CN101261403A - 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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- CN101261403A CN101261403A CNA2008100831230A CN200810083123A CN101261403A CN 101261403 A CN101261403 A CN 101261403A CN A2008100831230 A CNA2008100831230 A CN A2008100831230A CN 200810083123 A CN200810083123 A CN 200810083123A CN 101261403 A CN101261403 A CN 101261403A
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- liquid crystal
- aligning agent
- diamines
- methyl
- tetracarboxylic dianhydride
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- G02—OPTICS
- 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
Abstract
The invention relates to a liquid crystal aligning agent and a liquid crystal display element. The liquid crystal aligning agent includes: a polymer and/or imide polymer thereof that are prepared by reacting with at least one of selected two tetra carboxylic acid dianhydrides and at least one of selected four dianhydrides; a silicoorganic compound; and a solvent. The liquid crystal aligning agent has better printing property that can maintain high-voltage keeping rate of a liquid crystal aligning film of imide, and reduce accumulation electric charge. The liquid crystal display element is provided with the liquid crystal aligning film prepared by the liquid crystal aligning agent.
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 the aligning agent for liquid crystal that can form the good and liquid crystal orientation film that printing is good of electric property, and the liquid crystal display cells with the liquid crystal orientation film that makes by this aligning agent for liquid crystal.
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 the layer of nematic crystal 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).The liquid crystal display cells of MVA type, 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, the aligning agent for liquid crystal that makes its minimizing accumulate electric charge and have superior printing characteristics again when providing the liquid crystal orientation film that can make polyimide to keep high voltage holding ratio, and the liquid crystal display cells that adopts it.
According to the present invention, above-mentioned purpose of the present invention, first, reached by a kind of aligning agent for liquid crystal, it contains: by the prepared polymkeric substance of at least a reaction and/or its imide amination polymer at least a and diamines that is selected from following formula (3)～(6) expression among the tetracarboxylic dianhydride who is selected from following formula (1) and (2) expression; The compound of following formula (7) expression; And solvent;
(wherein, R
1～R
4Independently of one another for carbon number is that the alkyl of 1～40 straight chain shape, a chain or ring-type or carbon number are the thiazolinyl of 4～40 straight chain shape, a chain or ring-type, R
1～R
4Choose wantonly for 1～15 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),
(wherein, X
1For following formula (7-1) or (7-2) expression 1 valency group, m and n are 1～20 integer),
——R
5(C
2H
4O)
a(C
3H
6O)
bR
6 (7-1)
——R
5(C
2H
4O)
aR
6 (7-2)
(wherein, R
5Be methylene or polymethylene, R
6Be alkyl, a and b are 1～20 integer independently of one another).
According to the present invention, 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 aligning agent for liquid crystal.
Description of drawings
Fig. 1 is shown 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 polymkeric substance (hereinafter referred to as " specific polyamic acid ") and/or its imide amination polymer by at least a reaction gained at least a and diamines that is selected from above-mentioned formula (3)～(6) expression among the tetracarboxylic dianhydride who is selected from above-mentioned formula (1) and (2) expression.Below, the tetracarboxylic dianhydride and the diamines that can be used for the synthetic contained polymkeric substance of aligning agent for liquid crystal of the present invention described.
＜tetracarboxylic dianhydride 〉
Used tetracarboxylic dianhydride is contained and is selected from 2 of above-mentioned formula (1) expression in specific polyamic acid and/or its imide amination polymer synthetic, 3, the 5-(2 of 5-tricarboxylic basic ring amyl group acetic acid dianhydride and above-mentioned formula (2) expression, 5-dioxo tetrahydrochysene-3-furyl)-and 3-methyl-3-cyclohexene-1, at least a (hereinafter referred to as " the specific tetracarboxylic dianhydride ") in the 2-dicarboxylic acid anhydride.
When specific polyamic acid and/or its imide amination polymer synthetic, except that specific tetracarboxylic dianhydride, can also other tetracarboxylic dianhydrides of coupling.As other tetracarboxylic dianhydrides, can enumerate for example ester ring type tetracarboxylic dianhydride (except the wherein specific tetracarboxylic dianhydride), aliphatics tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.
As above-mentioned ester ring type 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, 2,3,4,5-tetrahydrofuran tetracarboxylic 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, 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)-and 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), 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 (I) or (II) compound etc. of expression,
(wherein, R
7And R
9Expression has the divalent organic group of aromatic rings, R
8And R
10Expression hydrogen atom or alkyl, the R of a plurality of existence
8And R
10Separately can be identical, also can be different).
As above-mentioned aliphatics tetracarboxylic dianhydride, can enumerate for example butane tetracarboxylic acid dianhydride etc.
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 (8)～(11) expression etc.
These other tetracarboxylic dianhydrides can be used alone or in combination of two or more.
Among above-mentioned other tetracarboxylic dianhydrides, from making the angle of the good liquid crystal aligning of its performance, as the ester ring type tetracarboxylic dianhydride, preferred 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-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-tricarboxylic basic ring amyl group acetic acid 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, 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-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)-and 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), the compound of following formula (15) expression in the compound of following formula (12)～(14) expression in the compound of above-mentioned formula (I) expression or the compound of above-mentioned formula (II) expression
As particularly preferred, can enumerate 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c] furans-1, the 3-diketone, cis-3,7-dibutyl ring suffering-1,5-diene-1,2,5, the 6-tetracarboxylic dianhydride, 1,2,4-tricarboxylic basic ring amyl group acetic acid dianhydride, 3,5,6-three carbonyls-2-carboxyl norbornane-2:3, the 5:6-dianhydride, 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, the compound of 4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone) or above-mentioned formula (12) expression.
Among above-mentioned other tetracarboxylic dianhydrides,, can enumerate butane tetracarboxylic acid dianhydride, pyromellitic acid dianhydride, 3 as preferred aliphatics tetracarboxylic dianhydride or aromatic tetracarboxylic acid's dianhydride, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-diphenyl sulfone tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydride or 1,4,5,8-naphthalene tetracarboxylic acid dianhydride.
As other tetracarboxylic dianhydrides, preferably use the ester ring type tetracarboxylic dianhydride.
When specific polyamic acid synthetic, when with specific tetracarboxylic dianhydride and other tetracarboxylic dianhydride's couplings, specific tetracarboxylic dianhydride's usage ratio is preferably 50 moles more than the % with respect to whole tetracarboxylic dianhydrides.
＜diamines 〉
Used diamines is at least a (hereinafter referred to as " specific diamines ") in the diamines that is selected from above-mentioned formula (3)～(6) expression in specific polyamic acid and/or its imide amination polymer synthetic.
When specific polyamic acid and/or its imide amination polymer synthetic, except that specific diamines, can also other diamines of coupling.As other diamines, can enumerate the diamines that has the nitrogen-atoms beyond two primary amino radicals and this primary amino radical in for example aromatic diamine, aliphatics or ester ring type diamines, the molecule, diamido organosiloxane etc.
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 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 (16) expression etc.,
(in the formula, R
11The expression carbon number is 1～12 alkyl, the R of a plurality of existence
11Can be the same or different separately, p is 1～3 integer, and q is 1～20 integer).
These other diamines can separately or be used in combination.
In these other diamines, preferred p-phenylenediamine (PPD), the 2-methyl isophthalic acid, the 4-phenylenediamine, 2-ethyl-1, the 4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,5-diethyl-1, the 4-phenylenediamine, 2,3,5,6-tetramethyl-1, the 4-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 2,2 '-dimethyl-4,4 '-benzidine, 1, the 5-diaminonaphthalene, 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 '-(to the phenylene diisopropylidene) diphenylamine, 4,4 '-(metaphenylene 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 or N-phenyl-3,6-diamido carbazole, more preferably 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-1,4-phenylenediamine or 2,3,5,6-tetramethyl-1,4-phenylenediamine.
In the time will improving the tilt angle expression power of aligning agent for liquid crystal of the present invention, except that specific diamines and optional above-mentioned other diamines that use, can also coupling be selected from following formula (Q-1)
(wherein, X
2For singly-bound ,-O-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-,-S-or arlydene, R
12Be 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) and the diamines of following formula (Q-2) expression at least a diamines.
(wherein, X
3For singly-bound ,-O-,-CO-,-COO-,-OCO-,-NHCO-,-CONH-,-S-or arlydene, R
13Being that carbon number is 4～40 the divalent organic group with ester ring type skeleton) they can a kind ofly be used alone or in combination of two or more.
In the above-mentioned formula (Q-1), as R
12The 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)
12With the R in the above-mentioned formula (Q-2)
13The 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)
12The 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.
X in the above-mentioned formula (Q-1)
2With the X in the above-mentioned formula (Q-2)
3For 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
2And X
3, be preferably especially-O-,-COO-,-group that OCO-represents.
Preferred concrete example as the diamines of group with 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 (17)～(26) expression.
As the preferred concrete example of the diamines of group, can enumerate the compound of following formula (27)～(29) expression with above-mentioned formula (Q-2) expression.
Wherein, as particularly preferred, can enumerate the compound of above-mentioned formula (17), (18), (23), (24) or (27) expression.
When specific polyamic acid synthetic when with specific diamines and other diamines and/or above-mentioned formula (Q-1) or (Q-2) during the diamines coupling of expression, the usage ratio of specific diamines is with respect to whole diamines, be preferably 1 mole more than the %, be preferably 5 moles especially more than the %.
Synthesizing of＜specific polyamic acid 〉
Below, the synthetic method of the specific polyamic acid that can contain in the aligning agent for liquid crystal of the present invention is described.
Specific polyamic acid can by with above-mentioned specific tetracarboxylic dianhydride and other tetracarboxylic dianhydrides as required 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 0.5～72 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 synthetic method of the imide amination polymer of＜specific polyamic acid 〉
Next, the synthetic method to the imide amination polymer of the specific polyamic acid that can contain in the aligning agent for liquid crystal of the present invention describes.
The imide amination polymer of specific polyamic acid can be by synthesizing part or all dehydration closed-loop in the amic acid structure that above-mentioned specific polyamic acid had.The ratio (below, be also referred to as " imidizate rate ") that has the repetitive of imide ring in whole repetitives of the imide amination polymer that can use in the present invention 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 make the image retention elimination time of gained liquid crystal orientation film shorter.
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 gained imide amination polymer 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 imide amination polymer.
＜end modified type polymkeric substance 〉
Used specific polyamic acid or its imide amination polymer 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, naphthyl isocyanate 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 polymkeric substance 〉
In the aligning agent for liquid crystal of the present invention, under the situation of not damaging effect of the present invention, the part of above-mentioned specific polyamic acid or its imide amination polymer can be replaced by at least a (hereinafter referred to as " other polymkeric substance ") that be selected from other polyamic acids and the imide amination polymer thereof.
Above-mentioned other polymkeric substance so long as polyamic acid or its imide amination polymer beyond the specific polyamic acid then have no particular limits it, are preferably polymkeric substance or its imide amination polymer by above-mentioned other tetracarboxylic dianhydrides and other diamine reactant gained.As other tetracarboxylic dianhydrides used herein, be preferably ester ring type tetracarboxylic dianhydride or aromatic tetracarboxylic acid's dianhydride, preferred especially 1,2,3,4-cyclo-butane tetracarboxylic dianhydride or pyromellitic acid dianhydride.As other diamines used herein, the optimization aromatic diamines, preferred especially 4,4 '-diaminodiphenyl-methane.
Synthesizing of this other polymkeric substance, can adopt other tetracarboxylic dianhydrides and other diamines to replace specific tetracarboxylic dianhydride and specific diamines, similarly carry out with the synthetic of specific polyamic acid and imide amination polymer thereof.
When aligning agent for liquid crystal of the present invention contained other polymkeric substance, the use amount of other polymkeric substance with respect to the total amount of specific polyamic acid and imide amination polymer and other polymkeric substance, was preferably below the 80 weight %, more preferably below the 60 weight %.
＜organo-silicon compound 〉
Aligning agent for liquid crystal of the present invention further contains the compound (below, be called " organo-silicon compound ") of above-mentioned formula (7) expression.
As radicals X in the above-mentioned formula (7)
1The R that is had
5Methylene or polymethylene, for example can enumerate particularly-CH
2-,-(CH
2)
2-,-(CH
2)
3-,-(CH
2)
4-etc.As R
6Alkyl, preferred carbon number is 1～10 alkyl.
The usage ratio of the organo-silicon compound in the aligning agent for liquid crystal of the present invention, with respect to the total amount of specific polyamic acid of 100 weight portions and imide amination polymer thereof (hereinafter referred to as " the total amount of polymkeric substance ".In addition, when aligning agent for liquid crystal of the present invention contained other polymkeric substance, " the total amount of polymkeric substance " was meant the total amount of specific polyamic acid and imide amination polymer and other polymkeric substance.Be preferably 0.01～3 weight portion, more preferably 0.1～2 weight portion down together).By making its consumption drop on this scope, it is good and can form the aligning agent for liquid crystal of the good liquid crystal orientation film of electric property to obtain printing.
＜other adjuvants 〉
Aligning agent for liquid crystal of the present invention contains at least a, the organo-silicon compound that are selected from above-mentioned specific polyamic acid and the imide amination polymer thereof and following solvent as essential composition, but in the scope of not damaging effect of the present invention, can also contain other adjuvants.As this other adjuvants, can enumerate the compound that contains functional silanes (hereinafter referred to as " other contain the compound of functional silanes ") that has in the molecule for example beyond the compound of two above epoxy radicals, the above-mentioned organo-silicon compound etc.
The compound (hereinafter referred to as " epoxy compounds ") that has two above epoxy radicals in the above-mentioned molecule can be to add for the printing that further improves the liquid crystal orientation film that is made by aligning agent for liquid crystal of the present invention.Object lesson as this epoxy compounds, preferably 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 usage ratio of epoxy compounds in the aligning agent for liquid crystal of the present invention with respect to the total amount of 100 parts by weight polymer, is preferably below 50 weight portions, more preferably 0.1～40 weight portion, more preferably 1～30 weight portion.
Other contain the compound of functional silanes, can be the angle of the bounding force of substrate to be considered and interpolation by the liquid crystal orientation film that aligning agent for liquid crystal of the present invention makes from further raising.Contain the object lesson of the compound of functional silanes as this other, 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.These other contain the blending ratio of the compound of functional silanes, with respect to the total amount of 100 parts by weight polymer, be preferably below 10 weight portions, more preferably 0.01～5 weight portion.
＜solvent 〉
As the solvent that aligning agent for liquid crystal of the present invention contained, be preferably organic solvent, particularly 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 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, diethyl carbitol, the ethyl carbitol acetic acid esters, butyl carbitol, triglyme, isobutyric acid isopentyl ester, isoamyl oxide etc.They can use separately, perhaps also can two or more mixing use.Particularly preferred solvent composition is the composition that makes above-mentioned solvent combination gained, is that the polymkeric substance in the alignment agent is separated out, and makes the alignment agent surface tension drop on the composition of 25～40mN/m scope.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention is to be selected from least a, organo-silicon compound in above-mentioned specific polyamic acid and the imide amination polymer thereof and solvent as essential composition, optional contain other adjuvants, preferably be modulated into and make the dissolving of the composition beyond the solvent in the aligning agent for liquid crystal be contained in solution state in the solvent.
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 the scope of preferred 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, thereby can not obtain good liquid crystal orientation film, and the viscosity that aligning agent for liquid crystal can occur increases the situation that causes applying the characteristic variation.
In addition, particularly preferred solids content concn scope, the method that is adopted when aligning agent for liquid crystal is coated on substrate and difference.For example, when adopting spin-coating method, be preferably the scope of 1.5～4.5 weight % especially.When adopting print process, especially preferably making solids content concn is the scope of 3～9 weight %, like this, can make solution viscosity drop on the scope of 12～50mPas.When adopting ink-jet method, especially preferably making solids content concn is the scope of 1～5 weight %, like this, can make solution viscosity drop on 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.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 removed organic solvent after applying, formation is filmed as alignment films, when aligning agent for liquid crystal of the present invention contains the polymkeric substance with amic acid structure, can also after the formation of filming, 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 usually.Like this, making films goes up generation liquid crystal molecular orientation energy, 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; the processing of carrying out the part irradiation ultraviolet radiation 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) and tilt angle being 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), make the vertical mutually or antiparallel of 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]
Prepare 127mm (D) * 127mm (W) * 1.1mm (H) glass substrate that on whole an of side, has formed as the ITO film of transparency electrode in advance, (Japan's description printing (strain) is made to adopt liquid crystal orientation film to be coated with the application printing machine, model " ォ Application グ ス ト ロ one マ one S-40L "), the aligning agent for liquid crystal that with the solids content concn that makes in each embodiment or the comparative example is 5 weight % is coated on the transparency electrode face of this glass substrate after the millipore filter that with the aperture is 0.2 μ m filters.Substrate after the coating by the heating plate driving fit formula pre-dryers that is set at 80 ℃ remove desolvate after, 200 ℃ of heating 10 minutes down, be about filming of 0.06 μ m again thereby on the glass substrate that has the ITO film, form thickness.The range estimation and by microscopic examination this is filmed, there are not pore or the uneven situation of coating to be judged as " excellent ", the situation of observing pore slightly or coating uneven (thickness is unequal) is judged as " very ", and the situation of significantly observing pore or coating inequality is judged as " bad ".
[evaluation of voltage retention]
Except adopting the glass substrate that has formed the ITO electrode that pattern that thickness is about 1mm forms on the one side, and it is beyond the aligning agent for liquid crystal of 3.5 weight % that aligning agent for liquid crystal adopts the solids content concn that makes in each embodiment or the comparative example, similarly makes a pair of (two) with above-mentioned [printing evaluation] and has 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.
[print evaluation]
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.That does not find print fully is designated as zero, and the Δ that is designated as of more weak print takes place.
Synthesis example
The synthesis example of＜specific diamines 〉
Synthesis example A-1 (synthesizing of 1-(3, the 5-diamino-phenyl)-3-octadecyl succinimide)
Add 12.81g (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 24.64g (0.07mol) octadecyl 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 30g (yield 83%) 1-(3, the 5-dinitrophenyl)-3-octadecyl succinimide with dry after the methanol wash.
Then, in 500ml flask by the nitrogen ventilation, add 30g (0.058mol) above synthetic 1-(3, the 5-dinitrophenyl)-3-octadecyl 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 14.6g (0.032mol, yield 55%) target product 1-(3, the 5-diamino-phenyl)-3-octadecyl succinimide.
Synthesis example A-2 (synthesizing of 1-(3, the 5-diamino-phenyl)-3-dodecyl succinimide)
Except using alternative 24.64g (0.07mol) the octadecyl succinic anhydride of 18.76g (0.07mol) dodecyl succinic anhydride, A-1 similarly operates with synthesis example, make 11g (0.030mol, yield 51%) 1-(3, the 5-diamino-phenyl)-3-dodecyl succinimide.
Synthesis example A-3 (synthesizing of 1-(3, the 5-diamino-phenyl)-3-heptadecyl-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 (8.0mmol) cupric iodide, 400ml ether and the 160ml HMPA (HMPA) that makes more than the 16.4g (80mmol), 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 600ml ether, add 600ml 4N-sulfuric acid, make solution become acidity.The water layer that separates is further washed with the 600ml 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 14.0g (0.04mol, yield 50%) 3-heptadecyl-4-methyl maleic anhydride.
In 200ml three-neck flask, add 6.4g (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-heptadecyl-4-methyl maleic anhydride that makes more than the 12.3g (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 14.6g (0.029mol, yield 81%) 1-(3, the 5-dinitrophenyl)-3-heptadecyl-4-methyl maleimide with dry after the methanol wash.
Then, in 300ml flask by the nitrogen ventilation, add 13.4g (0.026mol) 1-(3, the 5-dinitrophenyl)-3-heptadecyl-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 6.6g (0.015mol, yield 56%) target product 1-(3, the 5-diamino-phenyl)-3-heptadecyl-4-methyl maleimide with gained crude product heating for dissolving.
Synthesis example A-4 (synthesizing of 1-(3, the 5-diamino-phenyl)-3-hexadecane oxygen ylmethyl-4-methyl maleimide)
In 300ml three-neck flask, add 12.81g (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 synthesis example A-3.After reaction solution is cooled to room temperature, add 70ml methyl alcohol, leave standstill a night.Leach solid constituent,, obtain 18.9g (0.051mol, 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, 12.9g (0.049mol) 1-cetyl alcohol sodium salt and 100ml dimethyl sulfoxide (DMSO) 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 20.8g (0.039mol, yield 80%) 1-(3, the 5-dinitrophenyl)-3-hexadecane oxygen ylmethyl-4-methyl maleimide with dry after the methanol wash.
Then, in 300ml flask by the nitrogen ventilation, add 13.8g (0.026mol) 1-(3, the 5-dinitrophenyl)-3-hexadecane oxygen 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 8.2g (0.018mol, yield 67%) target product 1-(3, the 5-diamino-phenyl)-3-hexadecane oxygen ylmethyl-4-methyl maleimide with gained crude product heating for dissolving.
The synthesis example of＜specific polyamic acid and imide amination polymer thereof 〉
Synthesis example P-1～P-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 of amic acid unit in the solution, add the acetic anhydride of the pyridine of 3.0 times of moles and 3.0 times of moles 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 P-9 and P-10
Except diamines and tetracarboxylic dianhydride use in the table 1 listed, similarly make polyamic acid (A-9) and (A-10) with synthesis example P-1～P-8.In addition, in synthesis example P-9 and P-10, do not carry out the dehydration closed-loop reaction of polyamic acid.
Table 1
| Synthesis example | Diamine compound (mol ratio) | Acid anhydrides (mol ratio) | Polyamic acid | Imide amination polymer | Imidizate rate (%) |
| P-1 | Specific diamines A (20), diamines 1 (80) | T-1(20)，T-2(80) | A-1 | B-1 | 88 |
| P-2 | Specific diamines A (20), diamines 1 (80) | T-1(50)，T-2(50) | A-2 | B-2 | 82 |
| P-3 | Specific diamines B (20), diamines 1 (80) | T-1(20)，T-2(80) | A-3 | B-3 | 86 |
| P-4 | Specific diamines B (20), diamines 1 (80) | T-1(50)，T-2(50) | A-4 | B-4 | 81 |
| P-5 | Specific diamines C (20), diamines 1 (80) | T-1(20)，T-2(80) | A-5 | B-5 | 87 |
| P-6 | Specific diamines C (20), diamines 1 (80) | T-1(50)，T-2(50) | A-6 | B-6 | 83 |
| P-7 | Specific diamines D (20), diamines 1 (80) | T-1(20)，T-2(80) | A-7 | B-7 | 86 |
| P-8 | Specific diamines D (20), diamines 1 (80) | T-1(50)，T-2(50) | A-8 | B-8 | 80 |
| P-9 | Diamines 1 (100) | T-3(100) | A-9 | - | - |
| P-10 | Diamines 1 (100) | T-3(80)，T-4(20) | A-10 | - | - |
In the table 1, for diamines and tetracarboxylic dianhydride, the numeral content ratio (mol ratio) in the bracket, the abbreviation implication in the table is as follows.
＜diamines 〉
Specific diamines A:1-(3, the 5-diamino-phenyl)-3-octadecyl succinimide
Specific diamines B:1-(3, the 5-diamino-phenyl)-3-dodecyl succinimide
Specific diamines C:1-(3, the 5-diamino-phenyl)-3-heptadecyl-4-methyl maleimide
Specific diamines D:1-(3, the 5-diamino-phenyl)-3-hexadecane oxygen 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
Measure the SHIN-ETSU HANTOTAI polysiloxane KF-6011 (trade name of 0.005 weight portion with the polyamic acid A-9 (weight ratio 50: 50) that makes among the imide amination polymer B-1 that makes among the synthesis example P-1 and the synthesis example P-9 and with respect to 100 parts by weight polymer totals as organo-silicon compound, SHIN-ETSU HANTOTAI's chemical industry (strain) is produced, PEG-11 methyl ether dimethicone) be dissolved in gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/butyl cellosolve mixed solution (weight ratio 40: 30: 30), 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 the aligning agent for liquid crystal of two kinds of concentration.Wherein, solids content concn is that the viscosity of aligning agent for liquid crystal of 3.5 weight % is as shown in table 2.
Adopt these aligning agent for liquid crystal, carry out the evaluation of printing, voltage retention and print according to the method described above.The results are shown in table 5.
Embodiment 2～36
Except the kind of polymkeric substance and organo-silicon compound and consumption are as shown in table 2, modulate the aligning agent for liquid crystal 2～36 of 3.5 weight % and two kinds of concentration of 5 weight % similarly to Example 1 respectively.Solids content concn is that the viscosity of aligning agent for liquid crystal of 3.5 weight % is as shown in table 2.
And, adopt the table 5 that the results are shown in that these aligning agent for liquid crystal estimate according to the method described above.
Table 2
In the table 2, the abbreviation of organo-silicon compound is respectively following implication.
KF-6011: trade name " the polysiloxane KF-6011 of SHIN-ETSU HANTOTAI ", SHIN-ETSU HANTOTAI's chemical industry (strain) is produced, PEG-11 methyl ether dimethicone
KF-6012: trade name " the polysiloxane KF-6012 of SHIN-ETSU HANTOTAI ", SHIN-ETSU HANTOTAI's chemical industry (strain) is produced, PEG/PPG-20/22 butyl ether dimethicone
SH3773M: trade name ， East レ ダ ウ コ one ニ Application グ シ リ コ one Application (strain) is produced, polyoxyethylene methyl polysiloxane multipolymer
SH3749: trade name ， East レ ダ ウ コ one ニ Application グ シ リ コ one Application (strain) is produced, poly-(oxygen ethylene oxy propylene) methyl polysiloxane multipolymer
Embodiment 37
With the polyamic acid A-9 (weight ratio 50: 50) that makes among the imide amination polymer B-1 that makes among the synthesis example P-1 and the synthesis example P-9, measure the SHIN-ETSU HANTOTAI polysiloxane KF-6011 of 0.005 weight portion with respect to 100 parts by weight polymer totals as organo-silicon compound, and (molecular weight: about 400) be dissolved in gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/butyl cellosolve mixed solution (weight ratio 40: 30: 30), making solids content concn is two kinds of solution of 3.5 weight % and 5 weight % as the polyethyleneglycol diglycidylether of epoxy compounds to measure 20 weight portions with respect to 100 parts by weight polymer totals.With these solution is the filter filtration of 0.2 μ m with the aperture respectively, makes the aligning agent for liquid crystal of two kinds of concentration.Wherein, solids content concn is that the viscosity of aligning agent for liquid crystal of 3.5 weight % is as shown in table 3.
In addition, adopt these aligning agent for liquid crystal, that estimates according to the method described above the results are shown in table 5.
Embodiment 38～42
Except the kind of used organo-silicon compound and epoxy compounds is as shown in table 3, similarly modulate each aligning agent for liquid crystal of two kinds of concentration respectively with embodiment 37.Solids content concn is that the viscosity of aligning agent for liquid crystal of 3.5 weight % is as shown in table 3.
And, adopt the table 5 that the results are shown in that these aligning agent for liquid crystal estimate according to the method described above.
Table 3
| Embodiment | Polymkeric substance (weight ratio of components) | Organo-silicon compound | Epoxy compounds | Viscosity/solids content 3.5% (mPas) |
| 37 | B-1/A-9(50/50) | KF-6011 | Epoxy radicals A | 6.2 |
| 38 | B-1/A-9(50/50) | KF-6011 | Epoxy radicals B | 6.2 |
| 39 | B-1/A-9(50/50) | KF-6011 | Epoxy radicals C | 6.2 |
| 40 | B-1/A-9(50/50) | KF-6011 | Epoxy radicals D | 6.2 |
| 41 | B-1/A-9(50/50) | KF-6011 | Epoxy radicals E | 6.2 |
| 42 | B-1/A-9(50/50) | KF-6011 | Epoxy radicals F | 6.2 |
In the table 3, identical in the implication that organo-silicon compound are called for short and the table 2.The implication that epoxy radicals chemical combination is called for short is as follows.
Epoxy radicals A: polyethyleneglycol diglycidylether (molecular weight is about 400)
Epoxy radicals B:1, the 6-hexanediol diglycidyl ether
Epoxy radicals C:N, N, N ', N '-four glycidyl group-2,2 '-dimethyl-4,4 '-benzidine
Epoxy radicals D:N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane
Epoxy radicals E:1,3-two (N, N-diglycidyl amino methyl) cyclohexane
Epoxy radicals F:N, N, N ', N '-four glycidyl group-m-xylene diamine
Comparative example 1～8
Except not using organo-silicon compound, similarly modulate each aligning agent for liquid crystal of two kinds of concentration respectively with embodiment 1,5,9,13,17,21,25 and 29.Wherein, solids content concn is that the viscosity of aligning agent for liquid crystal of 3.5 weight % is as shown in table 4.
Adopt the table 5 that the results are shown in that these aligning agent for liquid crystal estimate according to the method described above.
Table 4
| Comparative example | Polymkeric substance (weight ratio of components) | Organo-silicon compound | Viscosity/solids content 3.5% (mPas) |
| 1 | B-1/A-9(50/50) | Do not have | 6.2 |
| 2 | B-2/A-9(50/50) | Do not have | 6.6 |
| 3 | B-3/A-9(50/50) | Do not have | 6.1 |
| 4 | B-4/A-9(50/50) | Do not have | 6.7 |
| 5 | B-5/A-9(50/50) | Do not have | 6.2 |
| 6 | B-6/A-9(50/50) | Do not have | 6.8 |
| 7 | B-7/A-9(50/50) | Do not have | 6.2 |
| 8 | B-8/A-9(50/50) | Do not have | 6.6 |
Table 5
Claims (3)
1. aligning agent for liquid crystal is characterized in that containing:
By the prepared polymkeric substance of at least a reaction and/or its imide amination polymer at least a and diamines that is selected from following formula (3)～(6) expression among the tetracarboxylic dianhydride who is selected from following formula (1) and (2) expression;
The compound of following formula (7) expression;
And solvent;
Wherein, R
1～R
4Independently of one another for carbon number is that the alkyl of 1～40 straight chain shape, a chain or ring-type or carbon number are the thiazolinyl of 4～40 straight chain shape, a chain or ring-type, R
1～R
4Choose wantonly for 1～15 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,
Wherein, X
1For following formula (7-1) or (7-2) expression 1 valency group, m and n are 1～20 integer,
——R
5(C
2H
4O)
a(C
3H
6O)
bR
6 (7-1)
——R
5(C
2H
4O)
aR
6 (7-2)
R wherein
5Be methylene or polymethylene, R
6Be alkyl, a and b are 1～20 integer independently of one another.
2. the described aligning agent for liquid crystal of claim 1, it further contains the compound that has two above epoxy radicals in the molecule.
3. a liquid crystal display cells is characterized in that having the liquid crystal orientation film that is made by claim 1 or 2 described aligning agent for liquid crystal.
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| JP2007056250 | 2007-03-06 | ||
| JP2007056250 | 2007-03-06 |
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|---|---|
| JP (1) | JP5013105B2 (en) |
| KR (1) | KR101017491B1 (en) |
| CN (1) | CN101261403A (en) |
| TW (1) | TWI457667B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329626A (en) * | 2010-06-30 | 2012-01-25 | Jsr株式会社 | Formation method, liquid crystal display device and the compound of liquid crystal aligning agent, liquid crystal orientation film |
| CN101805450B (en) * | 2009-02-12 | 2013-01-02 | Jsr株式会社 | Radiation-sensitive polyorganosiloxane, method for producing the same and liquid crystal aligning agent |
| 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 |
| CN111566554A (en) * | 2018-03-07 | 2020-08-21 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal element |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI431039B (en) | 2009-12-16 | 2014-03-21 | Cheil Ind Inc | Liquid crystal photo-alignment agent, liquid crystal photo-alignment layer manufactured using the same, and liquid crystal display device including the liquid crystal photo-alignment layer |
| CN102559205B (en) | 2010-12-29 | 2014-07-30 | 第一毛织株式会社 | Liquid crystal alignment agent, liquid crystal alignment film manufactured using the same, and liquid crystal display device |
| KR101444190B1 (en) | 2011-12-19 | 2014-09-26 | 제일모직 주식회사 | Liquid crystal alignment agent, liquid crystal alignment film using the same, and liquid crystal display device including the liquid crystal alignment film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1997043687A1 (en) * | 1996-05-16 | 1997-11-20 | Jsr Corporation | Liquid crystal aligning agent |
| CN1274345A (en) * | 1998-07-29 | 2000-11-22 | 智索股份有限公司 | Novel diamino compounds, polyamic acid, polyimide, liquid-crystal alignment film made from film of polyimide, and liquid-crystal display element containing same |
| JP2003049069A (en) * | 2001-08-07 | 2003-02-21 | Jsr Corp | Liquid crystal-orienting agent and liquid crystal display element |
| KR100491944B1 (en) * | 2002-12-09 | 2005-05-30 | 한국화학연구원 | Polyimide derivatives with pendant imide group and method for preparing them |
| KR100622026B1 (en) * | 2004-10-29 | 2006-09-19 | 한국화학연구원 | Insulator containing soluble polyimides and organic thin film transistor using them |
| KR100559264B1 (en) * | 2004-10-29 | 2006-03-15 | 한국화학연구원 | Composition of containing polyamic acid blends and liquid crystal alignment layer and cell using them |
| JP5209844B2 (en) * | 2004-11-30 | 2013-06-12 | 株式会社リコー | ELECTRONIC DEVICE AND METHOD FOR MANUFACTURING THE SAME, OPERATION ELEMENT AND DISPLAY ELEMENT |
| US8293371B2 (en) * | 2005-01-21 | 2012-10-23 | Mitsubishi Gas Chemical Company, Inc. | Polyimide resin, polyimide film, and polyimide laminate |
| KR20070035683A (en) * | 2005-09-28 | 2007-04-02 | 삼성전자주식회사 | Liquid crystal display and method for manufacturing the same |
| KR100782437B1 (en) * | 2005-12-30 | 2007-12-05 | 제일모직주식회사 | Alignment Agent of Liquid Crystal |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101805450B (en) * | 2009-02-12 | 2013-01-02 | Jsr株式会社 | Radiation-sensitive polyorganosiloxane, method for producing the same and liquid crystal aligning agent |
| CN102329626A (en) * | 2010-06-30 | 2012-01-25 | Jsr株式会社 | Formation method, liquid crystal display device and the compound of liquid crystal aligning agent, liquid crystal orientation film |
| CN102329626B (en) * | 2010-06-30 | 2015-01-14 | Jsr株式会社 | Liquid crystal aligning agent, method for forming liquid crystal alignment film, liquid crystal display device, and related compounds |
| 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 |
| CN111566554A (en) * | 2018-03-07 | 2020-08-21 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal element |
| CN111566554B (en) * | 2018-03-07 | 2023-07-18 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element and manufacturing method thereof |
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| TW200848884A (en) | 2008-12-16 |
| KR20080081846A (en) | 2008-09-10 |
| TWI457667B (en) | 2014-10-21 |
| JP5013105B2 (en) | 2012-08-29 |
| JP2008250301A (en) | 2008-10-16 |
| KR101017491B1 (en) | 2011-02-25 |
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