CN101135813B - Liquid crystal tropism agent, liquid crystal tropism film and liquid crystal display element - Google Patents
Liquid crystal tropism agent, liquid crystal tropism film and liquid crystal display element Download PDFInfo
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- CN101135813B CN101135813B CN200710145517XA CN200710145517A CN101135813B CN 101135813 B CN101135813 B CN 101135813B CN 200710145517X A CN200710145517X A CN 200710145517XA CN 200710145517 A CN200710145517 A CN 200710145517A CN 101135813 B CN101135813 B CN 101135813B
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- C09K19/56—Aligning agents
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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Abstract
The present invention relates to an aligning agent for liquid crystal, a liquid crystal alignment film and a liquid crystal display device. The subject of the invention is to provide a aligning agent for liquid crystal which can provides a liquid crystal alignment film with excellent electrical property and printing property and containing 4, 4'-amino- substitution product of diamino- phenyl group or 2, 7-amino- substitution product of diamino- fluorine.
Description
Technical field
The present invention relates to aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells.More particularly, relate to aligning agent for liquid crystal, this liquid crystal orientation film and the liquid crystal display cells that can form the good and liquid crystal orientation film that printing is good of electrical property with it.
Background technology
At present, as liquid crystal display cells, known TN type liquid crystal display cells with so-called TN type (Twisted Nematic) liquid crystal cell, it is being provided with the liquid crystal orientation film that formation is formed by polyamic acid, polyimide etc. on the substrate surface of nesa coating, substrate as used for liquid crystal display element, 2 these substrates are oppositely arranged, form nematic crystal layer betwixt in the crack with positive dielectric anisotropy, constitute the box of sandwich construction, the major axis of liquid crystal molecule is turned round continuously to another piece substrate from a substrate and is turn 90 degrees.And, also developed and compared the STN that contrast is higher, its view angle dependency is littler (Super Twisted Nematic) type liquid crystal display cells and vertical alignment-type liquid crystal display device with TN type liquid crystal display cells.This STN type liquid crystal display cells will be in nematic crystal fusion use as liquid crystal as the liquid crystal of the chirality agent of optically active substance, it utilizes by the major axis that makes liquid crystal molecule and be in the birefringence effect that the state of turning round the above amplitude of turnback continuously produces between substrate.By contrast, as described in non-patent literature 1 and patent documentation 1, proposed on ITO, to form the vertical alignment-type liquid crystal display device that is called the MVA mode that projection is controlled the liquid crystal aligning direction.The liquid crystal display cells of MVA mode not only visual angle, contrast etc. is good, and can also not carry out grinding process etc. in the process that forms liquid crystal orientation film, thereby also is good aspect manufacturing process.As the liquid crystal orientation film that is applicable to TN, STN, MVA mode, need the performances such as image retention elimination time weak point of liquid crystal display cells.In addition, as forming the used alignment agent of this liquid crystal orientation film, require in hectographic printing, to have superior printing characteristics.
[patent documentation 1] Japanese kokai publication hei 11-258605 communique
[non-patent literature 1] " liquid crystal " Vol.3 No.2,117 (1999)
Summary of the invention
The present invention makes in view of the above problems, its objective is to provide can be formed in to make the liquid crystal orientation film of accumulating the electric charge minimizing and aligning agent for liquid crystal when keeping voltage retention again with superior printing characteristics, and the liquid crystal display cells that this liquid crystal orientation film is provided and adopts it.
Other purposes of the present invention and advantage can be found out by the following description.
According to the present invention, above-mentioned purpose of the present invention and advantage are reached by a kind of aligning agent for liquid crystal, it is characterized in that containing at least a compound in the compound of the compound that is selected from following formula (A) expression and following formula (B) expression (below, be also referred to as specific compound)
(in the formula, R
1～R
8Be hydrogen atom, alkyl, alkoxy or aromatic group independently of one another, R
9And R
11Be aromatic group, and R
10And R
12Be hydrogen atom, alkyl or glycidyl independently of one another).
(in the formula, R
13And R
14Be hydrogen atom, alkyl, alkoxy or aromatic group independently of one another, R
15And R
17Be aromatic group, R
16And R
18Be hydrogen atom, alkyl or glycidyl independently of one another, and X represent divalent organic group ,-O-or-NH-).
In addition, aligning agent for liquid crystal of the present invention preferably also contains polyamic acid that is selected from following formula (I-1) expression and at least a polymkeric substance in the polyimide of (I-2) representing.
(in the formula, P
1Be the organic group of 4 valencys, and Q
1Organic group for divalent),
(in the formula, P
2Be the organic group of 4 valencys, and Q
2Organic group for divalent).
According to the present invention, can provide to can be formed in to make again when keeping voltage retention and accumulate liquid crystal orientation film and the aligning agent for liquid crystal with superior printing characteristics, this liquid crystal orientation film and the liquid crystal display cells that electric charge reduces with it.
Description of drawings
Fig. 1 tests the key diagram of the box of making for print.
Embodiment
Below, the present invention is carried out more specific description.
Aligning agent for liquid crystal of the present invention is dissolved in the organic solvent by at least a polymkeric substance (below, be also referred to as particular polymers) that makes specific compound and preferably be selected from polyamic acid and polyimide in addition and constitutes.
[specific compound 1]
With the compound of formula (A) expression as specific compound 1.
In formula (A), R
1～R
8Be hydrogen atom, alkyl, alkoxy or aromatic group independently of one another.As alkyl and alkoxy, preferred particularly carbon number is that 1～6 alkyl, carbon number are 1～6 alkoxy.As the alkyl in alkyl and the alkoxy, can enumerate for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 2-methyl-propyl group, 3-methyl-propyl group, n-pentyl, n-hexyl.In addition, as R
1～R
8Aromatic group, can enumerate phenyl.R
9, R
11Be aromatic group, can enumerate phenyl, naphthyl particularly.R
10, R
12Be hydrogen atom, alkyl or glycidyl independently of one another,, can enumerate methyl, ethyl, propyl group, butyl as alkyl.
In the formula (A), preferred R
2, R
4, R
5And R
7Be hydrogen, R
1, R
3, R
6And R
8Be hydrogen, methyl or ethyl independently of one another, R
9, R
11Be phenyl, R
10, R
12Be glycidyl.
As the particular compound of specific compound 1, can enumerate following compound.
In addition, in above-claimed cpd, Me is a methyl, and Et represents ethyl.
[specific compound 2]
With the compound of formula (B) expression as specific compound 2.
In formula (B), R
13, R
14Be hydrogen atom, alkyl, alkoxy or aromatic group independently of one another.As alkyl and alkoxy, preferred particularly carbon number is that 1～6 alkyl, carbon number are 1～6 alkoxy.As the alkyl in alkyl and the alkoxy, can enumerate for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 2-methyl-propyl group, 3-methyl-propyl group, n-pentyl, n-hexyl.In addition, as R
13, R
14Aromatic group, can enumerate phenyl.R
15, R
17Be aromatic group, can enumerate phenyl, naphthyl particularly.R
16, R
18Be hydrogen atom, alkyl or glycidyl independently of one another,, can enumerate methyl, ethyl, propyl group, butyl as alkyl.X be divalent organic group ,-O-or-NH-.As preferred divalent organic group, for example can enumerate-CH
2-or-CH
2CH
2-.
In the formula (B), preferred R
13, R
14Be hydrogen, R
15, R
17Be phenyl, R
16, R
18Being glycidyl, X is-NH-,-CH
2-or-CH
2CH
2-.
As the particular compound of specific compound 2, can enumerate following compound.
[polyamic acid]
＜tetrabasic carboxylic acid dicarboxylic anhydride 〉
As above-mentioned polyamic acid synthetic in used tetrabasic carboxylic acid dicarboxylic anhydride, can use ester ring type tetrabasic carboxylic acid dicarboxylic anhydride, aliphatics tetrabasic carboxylic acid dicarboxylic anhydride or aromatic tetracarboxylic acid's dicarboxylic anhydride.Wherein preferred ester ring type tetrabasic carboxylic acid dicarboxylic anhydride.As the object lesson of ester ring type tetrabasic carboxylic acid dicarboxylic anhydride, for example, can enumerate 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acid dicarboxylic anhydride, cis-3,7-dibutyl ring suffering-1,5-diene-1,2,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 5-(2,5-dioxo tetrahydrofuran methylene)-and 3-methyl-3-cyclohexene-1,2-dicarboxylic acid dicarboxylic anhydride, dicyclo [2.2.2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydro-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8,10-butanone, following formula (I) and the compound of (II) representing,
(in the formula, R
1And R
3Expression has the divalent organic group of aromatic rings, R
2And R
4Expression hydrogen atom or alkyl, the R of a plurality of existence
2And R
4Separately can be identical, also can be different).
In addition, can also enumerate aliphatics tetrabasic carboxylic acid dicarboxylic anhydrides such as BTCA dicarboxylic anhydride; The pyromellitic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-tetraphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-furans tetrabasic carboxylic acid dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dicarboxylic anhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two phthalic acid dicarboxylic anhydrides, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, two (phthalic acid) phosphniline oxide dicarboxylic anhydride, right-phenylene-two (triphenyl phthalic acid) dicarboxylic anhydride, between-phenylene-two (triphenyl phthalic acid) dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl ether dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl methane dicarboxylic anhydride, ethylene glycol-two (dehydration trimellitate), propylene glycol-two (dehydration trimellitate), 1,4-butylene glycol-two (dehydration trimellitate), 1,6-hexanediol-two (dehydration trimellitate), 1,8-ethohexadiol-two (dehydration trimellitate), 2,2-two (4-hydroxyphenyl) propane-two (dehydration trimellitate), aromatic tetracarboxylic acid's dicarboxylic anhydrides such as compound of following formula (1)～(4) expression.They can a kind be used singly or two or more kinds in combination.
In the above-mentioned tetrabasic carboxylic acid dicarboxylic anhydride, from making the angle of the good liquid crystal aligning of its performance, preferred 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrofuran methylene)-and 3-methyl-3-cyclohexene-1,2-dicarboxylic acid dicarboxylic anhydride, cis-3,7-dibutyl ring suffering-1,5-diene-1,2,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, dicyclo [2.2.2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydro-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8, the ester ring type tetrabasic carboxylic acid dicarboxylic anhydrides such as compound of following formula (8) expression in the compound of ester ring type tetrabasic carboxylic acid dicarboxylic anhydride such as the compound of following formula (5)～(7) expression in the compound of 10-butanone, above-mentioned formula (I) expression and above-mentioned formula (II) expression.As particularly preferred, can enumerate 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, cis-3,7-dibutyl ring suffering-1,5-diene-1,2,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydro-3-furyl)-and 3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid anhydride, 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8, the compound of 10-butanone and following formula (5) expression.
As preferred tetrabasic carboxylic acid dicarboxylic anhydride in other tetrabasic carboxylic acid dicarboxylic anhydrides beyond the ester ring type tetrabasic carboxylic acid dicarboxylic anhydride, can enumerate for example BTCA dicarboxylic anhydride, pyromellitic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride etc.
In these tetrabasic carboxylic acid dicarboxylic anhydrides, preferred ester ring type tetrabasic carboxylic acid dicarboxylic anhydride is 50 moles more than the % with respect to whole tetrabasic carboxylic acid dicarboxylic anhydrides.
＜diamines 〉
As polyamic acid synthetic in used diamines, for example, can enumerate p-phenylenediamine, between-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 2,2 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formailide, 4,4 '-diaminodiphenyl ether, 1, the 5-diaminonaphthalene, 2,2 '-two trifluoromethyls-4,4 '-benzidine, 3,3 '-two trifluoromethyls-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamido benzophenone, 3,4 '-diamido benzophenone, 4,4 '-diamido benzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 1,4-two (4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1,3-two (3-amino-benzene oxygen) benzene, 9,9-two (4-aminophenyl)-10-hydrogen anthracene, 2, the 7-diamino-fluorene, 9,9-dimethyl-2, the 7-diamino-fluorene, 9,9-two (4-aminophenyl) fluorenes, 4,4 '-methylene-two (2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamido-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 1,4,4 '-(right-the phenylene isopropylidene) diphenylamine, 4,4 '-(-the phenylene isopropylidene) diphenylamine, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-aromatic diamines such as octafluoro biphenyl;
1,1-m-xylene diamine, 1,3-propane diamine, butanediamine, pentanediamine, hexane diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 4,4-diamido heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene bicyclopentadiene diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0
2,7]-undecylene two methanediamines, 4,4 '-methylene two aliphatics and ester ring type diamines such as (cyclohexylamine);
2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamido-2,3-dicyano pyrazine, 5,6-diamido-2, the 4-dihydroxy-pyrimidine, 2,4-diamido-6-dimethylamino-1,3, the 5-triazine, 1,4-two (3-aminopropyl) piperazine, 2,4-diamido-6-isopropoxy-1,3, the 5-triazine, 2,4-diamido-6-methoxyl-1,3, the 5-triazine, 2,4-diamido-6-phenyl-1,3,5-triazines, 2,4-diamido-6-methyl-s-triazine, 2, the 4-diamino-1,3,5-triazines, 4,6-diamido-2-vinyl-s-triazine, 2,4-diamido-5-phenyl thiazole, 2, the 6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3, the 5-diaminostilbene, 2, the 4-triazole, 6,9-diamido-2-ethoxy acridine lactate, 3,8-diamido-6-phenylphenanthridineand, 1,4-diamido piperazine, 3, the 6-proflavin, two (4-aminophenyl) phenyl amine, 3,6-diamido carbazole, N-methyl-3,6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3 has the diamines of the nitrogen-atoms beyond 2 primary amino radicals and this primary amino radical in the 6-diamido carbazole equimolecular; The diamido organosiloxane of following formula (V) expression etc.These diamines can be used in combination separately or more than 2 kinds.
(in the formula, R
5The expression carbon number is 1～12 alkyl, the R of a plurality of existence
5Can be the same or different separately, p is 1～3 integer, and q is 1～20 integer).
Wherein, preferred p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 2,2 '-dimethyl-4,4 '-benzidine, 1, the 5-diaminonaphthalene, 2,2 '-two trifluoromethyls-4,4 '-benzidine, 2, the 7-diamino-fluorene, 9,9-dimethyl-2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(right-the phenylene diisopropylidene) diphenylamine, 4,4 '-(-the phenylene diisopropylidene) diphenylamine, 1, the 4-cyclohexane diamine, 4,4 '-methylene two (cyclohexylamine), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 3,6-diamido carbazole, N-methyl-3,6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole etc.
When making aligning agent for liquid crystal of the present invention have tilt angle performance performance, the Q among preferred above-mentioned formula (I-1), (I-2)
1, Q
2Part or all be at least a group of following formula (Q-1) and following formula (Q-2) expression.That is, adopt the diamines (below be also referred to as " specific diamines ") of group with following formula (Q-1) or following formula (Q-2) expression.They can a kind be used singly or two or more kinds in combination.
(in the formula, X
1For singly-bound ,-O-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-,-S-or arlydene, R
6Be that carbon number is that 10～20 alkyl, carbon number are that 4～40 1 valency organic group with ester ring type skeleton or carbon number are 1 valency organic group of 6～20 contain fluorine atoms).
(in the formula, X
2For singly-bound ,-O-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-,-S-or arlydene, R
7Be that carbon number is 4～40 the divalent organic group with ester ring type skeleton).
In the above-mentioned formula (Q-1), as R
6The carbon number of expression is 10～20 alkyl, can enumerate for example positive decyl, dodecyl, n-pentadecane base, n-hexadecyl, n-octadecane base, n-eicosane base etc.In addition, as the R of above-mentioned formula (Q-1)
6With the R in the above-mentioned formula (Q-2)
7The carbon number of expression is 4～40 the organic group with ester ring type skeleton, can enumerate the group of the ester ring type skeleton that for example has cycloalkanes such as deriving from cyclo-butane, cyclopentane, cyclohexane, cyclodecane; Group with steroid backbone such as cholesterol, cholestanols; Has the group of endocyclic skeletons such as norborene, diamantane etc.Wherein, the group that especially preferably has steroid backbone.Organic group with above-mentioned ester ring type skeleton can also be by halogen atom, preferred fluorine atom or fluoro-alkyl, the group that preferred trifluoromethyl replaces.
In addition, as the R of above-mentioned formula (Q-1)
6The carbon number of expression is the group of 6～20 contain fluorine atoms, can enumerate carbon numbers such as n-hexyl, n-octyl, positive decyl for example and be the straight chained alkyl more than 6; Carbon numbers such as cyclohexyl, ring octyl group are the ester ring type alkyl more than 6; Carbon number such as phenyl, xenyl is the group that the hydrogen atom of the organic groups such as aromatic hydrocarbyl more than 6 is partly or entirely replaced by fluoro-alkyls such as fluorine atom or trifluoromethyls.
In addition, the X of above-mentioned formula (Q-1)
1With the X in the above-mentioned formula (Q-2)
2For singly-bound ,-O-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-,-S-or arlydene.As arlydene, can enumerate for example phenylene, methylene phenyl, biphenylene, naphthylene etc.Wherein, be preferably especially-O-,-COO-,-group that OCO-represents.Object lesson as the diamines of group with above-mentioned formula (Q-1) expression, preferably can enumerate dodecyloxy-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2, the compound of 4-diaminobenzene, following formula (9)～(13) expression.
In addition, as the object lesson of the diamines of group, preferably can enumerate the diamines of following formula (14)～(16) expression with above-mentioned formula (Q-2) expression.
Wherein, as particularly preferred, can enumerate the compound of above-mentioned formula (9), (11), (13), (14) expression.
Specific diamines is with respect to the usage rate of whole diamines amounts, difference for the situation of TN type, STN type liquid crystal display cells, is preferably 0～5 mole of % along with the size of the tilt angle that will make its performance, for the situation of vertical alignment-type liquid crystal display device, be preferably 5～100 moles of %.
Synthesizing of＜polyamic acid 〉
Supply with the tetrabasic carboxylic acid dicarboxylic anhydride of polyamic acid synthetic reaction and the usage rate of diamines, preferably with respect to the amino of 1 equivalent diamines, the anhydride group that makes the tetrabasic carboxylic acid dicarboxylic anhydride is the ratio of 0.2～2 equivalent, more preferably is the ratio of 0.3～1.2 equivalent.
The synthetic reaction of polyamic acid in organic solvent, is preferable over-20 ℃～150 ℃, more preferably carries out under 0～100 ℃ temperature conditions.
Here, as organic solvent, as long as can dissolve synthetic polyamic acid, then it is had no particular limits, can illustration for example 1-Methyl-2-Pyrrolidone, N,N-dimethylacetamide, N, dinethylformamide, 3-butoxy-N, N-dimethyl propylene acid amides, 3-methoxyl-N, N-dimethyl propylene acid amides, the own oxygen base-N of 3-, aprotic polar solvents such as amide solvent, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, HMPA such as N-dimethyl propylene acid amides; Between phenol solvent such as sylvan, xylenols, phenol, halogenated phenol.In addition, to be preferably the total amount (β) that makes tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound usually be the amount of 0.1～30 weight % with respect to the total amount (alpha+beta) of reaction solution to the consumption of organic solvent (α).
In addition, in the scope that the polyamic acid that does not make generation is separated out, the poor solvent alcohols of all right coupling polyamic acid, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc. in the above-mentioned organic solvent.Object lesson as this poor solvent, can enumerate for example methyl alcohol, ethanol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4-methyl-2 pentanone, ethylene glycol, propylene glycol, 1, the 4-butylene glycol, triethylene glycol, glycol monoethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, diethy-aceto oxalate, diethyl malonate, ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, the ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic acid esters, the diethylene glycol monoethyl ether acetic acid esters, tetrahydrofuran, methylene chloride, 1, the 2-ethylene dichloride, 1, the 4-dichloroetane, trichloroethanes, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether etc.
As mentioned above, obtained dissolving the reaction solution of polyamic acid.Then, this reaction solution is put in a large amount of poor solvents, obtained precipitate, by this precipitate of drying under reduced pressure or with evaporator the reaction solution decompression distillation is removed, thereby obtain polyamic acid.And, this polyamic acid is dissolved in the organic solvent once more, then by carrying out once or with poor solvent it being separated out several times or, can make with extra care polyamic acid with the operation that evaporator is removed its decompression distillation.
＜dehydration closed-loop reaction 〉
Polyimide in the aligning agent for liquid crystal of the present invention can synthesize by part or all dehydration closed-loop with above-mentioned polyamic acid.
The dehydration closed-loop of polyamic acid can (i) by the method for heating polyamic acid, perhaps (ii) by polyamic acid is dissolved in the organic solvent, in this solution, adds the method for dewatering agent and dehydration closed-loop catalyzer and heating as required and carry out.
Temperature of reaction in the method for the heating polyamic acid of above-mentioned (i) is preferably 50～200 ℃, more preferably 60～170 ℃.When 50 ℃ of temperature of reaction less thaies, then the dehydration closed-loop reaction can not be carried out fully, if temperature of reaction surpasses 200 ℃, the situation of the molecular weight and molecular weight of gained imide amination polymer then can occur.
On the other hand, in the above-mentioned method of in polyamic acid solution, adding dewatering agent and dehydration closed-loop catalyzer (ii),, can use for example acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride as dewatering agent.The consumption of dewatering agent is decided according to required imidizate rate, preferably with respect to the repetitive of 1 mole of polyamic acid, is 0.01～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, collidine, lutidines, triethylamine.But, be not limited to these.The dehydration closed-loop catalyst consumption with respect to 1 mole of used dewatering agent, is preferably 0.01～10 mole.Above-mentioned dewatering agent, dehydration closed-loop catalyst consumption are many more, then can make the imidizate rate high more.In addition, as the organic solvent that uses in the dehydration closed-loop reaction, can enumerate as polyamic acid and synthesize middle solvent for use and illustrative organic solvent.And the temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 10～150 ℃.In addition, by the reaction solution that so obtains is carried out the operation same with the polyamic acid process for purification, can make with extra care the gained particular polymers.
The ratio (below, be also referred to as " imidizate rate ") that has the repetitive of imide ring among the present invention in the used whole repetitives of polyimide is 40 moles more than the %, is preferably 50 moles more than the %.By using the imidizate rate is 40 moles of polymkeric substance more than the %, can obtain to form the aligning agent for liquid crystal of short liquid crystal orientation film of image retention elimination time.The imidizate rate can obtain by the following method.
[the imidizate rate assay method of imide amination polymer]
At room temperature after the drying under reduced pressure, making it be dissolved in the deuterate dimethyl sulfoxide (DMSO) imide amination polymer, tetramethylsilane is at room temperature measured as primary standard substance
1H-NMR can (ii) obtain by following formula.
Imidizate rate (%)=(1-A
1/ A
2* α) * 100------------is (ii)
A
1: the peak area (10ppm) that derives from NH matrix
A
2: the peak area that derives from other protons
α: in the precursor of polymkeric substance (polyamic acid), with respect to the individual percentage of other proton of NH matrix.
＜end modified type polymkeric substance 〉
Used particular polymers can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting among the present invention.By using this end modified type polymkeric substance, can under the prerequisite of not damaging effect of the present invention, improve the coating characteristic of aligning agent for liquid crystal etc.This end modified type polymkeric substance can be by when polyamic acid synthetic, adds monobasic acid anhydrides, monoamine compound, monoisocyanates compound etc. and synthesize in reaction system.Wherein, as the monobasic acid anhydrides, can enumerate for example maleic anhydride, phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinic anhydride, n-tetradecane base succinic anhydride, n-hexadecyl succinic anhydride etc.In addition, as monoamine compound, can enumerate for example aniline, cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, n-pentadecane amine, n-hexadecane amine, n-heptadecane amine, n-octadecane amine, n-eicosane amine etc.In addition, as the monoisocyanates compound, can enumerate for example phenyl isocyanate, isocyanic acid naphthyl ester etc.
[solution viscosity]
Be used in the polymkeric substance of alignment agent of the present invention, under the situation of solution 10%, preferred 20～800mPas viscosity, more preferably 30～500mPas viscosity.
In addition, use specific solvent, cooperate the solution that is diluted to specific solids content concn, under 25 ℃, measure the solution viscosities (mPas) of polymkeric substance with E type rotational viscosimeter.
[aligning agent for liquid crystal]
Aligning agent for liquid crystal of the present invention normally constitutes by above-mentioned specific compound dissolving is contained in the organic solvent.
Temperature when modulating aligning agent for liquid crystal of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
Constitute the organic solvent of aligning agent for liquid crystal of the present invention, can enumerate as the synthetic reaction that is used for polyamic acid and the solvent of example.In addition, as poor solvent that can coupling in the synthetic reaction of polyamic acid, also can suitably select the poor solvent of coupling example.
Solids content concn is considered viscosity, volatility etc. and is selected in the aligning agent for liquid crystal of the present invention, is preferably the scope of 1～10 weight %.In other words, aligning agent for liquid crystal of the present invention is coated on substrate surface, formation is filmed as liquid crystal orientation film, and when solids content concn less than 1 weight %, the thickness that will cause this to film is too small, thereby can not obtain good liquid crystal orientation film; When solids content concn surpasses 10 weight %, will cause coating thickness blocked up, thereby can not obtain good liquid crystal orientation film, and the viscosity of aligning agent for liquid crystal increases, coating characteristic variation.
In addition, the scope of particularly preferred solids content concn, employed method is different during because of coated with liquid crystal alignment agent on substrate.For example, use the occasion of spin-coating method, the scope of preferred especially 1.5～4.5 weight %.Use the occasion of print process, solids content concn is the scope of 3～9 weight %, the scope of special preferred solution viscosity 12～50mPas.Use the occasion of ink jet printing method, solids content concn is 1～5 weight % scope, the scope of special preferred solution viscosity 3～15mPas.
As the organic solvent that constitutes aligning agent for liquid crystal of the present invention, for example, can enumerate 1-Methyl-2-Pyrrolidone, gamma-butyrolacton, butyrolactam, N, dinethylformamide, N, the N-dimethyl acetamide, 4-hydroxy-4-methyl-2 pentanone, glycol monoethyl ether, butyl lactate, butyl acetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic acid esters, the diethylene glycol monoethyl ether acetic acid esters, 3-butoxy-N, N-dimethyl propylene acid amides, 3-methoxyl-N, N-dimethyl propylene acid amides, the own oxygen base-N of 3-, N-dimethyl propylene acid amides, diisobutyl ketone (DIBK), isoamyl propionate, isoamyl isobutyrate, diisoamyl ether etc.They both can use separately, also can mix two or more uses.Wherein, 3-butoxy-N, N-dimethyl propylene acid amides, 3-methoxyl-N, N-dimethyl propylene acid amides, the own oxygen base-N of 3-, N-dimethyl propylene acid amides is preferred especially owing to show good printing.
Aligning agent for liquid crystal of the present invention is considered the fusible angle of substrate surface from improving in the scope of not damaging the purpose rerum natura, can also be contained compound, the epoxy compounds of functional silanes.As this compound that contains functional silanes, can enumerate for example 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-carbethoxyl group-3-TSL 8330, N-carbethoxyl group-3-aminopropyltriethoxywerene werene, N-tri-ethoxy silylpropyl diethylenetriamine, N-trimethoxy silane base propyl group diethylenetriamine, 10-trimethoxy silane-1,4,7-three azepine decane, 10-triethoxysilicane alkyl-1,4,7-three azepine decane, 9-trimethoxy silane base-3,6-diaza nonyl acetic acid esters, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, N-two (oxyethylene group)-3-TSL 8330, N-two (oxyethylene group)-3-aminopropyltriethoxywerene werene etc.As this epoxy compounds, can enumerate for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2, the 4-hexanediol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3-two (N, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, 3-(N-allyl-N-glycidyl) TSL 8330,3-(N, the N-diglycidyl) TSL 8330, N, N-diglycidyl-benzylamine, N, N-diglycidyl-amino methyl cyclohexane etc.The proportioning that these contain the functional silanes compound and contain epoxy compounds with respect to 100 parts by weight polymer, is preferably below 40 weight portions, more preferably 0.1～30 weight portion.
＜liquid crystal display cells 〉
With the liquid crystal display cells that aligning agent for liquid crystal of the present invention makes, can be by for example following method manufacturing.
(1) by hectographic printing method, spin-coating method or ink jet printing method, aligning agent for liquid crystal of the present invention is coated on the substrate one side that is provided with the nesa coating that forms pattern, then, film by the formation of heating applicator surface.Here, as substrate, can use for example glass such as float glass, soda-lime glass; Plastics system transparency carriers such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, the alicyclic polyolefin of polycarbonate.Simultaneously go up set nesa coating as substrate, can use tin oxide (SnO
2) system NESA film (U.S. PPG register of company trade mark), indium oxide-tin oxide (In
2O
3-SnO
2) the ITO film etc. of system, the formation of these electrically conducting transparent film figures is adopted photoetch method or is used the method for mask in advance.When the coating of aligning agent for liquid crystal, for the cohesive of further improving substrate surface and nesa coating and filming, can also be on this surface of substrate coating in advance contain functional silanes compound, contain the compound of functionality titanium etc.Behind the coated with liquid crystal alignment agent, inferior with the flow of liquid of the alignment agent that prevents to apply is purpose, preferably implements preparation heating (preroast).The temperature of preroast is preferably 30～300 ℃, more preferably 40～200 ℃, is preferably 50～150 ℃ especially.Afterwards, solvent is removed fully,, implemented calcining process (back roasting) to be purpose with the polyamic acid hot-imide.This roasting (back roasting) temperature is preferably 80～300 ℃, more preferably 120～250 ℃.Like this, contain the aligning agent for liquid crystal of the present invention of polyamic acid,, form filming as liquid crystal orientation film by removing organic solvent after the coating.Can also make it carry out dehydration closed-loop by further heating, form filming of further imidizate.The thickness of the liquid crystal orientation film that forms is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) formed film coated surface is carried out grinding process with the certain orientation friction with being tied with the roller of fibrous cloth such as nylon, regenerated fiber, cotton for example.Like this, be formed in produced on filming liquid crystal molecular orientation can liquid crystal orientation film.In addition; to the liquid crystal orientation film that forms by aligning agent for liquid crystal of the present invention; the processing of carrying out the part irradiation ultraviolet radiation shown in Japanese kokai publication hei 6-222366 communique for example or the Japanese kokai publication hei 6-281937 communique and tilt angle being changed; perhaps carrying out the liquid crystal orientation film upper surface after implementing grinding process shown in the Japanese kokai publication hei 5-107544 communique divides ground to form diaphragm; after carrying out grinding process with the direction different with previous grinding process; remove diaphragm; the processing that the liquid crystal aligning of liquid crystal orientation film can be changed can improve the visual field characteristic of liquid crystal display cells like this.
(3) make 2 substrates that as above form liquid crystal orientation film, 2 substrates are staggered relatively by gap (box gap), make the vertical mutually or antiparallel of polishing direction of liquid crystal orientation film separately, fitted with sealant in 2 substrate periphery positions, in the box gap that is partitioned into by substrate surface and sealant, annotate the topping up crystalline substance, the sealing filling orifice constitutes liquid crystal cell.Then,, promptly constitute on the another side of each substrate of liquid crystal cell at the outside surface of liquid crystal cell, the applying polaroid, it is consistent or vertical to make its polarization direction and this substrate simultaneously go up the polishing direction of formed liquid crystal orientation film, makes liquid crystal display cells.Here, as sealant, for example can use epoxy resin as the salic ball of hardening agent and separator etc.As liquid crystal, can enumerate nematic crystal and dish shape type liquid crystal, wherein preferred nematic crystal can use for example schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.In addition, can also add cholesteryl liquid crystal such as for example cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal and the chirality agent of selling with trade name " C-15 ", " CB-15 " (メ Le Network corporate system) etc. and using.And, can also use oxygen base benzylidene-in the last of the ten Heavenly stems to ferroelectric liquid crystals such as amino-2-methyl butyl cinnamates.In addition, as the polaroid of fitting on the liquid crystal cell outside surface, can enumerate polyvinyl alcohol (PVA) is extended that the polarizing coating that is referred to as the H film that orientation absorbs the iodine gained simultaneously is clipped in the acetate fiber diaphragm and the polaroid that polaroid of making or H film self are made.
Here, as sealant, for example can use epoxy resin as the salic ball of hardening agent and separator etc.
As liquid crystal, can enumerate nematic crystal and dish shape type liquid crystal, wherein preferred nematic crystal can use for example schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.In addition, can also add cholesteryl liquid crystal such as for example cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal and the chirality agent of selling with trade name " C-15 ", " CB-15 " (メ Le Network corporate system) etc. and using.And, can also use oxygen base benzylidene-in the last of the ten Heavenly stems to ferroelectric liquid crystals such as amino-2-methyl butyl cinnamates.
In addition, as the polaroid of fitting on the liquid crystal cell outside surface, can enumerate polyvinyl alcohol (PVA) is extended that the polarizing coating that is referred to as the H film that orientation absorbs the iodine gained simultaneously is clipped in the acetate fiber diaphragm and the polaroid that polaroid of making or H film self are made.
[embodiment]
Below, by embodiment the present invention is carried out more specific description, but the present invention is not limited to these embodiment.
[printing evaluation]
On whole an of side, formed in advance the glass substrate of 127mm (D) * 127mm (the W) * 1.1mm (H) of ITO film, is after the millipore filter of 0.2 μ m filters with the aligning agent for liquid crystal that obtains in the above-mentioned experiment by the aperture, being coated with application printing machine (Nissha Printing Co., Ltd makes, オ Application グ ス ト ロ one マ one S-40L) with liquid crystal orientation film is coated on the transparency electrode face of this glass substrate.Carry out drying by the heating plate driving fit formula pre-dryers that is set at 80 ℃, 200 ℃ of following roastings 60 minutes, on the glass substrate that has the ITO film, form liquid crystal orientation film again.Spot to the gained alignment films carries out visual assessment.
[voltage retention]
In 167 milliseconds time span, apply the voltage of 60 microsecond 5V below 60 ℃ to liquid crystal display cells, measure then from voltage and remove voltage retention after 167 milliseconds.Determinator adopts the (VHR-1 of strain) East Yang テ Network ニ カ system.
[print experiment]
Make the box that has the ITO electrode as shown in Figure 1.At room temperature, apply 24 hours 6.0V DC voltage, apply 24 hours 0.5V DC voltage to electrode B to electrode A.After discharging stress, apply 0.1～5.0V DC voltage with the gradient of 0.1V to electrode A, B.Luminance difference by each voltage bottom electrode A, B is judged the print characteristic.When luminance difference was big, it is poor that the print characteristic is judged as.
Synthesizing of＜specific compound 〉
Synthesis example 1
Under nitrogen environment, in the four neck flasks of 500ml, add toluene 20ml, catalyst acetic acid palladium (II) 0.42g (0.0018mol), tert-butyl group phosphine 1.5g (0.0075mol), after stirring a few minutes, drip 4, the toluene solution 100ml of 4 '-'-dibromobiphenyl 29.3g (0.094mol) further stirred 10 minutes.Then, behind the toluene solution 200ml of adding aniline 18.3g (0.196mol), add tert-butoxy sodium 15.86g (0.165mol) again, reflux made its reaction in 4 hours.Reaction adds entry after finishing in container, use extracted with diethyl ether.After the sodium sulphate dehydration, leach sodium sulphate, remove by Rotary Evaporators and desolvate.Crude product is made with extra care by silica gel column chromatography, obtained specific compound (A-1).
Synthesis example 2
Under nitrogen environment, in the four neck flasks of 500ml, add toluene 20ml, catalyst acetic acid palladium (II) 0.42g (0.0018mol), tert-butyl group phosphine 1.5g (0.0075mol), after stirring a few minutes, drip 2, the toluene solution 100ml of 7-dibromo fluorenes 30.4g (0.094mol) further stirred 10 minutes.Then, behind the toluene solution 200ml of adding aniline 18.3g (0.196mol), add tert-butoxy sodium 15.86g (0.165mol) again, reflux made its reaction in 4 hours.Reaction adds entry after finishing in container, use extracted with diethyl ether.With after the sodium sulphate dehydration, filtering sodium sulphate removes by Rotary Evaporators and to desolvate.Crude product is made with extra care by silica gel column chromatography, obtained specific compound (B-1).
Synthesis example 3
Except the aniline that will be in the synthesis example 1 uses substitutes with 4-n-pro-pyl aniline, synthesize according to the flow process identical with synthesis example 1, obtain compound (A-2).
Synthesis example 4
Except the aniline that will be in the synthesis example 2 uses substitutes with 4-n-pro-pyl aniline, synthesize according to the flow process identical with synthesis example 2, obtain compound (B-2).
Synthesis example 5
In the 500ml three-neck flask, specific compound (A-1) 3.36g (0.01mol), THF100ml, Sodamide 1.56g (0.04mol) are mixed.Make this vlil 2 hours.Cooled reaction solution drips epoxy bromopropane 3.42ml (0.04mol).After dripping end, be heated to 80 ℃ and stirred 6 hours.After removing THF by Rotary Evaporators, add chloroform.This solution is carried out the separatory washing with 10% aqueous hydrochloric acid solution, saturated aqueous common salt successively.With the organic layer anhydrous magnesium sulfate drying, behind the filtering anhydrous magnesium sulfate, remove by Rotary Evaporators and to desolvate.Distill except that desolvating from organic layer.Make with extra care by silica gel column chromatography again, obtain purpose specific compound (A-3).Specific compound (A-3) comprises 2 kinds of products as implied above.
Synthesis example 6
In the 500ml three-neck flask, compound (B-1) 17.4g (0.05mol), DMSO120ml, sal tartari 16.59g (0.12mol) are mixed.After this solution cooled off, drip the DMSO solution 160ml of epoxy bromopropane 16.44g (0.12mol) in ice bath.After dripping end, return and drop to room temperature, continue to stir 48 hours.Filtering reacting solution, filtrate concentrates by Rotary Evaporators, removes the epoxy bromopropane of excessive adding again by vacuum pump.In the gained crude product, add 200ml toluene and dilute, this solution is washed 4 times with distilled water 100ml.Add sodium sulphate, placed for 1 night after, filtering sodium sulphate removes by Rotary Evaporators and to desolvate.The gained crude product is made with extra care by silica gel column chromatography, obtained specific compound (B-3).B-3 comprises 2 kinds of products as implied above.
Synthesis example 7
Except the specific compound (A-1) that will be in the synthesis example 5 uses replaces to (A-2),, obtain specific compound (A-4) according to synthesizing with the same flow process of synthesis example 5.A-4 comprises 2 kinds of products as implied above.
Synthesis example 8
Except the specific compound (B-1) that will be in the synthesis example 6 uses replaces to (B-2),, obtain specific compound (B-4) according to synthesizing with the same flow process of synthesis example 6.B-4 comprises 2 kinds of products as implied above.
Polyimide synthesis example 1
Will be as 2 of tetrabasic carboxylic acid dicarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride 112g (0.50 mole) and 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1,3-diketone 157g (0.50 mole) is as the p-phenylenediamine 96g (0.89 mole) of diamine compound, 3,3 '-(tetramethyl disiloxane-1,3-two bases) two (propylamine) 25g (0.10 mole) and 3,6-two (4-aminobenzoic acyl-oxygen base) cholestane 13g (0.02 mole), n-octadecane base amine 8.1g (0.03 mole) as monoamine is dissolved in the 960gN-N-methyl-2-2-pyrrolidone N-, and it was reacted 6 hours down at 60 ℃.The polyamic acid solution that obtains divided slightly take out, add NMP, the measured in solution viscosity with solids content concn 10% is 60mPas.Then, in the polyamic acid solution that obtains, append 2700g N-N-methyl-2-2-pyrrolidone N-, add 396g pyridine and 409g acetic anhydride, make it 110 ℃ of following dehydration closed-loops 4 hours.After the imidization reaction, intrasystem solvent is carried out solvent exchange (in this operation with new gamma-butyrolacton, the pyridine and the acetic anhydride that are used in imidization reaction are removed to outside the system), obtain about 2000g solids content concn 15wt%, the solution viscosity 16mPas of (gamma-butyrolacton solution) during solids content concn 6.0%, the imidizate rate is about 95% imide amination polymer (it is as " polyimide (a-1) ") solution.
Polyimide synthesis example 2
Will be as 2 of tetrabasic carboxylic acid dicarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride 224g (1.0 moles), p-phenylenediamine 108g (1.0 moles) and 3 as diamine compound, 5-diaminobenzoic acid cholestane base ester 7.8g (0.015 mole) is dissolved in the 3039g N-N-methyl-2-2-pyrrolidone N-, it was reacted 6 hours down at 60 ℃, thereby obtain the polyamic acid solution that solution viscosity is about 260mPas.Then, in the polyamic acid solution that obtains, append 2700g N-N-methyl-2-2-pyrrolidone N-, add 396g pyridine and 306g acetic anhydride, make it 110 ℃ of following dehydration closed-loops 4 hours.After the imidization reaction, intrasystem solvent is carried out solvent exchange (in this operation with new gamma-butyrolacton, the pyridine and the acetic anhydride that are used in imidization reaction are removed to outside the system), obtain about 3000g solids content concn 9.0wt%, the solution viscosity 72mPas of (gamma-butyrolacton solution) during solids content concn 5.0%, the imidizate rate is about 89% imide amination polymer (it is as " imide amination polymer (a-2) ") solution.
Polyamic acid synthesis example 1
Will be as 1 of tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride 196g (1.0 moles), as 2 of diamine compound, 2 '-dimethyl-4,4 '-benzidine 212g (1.0 moles) is dissolved in 370g N-N-methyl-2-2-pyrrolidone N-and 3300g gamma-butyrolacton, make it 40 ℃ of down reactions 3 hours, polyamic acid (its conduct " polyamic acid (b-1) ") solution that to obtain about 3700g solution viscosity be 160mPas.
Polyamic acid synthesis example 2
Will be as 1 of tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride 95g (0.50 mole), pyromellitic acid dicarboxylic anhydride 109g (0.50 mole), as 2 of diamine compound, 7-diamino-fluorene 196g (1.0 moles) is dissolved in 230g N-N-methyl-2-2-pyrrolidone N-and 2060g gamma-butyrolacton, make it after 40 ℃ are reacted 3 hours down, append the 1350g gamma-butyrolacton, obtain polyamic acid (it is as " polyamic acid (b-2) ") solution of the solution viscosity 125mPas of about 3600g solids content concn 10%.
Embodiment 1
With the polyamic acid (b-1) that makes in the polyimide (a-1) that makes in the polyimide synthesis example 1 and the polyamic acid synthesis example 1 with polyimide: polyamic acid=20: 80 (weight ratio) is dissolved in gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/butyl cellosolve mixed solvent (weight ratio 71/17/12), add 2 weight portion N with respect to 100 parts by weight polymer, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, add 10 weight portion specific compounds (A-1) with respect to 100 parts by weight polymer, make solution that solids content concn is 3.5 weight % and the solution of 6.0 weight %.After each solution fully stirred, be that the filter of 1 μ m filters, modulate aligning agent for liquid crystal of the present invention with the aperture.
Adopting spin coater is that to be coated on thickness be (rotating speed: 2500rpm on the ITO film system nesa coating set on the one side of glass substrate of 1mm for the solution of 3.5 weight % with solids content concn in the above-mentioned aligning agent for liquid crystal, the coating time: 1 minute), drying is 1 hour under 200 ℃, and forming dry film thickness is the overlay film of 0.08 μ m.The sander of the roller that twines artificial fibrous cloth is equipped with in employing, is that 400rpm, operator's console translational speed are 3cm/ second at the roller rotating speed, and fine hair is clamp-oned under the condition that length is 0.4mm, and this overlay film is carried out grinding process.In ultrapure water, carry out 1 minute ultrasonic washing, with 100 ℃ cleaning oven dried 10 minutes.Then, on each outer rim of the above-mentioned liquid crystal orientation film coated substrate of a pair of transparency electrode/transparent electrode substrate with liquid crystal orientation film, it is the epoxy adhesive of the alumina balls of 5.5 μ m that coating has added diameter, then, the liquid crystal aligning face is relatively overlapped and pressing, bonding agent is solidified.Then, (メ Le Network society system MLC-6221), is sealed liquid crystal injecting port with the acrylic compounds Photocurable adhesive then, makes liquid crystal display cells of the present invention to fill nematic crystal by liquid crystal injecting port between substrate.The voltage retention of gained liquid crystal display cells and the evaluation of print are carried out according to above-described method.
In addition, adopting solids content concn is the solution of 6.0 weight %, carries out the printing evaluation according to above-described method.
Embodiment 2～8
Except polyimide, polyamic acid, specific compound use the material shown in the table 1, carry out according to flow process similarly to Example 1.
Embodiment 9
The polyimide (a-2) that makes in the polyimide synthesis example 2 is dissolved in N-N-methyl-2-2-pyrrolidone N-/butyl cellosolve mixed solvent (weight ratio 50/50), add 2 weight portion N with respect to 100 parts by weight polymer, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane adds 10 weight portion specific compounds (A-1) with respect to 100 parts by weight polymer, makes solution that solids content concn is 3.5 weight % and the solution of 6.0 weight %.After each solution fully stirred, be that the filter of 1 μ m filters, modulate aligning agent for liquid crystal of the present invention with the aperture.The evaluation method of the method for making of liquid crystal display cells, the evaluation method of liquid crystal display cells and alignment agent printing is carried out according to the method identical with embodiment 1.
Embodiment 10～12
Except specific compound uses the material shown in the table 1, carry out according to flow process similarly to Example 9.
Comparative example 1～2
Except polyimide, polyamic acid use the material shown in the table 1, and do not add beyond the specific compound, carry out according to flow process similarly to Example 1.
Comparative example 3
Except not adding specific compound, carry out according to flow process similarly to Example 9.
Comparative example 4～5
Except polyimide, polyamic acid use the material shown in the table 1, and use N, N '-diphenyl-N, N '-two (tolyl) biphenylamine (compound Z) to replace carrying out according to flow process similarly to Example 1 beyond the specific compound.
Comparative example 6
Except using N, N '-diphenyl-N, N '-two (tolyl) biphenylamine (compound Z) replace carrying out according to flow process similarly to Example 9 beyond the specific compound.
Table 1
| Polyimide | Polyamic acid | Specific compound | Voltage retention | Printing | ||
| Embodiment 1 | a-1 | b-1 | Specific compound A-1 | ＞99％ | ○ | ○ |
| Embodiment 2 | a-1 | b-1 | Specific compound B-1 | ＞99％ | ○ | ○ |
| Embodiment 3 | a-1 | b-1 | Specific compound A-4 | ＞99％ | ○ | ○ |
| Embodiment 4 | a-1 | b-1 | Specific compound B-4 | ＞99％ | ○ | ○ |
| Embodiment 5 | a-1 | b-2 | Specific compound A-3 | ＞99％ | ○ | ○ |
| Embodiment 6 | a-1 | b-2 | Specific compound B-3 | ＞99％ | ○ | ○ |
| Embodiment 7 | a-1 | b-2 | Specific compound A-4 | ＞99％ | ○ | ○ |
| Embodiment 8 | a-1 | b-2 | Specific compound B-4 | ＞99％ | ○ | ○ |
| Embodiment 9 | a-2 | - | Specific compound A-1 | ＞99％ | ○ | ○ |
| Embodiment 10 | a-2 | - | Specific compound B-1 | ＞99％ | ○ | ○ |
| Embodiment 11 | a-2 | - | Specific compound A-4 | ＞99％ | ○ | ○ |
| Embodiment 12 | a-2 | - | Specific compound B-4 | ＞99％ | ○ | ○ |
| Comparative example 1 | a-1 | b-1 | Do not have | ＞99％ | △ | ○ |
| Comparative example 2 | a-1 | b-2 | Do not have | ＞99％ | △ | ○ |
| Comparative example 3 | a-2 | - | Do not have | ＞99％ | △ | ○ |
| Comparative example 4 | a-1 | b-1 | Compound Z | 98％ | ○ | × |
| Comparative example 5 | a-1 | b-2 | Compound Z | 98％ | ○ | × |
| Comparative example 6 | a-2 | - | Compound Z | 98％ | ○ | × |
In the table, zero: excellent, △: good, *: poor
Claims (4)
1. aligning agent for liquid crystal, it is characterized in that containing at least a compound in the compound of the compound that is selected from following formula (A) expression and following formula (B) expression, and contain at least a polymkeric substance in the polyimide of the polyamic acid that is selected from following formula (I-1) expression and following formula (I-2) expression
In the formula, R
1～R
8Be that hydrogen atom or carbon number are 1～6 alkyl independently of one another, R
9And R
11Be phenyl or naphthyl, and R
10And R
12Be hydrogen atom or glycidyl independently of one another,
In the formula, R
13And R
14Be that hydrogen atom or carbon number are 1～6 alkyl independently of one another, R
15And R
17Be phenyl or naphthyl, R
16And R
18Be hydrogen atom or glycidyl independently of one another, and X represent divalent-CH
2-,-CH
2CH
2-,-O-or-NH-,
In the formula, P
1Be the organic group of 4 valencys, and Q
1Be the organic group of divalent,
In the formula, P
2Be the organic group of 4 valencys, and Q
2Organic group for divalent.
2. the described aligning agent for liquid crystal of claim 1, used tetrabasic carboxylic acid dicarboxylic anhydride comprised 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride during the polyimide of the polyamic acid of wherein above-mentioned formula (I-1) expression and above-mentioned formula (I-2) expression was synthetic.
3. liquid crystal orientation film, it adopts claim 1 or 2 described aligning agent for liquid crystal to make.
4. a liquid crystal display cells is characterized in that having the described liquid crystal orientation film of claim 3.
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| KR102273687B1 (en) | 2018-05-17 | 2021-07-05 | 주식회사 엘지화학 | Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film using the same |
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|---|---|---|---|---|
| US2407704A (en) * | 1944-01-01 | 1946-09-17 | Allied Chem & Dye Corp | Anthraquinone acid dyestuff |
| CN1140195A (en) * | 1994-05-17 | 1997-01-15 | 日本合成胶株式会社 | Liquid crystal aligning agent and liquid crystal display device |
| CN1540403A (en) * | 2003-04-22 | 2004-10-27 | Jsr株式会社 | Liquid crystal orientation agent |
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| JP3206401B2 (en) * | 1995-11-20 | 2001-09-10 | ジェイエスアール株式会社 | Liquid crystal alignment agent and liquid crystal display device |
| TWI291065B (en) | 2000-12-26 | 2007-12-11 | Nissan Chemical Ind Ltd | Diamines, polyimide precursors and polyimides produced by using the diamines, and liquid crystal aligning agents |
| JP4502119B2 (en) * | 2004-06-24 | 2010-07-14 | Ｊｓｒ株式会社 | Vertical liquid crystal display device having a reflective electrode |
| JP4434862B2 (en) * | 2004-07-08 | 2010-03-17 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2407704A (en) * | 1944-01-01 | 1946-09-17 | Allied Chem & Dye Corp | Anthraquinone acid dyestuff |
| CN1140195A (en) * | 1994-05-17 | 1997-01-15 | 日本合成胶株式会社 | Liquid crystal aligning agent and liquid crystal display device |
| CN1540403A (en) * | 2003-04-22 | 2004-10-27 | Jsr株式会社 | Liquid crystal orientation agent |
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| Title |
|---|
| JP昭61-296086A 1986.12.26 |
| JP特开平11-265004A 1999.09.28 |
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