe the coating unevenness of coated surfaces by visual observation and but by micro- Every 1cm that sem observation arrives²The number of defect be that 5 or more and 9 situations below are set as " qualification ", will by visual observation and not Observe every 1cm that the coating of coated surfaces is uneven but observes by microscope²The number of defect be 10 or more feelings Shape or by visual observation and the uneven situation of coating that recognizes coated surfaces is set as " bad ".As a result, in the present embodiment, The coating unevenness and defect for not observing coated surfaces, are judged as screening characteristics " excellent ".Furthermore COP film used in substrate Delay be 4nm.

2. utilizing the manufacture for the FFS type liquid crystal display element that optical alignment method carries out

Make FFS type liquid crystal display element 10 shown in FIG. 1.It is sequentially formed with firstly, single side is had without pattern Electrode pair made of common electrode 14, silicon nitride film and the patterned pixel electrode 16 for comb teeth-shaped as insulating layer 15 The COP film base material (the 2nd substrate 12) of glass baseplate (the 1st substrate 11) and the opposite substrate as not set electrode is set as one It is right, it is wherein respectively coated the system on one side in face with transparent electrode of the 1st substrate 11 and the 2nd substrate 12 using rotator Standby aligning agent for liquid crystal (A-1).Then, film is formed and carrying out 2 minutes prebake conditions to it on 120 DEG C of hot plate.After And 254nm's is included to each surface irradiation of these films using Hg-Xe lamp and Glan-Taylor prism self-reference substrate normal direction The polarisation ultraviolet light 300mJ/cm of bright line².Thereafter, carried out in library nitrogen displacement baking oven at 230 DEG C to glass Substrate carries out heating (rear baking) in 15 minutes, has carried out in the baking oven of nitrogen displacement in library at 120 DEG C to COP film base material Carry out heating in 15 minutes (rear baking).0.1 μm of average film thickness of liquid crystal orientation film is formed on each substrate as a result,.

The floor map of pixel electrode 16 used herein is shown in Fig. 3 and Fig. 4.Furthermore Fig. 4 is in Fig. 3 with dotted line The enlarged drawing of the part C1 of encirclement.In the present embodiment, using line width d1 with electrode be 4 μm, interelectrode distance d2 is 6 μm Pixel electrode 16 substrate.Furthermore as pixel electrode 16, as shown in figure 3, using electrode A, electrode B, electrode C and electrode D Four systems driving electrodes.In the situation, electrode of the common electrode 14 as the driving electrodes whole for four systems that act on And play a role, the region of the driving electrodes of four systems respectively becomes pixel electrode.In addition, the photo-irradiation treatment to film passes through If under type carries out, i.e., become double in Fig. 4 in the direction the plane of polarisation of polarisation ultraviolet light to be projected to the line segment to substrate After the mode in the direction of arrow sets plane of polarisation direction, self-reference substrate normal direction irradiates polarisation ultraviolet light.

Secondly, being incorporated with 3.5 μm of diameter of aluminium oxide in the outer rim coating for forming substrate in the film with electrode structure After the photo-hardening epoxy acrylic resin system solid of spacer, liquid crystal " MLC-6221 " (Merck of necessary amount is added dropwise (Merck) company manufactures).At this point, liquid crystal is added dropwise to multiple positions that film is formed on substrate.In addition, by the dropwise addition of liquid crystal Total amount is set as the volume that the area for being coated with solid is multiplied with spacer diameter and finds out being 0.98 times~1.0 Times, the dripping quantity at one is adjusted between 0.2g~1.0g.Then, the substrate of liquid crystal is set to vacuum forming apparatus dropwise addition It is interior, in after the setting of the opposite sides of the substrate is formed with the ilm substrate of film, implement fitting under vacuum.Terminate in fitting Afterwards, make solid partially hardened using the UV light of 365nm, then implement to anneal for 2 minutes in 120 DEG C of baking oven, thus make Make liquid crystal cells.

Secondly, by being bonded polarizer on the outside two sides of substrate, and manufacture FFS type liquid crystal display element 10.At this point, partially A piece of polarizer in tabula rasa is with plane of polarisation the penetrating on real estate of its polarization direction and the polarisation ultraviolet light of liquid crystal orientation film The parallel mode in shadow direction is attached, and another polarizer is orthogonal with the polarization direction of polarizer before with its polarization direction Mode attached.

3. the evaluation of liquid crystal aligning

For the FFS type liquid crystal display element manufactured in described 2., by microscope with 50 times of multiplying power observations by 5V's The presence or absence of the abnormal domain (domain) in light and shade variation when voltage turn-on disconnection (ONOFF) (apply and release).Evaluation It is that the situation for not observing abnormal domain is set as to liquid crystal aligning " good ", it will be observed that the situation in abnormal domain is set as liquid crystal aligning Property " bad ".As a result, liquid crystal aligning is " good " in the liquid crystal display element.

4. the evaluation of resistance to finger pressing property

It is using pull and push dynamometer, the flat pressure head in front end is vertical for the FFS type liquid crystal display element manufactured in described 2. Ground is attached on liquid crystal display element face, is situated between every cushion rubber, is applied 2kgf/cm in such a way that load is uniform²Pressure.By institute It states operation to repeat 10 times, carries out the evaluation of resistance to finger pressing property.Evaluation be by with described " 3. liquid crystal alignings are commented Valence " is carried out similarly micro- sem observation and carries out, and the situation for not observing abnormal domain and light leakage is judged as resistance to finger pressing property " good " will not observe abnormal domain but observe that the situation of light leakage is evaluated as resistance to finger pressing property " qualification ", it will be observed that is different The situation in normal domain is evaluated as resistance to finger pressing property " bad ".As a result, do not observed in the liquid crystal display element abnormal domain and Any one of light leakage, and it is judged as resistance to finger pressing property " good ".

[3~embodiment of embodiment 7]

Respectively using aligning agent for liquid crystal (A-2)~aligning agent for liquid crystal (A-5) shown in following table 2, similarly to Example 1 Carry out the manufacture and evaluation of liquid crystal display element.Furthermore about embodiment 5, liquid crystal orientation film only is formed on the 1st substrate 11. By each embodiment evaluation result is shown in table in 2.

[embodiment 2: utilizing the FFS type liquid crystal display element of friction orientation]

1. the evaluation that film forms the rub resistance of ilm substrate

Including Ah Dun (ARTON) film (Japan SYnthetic Rubber Co. Ltd (Japan Synthetic using rotator Rubber, JSR) company manufacture A Dun (ARTON)) substrate on be coated with preparation example 1 obtained in aligning agent for liquid crystal (A-1), After carrying out 1 minute prebake conditions on 80 DEG C of hot plate, it is small that progress 1 in 120 DEG C of baking oven of nitrogen displacement has been carried out in library Shi Jiare (rear baking), is consequently formed 0.1 μm of average film thickness of film.

Then, by having the friction mechanism for the roller for being wound with cotton, in roller revolving speed 1,000rpm, platform movement speed 20cm/ seconds, hair indentation length 0.4mm under to resulting film implement 2 friction treatments.It is resulting using optical microphotograph sem observation Generated foreign matter (fragment of film) is ground by friction on substrate, measures the foreign matter number in the region of 500 μm of 500 μ m. It is that 19 situations below are set as rub resistance " good ", 20 or more situations are set as antifriction that evaluation, which is by the number of foreign matter, Wipe property " bad " and carry out.As a result, not observing foreign matter, the rub resistance of the film is judged as " good ".Furthermore substrate Used in Ah 's (ARTON) film have biaxiality phase difference film performance.

2. utilizing the manufacture for the FFS type liquid crystal display element that friction treatment carries out

Firstly, using rotator in 2. with the embodiment 1 identical a pair of of the substrate of user each surface difference Coating of liquid crystalline alignment agent (A-1) and form film.Then, the film is being subjected to 1 minute prebake conditions on 80 DEG C of hot plate Afterwards, it has carried out carrying out heating in 2 hours (rear baking) in the baking oven of nitrogen displacement at 120 DEG C in library, and has formed average film Thick 0.1 μm of film.Then, with described 1. under the same conditions, using cotton to each of the film being formed on a pair of of substrate Friction treatment is implemented on surface, and liquid crystal orientation film is made.

Secondly, being incorporated with 3.5 μm of diameter of aluminium oxide in the outer rim coating for forming substrate in the film with electrode structure After the photo-hardening epoxy acrylic resin system solid of spacer, liquid crystal " MLC-6221 " (Merck of necessary amount is added dropwise (Merck) company manufactures).At this point, liquid crystal is added dropwise to multiple positions that film is formed on substrate.In addition, by the dropwise addition of liquid crystal Total amount is set as the volume that the area for being coated with solid is multiplied with spacer diameter and finds out being 0.98 times~1.0 Times, the dripping quantity at one is adjusted between 0.2g~1.0g.Then, the substrate of liquid crystal is set to vacuum forming apparatus dropwise addition It is interior, in after the setting of the opposite sides of the substrate is formed with the ilm substrate of film, implement fitting under vacuum.Terminate in fitting Afterwards, make solid partially hardened using the UV light of 365nm, then implement to anneal for 2 minutes in 120 DEG C of baking oven, thus make Make liquid crystal cells.Then, polarizer (attached drawing summary) is fitted in by base in the orthogonal mode of the polarization direction of two panels polarizer Thus the outside two sides of plate makes liquid crystal display element 10.

3. the evaluation of liquid crystal aligning

For the FFS type liquid crystal display element manufactured in described 2., liquid crystal is carried out similarly with the 3. of the embodiment 1 and is taken The evaluation of tropism.As a result, the liquid crystal display element is liquid crystal aligning " good ".

4. the evaluation of resistance to finger pressing property

For the FFS type liquid crystal display element manufactured in described 2., resistance to finger is evaluated in the same manner as the 4. of the embodiment 1 Pressing property.As a result, not observing abnormal domain and light leakage in the liquid crystal display element, and it is judged as that resistance to finger pressing property is " good It is good ".

[embodiment 8: utilizing the FFS type liquid crystal display element of friction orientation]

1. the evaluation of the screening characteristics of pair film base material

Using aligning agent for liquid crystal (A-6), the evaluation to the screening characteristics of film base material is carried out similarly with the embodiment 1.Its As a result, observing that the coating of film coated surface is uneven and is judged as " bad " by visual observation.In addition, the heating in 2 minutes at 120 DEG C Under the conditions of, there is viscosity in film coated surface, and speculate that solvent is not sufficiently dry.

2. the evaluation that film forms the rub resistance of ilm substrate

Due to judging that solvent is not sufficiently dry under 2 minutes heating conditions at 120 DEG C, uses rotator by liquid crystal Alignment agent (A-6) is coated in polyethylene terephthalate (polyethylene terephthalate, PET) ilm substrate, After carrying out 1 minute prebake conditions on 80 DEG C of hot plate, it is small that progress 1 in 150 DEG C of baking oven of nitrogen displacement has been carried out in library Shi Jiare (rear baking), is consequently formed 0.1 μm of average film thickness of film.Then, by having the friction for the roller for being wound with cotton Machinery implements 2 to resulting film under 000rpm, platform movement speed 20cm/ seconds, hair indentation length 0.4mm in roller revolving speed 1 Secondary friction treatment, using on the resulting substrate of optical microphotograph sem observation by friction be ground caused by foreign matter (film it is broken Piece), rub resistance is evaluated similarly to Example 2.As a result, confirming foreign matter is 15/0.25mm², the film it is resistance to Frictional property is judged as " good ".

3. utilizing the manufacture for the FFS type liquid crystal display element that friction treatment carries out

Other than the aligning agent for liquid crystal (A-6) for using the preparation, FFS type liquid is made in the same manner as the 2. of embodiment 2 Crystal display element 10.

4. the evaluation of liquid crystal aligning

For the FFS type liquid crystal display element manufactured in described 3., liquid crystal is carried out similarly with the 3. of the embodiment 1 and is taken The evaluation of tropism.As a result, the liquid crystal display element is liquid crystal aligning " good ".

5. the evaluation of resistance to finger pressing property

For the FFS type liquid crystal display element manufactured in described 3., resistance to finger is evaluated in the same manner as the 4. of the embodiment 1 Pressing property.As a result, observing abnormal domain and light leakage in the liquid crystal display element, and it is judged as resistance to finger pressing property " no It is good ".

[embodiment 9]

Using aligning agent for liquid crystal (A-7), manufacture and the evaluation (coating for the liquid crystal display element that is performed in the same manner as in Example 2 Property, liquid crystal aligning and resistance to finger pressing property).It shows the results of the evaluation in table 2.

[table 2]

For film base material, is using the aligning agent for liquid crystal containing poly- (methyl) acrylate and passing through light orientation processing And formed in the embodiment 1, embodiment 3, embodiment 4 of liquid crystal orientation film, even if rear baking temperature is set as 120 DEG C of low temperature In the case of also uneven almost without coating, screening characteristics " excellent " or " good ".In addition, the liquid of embodiment 1, embodiment 3, embodiment 4 The liquid crystal aligning of crystal display element and resistance to finger pressing property are also excellent, especially embodiment 1, in embodiment 3 be " good " Evaluation.

In addition, using the aligning agent for liquid crystal containing poly- (methyl) acrylate and forming liquid crystal aligning by friction treatment In the embodiment 2 of film, rub resistance is good, and the liquid crystal aligning of resulting liquid crystal display element and resistance to finger pressing property are also good It is good.

About the not formed liquid crystal orientation film in film base material side embodiment 5 and used the liquid crystal containing poly amic acid ester The embodiment 6 of alignment agent, resistance to finger pressing property are the evaluation of " qualification ", and screening characteristics and liquid crystal aligning are the evaluation of " good ".

About embodiment 7, the embodiment 8 for having used the aligning agent for liquid crystal containing polyamic acid, resistance to finger pressing property is " no It is good ", screening characteristics is also and less good, but liquid crystal aligning is the evaluation of " good ".By the inclusion of a large amount of specific solvent As solvent composition aligning agent for liquid crystal (A-7) and formed in the embodiment 9 of liquid crystal orientation film, even if being set by rear baking temperature In the case where 120 DEG C of low temperature, screening characteristics is also " good ".In addition, liquid crystal aligning and resistance to finger pressing property are also " good " Evaluation.

The disclosure be described according to embodiment, but can be regarded as the disclosure be not limited to the embodiment or Structure.The disclosure also includes the deformation in various modifications example or equivalency range.In addition to this, by various combinations or mode, into one Step is also included in the disclosure comprising only one element, other combinations of more than one or element below or mode in these Scope or thought range in.

The explanation of symbol

10: liquid crystal display element

11: the 1 substrates

12: the 2 substrates

13: liquid crystal layer

14: common electrode

16: pixel electrode

21,22: liquid crystal orientation film

Claims

1. a kind of liquid crystal cell including the 1st substrate, the 2nd substrate configured in opposite directions with the 1st substrate and is configured at described Liquid crystal layer between 1st substrate and the 2nd substrate,

At least one of 1st substrate and the 2nd substrate are to wrap resiniferous substrate, and the liquid crystal cell includes:

Common electrode is set on the 1st substrate；

Pixel electrode, the isolation velum that is situated between in the common electrode in the 1st substrate configure；And

Liquid crystal orientation film is formed at least one of the 1st substrate and described 2nd substrate, and adjacent with the liquid crystal layer It connects.

2. liquid crystal cell according to claim 1, wherein the 1st substrate is glass baseplate, the 2nd substrate be comprising The substrate of resin.

3. liquid crystal cell according to claim 1 or 2, wherein the liquid crystal orientation film contain selected from by with polymerism not At least one of group composed by the polymer of the monomer of saturated bond, polyamic acid, poly amic acid ester and polyimides is poly- Close object.

4. liquid crystal cell according to any one of claim 1 to 3, wherein be formed on wrapping resiniferous substrate containing The liquid crystal orientation film of the polymer of monomer with polyunsaturated bond.

5. liquid crystal cell according to any one of claim 1 to 4, wherein the liquid crystal orientation film is that have by containing The aligning agent for liquid crystal of the polymer of light orientation base and formed.

6. liquid crystal cell according to any one of claim 1 to 5, wherein the liquid crystal orientation film is selected from by containing The aligning agent for liquid crystal of at least one of the group as composed by silane compound and polysiloxanes compound and formed.

7. liquid crystal cell according to any one of claim 1 to 6, wherein the liquid crystal orientation film be respectively formed in it is described On 1st substrate and the 2nd substrate, the liquid crystal orientation film that is formed on the 1st substrate and it is formed on the 2nd substrate Liquid crystal orientation film is formed using aligning agent for liquid crystal different from each other is formed.

8. liquid crystal cell according to claim 7, wherein the 1st substrate is glass baseplate, the 2nd substrate be comprising The substrate of resin,

The liquid crystal orientation film being formed on the 1st substrate includes selected from by polyamic acid, poly amic acid ester and polyimides institute At least one of group of composition,

The liquid crystal orientation film being formed on the 2nd substrate includes the polymer of the monomer with polyunsaturated bond.

9. liquid crystal cell according to any one of claim 1 to 8, wherein the liquid crystal orientation film is that have by containing The aligning agent for liquid crystal of the compound of bridging property base and formed.

10. a kind of manufacturing method of liquid crystal cell, wherein the liquid crystal cell is matched in opposite directions including the 1st substrate, with the 1st substrate The 2nd substrate set and the liquid crystal layer being configured between the pair of substrate, and

At least one of 1st substrate and the 2nd substrate are to wrap resiniferous substrate,

Common electrode is provided on the 1st substrate and the pixel for completely cutting off velum and configuring that is situated between in the common electrode Electrode,

The manufacturing method of the liquid crystal cell includes:

The step of liquid crystal orientation film is formed at least one of the 1st substrate and the 2nd substrate coating of liquid crystalline alignment agent Suddenly；And

After forming the liquid crystal orientation film, Jie configures the 1st substrate and the 2nd substrate every the liquid crystal layer in opposite directions And the step of constructing liquid crystal cells.

11. the manufacturing method of liquid crystal cell according to claim 10, wherein including resin to being coated at 150 DEG C or less Substrate surface on aligning agent for liquid crystal heated.

12. the manufacturing method of liquid crystal cell described in 0 or 11 according to claim 1, wherein relative in the aligning agent for liquid crystal The total amount of contained solvent, in the aligning agent for liquid crystal selected from by n-methyl-2-pyrrolidone, gamma-butyrolacton and N- ethyl- The content ratio of at least one of group solvent composed by 2-Pyrrolidone is 30 mass % or less.