CN101458425A - 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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- CN101458425A CN101458425A CNA2008101718288A CN200810171828A CN101458425A CN 101458425 A CN101458425 A CN 101458425A CN A2008101718288 A CNA2008101718288 A CN A2008101718288A CN 200810171828 A CN200810171828 A CN 200810171828A CN 101458425 A CN101458425 A CN 101458425A
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- liquid crystal
- polyamic acid
- aligning agent
- dianhydride
- 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 provides a liquid crystal orientation agent not only suitable for TN type and STN type, but also suitable for a vertical orientation type liquid crystal displaying element and capable of forming liquid crystal orientation membrane with good liquid crystal orientation, voltage retention rate and excellent image retention performance. The liquid crystal orientation agent comprises at least one polymer selected from the groups constituted by polyamic acid and imide polymer thereof, wherein the polyamic acid is formed by reacting tetraearboxylic dianhydride with diamine and the tetraearboxylic dianhydride comprises 1,2,3,4-butanetetracarboxylic dianhydride and the diamine comprises compound represented by the above formula (1) and special compound using 3,5-bi(4-amino-benzamido)hexadecyl benzoate as represent.
Description
Technical field
The present invention relates to aligning agent for liquid crystal and liquid crystal display cells.More particularly, relate to the aligning agent for liquid crystal of the liquid crystal orientation film that can form voltage retention and image retention excellent performance and the liquid crystal display cells of image retention excellent performance.
Background technology
At present, as liquid crystal display cells, TN type liquid crystal display cells with so-called TN type (twisted-nematic) liquid crystal cell is widely known by the people, it forms liquid crystal orientation film on the substrate surface that is provided with nesa coatings such as ITO (indium oxide-tin oxide) film, substrate as used for liquid crystal display element, 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.In addition, also developed to compare and to have reached the more STN of high-contrast (supertwist is to row) type liquid crystal display cells with TN type liquid crystal display cells.The orientation of liquid crystal molecule is usually by the liquid crystal orientation film control of having carried out grinding process in above-mentioned TN type and the STN type liquid crystal display cells.
By contrast, also developed projection be set on nesa coating, and by the improvement of its control liquid crystal molecular orientation the MVA of viewing angle properties (multi-domain vertical alignment) type liquid crystal display cells (referring to patent documentation 1 and non-patent literature 1), by EVA (strengthening vertical orientated) the type liquid crystal display cells (referring to non-patent literature 2) of special electrode structure control liquid crystal molecular orientation, the vertical alignment-type liquid crystal display device vertical alignment-type liquid crystal display devices such as (referring to non-patent literatures 3) of employing optical alignment method.These vertical alignment-type liquid crystal display device viewing angle properties, contrast etc. are good, and can not carry out grinding process etc. in the process that forms liquid crystal orientation film, thereby also are good aspect manufacturing process.But, to compare with above-mentioned TN type, STN type liquid crystal display cells, performance also is not very good, particularly needs to improve the performance of aspects such as vertical orientated property and liquid crystal display cells image retention performance.
For addressing the above problem, attempted being conceived to the relation of voltage retention and image retention performance, to be used for liquid crystal orientation film by having allylic diamine compound synthetic polyimide or its imide amination polymer, to improve voltage retention, and improve residual performance (referring to patent documentation 2) thus, even but adopt this technology, it is good inadequately that the improvement of image retention performance remains.
In addition, also attempted using by containing 1,2,3, the polyamic acid that the tetracarboxylic dianhydride of 4-cyclo-butane tetracarboxylic dianhydride and pyromellitic acid dianhydride synthesizes improves voltage retention, residual charge, image retention performance (referring to patent documentation 3～6) as aligning agent for liquid crystal, has the problem that can not obtain enough voltage retention when still adopting these technology.
[patent documentation 1] Japanese kokai publication hei 11-258605 communique
[patent documentation 2] international WO2005/052028 trumpeter's volume that discloses
[patent documentation 3] Japanese Patent Application 2001-206168 communique
[patent documentation 4] Japanese Unexamined Patent Application Publication 2001-510497 communique
[patent documentation 5] TOHKEMY 2001-296525 communique
[patent documentation 6] Japanese kokai publication hei 10-197875 communique
[patent documentation 7] Japanese kokai publication hei 6-222366 communique
[patent documentation 8] Japanese kokai publication hei 6-281939 communique
[patent documentation 9] Japanese kokai publication hei 5-107544 communique
[non-patent literature 1] " liquid crystal ", Vol.3, No.2, p117 (1999).
[non-patent literature 2] " liquid crystal ", Vol.3, No.4, p272 (1999).
[non-patent literature 3] " Jpn Appl.phys. ", Vol.36, p428 (1997)
Summary of the invention
The present invention In view of the foregoing makes, a kind of TN type and STN type of not only being applicable to that provide is provided, and when being applicable to vertical alignment-type liquid crystal display device, also can form the aligning agent for liquid crystal of the liquid crystal orientation film that demonstrates good liquid crystal aligning and voltage retention and image retention excellent performance, and the liquid crystal display cells of residual excellent performance.
Other purposes of the present invention and advantage, by the following description as can be seen.
According to the present invention, above-mentioned purpose of the present invention, the first, reach by a kind of aligning agent for liquid crystal, its comprise by polyamic acid with and the group that constitutes of imide amination polymer at least a polymkeric substance selected, this polyamic acid is obtained by tetracarboxylic dianhydride and diamine reactant, and this tetracarboxylic dianhydride contains 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, this diamines contains the compound of following formula (1) expression and the compound of following formula (2) expression
(in the formula (2), n is 16～18 integer).
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 formed by above-mentioned aligning agent for liquid crystal.
Description of drawings
The mode chart of the liquid crystal cell that Fig. 1 makes for image retention performance evaluation.
Embodiment
＜polyamic acid 〉
Polyamic acid contained in the aligning agent for liquid crystal of the present invention can contain 1,2,3 by making, and 4-cyclo-butane tetracarboxylic dianhydride's tetracarboxylic dianhydride synthesizes with the diamine reactant of the compound of compound that contains above-mentioned formula (1) expression and above-mentioned formula (2) expression.
[tetracarboxylic dianhydride]
The tetracarboxylic dianhydride who uses during above-mentioned polyamic acid is synthetic contains 1,2,3,4-cyclo-butane tetracarboxylic dianhydride at least.During above-mentioned polyamic acid synthetic, can also coupling 1,2,3, other tetracarboxylic dianhydrides beyond the 4-cyclo-butane tetracarboxylic dianhydride.
As these other tetracarboxylic dianhydrides, can enumerate for example butane tetracarboxylic acid 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, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 3,5,6-three carboxyls norbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran 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, 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)-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)-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), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 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 (T-I) or aliphatics or the ester ring type tetracarboxylic dianhydrides such as compound that (T-II) represent;
(formula (T-I) and (T-II) in, R
1And R
3Expression has the divalent organic group of aromatic rings, R
2And R
4Expression hydrogen atom or alkyl, a plurality of R of existence
2And R
4Separately can be identical, also can be different)
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, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-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), aromatic tetracarboxylic acid's dianhydrides such as compound of following formula (T-1)～(T-4) expression.They can a kind ofly be used alone or in combination of two or more.
Wherein, from making the angle of the good liquid crystal aligning of its performance, preferred butane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid 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)-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, 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), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic anhydride, 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, pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 1,4,5, the compound of following formula (T-8) expression in the compound of following formula (T-5)～(T-7) expression in the compound of 8-naphthalene tetracarboxylic acid dianhydride, above-mentioned formula (T-I) expression and the compound of above-mentioned formula (T-II) expression.Particularly preferred other tetracarboxylic dianhydrides are pyromellitic acid dianhydride and 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride.
Among the tetracarboxylic dianhydride who uses in contained polyamic acid synthetic in the aligning agent for liquid crystal of the present invention, preferably contain 40 moles more than the % 1,2,3 with respect to whole tetracarboxylic dianhydrides, 4-cyclo-butane tetracarboxylic dianhydride is more preferably contained 60 moles more than the %.
In addition, among the synthetic middle tetracarboxylic dianhydride who uses of contained polyamic acid, preferably remove 1,2,3 in the aligning agent for liquid crystal of the present invention, beyond the 4-cyclo-butane tetracarboxylic dianhydride, also contain pyromellitic acid dianhydride or 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride.At this moment, the usage ratio of pyromellitic acid dianhydride with respect to whole tetracarboxylic dianhydrides, is preferably 10 moles below the %, more preferably 1～10 mole of %, further preferred 3～8 moles of %.
2,3, the usage ratio of 5-tricarboxylic basic ring amyl group acetic acid dianhydride with respect to whole tetracarboxylic dianhydrides, is preferably 50 moles below the %, more preferably 15～45 moles of %, further preferred 20～40 moles of %.Can also be with pyromellitic acid dianhydride and 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride carries out coupling with preferred above-mentioned scope respectively.
Use the tetracarboxylic dianhydride of containing each tetracarboxylic dianhydride respectively with aforementioned proportion, can obtain having the polymkeric substance of good solubility for following solvents, and, the liquid crystal orientation film orientation excellence that forms by the aligning agent for liquid crystal that contains it, saying from this point, is preferred.
[diamines]
The diamines that uses during above-mentioned polyamic acid is synthetic contains the compound of above-mentioned formula (1) expression and the compound of above-mentioned formula (2) expression.
When above-mentioned polyamic acid synthetic, can also coupling other diamines beyond their.
As these other diamines, can enumerate the diamines that for example has steroid backbone and other diamines.
As above-mentioned diamines with steroid backbone, can enumerate the compound of for example following formula (D-I) expression,
(in the formula (D-I), X
1Expression is selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R
5The 1 valency organic group that expression has steroid backbone), the compound of following formula (D-II) expression,
(in the formula (D-II), X
2Expression is selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R
6The divalent organic group that expression has steroid backbone).As their object lesson, the compound of above-mentioned formula (D-I) expression can be enumerated the compound of for example following formula (D-1)～(D-6) expression etc.;
The compound of above-mentioned formula (D-II) expression can be enumerated the compound of for example following formula (D-7)～(D-9) expression etc.,
As above-mentioned other diamines, can enumerate for example p-phenylenediamine (PPD), m-phenylene diamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formailide, 4,4 '-diaminodiphenyl ether, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 3,3 '-two (trifluoromethyl)-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-2,7-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]-aromatic diamines such as octafluoro biphenyl;
1,1-m-xylene diamine, 1,3-propane diamine, butanediamine, pentanediamine, hexane diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 4,4-diamido heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene bicyclopentadiene diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0
2,7] undecylene two methanediamines, 4,4 '-methylene two (cyclohexylamine), 1,3-two (amino methyl) cyclohexane, 1, aliphatics or ester ring type diamines such as 4-two (amino methyl) cyclohexane;
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-2,4-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, 3,6-diamido carbazole, N-methyl-3,6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole, N, N '-two (4-aminophenyl) biphenylamine, the compound of following formula (D-III) expression
(in the formula (D-III), R
7Expression is selected from the 1 valency organic group with nitrogen atom ring texture of pyridine, pyrimidine, triazine, piperidines and piperazine, X
3The organic group of expression divalent), the compound of following formula (D-IV) expression,
(in the formula (D-IV), R
8Expression is selected from the divalent organic group with nitrogen atom ring texture of pyridine, pyrimidine, triazine, piperidines and piperazine, X
4The organic group of expression divalent, a plurality of X of existence
4Separately can be identical, also can be different) have the diamines of the nitrogen-atoms beyond 2 primary amino radicals and this primary amino radical in the equimolecular;
The compound of following formula (D-V) expression,
(in the formula (D-V), X
5Expression is selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R
9It is 6～30 alkyl that expression has 1 valency organic group of fluorine atom or carbon number); The compound of following formula (D-VI) expression,
(in the formula (D-VI), R
10The expression carbon number is 1～12 alkyl, a plurality of R of existence
10Separately can be identical, also can be different, p is 1～3 integer, q is 1～20 integer); The following formula (D-10) or (D-11) compound etc. of expression,
(y in the formula (D-10) is 2～12 integer, and the z in the formula (D-11) is 1～5 integer).These diamines can separately or be used in combination.
Wherein, the diamines that preferably has steroid backbone, p-phenylenediamine (PPD), 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4,4 '-benzidine, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl 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, 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 1, the 4-cyclohexane diamine, 4,4 '-methylene two (cyclohexylamine), 1,3-two (amino methyl) cyclohexane, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 3,6-diamido carbazole, N-methyl-3,6-diamido carbazole, N-ethyl-3,6-diamido carbazole, N-phenyl-3,6-diamido carbazole, N, N '-two (4-aminophenyl) biphenylamine, the compound of following formula (D-12) expression in the compound of above-mentioned formula (D-III) expression, the compound of following formula (D-13) expression in the compound of above-mentioned formula (D-IV) expression;
Dodecyloxy-2 in the compound of above-mentioned formula (D-V) expression, 4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2, in the compound of the compound of 5-diaminobenzene, following formula (D-14)～(D-16) expression or above-mentioned formula (D-VI) expression 1,3-two (3-aminopropyl)-tetramethyl disiloxane.
Particularly preferred other diamines are the diamines with steroid backbone, wherein preferred above-mentioned formula (D-I) or the compound of (D-II) representing.
The synthetic used diamines of the polyamic acid that contains in the aligning agent for liquid crystal of the present invention preferably contains the compound that 40 moles of above-mentioned formulas more than the % (1) are represented with respect to whole diamines, more preferably contains 50～80 moles of %, further preferably contains 55～75 moles of %.The synthetic used diamines of above-mentioned polyamic acid preferably contains the compound that 20 moles of above-mentioned formulas more than the % (2) are represented with respect to whole diamines, more preferably contains 30～60 moles of %, further preferably contains 35～55 moles of %.
In the used diamines,, preferably contain diamines in above-mentioned polyamic acid synthetic with steroid backbone as other diamines, at this moment, usage ratio with diamines of steroid backbone is 50 moles below the % with respect to whole diamines preferably, more preferably 10～30 moles of %.
By using the diamines contain various diamines respectively with aforementioned proportion, can obtain forming the aligning agent for liquid crystal of the liquid crystal orientation film of voltage retention and image retention excellent performance, be preferred therefore.
[synthesizing of polyamic acid]
The polyamic acid that can contain in the aligning agent for liquid crystal of the present invention can contain 1,2,3 by making, and 4-cyclo-butane tetracarboxylic dianhydride's tetracarboxylic dianhydride makes with the diamine reactant of the compound of compound that contains above-mentioned formula (1) expression and above-mentioned formula (2) expression.
Supply with the tetracarboxylic dianhydride of 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.
The synthetic reaction of polyamic acid preferably in organic solvent, is preferable over-20～150 ℃, more preferably under 0～100 ℃ temperature conditions, preferably carries out 1～48 hour, more preferably carries out 2～12 hours.Here, as organic solvent, as long as can dissolve the polyamic acid of generation, 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-, non-proton property compounds such as amides compound, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, HMPA such as N-dimethyl propylene acid amides; Between phenolic compound such as sylvan, xylenols, phenol, halogenated phenol etc.It is the amount of 0.1～30 weight % with respect to the total amount (a+b) of reaction solution that the consumption of organic solvent (a) is preferably the total amount (b) that makes tetracarboxylic dianhydride and diamine compound usually.
In the above-mentioned organic solvent, in the scope that the polyamic acid that does not make generation is separated out, the poor solvent alcohols of all right coupling polyamic acid, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc.Object lesson as this poor solvent, can enumerate for example methyl alcohol, ethanol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4-methyl-2 pentanone, ethylene glycol, propylene glycol, 1, the 4-butylene glycol, triethylene glycol, glycol monoethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, diethy-aceto oxalate, diethyl malonate, ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, the ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic acid esters, the diethylene glycol monoethyl ether acetic acid esters, tetrahydrofuran, methylene chloride, 1, the 2-ethylene dichloride, 1, the 4-dichloroetane, trichloroethanes, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl oxide etc.
When organic solvent and poor solvent coupling, the use amount of poor solvent can suitably be set in the scope that the polyamic acid that does not make generation is separated out, and is below the 30 weight % with respect to whole quantity of solvent preferably, more preferably below the 20 weight %.
As mentioned above, obtained dissolving the reaction solution of polyamic acid.This reaction solution directly can be supplied with the preparation of aligning agent for liquid crystal, also polyamic acid contained in the reaction solution can be separated the back and supply with the preparation of aligning agent for liquid crystal, resupply the preparation of aligning agent for liquid crystal after perhaps also isolated polyamic acid can being made with extra care.The separation of polyamic acid can obtain precipitate by above-mentioned reaction solution is put in a large amount of poor solvents, and the method for this precipitate of drying under reduced pressure is perhaps carried out reaction solution with the method for evaporator decompression distillation again.In addition,, make its method of separating out with poor solvent then, or, can make with extra care polyamic acid with the operation of evaporator decompression distillation by carrying out that this polyamic acid is dissolved in the organic solvent once more.
＜imide amination polymer 〉
The imide amination polymer that aligning agent for liquid crystal of the present invention can contain can make by carrying out imidizate as above-mentioned polyamic acid dehydration closed-loop.
As used tetracarboxylic dianhydride in above-mentioned imide amination polymer synthetic, can enumerate and the used identical compound of tetracarboxylic dianhydride during above-mentioned polyamic acid is synthetic.And,, can enumerate and the used identical diamines of diamine compound during above-mentioned polyamic acid is synthetic as used diamines in contained imide amination polymer in the aligning agent for liquid crystal of the present invention synthetic.
Contained imide amination polymer in the aligning agent for liquid crystal of the present invention, it can be the complete imidizate thing of the contained amic acid structure fully dehydrating closed loop of polyamic acid raw material, also can be only a part of amic acid structure dehydration closed-loop, amic acid structure and imide ring structure and the part imidizate thing of depositing.
Contained imide amination polymer in the aligning agent for liquid crystal of the present invention, its imidizate rate is preferably more than 60%, more preferably more than 70%, more preferably more than 80%.By using the imidizate rate is imide amination polymer more than 60%, can obtain to form the aligning agent for liquid crystal of the liquid crystal orientation film of image retention excellent performance.
Above-mentioned imidizate rate is meant the total quantity with respect to amic acid structure in the imide amination polymer and imide ring structure, the value that the shared ratio of imide ring number of structures is represented with percent.At this moment, the part of imide ring can also be different imide ring.The imidizate rate can be a primary standard substance with the tetramethylsilane by imide amination polymer being dissolved in the suitable deuterated solvent (for example deuterated dimethyl sulfoxide), at room temperature measures
1H-NMR, by measurement result according to the following equation (i) obtain.
Imidizate rate (%)=(1-A
1/ A
2* α) * 100 (i)
(in the formula (i), A
1Be near the peak area that comes from NH matrix that occurs the chemical shift 10ppm, A
2For coming from the peak area of other protons, α is with respect to 1 NH matrix in the imide amination polymer precursor (polyamic acid), the number ratio of other protons).
The dehydration closed-loop of polyamic acid preferred (i) is by the method for heating polyamic acid, and perhaps (ii) by polyamic acid is dissolved in the organic solvent, the method that adds dewatering agent and dehydration closed-loop catalyzer and heating as required in this solution is carried out.
Temperature of reaction in the method for the heating polyamic acid of above-mentioned (i) is preferably 50～200 ℃, more preferably 60～170 ℃.Reaction time is preferably 1～120 hour, more preferably 2～48 hours.When 50 ℃ of temperature of reaction less thaies, then the dehydration closed-loop reaction can not be carried out fully, if temperature of reaction surpasses 200 ℃, the situation of the molecular weight and molecular weight of gained imide amination polymer then can occur.
On the other hand, in the above-mentioned method of in polyamic acid solution, adding dewatering agent and dehydration closed-loop catalyzer (ii),, can use for example acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride as dewatering agent.The consumption of dewatering agent is decided according to required imidizate rate, and preferably the amic acid structure with respect to 1 mole of polyamic acid is 0.01～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, collidine, lutidines, triethylamine.But, be not limited to these.The dehydration closed-loop catalyst consumption with respect to 1 mole of used dewatering agent, is preferably 0.01～10 mole.Above-mentioned dewatering agent, dehydration closed-loop catalyst consumption are many more, then can make the imidizate rate high more.As used organic solvent in the dehydration closed-loop reaction, can enumerate as 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 ℃.Reaction time is preferably 1～24 hour, more preferably 2～8 hours.
Said method (ii) in, obtain containing the reaction solution of aforesaid imide amination polymer.This reaction solution can directly be supplied with the preparation of aligning agent for liquid crystal, also can from reaction solution, remove dewatering agent and dehydration closed-loop catalyzer and supply with the preparation of aligning agent for liquid crystal afterwards, imide amination polymer can also be separated the back and supply with the preparation of aligning agent for liquid crystal, resupply the preparation of aligning agent for liquid crystal after perhaps also the imide amination polymer that separates can being made with extra care.Remove dewatering agent and dehydration closed-loop catalyzer from reaction solution, can adopt for example method such as solvent exchange.The separation of imide amination polymer, refining can be taked to carry out as the separating of polyamic acid, operation that process for purification is same with above-mentioned.
The polymkeric substance of-end modified type-
Polyamic acid or imide amination polymer contained in the aligning agent for liquid crystal of the present invention can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting.By using the polymkeric substance of this end modified type, can under the prerequisite of not damaging effect of the present invention, improve the coating characteristic of aligning agent for liquid crystal etc.This end modified type polymkeric substance can be by when polyamic acid synthetic, adds molecular weight regulator etc. and prepare in polymerization reaction system.As molecular weight regulator, can enumerate monobasic acid anhydrides, monoamine compound, monoisocyanates compound etc.
As above-mentioned 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 above-mentioned 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 above-mentioned monoisocyanates compound, can enumerate for example phenyl isocyanate, isocyanic acid naphthyl ester etc.
The usage ratio of molecular weight regulator, the total amount of employed tetracarboxylic dianhydride and diamines is preferably below 20 weight portions, more preferably below 10 weight portions when synthetic with respect to the acid of 100 weight parts of polyamide.
-solution viscosity-
The as above polyamic acid of gained or imide amination polymer preferably when being made into concentration when being the solution of 10 weight %, have the solution viscosity of 20～800mPas, more preferably have the solution viscosity of 30～500mPas.
The solution viscosity of above-mentioned polymkeric substance (mPas) is to adopt the good solvent (for example gamma-butyrolacton) of this polymkeric substance to be mixed with concentration when being the polymer solution of 10 weight %, with E type rotational viscosimeter 25 ℃ of values of measuring down.
＜other adjuvant 〉
Liquid crystal orientation film of the present invention contains at least a polymkeric substance that is selected from aforesaid polyamic acid and the imide amination polymer thereof.Polymkeric substance as contained in the aligning agent for liquid crystal of the present invention is preferably imide amination polymer.
Liquid crystal orientation film of the present invention contains aforesaid polymkeric substance as essential composition, and can contain other compositions as required.As this other compositions, can enumerate the compound (hereinafter referred to as " epoxy compounds ") that has two above epoxy radicals in the molecule for example, functional silanes compound etc.
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, N-diglycidyl) TSL 8330 etc.
Usage ratio as above-mentioned epoxy compounds, with respect to 100 parts by weight polymer total amounts (being meant the total amount of above-mentioned polyamic acid and imide amination polymer thereof contained in the aligning agent for liquid crystal), be preferably below 40 weight portions, more preferably 0.1～30 weight portion.
As above-mentioned 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.
As the usage ratio of above-mentioned functional silanes compound, with respect to 100 parts by weight polymer total amounts, be preferably below 2 weight portions, more preferably below 0.2 weight portion.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention is contained at least a and optional as required other adjuvant preferred dissolutions that mix of selecting in the group that is made of above-mentioned polyamic acid and imide amination polymer thereof in the organic solvent and constitutes.
As above-mentioned organic solvent, can enumerate as solvent used in the polyamic acid synthetic reaction and illustrative solvent.In addition, but can also suitably select coupling as the synthetic reaction of polyamic acid the time coupling and illustrative poor solvent.
As the particularly preferred organic solvent that uses 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,N-dimethylacetamide, 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, isoamyl propionate, isoamyl isobutyrate, isoamyl oxide etc.These solvents can use separately, perhaps also can two or more mixing use.
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 accounts for the ratio of aligning agent for liquid crystal general assembly (TW)) is considered viscosity, volatility etc. and is suited to select, is preferably the scope of 1～10 weight %.That is to say, with the aligning agent for liquid crystal of the present invention substrate surface that is coated on as described below, preferably by adding thermosetting as the filming of liquid crystal orientation film, 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, and the viscosity of aligning agent for liquid crystal increase, and causes applying degradation.
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, the scope of preferred especially 1.5～4.5 weight %.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 preparing 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 has the liquid crystal orientation film that is formed by aforesaid aligning agent for liquid crystal of the present invention.
Liquid crystal display cells of the present invention can be by for example operation manufacturing of following (1)～(3).
(1) at first, with two substrates that are provided with the nesa coating that forms pattern as a pair of, form on the face of nesa coating its each, by for example suitable coating methods such as rolling method, spin-coating method, hectographic printing method, ink jet printing method, apply aligning agent for liquid crystal of the present invention respectively, then, by being added thermosetting, each applicator surface films.Here, as substrate, can use for example glass such as float glass, soda-lime glass; Polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-plastics system transparency carriers such as (ester ring type alkene).Simultaneously go up the nesa coating that is provided with as substrate, can use tin oxide (SnO
2) system NE SA film (U.S. PPG register of company trade mark), indium oxide-tin oxide (In
2O
3-SnO
2) the ITO film etc. of system, forming the acquisition of the nesa coating of pattern, for example can adopt after forming patternless nesa coating to form method of patterning by photoengraving or employing has the mask of required pattern when nesa coating forms method etc.When the coating of aligning agent for liquid crystal, for the cohesive of further improving substrate surface and nesa coating and filming, can also will form on the face of filming in substrate surface, apply the pre-treatment of functional silanes compound, functionality titanium compound etc. in advance.
Heating-up temperature after the aligning agent for liquid crystal coating is preferably 30～300 ℃, more preferably 40～250 ℃, is preferably 1～30 minute heat time heating time, more preferably 5～20 minutes.The thickness of filming that forms is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) then, adopt the roller be tied with fibrous cloth such as nylon, regenerated fiber, cotton for example that the coated surface that as above forms is carried out grinding process with the certain orientation friction.Like this, making films goes up generation liquid crystal molecular orientation energy, makes liquid crystal orientation film.In addition, for vertical alignment-type liquid crystal display device, also have and not carry out grinding process.At this moment, above-mentioned filming directly can be used as 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 7 (Japanese kokai publication hei 6-222366 communique) for example or the patent documentation 8 (Japanese kokai publication hei 6-281939 communique); the processing that a part of irradiation ultraviolet radiation of liquid crystal orientation film is made the regional tilt angle of a liquid crystal orientation film part change; perhaps carry out shown in the patent documentation 9 (Japanese kokai publication hei 5-107544 communique); after forming diaphragm on the liquid crystal orientation film part surface; carry out the processing of removing diaphragm after the grinding process with the direction different with previous grinding process; make each zone of liquid crystal orientation film have different liquid crystal aligning energy, can improve the field-of-view characteristics of gained liquid crystal display cells like this.
(3) it is staggered relatively a pair of substrate that as above forms liquid crystal orientation film to be passed through gap (box gap), make the vertical or antiparallel of polishing direction of the liquid crystal orientation film of two substrates, 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, the polaroid of fitting on the outside surface of liquid crystal cell makes the polishing direction of the liquid crystal orientation film that forms on its polarization direction and each substrate consistent or vertical, so just can make liquid crystal display cells.Here, as sealant, can use epoxy resin that for example contains as the alumina balls 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 further add for example cholesteryl liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal; Chirality agent with trade name " C-15 ", " CB-15 " (manufacturing of メ Le Network company) sale; To oxygen base benzylidene-to ferroelectric liquid crystals such as amino-2-methyl butyl cinnamate etc. and using in the last of the ten Heavenly stems.
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 " 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 addition, the imidizate rate in the following synthesis example in the imide amination polymer is by with behind the at room temperature abundant drying under reduced pressure of imide amination polymer, be dissolved in the deuterated dimethyl sulfoxide, and with the tetramethylsilane primary standard substance, at room temperature measure
1H-NMR is obtained according to above-mentioned formula (i) by measurement result.
Synthesis example 1
Will be as tetracarboxylic dianhydride's 1,2,3,4-cyclo-butane tetracarboxylic dianhydride 98g (0.5 mole), and as 2 of diamine compound, the 4-diamino-N, N-diallyl aniline 61g (0.3 mole) and 3,5-two (4-aminobenzoic acylamino-) benzoic acid n-hexadecyl ester 123g (0.2 mole) is dissolved in the 1127g N-N-methyl-2-2-pyrrolidone N-, reacts 6 hours down at 60 ℃, obtains containing the polymer solution of polyamic acid.The gained polyamic acid solution that takes a morsel adds the N-N-methyl-2-2-pyrrolidone N-, is made into the solution that polyamic acid concentration is 10 weight %, and the solution viscosity of mensuration is 50mPas.
Then, in the gained polyamic acid solution, append 1409g N-N-methyl-2-2-pyrrolidone N-, add 198g pyridine and 204g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange (in this operation the pyridine and the acetic anhydride that use in the dehydration closed-loop reaction being removed to system) with new gamma-butyrolacton, obtain about 1300g and contain the polymer solution that the imidizate rate is about 94% imide amination polymer (A-1).This imide amination polymer solution that takes a morsel adds gamma-butyrolacton solution, is made into the solution that polymer concentration is 10 weight %, and the solution viscosity of mensuration is 60mPas.
Synthesis example 2
Will be as tetracarboxylic dianhydride's 1,2,3,4-cyclo-butane tetracarboxylic dianhydride 98g (0.5 mole), and as 2 of diamine compound, the 4-diamino-N, N-diallyl aniline 61g (0.3 mole) and 3,5-two (4-aminobenzoic acylamino-) benzoic acid n-octadecane base ester 128g (0.2 mole) is dissolved in the 1149g N-N-methyl-2-2-pyrrolidone N-, reacts 6 hours down at 60 ℃, obtains containing the polymer solution of polyamic acid.The gained polyamic acid solution that takes a morsel adds the N-N-methyl-2-2-pyrrolidone N-, is made into the solution that polyamic acid concentration is 10 weight %, and the solution viscosity of mensuration is 52mPas.
Then, in the gained polyamic acid solution, append 1437g N-N-methyl-2-2-pyrrolidone N-, add 198g pyridine and 204g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange (in this operation the pyridine and the acetic anhydride that use in the dehydration closed-loop reaction being removed to system) with new gamma-butyrolacton, obtain about 1310g and contain the polymer solution that the imidizate rate is about 95% imide amination polymer (A-2).This imide amination polymer solution that takes a morsel adds gamma-butyrolacton solution, is made into the solution that polymer concentration is 10 weight %, and the solution viscosity of mensuration is 63mPas.
Synthesis example 3
Will be as tetracarboxylic dianhydride's 1,2,3,4-cyclo-butane tetracarboxylic dianhydride 93g (0.48 mole) and pyromellitic acid dianhydride 5g (0.03 mole), and as 2 of diamine compound, the 4-diamino-N, N-diallyl aniline 61g (0.3 mole) and 3,5-two (4-aminobenzoic acylamino-) benzoic acid n-hexadecyl ester 123g (0.2 mole) is dissolved in the 1129g N-N-methyl-2-2-pyrrolidone N-, reacts 6 hours down at 60 ℃, obtains containing the polymer solution of polyamic acid.The gained polyamic acid solution that takes a morsel adds the N-N-methyl-2-2-pyrrolidone N-, is made into the solution that polyamic acid concentration is 10 weight %, and the solution viscosity of mensuration is 55mPas.
Then, in the gained polyamic acid solution, append 1411g N-N-methyl-2-2-pyrrolidone N-, add 198g pyridine and 204g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange (in this operation the pyridine and the acetic anhydride that use in the dehydration closed-loop reaction being removed to system) with new gamma-butyrolacton, obtain about 1320g and contain the polymer solution that the imidizate rate is about 94% imide amination polymer (A-3).This imide amination polymer solution that takes a morsel adds gamma-butyrolacton solution, is made into the solution that polymer concentration is 10 weight %, and the solution viscosity of mensuration is 65mPas.
Synthesis example 4
Will be as tetracarboxylic dianhydride's 1,2,3,4-cyclo-butane tetracarboxylic dianhydride 93g (0.48 mole) and pyromellitic acid dianhydride 5g (0.03 mole), and as 2 of diamine compound, the 4-diamino-N, N-diallyl aniline 61g (0.3 mole) and 3,5-two (4-aminobenzoic acylamino-) benzoic acid n-octadecane base ester 128g (0.2 mole) is dissolved in the 1152g N-N-methyl-2-2-pyrrolidone N-, reacts 6 hours down at 60 ℃, obtains containing the polymer solution of polyamic acid.The gained polyamic acid solution that takes a morsel adds the N-N-methyl-2-2-pyrrolidone N-, is made into the solution that polyamic acid concentration is 10 weight %, and the solution viscosity of mensuration is 56mPas.
Then, in the gained polyamic acid solution, append 1440g N-N-methyl-2-2-pyrrolidone N-, add 198g pyridine and 204g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange (in this operation the pyridine and the acetic anhydride that use in the dehydration closed-loop reaction being removed to system) with new gamma-butyrolacton, obtain about 1310g and contain the polymer solution that the imidizate rate is about 93% imide amination polymer (A-4).This imide amination polymer solution that takes a morsel adds gamma-butyrolacton solution, is made into the solution that polymer concentration is 10 weight %, and the solution viscosity of mensuration is 65mPas.
Synthesis example 5
Will be as tetracarboxylic dianhydride's 1,2,3,4-cyclo-butane tetracarboxylic dianhydride 93g (0.48 mole) and pyromellitic acid dianhydride 5g (0.03 mole), and as 2 of diamine compound, the 4-diamino-N, N-diallyl aniline 71g (0.35 mole), 3, the compound 26g (0.05 mole) of 5-two (4-aminobenzoic acylamino-) benzoic acid n-hexadecyl ester 61g (0.1 mole) and above-mentioned formula (D-3) expression is dissolved in the 1029g N-N-methyl-2-2-pyrrolidone N-, reacted 6 hours down at 60 ℃, obtain containing the polymer solution of polyamic acid.The gained polyamic acid solution that takes a morsel adds the N-N-methyl-2-2-pyrrolidone N-, is made into the solution that polyamic acid concentration is 10 weight %, and the solution viscosity of mensuration is 50mPas.
Then, in the gained polyamic acid solution, append 1286g N-N-methyl-2-2-pyrrolidone N-, add 198g pyridine and 204g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange (in this operation the pyridine and the acetic anhydride that use in the dehydration closed-loop reaction being removed to system) with new gamma-butyrolacton, obtain about 1300g and contain the polymer solution that the imidizate rate is about 93% imide amination polymer (A-5).This imide amination polymer solution that takes a morsel adds gamma-butyrolacton solution, is made into the solution that polymer concentration is 10 weight %, and the solution viscosity of mensuration is 60mPas.
Synthesis example 6
Will be as tetracarboxylic dianhydride's 1,2,3,4-cyclo-butane tetracarboxylic dianhydride 64g (0.33 mole), 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 34g (0.15 mole) and pyromellitic acid dianhydride 5g (0.03 mole), and as 2 of diamine compound, the 4-diamino-N, N-diallyl aniline 61g (0.3 mole) and 3,5-two (4-aminobenzoic acylamino-) benzoic acid n-hexadecyl ester 123g (0.2 mole) is dissolved in the 1146g N-N-methyl-2-2-pyrrolidone N-, reacts 6 hours down at 60 ℃, obtains containing the polymer solution of polyamic acid.The gained polyamic acid solution that takes a morsel adds the N-N-methyl-2-2-pyrrolidone N-, is made into the solution that polyamic acid concentration is 10 weight %, and the solution viscosity of mensuration is 55mPas.
Then, in the gained polyamic acid solution, append 1433g N-N-methyl-2-2-pyrrolidone N-, add 198g pyridine and 204g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange (in this operation the pyridine and the acetic anhydride that use in the dehydration closed-loop reaction being removed to system) with new gamma-butyrolacton, obtain about 1300g and contain the polymer solution that the imidizate rate is about 93% imide amination polymer (A-6).This imide amination polymer solution that takes a morsel adds gamma-butyrolacton solution, is made into the solution that polymer concentration is 10 weight %, and the solution viscosity of mensuration is 65mPas.
Compare synthesis example 1
Will be as tetracarboxylic dianhydride's 1,2,3,4-cyclo-butane tetracarboxylic dianhydride 98g (0.5 mole), and as 2 of diamine compound, the 4-diamino-N, N-diallyl aniline 61g (0.3 mole) and 4-[4-(the trans n-heptyl cyclohexyl of 4-) phenoxy group]-1,3-diaminobenzene 76g (0.2 mole) is dissolved in the 941g N-N-methyl-2-2-pyrrolidone N-, reacts 6 hours down at 60 ℃, obtains containing the polymer solution of polyamic acid.The gained polyamic acid solution that takes a morsel adds the N-N-methyl-2-2-pyrrolidone N-, is made into the solution that polyamic acid concentration is 10 weight %, and the solution viscosity of mensuration is 48mPas.
Then, in the gained polyamic acid solution, append 1177g N-N-methyl-2-2-pyrrolidone N-, add 198g pyridine and 204g acetic anhydride again, under 110 ℃, carry out dehydration closed-loop reaction in 4 hours.After the dehydration closed-loop reaction, by the solvent in the system is carried out solvent exchange (in this operation the pyridine and the acetic anhydride that use in the dehydration closed-loop reaction being removed to system) with new gamma-butyrolacton, obtain about 1300g and contain the polymer solution that the imidizate rate is about 95% imide amination polymer (B-1).This imide amination polymer solution that takes a morsel adds gamma-butyrolacton solution, is made into the solution that polymer concentration is 10 weight %, and the solution viscosity of mensuration is 55mPas.
Embodiment 1
The preparation of＜aligning agent for liquid crystal 〉
In the solution that contains imide amination polymer (A-1) that in above-mentioned synthesis example 1, makes, add gamma-butyrolacton (BL), N-N-methyl-2-2-pyrrolidone N-(NMP) and butyl cellosolve (BC), being made into solvent composition is that BL:NMP:BC=71:17:12 (weight ratio), solids content concn are the solution of 4 weight %, is the filter filtration of 1 μ m with this solution with the aperture, makes aligning agent for liquid crystal.
The evaluation of＜voltage retention 〉
Adopt liquid crystal orientation film printing machine (Japan's description printing machine (strain) is made), the aligning agent for liquid crystal of above-mentioned preparation is coated on the transparency electrode face of glass substrate of the transparency electrode that has ITO film system, heating is 1 minute on 80 ℃ heating plate, heated 10 minutes on 200 ℃ heating plate, forming average film thickness is 600 again
Film.Repeat this operation, make two (a pair of) and have the substrate of filming.With filming on these substrates is 20 times microscopic examination with multiplying power, finds printing inequality and pore, and screening characteristics is good.
Having on each outer rim with liquid crystal orientation film of this a pair of substrate of filming, coating makes the liquid crystal aligning face carry out overlapping and pressing relatively after having added the epoxy adhesive of alumina balls that diameter is 5.5 μ m, and bonding agent is solidified.Then, (メ Le Network company makes, and MLC-2038), with acrylic compounds Photocurable adhesive sealing liquid crystal injecting port, makes the liquid crystal cell that is used to estimate voltage retention then to fill negative type liquid crystal by liquid crystal injecting port between a pair of substrate.
Under 60 ℃ environment temperature, in 167 milliseconds time span, this liquid crystal cell is applied the voltage of 5V, the voltage application time is 60 microseconds, measures then from voltage and removes voltage retention after 167 milliseconds.Determinator adopts the (VHR-1 that strain) East Yang テ Network ニ カ makes.Voltage retention is that the situation voltage retention more than 95% is chosen as " qualified ".
The evaluation of＜image retention performance 〉
Except substrate adopts the substrate that has the ITO electrode shown in Figure 1, according to the evaluation of above-mentioned＜voltage retention〉described in method, make the liquid crystal cell that is used for image retention performance evaluation.At room temperature apply the DC voltage of 6.0V, apply the DC voltage of 0.5V, apply 24 hours to electrode B to electrode A.After voltage is removed, estimate the luminance difference of electrode A and B respective regions when electrode A, B apply 0.1～5.0V DC voltage with the gradient of 0.1V.If luminance difference is little, then image retention performance evaluation is " qualified ", and when luminance difference was big, image retention performance evaluation was " defective ".
Embodiment 2～6 and comparative example 1
Except using the solution contain polymkeric substance listed in the table 1 to replace containing the solution of imide amination polymer (A-1) respectively, similarly prepare aligning agent for liquid crystal with the foregoing description 1 and estimate.Evaluation result is listed in table 1.
Table 1
Claims (6)
1. aligning agent for liquid crystal, it is characterized in that comprising by polyamic acid with and the group that constitutes of imide amination polymer at least a polymkeric substance selected, this polyamic acid is obtained by tetracarboxylic dianhydride and diamine reactant, this tetracarboxylic dianhydride contains 1,2,3,4-cyclo-butane tetracarboxylic dianhydride, this diamines contains the compound of following formula (1) expression and the compound of following formula (2) expression
In the formula (2), n is 16～18 integer.
2. the described aligning agent for liquid crystal of claim 1, wherein, it is the pyromellitic acid dianhydride of 1～10 mole of % that the tetracarboxylic dianhydride is also contained with respect to whole tetracarboxylic dianhydrides.
3. claim 1 or 2 described aligning agent for liquid crystal wherein also contain the diamines with steroid backbone in the diamines.
4. each described aligning agent for liquid crystal of claim 1～3 wherein also contains 2,3 among the tetracarboxylic dianhydride, 5-tricarboxylic basic ring amyl group acetic acid dianhydride.
5. each described aligning agent for liquid crystal of claim 1～4 wherein also contains the compound that has two above epoxy radicals in the molecule.
6. 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 1～5.
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| JP2007321776A JP5083539B2 (en) | 2007-12-13 | 2007-12-13 | Liquid crystal aligning agent and liquid crystal display element |
| JP2007-321776 | 2007-12-13 | ||
| JP2007321776 | 2007-12-13 |
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| JP (1) | JP5083539B2 (en) |
| KR (1) | KR101501778B1 (en) |
| CN (1) | CN101458425B (en) |
| TW (1) | TWI427103B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010719A (en) * | 2009-09-04 | 2011-04-13 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, polyamic acid and polyimide |
| CN103969889A (en) * | 2013-01-28 | 2014-08-06 | 胜华科技股份有限公司 | Method for forming liquid crystal alignment film, manufacturing method of display board and display board |
| CN112225675A (en) * | 2020-09-22 | 2021-01-15 | 江苏三月科技股份有限公司 | Arylamine compound, liquid crystal aligning agent prepared from arylamine compound, liquid crystal aligning film and liquid crystal display element |
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| KR102104154B1 (en) * | 2012-11-30 | 2020-04-23 | 닛산 가가쿠 가부시키가이샤 | Method for producing liquid crystal alignment film, liquid crystal alignment film, and liquid crystal display element |
| KR102212324B1 (en) | 2014-02-21 | 2021-02-04 | 삼성디스플레이 주식회사 | Photo alignment agent and liquid crystal display device including the same |
| JP6447209B2 (en) * | 2014-05-12 | 2019-01-09 | Jsr株式会社 | Polymer composition, liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, and method for producing liquid crystal display element |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH10197875A (en) * | 1997-01-10 | 1998-07-31 | Nissan Chem Ind Ltd | Liquid crystal orientation treating agent |
| US6103322A (en) * | 1998-12-23 | 2000-08-15 | Elsicon Inc. | Materials for inducing alignment of liquid crystals and liquid crystal optical elements |
| JP2001072770A (en) * | 1999-06-30 | 2001-03-21 | Nissan Chem Ind Ltd | Diaminobenzene derivative, and polyimide and liquid crystal alignment film prepared by using same |
| JP2001311080A (en) * | 2000-04-28 | 2001-11-09 | Jsr Corp | Agent for orienting liquid crystal |
| US6919404B2 (en) * | 2002-05-31 | 2005-07-19 | Elsicon, Inc. | Hybrid polymer materials for liquid crystal alignment layers |
| WO2003102045A1 (en) * | 2002-05-31 | 2003-12-11 | Elsicon, Inc. | Hybrid polymer materials for liquid crystal alignment layers |
| CN100427529C (en) * | 2003-11-26 | 2008-10-22 | 日产化学工业株式会社 | Liquid crystal alignment treating agent for vertical alignment and liquid crystal display |
| KR101166003B1 (en) * | 2004-04-28 | 2012-07-18 | 닛산 가가쿠 고교 가부시키 가이샤 | Liquid-crystal aligning agent, liquid-crystal alignment film comprising the same, and liquid-crystal element |
| JP4968422B2 (en) * | 2004-12-15 | 2012-07-04 | Ｊｓｒ株式会社 | Method for producing liquid crystal alignment film |
| JP4779974B2 (en) * | 2004-12-22 | 2011-09-28 | 日産化学工業株式会社 | Liquid crystal aligning agent and liquid crystal display element using the same |
| CN100538478C (en) * | 2005-05-25 | 2009-09-09 | 日产化学工业株式会社 | Aligning agent for liquid crystal and use the liquid crystal display cells of this treating agent |
| WO2008062877A1 (en) * | 2006-11-24 | 2008-05-29 | Nissan Chemical Industries, Ltd. | Liquid crystal orientation treatment agent and liquid crystal display element produced by using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010719A (en) * | 2009-09-04 | 2011-04-13 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, polyamic acid and polyimide |
| CN102010719B (en) * | 2009-09-04 | 2014-10-29 | Jsr株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, polyamic acid and polyimide |
| CN103969889A (en) * | 2013-01-28 | 2014-08-06 | 胜华科技股份有限公司 | Method for forming liquid crystal alignment film, manufacturing method of display board and display board |
| CN112225675A (en) * | 2020-09-22 | 2021-01-15 | 江苏三月科技股份有限公司 | Arylamine compound, liquid crystal aligning agent prepared from arylamine compound, liquid crystal aligning film and liquid crystal display element |
| CN112225675B (en) * | 2020-09-22 | 2021-07-06 | 江苏三月科技股份有限公司 | Arylamine compound, liquid crystal aligning agent prepared from arylamine compound, liquid crystal aligning film and liquid crystal display element |
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| Publication number | Publication date |
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| CN101458425B (en) | 2012-01-04 |
| KR20090063143A (en) | 2009-06-17 |
| TWI427103B (en) | 2014-02-21 |
| JP5083539B2 (en) | 2012-11-28 |
| JP2009145536A (en) | 2009-07-02 |
| KR101501778B1 (en) | 2015-03-11 |
| TW200930747A (en) | 2009-07-16 |
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