CN1712491B - Vertical liquid crystal orienting agent and vertical liquid crystal display element agent with reflecting electrode - Google Patents
Vertical liquid crystal orienting agent and vertical liquid crystal display element agent with reflecting electrode Download PDFInfo
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- CN1712491B CN1712491B CN2005100773049A CN200510077304A CN1712491B CN 1712491 B CN1712491 B CN 1712491B CN 2005100773049 A CN2005100773049 A CN 2005100773049A CN 200510077304 A CN200510077304 A CN 200510077304A CN 1712491 B CN1712491 B CN 1712491B
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- 0 *C(*C(CC(O1)=*)(CC1=O)*=C)(C[C@](O)O1)CC1=O Chemical compound *C(*C(CC(O1)=*)(CC1=O)*=C)(C[C@](O)O1)CC1=O 0.000 description 5
- GHJWJRFCUPAKFI-UHFFFAOYSA-N CC[IH]N(C(C1C2C(N(C)C(C)CO)=O)C1=O)C2=O Chemical compound CC[IH]N(C(C1C2C(N(C)C(C)CO)=O)C1=O)C2=O GHJWJRFCUPAKFI-UHFFFAOYSA-N 0.000 description 1
- ZHERHYWFROIXGH-UHFFFAOYSA-N O=C(CC(C1)c(cc2)ccc2-c2ccc(C(CC(O3)=O)CC3=O)cc2)OC1=O Chemical compound O=C(CC(C1)c(cc2)ccc2-c2ccc(C(CC(O3)=O)CC3=O)cc2)OC1=O ZHERHYWFROIXGH-UHFFFAOYSA-N 0.000 description 1
- YYDRPSROEWQNFS-UHFFFAOYSA-N O=C(CC(C1)c2ccc(C(CC(O3)=O)CC3=O)cc2)OC1=O Chemical compound O=C(CC(C1)c2ccc(C(CC(O3)=O)CC3=O)cc2)OC1=O YYDRPSROEWQNFS-UHFFFAOYSA-N 0.000 description 1
- GCWMJBDJJCULIN-UHFFFAOYSA-N O=C(CC1c2ccc(C(CC(O3)=O)C3=O)cc2)OC1=O Chemical compound O=C(CC1c2ccc(C(CC(O3)=O)C3=O)cc2)OC1=O GCWMJBDJJCULIN-UHFFFAOYSA-N 0.000 description 1
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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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
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
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Abstract
The invention provides a liquid crystal aligning agent which brings about a vertical liquid crystal alignment layer excellent in image persistence characteristics and reliability even when used with a reflection electrode. The vertical liquid crystal aligning agent includes 100 weight parts of a polymer with an amic acid repeating unit and/or an imide repeating unit and at least 5 weight parts of a compound having at least two epoxy groups in a molecule.
Description
Technical field
The present invention relates to vertical liquid crystal orientating agent and vertical liquid crystal display element with reflecting electrode.More particularly, no matter relate to electrode for the formation liquid crystal display device of which kind of type, can both make the vertical liquid crystal orientating agent of the vertical liquid crystal oriented film of print characteristic good, and the liquid crystal display device that the reflective electrode that possesses this vertical liquid crystal oriented film is housed.
Background technology
At present, known TN type liquid crystal display device with TN (twisted nematic) type liquid crystal cell, this element by nesa coating between 2 substrates that form liquid crystal orientating membrane on the surface, formation has the nematic liquid crystal layer of positive dielectric anisotropy, constitute the box of sandwich structure, the major axis of above-mentioned liquid crystal molecule is turned round continuously to another piece substrate from a substrate and is turn 90 degrees.
In addition, also have STN (STN Super TN) type liquid crystal display device, it becomes the major axis of this liquid crystal molecule by the interpolation chiral reagent and turn round the state of turnback with upper span continuously between substrate, thereby utilizes consequent birefringence effect.In addition, recently also at exploitation a kind of guest-principal mode reflection type liquid crystal display element, it forms vertical (the ホ メ ォ ト ロ ピ ッ Network) nematic liquid crystal layer of directed state or the cholesteric liquid crystal layers of screw shaft and substrate normal parastate with negative dielectric anisotropic between opposing substrates, and adds pigment in these liquid crystal layers.The orientation of liquid crystal in these liquid crystal display device is manifested by the liquid crystal orientating membrane of implementing grinding process usually.Here, as the material of the liquid crystal orientating membrane that constitutes liquid crystal display device, according to the known polyimide of prior art, polymeric amide and polyester etc.Polyimide particularly is because thermotolerance, good with the affinity of liquid crystal, physical strength etc. is used in most liquid crystal display device.
Recently, carried out the research with the high-accuracy raising display quality that turns to representative of liquid crystal display device, low consumption electrification etc., the range of application of liquid crystal display device is also in continuous expansion.Reflection-type or the semi-transmission type liquid crystal display device that can keep high display quality during particularly owing to outdoor application are applied to mobile termination, show the performance of the outer light of reflection in order to make it, use various metal electrodes (hereinafter referred to as emitting electrode).But, in having the vertical liquid crystal display element of reflecting electrode, during the oriented film that before using, in the ITO electrode, uses, can be created in the problem of poor reliability such as producing print, the directed spot of appearance in the long-time illumination.
Summary of the invention
The object of the invention provides a kind of liquid crystal orientating agent, and it also can make the good vertical liquid crystal oriented film of print characteristic and reliability when using with reflecting electrode.
Another object of the present invention provides a kind of vertical liquid crystal display element, and it is equipped with the reflecting electrode that possesses the vertical liquid crystal oriented film that is made by liquid crystal orientating agent of the present invention.
Other purpose of the present invention and advantage can be clear that from the following description.
According to the present invention, above-mentioned purpose of the present invention and advantage realize by a kind of liquid crystal orientating agent, it is characterized in that comprising that 100 weight parts have the repeating unit of following formula (1) expression and/or the polymkeric substance of the repeating unit that following formula (2) is represented, and at least 5 weight part intramolecularly compound of having 2 epoxy group(ing) at least
(in the formula, P
1Be the organic group of 4 valencys, and Q
1Organic group for divalent),
(in the formula, P
2Be the organic group of 4 valencys, and Q
2Organic group for divalent).
Vertical liquid crystal oriented film by liquid crystal orientating agent of the present invention forms is not limited to situation about using with the ITO electrode, when using with reflecting electrode, also has good print characteristic and reliability, can be suitable for constituting liquid crystal display device.
Liquid crystal display device of the present invention can be used for various devices effectively, for example is applicable to display unit such as desk-top computer, wrist-watch, table clock, mobile telephone, counting display screen, word processor, Personal Computer, liquid crystal TV set.
Embodiment
Below, the present invention is described in detail.
Liquid crystal orientating agent among the present invention comprises the polymkeric substance (below, be called " particular polymers ") of the repeating unit of repeating unit with above-mentioned (1) expression and/or above-mentioned formula (2) expression.Particular polymers can be the polyamic acid of (1) repeating unit with above-mentioned (1) expression and the mixture of the polyimide of the repeating unit with above-mentioned formula (2) expression, and (2) also can be to have repeating unit random of the repeating unit of above-mentioned (1) expression and above-mentioned formula (2) expression or the polymkeric substance that the block-wise bonding forms (below be also referred to as " part imide amination polymer ") in a part.
Above-mentioned polyamic acid is by tetracarboxylic dianhydride and diamine compound open loop addition polymerization and make.Polyimide is made by the polyamic acid dehydration closed-loop usually in addition.The part imide amination polymer usually can be by making the method for polyamic acid partial dehydration closed loop, or make amido acid give the method that polymers and imide give polymers bonding synthetic segmented copolymer to make.
＜polyamic acid 〉
[tetracarboxylic dianhydride]
As the tetracarboxylic dianhydride, can enumerate for example butane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-two chloro-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene 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 (THF) tetracarboxylic dianhydride, 1,3,3 a, 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)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3 a, 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)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 5-(2,5-dioxo tetrahydrofuran (THF) methylene radical)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic acid dianhydride, 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 (THF)-2 ', 5 '-diketone), following formula (I) and aliphatics and the alicyclic ring shape tetracarboxylic dianhydrides such as compound that (II) represent
(in the formula, R
1And R
3Expression has the divalent organic group of aromatic nucleus, R
2And R
4Expression hydrogen atom or alkyl, the R of a plurality of existence
2And R
4Separately can be identical, also can be different);
Pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide 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 dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) sulfobenzide dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dicarboxylic anhydride, 3,3 ', 4,4 '-all fluorine isopropylidene two phthalandione dianhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, two (phthalandione) phosphniline oxide compound dicarboxylic anhydride, right-phenylene-two (triphenyl phthalandione) dianhydride, between-phenylene-two (triphenyl phthalandione) dianhydride, two (triphenyl phthalandiones)-4,4 '-phenyl ether dianhydride, two (triphenyl phthalandiones)-4,4 '-ditan dianhydride, ethylene glycol-two (dehydration trimellitate), propylene glycol-two (dehydration trimellitate), 1,4-butyleneglycol-two (dehydration trimellitate), 1,6-hexylene glycol-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 (1)～(4) expression.They can a kind of independent or 2 kinds or above being used in combination.
Wherein, from showing the angle of good liquid crystal aligning, preferred butane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3,4-pentamethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride, 5-(2,5-dioxo tetrahydrofuran (THF) methylene radical)-and 3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic 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)-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]-and Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, the compound of following formula (8) expression in the compound of following formula (5)～(7) expression in the compound of following formula (I) expression and the compound of following formula (II) expression, as particularly preferred, can enumerate 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene 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)-naphthalene [1,2-c]-furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), the compound of pyromellitic acid dianhydride and following formula (5) expression.
Especially, when the repeating unit (imide unit) of the repeating unit (amido acid unit) of above-mentioned (1) expression and above-mentioned formula (2) expression when existing simultaneously, (1) middle P
14 valency organic groups of expression and the middle P of the repeating unit (imide unit) of (2) expression
24 valency organic groups of expression separately can be identical, also can be different, and as P
1Preferred group, can enumerate following formula (i) and formula (the i ') group of expression separately.As P
2Preferred group can be enumerated the group with alicyclic ring skeleton, especially preferably enumerates following formula (ii) and (ii ') group of expression separately.
(in the formula, R is halogen atom, methyl or ethyl, and a is 0 or 1 integer, and b is 0～5 integer, and c and d are 0～4 integer independently of one another).
Object lesson as preferred tetracarboxylic dianhydride in each repeating unit, constitute the unitary tetracarboxylic dianhydride of amido acid and for example can enumerate 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,4,5-hexanaphthene tetracarboxylic dianhydride, pyromellitic acid dianhydride etc.In addition, constitute the preferred alicyclic ring shape of the unitary tetracarboxylic dianhydride of imide tetracarboxylic dianhydride, can enumerate 2 especially, 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)-and naphthalene [1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1,3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone) etc.
[diamine compound]
The synthetic middle diamine compound that uses as above-mentioned polyamic acid, can enumerate for example p-phenylenediamine, between-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diamino diphenylethane, 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino diphenyl sulfone, 3,3 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formylaniline, 4,4 '-diaminodiphenyl oxide, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 6-amino-1-(4 '-aminophenyl) 1,3,3-trimethylammonium indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamino benzophenone, 3,4 '-diamino benzophenone, 4,4 '-diamino 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-two (4-aminophenyl) fluorenes, 4,4 '-methylene radical-two (2-chloroaniline), 2,2 ', 5,5 '-tetrachloro-4,4 '-benzidine, 2,2 '-two chloro-4,4 '-diamino-5,5 '-dimethoxy-biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 1,4,4 '-(right-the phenylene isopropylidene) two (aniline), 4,4 '-(-the phenylene isopropylidene) two (aniline), 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl, 4-(4-n-heptyl cyclohexyl)-phenoxy group-2, aromatic diamines such as 4-diaminobenzene;
1, xylyene diamine (1 between 1-, 1-メ タ キ シ リ レ Application ジ ァ ミ Application), 1,3-propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 4,4-diamino heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene Dicyclopentadiene (DCPD) diamines, six hydrogen-4, the inferior indanyl dimethylene of 7-methylene radical diamines, three ring [6.2.1.0
2,7]-undecylene two methanediamines, 4,4 '-methylene radical two aliphatics and alicyclic ring shape diamines such as (hexahydroaniline);
2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamino-2,3-dicyano pyrazine, 5,6-diamino-2,4-dihydroxy-pyrimidine, 2,4-diamino-6-dimethylamino-1,3, the 5-triazine, 1,4-two (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3, the 5-triazine, 2,4-diamino-6-methoxyl group-1,3, the 5-triazine, 2,4-diamino-6-phenyl-1,3, the 5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diaminostilbene, 3, the 5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenyl thiazole, 2,6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3,5-diaminostilbene, 2, the 4-triazole, 6,9-diamino-2-oxyethyl group acridine lactate, 3,8-diamino-6-phenylphenanthridineand, 1,4-diamino piperazine, 3, the 6-proflavin, the diamines that has 2 primary aminos and this primary amino nitrogen-atoms in addition in the compound equimolecular of two (4-aminophenyl) phenyl amine and following formula (III)～(IV) expression
(in the formula, R
5Expression is selected from the 1 valency organic group with nitrogen atom ring texture of pyridine, pyrimidine, triazine, piperidines and piperazine, and X represents the divalent organic group),
(in the formula, X represents to be selected from the divalent organic group with nitrogen atom ring texture of pyridine, pyrimidine, triazine, piperidines and piperazine, R
6Expression divalent organic group, the X of a plurality of existence can be the same or different);
Single-substituted two amines that following formula V is represented; The diamino organo-siloxane of following formula (VI) expression;
(in the formula, R
7Expression is selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R
8It is 6～30 alkyl that expression has the 1 valency organic group of group of the steroid backbone of being selected from, trifluoromethyl and fluorine or carbonatoms),
(in the formula, R
9The expression carbonatoms is 1～12 alkyl, the R of a plurality of existence
9Can be the same or different separately, p is 1～3 integer, and q is 1～20 integer);
Can enumerate the compound of following formula (9)～(13) expression etc.These diamine compounds can be separately or 2 kinds or above being used in combination.
(in the formula, y is 2～12 integer, and z is 1～5 integer).
Wherein, preferred p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl oxide, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two [4-aminophenyl] HFC-236fa, 4,4 '-(right-the phenylene diisopropylidene) two (aniline), 4,4 '-(-the phenylene diisopropylidene) two (aniline), 1, the 4-cyclohexane diamine, 4,4 '-methylene radical two (hexahydroaniline), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4-(4-n-heptyl cyclohexyl) phenoxy group-2, the 4-diaminobenzene, the compound of above-mentioned formula (9)～(13) expression, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, the compound of following formula (14) expression in the compound of above-mentioned formula (III) expression, the compound of following formula (16)～(21) expression in the compound of following formula (15) expression in the compound of above-mentioned formula (IV) expression and the compound that above-mentioned formula V is represented.
[building-up reactions of polyamic acid]
Supply with the tetracarboxylic dianhydride of polyamic acid building-up reactions and the usage rate of diamine compound, preferably with respect to contained amino in the 1 equivalent diamine compound, the anhydride group that makes the tetracarboxylic dianhydride is 0.2～2 normal ratio, more preferably 0.3～1.2 normal ratio.
The building-up reactions of polyamic acid is preferable over-20～150 ℃, more preferably carries out under 0～100 ℃ temperature condition in organic solvent.Here, as organic solvent,, it is had no particular limits as long as can dissolve the synthetic polyamic acid.Can illustration for example N-N-methyl-2-2-pyrrolidone N-, N,N-dimethylacetamide, N, aprotic polar solvents such as dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, hexamethyl tricresyl phosphite acid amides; Between phenol solvent such as sylvan, xylenol, phenol, halogenated phenol.In addition, to be preferably the total amount (b) that makes tetracarboxylic dianhydride and diamine compound be the amount of 0.1～30 weight % with respect to the total amount (a+b) of reaction soln to the consumption of organic solvent (a).
[poor solvent]
In addition, in the scope that the polyamic acid that does not make generation is separated out, can also unite in the above-mentioned organic solvent and use polyamic acid poor solvent alcohols, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc.Object lesson as this poor solvent, can enumerate for example methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, 1, the 4-butyleneglycol, triglycol, ethylene glycol monomethyl ether, ethyl lactate, n-Butyl lactate, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, ritalin, vinyl acetic monomer, N-BUTYL ACETATE, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, oxalic acid diethyl ester, 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, diglyme, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic ester, the diethylene glycol monoethyl ether acetic ester, tetrahydrofuran (THF), methylene dichloride, 1, the 2-ethylene dichloride, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene etc.
As mentioned above, obtained dissolving the reaction soln of polyamic acid.Then, this reaction soln is put in a large amount of poor solvents, obtained precipitate.Can get polyamic acid by this precipitate of drying under reduced pressure.And, once more this polyamic acid is dissolved in the organic solvent, separate out with poor solvent then, by carrying out once or this operation several times, can make with extra care polyamic acid.
[imide amination polymer]
＜imide amination polymer 〉
The imide amination polymer that constitutes liquid crystal orientating agent of the present invention can be by preparing above-mentioned polyamic acid dehydration closed-loop.The dehydration closed-loop of polyamic acid perhaps (ii) is dissolved in polyamic acid in the organic solvent by for example method of (i) heating polyamic acid, and the method that adds dewatering agent and dehydration closed-loop catalyzer and heating as required in this solution is successfully carried out.
Temperature of reaction is preferably 50～200 ℃, more preferably 60～170 ℃ in the method for above-mentioned (i) heating polyamic acid.When 50 ℃ of temperature of reaction less thaies, the dehydration closed-loop reaction is difficult to carry out fully, if temperature of reaction surpasses 200 ℃, the situation that the molecular weight of gained imide amination polymer reduces can occur.
On the other hand, (ii) in polyamic acid solution, in the method for adding dewatering agent and dehydration closed-loop catalyzer,, can use for example acid anhydrides such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride above-mentioned as dewatering agent.The consumption of dewatering agent with respect to 1 mole of polyamic acid repeating unit, is preferably 0.01～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, collidine, lutidine, 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.In addition, as the organic solvent that uses in the dehydration closed-loop reaction, can enumerate the identical organic solvent of illustrative organic solvent with synthesize middle solvent for use as polyamic acid.And the temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 10～150 ℃.In addition, by the reaction soln that so obtains is carried out the operation same with the polyamic acid process for purification, can make with extra care imide amination polymer.
[part imide]
＜part imide amination polymer 〉
Used part imide amination polymer has the structure that above-mentioned polyamic acid part imidization is obtained among the present invention.Among the present invention in the used part imide amination polymer imidization rate be preferably 10～90%, more preferably 30～70%.Here, " imidization rate " is meant the sum with respect to repeating unit in the polymkeric substance, the value that the ratio of the number of repeat unit of formation imide ring is represented with %.At this moment, the part of imide ring can also be different imide ring.
Method as the composite part imide polymer, for example can use (i) by heating above-mentioned polyamic acid partly the method for dehydration closed-loop, (ii) by above-mentioned polyamic acid is dissolved in the organic solvent, in this solution, add dewatering agent and dehydration closed-loop catalyzer and as required heating carry out partly dehydration closed-loop and synthetic method or (iii) by tetracarboxylic dianhydride, diamine compound and diisocyanate cpd are mixed, heating is carried out condensation and the synthetic method as required.
In the method for above-mentioned (i), temperature of reaction is preferably 300 ℃ or following, more preferably 100～250 ℃.If temperature of reaction surpasses 300 ℃, the situation that molecular weight that gained contains the polyamic acid of imide reduces can appear.
On the other hand, as used dewatering agent in above-mentioned method (ii), can enumerate for example acid anhydrides such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride.The consumption of dewatering agent with respect to 1 mole of polyamic acid repeating unit, is preferably 0.2～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, collidine, lutidine, triethylamine.But, be not limited to these.And the consumption of imidization catalyst with respect to 1 mole of used dewatering agent, is preferably 0.1～10 mole.In addition, as the organic solvent that uses in the dehydration closed-loop reaction, can enumerate the identical organic solvent of illustrative organic solvent with synthesize middle solvent for use as polyamic acid.And the temperature of reaction of dehydration closed-loop is preferably 0～180 ℃, more preferably 60～150 ℃.In addition, by the reaction soln that so obtains is carried out the operation same with the polyamic acid process for purification, can the FF imide amination polymer.
As the object lesson of diisocyanate cpd used in the above-mentioned reaction (iii), can enumerate aliphatic diisocyanates such as hexamethylene diisocyanate; Hexanaphthene-1,2-vulcabond, 1-methylcyclohexane-2,4-vulcabond, 1,2-dimethyl cyclohexane-ω, ω '-vulcabond, 1,4-dimethyl cyclohexane-ω, ω '-vulcabond, isophorone diisocyanate, 1,3,5-trimethylammonium-2-2-propyl cyclohexane-1 ω, 2 ω-vulcabond, dicyclohexyl methyl hydride-4, alicyclic ring shape vulcabond such as 4 '-vulcabond; Ditan-4,4 '-vulcabond, 1,3-phenylene vulcabond, 1,4-phenylene vulcabond, 1-methyl-2,4-phenylene vulcabond, 1-methyl-2, the aromatic diisocyanates such as vulcabond of 6-phenylene vulcabond, following formula (22)～(26) expression.
Wherein, as preferably enumerating dicyclohexyl methyl hydride-4,4 '-vulcabond, ditan-4,4 '-vulcabond, 1-methyl-2,4-phenylene vulcabond, 1-methyl-2,6-phenylene vulcabond.They can be separately or 2 kinds or above being used in combination.In addition, the unessential especially catalyzer of above-mentioned reaction (iii), temperature of reaction is preferably 50～200 ℃, more preferably 100～160 ℃.
[end modified]
＜end modified type polymkeric substance 〉
Above-mentioned polyamic acid and part imide amination polymer can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting.By using this end modified type polymkeric substance, can under the prerequisite of not damaging effect of the present invention, improve the coating characteristics of liquid crystal orientating agent etc.This end modified type polymkeric substance can be by when polyamic acid synthetic, for example adds monoester anhydride, monoamine compound, monoisocyanates compound etc. and synthesize in reaction system.Here, as monoester anhydride, can enumerate for example maleic anhydride, anhydride phthalic acid, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc.In addition, as monoamine compound, can enumerate for example aniline, cyclo-hexylamine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, Pentadecane amine, n-hexadecane amine, n-heptadecane amine, Octadecane amine, NSC 62789 amine etc.In addition, as the monoisocyanates compound, can enumerate for example phenylcarbimide, isocyanic acid naphthyl ester etc.
[logarithm viscosity]
The logarithm viscosity of＜polymkeric substance 〉
As above the logarithm viscosity of gained polyamic acid and part imide amination polymer (η ln) value is preferably 0.05～10dl/g, more preferably 0.05～5dl/g.
Logarithm viscosity of the present invention (η ln) value is by using the N-N-methyl-2-2-pyrrolidone N-as solvent, is that the solution of 0.5g/100ml carries out viscosimetric analysis to concentration under 30 ℃, the value of being tried to achieve by following formula (A).
[liquid crystal orientating agent]
Liquid crystal orientating agent of the present invention advantageously is dissolved in the organic solvent by particular polymers and constitutes.
As the organic solvent that constitutes liquid crystal orientating agent of the present invention, can enumerate with as solvent for use in the polyamic acid building-up reactions and illustrative solvent phase with solvent.In addition, can also suitably select with as solvent that can coupling when the polyamic acid building-up reactions and the identical solvent of illustrative poor solvent is united use.
Solid component concentration is considered viscosity, volatility and is selected in the liquid crystal orientating agent of the present invention, is preferably 1～10 weight %.That is to say that liquid crystal orientating agent of the present invention is coated substrate surface, formation is filmed as liquid crystal orientating membrane, and when solid component concentration less than 1 weight %, the thickness that causes this to film is too small, is difficult to obtain good liquid crystal orientating membrane.When solid component concentration surpasses 10 weight %, cause coating thickness blocked up, be difficult to obtain good liquid crystal orientating membrane, and the viscosity of liquid crystal orientating agent increases, the easy variation of coating characteristics.Temperature when in addition, preparing liquid crystal orientating agent of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
At least contain the compound that 5 weight part intramolecularly have 2 epoxy group(ing) at least (below, be also referred to as " compound that contains epoxy group(ing) ") with respect to 100 weight part particular polymers in the liquid crystal orientating agent of the present invention.
As this compound that contains epoxy group(ing), 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 diglycidylether, 1,3,5,6-four glycidyl group-2, the 4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-benzene dimethylamine, 1,3-two (N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.The content of this epoxy compounds can contain the amount of the scope of not damaging the directing agent characteristic, and 100 weight part particular polymers with respect to contained in the directing agent are preferably 5～40 weight parts, more preferably 10～30 weight parts.
In addition, liquid crystal orientating agent of the present invention is optional can contain compound with functional group's property silicon (below, be also referred to as " silane coupling agent ").As this silane coupling agent, 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-ethoxycarbonyl-3-TSL 8330, N-ethoxycarbonyl-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 ester, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, N-two (hydroxyethyl)-3-TSL 8330, N-two (hydroxyethyl)-3-aminopropyltriethoxywerene werene, 3-glycidoxypropyltrime,hoxysilane etc.
The mixture ratio of these silane coupling agents with respect to 100 weight part particular polymers, is preferably 40 weight parts or following, more preferably 0.1～30 weight part.
＜liquid crystal display device 〉
With the liquid crystal display device that liquid crystal orientating agent of the present invention makes, can be by for example following method manufacturing.
(1) by for example methods such as roller coating machine method, spin coater method, print process, the method for the use of ink and water of disputing, liquid crystal orientating agent of the present invention is coated on the substrate one side that is provided with the nesa coating that forms pattern, then,, coated face 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, polybutyleneterephthalate, polyethersulfone, polycarbonate.Simultaneously go up set nesa coating as substrate, can use stannic oxide (SnO
2) system NESA film (U.S. PPG register of company trade mark), Indium sesquioxide-stannic oxide (In
2O
3-SnO
2) the ITO film etc. of system.The formation of these electrically conducting transparent film figures is adopted photoetch method and is used the method for mask in advance.Can use metals such as Al or Ag in the reflecting electrode, perhaps contain the alloy of these metals etc.As long as have enough reflectivity, it had no particular limits.When the coating of liquid crystal orientating agent, for the binding property of further improving substrate surface and nesa coating or reflecting electrode and filming, can also be on the surface of substrate coating in advance contain functional silanes compound, contain the compound of functionality titanium etc.Heating temperature behind the coating of liquid crystalline directing agent is preferably 80～300 ℃, more preferably 120～250 ℃.The liquid crystal orientating agent of the present invention that contains polyamic acid, by removing organic solvent after the coating, formation is filmed as oriented film, or carries out dehydration closed-loop by further heating, can form filming of further imidization.The thickness of filming that forms is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) film coated surface such as the open 2002-327058 communique of Japanese Patent that forms is shown in usefulness photosensitivity resin formation structure on the substrate, on it, forms the vertical liquid crystal oriented film.
(3) make 2 substrates that as above form the vertical liquid crystal oriented film, make 2 substrates staggered relatively, fitted with sealing agent in 2 substrate periphery positions, in the box gap that is partitioned into by substrate surface and sealing agent, inject filling liquid crystal by gap (box gap), the sealing filling orifice constitutes liquid crystal cell.Then, at the outside surface of liquid crystal cell, transparency carrier one side that promptly constitutes liquid crystal cell is provided with polaroid, makes liquid crystal display device.
Here, as sealing agent, for example can use Resins, epoxy as the salic ball of solidifying agent and separator etc.
As liquid crystal, can enumerate nematic liquid crystal and dish shape type liquid crystal, wherein preferred nematic liquid crystal can use for example schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, phenylcyclohexane class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexane class liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.In addition, also can add cholesteryl liquid crystal such as for example cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal and the chiral reagent sold with trade(brand)name " C-15 ", " CB-15 " (メ Le Network corporate system) etc. and using.And, can also use the strong dielectricity liquid crystal of oxygen base Ben Yajiaji-p-amino-2-methyl butyl styracin etc. in the last of the ten Heavenly stems.
In addition, as the polaroid of fitting on the liquid crystal cell outside surface, can enumerate will make polyvinyl alcohol extend that the directed polarizing coating that is referred to as the H film that absorbs iodine simultaneously is clipped in the cellulose acetate protective membrane and the polaroid that polaroid of making or H film make self.
By the following examples the present invention is carried out more specific description, but the present invention is not limited to these embodiment.The transparency, voltage residual rate, print are estimated by the following method in embodiment and the comparative example.
[transparency]
Determinator adopts HITACHI U-2010 type spectrophotometer (Hitachi (strain) system).The liquid crystal orientating agent of the present invention that adopts spin coater as above to prepare is coated on the quartz base plate that thickness is 1.5mm, and drying is 1 hour under 180 ℃, and forming dry film thickness is 800
Film.Filming of made carried out transmitance to be measured.Value when the mensuration of transmitance is obtained wavelength and is 700nm, 600mn, 500nm, 450nm, 400nm, 350nm and 300nm.Transmitance is 90% or be evaluated as when above very under arbitrary mensuration wavelength, and average evaluation in addition is bad.
[vertical orientation]
At off voltage and apply under the situation of 12V voltage of alternating current (peak-peak), observe liquid crystal display device by cross Nicol prism (Network ロ ス ニ コ Le).
[print]
Under 50 ℃ envrionment temperature, apply 30Hz, the 2.0V square wave of 1 hour stack 1.0V direct current, adopt flicker-null method to obtain the interior retained voltage of liquid crystal cell behind the cut-out voltage immediately as residual DC voltage to liquid crystal display device.No matter for the electrode of the formation liquid crystal display device of which kind of type, residual DC voltage is all at 2V or following, and the difference of residual DC is 0.5V or following is evaluated as very between each electrode type, and average evaluation in addition is bad.
[reliability test of liquid crystal display device (having or not of display defect)]
Under hot and humid environment (temperature is 70 ℃, and relative humidity is 80%),, after 100 hours, have or not display defect by polarized light microscope observing with the rectangular wave drive of used for liquid crystal display element 5V, 60Hz.
Synthesis example 1
Will be as tetracarboxylic dianhydride's 2,3,5-tricarboxylic basic ring amyl group acetic acid dianhydride 224.17g (1.0 moles), be dissolved in the 4500g N-N-methyl-2-2-pyrrolidone N-as the p-phenylenediamine 54.07g (0.5 mole) of diamine compound, the diamine compound 261.41g (0.5 mole) of above-mentioned formula (16) expression, reacted 6 hours down at 60 ℃.Then, reaction soln is injected in the big excessive methyl alcohol, makes the reaction product precipitation, then, use methanol wash, in 40 ℃ of dryings 15 hours, obtain the polyamic acid that 520g logarithm viscosity is 0.57dl/g (it is called as " polyamic acid (A-1) ") by under reduced pressure.
Synthesis example 2
In synthesis example 1 except the diamine compound that uses 94.62g (0.8 mole) p-phenylenediamine, 104.56g (0.2 mole) above-mentioned formula (16) expression as diamine compound, similarly operate with synthesis example 1, obtaining 390g logarithm viscosity is the polyamic acid of 0.46dl/g.30g gained polyamic acid is dissolved in the 570g N-N-methyl-2-2-pyrrolidone N-, add 5.7g pyridine and 7.4g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours, carry out above-mentioned same precipitation, washing, decompression, obtain the polyimide that 19.5g logarithm viscosity is 0.53dl/g (it is called as " polyimide (A-2) ").
Synthesis example 3
In synthesis example 2 except the diamine compound that uses 64.88g (0.6 mole) p-phenylenediamine, 209.13g (0.4 mole) above-mentioned formula (16) expression as diamine compound, similarly operate with synthesis example 2, obtaining 450g logarithm viscosity is the polyamic acid of 0.33dl/g.Then, except using 4.8g pyridine and 6.1g acetic anhydride, similarly operate, obtain the polyimide that 20.1g logarithm viscosity is 0.41 dl/g (it is called as " polyimide (A-3) ") with synthesis example 2.
Synthesis example 4
In synthesis example 2 except using 75.70g (0.7 mole) p-phenylenediamine, 39.65g (0.2 mole) 1, the diamine compound of 1-two (4-aminophenyl) methane, 52.28g (0.1 mole) above-mentioned formula (16) expression is as beyond the diamine compound, similarly operate with synthesis example 2, obtaining 363g logarithm viscosity is the polyamic acid of 0.39 dl/g.Then, except using 12.1g pyridine and 15.6g acetic anhydride, similarly operate, obtain the polyimide that 24.3g logarithm viscosity is 0.50dl/g (it is called as " polyimide (A-4) ") with synthesis example 2.
Synthesis example 5
In synthesis example 4, except using 37.66g (0.1 mole) 2,4-diaminostilbene-octadecane oxygen base benzene replaces diamine compound (16) in addition, similarly operates with synthesis example 4, obtains the polyimide that 24.3g logarithm viscosity is 0.42dl/g (it is called as " polyimide (A-5) ").
Synthesis example 6
In synthesis example 4, except using 36.65g (0.1 mole) 4-(4-n-heptyl cyclohexyl) phenoxy group-2, the 4-diaminobenzene replaces diamine compound (16) in addition, similarly operate with synthesis example 4, obtain the polyimide that 24.0g logarithm viscosity is 0.49dl/g (it is called as " polyimide (A-6) ").
Synthesis example 7
In synthesis example 1, except using 109.06g (0.5 mole) pyromellitic acid dianhydride and 98.06g (0.5 mole) tetramethylene tetracarboxylic dianhydride as the tetracarboxylic dianhydride, (198.27g 1.0 moles) 4,4 '-diaminodiphenyl-methane is as beyond the diamine compound, similarly operate with synthesis example 1, obtain the polyamic acid that 401g logarithm viscosity is 0.95dl/g (it is called as " polyamic acid (B-1) ").
Synthesis example 8
In synthesis example 7, except using 200.5g (1.01 moles) 4,4 '-diaminodiphenyl-methane is similarly operated with synthesis example 7 as beyond the diamine compound, obtains the polyamic acid that 410g logarithm viscosity is 0.81dl/g (it is called as " polyamic acid (B-2) ").
Synthesis example 9
In synthesis example 2, except using 85.43g (0.79 mole) p-phenylenediamine, similarly operate synthesizing imide with synthesis example 2 and give polymers, it is dissolved in the N-N-methyl-2-2-pyrrolidone N-, be made into the solution that solid component concentration is 10 weight %.And, use the polyamic acid (B-2) of gained in the above-mentioned synthesis example 8 to give polymers as amido acid, it is dissolved in the N-N-methyl-2-2-pyrrolidone N-, be made into the solution that solid component concentration is 10 weight %.Then, the 500g imide is given polymers solution to give polymers with the 500g amido acid and mixes, stir after 2 hours, reaction soln is injected in the big excessive methyl alcohol, make the reaction product precipitation, then, use methanol wash, in 40 ℃ of dryings 15 hours, obtain the part imide amination polymer that 99g logarithm viscosity is 0.67dl/g (it is called as " polymkeric substance (C-1) ") by under reduced pressure.
Synthesis example 10
In synthesis example 3, except using 63.80g (0.59 mole) p-phenylenediamine, similarly operate synthesizing imide with synthesis example 3 and give polymers, then, similarly operate with synthesis example 9, obtain the part imide amination polymer that 98g logarithm viscosity is 0.55dl/g (it is called as " polymkeric substance (C-2) ").
Synthesis example 11
In synthesis example 4, except using 74.62g (0.69 mole) p-phenylenediamine, similarly operate synthesizing imide with synthesis example 4 and give polymers, then, similarly operate with synthesis example 9, obtain the part imide amination polymer that 99g logarithm viscosity is 0.72dl/g (it is called as " polymkeric substance (C-3) ").
Embodiment 1
The polyamic acid (A-1) that makes in the synthesis example 1 is dissolved in the mixed solvent of N-N-methyl-2-2-pyrrolidone N-/gamma-butyrolactone (weight ratio 30/70), with respect to 100 parts by weight polymer, dissolve 10 weight part polyethyleneglycol diglycidylethers (molecular weight is about 400), make the solution that solid component concentration is 4 weight %, after fully stirring, is the filter filtration of 1 μ m with this solution with the aperture, prepares liquid crystal orientating agent of the present invention.Above-mentioned liquid crystal orientating agent is coated on the ITO film system nesa coating that is arranged on the thick glass substrate one side of 1mm and on the reflectance coating of Al system by spin coater, by descending drying 1 hour at 200 ℃, forming dry film thickness is filming of 0.08 μ m.Then, on each outer rim with the above-mentioned coating of liquid crystalline oriented film substrate of a pair of transparency electrode/transparent electrode substrate and a pair of transparency electrode/reflective electrode substrate with liquid crystal orientating membrane, it is the epoxy resin binder of the alumina balls of 5.5 μ m that coating adds diameter, then, the liquid crystal aligning face is relatively overlapped and carry out pressing, tackiness agent is solidified.Then, (メ Le Network society system MLC-6608), is sealed liquid crystal injecting port with the acrylic acid or the like Photocurable adhesive then, and bonding polaroid on the two sides in the substrate outside is made liquid crystal display device to fill negative type liquid crystal by liquid crystal injecting port between substrate.Print, reliability to the gained liquid crystal display device are estimated.Adopt spin coater to coat on the quartz base plate that thickness is 1.5mm the liquid crystal orientating agent of the present invention of as above preparation, similarly form during with the making liquid crystal display device and film.Filming of made estimated the transparency by transmitance mensuration.The results are shown in table 2.Confirmed that the liquid crystal orientating agent print and the reliability of gained is good among the present invention.
Embodiment 2～30
According to the prescription shown in following table 1 and the table 2, it is in the mixed solvent of main component that polyimide (A-2)～(A-6), polyamic acid (B-1)～(B-2), the part imide amination polymer (C-1)～(C-3) of gained in the synthesis example 2～7 and the compound, the silane coupling agent that contain epoxy group(ing) are dissolved in the gamma-butyrolactone, obtain solid component concentration and be 4.0% solution, is the filter filtration of 1 μ m with this solution with the aperture, modulates liquid crystal orientating agent of the present invention.Adopt synthetic liquid crystal orientating agent like this respectively, operation forms on substrate surface and films similarly to Example 1, with the substrate manufacture liquid crystal display device that forms this liquid crystal orientating membrane.And, the transparency, print characteristic and reliability are estimated.The results are shown in table 2.
Comparative example 1～5
According to the prescription shown in following table 1 and the table 2, similarly make liquid crystal display device with embodiment.And the transparency, voltage residual rate and print characteristic are estimated.The results are shown in table 2.
Claims (2)
1. the purposes of vertical liquid crystal orientating agent in having the vertical liquid crystal display element of reflecting electrode, it is characterized in that this vertical liquid crystal orientating agent comprises that 100 weight parts have the repeating unit of following formula (1) expression and/or the polymkeric substance of the repeating unit that following formula (2) is represented, and at least 5 weight part intramolecularly compound of having 2 epoxy group(ing) at least
In the formula, P
1Be the organic group of 4 valencys, and Q
1Organic group for divalent;
In the formula, P
2Be the organic group of 4 valencys, and Q
2Be the organic group of divalent,
Wherein the intramolecularly compound that has 2 epoxy group(ing) at least is at least a compound that contains epoxy group(ing) of the compound of the compound that is selected from following formula (3) expression and following formula (4) expression,
In the formula, R
01The aliphatic group of expression divalent,
In the formula, R
02The organic group of expression divalent.
2. the purposes of vertical liquid crystal orientating agent as claimed in claim 1 in having the vertical liquid crystal display element of reflecting electrode, wherein the transmitance of polymkeric substance in 300nm～700nm wavelength region be 90% or more than.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004185869A JP4502119B2 (en) | 2004-06-24 | 2004-06-24 | Vertical liquid crystal display device having a reflective electrode |
| JP2004185869 | 2004-06-24 | ||
| JP2004-185869 | 2004-06-24 |
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| CN1712491A CN1712491A (en) | 2005-12-28 |
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| JP5170372B2 (en) * | 2006-06-02 | 2013-03-27 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| CN101082741A (en) * | 2006-06-02 | 2007-12-05 | Jsr株式会社 | Liquid crystal tropism agent and liquid crystal display element |
| CN101135813B (en) * | 2006-08-29 | 2011-03-16 | Jsr株式会社 | Liquid crystal tropism agent, liquid crystal tropism film and liquid crystal display element |
| KR101310350B1 (en) * | 2006-10-10 | 2013-09-23 | 삼성디스플레이 주식회사 | Material For Alignment And Liquid Crysta Display Apparatus Using The Same |
| JP2008122942A (en) * | 2006-10-17 | 2008-05-29 | Jsr Corp | Liquid crystal aligning agent and liquid crystal display element |
| JP5516836B2 (en) * | 2006-12-28 | 2014-06-11 | Ｊｓｒ株式会社 | Vertical alignment type liquid crystal aligning agent and vertical alignment type liquid crystal display element |
| JP5041157B2 (en) * | 2007-01-10 | 2012-10-03 | Ｊｓｒ株式会社 | Vertical alignment type liquid crystal aligning agent and vertical alignment type liquid crystal display element |
| WO2008117615A1 (en) | 2007-03-26 | 2008-10-02 | Sharp Kabushiki Kaisha | Liquid crystal display device and polymer for aligning film material |
| JP5120047B2 (en) * | 2007-05-02 | 2013-01-16 | Ｊｓｒ株式会社 | Vertical alignment type liquid crystal aligning agent and liquid crystal display element |
| JP5077048B2 (en) * | 2007-05-02 | 2012-11-21 | Ｊｓｒ株式会社 | Vertical alignment type liquid crystal alignment agent |
| JP5360376B2 (en) * | 2008-03-07 | 2013-12-04 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| KR101212667B1 (en) | 2008-12-02 | 2012-12-14 | 제일모직주식회사 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display including same |
| JP5311054B2 (en) * | 2009-02-19 | 2013-10-09 | Ｊｓｒ株式会社 | Liquid crystal aligning agent, liquid crystal display element and manufacturing method thereof |
| TWI392935B (en) | 2009-10-02 | 2013-04-11 | Chi Mei Corp | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN102051185B (en) * | 2009-11-03 | 2013-07-17 | 奇美实业股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| JP5853728B2 (en) * | 2011-02-28 | 2016-02-09 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| WO2014168256A1 (en) | 2013-04-11 | 2014-10-16 | 住友化学株式会社 | Alignment layer for optically anisotropic film |
| CN104345370B (en) | 2013-08-09 | 2018-08-24 | 住友化学株式会社 | Optical film |
| CN104339796B (en) | 2013-08-09 | 2018-03-02 | 住友化学株式会社 | Layered product |
| TWI645962B (en) | 2013-08-09 | 2019-01-01 | 住友化學股份有限公司 | Optically anisotropic sheet |
| KR102223121B1 (en) | 2013-08-09 | 2021-03-05 | 스미또모 가가꾸 가부시키가이샤 | Process for producing long retardation film |
| JP6516096B2 (en) * | 2014-08-14 | 2019-05-22 | Jnc株式会社 | Triazole-containing tetracarboxylic acid dianhydride, liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display device |
| CN106318407A (en) * | 2016-08-17 | 2017-01-11 | 中节能万润股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film, preparation method of liquid crystal alignment film and liquid crystal display element |
| CN110520789A (en) * | 2017-03-31 | 2019-11-29 | 夏普株式会社 | Liquid crystal display device, the manufacturing method of liquid crystal display device, electronic equipment |
| KR101994430B1 (en) * | 2017-06-30 | 2019-09-24 | 주식회사 엘지화학 | Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film using the same |
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| JP3206401B2 (en) * | 1995-11-20 | 2001-09-10 | ジェイエスアール株式会社 | Liquid crystal alignment agent and liquid crystal display device |
| JP3840743B2 (en) * | 1997-06-03 | 2006-11-01 | Ｊｓｒ株式会社 | Liquid crystal alignment agent |
| JP3968823B2 (en) * | 1997-06-09 | 2007-08-29 | Ｊｓｒ株式会社 | Liquid crystal alignment agent |
| JP2002323701A (en) * | 2001-04-25 | 2002-11-08 | Jsr Corp | Homeotropic alignment type liquid crystal aligning agent |
| JP2004012795A (en) * | 2002-06-06 | 2004-01-15 | Sony Corp | Reflection type liquid crystal display element and liquid crystal display device |
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| KR100852578B1 (en) | 2008-08-18 |
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| KR20060049699A (en) | 2006-05-19 |
| TW200617481A (en) | 2006-06-01 |
| CN1712491A (en) | 2005-12-28 |
| JP2006010896A (en) | 2006-01-12 |
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