CN104737069B

CN104737069B - Aligning agent for liquid crystal and the liquid crystal display element for using the aligning agent for liquid crystal

Info

Publication number: CN104737069B
Application number: CN201380054892.7A
Authority: CN
Inventors: 桥本淳; 佐藤夏树; 后藤耕平; 平贺浩二; 元山贤; 元山贤一
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2012-08-30
Filing date: 2013-08-29
Publication date: 2018-08-10
Anticipated expiration: 2033-08-29
Also published as: WO2014034792A1; TW201431952A; JPWO2014034792A1; TWI637026B; KR102115015B1; CN104737069A; KR20150052120A; JP6233310B2

Abstract

The present invention provides a kind of aligning agent for liquid crystal, can form liquid crystal orientation film of the response speed after improving UV irradiations without reducing vertical orientation power；And a kind of liquid crystal display element, there is the liquid crystal orientation film obtained by the aligning agent for liquid crystal to be handled in the same manner as PSA modes using the liquid crystal for not adding liquid crystal polymerizable compound, the response speed after UV irradiations improves.A kind of aligning agent for liquid crystal contains polysiloxanes ((B) ingredient) obtained from the alkoxy silane polycondensation selected from least one of the group being made of polyamic acid and polyimides polymer ((A) ingredient) and the alkoxy silane for making the alkoxy silane indicated containing formula (1) and formula (3) indicate.R¹Expression (2), R²For the alkyl of carbon atom number 1~5.Y¹For singly-bound etc., Y²For singly-bound etc., Y³For singly-bound etc., Y⁴For bivalent cyclics base such as phenyl ring etc., Y⁵For bivalent cyclics base such as phenyl ring etc., Y⁶For the alkyl etc. of carbon atom number 1~18, n is 0~4.R³The alkyl that carbon atom number to be replaced by acryloyl group, acryloxy, methylacryloyl, methacryloxy or styryl is 1~30, R⁴For the alkyl of carbon atom number 1~5.R¹Si(OR²)₃ (1)R³Si(OR⁴)₃ (3)

Description

Aligning agent for liquid crystal and the liquid crystal display element for using the aligning agent for liquid crystal

Technical field

The liquid crystal orientation film and tool obtained the present invention relates to aligning agent for liquid crystal and by above-mentioned aligning agent for liquid crystal There is the liquid crystal display element of the liquid crystal orientation film.

Background technology

In recent years, in the display mode of liquid crystal display element, the liquid crystal display element of vertical (VA) mode is used extensively In the mobile purposes display unit of mobile phone (digital camera) etc. of the liquid crystal TV set of big picture, fine.VA modes In, it is known that the MVA modes (Multi of the protrusion of the inclined direction for controlling liquid crystal is formed on TFT substrate, filter substrate Vertical Alignment, multi-domain vertical alignment), formed and slit and utilize on ITO (indium-tin-oxide) electrode of substrate PVA (Patterned Vertical Alignment, pattern vertical orientation) mode of the inclined direction of electric field controls liquid crystal.

It is aligned as other, there is PSA (Polymer sustained Alignment, polymer stabilizing are orientated) side Formula.

In VA modes, PSA modes are the technologies to attract attention in recent years.In which, optical polymerism is added in liquid crystal Compound after making liquid crystal display panel, applies electric field, to liquid crystal display panel irradiation ultraviolet light (UV) in the state of LC tilt.Knot Photopolymerization occurs for fruit, polymerizable compound, and the differently- oriented directivity of liquid crystal is immobilized and generates pre-dumping as a result, and response speed improves. It is characterized in that, even if using slit is made on the unilateral electrode for constitute liquid crystal display panel, in the electrode pattern of opposite side Being not provided with the structure of slit as protrusion as MVA or PVA can also work, and can simplify manufacture, can obtain excellent Panel transmissivity (referring to patent document 1)

But in the liquid crystal display element of PSA modes, the dissolubility for being added to the polymerizable compound in liquid crystal is low, deposits The problem of being precipitated when increasing its additive amount in low temperature.In addition, when reducing the additive amount of polymerizable compound, it is unable to get good State of orientation well, response speed.In addition, there is also remain in the unreacted polymerizable compound in liquid crystal as in liquid crystal Impurity and make liquid crystal display element reliability reduce the problem of.

Therefore, it is proposed to following technology：Be used in the polymer that photoreactivity side chain has been imported in polymer molecule and Obtained aligning agent for liquid crystal is applied on substrate, and liquid crystal orientation film is obtained after calcining, and setting is contacted with the liquid crystal orientation film Liquid crystal layer, irradiate ultraviolet light while applying voltage to the liquid crystal layer, liquid crystal display element made, even if not existing as a result, Polymerizable compound is added in liquid crystal, can also meet with a response fireballing liquid crystal display element (referring to patent document 2)

On the other hand, together with the liquid crystal aligning membrane material of the organic systems such as the polyimides that used in the past it is known also whether there is or not The liquid crystal aligning membrane material of machine system.For example, the liquid crystal aligning membrane material of the inorganic system as application type, it is proposed that contain four alcoxyls The aligning agent for liquid crystal composition of the reaction product of base silane, trialkoxy silane, alcohol and oxalic acid, it was reported that it is in liquid crystal display The liquid crystal orientation film of vertical orientation, heat resistance and excellent in uniformity is formd on the electrode base board of element (referring to patent document 3)

In addition, it is proposed that contain tetraalkoxysilane, the reaction product of specific trialkoxy silane and water and specific Glycol ether series solvent aligning agent for liquid crystal composition, it was reported which form prevent from showing it is bad, driving for a long time Dynamic rear image retention characteristic is also good, it is few to reduce the reduction of voltage retention caused by the ability for making liquid crystal aligning and light and heat Liquid crystal orientation film (referring to patent document 4)

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2004-302061 bulletins

Patent document 2：Japanese Unexamined Patent Publication 2011-95967 bulletins

Patent document 3：Japanese Unexamined Patent Publication 09-281502 bulletins

Patent document 4：Japanese Unexamined Patent Publication 2005-250244 bulletins

Invention content

Problems to be solved by the invention

In the VA patterns of vertical orientation, need the strong vertical orientation power for making liquid crystal vertical-tropism, but without using In which of polymerizable compound, when improving vertical orientation power, the response speed after UV irradiations is slack-off, after improving UV irradiations When response speed, vertical orientation power reduces.Vertical orientation power is improved with the response speed after UV irradiations has anti-relationship of being contrary to.

The issue of the present invention is to provide a kind of aligning agent for liquid crystal, the liquid crystal obtained by the aligning agent for liquid crystal to take To film and the liquid crystal display element with the liquid crystal orientation film, which can form even if using not adding Add polymerizable compound liquid crystal, in the same manner as PSA modes handle improve UV irradiation after response speed mode liquid crystal Also liquid crystal orientation film of the response speed after UV irradiations without reducing vertical orientation power can be improved in display element.

The means to solve the problem

The present inventor has made intensive studies to achieve the goals above, as a result, it has been found that, it is selected from by polyamides by containing At least one of the group of amino acid and polyimides composition polymer ((A) ingredient) and specific polysiloxanes ((B) ingredient) Aligning agent for liquid crystal can realize above-mentioned purpose, so as to complete the present invention.

That is, the present invention has following main points.

1. a kind of aligning agent for liquid crystal, which is characterized in that containing following (A) ingredients and (B) ingredient,

(A) ingredient：Selected from least one of the group being made of polyamic acid and polyimides polymer,

(B) ingredient：Make the alkoxyl silicone of the alkoxy silane of the alkoxy silane and formula (3) expression that are indicated containing formula (1) Polysiloxanes obtained from alkane polycondensation.

R¹Si(OR²)₃ (1)

(R¹For the structure of following formula (2), R²For the alkyl of carbon atom number 1~5)

[changing 2]

(Y¹For singly-bound ,-(CH₂)_a(integer that a is 1~15) ,-O- ,-CH₂O- ,-COO- or-OCO-.

Y²The alkyl for the linear chain or branched chain that carbon atom number for singly-bound, containing double bond is 3~8 or-(CR¹⁷R¹⁸)_b-(b For 1~15 integer, R¹⁷、R¹⁸Hydrogen atom or carbon atom number are each independently as 1~3 alkyl).

Y³For singly-bound ,-(CH₂)_c(integer that c is 1~15) ,-O- ,-CH₂O- ,-COO- or-OCO-.

Y⁴For the bivalent cyclic base in phenyl ring, cyclohexyl ring and heterocycle, the arbitrary hydrogen in these cyclic groups is former Alkoxy that alkyl that son can be 1~3 by carbon atom number, carbon atom number are 1~3, carbon atom number be 1~3 containing fluoroalkyl, Fluoroalkoxy or the fluorine atom substitution that carbon atom number is 1~3.In addition, Y⁴It can be the carbon atom number with steroid skeleton For 12~25 bivalent organic group.

Y⁵For the bivalent cyclic base in the group being made of phenyl ring, cyclohexyl ring and heterocycle, appointing in these cyclic groups Alkoxy that alkyl that the hydrogen atom of meaning can be 1~3 by carbon atom number, carbon atom number are 1~3, carbon atom number are 1~3 Containing fluoroalkyl, the fluoroalkoxy that carbon atom number is 1~3 or fluorine atom substitution.

Y⁶For hydrogen atom or carbon atom number be 1~18 alkyl, carbon atom number be 1~18 containing fluoroalkyl, carbon atom The fluoroalkoxy that the alkoxy or carbon atom number that number is 1~18 are 1~18.The integer that n is 0~4)

R³Si(OR⁴)₃ (3)

(R³For can be by acryloyl group, acryloxy, methylacryloyl, methacryloxy or styryl The alkyl that substituted carbon atom number is 1~30, R⁴For the alkyl of carbon atom number 1~5)

2. according to the aligning agent for liquid crystal described in above-mentioned 1, wherein (B) ingredient is to make also to contain the alkane that following formula (4) indicates Polysiloxanes obtained from the alkoxy silane polycondensation of oxysilane.

(R⁵)_nSi(OR⁶)_4-n (4)

(in formula (4), R⁵For hydrogen atom or can be by hetero atom, halogen atom, amino, glycidoxy, sulfydryl, different Cyanic acid ester group, Carbamido substituted carbon atom number be 1~10 alkyl.R⁶For the alkyl of carbon atom number 1~5, n be 0~3 it is whole Number)

3. according to the aligning agent for liquid crystal described in above-mentioned 2, wherein the alkoxy silane that above-mentioned formula (4) indicates is tetramethyl Oxysilane or tetraethoxysilane.

4. according to the aligning agent for liquid crystal described in above-mentioned 1, wherein used in the manufacture of the polysiloxanes of (B) ingredient In whole alkoxy silanes, the alkoxy silane indicated using the formula (1) of 2~20 moles of %, and 5~80 moles of % of use The alkoxy silane that formula (3) indicates.

5. according to the aligning agent for liquid crystal described in above-mentioned 2 or 3, wherein the manufacture of the polysiloxanes of (B) ingredient is used Whole alkoxy silanes in, use 10~90 moles of % formula (4) indicate alkoxy silane.

6. according to the aligning agent for liquid crystal described in above-mentioned any one of 1~5, wherein relative to 100 mass of (A) ingredient Part, containing with the SiO of silicon atom possessed by (B) ingredient₂Scaled value is calculated as (B) ingredient of 0.5~80 mass parts.

7. according to the aligning agent for liquid crystal described in above-mentioned any one of 1~6, wherein also contain organic solvent, this is organic Solvent contains 90~99 mass % in aligning agent for liquid crystal.

8. a kind of liquid crystal orientation film, by the way that the aligning agent for liquid crystal described in above-mentioned any one of 1~7 is applied to base On plate and it is dried, calcines and obtain.

9. according to the liquid crystal orientation film described in above-mentioned 8, wherein carry out above-mentioned calcining at a temperature of 100~350 DEG C and carry out shape At liquid crystal orientation film.

10. according to the liquid crystal orientation film described in above-mentioned 8 or 9, wherein the thickness of the film after calcining is 5~300nm.

11. a kind of liquid crystal display element, with the liquid crystal orientation film described in above-mentioned any one of 8~10.

The effect of invention

According to the present invention, the response speed after capable of improving UV irradiations can be formed without reducing vertical orientation power by providing The aligning agent for liquid crystal of liquid crystal orientation film, the liquid crystal orientation film that is obtained by the aligning agent for liquid crystal and there is the liquid crystal Alignment films, the liquid crystal using polymerizable compound is not added, the response speed after processing, raising UV irradiations in the same manner as PSA modes The liquid crystal display element of the mode of degree.

Specific implementation mode

<(A) ingredient：Polyamic acid and/or polyimides>

Contain in the group being made of polyamic acid and polyimides at least in the aligning agent for liquid crystal of the present invention A kind of polymer.The concrete structure of the polyamic acid and polyimides is not particularly limited, such as can be that well known liquid crystal takes The polyamic acid or polyimides contained into inorganic agent.

Polyamic acid, which can be reacted by the derivative of tetrabasic carboxylic acid or tetrabasic carboxylic acid with (polycondensation) of diamines, to be readily available.

The polyamic acid of (A) ingredient used in the present invention and the manufacturing method of polyimides are not particularly limited. In general, make by the tetracarboxylic acid sour component that is constituted selected from one or more of the group being made of tetrabasic carboxylic acid or derivatives thereof with by The diamine component reaction that one or more kinds of diamine compounds is constituted obtains polyamic acid.

In addition, as the method for obtaining polyimides, the method imidated a polyamic acid can be used.

At this point, obtained polyamic acid can be appropriate by being carried out to the tetracarboxylic acid sour component and diamine component of being used as raw material It selects to obtain homopolymer or copolymer.

Herein, tetrabasic carboxylic acid or derivatives thereof is tetrabasic carboxylic acid, tetracarboxylic acid acid ihalide or tetracarboxylic dianhydride.Wherein, tetrabasic carboxylic acid The reactivity of dianhydride and diamine compound is high, therefore preferably.

Specifically, can enumerate：Pyromellitic Acid, 2,3,6,7- naphthalene tetracarboxylic acids, 1,2,5,6- naphthalene tetracarboxylic acids, 1,4,5, 8- naphthalene tetracarboxylic acids, 2,3,6,7- anthracenes tetrabasic carboxylic acid, 1,2,5,6- anthracenes tetrabasic carboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acids, 2,3,3 ', 4 '- Biphenyltetracarboxyacid acid, bis- (3,4- dicarboxyphenyis) ethers, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acids, bis- (3,4- dicarboxyphenyis) Sulfone, bis- (3,4- dicarboxyphenyis) methane, bis- (3,4- dicarboxyphenyis) propane of 2,2-, 1,1,1,3,3,3- hexafluoros -2,2- are double (3,4- dicarboxyphenyis) propane, bis- (3,4- dicarboxyphenyis) dimethylsilanes, bis- (3,4- dicarboxyphenyis) diphenyl silicon Bis- (3,4- dicarboxyphenyis) pyridines of alkane, 2,3,4,5- pyridines tetrabasic carboxylic acid, 2,6-, the bis- [4- (3,4- di carboxyl phenyloxies) of 2,2- Phenyl] propane, 3,3 ', 4,4 '-diphenylsulfone acids, 3,4,9,10- perylene tetracarboxylics, 1,3- diphenyl -1,2,3,4- Cyclobutane tetrabasic carboxylic acid, bis oxide O-phthalic tetrabasic carboxylic acid, 1,2,3,4- cyclobutane tetrabasic carboxylic acid, 1,2,3,4- pentamethylene tetrabasic carboxylic acid, 1,2,4,5- cyclopentanetetracarboxylics, 1,2,3,4- tetramethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acid, 1,2- dimethyl -1,2,3,4- Cyclobutane tetrabasic carboxylic acid, 1,3- dimethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acid, 1,2,3,4- cycloheptane tetrabasic carboxylic acid, 2,3,4,5- tetra- Hydrogen furans tetrabasic carboxylic acid, 3,4- dicarboxyl -1- cyclohexyl succinic acid, 2,3,5- tricarboxylic cyclopentyls acetic acid, dicarboxyl -1,2 3,4-, 3,4- tetrahydrochysene -1- naphthalene succinics, bicyclic [3,3,0] octane -2,4,6,8- tetrabasic carboxylic acids, bicyclic [4,3,0] nonane -2,4,7,9- four Carboxylic acid, bicyclic [4,4,0] decane -2,4,7,9- tetrabasic carboxylic acids, bicyclic [4,4,0] decane -2,4,8,10- tetrabasic carboxylic acids, tricyclic [6.3.0.0<2,6>] hendecane -3,5,9,11- tetrabasic carboxylic acids, 1,2,3,4- butane tetracarboxylic acid, alkene -2 bicyclic [2,2,2] octyl- 7-, The tetrabasic carboxylic acids such as 3,5,6- tetrabasic carboxylic acids, the 12 carbon alkane -4,5,9,10- tetrabasic carboxylic acids of Fourth Ring [6,2,1,1,0,2,7].Furthermore, it is possible to lift Go out the dihalide of these tetrabasic carboxylic acids or the dicarboxylic anhydride of tetrabasic carboxylic acid etc..

Wherein, from the aspect of the transparency of film, preferably ester ring type tetrabasic carboxylic acid, their dianhydride or their two Carboxylic acid dihalide.Particularly preferred 1,2,3,4- cyclobutane tetrabasic carboxylic acid, 2,3,5- tricarboxylic cyclopentyls acetic acid, 3,4- dicarboxyls- 1,2,3,4- tetrahydrochysene -1- naphthalene succinics, bicyclic [3,3,0] octane -2,4,6,8- tetrabasic carboxylic acids, these tetrabasic carboxylic acids dihalide or The dicarboxylic anhydride of these tetrabasic carboxylic acids.

Above-mentioned tetrabasic carboxylic acid or derivatives thereof can keep special according to liquid crystal aligning, the voltage when liquid crystal orientation film is made The characteristics such as property, accumulated charge using one kind or are used in mixed way two or more.

The diamines used in the manufacture of polyamic acid is not particularly limited.Specifically, can enumerate：P-phenylenediamine, 2, 3,5,6- tetramethyl-para-phenylene diamines, 2,5- dimethyl-p-phenylenediamines, m-phenylene diamine (MPD), 2,4- dimethyl-m-phenylenediamines, 2,5- diaminos Base toluene, 2,6- diaminotoluenes, 2,5- diaminophenols, 2,4- diaminophenols, 3,5- diaminophenols, 3,5- diamino Benzyl alcohol, 2,4- diaminobenzenes methanol, 4,6- diamino resorcins, 4,4 '-benzidines, 3,3 '-dimethyl -4,4 ' - Benzidine, 3,3 '-dimethoxy-4 's, 4 '-benzidines, 3,3 '-dihydroxy -4,4 '-benzidine, 3,3 '-two Carboxyl -4,4 '-benzidine, 3,3 '-two fluoro- 4,4 '-biphenyl, 3,3 '-trifluoromethyls -4,4 '-benzidine, 3,4 ' - Benzidine, 3,3 '-benzidines, 2,2 '-benzidines, 2,3 '-benzidines, 4,4 '-diamino-diphenyls Methane, 3,3 '-diaminodiphenyl-methanes, 3,4 '-diaminodiphenyl-methanes, 2,2 '-diaminodiphenyl-methanes, 2,3 '- Diaminodiphenyl-methane, 4,4 '-diaminodiphenyl ethers, 3,3 '-diaminodiphenyl ethers, 3,4 '-diaminodiphenyl ethers, 2,2 '- Diaminodiphenyl ether, 2,3 '-diaminodiphenyl ethers, 4,4 '-sulfonyldianilines, 3,3 '-sulfonyldianilines, bis- (4- amino Phenyl) silane, bis- (3- aminophenyls) silane, bis- (4- aminophenyls) silane of dimethyl, bis- (3- aminophenyls) silicon of dimethyl Alkane, 4,4 '-phenothiazines, 3,3 '-phenothiazines, 4,4 '-diamino-diphenylamines, 3,3 '-diamino-diphenylamines, 3,4 '- Diamino-diphenylamine, 2,2 '-diamino-diphenylamines, 2,3 '-diamino-diphenylamines, N- methyl (4,4 '-diamino-diphenyl) amine, N- methyl (3,3 '-diamino-diphenyl) amine, N- methyl (3,4 '-diamino-diphenyl) amine, N- methyl (2,2 '-diamino two Phenyl) amine, N- methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diaminobenzophenones, 3,3 '-diaminobenzophenones, 3,4 '-diaminobenzophenones, 1,4- diaminonaphthalenes, 2,2 '-diaminobenzophenones, 2,3 '-diaminobenzophenones, 1,5- Diaminonaphthalene, 1,6- diaminonaphthalenes, 1,7- diaminonaphthalenes, 1,8- diaminonaphthalenes, 2,5- diaminonaphthalenes, 2,6 diaminonaphthalenes, 2,7- Bis- (4- aminophenyls) ethane of diaminonaphthalene, 2,8- diaminonaphthalenes, 1,2-, bis- (3- aminophenyls) ethane of 1,2-, the bis- (4- of 1,3- Aminophenyl) propane, bis- (3- aminophenyls) propane of 1,3-, bis- (4- aminophenyls) butane of 1,4-, bis- (the 3- aminobenzenes of 1,4- Base) butane, bis- (3,5- diethyl -4- aminophenyls) methane, bis- (4- amino-benzene oxygens) benzene of 1,4-, bis- (the 4- aminobenzenes of 1,3- Oxygroup) benzene, bis- (4- aminophenyls) benzene of 1,4-, bis- (4- aminophenyls) benzene of 1,3-, bis- (4- aminobenzyls) benzene of 1,4-, 1,3- be bis- (4- amino-benzene oxygens) benzene, 4,4 '-[1,4- phenylenes are bis- (methylene)] diphenylamines, 4,4 '-[bis- (methylenes of 1,3- phenylenes Base)] diphenylamines, 3,4 '-[1,4- phenylenes are bis- (methylene)] diphenylamines, 3,4 '-[1,3- phenylenes are bis- (methylene)] hexichol Amine, 3,3 '-[1,4- phenylenes are bis- (methylene)] diphenylamines, 3,3 '-[1,3- phenylenes are bis- (methylene)] diphenylamines, 1,4- are sub- Phenyl bis- [(4- aminophenyls) ketones], 1,4- phenylenes bis- [(3- aminophenyls) ketones], bis- [(the 4- amino of 1,3- phenylenes Phenyl) ketone], 1,3- phenylenes bis- [(3- aminophenyls) ketones], 1,4- phenylenes bis- (4-aminobenzoic acid esters), 1,4- it is sub- Phenyl bis- (3- Aminobenzoates), 1,3- phenylenes bis- (4-aminobenzoic acid esters), bis- (the 3- aminobenzoic acids of 1,3- phenylenes Ester), bis- (4- aminophenyls) terephthalates, bis- (3- aminophenyls) terephthalates, bis- (4- aminophenyls) isophthalic Dicarboxylic acid esters, bis- (3- aminophenyls) isophthalic acid esters, N, N '-(1,4- phenylenes) bis- (4- aminobenzamides), N, N '- (1,3- phenylenes) bis- (4- aminobenzamides), N, N '-(1,4- phenylenes) bis- (3-ABs), N, N '-(1,3- Phenylene) bis- (3-ABs), N, bis- (4- aminophenyls) terephthalamides of N '-, N, N '-bis- (3- aminophenyls) Terephthalamide, N, bis- (4- aminophenyls) isophtalamides of N '-, N, bis- (3- aminophenyls) isophtalamides of N '-, Bis- (4- aminophenyls) anthracenes of 9,10-, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS)s, 2,2 '-bis- [4- (4- amino-benzene oxygens) benzene Base] propane, 2,2 '-bis- [4- (4- amino-benzene oxygens) phenyl] hexafluoropropane, 2,2 '-bis- (4- aminophenyls) hexafluoropropane, 2, 2 '-bis- (3- aminophenyls) hexafluoropropane, 2,2 '-bis- (3- amino -4- aminomethyl phenyls) hexafluoropropane, 2,2 '-bis- (4- aminobenzenes Base) propane, 2,2 '-bis- (3- aminophenyls) propane, 2,2 '-bis- (3- amino -4- aminomethyl phenyls) propane, 3,5- diaminobenzene first Bis- (4- amino-benzene oxygens) propane of acid, 2,5- diaminobenzoic acids, 1,3-, bis- (3- amino-benzene oxygens) propane of 1,3-, 1,4- are bis- Bis- (3- amino-benzene oxygens) butane of (4- amino-benzene oxygens) butane, 1,4-, bis- (4- amino-benzene oxygens) pentanes of 1,5-, 1,5- are bis- Bis- (4- amino-benzene oxygens) hexanes of (3- amino-benzene oxygens) pentane, 1,6-, bis- (3- amino-benzene oxygens) hexanes of 1,6-, 1,7- are bis- (4- amino-benzene oxygens) heptane, 1,7- (3- amino-benzene oxygens) heptane, bis- (4- amino-benzene oxygens) octanes of 1,8-, the bis- (3- of 1,8- Amino-benzene oxygen) octane, bis- (4- amino-benzene oxygens) nonanes of 1,9-, bis- (3- amino-benzene oxygens) nonanes of 1,9-, 1,10- (4- ammonia Phenoxyl) decane, 1,10- (3- amino-benzene oxygens) decane, 1,11- (4- amino-benzene oxygens) hendecane, 1,11- (3- amino Phenoxy group) hendecane, 1,12- (4- amino-benzene oxygens) dodecane, 1,12- (3- amino-benzene oxygens) dodecane, bis- (the 4- ammonia of 1,3- Base phenethyl) aromatic diamines such as urea；The fat such as bis- (4- aminocyclohexyls) methane, bis- (4- amino -3- methylcyclohexyls) methane Ring type diamines；1,3- diaminopropanes, 1,4- diaminobutanes, 1,5- 1,5-DAPs, 1,6- diamino hexanes, 1,7- diaminos Base heptane, 1,8- diamino-octanes, 1,9- diamino nonanes, 1,10- diamino decanes, 1,11- diamino undecanes, 1,12- Aliphatic diamines such as bis- (3- aminopropyls) tetramethyl disiloxanes of diamino dodecane, 1,3- etc..

Wherein, compatibility from electrology characteristic, with polysiloxanes etc. considers, it is preferable to use 3,5- diaminobenzene first Bis- (4- aminophenethyls) ureas of acid, 2,5- diaminobenzoic acids, 1,3-, bis- (3- aminopropyls) tetramethyl disiloxanes of 1,3-.

Furthermore it is possible to enumerate on two amine side chains have alkyl, containing fluoroalkyl, aromatic rings, aliphatic ring, heterocycle or By the diamines for the big cyclic annular substituent that these substituent groups are constituted.

Specifically, may be exemplified the diamines of following formula [A1]~[A20] expressions.

[changing 3]

(R₁For 1 or more and 22 alkyl below of carbon atom number or contain fluoroalkyl)

[changing 4]

(R₂For-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂,-O- ,-CO- or-NH-, R₃For hydrogen atom, carbon atom 1 or more and 22 alkyl below of number contains fluoroalkyl)

[changing 5]

(R₄For-O- ,-OCH₂-、-CH₂O-、-COOCH₂Or-CH₂OCO-, R₅For 1 or more and 22 alkane below of carbon atom number Base, contains fluoroalkyl or fluoroalkoxy at alkoxy)

[changing 6]

(R₆For-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂Or-CH₂-。 R₇For 1 or more and 22 alkyl below of carbon atom number, alkoxy, containing fluoroalkyl or fluoroalkoxy)

[changing 7]

(R₈For-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂-、- O- or-NH-, R₉For fluorine-based, cyano, trifluoromethyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group, hydroxyl or carboxylic Base)

[changing 8]

Further, it is also possible to enumerate the diamino radical siloxane etc. of following formula [A21] expression.

[changing 9]

(integer that m is 1~10)

Above-mentioned diamines can be according to liquid crystal aligning, voltage retention performance, the accumulated charge when being made liquid crystal orientation film Etc. characteristics using one kind or be used in mixed way two or more.

In the raw material of above-mentioned polyamic acid, when using diamines with hydroxyl or carboxyl, can improve polyamic acid or The reaction efficiency of polyimides and aftermentioned cross-linked compound.

As the concrete example of such diamines, can enumerate：2,5- diaminophenols, 2,4- diaminophenols, 3,5- bis- Amino-phenol, 3,5- diaminobenzenes methanol, 2,4- diaminobenzenes methanol, 3,3 '-dihydroxy -4,4 '-benzidine, 3,3 ' - Dicarboxyl -4,4 '-benzidine, 3,5- diaminobenzoic acids, 2,5- diaminobenzoic acids, formula [A22]~[A25] are indicated Diamines etc..

[changing 10]

(R₁₀For-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂,-O- ,-CO- or-NH-)

[changing 11]

(R₁₁For-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂-、- O- or-NH-.R₁₂For hydroxyl or carboxyl)

The solvent used when as manufacture polyamic acid, as long as the polyamic acid dissolving of generation is not particularly limited. If enumerating its concrete example, for：N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- Ethyl-2-pyrrolidone, N- methyl caprolactams, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, Gamma-butyrolacton, isopropanol, methoxy amylalcohol, cinene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl Isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetic acid Ester, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, third Glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethyl two Alcohol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol list second Ether, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, acetic acid 3- methyl -3- Methoxybutyl, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanols, diisopropyl ether, ethyl isobutyl ether, diisobutylene, acetic acid Pentyl ester, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ether, dioxanes, n-hexane, pentane, just Octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, N-butyl acetate, propyleneglycolmethyletheracetate list ether, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionates, 3- ethoxy-cs Sour methyl esters, 3- methoxypropionates, 3- ethoxy-propionic acids, 3- methoxypropionic acids, 3- methoxy propyls propyl propionate, 3- methoxy propyls Acid butyl ester, diethylene glycol dimethyl ether, 4- hydroxy-4-methyl-2-pentanones etc..

These solvents can be used alone, and can also be used in mixed way.Even in addition, the solvent of insoluble polyamic acid, It can also be mixed into the range of so that the polyamic acid of generation is precipitated and be used in above-mentioned solvent.In addition, in organic solvent Moisture can inhibit polymerisation, and then the reason of as making the polyamic acid of generation hydrolyze, therefore, organic solvent it is preferable to use The organic solvent dehydrated as far as possible.

Make the method that tetrabasic carboxylic acid or derivatives thereof reacts in organic solvent with diamines when as manufacture polyamic acid, it can To enumerate：Solution obtained from making diamines be dispersed or dissolved in organic solvent is stirred, directly add tetrabasic carboxylic acid or its Tetrabasic carboxylic acid or derivatives thereof is dispersed or dissolved in the method being added in organic solvent by derivative；Make on the contrary The method that diamines is added in solution obtained from tetrabasic carboxylic acid or derivatives thereof is dispersed or dissolved in organic solvent；Alternately addition four The method of carboxylic acid or derivatives thereof and diamines；Deng.It can be any one method in these methods.In addition, in tetrabasic carboxylic acid or In the case that its derivative or diamines are made of two or more compounds, it can be made anti-in the state of being pre-mixed It answers, can also individually react successively, can also make individually to react obtained low-molecular weight hybrid reaction and obtain height Molecular weight body.

Temperature when synthesizing polyamides acid can select the arbitrary temp in -20~150 DEG C, preferably -5~100 DEG C Range.

In addition, reaction can be carried out with arbitrary concentration.But concentration it is too low when, it is difficult to obtain the polymerization of high molecular weight Object, when excessive concentration, the viscosity of reaction solution is excessively high and is difficult to uniformly be stirred, it is therefore preferable that being 1 matter of mass %~50 Measure %, more preferably 5 mass of mass %~30 %.It can be reacted, be added again later organic with high concentration in initial reaction stage Solvent.

In the manufacture of polyamic acid, the ratio between the molal quantity of the molal quantity of diamine component relative to tetrabasic carboxylic acid or derivatives thereof is excellent It is selected as 0.8~1.2, more preferably 0.9~1.1.Same as common polycondensation reaction, which then generates closer to 1.0 The molecular weight of polyamic acid is bigger.

As the method for making polyamic acid imidizate, the hot-imide carried out generally by heating uses catalysis The catalyst imidizate of agent, but the catalyst imidizate for carrying out imidization reaction at relatively low temperatures is not easy to cause The reduction of the molecular weight of obtained polyimides, therefore preferably.

Catalyst imidizate can by by polyamic acid in organic solvent in the presence of basic catalyst and acid anhydrides It is lower to stir to carry out.Reaction temperature at this time is -20~250 DEG C, preferably 0~180 DEG C.Imidizate is fast when reaction temperature is high Speed carry out, but it is excessively high when polyimides molecular weight reduce sometimes.The amount of basic catalyst is rubbed for the 0.5~30 of amide acidic group That times, preferably 2~20 moles times, the amount of acid anhydrides is 1~50 mole times of amide acidic group, and preferably 3~30 moles again.Alkalinity When the amount of catalyst or acid anhydrides is few, reaction progress is insufficient, in addition, being difficult to remove completely when excessive, after reaction terminating.

As basic catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be enumerated, wherein pyridine has There is appropriate alkalinity for making reaction carry out, therefore preferably.

In addition, as acid anhydrides, acetic anhydride, trimellitic anhydride, pyromellitic acid anhydride etc. can be enumerated, wherein use second When acid anhydrides, purifying is easy after reaction terminating, therefore preferably.

Organic solvent when as catalyst imidizate, as long as the organic solvent of dissolving polyamic acid does not limit then It is fixed.If enumerating its concrete example, for：N, N '-dimethyl formamide, N, N '-dimethyl acetamide, N- methyl -2- pyrrolidines Ketone, N- ethyl-2-pyrrolidones, N- methyl caprolactams, dimethyl sulfoxide (DMSO), tetramethylurea, dimethyl sulfone, hexamethyl sulfoxide, Gamma-butyrolacton etc..The acid imide rate of catalyst imidizate can by catalytic amount, reaction temperature, the reaction time into Row adjusts to control.

The polyimides of generation can be by putting into above-mentioned reaction solution in poor solvent and recycling the precipitation of generation To obtain.At this point, used poor solvent is not particularly limited.For example, can enumerate：Methanol, acetone, hexane, butyl are molten Fine agent, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, toluene, benzene, water etc..It puts into poor solvent and precipitates poly- Acid imide after filtration, can be dried under room temperature or heating and powder is made under normal or reduced pressure.This can also be gathered Acid imide powder, which is further dissolved into organic solvent, makes its reprecipitation, and aforesaid operations are repeated to come to polyimides for 2~10 times It is purified.By primary sedimentation reclaimer operation can not cleared impurity when, preferably carry out the purification step.

The molecular weight of the polyimides used in the present invention is not particularly limited, when being formed from the easiness and film of processing It is preferably 2000~200000 with Weight-average molecular gauge from the aspect of the stability of characteristic, more preferably 4000~50000. Molecular weight is the molecular weight found out by GPC (gel permeation chromatography).

<(B) ingredient：Polysiloxanes>

In the aligning agent for liquid crystal of the present invention (B) ingredient for containing be the alkoxy silane that makes to indicate containing formula (1) with Polysiloxanes obtained from the alkoxy silane polycondensation for the alkoxy silane that formula (3) indicates.

R¹Si(OR²)₃ (1)

[changing 12]

R³Si(OR⁴)₃ (3)

(R³To be replaced by acryloyl group, acryloxy, methylacryloyl, methacryloxy or styryl Carbon atom number be 1~30 alkyl, R⁴For the alkyl of carbon atom number 1~5)

The R for the alkoxy silane that formula (1) indicates¹(hereinafter also referred to specific organic group) is that above-mentioned formula [2] indicates Structure.

In formula (2), Y¹For singly-bound ,-(CH₂)_a(integer that a is 1~15) ,-O- ,-CH₂O- ,-COO- or-OCO-.Its In, from the aspect of the easy synthesis for carrying out side-chain structure, preferably select singly-bound ,-(CH₂)_a(integer that a is 1~15) ,- O-、-CH₂O- or-COO-.Wherein, singly-bound ,-(CH are more preferably selected₂)_a(integer that a is 1~10) ,-O- ,-CH₂O- or- COO-。

Y²The alkyl for the linear chain or branched chain that carbon atom number for singly-bound, containing double bond is 3~8 or-(CR¹⁷R¹⁸)_b-(b For 1~15 integer, R¹⁷、R¹⁸Hydrogen atom or carbon atom number are each independently as 1~3 alkyl).Wherein, from significantly more From the aspect of the response speed for improving liquid crystal display element, preferably-(CH₂)_b(integer that b is 1~10).

Y³For singly-bound ,-(CH₂)_c(integer that c is 1~15) ,-O- ,-CH₂O- ,-COO- or-OCO-.Wherein, from easy From the aspect of the synthesis for carrying out side-chain structure, singly-bound ,-(CH are preferably selected₂)_c(integer that c is 1~15) ,-O- ,- CH₂O- ,-COO- or-OCO-.Wherein, singly-bound ,-(CH are more preferably selected₂)_c(integer that c is 1~10) ,-O- ,-CH₂O-、- COO- or-OCO-.

Y⁴For the bivalent cyclic base in the group being made of phenyl ring, cyclohexane ring and heterocycle, appointing in these cyclic groups Alkoxy that alkyl that the hydrogen atom of meaning can be 1~3 by carbon atom number, carbon atom number are 1~3, carbon atom number are 1~3 Containing fluoroalkyl, the fluoroalkoxy that carbon atom number is 1~3 or fluorine atom substitution.In addition, Y⁴Can be selected from steroids bone Bivalent organic group in the organic group that the carbon atom number of frame is 12~25.Wherein, preferably there is phenyl ring, cyclohexane ring or class The organic group that the carbon atom number of any one is 12~25 among sterol skeleton.

Y⁵It is arbitrary in these cyclic groups for the cyclic group in the group being made of phenyl ring, cyclohexane ring and heterocycle Alkoxy that alkyl that hydrogen atom can be 1~3 by carbon atom number, carbon atom number are 1~3, carbon atom number be 1~3 it is fluorine-containing Alkyl, the fluoroalkoxy that carbon atom number is 1~3 or fluorine atom substitution.

The integer that n is 0~4.Preferably 0~2 integer.

Y⁶For the alkyl of carbon atom number 1~18, the alkoxy containing fluoroalkyl, carbon atom number 1~18 of carbon atom number 1~18 Or the fluoroalkoxy of carbon atom number 1~18.Wherein, preferably carbon atom number is 1~18 alkyl, carbon atom number are 1~10 Containing fluoroalkyl, carbon atom number be 1~18 alkoxy or carbon atom number be 1~10 fluoroalkoxy.More preferable carbon atom number The alkoxy that alkyl or carbon atom number for 1~12 are 1~12.The alkyl or carbon atom that further preferred carbon atom number is 1~9 The alkoxy that number is 1~9.

It is handled about liquid crystal aligning obtained from being imported with the polysiloxanes of such side chain and photoreactive group is used It is still uncertain why agent can have both response speed characteristic and good vertical orientation, thus it is speculated that by using with liquid crystal bone The side chain of the similar structure of frame and had both the response speed and vertical orientation for being generally in the inverse relation that is contrary to.

As the Y in formula (2)¹、Y²、Y³、Y⁴、Y⁵、Y⁶With the preferred combination of n, can enumerate and International Publication bulletin (2-1)~(2-629) phases described in 6~table of table 47 of page 13 of WO2011/132751 (2011.10.27 is disclosed)~page 34 Same combination.It should be noted that in each table of International Publication bulletin, the Y in the present invention¹~Y⁶Shown in a manner of Y1~Y6 Go out, Y1~Y6 is changed to Y¹~Y⁶.

The R for the alkoxy silane that formula (1) indicates²For the alkyl of carbon atom number 1~5, preferably 1~3.More preferable R²For methyl Or ethyl.

The alkoxy silane that such formula (1) indicates can pass through well known method (Japanese Unexamined Patent Application 61-28639 public affairs Report) it manufactures.

Its concrete example is enumerated below, and but not limited to this.

[changing 13]

[changing 14]

[changing 15]

[changing 16]

[changing 17]

[changing 18]

(R⁵For-O- ,-OCH₂-、-CH₂O-、-COOCH₂Or-CH₂OCO-, R⁶Alkyl, alcoxyl for carbon atom number 1~22 Base contains fluoroalkyl or fluoroalkoxy)

[changing 19]

(R⁷For singly-bound ,-COO- ,-OCO- ,-COOCH₂-、-CH₂OCO-、-(CH₂)_nO- (integer that n is 1~5) ,-OCH₂- Or-CH₂, R⁸For the alkyl of carbon atom number 1~22, alkoxy, containing fluoroalkyl or fluoroalkoxy)

[changing 20]

(R⁹For-COO- ,-OCO- ,-COOCH₂-、-CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂Or-O-, R¹⁰For fluorine-based, cyanogen Base, fluoroform alkyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group or hydroxyl)

[changing 21]

(R¹¹Cis- trans-isomerism for the alkyl of carbon atom number 3~12,1 or 4 cyclohexylidene is respectively transisomer)

[changing 22]

(R¹²Cis- trans-isomerism for the alkyl of carbon atom number 3~12,1 or 4 cyclohexylidene is respectively transisomer)

[changing 23]

(B₄The alkyl that carbon atom number for that can be replaced by fluorine atoms is 3~20, B₃It is sub- for 1,4- cyclohexylidenes or 1,4- Phenyl.

B₂(associative key and B of " * " wherein, are carried for oxygen atom or-COO-*₃Bonding), B₁For oxygen atom or-COO-* (its In, the associative key with " * " and (CH₂)a₂) bonding).

In addition, a₁For 0 or 1 integer, a₂For 2~10 integer, a₃Integer for 0 or 1)

Above-mentioned alkoxy silane can also according to when siloxane polymer is made to the dissolubility of solvent, liquid crystal aligning is made The characteristics such as orientation, pre-tilt angle characteristic, voltage retention, the accumulated charge of liquid crystal when film using one kind or are used in mixed way two Kind or more.Alternatively, it is also possible to sharing for the alkoxy silane with the chain alkyl for being 10~18 containing carbon atom number.

Good liquid crystal aligning in order to obtain, the alkoxyl silicone that the above-mentioned formula (1) with specific organic group indicates Alkane is for obtaining preferably 1 mole of % or more in whole alkoxy silanes used in polysiloxanes.More preferably 1.5 rub You are % or more.Further preferably 2 moles of % or more.In addition, being formed by the sufficient solidification of liquid crystal orientation film in order to obtain Characteristic, preferably 30 moles of % or less.More preferably 25 moles of % or less.Further preferably 20 moles of % or less.

The R for the alkoxy silane that formula (3) indicates³(the hereinafter also referred to second specific organic group) is by acryloyl group, third Alkene acyloxy, methylacryloyl, methacryloxy or the alkyl of styryl substitution.Substituted hydrogen atom is 1 More than, preferably 1.The carbon atom number of alkyl is preferably 1~30, and more preferably 1~20.Further preferably 1~10.

The R for the alkoxy silane that formula (3) indicates⁴For the alkyl of carbon atom number 1~5, the preferably alkane of carbon atom number 1~3 Base, the particularly preferably alkyl of carbon atom number 1~2.

The concrete example of the alkoxy silane of formula (3) expression is enumerated, but is not limited to these.For example,：3- metering systems Acryloxypropylethoxysilane triethoxysilane, methacryloxymethyl trimethoxy silane, three second of methacryloxymethyl Oxysilane, 3- acryloyloxypropyltrimethoxysilanes, 3- acryloxypropyls triethoxysilane, acryloxy Ethyl trimethoxy silane, acryloyl-oxyethyl triethoxysilane, styryl ethyl trimethoxy silane, styryl Ethyl triethoxysilane, 3- (N- styrylmethyl -2- aminoethylaminos) propyl trimethoxy silicane etc..Wherein, excellent Select 3- methacryloxypropyl trimethoxy silanes, vinyltrimethoxysilane or styryl ethyl trimethoxy silicon Alkane.

When the manufacture of the polysiloxanes as (B) ingredient, indicated in addition to the alkoxy silane and formula (3) of formula (1) expression Other than alkoxy silane, in order to improve with the compatibility of the adaptation of substrate, improvement and liquid crystal molecule etc., it can also not damage One or more of the alkoxy silane indicated using following formula (4) in the case of the effect of the present invention.

The alkoxy silane that formula (4) indicates can assign various characteristics to polysiloxanes, and characteristic that can be as needed is selected One or more are selected to use.

(R⁵)_nSi(OR⁶)_4-n (4)

(R⁵For hydrogen atom or can be by hetero atom, halogen atom, amino, glycidoxy, sulfydryl, isocyanates Base, Carbamido substituted carbon atom number be 1~10 alkyl.R⁶For the alkyl of carbon atom number 1~5, preferably 1~3.N be 0~3, it is excellent Select 0~2 integer)

The R for the alkoxy silane that formula (4) indicates⁵The organic group for being 1~10 for hydrogen atom or carbon atom number is (following to be also referred to as For third organic group).As the example of third organic group, it is：Aliphatic hydrocarbon；Aliphatic ring, aromatic rings, as heterocycle Ring structure；Unsaturated bond；Can containing hetero atoms such as oxygen atom, nitrogen-atoms, sulphur atom etc. and can with branched structure carbon The organic group that atomicity is 1~6.In addition, the organic group can be by halogen atom, amino, glycidoxy, sulfydryl, different The substitutions such as cyanic acid ester group, urea groups.

The concrete example of the alkoxy silane of formula (4) expression is enumerated, but not limited to this.For example,：3- (2- ammonia Base diethylaminobutyyl) trimethoxy silane, 3- (2- aminoethylaminopropyls) triethoxysilane, 2- aminoethylaminos Methyltrimethoxysilane, 2- (2- amino-ethyl sulphur ethyl) triethoxysilane, 3- Mercaptopropyltriethoxysilanes, sulfydryl Methyltrimethoxysilane, vinyltriethoxysilane, 3- isocyanate propyl triethoxysilanes, trifluoro propyl trimethoxy Base silane, chloropropyl triethoxysilane, bromopropyl triethoxysilane, 3-mercaptopropyi trimethoxy silane, dimethyl two Ethoxysilane, dimethyldimethoxysil,ne, diethyldiethoxysilane, diethyldimethoxysilane, diphenyl two Methoxy silane, diphenyl diethoxy silane, 3-amino propyl methyl diethoxy silane, 3- dimethyl ethoxies Base silane, trimethylethoxysilane, trimethylmethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureido-propyl Trimethoxy silane, γ-ureido-propyl tripropoxy silane etc..

In the alkoxy silane that formula (4) indicates, the alkoxy silane that n is 0 is tetraalkoxysilane.Tetraalkoxysilane holds The alkoxy silane easily indicated with formula (1) and (3) is condensed, and is preferred for obtaining the polysiloxanes of the present invention therefore.

In such formula (4), the alkoxy silane for being 0 as n, more preferable tetramethoxy-silicane, tetraethoxysilane, four Npropoxysilane or four butoxy silanes, particularly preferred tetramethoxy-silicane or tetraethoxysilane.

In the present invention, alkoxy silane whole alkane used in the manufacture of the polysiloxanes of (B) ingredient of formula (1) expression It is preferable to use 2~20 moles of % in oxysilane, particularly preferably use 3~15 moles of %, and the alkoxyl silicone that formula (3) indicates It is especially excellent it is preferable to use 5~80 moles of % in alkane whole alkoxy silanes used in the manufacture of the polysiloxanes of (B) ingredient Choosing uses 10~70 moles of %.

In addition, formula (4) indicate alkoxy silane in the case of the manufacture of the polysiloxanes for (B) ingredient, in institute It is preferable to use 10~90 moles of % in the whole alkoxy silanes used, particularly preferably use 20~90 moles of %.

[manufacturing method of the polysiloxanes of (B) ingredient]

The method for obtaining the polysiloxanes used in the present invention is not particularly limited, and makes with the alkoxyl silicone of above-mentioned formula (1) Alkane as neccessary composition alkoxy silane in organic solvent polycondensation and obtain.Therefore, polysiloxanes with uniform dissolution in having The form of solution in solvent obtains.

For example, can enumerate the side of alkoxy silane hydrolysis-condensation in alcohol or solvents such as glycols of above-mentioned formula (1) Method.At this point, hydrolysis-condensation reaction can be any one in partial hydrolysis and complete hydrolysis.In the case of complete hydrolysis, 0.5 times mole of water of whole alkoxide groups in alkoxy silane is theoretically added, but generally preferably addition rubs than 0.5 times The excessive water of that.

In the present invention, the amount of the water used in above-mentioned reaction can suitably be selected according to it is expected, but usually in alkoxy It is carried out in the range of 0.5~2.5 times mole of whole alkoxies in silane.Preferably 0.5~2.5 times mole, more preferably 0.5~1.5 times mole.

In addition, in general, in order to promote hydrolysis-condensation to react, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, horse are used Carry out the acid such as sour, fumaric acid；The alkali such as ammonia, methylamine, ethamine, ethanol amine, triethylamine；The metal salt of hydrochloric acid, sulfuric acid, nitric acid etc.；Etc. urging Agent.In addition, being also further to promote hydrolysis-condensation to react by being heated to the solution that alkoxy silane dissolves Common practice.At this point, heating temperature and heating time can suitably select according to it is expected.For example, at 50 DEG C Heating, stirring 24 hours；It heats, stir 1 hour under reflux；The methods of.

In addition, as other methods, for example, by the heating of the mixture of alkoxy silane, solvent and oxalic acid come into The method of row polycondensation.Specifically, being following method：Oxalic acid is added in alcohol in advance and after obtaining the alcoholic solution of oxalic acid, will In the state of solution heating, mixed oxyalkyl silane.At this point, the amount of used oxalic acid is had relative to alkoxy silane 1 mole of whole alkoxies be preferably set to 0.2~2 mole.In this method heating can under 50~180 DEG C of liquid temperature into Row.In order not to cause the evaporation of liquid, be vaporized, the method that preferably heats a few hours of dozens of minutes~ten under reflux.

It, can be in advance by two or more alkane in the case where obtaining polysiloxanes using two or more alkoxy silanes Make its reaction after oxysilane mixing, two or more alkoxy silanes can also be mixed successively and make its reaction.

Make the solvent (hereinafter also referred to polymer solvent) used when alkoxy silane polycondensation as long as alkoxy silane is molten The solvent of solution, is not particularly limited.In addition, even if undissolved in alkoxy silane, as long as with alkoxy The progress of the polycondensation reaction of silane and make alkoxy silane dissolve solvent.In general, the contracting for passing through alkoxy silane Poly- reaction generates alcohol, therefore, using alcohols, glycols, glycol ethers or with the good organic solvent of compatibility of alcohols.

As the concrete example of above-mentioned polymer solvent, can enumerate：The alcohols such as methanol, ethyl alcohol, propyl alcohol, butanol, diacetone alcohol； Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3- propylene glycol, 1,2- butanediols, 1,3 butylene glycol, 1,4- Butanediol, 2,3- butanediols, 1,2- pentanediols, 1,3- pentanediols, 1,4- pentanediols, 1,5- pentanediols, 2,4-PD, 2,3- The glycols such as pentanediol, 1,6-HD；Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol only son Ether, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, butyl cellosolve, diethylene glycol monomethyl ether, diethyl two Alcohol list ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Dipropyl ether, dibutyl ethylene glycol ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, third The glycol ethers such as glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol butyl oxide；N, N '-dimethyl formyl Amine, N, N '-dimethyl acetamide, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidones, N- methyl caprolactams, diformazan Base sulfoxide, tetramethylurea, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, metacresol etc..In the present invention, it can be used in mixed way Two or more above-mentioned polymer solvents.

By the polymeric solution (hereinafter also referred to polymeric solution) of polysiloxanes obtained by the above method using will be as raw material The silicon atom of whole alkoxy silanes of input is scaled SiO₂Obtained from concentration (hereinafter also referred to SiO₂Converted score) meter it is excellent 20 mass % are selected as hereinafter, being particularly preferably set as 5~15 mass %.By selecting arbitrary concentration in the concentration range, It can inhibit the generation of gel, the solution of homogeneous can be obtained.

[solution of the polysiloxanes of (B) ingredient]

In the present invention, can by by the polymeric solution of polysiloxanes obtained by the above method directly as (B) ingredient Solution, will can also be concentrated or be added by solution obtained by the above method as needed solvent be diluted or It is replaced into other solvents and obtains the solution of (B) ingredient.

At this point, used solvent (hereinafter also referred to adding solvent) can be identical as polymer solvent, or other Solvent.As long as the addition solvent equably dissolves polysiloxanes, it is not particularly limited, can arbitrarily selects one or two It uses above.

Concrete example as addition solvent may be used also other than the solvent enumerated as the example of above-mentioned polymer solvent To enumerate esters such as the ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl acetate, ethyl acetate, ethyl lactate etc..

These solvents can adjust the viscosity of aligning agent for liquid crystal, or can improve through spin coating, flexographic printing, spray Coating when aligning agent for liquid crystal is applied on substrate by ink etc..

In the present invention, from as (A) ingredient polyamic acid and/or from the aspect of polyimides mixes, as (B) The solvent used in the solution of ingredient, preferably：N, N '-dimethyl formamide, N, N '-dimethyl acetamide, N- methyl -2- pyrroles Alkanone, N- ethyl-2-pyrrolidones, N- methyl caprolactams, dimethyl sulfoxide (DMSO), tetramethylurea, dimethyl sulfone, hexamethyl are sub- Sulfone, gamma-butyrolacton, ethylene glycol monobutyl ether.

In addition, in the present invention, more preferably with as (A) ingredient polyamic acid and/or before polyimides mixes, Normal pressure or decompression under by manufacture polysiloxanes when using or generate alcohol be distilled off.

[aligning agent for liquid crystal]

The content of (B) ingredient (polysiloxanes) in the aligning agent for liquid crystal of the present invention is relative to containing polyamic acid And/or 100 mass parts of (A) ingredient of polyimides are with the SiO of silicon atom possessed by (B) ingredient₂Scaled value is calculated as 0.5~80 Mass parts, preferably 0.5~50 mass parts.In addition, in the case of the vertical orientating types such as MVA, PVA, PSA, in order not to reduce The content of the vertical orientation of liquid crystal, (B) ingredient (polysiloxanes) is more preferably 10~80 mass parts in terms of identical benchmark, into One step is preferably 20~70 mass parts.

The aligning agent for liquid crystal of the present invention is not particularly limited, but is usually needed in base when making liquid crystal orientation film 0.01 μm~1.0 μm of uniform film is formed on plate, it is therefore preferable that making this also to contain other than (A) ingredient and (B) ingredient The coating fluid of the organic solvent of a little ingredient dissolvings.

It is uniformly thin from being formed by coating in the case where the aligning agent for liquid crystal of the present invention contains above-mentioned organic solvent From the aspect of film, the content of preferable organic solvent is 90~99 mass % in aligning agent for liquid crystal, more preferably 92~ 97 mass %.The content of these organic solvents can suitably change according to the film thickness of the liquid crystal orientation film as target.

The concrete example of the organic solvent used in aligning agent for liquid crystal as the present invention, can enumerate above-mentioned polyamides The organic solvent used in the synthetic reaction of amino acid or polyimides.Particularly preferably N,N-dimethylformamide, N, N- diformazans Yl acetamide, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidones, dimethyl sulfoxide (DMSO), gamma-butyrolacton etc..These are organic Solvent can use one kind, can also share two or more.

In addition, in organic solvent, in order to improve the uniformity of film, glycol monoethyl ether, ethylene glycol list second are preferably comprised Ether, ethylene glycol ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol monohexylether, diethylene glycol monomethyl ether, diethyl two Alcohol list ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Monoethyl ether acetate, ethylene glycol, 1- methoxy-2-propanols, 1- ethyoxyl -2- propyl alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy groups - 2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol -1- monomethyl ether -2- acetic acid esters, propylene glycol -1- list second Ether -2- acetic acid esters, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 4- hydroxy-4-methyl-2-pentanones, 2- (2- Ethoxy-c oxygroup) propyl alcohol, diacetone alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate Deng the solvent with low surface tension.

These solvents are usually using one kind or are used in mixed way two or more.In general, these solvents make polyamic acid or The ability of polyimides dissolving is low, it is therefore preferable that for 80 mass % in organic solvent hereinafter, more preferably 60 mass % with Under.In addition, if expecting the uniformity of raising film, the 5 mass % or more preferably in organic solvent, more preferably 20 matter Measure % or more.

In addition, the liquid crystal mesogens aligning agent of the present invention can contain the chemical combination for the adaptation for being improved film and substrate Object, the surfactant of flatness etc. for improving film.

The concrete example of compound as the adaptation for improving film and substrate can be enumerated and as follows contain function The compound etc. of property silane.For example,：3- TSL 8330s, 3-aminopropyltriethoxysilane, 2- amino Propyl trimethoxy silicane, 2- aminopropyltriethoxywerene werenes, N- (2- amino-ethyls) -3- aminopropyl trimethoxy silicon Alkane, N- (2- amino-ethyls) -3- aminopropylmethyldimethoxysilanes, N- ethoxy carbonyl -3- aminopropyl trimethoxies Silane, N- ethoxy carbonyls -3-aminopropyltriethoxysilane, N- triethoxysilylpropyltetrasulfides diethylenetriamine, N- trimethoxy-silylpropyls diethylenetriamine, three azepine decane of 10- trimethoxysilyls -1,4,7-, 10- tri- Three azepine decane of triethoxysilyl -1,4,7-, 9- trimethoxysilyl -3,6- diaza nonyls acetic acid esters, 9- tri- Triethoxysilyl -3,6- diaza nonyls acetic acid esters, N- benzyl -3- TSL 8330s, N- benzyl -3- ammonia Base propyl-triethoxysilicane, N- phenyl -3- TSL 8330s, N- phenyl -3- aminopropyl triethoxysilicanes Bis- (the ethylene oxide) -3- aminopropyl triethoxysilicanes of bis- (the ethylene oxide) -3- TSL 8330s of alkane, N-, N- Alkane etc..

From the aspect of the effect that can obtain adaptation raising and the orientation for not reducing liquid crystal, these compounds Additive amount is preferably 0.1~30 mass parts relative to 100 mass parts of (A) ingredient, more preferably 1~20 mass parts, particularly preferably For 1~10 mass parts.

As the surfactant of the flatness for improving film, fluorine class surfactant, organic silicon can be enumerated Surfactant, nonionic surface active agent etc..More specifically, for example, Eftop EF301, EF303, EF352 (above is the manufacture of Tohkem Products companies), MEGAFACE F171, F173, R-30 (are above big Japanese ink Company manufactures), Fluorad FC430, FC431 (manufacture above for Sumitomo 3M companies), Aashi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (being manufactured above for Asahi Glass company) etc..

The content of these surfactants is preferably 0.01~2 mass parts relative to 100 mass parts of (A) ingredient, more preferably For 0.01~1 mass parts.

The present invention aligning agent for liquid crystal can be applied on substrate, after calcining, by friction treatment, light irradiate etc. into Row orientation process, or in vertical orientation purposes etc., liquid crystal orientation film can also be made in the case where No yield point is handled It uses.

At this point, as used substrate, as long as transparent high substrate is not particularly limited, glass can be used Substrate；The plastic bases such as acrylic resin substrate, polycarbonate substrate；Deng.In addition, using being formed with for liquid crystal drive The substrate of ITO electrode, IZO (indium-zinc oxide) electrode etc. conforms to the principle of simplicity from the aspect of chemical industry skill to be preferred.In addition, reflecting In the liquid crystal display element of type, if it is unilateral substrate, then the opaque materials such as silicon wafer, electricity in this case can also be used Pole can also use the material of the reflected lights such as metallic aluminium.

The coating method of aligning agent for liquid crystal is not particularly limited, generally by silk-screen printing, hectographic printing, soft version The method of the progress such as printing, ink-jet.As other coating methods, there are dipping, roll coater, slit coater, spin coater etc., it can To use these coating methods according to purpose.

Substrate after coating of liquid crystalline aligning agent is placed about 1 minute~3 minutes in 70~100 DEG C of heating plate, is made Solvent volatilizees and dries, and then, is calcined.Calcining can carry out under 100~350 DEG C of arbitrary temp, but preferably 120 ~300 DEG C, further preferably 150~250 DEG C.The calcining can using heating plate, recirculation furnace, infrared heating heating furnace etc. come into Row.

When the thickness of film after calcining is blocked up, become unfavorable in the consumption concerned power of liquid crystal display element, when excessively thin, The reliability of liquid crystal display element reduces sometimes, it is therefore preferable that for 5~300nm, more preferably 10~150nm, further preferably For 50~100nm.In the case where making liquid crystal be horizontally oriented or tilted alignment, the film after calcining is passed through into friction or polarised light Ultraviolet light irradiation etc. is handled.

About the liquid crystal display element of the present invention, the base with liquid crystal orientation film is obtained by the aligning agent for liquid crystal of the present invention After plate, liquid crystal cells are made by well known method, to which display element be made.If enumerating the one of liquid crystal cells making Example, may be exemplified：Prepare to be formed with a pair of of substrate of liquid crystal orientation film, formed on the liquid crystal orientation film of a substrate intercolumniation every Object spreads pearl spacer, and to make liquid crystal alignment film surface be bonded another substrate in the way of inside, decompression injection liquid crystal is simultaneously The method of sealing；Alternatively, being formed with intercolumniation parting or being scattered in the liquid crystal alignment film surface of pearl spacer after dropwise addition liquid crystal, Adhesive substrates and the method etc. being sealed.The thickness of spacer at this time is preferably 1~30 μm, more preferably 2~10 μm.

[embodiment]

Hereinafter, the present invention is further specifically described by embodiment, but not by these embodiment being defined property solutions It releases.

Abbreviation in the compound used in embodiment is as described below.

(alkoxy silane monomer)

TEOS：Tetraethoxysilane

C18：Octadecyltriethoxy silane

C12：Dodecyl triethoxysilane

UPS：3- ureidopropyltriethoxysilanes

MPMS：3- methacryloxypropyl trimethoxy silanes

VTMS：Vinyltrimethoxysilane

STMS：Styryl ethyl trimethoxy silane

MTES：Methyltriethoxysilane

(tetracarboxylic dianhydride)

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

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

PMDA：Pyromellitic acid anhydride

BODA：Bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydrides

[changing 24]

(diamine compound)

m-PDA：M-phenylene diamine (MPD)

DBA：3,5- diaminobenzoic acids

DDM：4,4 '-diaminodiphenyl-methanes

4,4’DADPA：4,4 '-diamino-diphenylamines

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

Sin0：Bis- (3- aminopropyls) tetramethyl disiloxanes of 1,3-

PCH7DAB：1,3- diamino -4- [4- (trans- -4- n-heptyls cyclohexyl) phenoxy group] benzene

[changing 25]

(organic solvent)

THF：Tetrahydrofuran

DMF：Dimethylformamide

NMP：N-methyl-2-pyrrolidone

BCS：Butoxy ethanol

The measurement of NMR, the measurement of molecular weight, measurement of acid imide rate etc. carry out as follows.

(¹The measurement of H-NMR)

¹The NMR analyzers (JNW-ECA500) that H-NMR (500MHz, proton NMR) is manufactured using DATUM companies of Japan, Deuterochloroform (CDCl₃) in use tetramethylsilane (TMS) to be measured as internal standard.

(molecular weight determination of polyamic acid and polyimides)

Room temperature gel permeation chromatography (GPC) device (GPC-101), Shodex of the molecular weight using the manufacture of Showa electrician company The chromatographic column (KD-803, KD-805) of company's manufacture, is measured as follows.

Column temperature：50℃

Eluent：N, N '-dimethyl formamide is (as additive, lithium bromide-hydrate (LiBrH₂O) it is 30mmol/ L (liter), phosphoric acid anhydrous crystal (o- phosphoric acid) are 30mmol/L, tetrahydrofuran (THF) is 10ml (milliliter)/L)

Flow velocity：1.0ml/ minute

Standard sample for making standard curve：(molecular weight is about for the TSK standards polyethylene oxide of Tosoh company manufacture 900000,150000,100000 and 30000) and Polymer Laboratories companies manufacture polyethylene glycol (molecular weight About 12000,4000 and 1000).

(measurement of acid imide rate)

By polyimide powder 20mg be packed into NMR sample cells (the NMR sampling pipe standard types of wasteland's scientific company manufacture, ) in, deuterated dimethyl sulfoxide (DMSO-d6,0.05 mass %TMS (tetramethylsilane) melange) 0.53mL is added, is applied super Sound wave makes it completely dissolved.The NMR analyzers (JNW-ECA500) manufactured using Japan Electronics DATUM companies measure the solution The proton NMR of 500MHz.About acid imide rate, the proton to come from the not changed structure before and after imidizate is made On the basis of proton determine, using the proton peak integrated value and appear in the amic acid that comes near 9.5~10.0ppm The proton peak integrated value of NH bases finds out acid imide rate by following formula.

Acid imide rate (%)=(1- α x/y) × 100

In above formula, x is the proton peak integrated value for the NH bases for coming from amic acid, and the peak integrated value of proton, α are on the basis of y Ratio of the number of reference proton relative to 1 NH matrix of amic acid in the case of polyamic acid (acid imide rate is 0%) Example.

[changing 26]

Compound 930.00g, potassium carbonate 25.24g and DMF are put into the 500mL four-hole boiling flasks for having magnetic stir bar Allyl bromide, bromoallylene 22.10g is added dropwise in 120g at room temperature.Then, it is stirred 11 hours at 50 DEG C.By the acetic acid of reaction solution 500g Ethyl ester dilutes, and organic layer is cleaned 3 times with the pure water of 200g.The organic layer isolated is dried with sodium sulphate, and it is carried out Filtering.Then, filtrate is concentrated and dried, obtains compound 1034.80g (yield 100%).

¹H-NMR(500MHz)CDCl₃In:0.90ppm (t, J=7.2Hz, 3H), 0.99-1.09ppm (m, 2H), 1.18- 1.46ppm (m, 11H), 1.84-1.89ppm (m, 4H), 2.37-2.44ppm (m, 1H), 4.51ppm (dt, J=5.4Hz, 1.6Hz, 2H), 5.26ppm (dq, J=10.6Hz, 1.6Hz, 1H), 5.40ppm (dq, J=17.2Hz, 1.6Hz, 1H), 6.07ppm (ddd, J=17.2Hz, 10.6Hz, 5.4Hz, 1H), 6.83ppm (dd, J=8.8Hz, 2.9Hz, 2H), 7.10ppm (dd, J=8.8Hz, 2.9Hz, 2H)

Compound 1020.00g and toluene 120g is put into the 300mL four-hole boiling flasks for having magnetic stir bar, in room temperature Lower stirring.Then, addition karstedt catalyst (platinum (0) -1,1,3,3- tetramethyl disiloxane complex compound, 0.1mol/L bis- Toluene solution) after 700 μ l, trimethoxy silane 12.4mL is added dropwise.After being stirred at room temperature 29 hours, reaction solution is concentrated dry It is dry, obtain crude product.Obtained crude product is evaporated under reduced pressure, distillates, obtains under conditions of 0.8 support of warm 245 DEG C/pressure outside Compound 1112.15g (yield 43%).

¹H-NMR(500MHz)CDCl₃In:0.76-0.82ppm (m, 2H), 0.89ppm (t, J=7.2Hz, 3H), 0.98- 1.08ppm(m,2H),1.18-1.45ppm(m,11H),1.84-1.93ppm(m,6H),2.36-2.43ppm(m,1H), 3.58ppm (s, 9H), 3.91ppm (t, J=6.8Hz, 2H), 6.81ppm (d, J=8.8Hz, 2H), 7.08ppm (d, J= 8.8Hz,2H)

[synthesis of (A) ingredient (polyamic acid and polyimides)]

By as the CBDA 97.1g (0.5mol) of tetracarboxylic dianhydride's ingredient, as the DBA76.1g of diamine component (0.5mol) is mixed in NMP 1270g, is reacted 5 hours at room temperature, is obtained polyamic acid solution.Polymerisation is easy and equal It carries out evenly.The number-average molecular weight of obtained polyamic acid is 16800, weight average molecular weight 48300.In turn, in the solution Middle addition NMP and BCS, it be 76 weight %, BCS is 20 weight % to make polyamic acid be 4 weight %, NMP, and it is molten to obtain polyamic acid Liquid (A1).

By as the BDA 79.1g (0.4mol) of tetracarboxylic dianhydride's ingredient, as the DBA60.9g of diamine component (0.4mol) is mixed in NMP 560g, is reacted 7 hours at room temperature, is obtained polyamic acid solution.Polymerisation is easy and equal It carries out evenly.The number-average molecular weight of obtained polyamic acid is 9800, weight average molecular weight 31300.In turn, in the solution NMP and BCS is added, it be 76 weight %, BCS is 20 weight % to make polyamic acid be 4 weight %, NMP, obtains polyamic acid solution (A2)。

By as the PMDA 106.1g (0.49mol) of tetracarboxylic dianhydride's ingredient, as the DBA76.1g of diamine component (0.5mol) is mixed in NMP 1336g, is reacted 5 hours at room temperature, is obtained polyamic acid solution.Polymerisation is easy and equal It carries out evenly.The number-average molecular weight of obtained polyamic acid is 15600, weight average molecular weight 44300.In turn, in the solution Middle addition NMP and BCS, it be 76 weight %, BCS is 20 weight % to make polyamic acid be 4 weight %, NMP, and it is molten to obtain polyamic acid Liquid (A3).

By as the PMDA 102.8g (0.47mol) of tetracarboxylic dianhydride's ingredient, as the BAPU149.2g of diamine component (0.5mol) is mixed in NMP 1843g, is reacted 5 hours at room temperature, is obtained polyamic acid solution.Polymerisation is easy and equal It carries out evenly.The number-average molecular weight of obtained polyamic acid is 13800, weight average molecular weight 41400.In turn, in the solution Middle addition NMP and BCS, it be 76 weight %, BCS is 20 weight % to make polyamic acid be 4 weight %, NMP, and it is molten to obtain polyamic acid Liquid (A4).

By as the CBDA 94.1g (0.48mol) of tetracarboxylic dianhydride's ingredient, as the BAPU149.2g of diamine component (0.5mol) is mixed in NMP 1784g, is reacted 5 hours at room temperature, is obtained polyamic acid solution.Polymerisation is easy and equal It carries out evenly.The number-average molecular weight of obtained polyamic acid is 15200, weight average molecular weight 46700.In turn, in the solution Middle addition NMP and BCS, it be 76 weight %, BCS is 20 weight % to make polyamic acid be 4 weight %, NMP, and it is molten to obtain polyamic acid Liquid (A5).

By as the CBDA 78.2g (0.4mol) of tetracarboxylic dianhydride's ingredient, as the m-PDA43.2g of diamine component (0.4mol) is mixed in NMP 664g, is reacted 5 hours at room temperature, is obtained polyamic acid solution.Polymerisation is easy and equal It carries out evenly.The number-average molecular weight of obtained polyamic acid is 21800, weight average molecular weight 51500.In turn, in the solution Middle addition NMP and BCS, it be 76 weight %, BCS is 20 weight % to make polyamic acid be 4 weight %, NMP, and it is molten to obtain polyamic acid Liquid (A6).

By as the CBDA 19.2g (0.098mol) of tetracarboxylic dianhydride's ingredient, as the DDM19.8g of diamine component (0.1mol) is mixed in NMP 221.3g, is reacted 24 hours at room temperature, is obtained polyamic acid solution.Polymerisation be easy and Equably carry out.The number-average molecular weight of obtained polyamic acid is 18800, weight average molecular weight 52300.In turn, molten at this NMP and BCS is added in liquid, it be 76 weight %, BCS is 20 weight % to make polyamic acid be 4 weight %, NMP, obtains polyamic acid Solution (A7).

By as the CBDA 19.6g (0.1mol) of tetracarboxylic dianhydride's ingredient, as 4,4 ' DADPA18.7g of diamine component (0.094mol) is mixed in NMP 345.1g, is reacted 5 hours at room temperature, is obtained polyamic acid solution.Polymerisation is easy And it equably carries out.The number-average molecular weight of obtained polyamic acid is 17500, weight average molecular weight 48100.In turn, at this NMP and BCS is added in solution, it be 76 weight %, BCS is 20 weight % to make polyamic acid be 4 weight %, NMP, obtains polyamide Acid solution (A8).

BODA 150.1g (0.6mol), DBA 60.9g (0.4mol) and PCH7DAB 152.2g (0.4mol) are existed It mixes in NMP1290g, is reacted 5 hours at 80 DEG C.Then, addition CBDA 38.8g (0.2mol) and NMP 320g, at 40 DEG C Lower reaction 3 hours, obtains polyamic acid solution.NMP is added in polyamic acid solution 100.8g, is diluted to 6 mass %.So Afterwards, acetic anhydride 10.66g and pyridine 8.26g of the addition as imidization catalyst, reacts 3 hours at 80 DEG C.Then, will The reaction solution is put into methanol 1300ml, and obtained sediment is filtered out.The sediment is cleaned with methanol, is then existed It is dried under reduced pressure at 100 DEG C, obtains polyimide powder (C1).The acid imide rate of the polyimides is 55%, number-average molecular weight It is 28500, weight average molecular weight 66100.

NMP 41.9g are added in polyimide powder (C1) 7.4g, are stirred 40 hours and are made it dissolve at 80 DEG C.Into And NMP and BCS is added in the solution, it be 76 weight %, BCS is 20 weight % to make polyimides be 4 weight %, NMP, is obtained To polyimide solution (A9).

By BODA 7.5g (30.0mmol), DBA 1.8 (12.0mmol), Sin02.0g (8.0mmol) and PCH7DAB7.6g (20.0mmol) is mixed in NMP 55g, is reacted 5 hours at 80 DEG C.Then, CBDA1.9g is added (10.0mmol) and NMP 27.0g react 3 hours at 40 DEG C, obtain polyamic acid solution.In the polyamic acid solution NMP is added in 30.0g, is diluted to 6 mass %.Then, acetic anhydride 2.99g and pyridine of the addition as imidization catalyst 2.32g reacts 3 hours at 80 DEG C.Then, which is put into methanol 370ml, filters out obtained precipitation Object.The sediment is cleaned with methanol, is then dried under reduced pressure at 100 DEG C, polyimide powder (C2) is obtained.The polyimides Acid imide rate be 57%, number-average molecular weight 26800, weight average molecular weight 63400.

NMP 41.9g are added in polyimide powder (C2) 7.4g, are stirred 40 hours and are made it dissolve at 80 DEG C.Into And NMP and BCS is added in the solution, it be 76 weight %, BCS is 20 weight % to make polyamic acid be 4 weight %, NMP, is obtained To polyimide solution (A10).

[synthesis of (B) ingredient (polysiloxanes)]

In the four mouthfuls of reaction flasks for the 200mL for having thermometer and return duct, by BCS 29.5g, TEOS 38.8g and The compound 11 4.1g mixing obtained among the above, prepares the solution of alkoxy silane monomer.It is molten to this with 30 minutes at room temperature The solution for being in advance obtained by mixing BCS 14.7g, water 10.8g and oxalic acid 0.2g as catalyst, Jin Er are added dropwise in liquid It stirs 30 minutes at room temperature.Then, it is heated using oil bath, after flowing back 30 minutes, adds the first that UPS contents are 92 mass % The mixed liquor of alcoholic solution 1.2g and BCS 0.9g.It flows back again 30 minutes, then natural cooling, obtains SiO₂Converted score is 12 weights Measure the polysiloxane solution of %.

Obtained polysiloxane solution 10.0g and NMP 20.0g are mixed, SiO is obtained₂Converted score is 4 weight % Polysiloxane solution [B1].

In the four mouthfuls of reaction flasks for the 200mL for having thermometer and return duct, by BCS 29.4g, TEOS 38.8g and C18 4.2g mixing, prepares the solution of alkoxy silane monomer.It was added dropwise BCS in advance into the solution with 30 minutes at room temperature The solution that 14.7g, water 10.8g and oxalic acid 0.2g as catalyst are obtained by mixing, and then be stirred at room temperature 30 minutes.So Afterwards, it is heated using oil bath, after flowing back 30 minutes, methanol solution 1.2g and BCS that addition UPS contents are 92 mass % The mixed liquor of 0.9g.It flows back again 30 minutes, then natural cooling, obtains SiO₂Converted score is that the polysiloxanes of 12 weight % is molten Liquid.

Obtained polysiloxane solution 10.0g and NMP 20.0g are mixed, SiO is obtained₂Converted score is 4 weight % Polysiloxane solution [B2].

In the four mouthfuls of reaction flasks for the 200mL for having thermometer and return duct, by BCS 30.2g, TEOS 39.6g and The compound 11 4.1g mixing obtained among the above, prepares the solution of alkoxy silane monomer.It is molten to this with 30 minutes at room temperature The solution for being in advance obtained by mixing BCS 14.7g, water 10.8g and oxalic acid 0.2g as catalyst, Jin Er are added dropwise in liquid It stirs 30 minutes at room temperature.Then, it is heated, is flowed back 60 minutes, then natural cooling, obtains SiO using oil bath₂It converts dense Degree is the polysiloxane solution of 12 weight %.

Obtained polysiloxane solution 10.0g and NMP 20.0g are mixed, SiO is obtained₂Converted score is 4 weight % Polysiloxane solution [B3].

In the four mouthfuls of reaction flasks for the 200mL for having thermometer and return duct, by BCS 28.2g, TEOS 37.5g and The compound 11 4.1g mixing obtained among the above, prepares the solution of alkoxy silane monomer.It is molten to this with 30 minutes at room temperature The solution for being in advance obtained by mixing BCS 14.1g, water 10.8g and oxalic acid 0.4g as catalyst, Jin Er are added dropwise in liquid It stirs 30 minutes at room temperature.Then, it is heated using oil bath, after flowing back 30 minutes, adds the first that UPS contents are 92 mass % The mixed liquor of alcoholic solution 2.9g and BCS2.1g.It flows back again 30 minutes, then natural cooling, obtains SiO₂Converted score is 12 weights Measure the polysiloxane solution of %.

Obtained polysiloxane solution 10.0g and NMP 20.0g are mixed, SiO is obtained₂Converted score is 4 weight % Polysiloxane solution [B4].

In the four mouthfuls of reaction flasks for the 200mL for having thermometer and return duct, by BCS 25.4g, TEOS 20.0g, on The 11 8.2g and MPMS 19.9g mixing of compound obtained in stating, prepares the solution of alkoxy silane monomer.At room temperature with 30 Minute be added dropwise into the solution BCS 12.7g, water 10.8g and oxalic acid 1.1g as catalyst are obtained by mixing in advance it is molten Liquid, and then be stirred at room temperature 30 minutes.Then, it is heated using oil bath, after flowing back 30 minutes, addition UPS contents are 92 The mixed liquor of the methanol solution 1.2g and BCS 0.9g of quality %.It flows back again 30 minutes, then natural cooling, obtains SiO₂Conversion The polysiloxane solution of a concentration of 12 weight %.

Obtained polysiloxane solution 10.0g and NMP 20.0g are mixed, SiO is obtained₂Converted score is 4 weight % Polysiloxane solution [B5].

In the four mouthfuls of reaction flasks for the 200mL for having thermometer and return duct, by BCS 25.2g, TEOS 20.0g, on The 11 8.2g and STMS 20.2g mixing of compound obtained in stating, prepares the solution of alkoxy silane monomer.At room temperature with 30 Minute be added dropwise into the solution BCS 12.6g, water 10.8g and oxalic acid 1.1g as catalyst are obtained by mixing in advance it is molten Liquid, and then be stirred at room temperature 30 minutes.Then, it is heated using oil bath, after flowing back 30 minutes, addition UPS contents are 92 The mixed liquor of the methanol solution 1.2g and BCS 0.9g of quality %.It flows back again 30 minutes, then natural cooling, obtains SiO₂Conversion The polysiloxane solution of a concentration of 12 weight %.

Obtained polysiloxane solution 10.0g and NMP 20.0g are mixed, SiO is obtained₂Converted score is 4 weight % Polysiloxane solution [B6].

In the four mouthfuls of reaction flasks for the 200mL for having thermometer and return duct, by BCS 25.8g, TEOS 20.0g, C18 4.2g, C12 3.3g and MPMS 19.9g mixing, prepare the solution of alkoxy silane monomer.At room temperature with 30 minutes to The solution for being in advance obtained by mixing BCS 12.9g, water 10.8g and oxalic acid 1.1g as catalyst is added dropwise in the solution, into And it is stirred at room temperature 30 minutes.Then, it is heated using oil bath, after flowing back 30 minutes, addition UPS contents are 92 mass % Methanol solution 1.2g and BCS 0.9g mixed liquor.It flows back again 30 minutes, then natural cooling, obtains SiO₂Converted score is The polysiloxane solution of 12 weight %.

Obtained polysiloxane solution 10.0g and NMP 20.0g are mixed, SiO is obtained₂Converted score is 4 weight % Polysiloxane solution [B7].

In the four mouthfuls of reaction flasks for the 200mL for having thermometer and return duct, by BCS 31.5g, TEOS 37.1g and MTES 3.6g mixing, prepares the solution of alkoxy silane monomer.It was added dropwise into the solution with 30 minutes and in advance will at room temperature The solution that BCS 15.7g, water 10.8g and oxalic acid 0.1g as catalyst are obtained by mixing, and then it is stirred at room temperature 30 points Clock.Then, it is heated using oil bath, after sixty minutes, natural cooling obtains SiO for reflux₂Converted score is the poly- of 12 weight % Siloxane solution.

Obtained polysiloxane solution 10.0g and NMP 20.0g are mixed, SiO is obtained₂Converted score is 4 weight % Polysiloxane solution [B8].

In the four mouthfuls of reaction flasks for the 200mL for having thermometer and return duct, by BCS 26.2g, TEOS 20.8g, on Compound 118 .2g and MPMS the 19.9g mixing obtained in stating, prepares the solution of alkoxy silane monomer.At room temperature with 30 Minute be added dropwise into the solution BCS 13.1g, water 10.8g and oxalic acid 1.1g as catalyst are obtained by mixing in advance it is molten Liquid, and then be stirred at room temperature 30 minutes.Then, it is heated using oil bath, after flowing back 30 minutes, addition UPS contents are 92 The mixed liquor of the methanol solution 0.6g and BCS0.4g of quality %.It flows back again 30 minutes, then natural cooling, obtains SiO₂Conversion The polysiloxane solution of a concentration of 12 weight %.

Obtained polysiloxane solution 10.0g and NMP 20.0g are mixed, SiO is obtained₂Converted score is 4 weight % Polysiloxane solution [B9].

The making of liquid crystal cells and electrology characteristic, vertical orientation, re-workability, weighting characteristics, response speed etc. Evaluation is following to be carried out.

[making of liquid crystal cells]

Aligning agent for liquid crystal is spun to the ITO electrode substrate for being formed with solid ITO electrode or is formed with pixel ruler It is very little be 100 μ m 300 μm (microns) and line width/line-spacing be respectively 5 μm ITO electrode pattern ITO electrode substrate ito surface On.Then, after being dried 2 minutes using 80 DEG C of heating plate, 30 are carried out in 200 DEG C or 220 DEG C of heated air circulation type baking oven Minute calcining forms the liquid crystal orientation film that film thickness is 100nm.Prepare the two panels substrate (between solid substrate or solid substrate And pattern substrate), after spreading 4 μm or 6 μm of pearl spacer in the liquid crystal alignment film surface of a substrate, print from the upper side close Seal agent.Make the liquid crystal alignment film surface of another substrate in inside, after two substrates are bonded, makes sealant cures, make dummy cell. Then, injection liquid crystal MLC-6608 in normal direction dummy cell (Merck ＆ Co., Inc.'s manufacture, trade name) is injected using decompression, is fabricated to liquid crystal Unit.

After making liquid crystal cells, by heating or irradiating purple while liquid crystal cells are applied with the voltage of AC or DC Outside line can control the orientation of liquid crystal molecule.

[evaluation of electrology characteristic (voltage retention and ion concentration)]

Liquid crystal cells are applied to the voltage of 60 microsecond 1V at a temperature of 60 DEG C, the voltage after 1667 milliseconds are measured, with electricity The form calculus of pressure conservation rate (VHR) goes out which kind of degree voltage can remain to.

In turn, using above-mentioned liquid crystal cells, the measurement of ion concentration is carried out at a temperature of 60 DEG C.That is, measuring to liquid Brilliant unit applies the ion concentration when triangular wave of voltage ± 10V, frequency 0.01Hz.Measurement device uses Dongyang technology company system The 6245 type liquid crystal evaluation of physical property devices made.

[evaluation of vertical orientation]

Liquid crystal cells are carried out in 100 DEG C of circulating baking oven to annealing in 30 minutes.Then, polarizing film is made to be in just It hands over the unit under Nicolle state to taking-up to carry out micro- sem observation, observes the shape on the farmland (Domain) of the orientation disorder of liquid crystal State.

[evaluation of re-workability]

Aligning agent for liquid crystal is spun on the ITO electrode substrate for being formed with solid ITO electrode.Then, using 80 DEG C Heating plate dry 2 minutes after, is carried out in 200 DEG C or 220 DEG C of heated air circulation type baking oven 30 minutes calcine, formation film thickness The liquid crystal orientation film of 100nm.The substrate is impregnated after ten minutes in the NMD-3 that 50 DEG C of Tokyo answers chemical industry company to manufacture, Washing, it is 10 minutes dry in 80 DEG C of heated air circulation type baking oven.Then, it is visually observed and is connect to impregnating front and back state Feeler measures, and contact angle is restored to be evaluated as to reprocess to the sample of the state before the coating of aligning agent for liquid crystal：Zero, it will Contact angle does not restore to be evaluated as to reprocess to the sample of the state before the coating of aligning agent for liquid crystal：×.

[evaluations of weighting characteristics]

Aligning agent for liquid crystal is spun on chrome substrate (vapor deposition has the glass substrate of chromium), in 23 DEG C of temperature, relatively wet It is placed under the atmosphere of degree 60% 10 minutes, then, visually observes the condensation product whether coated surface end produces polymer.

[evaluation of response speed]

When obtaining the rectangular wave to the AC voltages of liquid crystal cells application ± 5V, frequency 1kHz using oscillograph, liquid crystal surface The time change of the brightness of plate.Brightness when using no applied voltage is as 0%, the brightness of saturation when by the voltage of application ± 5V Value as 100%, brightness is changed to 90% time as the response speed started by 10%, is carried out according to above-mentioned liquid crystal The production method of unit is heated or is irradiated ultraviolet light to obtained unit while applying the voltage of AC or DC The evaluation of response speed afterwards.

(reference example 1)

Using polysiloxane solution (B1) as aligning agent for liquid crystal, carry out [evaluation of vertical orientation] and [again plus The evaluation of work].As a result shown in table 1 and table 3.In turn, it carries out voltage retention according to [evaluation of electrology characteristic] and ion is close The evaluation of degree.As a result it is shown in table 2.

(reference example 2)

Polysiloxane solution (B1) 3.0g and polyamic acid solution (A1) 7.0g is mixed, aligning agent for liquid crystal is obtained (1).Using the aligning agent for liquid crystal, [evaluation of re-workability], [evaluations of weighting characteristics] and [vertical orientation are carried out Evaluation].As a result table 3, table 4 and table 5 are shown in.In turn, voltage retention and ion concentration are carried out according to [evaluation of electrology characteristic] Evaluation.As a result it is shown in table 6.

(reference example 3)

Polysiloxane solution (B1) 3.0g and polyamic acid solution (A2) 7.0g is mixed, aligning agent for liquid crystal is obtained (2).Using the aligning agent for liquid crystal, carry out [evaluation of re-workability].As a result it is shown in table 3.

(reference example 4)

Polysiloxane solution (B1) 3.0g and polyamic acid solution (A3) 7.0g is mixed, aligning agent for liquid crystal is obtained (3).Using the aligning agent for liquid crystal, carry out [evaluation of re-workability].As a result it is shown in table 3.

(reference example 5)

Polysiloxane solution (B1) 3.0g and polyamic acid solution (A4) 7.0g is mixed, aligning agent for liquid crystal is obtained (4).Using the aligning agent for liquid crystal, carry out [evaluation of re-workability].As a result it is shown in table 3.

(reference example 6)

Polysiloxane solution (B1) 3.0g and polyamic acid solution (A5) 7.0g is mixed, aligning agent for liquid crystal is obtained (5).Using the aligning agent for liquid crystal, [evaluation of re-workability], [evaluations of weighting characteristics] and [vertical orientation are carried out Evaluation].As a result table 3, table 4 and table 5 are shown in.In turn, voltage retention and ion concentration are carried out according to [evaluation of electrology characteristic] Evaluation.As a result it is shown in table 6.

(reference example 7)

Polysiloxane solution (B4) 3.0g and polyamic acid solution (A1) 7.0g is mixed, aligning agent for liquid crystal is obtained (6).Using the aligning agent for liquid crystal, carry out [evaluations of weighting characteristics].As a result it is shown in table 6.

(reference example 8)

Polysiloxane solution (B4) 3.0g and polyamic acid solution (A2) 7.0g is mixed, aligning agent for liquid crystal is obtained (7).Using the aligning agent for liquid crystal, carry out [evaluations of weighting characteristics].As a result it is shown in table 6.

(embodiment 1)

Polysiloxane solution (B5) 3.0g and polyamic acid solution (A1) 7.0g is mixed, aligning agent for liquid crystal is obtained (8).Using the aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientation].As a result it is shown in table 7。

(embodiment 2)

Polysiloxane solution (B5) 3.0g and polyamic acid solution (A2) 7.0g is mixed, aligning agent for liquid crystal is obtained (9).Using the aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientation].As a result it is shown in table 7。

(embodiment 3)

Polysiloxane solution (B5) 3.0g and polyamic acid solution (A3) 7.0g is mixed, aligning agent for liquid crystal is obtained (10).Using the aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientation].As a result it is shown in table 7。

(embodiment 4)

Polysiloxane solution (B5) 3.0g and polyamic acid solution (A4) 7.0g is mixed, aligning agent for liquid crystal is obtained (11).Using the aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientation].As a result it is shown in table 7。

(embodiment 5)

Polysiloxane solution (B5) 3.0g and polyamic acid solution (A5) 7.0g is mixed, aligning agent for liquid crystal is obtained (12).Using the aligning agent for liquid crystal, [evaluation of response speed], [evaluation of vertical orientation] and [re-workability are carried out Evaluation].As a result table 7, table 8 and table 10 are shown in.In turn, it carries out voltage retention according to [evaluation of electrology characteristic] and ion is close The evaluation of degree.As a result it is shown in table 9.

(embodiment 6)

Polysiloxane solution (B5) 3.0g and polyamic acid solution (A6) 7.0g is mixed, aligning agent for liquid crystal is obtained (13).Using the aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientation].As a result it is shown in table 7。

(embodiment 7)

Polysiloxane solution (B5) 3.0g and polyamic acid solution (A7) 7.0g is mixed, aligning agent for liquid crystal is obtained (14).Using the aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientation].As a result it is shown in table 7。

(embodiment 8)

Polysiloxane solution (B5) 3.0g and polyamic acid solution (A8) 7.0g is mixed, aligning agent for liquid crystal is obtained (15).Using the aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientation].As a result it is shown in table 7.In turn, the evaluation of voltage retention and ion concentration is carried out according to [evaluation of electrology characteristic].As a result it is shown in table 9.

(embodiment 9)

Polysiloxane solution (B5) 3.0g and polyamic acid solution (A9) 7.0g is mixed, aligning agent for liquid crystal is obtained (16).Using the aligning agent for liquid crystal, [evaluation of response speed], [evaluation of vertical orientation] and [re-workability are carried out Evaluation].As a result table 7 and table 10 are shown in.

(embodiment 10)

Polysiloxane solution (B5) 3.0g and polyamic acid solution (A10) 7.0g is mixed, aligning agent for liquid crystal is obtained (17).Using the aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientation].As a result it is shown in table 7。

(embodiment 11)

Polysiloxane solution (B6) 3.0g and polyamic acid solution (A1) 7.0g is mixed, aligning agent for liquid crystal is obtained (18).Using the aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientation].As a result it is shown in table 7 and table 8.

(comparative example 1)

Using polysiloxane solution (B2) as aligning agent for liquid crystal, carry out [evaluation of vertical orientation] and [again plus The evaluation of work].As a result shown in table 1 and table 3.

(comparative example 2)

Using polysiloxane solution (B3) as aligning agent for liquid crystal, voltage guarantor is carried out according to [evaluation of electrology characteristic] The evaluation of holdup and ion concentration.As a result it is shown in table 2.In turn, [evaluation of re-workability] is carried out.As a result it is shown in table 3.

(comparative example 3)

Polysiloxane solution (B2) 3.0g and polyamic acid solution (A1) 7.0g is mixed, aligning agent for liquid crystal is obtained (19).Using the aligning agent for liquid crystal, carry out [evaluation of vertical orientation] and [evaluations of weighting characteristics].As a result it is shown in table 4 and table 5.

(comparative example 4)

Polysiloxane solution (B2) 3.0g and polyamic acid solution (A5) 7.0g is mixed, aligning agent for liquid crystal is obtained (20).Using the aligning agent for liquid crystal, carry out [evaluation of vertical orientation] and [evaluations of weighting characteristics].As a result it is shown in table 4 and table 5.

(comparative example 5)

Polysiloxane solution (B3) 3.0g and polyamic acid solution (A1) 7.0g is mixed, aligning agent for liquid crystal is obtained (21).Using the aligning agent for liquid crystal, the evaluation of voltage retention and ion concentration is carried out according to [evaluation of electrology characteristic]. As a result it is shown in table 6.

(comparative example 6)

Polysiloxane solution (B3) 3.0g and polyamic acid solution (A5) 7.0g is mixed, aligning agent for liquid crystal is obtained (22) The obtains.Using the aligning agent for liquid crystal, voltage retention and ion concentration are carried out according to [evaluation of electrology characteristic] Evaluation.As a result it is shown in table 6.

(comparative example 7)

Polysiloxane solution (B7) 3.0g and polyamic acid solution (A1) 7.0g is mixed, aligning agent for liquid crystal is obtained (23).Using the aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientation].As a result it is shown in table 7。

(comparative example 8)

Using polyimide/polyamide acid solution (A9) as aligning agent for liquid crystal, carry out [evaluation of response speed] [evaluation of vertical orientation].As a result table 7 and table 8 are shown in.

(comparative example 9)

Polysiloxane solution (B8) 3.0g and polyamic acid solution (A5) 7.0g is mixed, aligning agent for liquid crystal is obtained (24).Using the aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientation].As a result it is shown in table 7.In turn, the evaluation of voltage retention and ion concentration is carried out according to [evaluation of electrology characteristic].As a result it is shown in table 9.

(comparative example 10)

Polysiloxane solution (B8) 3.0g and polyamic acid solution (A8) 7.0g is mixed, aligning agent for liquid crystal is obtained (25).Using the aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientation].As a result it is shown in table 7.In turn, the evaluation of voltage retention and ion concentration is carried out according to [evaluation of electrology characteristic].As a result it is shown in table 9.

(comparative example 11)

Polysiloxane solution (B5) 3.0g and polysiloxane solution (B9) 7.0g is mixed, aligning agent for liquid crystal is obtained (26).Using the aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of re-workability].As a result it is shown in table 8 With table 10.

(comparative example 12)

Polysiloxane solution (B6) 3.0g and polysiloxane solution (B9) 7.0g is mixed, aligning agent for liquid crystal is obtained (27).Using the aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of re-workability].As a result it is shown in table 8 With table 10.

[table 1]

	Polysiloxanes	Farmland
			Reference example 1	B1	○
Comparative example 1	B2	△

In table 1, in the liquid crystal cells of reference example 1, after annealing, the farmland of orientation disorder is not observed completely.On the other hand, In the liquid crystal cells of comparative example 1, after annealing, the farmland of multiple orientation disorders is observed.

[table 2]

In table 2, about electrology characteristic it is found that the aligning agent for liquid crystal (reference example 1) containing urea groups with do not contain urea groups Aligning agent for liquid crystal (comparative example 2) compare, VHR (voltage retention) is high, and ion concentration is low.

[table 3]

In table 3, about re-workability it is found that compared with the aligning agent for liquid crystal for containing only polysiloxane ingredient, contain The re-workability of aligning agent for liquid crystal selected from least one of the group being made of polyamic acid and polyimides polymer Higher.

[table 4]

It is found that the aligning agent for liquid crystal containing urea groups is compared with the aligning agent for liquid crystal without containing urea groups, in vain in table 4 Change excellent.

[table 5]

It is same as table 1 in table 5, in the liquid crystal cells of reference example 2,6, after annealing, do not observe orientation disorder completely Farmland.On the other hand, in the liquid crystal cells of comparative example 3,4, after annealing, the farmland of multiple orientation disorders is observed.

[table 6]

It is same as table 2 in table 6, about electrology characteristic it is found that the aligning agent for liquid crystal (reference example 2,6) containing urea groups Compared with the aligning agent for liquid crystal (comparative example 5,6) without containing urea groups, VHR high, ion concentration is low.

[table 7]

The judgement zero of response speed：Soon (good) ×：Slowly (poor)

Observe result in farmland after annealing

×：Observe multiple farmlands

○：Well

◎：It is very good

In table 7, in embodiment 1, the fast response time after UV irradiations, and the farmland observation result after annealing is also good As a result.On the other hand, in comparative example 8, the farmland observation result after annealing is very good, but the response speed after UV irradiations is slow.Than Compared in example 7, fast response time, but observe multiple farmlands after annealing.

In addition, in embodiment 2~11, comparative example 9 and 10, the fast response time after UV irradiations, and the farmland after annealing is seen It examines result and also shows that very good result.

[table 8]

The judgement of response speed

○：(very good) soon<50 milliseconds

△：(good) soon<50~100 milliseconds

×：Slowly (poor)>200 milliseconds

It is about the response speed to UV exposures it is found that independent by poly- silica with comparative example 11 and comparative example 12 in table 8 The aligning agent for liquid crystal that alkane is constituted is compared, containing poly- selected from least one of group being made of polyamic acid and polyimides The aligning agent for liquid crystal for closing object is wider to the range of the raising of the UV response speeds irradiated.

[table 9]

It is same as table 2 and table 6 in table 9, about electrology characteristic it is found that the aligning agent for liquid crystal containing urea groups be free of There is the aligning agent for liquid crystal of urea groups to compare, VHR high, ion concentration is low.

[table 10]

	(B) ingredient	(A) ingredient	Re-workability
				Embodiment 5	B5	A5	○
Embodiment 9	B5	A9	○
				Comparative example 11	B5、B9	Nothing	×
Comparative example 12	B6、B9	Nothing	×

It is same as table 3 in table 10, it is known that with individually by the aligning agent for liquid crystal that inorganic compound is constituted compared with, contain The re-workability of aligning agent for liquid crystal selected from least one of the group being made of polyamic acid and polyimides polymer Higher.

Industrial applicibility

The liquid crystal orientation film formed using the aligning agent for liquid crystal of the present invention will not make the reduction of vertical orientation power, UV irradiations Response speed afterwards is also excellent, has the liquid crystal display element of the liquid crystal orientation film of the present invention for TFT liquid crystal display elements, TN Liquid crystal display element, VA liquid crystal display elements etc. are useful.

It should be noted that the specification for the Japanese patent application 2012-190328 that August in 2012 is submitted on the 30th, The full content of claims and abstract is quoted so far, this Shen is incorporated to as the disclosure of the specification of the present invention Please.

Claims

(A) ingredient：Selected from least one of the group being made of polyamic acid and polyimides polymer, the polyamic acid is By making containing bis- selected from 3,5- diaminobenzoic acids, 2,5- diaminobenzoic acids, bis- (4- aminophenethyls) ureas of 1,3-, 1,3- Obtained from the diamine component of at least one of (3- aminopropyls) tetramethyl disiloxane diamines is reacted with tetracarboxylic acid sour component,

(B) ingredient：Make the alkoxy silane polycondensation of the alkoxy silane indicated containing formula (1), formula (3) and following formula (4) and obtains The polysiloxanes arrived,

R¹Si(OR²)₃ (1)

R¹For the structure of following formula (2), R²For the alkyl of carbon atom number 1~5,

[changing 1]

Y¹For-(CH₂)_aOr-CH₂The integer that O-, a are 1~15,

Y²The hydrocarbon for the linear chain or branched chain that carbon atom number for singly-bound, containing double bond is 3~8 or-(CR¹⁷R¹⁸)_b, b is 1~15 Integer, R¹⁷、R¹⁸It is each independently the alkyl that hydrogen atom or carbon atom number are 1~3,

Y³For singly-bound ,-(CH₂)_c-、-O-、-CH₂O- ,-COO- or-OCO-, the integer that c is 1~15,

Y⁴For the bivalent cyclic base in phenyl ring, cyclohexyl ring and heterocycle, arbitrary hydrogen atom in these cyclic groups can be with It is 1~3 containing fluoroalkyl, carbon atom by alkoxy that alkyl that carbon atom number is 1~3, carbon atom number are 1~3, carbon atom number Number replaces for 1~3 fluoroalkoxy or fluorine atom, in addition, Y⁴Can be the carbon atom number with steroid skeleton be 12~ 25 bivalent organic group,

Y⁵For the bivalent cyclic base in the group being made of phenyl ring, cyclohexyl ring and heterocycle, the arbitrary hydrogen in these cyclic groups Alkoxy that alkyl that atom can be 1~3 by carbon atom number, carbon atom number are 1~3, carbon atom number are 1~3 to contain fluothane Base, the fluoroalkoxy that carbon atom number is 1~3 or fluorine atom substitution,

Y⁶For hydrogen atom, carbon atom number be 1~18 alkyl, carbon atom number be 1~18 containing fluoroalkyl, carbon atom number be 1~18 Alkoxy or carbon atom number be 1~18 fluoroalkoxy, n be 0~4 integer,

R³Si(OR⁴)₃ (3)

R³For the carbon original replaced by acryloyl group, acryloxy, methylacryloyl, methacryloxy or styryl The alkyl that subnumber is 1~30, R⁴For the alkyl of carbon atom number 1~5,

(R⁵)_nSi(OR⁶)_4-n (4)

R⁵For the alkyl that can be 1~10 by the carbon atom number of Carbamido substituted, R⁶For the alkyl of carbon atom number 1~5, n is 0~3 Integer.

2. aligning agent for liquid crystal according to claim 1, wherein the alkoxy silane that the formula (4) indicates is tetramethyl Oxysilane or tetraethoxysilane.

3. aligning agent for liquid crystal according to claim 1, wherein used in the manufacture of the polysiloxanes of (B) ingredient In whole alkoxy silanes, the alkoxy silane indicated using the formula (1) of 2~20 moles of %, and 5~80 moles of % of use The alkoxy silane that formula (3) indicates.

4. aligning agent for liquid crystal according to claim 1 or 2, wherein the manufacture of the polysiloxanes of (B) ingredient is used Whole alkoxy silanes in, use 10~90 moles of % formula (4) indicate alkoxy silane.

5. aligning agent for liquid crystal according to claim 1 or 2, wherein relative to 100 mass parts of (A) ingredient, containing with (B) SiO of silicon atom possessed by ingredient₂Scaled value is calculated as (B) ingredient of 0.5~80 mass parts.

6. aligning agent for liquid crystal according to claim 1 or 2, wherein also contain organic solvent, the organic solvent is in liquid Contain 90~99 mass % in brilliant aligning agent.

7. a kind of liquid crystal orientation film, by the way that aligning agent for liquid crystal according to any one of claims 1 to 6 is applied to base On plate and dry, calcining obtains.

8. liquid crystal orientation film according to claim 7, wherein carried out at a temperature of 100~350 DEG C it is described calcining and shape At liquid crystal orientation film.

9. liquid crystal orientation film according to claim 7 or 8, wherein the thickness of the film after calcining is 5~300nm.

10. a kind of liquid crystal display element, with the liquid crystal orientation film described in any one of claim 7~9.