CN104737069A - Liquid crystal aligning agent and liquid crystal display element using same - Google Patents

Liquid crystal aligning agent and liquid crystal display element using same Download PDF

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CN104737069A
CN104737069A CN201380054892.7A CN201380054892A CN104737069A CN 104737069 A CN104737069 A CN 104737069A CN 201380054892 A CN201380054892 A CN 201380054892A CN 104737069 A CN104737069 A CN 104737069A
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liquid crystal
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aligning agent
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solution
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CN104737069B (en
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桥本淳
佐藤夏树
后藤耕平
平贺浩二
元山贤一
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Nissan Chemical Corp
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Abstract

Provided are: a liquid crystal aligning agent which is capable of forming a liquid crystal alignment film that is able to improve the response speed after UV irradiation without being decreased in vertical alignment ability; and a liquid crystal display element which comprises a liquid crystal alignment film obtained from the liquid crystal aligning agent and is processed similarly to PSA type liquid crystal display elements using liquid crystals to which a liquid crystal polymerizable compound is not added, said liquid crystal display element having improved response speed after UV irradiation. A liquid crystal aligning agent which contains: at least one kind of a polymer (component (A)) that is selected from the group consisting of polyamic acids and polyimides; and a polysiloxane (component (B)) that is obtained by polycondensing alkoxysilanes including an alkoxysilane represented by formula (1) and an alkoxysilane represented by formula (3). R1Si(OR2)3 (1) (R1 represents a group represented by formula (2); and R2 represents an alkyl group having 1-5 carbon atoms.) (Y1 represents a single bond or the like; Y2 represents a single bond or the like; Y3 represents a single bond or the like; Y4 represents a divalent cyclic group such as a benzene ring, or the like; Y5 represents a divalent cyclic group such as a benzene ring, or the like; Y6 represents an alkyl group having 1-18 carbon atoms, or the like; and n represents a number of 0-4.) R3Si(OR4)3 (3) (R3 represents an acryl group, an acryloxy group, a methacryl group, a methacryloxy group or an alkyl group having 1-30 carbon atoms and substituted by a styryl group; and R4 represents an alkyl group having 1-5 carbon atoms.)

Description

Aligning agent for liquid crystal and use the liquid crystal display cells of this aligning agent for liquid crystal
Technical field
The liquid crystal orientation film that the present invention relates to aligning agent for liquid crystal and obtained by above-mentioned aligning agent for liquid crystal and the liquid crystal display cells with this liquid crystal orientation film.
Background technology
In recent years, in the display mode of liquid crystal display cells, the liquid crystal display cells of vertical (VA) mode is widely used in the liquid crystal TV set of large picture, the mobile purposes (display part of digital camera, mobile phone) etc. of fine.In VA mode, known MVA mode (the Multi Vertical Alignment forming the projection of vergence direction for controlling liquid crystal on TFT substrate, filter substrate, multi-domain vertical alignment), on ITO (indium-tin-oxide) electrode of substrate, form slit and utilize PVA (Patterned Vertical Alignment, pattern the is vertical orientated) mode of the vergence direction of electric field controls liquid crystal.
Aligned as other, there is PSA (Polymer sustained Alignment, polymer stabilizing orientation) mode.
In VA mode, PSA mode is the technology received publicity in recent years.In which, in liquid crystal, add photopolymerizable compound, after making liquid crystal panel, apply electric field, to liquid crystal panel irradiation ultraviolet radiation (UV) under the state of LC tilt.As a result, polymerizable compound generation photopolymerization, thus, the direction of orientation of liquid crystal is immobilized and produces pre-dumping, and response speed improves.It is characterized in that, even if be used in form liquid crystal panel one-sided electrode on make slit, the structure that is not provided with the such projection of MVA or the such slit of PVA in the electrode pattern of opposite side also can work, can manufacture be simplified, excellent panel transmissivity (see patent documentation 1) can be obtained
But in the liquid crystal display cells of PSA mode, the dissolubility of adding the polymerizable compound in liquid crystal to is low, there is the problem separated out when low temperature when increasing its addition.In addition, when reducing the addition of polymerizable compound, good state of orientation, response speed cannot be obtained.In addition, also there is the unreacted polymerizable compound remained in liquid crystal become the impurity in liquid crystal and make the problem that the reliability of liquid crystal display cells reduces.
Therefore, propose following technology: the polymkeric substance having imported photoreactivity side chain will be used in polymer molecule and the aligning agent for liquid crystal obtained is applied on substrate, liquid crystal orientation film is obtained after calcining, the liquid crystal layer contacted with this liquid crystal orientation film is set, irradiation ultraviolet radiation executing alive to this liquid crystal layer while, make liquid crystal display cells, thus, even if do not add polymerizable compound in liquid crystal, also can meet with a response fireballing liquid crystal display cells (see patent documentation 2)
On the other hand, with the liquid crystal aligning membrane material also having inorganic system that the liquid crystal aligning membrane material of the organic system such as the polyimide used is together known in the past.Such as, as the liquid crystal aligning membrane material of the inorganic system of application type, propose the aligning agent for liquid crystal composition of the reaction product containing tetraalkoxysilane, trialkoxy silane, alcohol and oxalic acid, it is reported that it defines the liquid crystal orientation film (see patent documentation 3) of vertical orientated property, thermotolerance and excellent in uniformity on the electrode base board of liquid crystal display cells
In addition, propose the aligning agent for liquid crystal composition of reaction product containing tetraalkoxysilane, specific trialkoxy silane and water and specific glycol ethers series solvent, it is reported which form prevent from showing bad, after driving for a long time image retention characteristic also good, can not reduce and make the ability of liquid crystal aligning and the few liquid crystal orientation film (see patent documentation 4) of the reduction of voltage retention that causes of light and heat
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2004-302061 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2011-95967 publication
Patent documentation 3: Japanese Unexamined Patent Publication 09-281502 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2005-250244 publication
Summary of the invention
Invent problem to be solved
In vertical orientated VA pattern, need the strong vertical orientated power for making liquid crystal vertical-tropism, but do not using in which of polymerizable compound, when improving vertical orientated power, the postradiation response speed of UV is slack-off, and when improving the postradiation response speed of UV, vertical orientated power reduces.Vertical orientated power and the postradiation response speed of UV improve and there is anti-relation of being contrary to.
Problem of the present invention is the liquid crystal display cells providing a kind of aligning agent for liquid crystal, the liquid crystal orientation film obtained by this aligning agent for liquid crystal and have this liquid crystal orientation film, even if this aligning agent for liquid crystal can be formed also can improve the postradiation response speed of UV in the liquid crystal not adding polymerizable compound, the liquid crystal display cells processing the mode improving the postradiation response speed of UV in the same manner as PSA mode and the liquid crystal orientation film that can not reduce vertical orientated power using.
Solve the means of problem
The present inventor conducts in-depth research to achieve these goals, found that, can above-mentioned purpose be realized by the aligning agent for liquid crystal containing at least one polymkeric substance ((A) composition) be selected from the group that is made up of polyamic acid and polyimide and specific polysiloxane ((B) composition), thus complete the present invention.
That is, the present invention has following main points.
1. an aligning agent for liquid crystal, is characterized in that, containing following (A) composition and (B) composition,
(A) composition: be selected from least one polymkeric substance in the group be made up of polyamic acid and polyimide,
(B) composition: the alkoxy silane polycondensation of the alkoxy silane that the alkoxy silane that represents containing formula (1) and formula (3) are represented and the polysiloxane obtained.
R 1Si(OR 2) 3(1)
(R 1for the structure of following formula (2), R 2alkyl for carbon number 1 ~ 5)
[changing 2]
(Y 1for singly-bound ,-(CH 2) a-(a is the integer of 1 ~ 15) ,-O-,-CH 2o-,-COO-or-OCO-.
Y 2for alkyl or-(CR that singly-bound, carbon number containing double bond are the straight or branched of 3 ~ 8 17r 18) b-(b is the integer of 1 ~ 15, R 17, R 18independently of one another for hydrogen atom or carbon number are the alkyl of 1 ~ 3).
Y 3for singly-bound ,-(CH 2) c-(c is the integer of 1 ~ 15) ,-O-,-CH 2o-,-COO-or-OCO-.
Y 4for being selected from the bivalent cyclic base in phenyl ring, cyclohexyl ring and heterocycle, alkyl, carbon number that the arbitrary hydrogen atom in these cyclic group can be 1 ~ 3 by carbon number be 1 ~ 3 alkoxy, carbon number be 1 ~ 3 containing fluoroalkyl, carbon number be 1 ~ 3 fluoroalkoxy or fluorine atom replace.In addition, Y 4can be the divalent organic group of 12 ~ 25 for the carbon number with steroid skeleton.
Y 5for being selected from the bivalent cyclic base in the group that is made up of phenyl ring, cyclohexyl ring and heterocycle, alkyl, carbon number that the arbitrary hydrogen atom in these cyclic group can be 1 ~ 3 by carbon number be 1 ~ 3 alkoxy, carbon number be 1 ~ 3 containing fluoroalkyl, carbon number be 1 ~ 3 fluoroalkoxy or fluorine atom replace.
Y 6for hydrogen atom or carbon number be 1 ~ 18 alkyl, carbon number be 1 ~ 18 containing fluoroalkyl, carbon number be 1 ~ 18 alkoxy or carbon number be the fluoroalkoxy of 1 ~ 18.N is the integer of 0 ~ 4)
R 3Si(OR 4) 3(3)
(R 3for the carbon number that can be replaced by acryloyl group, acryloxy, methacryl, methacryloxy or styryl is the alkyl of 1 ~ 30, R 4alkyl for carbon number 1 ~ 5)
2. the aligning agent for liquid crystal according to above-mentioned 1, wherein, the polysiloxane that (B) composition obtains for making the alkoxy silane polycondensation of the alkoxy silane also represented containing following formula (4).
(R 5) nSi(OR 6) 4-n(4)
(in formula (4), R 5for hydrogen atom or can be the alkyl of 1 ~ 10 by the carbon number of heteroatoms, halogen atom, amino, glycidoxy, sulfydryl, isocyanate group, Carbamido substituted.R 6for the alkyl of carbon number 1 ~ 5, n is the integer of 0 ~ 3)
3. the aligning agent for liquid crystal according to above-mentioned 2, wherein, the alkoxy silane that above-mentioned formula (4) represents is tetramethoxy-silicane or tetraethoxysilane.
4. the aligning agent for liquid crystal according to above-mentioned 1, wherein, (B) in whole alkoxy silanes that the manufacture of the polysiloxane of composition uses, use the alkoxy silane that the formula (1) of 2 ~ 20 % by mole represents, and use the alkoxy silane that the formula of 5 ~ 80 % by mole (3) represents.
5. the aligning agent for liquid crystal according to above-mentioned 2 or 3, wherein, in whole alkoxy silanes that the manufacture of the polysiloxane of (B) composition uses, uses the alkoxy silane that the formula (4) of 10 ~ 90 % by mole represents.
6. the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 5, wherein, relative to (A) composition 100 mass parts, the SiO containing the silicon atom had with (B) composition 2scaled value counts (B) composition of 0.5 ~ 80 mass parts.
7. the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 6, wherein, also containing organic solvent, this organic solvent contains 90 ~ 99 quality % in aligning agent for liquid crystal.
8. a liquid crystal orientation film, it is by be applied to the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 7 on substrate and to carry out drying, calcining and obtaining.
9. the liquid crystal orientation film according to above-mentioned 8, wherein, carries out above-mentioned calcining to form liquid crystal orientation film at the temperature of 100 ~ 350 DEG C.
10. the liquid crystal orientation film according to above-mentioned 8 or 9, wherein, the thickness of the film after calcining is 5 ~ 300nm.
11. 1 kinds of liquid crystal display cells, it has the liquid crystal orientation film according to any one of above-mentioned 8 ~ 10.
The effect of invention
According to the present invention, provide to be formed and can improve the postradiation response speed of UV and the aligning agent for liquid crystal of the liquid crystal orientation film of vertical orientated power, the liquid crystal orientation film obtained by this aligning agent for liquid crystal can not be reduced and there is this liquid crystal orientation film, use and do not add the liquid crystal of polymerizable compound, process, improve the liquid crystal display cells of the mode of the postradiation response speed of UV in the same manner as PSA mode.
Embodiment
< (A) composition: polyamic acid and/or polyimide >
Containing at least one polymkeric substance be selected from the group that is made up of polyamic acid and polyimide in aligning agent for liquid crystal of the present invention.The concrete structure of this polyamic acid and polyimide is not particularly limited, such as, can be the polyamic acid or polyimide contained in known aligning agent for liquid crystal.
Polyamic acid can be reacted by tetrabasic carboxylic acid or the derivant of tetrabasic carboxylic acid and (polycondensation) of diamines and easily obtain.
Be not particularly limited as the polyamic acid of (A) composition used in the present invention and the manufacture method of polyimide.Usually, make reacted with the diamine component be made up of one or more diamine compound by one or more the tetrabasic carboxylic acid compositions formed be selected from the group that is made up of tetrabasic carboxylic acid or derivatives thereof and obtain polyamic acid.
In addition, as the method obtaining polyimide, can use the method for polyamic acid imidizate.
Now, the polyamic acid obtained can by suitably selecting as the tetrabasic carboxylic acid composition of raw material and diamine component and obtain homopolymer or multipolymer.
Herein, tetrabasic carboxylic acid or derivatives thereof is tetrabasic carboxylic acid, tetrabasic carboxylic acid dihalide or tetracarboxylic dianhydride.Wherein, the reactivity of tetracarboxylic dianhydride and diamine compound is high, therefore preferably.
Specifically, can enumerate: Pyromellitic Acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid, 2,3,6,7-anthracene tetrabasic carboxylic acid, 1,2,5,6-anthracene tetrabasic carboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid, two (3,4-dicarboxyphenyi) ether, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid, two (3,4-dicarboxyphenyi) sulfone, two (3,4-dicarboxyphenyi) methane, two (3, the 4-dicarboxyphenyi) propane of 2,2-, two (3, the 4-dicarboxyphenyi) propane of 1,1,1,3,3,3-hexafluoro-2,2-, two (3,4-dicarboxyphenyi) dimethylsilane, two (3,4-dicarboxyphenyi) diphenyl silane, 2,3,4,5-pyridine tetrabasic carboxylic acid, two (3, the 4-dicarboxyphenyi) pyridine of 2,6-, two [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane of 2,2-, 3,3 ', 4,4 '-diphenylsulfone acid, 3,4,9,10-perylene tetracarboxylic, 1,3-diphenyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid, bis oxide O-phthalic tetrabasic carboxylic acid, 1,2,3,4-cyclo-butane tetrabasic carboxylic acid, 1,2,3,4-cyclopentane tetrabasic carboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid, 1,2-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid, 1,2,3,4-cycloheptane tetrabasic carboxylic acid, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acid, 3,4-dicarboxyl-1-cyclohexyl succinic acid, 2,3,5-tricarboxylic cyclopentyl acetic acid, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic, dicyclo [3,3,0] octane-2,4,6,8-tetrabasic carboxylic acid, dicyclo [4,3,0] nonane-2,4,7,9-tetrabasic carboxylic acid, dicyclo [4,4,0] decane-2,4,7,9-tetrabasic carboxylic acid, dicyclo [4,4,0] decane-2,4,8,10-tetrabasic carboxylic acid, three rings [6.3.0.0<2,6>] undecane-3,5,9,11-tetrabasic carboxylic acid, 1,2,3,4-BTCA, dicyclo [2,2,2] pungent-7-alkene-2,3,5,6-tetrabasic carboxylic acid, the tetrabasic carboxylic acids such as Fourth Ring [6,2,1,1,0,2,7] 12 carbon alkane-4,5,9,10-tetrabasic carboxylic acid.In addition, the dihalide of these tetrabasic carboxylic acids or the dicarboxylic anhydride etc. of tetrabasic carboxylic acid can be enumerated.
Wherein, from the viewpoint of the transparency of film, preferred ester ring type tetrabasic carboxylic acid, their dianhydride or their dicarboxylic acid dihalide.Particularly preferably 1,2,3,4-cyclo-butane tetrabasic carboxylic acid, 2,3,5-tricarboxylic cyclopentyl acetic acid, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinics, dicyclo [3,3,0] octane-2,4, the dihalide of 6,8-tetrabasic carboxylic acid, these tetrabasic carboxylic acids or the dicarboxylic anhydride of these tetrabasic carboxylic acids.
Above-mentioned tetrabasic carboxylic acid or derivatives thereof can use a kind of or used in combination two or more according to the characteristic such as liquid crystal aligning, voltage retention performance, accumulated charge when making liquid crystal orientation film.
The diamines used in the manufacture of polyamic acid is not particularly limited.Specifically, can enumerate: p-phenylenediamine (PPD), 2,3,5,6-tetramethyl-para-phenylene diamine, 2,5-dimethyl-p-phenylenediamine, m-phenylene diamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzene methyl alcohol, 2,4-diaminobenzene methyl alcohol, 4,6-diaminoresorcinol, 4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxy-4,4 '-benzidine, 3,3 '-dicarboxyl-4,4 '-benzidine, 3,3 '-two fluoro-4,4 '-biphenyl, 3,3 '-trifluoromethyl-4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-benzidine, 2,3 '-benzidine, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methane, 2,3 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 2,2 '-diaminodiphenyl ether, 2,3 '-diaminodiphenyl ether, diaphenylsulfone, 3,3 '-sulfonyldianiline, two (4-aminophenyl) silane, two (3-aminophenyl) silane, two (4-aminophenyl) silane of dimethyl, two (3-aminophenyl) silane of dimethyl, 4,4 '-phenothiazine, 3,3 '-phenothiazine, 4,4 '-diamino-diphenylamine, 3,3 '-diamino-diphenylamine, 3,4 '-diamino-diphenylamine, 2,2 '-diamino-diphenylamine, 2,3 '-diamino-diphenylamine, 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-diphenyl) amine, N-methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, Isosorbide-5-Nitrae-diaminonaphthalene, 2,2 '-diaminobenzophenone, 2,3 '-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6 diaminonaphthalenes, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, two (4-aminophenyl) ethane of 1,2-, two (3-aminophenyl) ethane of 1,2-, two (4-aminophenyl) propane of 1,3-, two (3-aminophenyl) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) butane, Isosorbide-5-Nitrae-bis-(3-aminophenyl) butane, two (3,5-diethyl-4-aminophenyl) methane, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) benzene, two (4-aminophenyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminobenzyl) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, 4,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene)] diphenylamine, 4,4 '-[1,3-phenylene two (methylene)] diphenylamine, 3,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene)] diphenylamine, 3,4 '-[1,3-phenylene two (methylene)] diphenylamine, 3,3 '-[Isosorbide-5-Nitrae-phenylene two (methylene)] diphenylamine, 3,3 '-[1,3-phenylene two (methylene)] diphenylamine, Isosorbide-5-Nitrae-phenylene two [(4-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two [(3-aminophenyl) ketone], 1,3-phenylene two [(4-aminophenyl) ketone], 1,3-phenylene two [(3-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two (PABA ester), Isosorbide-5-Nitrae-phenylene two (3-Aminobenzoate), 1,3-phenylene two (PABA ester), 1,3-phenylene two (3-Aminobenzoate), two (4-aminophenyl) terephthalate, two (3-aminophenyl) terephthalate, two (4-aminophenyl) isophthalic acid ester, two (3-aminophenyl) isophthalic acid ester, N, N '-(Isosorbide-5-Nitrae-phenylene) two (4-aminobenzamide), N, N '-(1,3-phenylene) two (4-aminobenzamide), N, N '-(Isosorbide-5-Nitrae-phenylene) two (3-AB), N, N '-(1,3-phenylene) two (3-AB), N, N '-bis-(4-aminophenyl) terephthalamide, N, N '-bis-(3-aminophenyl) terephthalamide, N, N '-bis-(4-aminophenyl) isophtalamide, N, N '-bis-(3-aminophenyl) isophtalamide, two (4-aminophenyl) anthracene of 9,10-, 4,4 '-bis-(4-amino-benzene oxygen) diphenylsulphone, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2 '-bis-(4-aminophenyl) HFC-236fa, 2,2 '-bis-(3-aminophenyl) HFC-236fa, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) HFC-236fa, 2,2 '-bis-(4-aminophenyl) propane, 2,2 '-bis-(3-aminophenyl) propane, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, two (4-amino-benzene oxygen) propane of 1,3-, two (3-amino-benzene oxygen) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) butane, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) butane, two (4-amino-benzene oxygen) pentane of 1,5-, two (3-amino-benzene oxygen) pentane of 1,5-, two (4-amino-benzene oxygen) hexane of 1,6-, two (3-amino-benzene oxygen) hexane of 1,6-, two (4-amino-benzene oxygen) heptane of 1,7-, 1,7-(3-amino-benzene oxygen) heptane, two (4-amino-benzene oxygen) octane of 1,8-, two (3-amino-benzene oxygen) octane of 1,8-, two (4-amino-benzene oxygen) nonane of 1,9-, two (3-amino-benzene oxygen) nonane of 1,9-, 1,10-(4-amino-benzene oxygen) decane, 1,10-(3-amino-benzene oxygen) decane, 1,11-(4-amino-benzene oxygen) undecane, 1,11-(3-amino-benzene oxygen) undecane, 1,12-(4-amino-benzene oxygen) dodecane, 1,12-(3-amino-benzene oxygen) dodecane, the aromatic diamines such as two (4-aminophenethyl) ureas of 1,3-, the ester ring type diamines such as two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropanes, 1,4-Diaminobutane, 1,5-1,5-DAP, 1,6-diamino hexane, 1,7-diaminoheptane, 1,8-diamino-octane, 1,9-diamino nonane, 1,10-diamino decane, 1, the aliphatic diamines etc. such as 11-diamino undecane, 1,12-diamino dodecane, 1,3-two (3-aminopropyl) tetramethyl disiloxanes.
Wherein, from the viewpoint of electrology characteristic, with the compatibility etc. of polysiloxane, preferably use 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-two (4-aminophenethyl) urea, 1,3-two (3-aminopropyl) tetramethyl disiloxane.
In addition, can enumerate and there is alkyl on two amine side chains, containing fluoroalkyl, aromatic rings, aliphatics ring, heterocycle or the diamines of large ring-type substituent that is made up of these substituting groups.
Specifically, the diamines that following formula [A1] ~ [A20] represents can be illustrated.
[changing 3]
(R 1for carbon number more than 1 and the alkyl of less than 22 or containing fluoroalkyl)
[changing 4]
(R 2for-COO-,-OCO-,-CONH-,-NHCO-,-CH 2-,-O-,-CO-or-NH-, R 3for hydrogen atom, carbon number more than 1 and the alkyl of less than 22 or containing fluoroalkyl)
[changing 5]
(R 4for-O-,-OCH 2-,-CH 2o-,-COOCH 2-or-CH 2oCO-, R 5for carbon number more than 1 and the alkyl of less than 22, alkoxy, containing fluoroalkyl or fluoroalkoxy)
[changing 6]
(R 6for-COO-,-OCO-,-CONH-,-NHCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-or-CH 2-.R 7for carbon number more than 1 and the alkyl of less than 22, alkoxy, containing fluoroalkyl or fluoroalkoxy)
[changing 7]
(R 8for-COO-,-OCO-,-CONH-,-NHCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-,-CH 2-,-O-or-NH-, R 9for fluorine-based, cyano group, trifluoromethyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group, hydroxyl or carboxyl)
[changing 8]
In addition, the diamido siloxane etc. that following formula [A21] represents can also be enumerated.
[changing 9]
(m is the integer of 1 ~ 10)
Above-mentioned diamines can use a kind of or used in combination two or more according to the characteristic such as liquid crystal aligning, voltage retention performance, accumulated charge when making liquid crystal orientation film.
In the raw material of above-mentioned polyamic acid, when use has the diamines of hydroxyl or carboxyl, the reaction efficiency of polyamic acid or polyimide and cross-linked compound described later can be improved.
As the concrete example of such diamines, can enumerate: 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzene methyl alcohol, 2,4-diaminobenzene methyl alcohol, 3,3 '-dihydroxy-4,4 '-benzidine, 3,3 '-dicarboxyl-4,4 '-benzidine, 3, the diamines etc. that 5-diaminobenzoic acid, 2,5-diaminobenzoic acids, formula [A22] ~ [A25] represent.
[changing 10]
(R 10for-COO-,-OCO-,-CONH-,-NHCO-,-CH 2-,-O-,-CO-or-NH-)
[changing 11]
(R 11for-COO-,-OCO-,-CONH-,-NHCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-,-CH 2-,-O-or-NH-.R 12for hydroxyl or carboxyl)
As the solvent used when manufacturing polyamic acid, be not particularly limited as long as the polyamic acid of generation is dissolved.If enumerate its concrete example, be: DMF then, DMA, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, isopropyl alcohol, methoxy amylalcohol, cinene, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, DPE, 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-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, diox, normal hexane, n-pentane, normal 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 propionate, 3-ethoxypropanoate, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone etc.
These solvents can be used alone, also can be used in combination.In addition, even the solvent of insoluble solution polyamic acid, also can be mixed in above-mentioned solvent in the scope not making the polyamic acid of generation separate out and use.In addition, the moisture in organic solvent can suppress polyreaction, and then becomes and make the acid-hydrolyzed reason of the polyamide of generation, and therefore, organic solvent preferably uses the organic solvent dehydrated as far as possible.
As the method making tetrabasic carboxylic acid or derivatives thereof and diamines react in organic solvent during manufacture polyamic acid, can enumerate: be dispersed or dissolved in the solution obtained in organic solvent to making diamines and stir, directly add tetrabasic carboxylic acid or derivatives thereof or tetrabasic carboxylic acid or derivatives thereof be dispersed or dissolved in the method for carrying out in organic solvent adding; The method of diamines is added on the contrary in the solution making tetrabasic carboxylic acid or derivatives thereof be dispersed or dissolved in obtain in organic solvent; Alternately add the method for tetrabasic carboxylic acid or derivatives thereof and diamines; Deng.It can be any one method in these methods.In addition, when tetrabasic carboxylic acid or derivatives thereof or diamines are made up of two or more compounds, can it be made to react under the state be pre-mixed, also can individually react successively, can also make individually to react obtained low-molecular weight hybrid reaction and obtain high molecular body.
Temperature during synthesizing polyamides acid can select the arbitrary temp in-20 ~ 150 DEG C, is preferably the scope of-5 ~ 100 DEG C.
In addition, reaction can be carried out with arbitrary concentration.But when concentration is too low, be difficult to the polymkeric substance obtaining high molecular, during excessive concentration, the viscosity of reactant liquor is too high and be difficult to stir uniformly, therefore, be preferably 1 quality % ~ 50 quality %, be more preferably 5 quality % ~ 30 quality %.Can react with high concentration in initial reaction stage, add organic solvent more afterwards.
In the manufacture of polyamic acid, the molal quantity of diamine component is preferably 0.8 ~ 1.2 relative to the ratio of the molal quantity of tetrabasic carboxylic acid or derivatives thereof, is more preferably 0.9 ~ 1.1.Same with common polycondensation reaction, this mol ratio is more close to 1.0, then the molecular weight of the polyamic acid generated is larger.
As the method making polyamic acid imidizate, generally by heating the hot-imide carried out, the catalyzer imidizate using catalyzer, but the catalyzer imidizate carrying out imidization reaction at relatively low temperatures not easily causes the reduction of the molecular weight of obtained polyimide, therefore preferably.
Catalyzer imidizate can be undertaken by being stirred under the existence of base catalyst and acid anhydrides in organic solvent by polyamic acid.Temperature of reaction is now-20 ~ 250 DEG C, is preferably 0 ~ 180 DEG C.During temperature of reaction height, imidizate carries out fast, but time too high, the molecular weight of polyimide reduces sometimes.The amount of base catalyst is 0.5 ~ 30 mole times of acid amides acidic group, is preferably 2 ~ 20 moles doubly, and the amount of acid anhydrides is 1 ~ 50 mole times of acid amides acidic group, is preferably 3 ~ 30 moles times.When the amount of base catalyst or acid anhydrides is few, reaction is carried out insufficient, in addition, time too much, is difficult to remove completely after reaction terminating.
As base catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be enumerated, wherein, pyridine have for make reaction carry out for appropriateness alkalescence, therefore preferably.
In addition, as acid anhydrides, acetic anhydride, trimellitic anhydride, pyromellitic acid anhydride etc. can be enumerated, wherein, when using acetic anhydride, easy purifying after reaction terminating, therefore preferably.
As organic solvent during catalyzer imidizate, as long as the organic solvent dissolving polyamic acid does not then limit.If enumerate its concrete example, be then: N, N '-dimethyl formamide, N, N '-dimethyl acetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethylurea, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton etc.The acid imide rate of catalyzer imidizate can by regulating control catalytic amount, temperature of reaction, reaction time.
The polyimide generated can obtain by above-mentioned reaction solution being put into the precipitation also reclaiming generation in poor solvent.Now, the poor solvent used is not particularly limited.Such as, can enumerate: methyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water etc.Put into poor solvent and the polyimide that precipitates after filtration, can be dry under normal temperature or heating under normal or reduced pressure and make powder.Also this polyimide powder can be dissolved in organic solvent further makes it precipitate again, is repeated to carry out purifying to polyimide 2 ~ 10 times by aforesaid operations.By primary sedimentation reclaimer operation cannot Ex-all impurity time, preferably carry out this purification step.
The molecular weight of the polyimide used in the present invention is not particularly limited, and the stability of characteristic when being formed from the viewpoint of the easiness of process and film, is preferably 2000 ~ 200000 with Weight-average molecular gauge, is more preferably 4000 ~ 50000.The molecular weight of molecular weight for being obtained by GPC (gel permeation chromatography).
< (B) composition: polysiloxane >
(B) composition contained in aligning agent for liquid crystal of the present invention is for the alkoxy silane polycondensation of alkoxy silane that makes the alkoxy silane that represents containing formula (1) and formula (3) and represent and the polysiloxane obtained.
R 1Si(OR 2) 3(1)
(R 1for the structure of following formula (2), R 2alkyl for carbon number 1 ~ 5)
[changing 12]
R 3Si(OR 4) 3(3)
(R 3for the carbon number replaced by acryloyl group, acryloxy, methacryl, methacryloxy or styryl is the alkyl of 1 ~ 30, R 4alkyl for carbon number 1 ~ 5)
The R of the alkoxy silane that formula (1) represents 1the structure that (hereinafter also referred to specific organic group) represents for above-mentioned formula [2].
In formula (2), Y 1for singly-bound ,-(CH 2) a-(a is the integer of 1 ~ 15) ,-O-,-CH 2o-,-COO-or-OCO-.Wherein, from the viewpoint of the synthesis easily carrying out side-chain structure, singly-bound ,-(CH is preferably selected 2) a-(a is the integer of 1 ~ 15) ,-O-,-CH 2o-or-COO-.Wherein, singly-bound ,-(CH is more preferably selected 2) a-(a is the integer of 1 ~ 10) ,-O-,-CH 2o-or-COO-.
Y 2for alkyl or-(CR that singly-bound, carbon number containing double bond are the straight or branched of 3 ~ 8 17r 18) b-(b is the integer of 1 ~ 15, R 17, R 18independently of one another for hydrogen atom or carbon number are the alkyl of 1 ~ 3).Wherein, from the viewpoint of the response speed improving liquid crystal display cells more significantly, preferably-(CH 2) b-(b is the integer of 1 ~ 10).
Y 3for singly-bound ,-(CH 2) c-(c is the integer of 1 ~ 15) ,-O-,-CH 2o-,-COO-or-OCO-.Wherein, from the viewpoint of the synthesis easily carrying out side-chain structure, singly-bound ,-(CH is preferably selected 2) c-(c is the integer of 1 ~ 15) ,-O-,-CH 2o-,-COO-or-OCO-.Wherein, singly-bound ,-(CH is more preferably selected 2) c-(c is the integer of 1 ~ 10) ,-O-,-CH 2o-,-COO-or-OCO-.
Y 4for being selected from the bivalent cyclic base in the group that is made up of phenyl ring, cyclohexane ring and heterocycle, alkyl, carbon number that the arbitrary hydrogen atom in these cyclic group can be 1 ~ 3 by carbon number be 1 ~ 3 alkoxy, carbon number be 1 ~ 3 containing fluoroalkyl, carbon number be 1 ~ 3 fluoroalkoxy or fluorine atom replace.In addition, Y 4can be divalent organic group in the organic group of 12 ~ 25 for being selected from the carbon number with steroid skeleton.Wherein, preferably having the carbon number of any one among phenyl ring, cyclohexane ring or steroid skeleton is the organic group of 12 ~ 25.
Y 5for being selected from the cyclic group in the group that is made up of phenyl ring, cyclohexane ring and heterocycle, alkyl, carbon number that the arbitrary hydrogen atom in these cyclic group can be 1 ~ 3 by carbon number be 1 ~ 3 alkoxy, carbon number be 1 ~ 3 containing fluoroalkyl, carbon number be 1 ~ 3 fluoroalkoxy or fluorine atom replace.
N is the integer of 0 ~ 4.Be preferably the integer of 0 ~ 2.
Y 6for the alkyl of carbon number 1 ~ 18, carbon number 1 ~ 18 containing fluoroalkyl, the alkoxy of carbon number 1 ~ 18 or the fluoroalkoxy of carbon number 1 ~ 18.Wherein, preferred carbon number to be alkyl, the carbon number of 1 ~ 18 be 1 ~ 10 containing fluoroalkyl, carbon number be 1 ~ 18 alkoxy or carbon number be the fluoroalkoxy of 1 ~ 10.More preferably carbon number be 1 ~ 12 alkyl or carbon number be the alkoxy of 1 ~ 12.Further preferably carbon number be 1 ~ 9 alkyl or carbon number be the alkoxy of 1 ~ 9.
About using the polysiloxane being imported with such side chain and photoreactive group, why the aligning agent for liquid crystal obtained can have response speed characteristic concurrently and good vertical orientated property is still uncertain, infers and has the side chain of the structure similar with liquid crystal skeleton by use and had the response speed and vertical orientated property that are usually in the inverse relation that is contrary to concurrently.
As the Y in formula (2) 1, Y 2, Y 3, Y 4, Y 5, Y 6with the preferred compositions of n, can enumerate and the combination that (2-1) ~ (2-629) is identical recorded in the table 6 ~ table 47 of 13 pages of International Publication publication WO2011/132751 (2011.10.27 is open) ~ 34 pages.It should be noted that, in each table of International Publication publication, the Y in the present invention 1~ Y 6illustrate in the mode of Y1 ~ Y6, Y1 ~ Y6 is changed to Y 1~ Y 6.
The R of the alkoxy silane that formula (1) represents 2for the alkyl of carbon number 1 ~ 5, preferably 1 ~ 3.More preferably R 2for methyl or ethyl.
The alkoxy silane that such formula (1) represents can be manufactured by known method (Japanese Laid-Open Patent Publication 61-28639 publication).
Below enumerate its concrete example, but be not limited thereto.
[changing 13]
[changing 14]
[changing 15]
[changing 16]
[changing 17]
[changing 18]
(R 5for-O-,-OCH 2-,-CH 2o-,-COOCH 2-or-CH 2oCO-, R 6for the alkyl of carbon number 1 ~ 22, alkoxy, containing fluoroalkyl or fluoroalkoxy)
[changing 19]
(R 7for singly-bound ,-COO-,-OCO-,-COOCH 2-,-CH 2oCO-,-(CH 2) no-(n is the integer of 1 ~ 5) ,-OCH 2-or-CH 2-, R 8for the alkyl of carbon number 1 ~ 22, alkoxy, containing fluoroalkyl or fluoroalkoxy)
[changing 20]
(R 9for-COO-,-OCO-,-COOCH 2-,-CH 2oCO-,-CH 2o-,-OCH 2-,-CH 2-or-O-, R 10for fluorine-based, cyano group, fluoroform alkyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group or hydroxyl)
[changing 21]
(R 11for the alkyl of carbon number 3 ~ 12, the cis-trans-isomerism of Isosorbide-5-Nitrae-cyclohexylidene is respectively trans-isomer)
[changing 22]
(R 12for the alkyl of carbon number 3 ~ 12, the cis-trans-isomerism of Isosorbide-5-Nitrae-cyclohexylidene is respectively trans-isomer)
[changing 23]
(B 4for the carbon number that can be replaced by fluorine atoms is the alkyl of 3 ~ 20, B 3for Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene.
B 2for oxygen atom or-COO-* are (wherein, with associative key and the B of " * " 3bonding), B 1for oxygen atom or-COO-* are (wherein, with associative key and the (CH of " * " 2) a 2) bonding).
In addition, a 1be the integer of 0 or 1, a 2be the integer of 2 ~ 10, a 3be the integer of 0 or 1)
Above-mentioned alkoxy silane also can according to when making siloxane polymer to the dissolubility of solvent, make liquid crystal orientation film time the characteristic such as orientation, tilt angle characteristic, voltage retention, accumulated charge of liquid crystal use a kind of or used in combination two or more.In addition, also can with the share of alkoxy silane of chain alkyl containing carbon number being 10 ~ 18.
In order to obtain good liquid crystal aligning, the alkoxy silane that the above-mentioned formula (1) with specific organic group represents is being preferably more than 1 % by mole for obtaining in whole alkoxy silanes that polysiloxane uses.Be more preferably more than 1.5 % by mole.More preferably more than 2 % by mole.In addition, in order to obtain the sufficient curing characteristics of formed liquid crystal orientation film, preferably less than 30 % by mole.Be more preferably less than 25 % by mole.More preferably less than 20 % by mole.
The R of the alkoxy silane that formula (3) represents 3(hereinafter also referred to the second specific organic group) is the alkyl replaced by acryloyl group, acryloxy, methacryl, methacryloxy or styryl.The hydrogen atom be substituted is more than 1, is preferably 1.The carbon number of alkyl is preferably 1 ~ 30, is more preferably 1 ~ 20.More preferably 1 ~ 10.
The R of the alkoxy silane that formula (3) represents 4for the alkyl of carbon number 1 ~ 5, be preferably the alkyl of carbon number 1 ~ 3, be particularly preferably the alkyl of carbon number 1 ~ 2.
Enumerate the concrete example of the alkoxy silane that formula (3) represents, but be not limited to these.Be such as: 3-methacryloxypropyl, methacryloxymethyl trimethoxy silane, methacryloxymethyl triethoxysilane, 3-acryloxypropyl trimethoxy silane, 3-acryloxypropyl triethoxysilane, acryloyl-oxyethyl trimethoxy silane, acryloyl-oxyethyl triethoxysilane, styryl ethyl trimethoxy silane, styryl ethyl triethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino) propyl trimethoxy silicane etc.Wherein, preferred 3-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane or styryl ethyl trimethoxy silane.
During manufacture as the polysiloxane of (B) composition, except the alkoxy silane that the alkoxy silane represented except formula (1) and formula (3) represent, in order to improve with the adaptation of substrate, improve and the compatibility etc. of liquid crystal molecule, one or more in the alkoxy silane that following formula (4) also can be used when not damaging effect of the present invention to represent.
The alkoxy silane that formula (4) represents can give various characteristic to polysiloxane, characteristic as required can select one or more to use.
(R 5) nSi(OR 6) 4-n(4)
(R 5for hydrogen atom or can be the alkyl of 1 ~ 10 by the carbon number of heteroatoms, halogen atom, amino, glycidoxy, sulfydryl, isocyanate group, Carbamido substituted.R 6for the alkyl of carbon number 1 ~ 5, preferably 1 ~ 3.N is the integer of 0 ~ 3, preferably 0 ~ 2)
The R of the alkoxy silane that formula (4) represents 5for the organic group (hereinafter also referred to the 3rd organic group) that hydrogen atom or carbon number are 1 ~ 10.As the example of the 3rd organic group, for: aliphatic hydrocarbon; The ring structure that aliphatics ring, aromatic rings, heterocycle are such; Unsaturated link; Heteroatomss such as oxygen atom, nitrogen-atoms, sulphur atom etc. can be contained and the carbon number can with branched structure is the organic group of 1 ~ 6.In addition, this organic group can by replacements such as halogen atom, amino, glycidoxy, sulfydryl, isocyanate group, urea groups.
Enumerate the concrete example of the alkoxy silane that formula (4) represents, but be not limited thereto.Such as can enumerate: 3-(2-aminoethylaminopropyl) trimethoxy silane, 3-(2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyl trimethoxy silane, 2-(2-amino-ethyl sulphur ethyl) triethoxysilane, 3-Mercaptopropyltriethoxysilane, mercapto methyl trimethoxy silane, vinyltriethoxysilane, 3-isocyanates propyl-triethoxysilicane, trifluoro propyl trimethoxy silane, chloropropyl triethoxysilane, bromopropyl triethoxysilane, 3-mercaptopropyi trimethoxy silane, dimethyldiethoxysilane, dimethyldimethoxysil,ne, diethyldiethoxysilane, diethyldimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, 3-amino propyl methyl diethoxy silane, 3-dimethyl Ethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureido-propyl trimethoxy silane, γ-ureido-propyl tripropoxy silane etc.
In the alkoxy silane that formula (4) represents, n be 0 alkoxy silane be tetraalkoxysilane.Tetraalkoxysilane easily and the alkoxy silane condensation that represents of formula (1) and (3), therefore, is preferred for obtaining for polysiloxane of the present invention.
In such formula (4), be the alkoxy silane of 0 as n, more preferably tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane or four butoxy silanes, particularly preferably tetramethoxy-silicane or tetraethoxysilane.
In the present invention, preferably 2 ~ 20 % by mole are used in whole alkoxy silanes that the alkoxy silane that formula (1) represents uses in the manufacture of the polysiloxane of (B) composition, particularly preferably use 3 ~ 15 % by mole, and preferably use 5 ~ 80 % by mole in whole alkoxy silanes that the alkoxy silane that formula (3) represents uses in the manufacture of the polysiloxane of (B) composition, particularly preferably use 10 ~ 70 % by mole.
In addition, the alkoxy silane that formula (4) represents, when the manufacture of the polysiloxane for (B) composition, preferably uses 10 ~ 90 % by mole, particularly preferably uses 20 ~ 90 % by mole in used whole alkoxy silanes.
[manufacture method of the polysiloxane of (B) composition]
The method obtaining the polysiloxane used in the present invention is not particularly limited, and makes the polycondensation and obtaining in organic solvent of the alkoxy silane using the alkoxy silane of above-mentioned formula (1) as neccessary composition.Therefore, polysiloxane obtains with the form of the solution of uniform dissolution in organic solvent.
Such as, can enumerate the method for alkoxy silane hydrolysis-condensation in alcohol or solvents such as glycols of above-mentioned formula (1).Now, hydrolysis-condensation reaction can be any one in partial hydrolysis and complete hydrolysis.When complete hydrolysis, add the water of 0.5 times mole of the whole alkoxide groups in alkoxy silane in theory, but usually preferably add the water than 0.5 times of molar excess.
In the present invention, the amount of the water used in above-mentioned reaction suitably can be selected according to expectation, but carries out in the scope of 0.5 ~ 2.5 times mole of whole alkoxys usually in alkoxy silane.Be preferably 0.5 ~ 2.5 times mole, be more preferably 0.5 ~ 1.5 times mole.
In addition, usually, in order to facilitation of hydrolysis-condensation reaction, the acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, fumaric acid are used; The alkali such as ammonia, methylamine, ethamine, monoethanolamine, triethylamine; The slaine of hydrochloric acid, sulfuric acid, nitric acid etc.; Deng catalyzer.In addition, by alkoxy silane is dissolved the solution obtained carry out heating come further facilitation of hydrolysis-condensation reaction be also common way.Now, heating-up temperature and heat time suitably can be selected according to expectation.Such as can enumerate heating at 50 DEG C, stir 24 hours; Heat under reflux, stir 1 hour; Etc. method.
In addition, as additive method, such as, can enumerate the method for the heating of the potpourri of alkoxy silane, solvent and oxalic acid being carried out polycondensation.Specifically, be following method: in alcohol, add oxalic acid in advance and after obtaining the alcoholic solution of oxalic acid, under the state that this solution is heated, mixed oxyalkyl silane.Now, whole alkoxys 1 mole that the amount of the oxalic acid used has relative to alkoxy silane are preferably set to 0.2 ~ 2 mole.Heating in the method can be carried out under the liquid temperature of 50 ~ 180 DEG C.In order to not cause the evaporation of liquid, be vaporized, preferably heat the method for several tens minutes ~ ten a few hours under reflux.
When using two or more alkoxy silanes to obtain polysiloxane, after can being mixed by two or more alkoxy silanes in advance, making it react, also can it be made to react the mixing of two or more alkoxy silanes successively.
Make the solvent (hereinafter also referred to polymer solvent) used during alkoxy silane polycondensation as long as by the solvent of alkoxy silane dissolving, be not particularly limited.In addition, even if in the undissolved situation of alkoxy silane, as long as the solvent making alkoxy silane dissolve along with the carrying out of the polycondensation reaction of alkoxy silane.Generally speaking, generate alcohol by the polycondensation reaction of alkoxy silane, therefore, use alcohols, glycols, glycol ethers or the organic solvent good with the compatibility of alcohols.
As the concrete example of above-mentioned polymer solvent, can enumerate: the alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, diacetone alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-PD, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-PD, 2,4-pentanediols, 2, the glycolss such as 3-pentanediol, 1,6-hexanediol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol bisthioglycolate propyl ether, butyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl 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, Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, the glycol ethers such as propylene glycol butyl oxide, N, N '-dimethyl formamide, N, N '-dimethyl acetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethylurea, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, metacresol etc.In the present invention, can two or more above-mentioned polymer solvent used in combination.
The polymeric solution (hereinafter also referred to polymeric solution) of the polysiloxane obtained by said method is to be scaled SiO by the silicon atom of the whole alkoxy silanes dropped into as raw material 2and the concentration obtained is (hereinafter also referred to SiO 2converted score) meter preferably below 20 quality %, be particularly preferably set as 5 ~ 15 quality %.By selecting arbitrary concentration in this concentration range, the generation of gel can be suppressed, the solution of homogeneous can be obtained.
[solution of the polysiloxane of (B) composition]
In the present invention, can using the polymeric solution of polysiloxane that obtained by said method directly as the solution of (B) composition, also can carry out the solution obtained by said method concentrating or add solvent as required and carry out diluting or being replaced into other solvent and obtain the solution of (B) composition.
Now, the solvent (hereinafter also referred to interpolation solvent) used can be identical with polymer solvent, also can be other solvents.As long as this interpolation solvent dissolves polysiloxane equably, be not particularly limited, can at random select one or more to use.
As the concrete example adding solvent, except the solvent enumerated as the example of above-mentioned polymer solvent, the ester classes etc. such as the ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, ethyl lactate can also be enumerated.
These solvents can the viscosity of adjustable liquid crystal display aligning agent, or can improve coating when being applied on substrate by aligning agent for liquid crystal by spin coating, flexographic printing, ink-jet etc.
In the present invention, from the viewpoint of what mix with as the polyamic acid of (A) composition and/or polyimide, the solvent used in solution as (B) composition, preferred: N, N '-dimethyl formamide, N, N '-dimethyl acetamide, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethylurea, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, ethylene glycol monobutyl ether.
In addition, in the present invention, more preferably before mixing with as the polyamic acid of (A) composition and/or polyimide, the alcohol distillation removing using when will manufacture polysiloxane under normal or reduced pressure or produce.
[aligning agent for liquid crystal]
The SiO of the silicon atom that the content of (B) composition (polysiloxane) in aligning agent for liquid crystal of the present invention has with (B) composition relative to (A) composition 100 mass parts containing polyamic acid and/or polyimide 2scaled value counts 0.5 ~ 80 mass parts, is preferably 0.5 ~ 50 mass parts.In addition, when vertical orientating types such as MVA, PVA, PSA, in order to not reduce the vertical orientated property of liquid crystal, the content of (B) composition (polysiloxane) is more preferably 10 ~ 80 mass parts in identical benchmark, more preferably 20 ~ 70 mass parts.
Aligning agent for liquid crystal of the present invention is not particularly limited, but usually when making liquid crystal orientation film, need the homogeneous film forming 0.01 μm ~ 1.0 μm on substrate, therefore, to be preferably except (A) composition and (B) composition also containing the coating fluid of organic solvent making these component dissolves.
When aligning agent for liquid crystal of the present invention contains above-mentioned organic solvent, form homogeneous film from the viewpoint of by coating, the content of preferred organic solvent is 90 ~ 99 quality % in aligning agent for liquid crystal, be more preferably 92 ~ 97 quality %.The content of these organic solvents suitably can change according to the thickness of the liquid crystal orientation film as target.
As the concrete example of the organic solvent used in aligning agent for liquid crystal of the present invention, the organic solvent used in the synthetic reaction of above-mentioned polyamic acid or polyimide can be enumerated.Be particularly preferably DMF, DMA, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), gamma-butyrolacton etc.These organic solvents can use one, also can share two or more.
In addition, in organic solvent, in order to improve the homogeneity of film, preferably containing glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetic acid esters, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, propylene glycol-1-single ether-2-acetic acid esters, dipropylene glycol, dipropylene glycol monomethyl ether, DPE, 4-hydroxy-4-methyl-2-pentanone, 2-(2-ethoxy propoxyl group) propyl alcohol, diacetone alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactates etc. have the solvent of low surface tension.
These solvents use a kind of or used in combination two or more usually.Generally speaking, the ability that these solvents make polyamic acid or polyimide dissolve is low, therefore, is preferably below the 80 quality % in organic solvent, is more preferably below 60 quality %.In addition, if expect the homogeneity improving film, be then preferably more than the 5 quality % in organic solvent, be more preferably more than 20 quality %.
In addition, liquid crystal mesogens aligning agent of the present invention can containing be improved film and substrate adaptation compound, for improving the surfactant etc. of the flatness of film.
As the concrete example of compound of adaptation improving film and substrate, the as follows compound etc. containing functional silanes can be enumerated.Be such as: 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (the ethylene oxide)-3-TSL 8330 of N-, two (the ethylene oxide)-APTESs of N-etc.
From the viewpoint of can obtaining effect that adaptation improves and not reducing the orientation of liquid crystal, the addition of these compounds is preferably 0.1 ~ 30 mass parts relative to (A) composition 100 mass parts, be more preferably 1 ~ 20 mass parts, be particularly preferably 1 ~ 10 mass parts.
As the surfactant of the flatness for improving film, fluorine class surfactant, organosilicone surfactants, non-ionics etc. can be enumerated.More particularly, Eftop EF301, EF303, EF352 (above is the manufacture of Tohkem Products company), MEGAFACE F171, F173, R-30 (above for large Japanese ink company manufactures), Fluorad FC430, FC431 (above is the manufacture of Sumitomo 3M company), Aashi GuardAG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above for Asahi Glass company manufactures) etc. can such as be enumerated.
The content of these surfactants is preferably 0.01 ~ 2 mass parts relative to (A) composition 100 mass parts, is more preferably 0.01 ~ 1 mass parts.
< liquid crystal orientation film, liquid crystal display cells >
Aligning agent for liquid crystal of the present invention can be applied on substrate, after calcining, to be penetrated etc. and carries out orientation process, or in vertical orientated purposes etc., also can make liquid crystal orientation film to use when No yield point process by friction treatment, illumination.
Now, as used substrate, as long as the high substrate of the transparency is not particularly limited, glass substrate can be used; The plastic bases such as acrylic resin substrate, polycarbonate substrate; Deng.In addition, the substrate that is formed for the ITO electrode, IZO (indium-zinc oxide) electrode etc. of liquid crystal drive is used to be preferred from the viewpoint of Simplified flowsheet.In addition, in the liquid crystal display cells of reflection-type, if one-sided substrate, then also can use the opaque materialss such as silicon wafer, the electrode in this situation also can use the material of the reflected light such as metallic aluminium.
The coating process of aligning agent for liquid crystal is not particularly limited, generally by the method that serigraphy, hectographic printing, flexographic printing, ink-jet etc. are carried out.As other coating process, there are dipping, roll coater, slit coater, spin coater etc., these coating processes can be used according to object.
Substrate after coating of liquid crystalline aligning agent places about 1 minute ~ 3 minutes on the heating plate of 70 ~ 100 DEG C, make solvent volatilize and dry, then, calcine.Calcining can be carried out under the arbitrary temp of 100 ~ 350 DEG C, but is preferably 120 ~ 300 DEG C, more preferably 150 ~ 250 DEG C.This calcining can use heating plate, recirculation furnace, infrared heating heating furnace etc. to carry out.
When the thickness of the film after calcining is blocked up, in the power consumption of liquid crystal display cells, become unfavorable, when crossing thin, the reliability of liquid crystal display cells reduces sometimes, therefore, is preferably 5 ~ 300nm, is more preferably 10 ~ 150nm, more preferably 50 ~ 100nm.When making liquid crystal horizontal alignment or tilted alignment, the film after calcining is processed by friction or polarized ultraviolet irradiation etc.
About liquid crystal display cells of the present invention, obtained the substrate of band liquid crystal orientation film by aligning agent for liquid crystal of the present invention after, make liquid crystal cells by known method, thus make display element.If enumerate the example that liquid crystal cells makes, can illustrate: a pair substrate preparing to be formed with liquid crystal orientation film, the liquid crystal orientation film of a substrate is formed intercolumniation parting or scatters pearl sept, to make mode that liquid crystal aligning face is inner side fit another substrate, decompression injects liquid crystal and the method for sealing; Or, after the liquid crystal aligning face being formed with intercolumniation parting or being scattered with pearl sept drips liquid crystal, the method etc. that adhesive substrates carrying out seals.The thickness of sept is now preferably 1 ~ 30 μm, is more preferably 2 ~ 10 μm.
[embodiment]
Below, specifically describe the present invention further by embodiment, but and can't help these embodiments and carry out limited explanation.
Abbreviation in the compound used in embodiment is as described below.
(alkoxy silane monomer)
TEOS: tetraethoxysilane
C18: octadecyltriethoxy silane
C12: dodecyl triethoxysilane
UPS:3-ureidopropyltriethoxysilane
MPMS:3-methacryloxypropyl trimethoxy silane
VTMS: vinyltrimethoxy silane
STMS: styryl ethyl trimethoxy silane
MTES: methyl triethoxysilane
(tetracarboxylic dianhydride)
CBDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
BDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
PMDA: pyromellitic acid anhydride
BODA: dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
[changing 24]
(diamine compound)
M-PDA: m-phenylene diamine
DBA:3,5-diaminobenzoic acid
DDM:4,4 '-diaminodiphenyl-methane
4,4 ' DADPA:4,4 '-diamino-diphenylamine
Two (4-aminophenethyl) urea of BAPU:1,3-
Two (3-aminopropyl) tetramethyl disiloxane of Sin0:1,3-
PCH7DAB:1,3-diamido-4-[4-(trans-4-n-heptyl cyclohexyl) phenoxy group] benzene
[changing 25]
(organic solvent)
THF: tetrahydrofuran
DMF: dimethyl formamide
NMP:N-N-methyl-2-2-pyrrolidone N-
BCS:2-butyl cellosolve
The mensuration etc. of the mensuration of NMR, the mensuration of molecular weight, acid imide rate is carried out as follows.
( 1the mensuration of H-NMR)
1the NMR analyzer (JNW-ECA500) that H-NMR (500MHz, proton N MR) uses Japanese DATUM company to manufacture, at deuterochloroform (CDCl 3) in use tetramethylsilane (TMS) measure as interior mark.
(molecular weight determination of polyamic acid and polyimide)
The chromatographic column (KD-803, KD-805) that normal temperature gel permeation chromatography (GPC) device (GPC-101) that molecular weight uses Showa electrician company to manufacture, Shodex company manufacture, measures as follows.
Column temperature: 50 DEG C
Eluent: N, and N '-dimethyl formamide (as adjuvant, lithium bromide-hydrate (LiBrH 2o) for 30mmol/L (liter), phosphoric acid anhydrous crystal (o-phosphoric acid) be 30mmol/L, tetrahydrofuran (THF) is 10ml (milliliter)/L)
Flow velocity: 1.0ml/ minute
Standard model for production standard curve: the TSK standard polyethylene oxide (molecular weight about 900000,150000,100000 and 30000) that Dong Cao company manufactures and the polyglycol (molecular weight about 12000,4000 and 1000) that Polymer Laboratories company manufactures.
(mensuration of acid imide rate)
Polyimide powder 20mg is loaded NMR sample hose (the NMR sampling pipe standard form that wasteland's scientific company manufactures, ) in, add deuterated dimethyl sulfoxide (DMSO-d6,0.05 quality %TMS (tetramethylsilane) melange) 0.53mL, apply ultrasound wave and make it dissolve completely.The NMR analyzer (JNW-ECA500) using NEC DATUM company to manufacture measures the proton N MR of the 500MHz of this solution.About acid imide rate, determine using the proton coming from the structure do not changed before and after imidizate as reference proton, use the peak integrated value of this proton and appear at the proton peak integrated value coming from the NH base of amic acid near 9.5 ~ 10.0ppm, obtain acid imide rate by following formula.
Acid imide rate (%)=(1-α x/y) × 100
In above formula, x is the proton peak integrated value of the NH base coming from amic acid, and y is the peak integrated value of reference proton, and when α is polyamic acid (acid imide rate is 0%), the number of reference proton is relative to the ratio of 1 NH matrix of amic acid.
[changing 26]
The synthesis > of < compound 10
In the 500mL four-hole boiling flask possessing magnetic stir bar, drop into compound 930.00g, sal tartari 25.24g and DMF 120g, at room temperature drip allyl bromide, bromoallylene 22.10g.Then, stir 11 hours at 50 DEG C.By the diluted ethyl acetate of reactant liquor 500g, the pure water of organic layer 200g is cleaned 3 times.Isolated organic layers with sodium sulfate is dry, and it is filtered.Then, by filtrate concentrate drying, obtain compound 1034.80g (yield 100%).
1h-NMR (500MHz) CDCl 3in: 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)
The synthesis > of < compound 11
In the 300mL four-hole boiling flask possessing magnetic stir bar, drop into compound 1020.00g and toluene 120g, at room temperature stir.Then, after adding karstedt catalyzer (platinum (0)-1,1,3,3-tetramethyl disiloxane complex compound, 0.1mol/L xylene solution) 700 μ l, trimethoxy silane 12.4mL is dripped.At room temperature stir after 29 hours, by reactant liquor concentrate drying, obtain crude product.By obtained crude product decompression distillation, distillate under the condition that temperature 245 DEG C/pressure 0.8 holds in the palm outside, obtain compound 1112.15g (yield 43%).
1h-NMR (500MHz) CDCl 3in: 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) composition (polyamic acid and polyimide)]
< synthesis example 1>
CBDA 97.1g (0.5mol) as tetracarboxylic dianhydride's composition, the DBA76.1g (0.5mol) as diamine component are mixed in NMP 1270g, at room temperature reacts 5 hours, obtain polyamic acid solution.Polyreaction easily and carry out equably.The number-average molecular weight of the polyamic acid obtained is 16800, and weight-average molecular weight is 48300.And then, in this solution, add NMP and BCS, make that polyamic acid is 4 % by weight, NMP is 76 % by weight, BCS is 20 % by weight, obtain polyamic acid solution (A1).
< synthesis example 2>
BDA 79.1g (0.4mol) as tetracarboxylic dianhydride's composition, the DBA60.9g (0.4mol) as diamine component are mixed in NMP 560g, at room temperature reacts 7 hours, obtain polyamic acid solution.Polyreaction easily and carry out equably.The number-average molecular weight of the polyamic acid obtained is 9800, and weight-average molecular weight is 31300.And then, in this solution, add NMP and BCS, make that polyamic acid is 4 % by weight, NMP is 76 % by weight, BCS is 20 % by weight, obtain polyamic acid solution (A2).
< synthesis example 3>
PMDA 106.1g (0.49mol) as tetracarboxylic dianhydride's composition, the DBA76.1g (0.5mol) as diamine component are mixed in NMP 1336g, at room temperature reacts 5 hours, obtain polyamic acid solution.Polyreaction easily and carry out equably.The number-average molecular weight of the polyamic acid obtained is 15600, and weight-average molecular weight is 44300.And then, in this solution, add NMP and BCS, make that polyamic acid is 4 % by weight, NMP is 76 % by weight, BCS is 20 % by weight, obtain polyamic acid solution (A3).
< synthesis example 4>
PMDA 102.8g (0.47mol) as tetracarboxylic dianhydride's composition, the BAPU149.2g (0.5mol) as diamine component are mixed in NMP 1843g, at room temperature reacts 5 hours, obtain polyamic acid solution.Polyreaction easily and carry out equably.The number-average molecular weight of the polyamic acid obtained is 13800, and weight-average molecular weight is 41400.And then, in this solution, add NMP and BCS, make that polyamic acid is 4 % by weight, NMP is 76 % by weight, BCS is 20 % by weight, obtain polyamic acid solution (A4).
< synthesis example 5>
CBDA 94.1g (0.48mol) as tetracarboxylic dianhydride's composition, the BAPU149.2g (0.5mol) as diamine component are mixed in NMP 1784g, at room temperature reacts 5 hours, obtain polyamic acid solution.Polyreaction easily and carry out equably.The number-average molecular weight of the polyamic acid obtained is 15200, and weight-average molecular weight is 46700.And then, in this solution, add NMP and BCS, make that polyamic acid is 4 % by weight, NMP is 76 % by weight, BCS is 20 % by weight, obtain polyamic acid solution (A5).
< synthesis example 6>
CBDA 78.2g (0.4mol) as tetracarboxylic dianhydride's composition, the m-PDA43.2g (0.4mol) as diamine component are mixed in NMP 664g, at room temperature reacts 5 hours, obtain polyamic acid solution.Polyreaction easily and carry out equably.The number-average molecular weight of the polyamic acid obtained is 21800, and weight-average molecular weight is 51500.And then, in this solution, add NMP and BCS, make that polyamic acid is 4 % by weight, NMP is 76 % by weight, BCS is 20 % by weight, obtain polyamic acid solution (A6).
< synthesis example 7>
CBDA 19.2g (0.098mol) as tetracarboxylic dianhydride's composition, the DDM19.8g (0.1mol) as diamine component are mixed in NMP 221.3g, at room temperature reacts 24 hours, obtain polyamic acid solution.Polyreaction easily and carry out equably.The number-average molecular weight of the polyamic acid obtained is 18800, and weight-average molecular weight is 52300.And then, in this solution, add NMP and BCS, make that polyamic acid is 4 % by weight, NMP is 76 % by weight, BCS is 20 % by weight, obtain polyamic acid solution (A7).
< synthesis example 8>
CBDA 19.6g (0.1mol) as tetracarboxylic dianhydride's composition, 4,4 ' DADPA18.7g (0.094mol) as diamine component are mixed in NMP 345.1g, at room temperature reacts 5 hours, obtain polyamic acid solution.Polyreaction easily and carry out equably.The number-average molecular weight of the polyamic acid obtained is 17500, and weight-average molecular weight is 48100.And then, in this solution, add NMP and BCS, make that polyamic acid is 4 % by weight, NMP is 76 % by weight, BCS is 20 % by weight, obtain polyamic acid solution (A8).
< synthesis example 9>
BODA 150.1g (0.6mol), DBA 60.9g (0.4mol) and PCH7DAB 152.2g (0.4mol) are mixed in NMP1290g, reacts 5 hours at 80 DEG C.Then, add CBDA 38.8g (0.2mol) and NMP 320g, react 3 hours at 40 DEG C, obtain polyamic acid solution.In this polyamic acid solution 100.8g, add NMP, be diluted to 6 quality %.Then, add the acetic anhydride 10.66g as imidization catalyst and pyridine 8.26g, react 3 hours at 80 DEG C.Then, this reaction solution is put in methyl alcohol 1300ml, leach obtained sediment.By this sediment washed with methanol, then drying under reduced pressure at 100 DEG C, obtains polyimide powder (C1).The acid imide rate of this polyimide is 55%, and number-average molecular weight is 28500, and weight-average molecular weight is 66100.
In this polyimide powder (C1) 7.4g, add NMP 41.9g, stir at 80 DEG C and make it dissolve in 40 hours.And then, in this solution, add NMP and BCS, make that polyimide is 4 % by weight, NMP is 76 % by weight, BCS is 20 % by weight, obtain polyimide solution (A9).
< synthesis example 10>
BODA 7.5g (30.0mmol), DBA 1.8 (12.0mmol), Sin02.0g (8.0mmol) and PCH7DAB7.6g (20.0mmol) are mixed in NMP 55g, reacts 5 hours at 80 DEG C.Then, add CBDA1.9g (10.0mmol) and NMP 27.0g, react 3 hours at 40 DEG C, obtain polyamic acid solution.In this polyamic acid solution 30.0g, add NMP, be diluted to 6 quality %.Then, add the acetic anhydride 2.99g as imidization catalyst and pyridine 2.32g, react 3 hours at 80 DEG C.Then, this reaction solution is put in methyl alcohol 370ml, leach obtained sediment.By this sediment washed with methanol, then drying under reduced pressure at 100 DEG C, obtains polyimide powder (C2).The acid imide rate of this polyimide is 57%, and number-average molecular weight is 26800, and weight-average molecular weight is 63400.
In this polyimide powder (C2) 7.4g, add NMP 41.9g, stir at 80 DEG C and make it dissolve in 40 hours.And then, in this solution, add NMP and BCS, make that polyamic acid is 4 % by weight, NMP is 76 % by weight, BCS is 20 % by weight, obtain polyimide solution (A10).
[synthesis of (B) composition (polysiloxane)]
< synthesis example 11>
In the four mouthfuls of reaction flasks of 200mL possessing thermometer and recirculatory pipe, by BCS 29.5g, TEOS 38.8g and above-mentioned in compound 11 4.1g that obtains mix, prepare the solution of alkoxy silane monomer.At room temperature with dripping in 30 points of this solution of clockwise in advance using BCS 14.7g, water 10.8g and the solution that is obtained by mixing as the oxalic acid 0.2g of catalyzer, and then at room temperature stir 30 minutes.Then, use oil bath to heat, reflux after 30 minutes, adding UPS content is the methanol solution 1.2g of 92 quality % and the mixed liquor of BCS 0.9g.Reflux again 30 minutes, then naturally cool, obtain SiO 2converted score is the polysiloxane solution of 12 % by weight.
Obtained polysiloxane solution 10.0g and NMP 20.0g is mixed, obtains SiO 2converted score is the polysiloxane solution [B1] of 4 % by weight.
< synthesis example 12>
In the four mouthfuls of reaction flasks of 200mL possessing thermometer and recirculatory pipe, BCS 29.4g, TEOS 38.8g and C18 4.2g are mixed, prepares the solution of alkoxy silane monomer.At room temperature with dripping in 30 points of this solution of clockwise in advance using BCS 14.7g, water 10.8g and the solution that is obtained by mixing as the oxalic acid 0.2g of catalyzer, and then at room temperature stir 30 minutes.Then, use oil bath to heat, reflux after 30 minutes, adding UPS content is the methanol solution 1.2g of 92 quality % and the mixed liquor of BCS 0.9g.Reflux again 30 minutes, then naturally cool, obtain SiO 2converted score is the polysiloxane solution of 12 % by weight.
Obtained polysiloxane solution 10.0g and NMP 20.0g is mixed, obtains SiO 2converted score is the polysiloxane solution [B2] of 4 % by weight.
< synthesis example 13>
In the four mouthfuls of reaction flasks of 200mL possessing thermometer and recirculatory pipe, by BCS 30.2g, TEOS 39.6g and above-mentioned in compound 11 4.1g that obtains mix, prepare the solution of alkoxy silane monomer.At room temperature with dripping in 30 points of this solution of clockwise in advance using BCS 14.7g, water 10.8g and the solution that is obtained by mixing as the oxalic acid 0.2g of catalyzer, and then at room temperature stir 30 minutes.Then, use oil bath to heat, reflux 60 minutes, then naturally cool, obtain SiO 2converted score is the polysiloxane solution of 12 % by weight.
Obtained polysiloxane solution 10.0g and NMP 20.0g is mixed, obtains SiO 2converted score is the polysiloxane solution [B3] of 4 % by weight.
< synthesis example 14>
In the four mouthfuls of reaction flasks of 200mL possessing thermometer and recirculatory pipe, by BCS 28.2g, TEOS 37.5g and above-mentioned in compound 11 4.1g that obtains mix, prepare the solution of alkoxy silane monomer.At room temperature with dripping in 30 points of this solution of clockwise in advance using BCS 14.1g, water 10.8g and the solution that is obtained by mixing as the oxalic acid 0.4g of catalyzer, and then at room temperature stir 30 minutes.Then, use oil bath to heat, reflux after 30 minutes, add the mixed liquor that UPS content is methanol solution 2.9g and the BCS2.1g of 92 quality %.Reflux again 30 minutes, then naturally cool, obtain SiO 2converted score is the polysiloxane solution of 12 % by weight.
Obtained polysiloxane solution 10.0g and NMP 20.0g is mixed, obtains SiO 2converted score is the polysiloxane solution [B4] of 4 % by weight.
< synthesis example 15>
In the four mouthfuls of reaction flasks of 200mL possessing thermometer and recirculatory pipe, by BCS 25.4g, TEOS 20.0g, above-mentioned in compound 11 8.2g and the MPMS 19.9g that obtains mix, prepare the solution of alkoxy silane monomer.At room temperature with dripping in 30 points of this solution of clockwise in advance using BCS 12.7g, water 10.8g and the solution that is obtained by mixing as the oxalic acid 1.1g of catalyzer, and then at room temperature stir 30 minutes.Then, use oil bath to heat, reflux after 30 minutes, adding UPS content is the methanol solution 1.2g of 92 quality % and the mixed liquor of BCS 0.9g.Reflux again 30 minutes, then naturally cool, obtain SiO 2converted score is the polysiloxane solution of 12 % by weight.
Obtained polysiloxane solution 10.0g and NMP 20.0g is mixed, obtains SiO 2converted score is the polysiloxane solution [B5] of 4 % by weight.
< synthesis example 16>
In the four mouthfuls of reaction flasks of 200mL possessing thermometer and recirculatory pipe, by BCS 25.2g, TEOS 20.0g, above-mentioned in compound 11 8.2g and the STMS 20.2g that obtains mix, prepare the solution of alkoxy silane monomer.At room temperature with dripping in 30 points of this solution of clockwise in advance using BCS 12.6g, water 10.8g and the solution that is obtained by mixing as the oxalic acid 1.1g of catalyzer, and then at room temperature stir 30 minutes.Then, use oil bath to heat, reflux after 30 minutes, adding UPS content is the methanol solution 1.2g of 92 quality % and the mixed liquor of BCS 0.9g.Reflux again 30 minutes, then naturally cool, obtain SiO 2converted score is the polysiloxane solution of 12 % by weight.
Obtained polysiloxane solution 10.0g and NMP 20.0g is mixed, obtains SiO 2converted score is the polysiloxane solution [B6] of 4 % by weight.
< synthesis example 17>
In the four mouthfuls of reaction flasks of 200mL possessing thermometer and recirculatory pipe, BCS 25.8g, TEOS 20.0g, C18 4.2g, C12 3.3g and MPMS 19.9g are mixed, prepares the solution of alkoxy silane monomer.At room temperature with dripping in 30 points of this solution of clockwise in advance using BCS 12.9g, water 10.8g and the solution that is obtained by mixing as the oxalic acid 1.1g of catalyzer, and then at room temperature stir 30 minutes.Then, use oil bath to heat, reflux after 30 minutes, adding UPS content is the methanol solution 1.2g of 92 quality % and the mixed liquor of BCS 0.9g.Reflux again 30 minutes, then naturally cool, obtain SiO 2converted score is the polysiloxane solution of 12 % by weight.
Obtained polysiloxane solution 10.0g and NMP 20.0g is mixed, obtains SiO 2converted score is the polysiloxane solution [B7] of 4 % by weight.
< synthesis example 18>
In the four mouthfuls of reaction flasks of 200mL possessing thermometer and recirculatory pipe, BCS 31.5g, TEOS 37.1g and MTES 3.6g are mixed, prepares the solution of alkoxy silane monomer.At room temperature with dripping in 30 points of this solution of clockwise in advance using BCS 15.7g, water 10.8g and the solution that is obtained by mixing as the oxalic acid 0.1g of catalyzer, and then at room temperature stir 30 minutes.Then, use oil bath to heat, reflux after 60 minutes, naturally cool, obtain SiO 2converted score is the polysiloxane solution of 12 % by weight.
Obtained polysiloxane solution 10.0g and NMP 20.0g is mixed, obtains SiO 2converted score is the polysiloxane solution [B8] of 4 % by weight.
< synthesis example 19>
In the four mouthfuls of reaction flasks of 200mL possessing thermometer and recirculatory pipe, by BCS 26.2g, TEOS 20.8g, above-mentioned in the compound 118 .2g that obtains and MPMS 19.9g mix, prepare the solution of alkoxy silane monomer.At room temperature with dripping in 30 points of this solution of clockwise in advance using BCS 13.1g, water 10.8g and the solution that is obtained by mixing as the oxalic acid 1.1g of catalyzer, and then at room temperature stir 30 minutes.Then, use oil bath to heat, reflux after 30 minutes, add the mixed liquor that UPS content is methanol solution 0.6g and the BCS0.4g of 92 quality %.Reflux again 30 minutes, then naturally cool, obtain SiO 2converted score is the polysiloxane solution of 12 % by weight.
Obtained polysiloxane solution 10.0g and NMP 20.0g is mixed, obtains SiO 2converted score is the polysiloxane solution [B9] of 4 % by weight.
The evaluation of the making of liquid crystal cells and electrology characteristic, vertical orientated property, re-workability, weighting characteristics, response speed etc. is carried out as follows.
[making of liquid crystal cells]
Aligning agent for liquid crystal is spun to the ITO electrode substrate that is formed with solid ITO electrode or is formed with Pixel Dimensions and be 100 μm × 300 μm (micron) and live width/line-spacing is respectively on the ito surface of the ITO electrode substrate of the ITO electrode pattern of 5 μm.Then, use the heating plate of 80 DEG C after dry 2 minutes, in the heated air circulation type baking oven of 200 DEG C or 220 DEG C, carry out calcining in 30 minutes, forming thickness is the liquid crystal orientation film of 100nm.Prepare two panels this substrate (between solid substrate or solid substrate and pattern substrate), after the liquid crystal aligning face of a substrate scatters the pearl sept of 4 μm or 6 μm, printing and sealing agent from the upper side.Make the liquid crystal aligning face of another substrate in inner side, after being fitted by two substrates, make sealant cures, make dummy cell.Then, utilize decompression injection method in dummy cell, inject liquid crystal MLC-6608 (Merck & Co., Inc.'s manufacture, trade name), be made into liquid crystal cells.
After making liquid crystal cells, by heating or irradiation ultraviolet radiation while voltage liquid crystal cells being applied to interchange or direct current, the orientation of liquid crystal molecule can be controlled.
[evaluation of electrology characteristic (voltage retention and ion concentration)]
Liquid crystal cells is applied at the temperature of 60 DEG C the voltage of 60 microsecond 1V, the voltage after measuring 1667 milliseconds, goes out voltage with the form calculus of voltage retention (VHR) and can remain to which kind of degree.
And then, use above-mentioned liquid crystal cells, at the temperature of 60 DEG C, carry out the mensuration of ion concentration.That is, the ion concentration during triangular wave to liquid crystal cells applying voltage ± 10V, frequency 0.01Hz is measured.The 6245 type liquid crystal evaluation of physical property devices that determinator uses Dongyang technology company to manufacture.
[evaluation of vertical orientated property]
Liquid crystal cells is carried out in the circulating baking oven of 100 DEG C the annealing of 30 minutes.Then, under making polaroid be in cross Nicols state, microscopic examination is carried out to the unit taken out, observe the state on the farmland (Domain) of the orientation disorder of liquid crystal.
[evaluation of re-workability]
Aligning agent for liquid crystal is spun to and is formed on the ITO electrode substrate of solid ITO electrode.Then, use the heating plate of 80 DEG C after dry 2 minutes, in the heated air circulation type baking oven of 200 DEG C or 220 DEG C, carry out calcining in 30 minutes, form the liquid crystal orientation film of thickness 100nm.In the NMD-3 answering chemical industry company to manufacture in the Tokyo of 50 DEG C this substrate, dipping is after 10 minutes, washing, in the heated air circulation type baking oven of 80 DEG C dry 10 minutes.Then, visualization and contact angle determination are carried out to the state before and after dipping, sample contact angle being returned to the state before the coating of aligning agent for liquid crystal is evaluated as can reprocess: zero, and sample contact angle not being returned to the state before the coating of aligning agent for liquid crystal is evaluated as can not reprocess: ×.
[evaluation of weighting characteristics]
Be spun to by aligning agent for liquid crystal on chrome substrate (evaporation has the glass substrate of chromium), place 10 minutes under the atmosphere of temperature 23 DEG C, relative humidity 60%, then, whether visualization coated surface end creates the condensation product of polymkeric substance.
[evaluation of response speed]
The time variations of brightness during the square wave using oscillograph to obtain the AC voltage of liquid crystal cells applying ± 5V, frequency 1kHz, liquid crystal panel.Using brightness when not applying voltage as 0%, to apply ± voltage of 5V time the value of saturated brightness as 100%, using brightness by 10% time being changed to 90% as the response speed of starting, carry out according to above-mentioned liquid crystal cells method for making to obtained unit apply to exchange or direct current voltage while heat or the evaluation of response speed after irradiation ultraviolet radiation.
(reference example 1)
Use polysiloxane solution (B1) as aligning agent for liquid crystal, carry out [evaluation of vertical orientated property] and [evaluation of re-workability].Result is shown in table 1 and table 3.And then, the evaluation of voltage retention and ion concentration is carried out according to [evaluation of electrology characteristic].Result is shown in table 2.
(reference example 2)
Polysiloxane solution (B1) 3.0g and polyamic acid solution (A1) 7.0g is mixed, obtains aligning agent for liquid crystal (1).Use this aligning agent for liquid crystal, carry out [evaluation of re-workability], [evaluation of weighting characteristics] and [evaluation of vertical orientated property].Result is shown in table 3, table 4 and table 5.And then, the evaluation of voltage retention and ion concentration is carried out according to [evaluation of electrology characteristic].Result is shown in table 6.
(reference example 3)
Polysiloxane solution (B1) 3.0g and polyamic acid solution (A2) 7.0g is mixed, obtains aligning agent for liquid crystal (2).Use this aligning agent for liquid crystal, carry out [evaluation of re-workability].Result is shown in table 3.
(reference example 4)
Polysiloxane solution (B1) 3.0g and polyamic acid solution (A3) 7.0g is mixed, obtains aligning agent for liquid crystal (3).Use this aligning agent for liquid crystal, carry out [evaluation of re-workability].Result is shown in table 3.
(reference example 5)
Polysiloxane solution (B1) 3.0g and polyamic acid solution (A4) 7.0g is mixed, obtains aligning agent for liquid crystal (4).Use this aligning agent for liquid crystal, carry out [evaluation of re-workability].Result is shown in table 3.
(reference example 6)
Polysiloxane solution (B1) 3.0g and polyamic acid solution (A5) 7.0g is mixed, obtains aligning agent for liquid crystal (5).Use this aligning agent for liquid crystal, carry out [evaluation of re-workability], [evaluation of weighting characteristics] and [evaluation of vertical orientated property].Result is shown in table 3, table 4 and table 5.And then, the evaluation of voltage retention and ion concentration is carried out according to [evaluation of electrology characteristic].Result is shown in table 6.
(reference example 7)
Polysiloxane solution (B4) 3.0g and polyamic acid solution (A1) 7.0g is mixed, obtains aligning agent for liquid crystal (6).Use this aligning agent for liquid crystal, carry out [evaluation of weighting characteristics].Result is shown in table 6.
(reference example 8)
Polysiloxane solution (B4) 3.0g and polyamic acid solution (A2) 7.0g is mixed, obtains aligning agent for liquid crystal (7).Use this aligning agent for liquid crystal, carry out [evaluation of weighting characteristics].Result is shown in table 6.
(embodiment 1)
Polysiloxane solution (B5) 3.0g and polyamic acid solution (A1) 7.0g is mixed, obtains aligning agent for liquid crystal (8).Use this aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientated property].Result is shown in table 7.
(embodiment 2)
Polysiloxane solution (B5) 3.0g and polyamic acid solution (A2) 7.0g is mixed, obtains aligning agent for liquid crystal (9).Use this aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientated property].Result is shown in table 7.
(embodiment 3)
Polysiloxane solution (B5) 3.0g and polyamic acid solution (A3) 7.0g is mixed, obtains aligning agent for liquid crystal (10).Use this aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientated property].Result is shown in table 7.
(embodiment 4)
Polysiloxane solution (B5) 3.0g and polyamic acid solution (A4) 7.0g is mixed, obtains aligning agent for liquid crystal (11).Use this aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientated property].Result is shown in table 7.
(embodiment 5)
Polysiloxane solution (B5) 3.0g and polyamic acid solution (A5) 7.0g is mixed, obtains aligning agent for liquid crystal (12).Use this aligning agent for liquid crystal, carry out [evaluation of response speed], [evaluation of vertical orientated property] and [evaluation of re-workability].Result is shown in table 7, table 8 and table 10.And then, the evaluation of voltage retention and ion concentration is carried out according to [evaluation of electrology characteristic].Result is shown in table 9.
(embodiment 6)
Polysiloxane solution (B5) 3.0g and polyamic acid solution (A6) 7.0g is mixed, obtains aligning agent for liquid crystal (13).Use this aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientated property].Result is shown in table 7.
(embodiment 7)
Polysiloxane solution (B5) 3.0g and polyamic acid solution (A7) 7.0g is mixed, obtains aligning agent for liquid crystal (14).Use this aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientated property].Result is shown in table 7.
(embodiment 8)
Polysiloxane solution (B5) 3.0g and polyamic acid solution (A8) 7.0g is mixed, obtains aligning agent for liquid crystal (15).Use this aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientated property].Result is shown in table 7.And then, the evaluation of voltage retention and ion concentration is carried out according to [evaluation of electrology characteristic].Result is shown in table 9.
(embodiment 9)
Polysiloxane solution (B5) 3.0g and polyamic acid solution (A9) 7.0g is mixed, obtains aligning agent for liquid crystal (16).Use this aligning agent for liquid crystal, carry out [evaluation of response speed], [evaluation of vertical orientated property] and [evaluation of re-workability].Result is shown in table 7 and table 10.
(embodiment 10)
Polysiloxane solution (B5) 3.0g and polyamic acid solution (A10) 7.0g is mixed, obtains aligning agent for liquid crystal (17).Use this aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientated property].Result is shown in table 7.
(embodiment 11)
Polysiloxane solution (B6) 3.0g and polyamic acid solution (A1) 7.0g is mixed, obtains aligning agent for liquid crystal (18).Use this aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientated property].Result is shown in table 7 and table 8.
(comparative example 1)
Use polysiloxane solution (B2) as aligning agent for liquid crystal, carry out [evaluation of vertical orientated property] and [evaluation of re-workability].Result is shown in table 1 and table 3.
(comparative example 2)
Use polysiloxane solution (B3) as aligning agent for liquid crystal, carry out the evaluation of voltage retention and ion concentration according to [evaluation of electrology characteristic].Result is shown in table 2.And then, carry out [evaluation of re-workability].Result is shown in table 3.
(comparative example 3)
Polysiloxane solution (B2) 3.0g and polyamic acid solution (A1) 7.0g is mixed, obtains aligning agent for liquid crystal (19).Use this aligning agent for liquid crystal, carry out [evaluation of vertical orientated property] and [evaluation of weighting characteristics].Result 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, obtains aligning agent for liquid crystal (20).Use this aligning agent for liquid crystal, carry out [evaluation of vertical orientated property] and [evaluation of weighting characteristics].Result 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, obtains aligning agent for liquid crystal (21).Use this aligning agent for liquid crystal, carry out the evaluation of voltage retention and ion concentration according to [evaluation of electrology characteristic].Result is shown in table 6.
(comparative example 6)
Polysiloxane solution (B3) 3.0g and polyamic acid solution (A5) 7.0g is mixed, obtains aligning agent for liquid crystal (22) The and obtain.Use this aligning agent for liquid crystal, carry out the evaluation of voltage retention and ion concentration according to [evaluation of electrology characteristic].Result is shown in table 6.
(comparative example 7)
Polysiloxane solution (B7) 3.0g and polyamic acid solution (A1) 7.0g is mixed, obtains aligning agent for liquid crystal (23).Use this aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientated property].Result is shown in table 7.
(comparative example 8)
Use polyimide/polyamide acid solution (A9) as aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientated property].Result is shown in table 7 and table 8.
(comparative example 9)
Polysiloxane solution (B8) 3.0g and polyamic acid solution (A5) 7.0g is mixed, obtains aligning agent for liquid crystal (24).Use this aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientated property].Result is shown in table 7.And then, the evaluation of voltage retention and ion concentration is carried out according to [evaluation of electrology characteristic].Result is shown in table 9.
(comparative example 10)
Polysiloxane solution (B8) 3.0g and polyamic acid solution (A8) 7.0g is mixed, obtains aligning agent for liquid crystal (25).Use this aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of vertical orientated property].Result is shown in table 7.And then, the evaluation of voltage retention and ion concentration is carried out according to [evaluation of electrology characteristic].Result is shown in table 9.
(comparative example 11)
Polysiloxane solution (B5) 3.0g and polysiloxane solution (B9) 7.0g is mixed, obtains aligning agent for liquid crystal (26).Use this aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of re-workability].Result is shown in table 8 and table 10.
(comparative example 12)
Polysiloxane solution (B6) 3.0g and polysiloxane solution (B9) 7.0g is mixed, obtains aligning agent for liquid crystal (27).Use this aligning agent for liquid crystal, carry out [evaluation of response speed] and [evaluation of re-workability].Result is shown in table 8 and table 10.
[table 1]
Polysiloxane 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 disorder is observed.
[table 2]
In table 2, known about electrology characteristic, the aligning agent for liquid crystal (reference example 1) containing urea groups is compared with the aligning agent for liquid crystal (comparative example 2) not containing urea groups, and VHR (voltage retention) is high, and ion concentration is low.
[table 3]
In table 3, known about re-workability, compared with the aligning agent for liquid crystal only containing polysiloxane ingredient, the re-workability of the aligning agent for liquid crystal containing at least one polymkeric substance be selected from the group that is made up of polyamic acid and polyimide is higher.
[table 4]
Known in table 4, the aligning agent for liquid crystal containing urea groups is compared with the aligning agent for liquid crystal not containing urea groups, and weighting characteristics is excellent.
[table 5]
In table 5, same with table 1, in the liquid crystal cells of reference example 2,6, after annealing, do not observe the farmland of orientation disorder completely.On the other hand, in the liquid crystal cells of comparative example 3,4, after annealing, the farmland of multiple orientation disorder is observed.
[table 6]
In table 6, same with table 2, known about electrology characteristic, the aligning agent for liquid crystal (reference example 2,6) containing urea groups is compared with the aligning agent for liquid crystal (comparative example 5,6) not containing urea groups, and VHR is high, and ion concentration is low.
[table 7]
The judgement zero of response speed: fast (well) ×: slow (poor)
Farmland observations after annealing
×: observe multiple farmland
Zero: good
◎: very good
In table 7, in embodiment 1, the postradiation fast response time of UV, and the farmland observations after annealing is also good result.On the other hand, in comparative example 8, the farmland observations after annealing is very good, but the postradiation response speed of UV is slow.In comparative example 7, fast response time, but observe multiple farmland after annealing.
In addition, in embodiment 2 ~ 11, comparative example 9 and 10, the postradiation fast response time of UV, and the farmland observations after annealing also demonstrates very good result.
[table 8]
The judgement of response speed
Zero: fast (very good) <50 millisecond
△: fast (well) <50 ~ 100 millisecond
×: slow (poor) >200 millisecond
In table 8, about known to the response speed of UV exposure, compare with the independent aligning agent for liquid crystal be made up of polysiloxane of comparative example 12 with comparative example 11, the scope of aligning agent for liquid crystal to the raising of the response speed that UV irradiates containing at least one polymkeric substance be selected from the group that is made up of polyamic acid and polyimide is wider.
[table 9]
In table 9, same with table 2 and table 6, known about electrology characteristic, the aligning agent for liquid crystal containing urea groups is compared with the aligning agent for liquid crystal not containing urea groups, and VHR is high, and ion concentration is low.
[table 10]
(B) composition (A) composition Re-workability
Embodiment 5 B5 A5 ○
Embodiment 9 B5 A9 ○
Comparative example 11 B5、B9 Nothing ×
Comparative example 12 B6、B9 Nothing ×
In table 10, same with table 3, known and independent compared with the aligning agent for liquid crystal that mineral compound is formed, the re-workability of the aligning agent for liquid crystal containing at least one polymkeric substance be selected from the group that is made up of polyamic acid and polyimide is higher.
Industrial applicibility
The liquid crystal orientation film using aligning agent for liquid crystal of the present invention to be formed can not make vertical orientated power reduce, the postradiation response speed of UV is also excellent, and the liquid crystal display cells with liquid crystal orientation film of the present invention is useful for TFT liquid crystal display cells, TN liquid crystal display cells, VA liquid crystal display cells etc.
It should be noted that, the full content of the instructions of No. 2012-190328, the Japanese patent application of submission on August 30th, 2012, claims and summary is quoted so far, it can be used as the disclosure of instructions of the present invention to be incorporated to the application.

Claims (11)

1. an aligning agent for liquid crystal, is characterized in that, containing following (A) composition and (B) composition,
(A) composition: be selected from least one polymkeric substance in the group be made up of polyamic acid and polyimide,
(B) composition: the alkoxy silane polycondensation of the alkoxy silane that the alkoxy silane that represents containing formula (1) and formula (3) are represented and the polysiloxane obtained,
R 1Si(OR 2) 3(1)
R 1for the structure of following formula (2), R 2for the alkyl of carbon number 1 ~ 5,
[changing 1]
Y 1for singly-bound ,-(CH 2) a-,-O-,-CH 2o-,-COO-or-OCO-, a is the integer of 1 ~ 15,
Y 2for hydrocarbon or-(CR that singly-bound, carbon number containing double bond are the straight or branched of 3 ~ 8 17r 18) b-, b is the integer of 1 ~ 15, R 17, R 18independently of one another for hydrogen atom or carbon number are the alkyl of 1 ~ 3,
Y 3for singly-bound ,-(CH 2) c-,-O-,-CH 2o-,-COO-or-OCO-, c is the integer of 1 ~ 15,
Y 4for being selected from the bivalent cyclic base in phenyl ring, cyclohexyl ring and heterocycle, alkyl, carbon number that arbitrary hydrogen atom in these cyclic group can be 1 ~ 3 by carbon number be 1 ~ 3 alkoxy, carbon number be 1 ~ 3 containing fluoroalkyl, carbon number be 1 ~ 3 fluoroalkoxy or fluorine atom replace, in addition, Y 4can be the divalent organic group of 12 ~ 25 for the carbon number with steroid skeleton,
Y 5for being selected from the bivalent cyclic base in the group that is made up of phenyl ring, cyclohexyl ring and heterocycle, alkyl, carbon number that arbitrary hydrogen atom in these cyclic group can be 1 ~ 3 by carbon number be 1 ~ 3 alkoxy, carbon number be 1 ~ 3 containing fluoroalkyl, carbon number be 1 ~ 3 fluoroalkoxy or fluorine atom replace
Y 6for hydrogen atom, carbon number be 1 ~ 18 alkyl, carbon number be 1 ~ 18 containing fluoroalkyl, carbon number be 1 ~ 18 alkoxy or carbon number be the fluoroalkoxy of 1 ~ 18, n is the integer of 0 ~ 4,
R 3Si(OR 4) 3(3)
R 3for the carbon number replaced by acryloyl group, acryloxy, methacryl, methacryloxy or styryl is the alkyl of 1 ~ 30, R 4for the alkyl of carbon number 1 ~ 5.
2. aligning agent for liquid crystal according to claim 1, wherein, the polysiloxane that (B) composition obtains for making the alkoxy silane polycondensation of the alkoxy silane also represented containing following formula (4),
(R 5) nSi(OR 6) 4-n(4)
R 5for hydrogen atom or can be the alkyl of 1 ~ 10 by the carbon number of heteroatoms, halogen atom, amino, glycidoxy, sulfydryl, isocyanate group, Carbamido substituted, R 6for the alkyl of carbon number 1 ~ 5, n is the integer of 0 ~ 3.
3. aligning agent for liquid crystal according to claim 2, wherein, the alkoxy silane that described formula (4) represents is tetramethoxy-silicane or tetraethoxysilane.
4. aligning agent for liquid crystal according to claim 1, wherein, (B) in whole alkoxy silanes that the manufacture of the polysiloxane of composition uses, use the alkoxy silane that the formula (1) of 2 ~ 20 % by mole represents, and use the alkoxy silane that the formula of 5 ~ 80 % by mole (3) represents.
5. the aligning agent for liquid crystal according to Claims 2 or 3, wherein, in whole alkoxy silanes that the manufacture of the polysiloxane of (B) composition uses, uses the alkoxy silane that the formula (4) of 10 ~ 90 % by mole represents.
6. the aligning agent for liquid crystal according to any one of Claims 1 to 5, wherein, relative to (A) composition 100 mass parts, the SiO containing the silicon atom had with (B) composition 2scaled value counts (B) composition of 0.5 ~ 80 mass parts.
7. the aligning agent for liquid crystal according to any one of claim 1 ~ 6, wherein, also containing organic solvent, this organic solvent contains 90 ~ 99 quality % in aligning agent for liquid crystal.
8. a liquid crystal orientation film, it is by being applied to also drying on substrate, calcining and obtain by the aligning agent for liquid crystal according to any one of claim 1 ~ 7.
9. liquid crystal orientation film according to claim 8, wherein, carries out described calcining and forms liquid crystal orientation film at the temperature of 100 ~ 350 DEG C.
10. liquid crystal orientation film according to claim 8 or claim 9, wherein, the thickness of the film after calcining is 5 ~ 300nm.
11. 1 kinds of liquid crystal display cells, it has the liquid crystal orientation film according to any one of claim 8 ~ 10.
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