CN101261404B - Liquid crystal oriented agent and liquid crystal display element - Google Patents
Liquid crystal oriented agent and liquid crystal display element Download PDFInfo
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- CN101261404B CN101261404B CN2008100831245A CN200810083124A CN101261404B CN 101261404 B CN101261404 B CN 101261404B CN 2008100831245 A CN2008100831245 A CN 2008100831245A CN 200810083124 A CN200810083124 A CN 200810083124A CN 101261404 B CN101261404 B CN 101261404B
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- 0 CCC(CC)(C(C)(C)CN)[Si](*)(*)OC(C)(C)[Si](*)(*)C(C)(C)CN Chemical compound CCC(CC)(C(C)(C)CN)[Si](*)(*)OC(C)(C)[Si](*)(*)C(C)(C)CN 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- G—PHYSICS
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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
本发明涉及一种液晶取向剂和液晶显示元件，该液晶取向剂含有具有下述式(I-1)表示的结构单元的聚合物，式(I-1)中，P1为4价的有机基团，Q1为2价基团。本发明的液晶取向剂具有优良的印刷性，其能形成垂直取向性优良、在维持电压保持率的同时又使蓄积电荷减少的液晶取向膜。本发明的液晶显示元件具有由上述液晶取向剂形成的液晶取向膜，其显示性能优良。 The present invention relates to a liquid crystal aligning agent and a liquid crystal display element. The liquid crystal aligning agent contains a polymer having a structural unit represented by the following formula (I-1). In the formula (I-1), P is a tetravalent organic Group, Q 1 is a divalent group. The liquid crystal aligning agent of the present invention has excellent printability, and can form a liquid crystal aligning film that is excellent in vertical alignment and can reduce accumulated charges while maintaining voltage retention. The liquid crystal display element of this invention has the liquid crystal aligning film formed from the said liquid crystal aligning agent, and is excellent in display performance.
Description
Technical field
The present invention relates to be used to form the aligning agent for liquid crystal of the liquid crystal orientation film of liquid crystal display cells, and liquid crystal display cells.More particularly, relate to can form that vertical orientated property is good, electric property is good and the aligning agent for liquid crystal of the liquid crystal orientation film that printing is good, and display performance liquid crystal display device with excellent.
Background technology
At present, as liquid crystal display cells, known TN type liquid crystal display cells with so-called TN (twisted-nematic) type liquid crystal cell, it forms the liquid crystal orientation film that is formed by polyamic acid, polyimide etc. on the substrate surface that is provided with ITO nesa coatings such as (indium oxide-tin oxide), as the used for liquid crystal display element substrate, two 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 (supertwist is to row) type liquid crystal display cells 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.
In addition, also proposed on nesa coating to form projection with the vertical alignment-type liquid crystal display device that is called MVA (multi-domain vertical alignment) type of the direction of orientation of control liquid crystal (refer to Patent Document 1 and non-patent literature 1).MVA type liquid crystal display cells, not only visual angle, contrast etc. are good, and can not need to carry out grinding process etc. in the process that forms liquid crystal orientation film, also are good aspect manufacturing process.
As the liquid crystal orientation film that is applicable to above-mentioned TN, STN and MVA type, require to have the short electric property that waits of image retention elimination time of liquid crystal display cells.And,, require in hectographic printing, to have superior printing characteristics as forming the used alignment agent of these liquid crystal orientation films.
[patent documentation 1] Japanese kokai publication hei 11-258605 communique
[patent documentation 2] Japanese kokai publication hei 6-222366 communique
[patent documentation 3] Japanese kokai publication hei 6-281937 communique
[patent documentation 4] Japanese kokai publication hei 5-107544 communique
[non-patent literature 1] " liquid crystal " Vol.3 (No.2), p117 (1999)
Summary of the invention
The present invention is based on above-mentioned situation and makes, its objective is, provide can form vertical orientated property good, when keeping voltage retention, make again and accumulate liquid crystal orientation film that electric charge reduces and aligning agent for liquid crystal, and the liquid crystal display cells that adopts it with good printing.
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, the first, to reach by a kind of aligning agent for liquid crystal, it contains the polymkeric substance of the structural unit with following formula (I-1) expression,
(in the formula (I-1), P
1Be the organic group of 4 valencys, Q
1Divalent group for following formula (II-1)～(II-4) expression),
(in the formula (II-1)～(II-4), R
1～R
4Independently of one another for carbon number is that the alkyl of 1～11 straight chain shape, a chain or ring-type or carbon number are the thiazolinyl of 4～11 straight chain shape, a chain or ring-type, R
1～R
4Choose wantonly for 1～7 in the hydrogen atom that is had and to be replaced A by fluorine atom
1And A
2Be hydrogen atom or methyl independently of one another).
Aligning agent for liquid crystal of the present invention preferably further contains the structural unit with following formula (I-2) expression and does not have the polymkeric substance of the structural unit of above-mentioned formula (I-1) expression,
(in the formula (I-2), P
2Be the organic group of 4 valencys, Q
2Organic group for divalent).
Above-mentioned purpose of the present invention, the second, to reach by a kind of liquid crystal display cells, it has the liquid crystal orientation film that is made by above-mentioned arbitrary aligning agent for liquid crystal.
Description of drawings
Fig. 1 is expressed as print evaluation in embodiment and the comparative example and the synoptic diagram of the ITO electrode pattern of the liquid crystal display cells made.
Embodiment
Aligning agent for liquid crystal of the present invention contains the polymkeric substance (hereinafter referred to as " particular polymers ") of the structural unit (hereinafter referred to as " structural unit (I-1) ") with above-mentioned formula (I-1) expression.
＜particular polymers 〉
As P in the above-mentioned formula (I-1)
14 valency organic groups, can enumerate 4 valency organic groups, the 4 valency organic groups of from fatty compound, removing 4 hydrogen atom gained, have 4 valency organic groups of aromatic rings etc. with ester ring type structure, as its preferred group, can enumerate 4 valency organic groups of following formula (III-1)～(III-4) expression particularly.
In the 4 valency organic groups of above-mentioned formula (III-1)～(III-4) expression, preferred especially above-mentioned formula (III-1) or the 4 valency organic groups of (III-2) representing.
Q in the above-mentioned general formula (I-1)
1Divalent group for above-mentioned formula (II-1)～(II-4) expression.
In the scope of not damaging effect of the present invention, particular polymers can also have structural unit (I-1) other structural units in addition.Here, so-called other structural units are meant in the above-mentioned general formula (I-1) Q
1Structural unit for above-mentioned formula (II-1)～(II-4) divalent organic group in addition.The ratio of structural unit (I-1) is preferably 10 moles more than the % in the entire infrastructure unit of particular polymers, more preferably 20 moles more than the %.
This particular polymers can be by making following formula (III ') expression tetracarboxylic dianhydride and the diamines that is selected from following formula (II-1 ')～(II-4 ') expression in the amic acid cell mesh that had of the polyamic acid (below be also referred to as " specific polyamic acid ") of at least a reaction gained or all imidizate make
(in the above-mentioned formula, P
1Identical with the implication in the above-mentioned formula (I-1)),
(above-mentioned formula (II-1 ')～(II-4 ') in, R
1～R
4And A
1And A
2Identical with the implication in the above-mentioned formula (II-1)～(II-4)).P in the above-mentioned formula (I-1)
1Derive from the P in the above-mentioned formula (III ')
1, Q
2Derive from the structure that each diamines of above-mentioned formula (II-1 ')～(II-4 ') is removed two amino gained that it had respectively.
Below, preferred tetracarboxylic dianhydride and the diamines that uses in the contained particular polymers of aligning agent for liquid crystal of the present invention synthetic described.
＜tetracarboxylic dianhydride 〉
Used tetracarboxylic dianhydride be the compound that above-mentioned formula (III ') is represented in above-mentioned particular polymers synthetic, can enumerate for example aliphatics tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.
As above-mentioned aliphatics tetracarboxylic dianhydride, can enumerate for example butane tetracarboxylic acid dianhydride etc.
As above-mentioned alicyclic tetracarboxylic dianhydride, for example can enumerate 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, cis-3,7-dibutyl ring suffering-1,5-diene-1,2,5, the 6-tetracarboxylic dianhydride, 3,5,6-three carbonyls-2-carboxyl norbornane-2:3,5:6-dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 1,2,4-tricarboxylic basic ring amyl group acetic acid dianhydride, Fourth Ring [4,4,0,1
2,5, 1
7,10] dodecane-3,4,8, the 9-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 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)-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)-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)-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-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, the 5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid anhydride, dicyclo [2.2.2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 4,9-two oxatricyclo [5.3.1.0
2,6] undecane-3,5,8,10-tetraketone, following formula (a) or (b) compound etc. of expression,
(formula (a) and (b) in, R
5And R
7Expression has the divalent organic group of aromatic rings, R
6And R
8Expression hydrogen atom or alkyl, the R of a plurality of existence
6And R
8Separately can be identical, also can be different).
As above-mentioned aromatic tetracarboxylic acid's dianhydride, can enumerate for example pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dianhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two O-phthalic acid dianhydrides, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, two (phthalic acid) phosphniline oxide dianhydride, to phenylene-two (triphenyl phthalic acid) dianhydride, metaphenylene-two (triphenyl phthalic acid) dianhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl ether dianhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl methane dianhydride, 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), the compound of following formula (1)～(4) expression etc.
These tetracarboxylic dianhydrides can a kind ofly be used alone or in combination of two or more.
Among these tetracarboxylic dianhydrides, from making the angle of the good liquid crystal aligning of its performance, preferred butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 5-(2, the 5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid 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)-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)-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, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, the compound of following formula (8) expression in the compound of following formula (5)～(7) expression in the compound of above-mentioned formula (a) expression or the compound of above-mentioned formula (b) expression
More preferably 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 5-(2,5-dioxo tetrahydrochysene-3-furyl)-and 3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid anhydride, 1,3,3a, 4,5,9b-six hydrogen-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-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-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-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, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), the compound of pyromellitic acid dianhydride or above-mentioned formula (5) expression, 2,3 of more preferably following formula (III-1 ')～(III-4 ') expression, 5-tricarboxylic basic ring amyl group acetic acid dianhydride, 5-(2, the 5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid anhydride, 1,2,3,4-cyclo-butane tetracarboxylic dianhydride or pyromellitic acid dianhydride
The compound of preferred especially above-mentioned formula (III-1 ') or (III-2 ') expression.
In the synthetic aligning agent for liquid crystal of the present invention among the used tetracarboxylic dianhydride of contained particular polymers, the total consumption of the compound of above-mentioned formula (III-1 ')～(III-4 ') expression is with respect to whole tetracarboxylic dianhydrides' consumption, be preferably 20 moles more than the %, more preferably 40 moles more than the %.In addition, the total consumption of the compound of above-mentioned formula (III-1 ') or (III-2 ') expression is preferably 60 moles more than the % with respect to whole tetracarboxylic dianhydrides' consumption, more preferably 80 moles more than the %.
＜diamines 〉
The used preferred diamines of synthetic particular polymers of the present invention is at least a (hereinafter referred to as " specific diamines ") in the compound that is selected from above-mentioned formula (II-1 ')～(II-4 ') expression.
In the diamines of above-mentioned formula (II-1 ')～(II-4 ') expression, as R
1～R
4The carbon number of expression is 1～11 straight chain shape alkyl, can enumerate for example n-hexyl, n-octyl, positive decyl etc.;
As branched-chain alkyl, can enumerate for example 1-methyl hexyl, 1-ethylhexyl, 2-methyl hexyl, 2-ethylhexyl, 1-ethyl octyl group, 2-ethyl octyl group, 3-ethyl octyl group, 1,2-dimethyl hexyl, 1,2-diethylhexyl, 1,2-dimethyl octyl group 1-methyl decyl, 2-methyl decyl etc.;
As cyclic alkyl, can enumerate the group of for example removing a hydrogen atom gained from cycloalkanes such as cyclo-butane, cyclopentane, cyclohexane, cyclodecane, norbornane, double-octane, dicyclo undecane, diamantane.
As R
1～R
4The carbon number of expression is 4～11 straight chain shape, chain or ring-type thiazolinyl, can enumerate the group that changes two keys more than in the carbon-carbon bond that above-mentioned illustrative alkyl has.
When particular polymers synthetic, except specific diamines, can also other diamines of coupling, make particular polymers except that structure unit (I-1), also contain other structural units.
As this other diamines, can enumerate the diamines that has the nitrogen-atoms beyond two primary amino radicals and this primary amino radical in aliphatics for example or ester ring type diamines, the molecule, diamido organosiloxane, aromatic diamine etc.
As above-mentioned aliphatics or ester ring type diamines, for example can enumerate 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 (cyclohexylamine) etc.;
As the diamines that has two primary amino radicals and this primary amino radical nitrogen-atoms in addition in the above-mentioned molecule, for example can enumerate 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-1,3,5-triazines, 1,4-two (3-aminopropyl) piperazine, 2,4-diamido-6-isopropoxy-1,3,5-triazines, 2,4-diamido-6-methoxyl-1,3, the 5-triazine, 2,4-diamido-6-phenyl-1,3, the 5-triazine, 2,4-diamido-6-methyl-s-triazine, 2, the 4-diaminostilbene, 3, the 5-triazine, 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 etc.;
As above-mentioned diamido organosiloxane, can enumerate the compound of for example following formula (9) expression etc.,
(in the formula (9), a plurality of R
9Be 1～12 alkyl independently of one another for carbon number, p is 1～3 integer, and q is 1～20 integer);
As above-mentioned aromatic diamine, can enumerate for example p-phenylenediamine (PPD), the 2-methyl isophthalic acid, the 4-phenylenediamine, 2-ethyl-1, the 4-phenylenediamine, 2,5-dimethyl-1, the 4-phenylenediamine, 2,5-diethyl-1, the 4-phenylenediamine, 2,3,5,6-tetramethyl-1, the 4-phenylenediamine, m-phenylene diamine, 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, 3,3-dimethyl-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 '-(to the phenylene isopropylidene) diphenylamine, 4,4 '-(metaphenylene 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]-octafluoro biphenyl, 3,6-diamido carbazole, N-methyl-3,6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole, the following formula (Q-1) or (Q-2) compound etc. of expression
(formula (Q-1) and (Q-2) in, X be independently of one another singly-bound ,-O-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-,-S-, arlydene, R
10Be 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, R
11Be that carbon number is 4～40 the divalent organic group with ester ring type skeleton).
In the above-mentioned formula (Q-1), as R
10The 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.
R as above-mentioned formula (Q-1)
10With the R in the above-mentioned formula (Q-2)
11The carbon number of expression is 4～40 1 valency with ester ring type skeleton or divalent organic group, 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 norbornane, diamantane etc.Wherein, the group that especially preferably has steroid backbone.Above-mentioned organic group with ester ring type skeleton, part or all of the hydrogen atom that it had is optional can be replaced by halogen atom (preferred fluorine atom) or fluoro-alkyl (preferred trifluoromethyl).
R as above-mentioned formula (Q-1)
10The 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 6～20 straight chained alkyl; Carbon numbers such as cyclohexyl, ring octyl group are 6～20 ester ring type alkyl; Carbon number such as phenyl, xenyl is part or all group that is replaced by fluoro-alkyls such as fluorine atom or trifluoromethyls of hydrogen atom in 6～20 the organic groups such as aromatic hydrocarbyl.
Above-mentioned formula (Q-1) and (Q-2) in X be singly-bound ,-O-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-,-S-or arlydene, as arlydene, can enumerate for example phenylene, methylene phenyl, biphenylene, naphthylene etc.As X, be preferably especially-O-,-COO-,-group that OCO-represents.
Preferred concrete example as the diamines of above-mentioned formula (Q-1) expression, 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 or following formula (10)～(19) expression.
As the preferred concrete example of the diamines of above-mentioned formula (Q-2) expression, can enumerate the compound of following formula (20)～(22) expression.
Wherein, as particularly preferred, can enumerate the compound of above-mentioned formula (10), (11), (16), (17) or (20) expression.
When with specific diamines and other diamines couplings, the usage ratio of specific diamines is preferably 10 moles more than the % with respect to whole diamines, is preferably 20 moles especially more than the % when particular polymers synthetic.
Synthesizing of＜particular polymers 〉
Below, the preferred synthetic method of particular polymers is described.
Particular polymers can synthesize by part or all dehydration closed-loop in the amic acid structure that above-mentioned tetracarboxylic dianhydride and specific diamines and the prepared specific polyamic acid of other diamine reactants as required (hereinafter referred to as " specific polyamic acid ") are had.
Below, at first the synthetic method to specific polyamic acid describes, and next reaction describes to the dehydration closed-loop of specific polyamic acid again.
Synthesizing of＜specific polyamic acid 〉
Specific polyamic acid can by with above-mentioned tetracarboxylic dianhydride and specific diamines and other diamines as required preferably in organic solvent, preferably-20 ℃～150 ℃, more preferably under 0～100 ℃ the temperature conditions, preferably make its reaction 1～30 hour and synthesize.
Supply with the tetracarboxylic dianhydride of specific polyamic acid synthetic reaction and the usage ratio of diamines, preferably with respect to the amino of 1 equivalent diamines, the anhydride group that makes the tetracarboxylic dianhydride is the ratio of 0.5～2 equivalent, more preferably is the ratio of 0.7～1.2 equivalent.
Here, as organic solvent, as long as can dissolve synthetic specific 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 tetracarboxylic dianhydride and diamine compound be the amount of 0.1～30 weight % with respect to the ratio (volumetric molar concentration) of the total amount (alpha+beta) of reaction solution to the consumption of organic solvent (α).
In the above-mentioned organic solvent, in the scope that the specific polyamic acid that does not make generation is separated out, the poor solvent alcohols of all right specific polyamic acid of coupling, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc.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, isoamyl propionate, isoamyl isobutyrate, isoamyl oxide etc.
As mentioned above, obtained dissolving the reaction solution of specific polyamic acid.Then, this reaction solution is put in a large amount of poor solvents, obtained precipitate,, can get polyamic acid by this precipitate of drying under reduced pressure or with reaction solution evaporator decompression distillation.And, this specific polyamic acid is dissolved in the organic solvent once more, with poor solvent it is separated out then, or use the evaporator decompression distillation, carry out once or this operation several times, can make with extra care specific polyamic acid.
The specific polyamic acid that so makes has the structural unit of following formula (I-3) expression,
(in the formula (I-3), P
1And Q
1Identical with implication in the above-mentioned formula (I-1) respectively).
The dehydration closed-loop reaction of＜specific polyamic acid 〉
Particular polymers contained in the aligning agent for liquid crystal of the present invention can be by synthesizing part or all dehydration closed-loop in the amic acid structural unit that above-mentioned specific polyamic acid had.
Dehydration closed-loop reaction by specific polyamic acid can be imide structure with the amic acid thaumatropy, thereby make particular polymers.In the particular polymers, imide structure unit number a accounts for the total number purpose ratio (a/ (a+b)) that imide structure unit number a and amic acid structural unit are counted b, and promptly the imidizate rate of particular polymers is preferably 50～100%, and more preferably 70～100%.The imidizate rate of polymkeric substance can be by polymkeric substance
1H-NMR obtains by following formula (1).
Imidizate rate (%)=(1-A1/A2 * α) * 100 (1)
(in the formula (1), A1 comes near the peak area of NH base proton chemical shifts 10ppm, A2 is near the peak area of chemical shift 7～8ppm that comes from aromatic protons, and α is with respect to NH matrix in the polyamic acid before the imidization reaction, the number ratio of aromatic protons).
The dehydration closed-loop reaction of specific polyamic acid can be by the method for the specific polyamic acid of (i) heating, perhaps (ii) specific 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.
In the method for the specific polyamic acid of heating of above-mentioned (i), temperature of reaction 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 the polymkeric substance behind the gained dehydration closed-loop then can occur.
On the other hand, in the above-mentioned method of in specific 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 specific polyamic acid, is 0.01～20 mole.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.As used organic solvent in the dehydration closed-loop reaction, can enumerate as specific polyamic acid and synthesize middle solvent for use and illustrative organic solvent.The temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 10～150 ℃.By the reaction solution that so obtains is carried out with specific polyamic acid process for purification in same operation, can make with extra care the gained particular polymers.
＜end modified type polymkeric substance 〉
Used particular polymers among the present invention can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting.By using 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 specific 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.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.As the monoisocyanates compound, can enumerate for example phenyl isocyanate, isocyanic acid naphthyl ester etc.
The solution viscosity of＜polymkeric substance 〉
The as above specific polyamic acid and the imide amination polymer thereof of gained preferably when the solution that is made into 10%, have the viscosity of 20～800mPas, more preferably have the viscosity of 30～500mPas.
In addition, the solution viscosity of polymkeric substance (mPas) is to adopt specified solvent, and dilution is that 10% solution adopts E type rotational viscosimeter to measure down at 25 ℃ to solids content concn.
＜other compositions 〉
Aligning agent for liquid crystal of the present invention contains above-mentioned particular polymers as essential composition, but can also further randomly contain other compositions.As this other adjuvants, can enumerate polymkeric substance beyond the particular polymers for example, functional silanes compound, epoxy compounds etc.
＜other polymkeric substance 〉
In the aligning agent for liquid crystal of the present invention, except that above-mentioned particular polymers, can also preferably further contain particular polymers polymkeric substance (hereinafter referred to as " other polymkeric substance ") in addition.Other polymkeric substance are preferably the structural unit with above-mentioned formula (I-2) expression and do not have the polymkeric substance of the structural unit of above-mentioned formula (I-1) expression.
Preferred P in the above-mentioned formula (I-2)
2With preferred P in the above-mentioned formula (I-1)
1Identical, Q
2Be preferably the structural unit group in addition of above-mentioned formula (II-1)～(II-4) expression.
This preferred other polymkeric substance can adopt spendable above-mentioned tetracarboxylic dianhydride and other diamines in particular polymers is synthetic, similarly synthesize with the synthetic of specific polyamic acid.
As can be the tetracarboxylic dianhydride of use in other polymkeric substance synthetic, optimization aromatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride can preferably use pyromellitic acid dianhydride or 1,2,3 especially, 4-cyclo-butane tetracarboxylic dianhydride.As can be at the diamines of use in other polymkeric substance synthetic, the optimization aromatic diamines can preferably use 4,4 '-diaminodiphenyl-methane especially.
The consumption of other polymkeric substance (is meant the whole of particular polymers and other polymkeric substance with respect to whole polymkeric substance.Total amount down together) is preferably below 90 weight portions, more preferably 20～80 weight portions.
＜functional silanes compound 〉
Above-mentioned functional silanes compound can be for further improving the gained liquid crystal orientation film cohesive of substrate surface to be added.Object lesson as this functional silanes compound, 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.
The consumption of functional silanes compound respectively with respect to the whole polymkeric substance of 100 weight portions, is preferably below 2 weight portions, more preferably 0.2 weight portion.
＜epoxy compounds 〉
As above-mentioned 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-benzyl amine, N, N-diglycidyl-amino methyl cyclohexane etc.
The consumption of epoxy compounds respectively with respect to the whole polymkeric substance of 100 weight portions, is preferably below 40 weight portions, more preferably 0.1～30 weight portion.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention is modulated into particular polymers and optional other composition preferred dissolutions that add and is contained in solution state in the organic solvent.
As the organic solvent that constitutes aligning agent for liquid crystal of the present invention, can enumerate as solvent for use in the specific polyamic acid synthetic reaction and illustrative solvent.In addition, can also suitably select coupling as poor solvent that can coupling when the specific polyamic acid synthetic reaction and illustrative poor solvent.
As particularly preferred organic solvent used in the aligning agent for liquid crystal of the present invention, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, 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, propionic acid isopentyl ester, isobutyric acid isopentyl ester, isoamyl oxide, 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, diethyl carbitol, the ethyl carbitol acetic acid esters, butyl carbitol, triglyme etc.They can use separately, perhaps also can two or more mixing use.The composition of particularly preferred solvent composition for above-mentioned solvent combination is obtained, polymkeric substance is not separated out in the alignment agent, and the surface tension of alignment agent is at the composition of the scope of 25～40mN/m.
Solids content concn in the aligning agent for liquid crystal of the present invention (the total weight of the composition beyond desolventizing in the aligning agent for liquid crystal is divided by the value of the general assembly (TW) of aligning agent for liquid crystal) is considered viscosity, volatility etc. and is selected.Be preferably the scope of 1～10 weight %.That is to say, 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; On the other hand, when solids content concn surpasses 10 weight %, will cause coating thickness blocked up, and can not obtain good liquid crystal orientation film equally, and the viscosity of aligning agent for liquid crystal increases, and causes applying the 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 %, and thus, special preferred solution viscosity is the scope of 12～50mPas.Use the occasion of ink jet printing method, solids content concn is the scope of 1～5 weight %, and thus, special preferred solution viscosity is the scope of 3～15mPas.
Temperature when modulating aligning agent for liquid crystal of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
＜liquid crystal display cells 〉
Liquid crystal display cells of the present invention is characterised in that to have the liquid crystal orientation film that is made by the aligning agent for liquid crystal of the present invention that as above obtains.
Liquid crystal display cells of the present invention can be made by for example following operation (1)～(3).
(1) by suitable coating methods such as hectographic printing method, spin-coating method or ink jet printing methods, 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,, applicator surface films by being added thermosetting.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, polycarbonate etc.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 pattern of these nesa coatings adopts photoetch method or use the method etc. of mask in advance when nesa coating forms.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.Heating-up temperature behind the coated with liquid crystal alignment agent is preferably 80～300 ℃, more preferably 120～250 ℃.In addition, aligning agent for liquid crystal of the present invention is by removing organic solvent after its coating, can form filming as liquid crystal orientation film, when aligning agent for liquid crystal of the present invention contains the polymkeric substance with amic acid structure, can also further make amic acid structure dehydration closed-loop, to form filming of further imidizate by heating.
The thickness of filming that forms is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) then, the film coated surface that forms is as mentioned above 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, making films goes up the orientation energy that produces liquid crystal molecule, makes liquid crystal orientation film.In addition; to the liquid crystal orientation film that forms by aligning agent for liquid crystal of the present invention; carry out shown in patent documentation 2 (Japanese kokai publication hei 6-222366 communique) for example or the patent documentation 3 (Japanese kokai publication hei 6-281937 communique); part irradiation ultraviolet radiation and processing that tilt angle is changed; perhaps carrying out the liquid crystal orientation film upper surface after implementing grinding process shown in the patent documentation 4 (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 field-of-view characteristics of liquid crystal display cells like this.
(3) make two substrates as formation liquid crystal orientation film as described in above (1) or (2), two substrates are staggered relatively by gap (box gap), so that the mutually vertical or antiparallel of the polishing direction of liquid crystal orientation film separately, fitted with sealant in two 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 " (manufacturing of メ Le Network company) 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.
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.
In following embodiment, comparative example, the evaluation of the aligning agent for liquid crystal modulated is carried out according to following method.
[printing evaluation]
(Japan's description printing (strain) is made to adopt liquid crystal orientation film to be coated with the application printing machine, model " オ Application グ ス ト ロ one マ one S-40L "), with the solids content concn of modulating in each embodiment or the comparative example is the aligning agent for liquid crystal of 5 weight %, and being coated in thickness in continuous 10 minutes with certain amount is on the ITO film system nesa coating set on the one side of glass substrate of 1mm.After carrying out 10 minutes continuously coatings,, form the overlay film that thickness is about 0.06 μ m 200 ℃ of heating 60 minutes down.This overlay film of visual observations has or not coating uneven, almost do not observe coating uneven be chosen as grade 1, significantly observe the uneven situation of coating and be chosen as class 5, printing is estimated with 5 grades.
[evaluation of voltage retention]
Forming on the one side on the ITO electrode of glass substrate of pattern-like ITO electrode that thickness is about 1mm, adopting spin-coating method to apply the solids content concn of modulating in each embodiment or the comparative example is the aligning agent for liquid crystal of 3.5 weight %, heated 60 minutes down at 200 ℃, make a pair of (two) and have the glass substrate of filming that thickness is about 0.06 μ m.
Next, on each outer rim of the above-mentioned liquid crystal orientation film coated substrate of a pair of transparency electrode/transparency carrier with liquid crystal orientation film, except that liquid crystal injecting port, it is the epoxy adhesive of the alumina balls of 5.5 μ m that coating has added diameter, the liquid crystal aligning face is relatively overlapped and pressing, bonding agent is solidified.Then, between substrate, fill nematic crystal (minus, the manufacturing of メ Le Network company by liquid crystal injecting port, MLC-6608) after, with the acrylic compounds Photocurable adhesive liquid crystal injecting port is sealed, the polaroid of fitting on the two sides in the substrate outside is made liquid crystal display cells.
At room temperature in 16.7 milliseconds time span, this liquid crystal display cells is applied the voltage of 5V, the voltage application time is 60 microseconds, measures then from voltage and removes voltage retention after 16.7 milliseconds.Determinator adopts the (VHR-1 that strain) East Yang テ Network ニ カ makes.
[evaluation of vertical orientated property]
Adopt with above-mentioned [evaluation of voltage retention] in the same liquid crystal display cells of making, when under the cross Nicol prism, observing voltage and disconnecting and the state of orientation when applying 12V alternating current (peak-peak).Orientation homogeneous in the face, orientation is good, is designated as " zero ".
[print experiment]
Except the glass substrate that uses one side to be provided with to have the ITO film of pattern as shown in Figure 1, and similarly make liquid crystal display cells in above-mentioned [evaluation of voltage retention].
This liquid crystal display cells is at room temperature applied the DC voltage of 24 hours 6.0V to electrode A, apply the DC voltage of 24 hours 0.5V to electrode B.Voltage applies 0.1～5.0V DC voltage with the gradient of 0.1V respectively to electrode A and B after removing, and judges the print characteristic by the luminance difference of each voltage bottom electrode A and B.That is, when luminance difference was big, it is poor that the print characteristic is judged as.Do not find be designated as " zero " of print fully.
The synthesis example of＜monomer 〉
Monomer synthesis example 1 (synthesizing of 1-(3, the 5-diamino-phenyl)-3-decyl succinimide)
Add 12.82g (0.07mol) 3 in the 300ml three-neck flask by the nitrogen ventilation, 5-dinitroaniline and 70ml acetic acid stir while feed nitrogen, make the solid matter dissolving.To wherein adding 16.8g (0.07mol) decyl succinic anhydride, made its reaction in 20 hours in refluxed under nitrogen.After reactant liquor is cooled to room temperature, add 70ml methyl alcohol, leave standstill a night.Leach the solid of separating out,, obtain 23g (0.057mol, yield 81%) 1-(3, the 5-dinitrophenyl)-3-decyl succinimide with dry after the methanol wash.
Then, in 500ml flask by the nitrogen ventilation, add 22.7g (0.056mol) above synthetic 1-(3, the 5-dinitrophenyl)-3-decyl succinimide, 100ml ethanol, 100ml tetrahydrofuran (THF) and 25g reducing catalyst palladium carbon (Pd/C), stirred 1 hour down at 70 ℃.To wherein adding 42.5ml (43.75g) hydrazine monohydrate, reflux made its reaction in 6 hours.Leach Pd/C, filtrate is concentrated in rotary evaporator.After gained crude product heating for dissolving was in the N-N-methyl-2-2-pyrrolidone N-, the cooling recrystallization obtained 11.2g (0.032mol, yield 58%) target product 1-(3, the 5-diamino-phenyl)-3-decyl succinimide.
Monomer synthesis example 2 (synthesizing of 1-(3, the 5-diamino-phenyl)-3-octyl group succinimide)
Except using alternative 16.8g (0.07mol) decyl succinic anhydride of 14.84g (0.07mol) octyl group succinic anhydride, similarly operate with monomer synthesis example 1, make 8.88g (0.028mol, yield 50%) 1-(3, the 5-diamino-phenyl)-3-octyl group succinimide.
Monomer synthesis example 3 (synthesizing of 1-(3, the 5-diamino-phenyl)-3-undecyl-4-methyl maleimide)
In 2000ml three-neck flask, add 31.5g (0.25mol) dimethyl maleic anhydride, 89.0g (0.5mol) N-bromosuccinimide, 1.0g (4.15mmol) dibenzoyl peroxide and 1500ml phenixin, reflux 5 hours by the nitrogen ventilation.Reactant liquor is cooled to room temperature, at room temperature leave standstill a night after, filter.After the filtrate water washing, organic layer is concentrated in rotary evaporator.Gained oily crude product is distilled (120～125 ℃/2mmHg), obtain 20.0g (0.1mol, yield 39%) intermediate 3-bromomethyl-4-methyl maleic anhydride under high vacuum.
Then, after in 2000ml three-neck flask, adding 3-bromomethyl-4-methyl maleic anhydride, 1.52g (8mmol) cupric iodide, 400ml ether and the 160ml HMPA (HMPA) that makes more than the 16.4g (0.08mol), under the condition that feeds argon gas, be cooled to-5～0 ℃ by the argon gas ventilation.Stir on one side this potpourri, through about 20 minute drip the solution of the 400mmol bromination cetyl magnesium that is dissolved in 400ml ether in addition prepared on one side.Mixed liquor is gone up to room temperature, stirred again 8 hours.Then, after the dilution of this mixed solution usefulness 600ml ether, add 600ml 4N-sulfuric acid, make solution become acidity.The water layer that separates is washed with the 15ml ether, merge organic layer.Organic layer is washed with water, and after dewatering with sodium sulphate, concentrated solution in rotary evaporator obtains the crude product of oily.This crude product is made with extra care in the silicagel column of petrol ether/ethyl acetate (19: 1) mixed solution as eluting solvent, obtained 10.8g (yield 50%) 3-undecyl-4-methyl maleic anhydride.
In 200ml three-neck flask, add 6.41g (0.035mol) 3,5-dinitroaniline and 35ml acetic acid then by the nitrogen ventilation.Stir while feeding nitrogen, make the solid matter dissolving.To wherein adding the 3-undecyl-4-methyl maleic anhydride that makes more than the 9.31g (0.035mol), made its reaction in 20 hours in refluxed under nitrogen.After reactant liquor is cooled to room temperature, add 35ml methyl alcohol, leave standstill a night.Leach solid constituent,, obtain 12.3g (yield 82%) 1-(3, the 5-dinitrophenyl)-3-undecyl-4-methyl maleimide with dry after the methanol wash.
Then, in 300ml flask by the nitrogen ventilation, add 11.2g (0.026mol) 1-(3, the 5-dinitrophenyl)-3-undecyl-4-methyl maleimide, 50ml ethanol, 50ml THF and 12.5g reducing catalyst Pd/C, stirred 1 hour down at 70 ℃.Add 19ml (19.6g) hydrazine monohydrate then, reflux made its reaction in 6 hours.Leach Pd/C, filtrate is concentrated in rotary evaporator.In the N-N-methyl-2-2-pyrrolidone N-, the cooling recrystallization obtains 5.5g (0.015mol, yield 57%) target product 1-(3, the 5-diamino-phenyl)-3-undecyl-4-methyl maleimide with gained crude product heating for dissolving.
Monomer synthesis example 4 (synthesizing of 1-(3, the 5-diamino-phenyl)-3-oxygen in last of the ten Heavenly stems ylmethyl-4-methyl maleimide)
In 500ml three-neck flask, add 12.82g (0.07mol) 3, behind 5-dinitroaniline and the 70ml acetic acid, stir, make the solid matter dissolving while feed nitrogen by the nitrogen ventilation.To wherein adding 14.35g (0.07mol) 3-(the bromomethyl)-4-methyl maleic anhydride similarly synthetic, made its reaction in 20 hours in refluxed under nitrogen with the intermediate of monomer synthesis example 3.After reaction solution is cooled to room temperature, add 70ml methyl alcohol, leave standstill a night.Leach solid constituent,, obtain 18.9g (yield 73%) 1-(3, the 5-dinitrophenyl)-3-bromomethyl-4-methyl maleimide with dry after the methanol wash.
Then, in 500ml three-neck flask, add 18.1g (0.049mol) 1-(3 by the nitrogen ventilation, the 5-dinitrophenyl)-3-bromomethyl-4-methyl maleimide, 8.82g (0.049mol) 1-cetyl alcohol sodium salt and 100ml dimethyl sulfoxide after, stir down at 100 ℃ and to make its reaction in 10 hours.After reactant liquor is cooled to room temperature, add 70ml methyl alcohol, leave standstill a night.Leach solid constituent,, obtain 17.7g (yield 81%) 1-(3, the 5-dinitrophenyl)-3-oxygen in last of the ten Heavenly stems ylmethyl-4-methyl maleimide with dry after the methanol wash.
Then, in 300ml flask by the nitrogen ventilation, add 11.6g (0.026mol) 1-(3, the 5-dinitrophenyl)-3-oxygen in last of the ten Heavenly stems ylmethyl-4-methyl maleimide, 50ml ethanol, 50ml THF and 12.5g reducing catalyst Pd/C, stirred 1 hour down at 70 ℃.Add 19ml (19.6g) hydrazine monohydrate then, reflux made its reaction in 6 hours.Leach Pd/C, filtrate is concentrated in rotary evaporator.In the N-N-methyl-2-2-pyrrolidone N-, the cooling recrystallization obtains 6.5g (0.017mol, yield 65%) target product 1-(3, the 5-diamino-phenyl)-3-oxygen in last of the ten Heavenly stems ylmethyl-4-methyl maleimide with gained crude product heating for dissolving.
The synthesis example of＜polymkeric substance 〉
Synthesis example 1～8
In N-Methyl pyrrolidone, add diamines and the tetracarboxylic dianhydride who forms shown in the table 1 in proper order, be made into the solution that monomer concentration is 20 weight %, it was reacted 4 hours down at 60 ℃, obtain containing the solution of polyamic acid (A-1)～(A-8) according to it.In each polyamic acid solution of gained, with respect to the total amount (mole) of amic acid unit in the solution, add the acetic anhydride of the pyridine of 3.0 times of moles (equivalent) and 3.0 times of moles (equivalent) respectively after, 110 ℃ down heating carried out the dehydration closed-loop reaction in 4 hours.By gained solution is precipitated once more, reclaims and drying under reduced pressure, obtain imide amination polymer (B-1)～(B-8) in ether.The imidizate rate of these imide amination polymers is as shown in table 1.
Synthesis example 9,10
In N-Methyl pyrrolidone, add diamines and the tetracarboxylic dianhydride who forms shown in the table 1 in proper order, be made into the solution that monomer concentration is 20 weight %, it was reacted 4 hours down at 60 ℃ according to it.By gained solution is precipitated once more, reclaims and drying under reduced pressure, obtain polyamic acid (A-9) and (A-10) in ether.In addition, in polymkeric substance synthesis example 9 and 10, do not carry out imidization reaction.
Table 1
| Synthesis example | Diamines (mol ratio) | Tetracarboxylic dianhydride's (mol ratio) | Polyamic acid | Imide amination polymer | Imidizate rate (%) |
| 1 | Specific diamines A (20), diamines 1 (80) | T-1(20)，T-2(80) | A-1 | B-1 | 88 |
| 2 | Specific diamines A (20), diamines 1 (80) | T-1(50)，T-2(50) | A-2 | B-2 | 82 |
| 3 | Specific diamines B (20), diamines 1 (80) | T-1(20)，T-2(80) | A-3 | B-3 | 87 |
| 4 | Specific diamines B (20), diamines 1 (80) | T-1(50)，T-2(50) | A-4 | B-4 | 83 |
| 5 | Specific diamines C (20), diamines 1 (80) | T-1(20)，T-2(80) | A-5 | B-5 | 88 |
| 6 | Specific diamines C (20), diamines 1 (80) | T-1(50)，T-2(50) | A-6 | B-6 | 81 |
| 7 | Specific diamines D (20), diamines 1 (80) | T-1(20)，T-2(80) | A-7 | B-7 | 86 |
| 8 | Specific diamines D (20), diamines 1 (80) | T-1(50)，T-2(50) | A-8 | B-8 | 83 |
| 9 | Diamines 1 (100) | T-3(100) | A-9 | - | - |
| 10 | Diamines 1 (100) | T-3(80)，T-4(20) | A-10 | - | - |
In the table 1, for diamines and acid anhydrides, the numeral content ratio (mol ratio) in the bracket, the implication of symbol is as follows in the table.
＜diamines 〉
Specific diamines A:1-(3, the 5-diamino-phenyl)-3-decyl succinimide
Specific diamines B:1-(3, the 5-diamino-phenyl)-3-octyl group succinimide
Specific diamines C:1-(3, the 5-diamino-phenyl)-3-undecyl-4-methyl maleimide
Specific diamines D:1-(3, the 5-diamino-phenyl)-3-oxygen in last of the ten Heavenly stems ylmethyl-4-methyl maleimide
Diamines 1:4,4 '-diaminodiphenyl-methane
＜tetracarboxylic dianhydride 〉
T-1:2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride
T-2:5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid anhydride
T-3: pyromellitic acid dianhydride
T-4:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
Embodiment 1
The polyamic acid A-9 that makes in the imide amination polymer B-1 that makes in the synthesis example 1 and the synthesis example 9 is dissolved in gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/butyl cellosolve mixed solution (weight ratio 40: 30: 30), and making solids content concn is two kinds of solution of 3.5 weight % and 5 weight %.With these solution is the filter filtration of 0.2 μ m with the aperture respectively, makes two kinds of different aligning agent for liquid crystal of solids content concn.
Adopt these aligning agent for liquid crystal, carry out various evaluations according to the method described above.The results are shown in table 2.
Embodiment 2～14
The kind of the polymkeric substance that is cooperated and consumption are as shown in table 2, modulate aligning agent for liquid crystal similarly to Example 1 respectively in aligning agent for liquid crystal.Adopt the table 2 that the results are shown in that these alignment agents estimate according to the method described above.
Table 2
| Polymkeric substance (weight ratio of components) | Printing | Voltage retention | Vertical orientated property | ||
| Embodiment 1 | B-1/A-9(50/50) | Grade 2 | ＞99％ | ○ | ○ |
| Embodiment 2 | B-2/A-9(50/50) | Grade 2 | ＞99％ | ○ | ○ |
| Embodiment 3 | B-3/A-9(50/50) | Grade 1 | ＞99％ | ○ | ○ |
| Embodiment 4 | B-4/A-9(50/50) | Grade 1 | ＞99％ | ○ | ○ |
| Embodiment 5 | B-5/A-9(50/50) | Grade 2 | ＞99％ | ○ | ○ |
| Embodiment 6 | B-6/A-9(50/50) | Grade 2 | ＞99％ | ○ | ○ |
| Embodiment 7 | B-7/A-9(50/50) | Grade 2 | ＞99％ | ○ | ○ |
| Embodiment 8 | B-8/A-9(50/50) | Grade 2 | ＞99％ | ○ | ○ |
| Embodiment 9 | B-1/A-10(50/50) | Grade 2 | ＞99％ | ○ | ○ |
| Embodiment 10 | B-3/A-10(50/50) | Grade 2 | ＞99％ | ○ | ○ |
| Embodiment 11 | B-1/A-9(30/70) | Grade 1 | ＞99％ | ○ | ○ |
| Embodiment 12 | B-3/A-9(30/70) | Grade 1 | ＞99％ | ○ | ○ |
| Embodiment 13 | B-1(100) | Grade 2 | ＞99％ | ○ | ○ |
| Embodiment 14 | B-3(100) | Grade 1 | ＞99％ | ○ | ○ |
Claims (4)
1. aligning agent for liquid crystal is characterized in that containing the polymkeric substance of the structural unit with following formula (I-1) expression,
In the formula (I-1), P
1Be the organic group of 4 valencys from the group of following formula (III-1)～(III-4) expression, selected,
Q
1Be the divalent group of following formula (II-1)～(II-4) expression,
In the formula (II-1)～(II-4), R
1～R
4Independently of one another for carbon number is that the alkyl of 1～11 straight chain shape, a chain or ring-type or carbon number are the thiazolinyl of 4～11 straight chain shape, a chain or ring-type, R
1～R
4Choose wantonly for 1～7 in the hydrogen atom that is had and to be replaced A by fluorine atom
1And A
2Be hydrogen atom or methyl independently of one another.
2. the described aligning agent for liquid crystal of claim 1, the P in the wherein above-mentioned formula (I-1)
1In at least a portion have at least a in the structural unit that is selected from following formula (III-1) and (III-2) represents,
3. claim 1 or 2 described aligning agent for liquid crystal, the polymkeric substance that it further contains the structural unit with following formula (I-2) expression and does not have the structural unit of above-mentioned formula (I-1) expression,
In the formula (I-2), P
2Be the organic group of 4 valencys from the group of above-mentioned formula (III-1)～(III-4) expression, selected, Q
2Be the organic group of the divalent beyond the group of above-mentioned formula (II-1)～(II-4) expression, and derive from diamines, diamido organosiloxane or the aromatic diamine that has the nitrogen-atoms beyond two primary amino radicals and this primary amino radical in aliphatics or ester ring type diamines, the molecule.
4. a liquid crystal display cells is characterized in that having the liquid crystal orientation film that is formed by each described aligning agent for liquid crystal of claim 1～3.
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| JP2007-057758 | 2007-03-07 | ||
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| KR (1) | KR101042059B1 (en) |
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| KR102247840B1 (en) * | 2016-03-18 | 2021-05-03 | 제이에스알 가부시끼가이샤 | Substrate for display device, manufacturing method of the substrate for display device, and display device |
| CN105778929A (en) * | 2016-04-27 | 2016-07-20 | 深圳市道尔顿电子材料有限公司 | Liquid crystal orientation agent, diamine compound and polyamide acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0683418A2 (en) * | 1994-05-17 | 1995-11-22 | Japan Synthetic Rubber Co., Ltd. | Liquid crystal aligning agent and liquid crystal display device |
| US6685997B1 (en) * | 1999-04-09 | 2004-02-03 | Chisso Corporation | Varnish composition and liquid-crystal display element |
| CN1564840A (en) * | 2002-07-29 | 2005-01-12 | Jsr株式会社 | Diamine compound, polyamic acid, imide polymer, liquid crystal alignment agent and liquid crystal display |
| CN1779531A (en) * | 2004-11-26 | 2006-05-31 | Jsr株式会社 | Liquid crystal aligning agent and lateral field style liquid crystal display element |
| CN1922540A (en) * | 2004-02-26 | 2007-02-28 | 日产化学工业株式会社 | Liquid crystal aligning agent for photoalignment and liquid crystal display device utilizing the same |
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| KR100552135B1 (en) * | 2004-06-14 | 2006-02-14 | 한국화학연구원 | Liquid Crystal Alignment Film Composition |
| KR100552134B1 (en) * | 2004-06-14 | 2006-02-14 | 한국화학연구원 | Aliphatic Ring-Soluble Polyimide Resin with Alkyl Succinimide Side Chain |
| KR100559264B1 (en) * | 2004-10-29 | 2006-03-15 | 한국화학연구원 | Vertical alignment composition containing low polar polyamic acid resin, and liquid crystal aligning film and liquid crystal cell using the same |
| TWI432852B (en) * | 2005-07-12 | 2014-04-01 | Jsr Corp | Liquid crystal orientation agent and liquid crystal display device |
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- 2008-02-21 JP JP2008039747A patent/JP5088563B2/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0683418A2 (en) * | 1994-05-17 | 1995-11-22 | Japan Synthetic Rubber Co., Ltd. | Liquid crystal aligning agent and liquid crystal display device |
| US6685997B1 (en) * | 1999-04-09 | 2004-02-03 | Chisso Corporation | Varnish composition and liquid-crystal display element |
| CN1564840A (en) * | 2002-07-29 | 2005-01-12 | Jsr株式会社 | Diamine compound, polyamic acid, imide polymer, liquid crystal alignment agent and liquid crystal display |
| CN1922540A (en) * | 2004-02-26 | 2007-02-28 | 日产化学工业株式会社 | Liquid crystal aligning agent for photoalignment and liquid crystal display device utilizing the same |
| CN1779531A (en) * | 2004-11-26 | 2006-05-31 | Jsr株式会社 | Liquid crystal aligning agent and lateral field style liquid crystal display element |
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| KR101042059B1 (en) | 2011-06-16 |
| JP5088563B2 (en) | 2012-12-05 |
| KR20080082493A (en) | 2008-09-11 |
| JP2008250302A (en) | 2008-10-16 |
| TWI422930B (en) | 2014-01-11 |
| TW200844611A (en) | 2008-11-16 |
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