CN1661428A - Liquid crystal orientation agent - Google Patents
Liquid crystal orientation agent Download PDFInfo
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- CN1661428A CN1661428A CN200510007467XA CN200510007467A CN1661428A CN 1661428 A CN1661428 A CN 1661428A CN 200510007467X A CN200510007467X A CN 200510007467XA CN 200510007467 A CN200510007467 A CN 200510007467A CN 1661428 A CN1661428 A CN 1661428A
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- liquid crystal
- dicarboxylic anhydride
- carboxylic acid
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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
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
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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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- Crystallography & Structural Chemistry (AREA)
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- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Liquid Crystal (AREA)
Abstract
The invention is to provide a liquid crystal aligning agent for a liquid crystal display device to obtain a liquid crystal alignment layer having excellent burning characteristics even when not only an ITO but a reflective electrode is used, and to provide a liquid crystal display device having a liquid crystal alignment layer obtained from the agent. The liquid crystal aligning agent comprises 100 parts by weight of a polymer having an amic acid repeating unit and an imide repeating unit, with the proportion of the amic acid repeating unit by 40 to 60% by weight in the entire repeating units, and at least 5 parts by weight of a compound having at least two epoxy groups in the molecule.
Description
Technical field
The present invention relates to aligning agent for liquid crystal.In more detail, relate to and be not limited to the type of electrodes that constitutes liquid crystal display cells and the good aligning agent for liquid crystal of sintering characteristic.
Background technology
Past, the TN type liquid crystal display cells of having that people know has TN (Twisted Nematic) type liquid crystal cell, in its TN type liquid crystal cell, at 2 pieces of insertion nesa coatings and between the substrate of surface formation liquid crystal orientation film, formation has the element that just conducts electricity anisotropic nematic crystal layer and form rhythmo structure, and the major axis of above-mentioned liquid crystal molecule is turned round continuously towards another substrate from a substrate and turn 90 degrees.
In addition, also exist interpolation by the chirality agent to realize that the major axis of this liquid crystal molecule turning round turnback or the state more than 180 degree continuously between substrate, utilize STN (Super Twisted Nematic) the type liquid crystal display cells of consequent birefringence effect.And recently, also developed and between the subtend substrate, formed nematic crystal layer with anisotropic vertical (homeotropic) state of orientation of negative conduction, or screw axis and substrate normal be the cholesterol liquid crystal layer of parastate, adds visitor (guest)-host (host) the type reflection type liquid crystal display element of pigment in these liquid crystal layers.The liquid crystal aligning of these liquid crystal display cells usually, is realized by the liquid crystal orientation film of implementing friction treatment.Here, the liquid crystal aligning membrane material as constituting liquid crystal display cells uses polyimide in the past, and polyamide and polyester etc. is known.Polyimide particularly because thermotolerance, with excellences such as the compatibility of liquid crystal, physical strength, so in most liquid crystal display cells, use.
Recently, in the high-precision research of carrying out with liquid crystal display cells that is refined as main display quality raising, low power consumption quantification etc., the scope of utilizing of liquid crystal display cells is also enlarging.Especially, when outdoor application, also can keep the reflection-type of high display quality or semi-transmission type liquid crystal display cells, use various metal electrodes (below, be called reflecting electrode) in order to bring into play the function that reflects ambient light owing to carrying terminal the use.But, if the liquid crystal display cells with reflecting electrode is with the alignment films of using in the existing ITO electrode then produce the problem of sintering.
Summary of the invention
Be not limited to obtain the used for liquid crystal display element aligning agent for liquid crystal of the liquid crystal orientation film of sintering characteristic excellence under the situation of reflecting electrode of ITO even the object of the present invention is to provide in use.
Other purpose of the present invention and advantage just can be understood from following explanation.
According to the present invention, above-mentioned purpose of the present invention and advantage, realize by aligning agent for liquid crystal, it is characterized in that this aligning agent for liquid crystal contains ratio that 100 weight portions have the represented recurring unit of the represented recurring unit of the represented recurring unit of following formula (I-1) and following formula (I-2) and formula (I-1) and accounts for the compound that has 2 epoxy radicals at least in 40%～60% polymkeric substance of whole recurring units and at least 5 weight portion molecules by weight.
[changing 1]
(in the formula, P
1Be 4 valency organic groups, and Q
1It is the divalent organic group.)
[changing 2]
(in the formula, P
2Be 4 valency organic groups, and Q
2It is the divalent organic group.)
The liquid crystal orientation film that forms by aligning agent for liquid crystal of the present invention, even be not limited in use under the situation of reflecting electrode of ITO, also can obtain the liquid crystal orientation film of sintering characteristic excellence, can suit be formation TN type liquid crystal display cells, STN type liquid crystal display cells uses in the various liquid crystal display cells such as reflection type liquid crystal display element and semi-transmission type liquid crystal display cells.
Liquid crystal display cells of the present invention can use in various devices effectively.For example, can suit to use as display device such as desk-top computer, wrist-watch, timer, mobile phone, counting display board, word processor, PC, LCD TV.
Embodiment
Below, to the detailed description of the invention.
Aligning agent for liquid crystal of the present invention contains the polymkeric substance (hereinafter referred to as " particular polymers ") with the represented recurring unit of above-mentioned formula (I-1) and the represented recurring unit of above-mentioned formula (I-2).This polymkeric substance can be the polyamic acid and the potpourri with polyimide of the represented recurring unit of above-mentioned formula (I-2) that (1) has the represented recurring unit of above-mentioned formula (I-1), also can be that (2) are by above-mentioned formula (I-1) represented recurring unit and the represented recurring unit of above-mentioned formula (I-2), random or block-wise bonding in a part and the polymkeric substance that forms (below, be called " part imide amination polymer ").
Above-mentioned polyamic acid can make tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound ring-opening polymerization addition and obtains.In addition, polyimide is usually the polyamic acid dehydration closed-loop to be obtained.The part imide amination polymer is usually can be by making the method for polyamic acid partial dehydration closed loop, or with the method for amic acid prepolymer and imide prepolymer bonding synthetic segmented copolymer and obtain.
＜polyamic acid 〉
[tetrabasic carboxylic acid dicarboxylic anhydride]
As the tetrabasic carboxylic acid dicarboxylic anhydride, for example can enumerate butanetetra-carboxylic acid dicarboxylic anhydride, 1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,2-dimethyl-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,3-two chloro-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,2,3,4-encircles penta tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-hexamethylene tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-two hexamethylene tetrabasic carboxylic acid dicarboxylic anhydrides, 2,3,5-tricarboxylic basic ring amyl group acetate dicarboxylic anhydride, 3,5,6-three carboxyls norbornane-2-acetate dicarboxylic anhydride, 2,3,4,5-tetrahydrofuran tetrabasic carboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[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)-naphtho-[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)-naphtho-[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)-naphtho-[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)-naphtho-[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)-naphtho-[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)-naphtho-[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)-naphtho-[1,2-c]-furans-1, the 3-diketone, 5-(2,5-dioxo tetrahydrofurfuryl)-and 3-methyl-3-cyclohexane-1,2-dicarboxylic acid dicarboxylic anhydride, dicyclo [2,2,2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3-oxo dicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), following formula (I) and (II) represented aliphatics and ester ring type tetrabasic carboxylic acid dicarboxylic anhydrides such as compound;
[changing 3]
(in the formula, R
1And R
3, expression has the divalent organic group of aromatic rings, R
2And R
4, expression hydrogen atom and alkyl, a plurality of R of existence
2And R
4, can be the same or different respectively.)
Equal benzene tertacarbonic acid's dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl ether tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-tetraphenyl silane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-furans tetrabasic carboxylic acid dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylsulfide dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfone dicarboxylic anhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl propane dicarboxylic anhydride, 3,3 ', 4,4 '-perfluor isopropylidene, two phthalic acid dicarboxylic anhydrides, 3,3 ', 4,4 '-diphenyl tetrabasic carboxylic acid dicarboxylic anhydride, two (phthalic acid) phenyl phosphine oxide dicarboxylic anhydride is to penylene-two (triphenyl phthalic acid) dicarboxylic anhydride, between penylene-two (triphenyl phthalic acid) dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl ether dicarboxylic anhydride, two (triphenyl phthalic acids)-4,4 '-diphenyl methane dicarboxylic anhydride, ethylene glycol-two (dehydration trimellitate), propylene glycol-two (dehydration trimellitate), 1,4-butylene glycol-two (dehydration trimellitate), 1,6-hexanediol-two (dehydration trimellitate), 1,8-ethohexadiol-two (dehydration trimellitate), 2, two (4-hydroxy phenyl) propane-two (dehydration trimellitate) of 2-, following formula (1)～(4) represented aromatic tetracarboxylic acid's anhydride compounds such as compound.They can a kind separately or will at least 2 kinds be used in combination.
[changing 4]
Wherein, from bringing into play the viewpoint of good liquid crystal aligning, preferred butanetetra-carboxylic acid dicarboxylic anhydride, 1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,2-dimethyl-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,3-two chloro-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,2,3,4-encircles penta tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-hexamethylene tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrofurfuryl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[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 naphtho-[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)-naphtho-[1,2-c]-furans-1, the 3-diketone, dicyclo [2,2,2]-and Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3-oxo dicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), equal benzene tertacarbonic acid's dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic acid dicarboxylic anhydride, the represented compound of following formula (8) in compound that following formula (5)～(7) in the represented compound of above-mentioned formula (I) are represented and the represented compound of above-mentioned formula (II).As particularly preferred compound, can enumerate 1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,2-dimethyl-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,3-two chloro-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,2,4,5-hexamethylene tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c] furans-1,3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[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 naphtho-[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)-naphtho-[1,2-c]-furans-1, the 3-diketone, 3-oxo dicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), equal benzene tertacarbonic acid's dicarboxylic anhydride, all benzene tertacarbonic acid's dicarboxylic anhydride and the represented compound of following formula (5).
[changing 5]
P in the represented recurring unit (amic acid unit) of above-mentioned formula (I-1)
1P in the represented recurring unit (acid imide unit) of 4 represented valency organic groups and above-mentioned formula (I-2)
24 represented valency organic groups all are to be derived and next group by the tetrabasic carboxylic acid dicarboxylic anhydride.They can be the same or different.As P in the above-mentioned formula (I-1)
1Preferred embodiment, can enumerate respectively by following formula (i) and (i ') represented group.As P in the above-mentioned formula (I-2)
2Preferred embodiment, can enumerate group, especially preferably respectively (ii) and (ii ') represented group by following formula with alicyclic ring skeleton.
[changing 6]
(in the formula, R is a halogen atom, and methyl or ethyl, a are 0 or 1 integers, and b is 0～6 integer, and c is 0～4 integer, and d is 0～5 integer.)
As the instantiation of preferred tetrabasic carboxylic acid dicarboxylic anhydride in each recurring unit,, can enumerate 1,2 as the tetrabasic carboxylic acid dicarboxylic anhydride that constitutes amic acid unit, 3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,2-dimethyl-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,3-two chloro-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-ring butanetetra-carboxylic acid dicarboxylic anhydride, 1,2,4,5-hexamethylene tetrabasic carboxylic acid dicarboxylic anhydride, equal benzene tertacarbonic acid's dicarboxylic anhydride etc., in addition, be to enumerate ester ring type tetrabasic carboxylic acid dicarboxylic anhydride as the tetrabasic carboxylic acid dicarboxylic anhydride that constitutes acid imide unit, particularly can enumerate 2,3,5-tricarboxylic basic ring amyl group acetate dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1,3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1,3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1,3-diketone etc.
[diamine compound]
As the synthetic middle diamine compound that uses of above-mentioned polyamic acid, 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 '-diamino-diphenyl ether, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (4-aminophenyl) HFC-236fa of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] sulfones of 2-, 1, two (4-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 3-, 9, two (4-the aminophenyl)-10-hydrogen anthracenes of 9-, 2, the 7-diamino-fluorene, 9, two (4-aminophenyl) fluorenes of 9-, 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 penylene isopropylidene) biphenylamine, 4,4 '-(a penylene isopropylidene) biphenylamine, 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, the 4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene bicyclopentadiene diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0
2,7]-hendecene dimethyl diamines, 4,4 '-di-2-ethylhexylphosphine oxide aliphatics and ester ring type diamines such as (cyclo-hexylamine);
2,3-diamino-pyridine, 2,6-diamino-pyridine, 3,4-diamino-pyridine, 2, the 4-diamino-pyridine, 5,6-diamido-2,3-dicyano pyrazine, 5,6-diamido-2, the 4-dihydroxy-pyrimidine, 2,4-diamido-6-dimethylamino-1,3,5-triazine, 1, two (3-aminopropyl) piperazines of 4-, 2,4-diamido-6-isopropoxy-1,3,5-triazine, 2,4-diamido-6-methoxyl-1,3,5-triazines, 2,4-diamido-6-phenyl-1,3, the 5-triazine, 2,4-diamido-6-methyl-s-triazine, 2,4-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, 2,4-triazole, 6,9-diamido-2-ethoxy acridine lactate, 3,8-diamido-6-phenylphenanthridineand, 1,4-diamido piperazine, 3, the 6-proflavin, the compound that two (4-aminophenyl) aniline and following formula (III)～(IV) are represented etc., the diamines of the nitrogen-atoms beyond 2 primary amino radicals and this primary amino radical had in the molecule;
[changing 7]
(in the formula, R
5Expression has the pyridine of being selected from, pyrimidine, and triazine, 1 valency organic group of the ring structure that contains nitrogen-atoms of piperidines and piperazine, X represents the divalent organic group.)
[changing 8]
(in the formula, X represents to have the pyridine of being selected from, pyrimidine, triazine, the divalent organic group of the ring structure that contains nitrogen-atoms of 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 diamido organosiloxane that following formula (VI) is represented;
[changing 9]
(in the formula, R
7Expression is selected from-O-,-COO-,-OCO-,-NHCO-,-CONH-and-the divalent organic group of CO-, R
8Expression has the steroid skeleton of being selected from, the 1 valency organic group of the group of trifluoromethyl and fluorine or the alkyl of carbon number 6～30.)
[changing 10]
(in the formula, R
9The alkyl of expression carbon number 1～12, the R of a plurality of existence
9Can be the same or different respectively, p is 1～3 integer, and q is 1～20 integer.)
The compound that following formula (9)～(13) are represented etc.These diamine compounds can be separately also can 2 kinds be used in combination at least.
(in the formula, y is 2～12 integer, and z is 1～5 integer.)
Wherein, preferred p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl thioether, 1,5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 9, two (4-aminophenyl) fluorenes of 9-, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2-, 2, two (4-aminophenyl) HFC-236fa of 2-, 4,4 '-(to the benzene diisopropylidene) biphenylamine, 4,4 '-(a benzene diisopropylidene) biphenylamine, 1, the 4-cyclohexanediamine, 4,4 '-methylene bis (cyclohexylamine), 1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, above-mentioned formula (9)～(13) represented compound, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, the represented compound of following formula (14) in the represented compound of above-mentioned formula (III), following formula (16)～(21) the represented compound in the represented compound of compound that the following formula (15) in the represented compound of above-mentioned formula (IV) is represented and above-mentioned formula (V).
[changing 12]
[synthetic reaction of polyamic acid]
For the tetrabasic carboxylic acid dicarboxylic anhydride of polyamic acid synthetic reaction and the usage ratio of diamine compound, with respect to the amino that contains in the 1 equivalent diamine compound, the anhydride group of tetrabasic carboxylic acid dicarboxylic anhydride is preferably 0.2～2 equivalent, and 0.3～1.2 equivalent more preferably.
The synthetic reaction of polyamic acid preferably in organic solvent, at-20～150 ℃, is more preferably carried out under 0～100 ℃ the temperature conditions.Here, as organic solvent, just be not particularly limited as long as can dissolve synthetic polyamic acid, for example, can illustration N-N-methyl-2-2-pyrrolidone N-, N,N-dimethylacetamide, N, dinethylformamide, dimethyl sulfoxide, gamma-butyrolacton, 4-methyl urea, aprotic polar solvents such as HMPA; Metacresol, xylenols, phenol, phenol solvents such as halogenated phenol.In addition, the use amount of organic solvent (a) is preferably the total amount (b) that makes tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound, is the amount of 0.1～30 weight % with respect to the amount (a+b) of total overall reaction solution.
[Weak solvent]
In above-mentioned organic solvent, can in the scope that the polyamic acid that is generated is not separated out, unite the Weak solvent alcohols that uses polyamic acid, ketone, ester class, ethers, halogenated hydrocarbon, hydro carbons etc.As the instantiation of this Weak solvent, for example, can enumerate methyl alcohol, ethanol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butylene glycol, triethylene glycol, glycol monoethyl ether, ethyl lactate, butyl lactate, acetone, MEK, methylisobutylketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy base propionic ester, ethyl ethoxy-c acid esters, diethy-aceto oxalate, diethyl malonate, ether, Ethylene Glycol Methyl ether, glycol ethyl ether, the ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, tetrahydrofuran, methylene chloride, 1,2-ethylene dichloride, 1, the 4-dichloroetane, trichloroethanes, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene etc.
As mentioned above, obtained dissolving polyamic acid and reaction solution.Then, this reaction solution is injected a large amount of Weak solvents obtain precipitate, by this precipitate drying under reduced pressure can be obtained polyamic acid.In addition, by carrying out 1 time or for several times this polyamic acid being dissolved in the operation of separating out then in the organic solvent once more in Weak solvent, can make with extra care polyamic acid.
[imide amination polymer]
＜imide amination polymer 〉
Constitute the imide amination polymer of aligning agent for liquid crystal of the present invention, can be by above-mentioned polyamic acid dehydration closed-loop be prepared.The dehydration closed-loop of polyamic acid, for example can (i) by method with the polyamic acid heating, perhaps, in this solution, add the method for dewatering agent and dehydration closed-loop catalyzer and heating as required and carry out easily (ii) by polyamic acid is dissolved in the organic solvent.
The temperature of reaction with the polyamic acid heating means of above-mentioned (i) is preferably 50～200 ℃, more preferably 60～170 ℃.50 ℃ of temperature of reaction less thaies, the dehydration closed-loop reaction is difficult to carry out fully, and temperature of reaction surpasses 200 ℃, and gained imide amination polymer molecular weight can reduce.
On the other hand, in the above-mentioned method of in polyamic acid solution, adding dewatering agent and dehydration closed-loop catalyzer (ii),, for example can use acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride as dewatering agent.The use amount of dewatering agent is preferably 0.01～20 mole with respect to 1 mole of polyamic acid recurring unit.In addition, as the dehydration closed-loop catalyzer, can use for example pyridine, trimethylpyridine, lutidines, tertiary amines such as triethylamine.But, be not limited to these.The use amount of dehydration closed-loop catalyzer is preferably 0.01～10 mole with respect to 1 mole of employed dewatering agent.In addition, as the organic solvent that uses in the dehydration closed-loop reaction, can enumerate the identical organic solvent of the illustrated organic solvent of solvent that in polyamic acid is synthetic, uses with conduct.And the temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 10～150 ℃.In addition, for the reaction solution that obtains like this,, can make with extra care imide amination polymer by carrying out the operation same with the polyamic acid process for purification.
[part acid imide]
＜contain the polyamic acid of imino group 〉
The polyamic acid that contains imino group that uses among the present invention has the above-mentioned polyamic acid structure of imino group gained partly.Imidizate rate in the polyamic acid that contains imino group that uses among the present invention is preferably 10～90%, and more preferably 30～70%.Herein, so-called " imidizate rate " is meant the recurring unit's sum of representing with % with respect to polymkeric substance, form imide ring and the ratio of recurring unit's number.At this moment, the part of imidizate can be different imide ring.
As the synthetic method that contains the polyamic acid of imino group, can use for example (i) method by above-mentioned polyamic acid heating part dehydration closed-loop is synthesized, (ii) above-mentioned polyamic acid is dissolved in the organic solvent, in this solution, add dewatering agent and dehydration closed-loop catalyzer and heating as required, partial dehydration closed loop and synthetic method, or (iii) mix the tetrabasic carboxylic acid dicarboxylic anhydride, diamine compound and diisocyanate cpd, and heat as required, the synthetic method of condensation (iv) makes polyamic acid prepolymer and imide prepolymer bonding obtain the method for segmented copolymer thus.
In the method for above-mentioned (i), temperature of reaction is preferably and is not higher than 300 ℃, more preferably 100～250 ℃.If surpassing the molecular weight of the polyamic acid that contains imino group of 300 ℃ of gained, temperature of reaction can reduce.
On the other hand, as the dewatering agent that in above-mentioned method (ii), uses, can enumerate for example acetic anhydride, propionic andydride, acid anhydrides such as trifluoroacetic anhydride.The use amount of dewatering agent is preferably 0.2～20 mole with respect to 1 mole of polyamic acid recurring unit.In addition, as the dehydration closed-loop catalyzer, can use for example pyridine, trimethylpyridine, lutidines, tertiary amines such as triethylamine.But, be not limited to these.In addition, the use amount of imidization catalyst is preferably with respect to 1 mole of employed dewatering agent and 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 the illustrated organic solvent of solvent that in polyamic acid is synthetic, uses with conduct.And the temperature of reaction of dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 60～150 ℃.In addition, for the reaction solution that obtains like this,, can make with extra care the polyamic acid that contains imino group by carrying out the operation same with the polyamic acid process for purification.
As the instantiation of the diisocyanate cpd that in above-mentioned (iii) reaction, uses, can enumerate aliphatic diisocyanates such as HDI; Cyclohexane-1,2-diisocyanate, 1-methylcyclohexane-2, the 4-diisocyanate, 1,2-dimethyl cyclohexane-ω, ω '-diisocyanate, 1,4-dimethyl cyclohexane-ω, ω '-diisocyanate, isophorone diisocyanate, 1,3,5-trimethyl-2-propyl cyclohexane 1 ω, 2 ω-diisocyanate, dicyclohexyl methyl hydride-4, ester ring type diisocyanate such as 4 '-diisocyanate; Diphenyl methane-4,4 '-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, following formula (22)～(26) represented aromatic diisocyanates such as diisocyanate.
Wherein, can enumerate dicyclohexyl methyl hydride-4,4 '-diisocyanate, diphenyl methane-4,4 '-diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate as preferred example.They can be used in combination separately or with at least 2 kinds.In addition, above-mentioned catalysts (iii) is not necessary especially, and temperature of reaction is preferably 50～200 ℃, more preferably 100～160 ℃.
In above-mentioned method (iv), the amic acid prepolymer becomes except that the amount ratio of adjusting tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound the polymkeric substance that end has amino or anhydride group, can also obtain by the method identical with above-mentioned polyamic acid synthetic method.
Imide prepolymer, removing can be by the method with above-mentioned amic acid prepolymer dehydration closed-loop, perhaps, adjust the amount ratio of diisocyanate cpd and diamine compound and become beyond the polymkeric substance that end has amino or isocyanate group, can also be by obtaining with above-mentioned (iii) identical method.
By amino and the anhydride group that makes each end in these prepolymers, perhaps amino and isocyanates radical reaction can synthetic segmented copolymer.
[end modified]
＜end modified type polymkeric substance 〉
Above-mentioned polyamic acid and the polyamic acid that contains imino group can be the end modified type polymkeric substance of having regulated molecular weight.By using this end modified type polymkeric substance, can improve the coating characteristics etc. of aligning agent for liquid crystal and can not make effect of the present invention impaired.This end modified type polymkeric substance can add monoester anhydride by in synthesizing polyamides when acid in reaction system, monoamine compound, monoisocyanates compound etc. and synthesizing.Here,, can enumerate maleic anhydride, phthalic anhydride, itaconicacid acid anhydride, positive decyl succinic anhydride, dodecyl succinic anhydride, n-tetradecane base succinic anhydride, n-hexadecyl succinic anhydride etc. as monoester anhydride.In addition, as monoamine compound,, can enumerate for example aniline, cyclo-hexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, positive undecylamine, positive lauryl amine, positive tridecyl amine, positive tetradecy lamine, positive pentadecyl amine, positive cetylamine, positive heptadecyl-amine, positive octadecylamine, positive 20 amine etc.In addition, as the monoisocyanates compound, can enumerate for example phenyl isocyanate, naphthyl isocyanate etc.
[logarithm viscosity]
The logarithm viscosity of＜polymkeric substance 〉
Polyamic acid that as above obtains and the logarithm viscosity (η that contains the polyamic acid of imino group
Ln) value is preferably 0.05～10dl/g, 0.05～5dl/g more preferably.
Logarithm viscosity (η of the present invention
Ln) value, can use the N-N-methyl-2-2-pyrrolidone N-as solvent, be that the solution of 0.5g/100 milliliter carries out viscosimetric analysis at 30 ℃ to concentration, (A) obtains by following formula.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention, preferably dissolving contains above-mentioned polymkeric substance and constitutes in organic solvent.Constitute the polymkeric substance of aligning agent for liquid crystal of the present invention, contain the represented recurring unit of above-mentioned formula (I-1) that accounts for whole recurring units 40～60%.The represented recurring unit of above-mentioned formula (I-1): the ratio of the recurring unit that above-mentioned formula (I-2) is represented is preferably 4: 6～and 6: 4, more preferably 5: 5.
As the organic solvent that constitutes aligning agent for liquid crystal of the present invention, can enumerate the illustrated solvent of solvent that uses as in polyamic acid is synthetic.The illustrative Weak solvent of solvent of uniting use in the time of in addition, also can suiting to select and be used in the polyamic acid synthetic reaction.
Solid component concentration in the aligning agent for liquid crystal of the present invention can be considered viscosity, and back selection such as volatility is preferably in the scope of 1～10 weight %.That is, aligning agent for liquid crystal of the present invention is coated on substrate surface, becomes filming of liquid crystal orientation film, but under the situation of solid component concentration less than 1 weight %, and this thickness of filming is too small and be difficult to obtain good liquid crystal orientation film.Solid component concentration surpasses under the situation of 10 weight %, and the thickness of filming is excessive and can not obtain good liquid crystal orientation film, and in addition, the viscosity of aligning agent for liquid crystal increases the easy variation of coating characteristics.In addition, the temperature when preparing aligning agent for liquid crystal of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
Aligning agent for liquid crystal of the present invention contains the compound that has 2 epoxy radicals in the 5 weight portion molecules at least (below be called " compound that contains epoxy radicals ") at least with respect to 100 parts by weight polymer.
As this change thing that contains epoxy radicals, can enumerate for example represented compound of following formula (1)
[changing 14]
Here, R
10Expression divalent fat-based, and the represented compound of following formula (2)
[changing 15]
Here, R
11Expression divalent organic group.Contain epoxy compounds, can be separately or at least 2 kinds be used in combination.
Contain epoxy compounds as this, preferably can enumerate for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2,4-hexanediol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (N, the N-diglycidyl amino methyl) cyclohexanes of 3-, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.Contain the content of epoxy compounds as this, be preferably 5～40 weight portions with respect to containing above-mentioned particular polymers in the 100 weight portion alignment agents, more preferably 10～30 weight portions can contain in harmless degree as the alignment agent characteristic.
In addition, aligning agent for liquid crystal of the present invention can contain the compound of functional silanes.Contain the compound of functional silanes as this, 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-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-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, two (the ethylene oxide)-3-TSL 8330s of N-, two (the ethylene oxide)-3-aminopropyltriethoxywerene werene of N-etc.
These contain the blending ratio of the compound of functional silanes, with respect to 100 parts by weight polymer, are preferably and are not higher than 40 weight portions, more preferably 0.1～30 weight portion.
＜liquid crystal display cells 〉
The liquid crystal display cells that uses aligning agent for liquid crystal of the present invention to obtain can pass through for example following method manufacturing.
(1) by for example roll coating process, rotary process, print process, methods such as ink-jet method, coating aligning agent for liquid crystal of the present invention then, is filmed by coated face is added thermosetting on the one side of the substrate that is provided with the Butut nesa coating.Here, as substrate, for example can use glass such as float glass, soda-lime glass; By polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, the transparency carrier that plastics such as polycarbonate form.Nesa coating as being arranged on the substrate one side can use by tin oxide (SnO
2) the NESA film (U.S. PPG register of company trade mark) that forms, indium oxide-tin oxide (In
2O
3-SnO
2) the ITO film that forms etc.The pattern of these nesa coatings can use photo-engraving process or with the method for pre-mask.Can use metals such as Al or Ag in the reflecting electrode, perhaps, contain the alloy of these metals etc.Just be not limited to these as long as have sufficient reflectivity.During the coating of aligning agent for liquid crystal, better for the cohesive that makes substrate surface and nesa coating or reflecting electrode and film, can be coated with the compound that contains functional silanes, the compound that contains the functionality titanium etc. on this surface of substrate in advance.Heating-up temperature after the aligning agent for liquid crystal coating is preferably 80～300 ℃, more preferably 120～250 ℃.The aligning agent for liquid crystal of the present invention that contains polyamic acid, removing organic solvent by coating becomes filming of alignment films, carries out dehydration closed-loop by heating again, can become filming of further imidizate.The thickness that formation is filmed is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) coated surface that forms is rubbed in a certain direction and carries out friction treatment with being tied with the cylinder of for example being rolled by fibroplastic cloth such as nylon, rayon, cotton.Like this, on filming, give the liquid crystal molecular orientation ability, formed liquid crystal orientation film.
In addition; the liquid crystal orientation film that forms by aligning agent for liquid crystal of the present invention; by carrying out shown in Japanese kokai publication hei 6-222366 communique or Japanese kokai publication hei 6-281937 communique; change the processing at pre-oblique angle by the local irradiation ultraviolet ray; perhaps carry out shown in Japanese kokai publication hei 5-107544 communique; form diaphragm at the liquid crystal orientation film surface local of implementing friction treatment; carry out removing diaphragm after the friction treatment with previous friction treatment different directions; with the processing of the liquid crystal aligning ability that changes liquid crystal orientation film, can improve the visual field characteristic of liquid crystal display cells.
(3) make two substrates that form liquid crystal orientation film as mentioned above, make the vertical or antiparallel of frictional direction of liquid crystal orientation film respectively, two plate bases are inserted gap (unit interval) subtend configuration, peripheral part of two plate bases is pasted with sealant, inject filling liquid crystal in the gap of distinguishing by substrate surface and sealant, the sealing filling orifice also constitutes liquid crystal cell.And the outside surface of liquid crystal cell promptly, constitutes transparency carrier one side of liquid crystal cell, by the configuration Polarizer, obtains liquid crystal display cells.
Here, as sealant, can use hardening agent for example and as epoxy resin that contains alumina balls of pad etc.
As liquid crystal, can enumerate nematic crystal and smectic liquid crystal.Wherein preferred nematic crystal, for example can use the Schiff bases liquid crystal, azoxy class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal, ester liquid crystal, terphenyl class liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal; dioxane liquid crystal, bicyclooctane class liquid crystal, cube alkanes liquid crystal etc.In addition, can in these liquid crystal, add for example cholesterol chloride, Cholesteryl pelargonate, the cholesterol liquid crystal such as cholesterol carbonic ester or the chirality agent of selling as trade name " C-15 " " CB-15 " (メ Le Network society system) etc. and use.And, also can use oxygen base benzal-in the last of the ten Heavenly stems strong conductive liquid-crystal such as amino-2-methyl butyl cinnamic acid ester.
In addition; as the polarized light piece on the outside surface that sticks on liquid crystal cell, can enumerate the polarization film that is called as the H film that for example when making polyvinyl alcohol (PVA) stretch orientation, absorbs the iodine polarized light piece of cellulose acetate diaphragm clamping or the polarized light piece that H film self forms.
[embodiment]
Below, by embodiment the present invention is specified, but the present invention is not limited to these embodiment.The transparency of embodiment and comparative example, voltage retention, agglutinating property are estimated by the following method.
[transparency]
Determinator uses HITACHI U-2010 type spectrophotometer (Hitachi (strain) system).On the quartz base plate of thickness 1.5mm,,, form filming of dry film thickness 800 by 180 ℃ of dryings 1 hour with the as above aligning agent for liquid crystal of the present invention of preparation of spinner coating.Carry out the mensuration of the transmitance of filming of made.Transmitance is measured, and obtains at wavelength 700nm 600nm, 500nm, 450nm, 400nm, the value of 350nm and 300nm.Transmitance at any mensuration wavelength all is judged as well in the situation that is not less than 90%, and situation in addition is judged as bad.
[voltage retention]
On liquid crystal display cells in the pressing time of 60 microseconds, apply the voltage of 5V with 167 milliseconds intervals after, measure from releasing and be pressurized to voltage retention after 167 milliseconds.Determinator uses (strain) Dongyang テ Network ニ カ system VHR-1.Voltage retention is judged as well for being not less than 90%, in addition is judged as bad.
[sintering]
Applying 1 hour galvanic 30Hz of intensive 1.0V on the liquid crystal display cells under 70 ℃ environment temperature, the square wave of 2.0V is obtained residual dc voltage with just cutting off after the DC voltage in the liquid crystal cell residual voltage by the flicker null method.The type of electrodes that residual DC value is not limited to constitute liquid crystal display cells is not for being higher than 2V, and the difference of the residual DC between each type of electrodes is judged as well for the situation that is not higher than 0.5V, and situation in addition is judged as bad.
Synthesis example 1
With 224.17g (0.5 mole) 2,3,5-tricarboxylic basic ring amyl group acetate dicarboxylic anhydride and 157.14g (0.5 mole) 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone is as the tetrabasic carboxylic acid dicarboxylic anhydride, 94.62g (0.875 mole) p-phenylenediamine (PPD), 32.02g (0.1 mole) 2,2 '-two trifluoromethyls-4,4 '-benzidine and 6.43g (0.01 mole) 3, two (the 4-aminobenzoic acyl-oxygen base) cholesterol of 6-are as diamine compound, and 10.85g (0.03 mole) 4-aminophenyl octadecyl ether is dissolved in 4 as monoamine, in the 500gN-N-methyl-2-2-pyrrolidone N-, 60 ℃ of reactions 6 hours.Then, reaction solution is injected excessive methyl alcohol and make the reaction product precipitation.Then, use methanol wash, decompression obtains the polyamic acid of 410g logarithm viscosity 0.87dl/g down 40 ℃ of dryings 15 hours.30g gained polyamic acid is dissolved in the 570gN-N-methyl-2-2-pyrrolidone N-, add 23.4g pyridine and 18.1g acetic anhydride and 110 ℃ of dehydration closed-loops 4 hours, similarly precipitate, wash, reduce pressure with above-mentioned, obtain the polyimide (being referred to as " polyimide " (A-1)) of 17.5g logarithm viscosity 0.80dl/g.
Synthesis example 2
With 224.17g (0.5 mole) 2,3,5-tricarboxylic basic ring amyl group acetate dicarboxylic anhydride and 157.14g (0.5 mole) 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c]-furans-1, the 3-diketone is as the tetrabasic carboxylic acid dicarboxylic anhydride, (94.62g 0.875 mole) p-phenylenediamine (PPD), (24.85g 0.1 mole) two aminopropyl tetramethyl disiloxanes and 6.43g (0.01 mole) 3, two (the 4-aminobenzoic acyl-oxygen base) cholesterol of 6-are as diamine compound, and 10.85g (0.03 mole) 4-aminophenyl octadecyl ether is dissolved in 4 as monoamine, in the 500gN-N-methyl-2-2-pyrrolidone N-, 60 ℃ of reactions 6 hours.Then, reaction solution is injected excessive methyl alcohol and make the reaction product precipitation.Then, use methanol wash, decompression obtains the polyamic acid of 370g logarithm viscosity 0.82dl/g down 40 ℃ of dryings 15 hours.30g gained polyamic acid is dissolved in the 570gN-N-methyl-2-2-pyrrolidone N-, add 23.4g pyridine and 18.1g acetic anhydride and 110 ℃ of dehydration closed-loops 4 hours, similarly precipitate, wash, reduce pressure with above-mentioned, obtain the polyimide (being referred to as " polyimide " (A-2)) of 18.5g logarithm viscosity 0.77dl/g.
Synthesis example 3
With 22.42g (0.05 mole) 2,3,5-tricarboxylic basic ring amyl group acetate dicarboxylic anhydride and 298.57g (0.95 mole) 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c]-furans-1, the 3-diketone is as the tetrabasic carboxylic acid dicarboxylic anhydride, 83.81g (0.775 mole) p-phenylenediamine (PPD), 64.04g (0.2 mole) 2,2 '-two trifluoromethyls-4,4 '-benzidine and 6.43g (0.01 mole) 3, two (the 4-aminobenzoic acyl-oxygen base) cholesterol of 6-are as diamine compound, and 2.79g (0.03 mole) aniline is dissolved in 4 as monoamine, in the 500gN-N-methyl-2-2-pyrrolidone N-, 60 ℃ of reactions 6 hours.Then, reaction solution is injected excessive methyl alcohol and make the reaction product precipitation.Then, use methanol wash, decompression obtains the polyamic acid of 410g logarithm viscosity 0.85dl/g down 40 ℃ of dryings 15 hours.30g gained polyamic acid is dissolved in the 570gN-N-methyl-2-2-pyrrolidone N-, add 23.4g pyridine and 18.1g acetic anhydride and 110 ℃ of dehydration closed-loops 4 hours, similarly precipitate, wash, reduce pressure with above-mentioned, obtain the polyimide (being referred to as " polyimide " (A-3)) of 15.1g logarithm viscosity 0.83dl/g.
Synthesis example 4
In synthesis example 2, with 95.7g (0.885 mole) p-phenylenediamine (PPD), (24.85g 0.1 mole) two aminopropyl tetramethyl disiloxanes (the represented compound of above-mentioned formula (VI)) and as monoamine with beyond 8.09g (0.03 mole) the n-octadecane base amine, with synthesis example 2 similarly, obtain the polyimide (being referred to as " polyimide " (A-4)) of 19.4g logarithm viscosity 0.65dl/g.
Synthesis example 5
196.12g (1.0 moles) is encircled the butanetetra-carboxylic acid dicarboxylic anhydride as the tetrabasic carboxylic acid dicarboxylic anhydride, with 212g (1.0 moles) 2,2 '-dimethyl-4,4 '-benzidine are dissolved in the 4500gN-N-methyl-2-2-pyrrolidone N-and at 60 ℃ as diamine compound and reacted 6 hours.Then, reactant liquor is injected excessive methyl alcohol precipitation reaction product.Then, by using methanol wash, decompression obtains the polyamic acid (being referred to as " polyamic acid " (B-1)) of 410g logarithm viscosity 0.90dl/g down 40 ℃ of dryings 15 hours.
Synthesis example 6
In synthesis example 5, remove with equal benzene tertacarbonic acid's dicarboxylic anhydride of 109.06g (0.5 mole) and 98.06g (0.5 mole) and encircle the butanetetra-carboxylic acid dicarboxylic anhydride as the tetrabasic carboxylic acid dicarboxylic anhydride, with 200.2g (1.0 moles) 4,4 '-diamino-diphenyl ether is as beyond the diamine compound, with synthesis example 5 similarly, obtain the polyamic acid that 410g logarithm viscosity is 0.93dl/g (being referred to as " polyamic acid " (B-2)).
Synthesis example 7
In synthesis example 5, remove with equal benzene tertacarbonic acid's dicarboxylic anhydride of 109.06g (0.5 mole) and 98.06g (0.5 mole) and encircle the butanetetra-carboxylic acid dicarboxylic anhydride as the tetrabasic carboxylic acid dicarboxylic anhydride, with 198.3g (1.0 moles) 4,4 '-diaminodiphenyl-methane is as beyond the diamine compound, with synthesis example 5 similarly, obtain the polyamic acid that 410g logarithm viscosity is 0.95dl/g (being referred to as " polyamic acid " (B-3)).
Synthesis example 8
Remove the monoamine compound 4-aminophenyl octadecyl ether in the synthesis example 1, beyond 96.24g (0.89 mole) p-phenylenediamine (PPD), with synthesis example 1 synthesizing imide prepolymer similarly, it is dissolved in the N-N-methyl-2-2-pyrrolidone N-, and to form solid component concentration be the solution of 10 weight %.In addition, the polyamic acid (B-2) that above-mentioned synthesis example 6 is obtained is used as the amic acid prepolymer, and similarly being dissolved in N-N-methyl-2-2-pyrrolidone N-formation solid component concentration is the solution of 10 weight %.Then, after 500g imide prepolymer solution and the mixing of 500g amic acid prepolymer and stirring 2 hours, reaction solution is injected excessive methyl alcohol precipitation reaction product.Then, by using methanol wash, decompression is down 40 ℃ of dryings 15 hours, obtains 100g logarithm viscosity and be the polymkeric substance (ratio of polyamic acid counts 50% with weight ratio) that is formed by polyamic acid and polyimide (be referred to as " polymkeric substance (C-1)) of 0.95dl/g.
Synthesis example 9
In synthesis example 2, remove monoamine 4-aminophenyl octadecyl ether, outside 96.24g (0.89 mole) p-phenylenediamine (PPD), with synthesis example 2 synthesizing imide prepolymer similarly, it is dissolved in to form solid component concentration in the N-N-methyl-2-2-pyrrolidone N-be the solution of 10 weight %.In addition, the polyamic acid (B-1) that above-mentioned synthesis example 5 is obtained is used as the amic acid prepolymer, similarly it is dissolved in the solution that forms solid component concentration 10 weight % in the N-N-methyl-2-2-pyrrolidone N-.Then, after 500g imide prepolymer solution and the mixing of 500g amic acid prepolymer and stirring 2 hours, reaction solution is injected excessive methyl alcohol precipitation reaction product.Then, by using methanol wash, decompression is down 40 ℃ of dryings 15 hours, obtains 100g logarithm viscosity and be the polymkeric substance (ratio of polyamic acid is 50% by weight) that is formed by polyamic acid and polyimide (be referred to as " polymkeric substance (C-2)) of 0.93dl/g.
Synthesis example 10
In synthesis example 4, remove monoamine 4-aminophenyl octadecyl ether, outside 97.32g (0.90 mole) p-phenylenediamine (PPD), with synthesis example 4 synthesizing imide prepolymer similarly, it is dissolved in to form solid component concentration in the N-N-methyl-2-2-pyrrolidone N-be the solution of 10 weight %.In addition, the polyamic acid (B-3) that above-mentioned synthesis example 7 is obtained is used as the amic acid prepolymer, similarly it is dissolved in the solution that forms solid component concentration 10 weight % in the N-N-methyl-2-2-pyrrolidone N-.Then, after 500g imide prepolymer solution and the mixing of 500g amic acid prepolymer and stirring 2 hours, reaction solution is injected excessive methyl alcohol precipitation reaction product.Then, by using methanol wash, decompression is down 40 ℃ of dryings 15 hours, obtains 100g logarithm viscosity and be the polymkeric substance (ratio of polyamic acid is 50% by weight) that is formed by polyamic acid and polyimide (be referred to as " polymkeric substance (C-3)) of 0.97dl/g.
Embodiment 1
Make polyamic acid (B-1) that polyimide (A-1) that synthesis example 1 obtains and synthesis example 5 obtain with polyimide: polyamic acid=50: 50 (weight ratio), be dissolved in the mixed solvent of N-N-methyl-2-2-pyrrolidone N-/gamma-butyrolacton (weight ratio 30/70), dissolving 10 weight portions (phr) polyethyleneglycol diglycidylether (molecular weight about 400) formation solid component concentration with respect to 100 parts by weight polymer is the solution of 4 weight %, after fully stirring, the filtrator of this solution with aperture 1 μ m filtered, modulate aligning agent for liquid crystal of the present invention.Above-mentioned aligning agent for liquid crystal is coated with (rotation number: 2 with spinner; 000rpm; the coating time: 1 minute) to by on the film formed nesa coating of ITO that is arranged on the glass substrate one side that thickness is 1mm; on the reflectance coating that is formed by Al, forming dry film thickness in 1 hour 200 ℃ of dryings is the diaphragm of 0.08 μ m.With having the strigil of the cylinder that has twined rayon cloth, with the revolution 400rpm of cylinder, platform translational speed 3cm/ second, the hairbrush pin is pressed into length 0.4mm and carries out friction treatment on this diaphragm.Above-mentioned liquid crystal orientation film coated substrates flooded 1 minute in isopropyl alcohol after, on 100 ℃ electric hot plate dry 5 minutes.Then, has a pair of transparency electrode/transparent electrode substrate, with the liquid crystal orientation film of the above-mentioned liquid crystal orientation film coated substrates of a pair of transparency electrode/reflective electrode substrate respectively in periphery, after the epoxy adhesive that mixes alumina balls of coating diameter 5.5 μ m, close with respect to liquid crystal aligning face pressed and overlapped, bonding agent is solidified.Then, from liquid crystal injecting port between substrate, fill nematic crystal (メ Le Network society system, MLC-6221) after, with acrylic compounds Photocurable adhesive encapsulated liquid crystals inlet,, make liquid crystal display cells at the bonding polarized light piece in the two sides, the outside of substrate.Estimate voltage retention, the agglutinating property of gained liquid crystal display cells.At thickness is on the quartz base plate of 1.5mm, is coated with the aligning agent for liquid crystal of the present invention of above-mentioned modulation with spinner, similarly forms when making with liquid crystal display cells and films.From the transmitance evaluation of measuring transparency of filming of making.The results are shown in the table 1.Voltage retention and the blinking characteristic that can confirm gained aligning agent for liquid crystal of the present invention are good.
Embodiment 2～15
According to the described scheme of following table 1, polyimide (A-1)～(A-4), polyamic acid (B-1)～(B-3), the part acid imide (C-1)～(C-3) of synthesis example 1～10 gained and the compound dissolution that contains epoxy radicals are obtained solid component concentration in the mixed solvent that with the gamma-butyrolacton is major component be 4.0% solution, is the filtrator filtration of 1 μ m with this solution by the aperture, modulates aligning agent for liquid crystal of the present invention.With the aligning agent for liquid crystal of so modulating, in embodiment 1 similarly, on substrate surface, form diaphragm respectively, use the substrate manufacture liquid crystal display cells of this formation liquid crystal orientation film.And, estimate the transparency, voltage retention and agglutinating property.The results are shown in table 1.
Comparative example 1～5
According to the scheme shown in the following table 1, similarly make liquid crystal display cells in embodiment.And, estimate the transparency, voltage retention and agglutinating property.The results are shown in table 1.
Table 1
| Polymkeric substance | The polymer mixed ratio | Additive types | Addition (phr) | The transparency | Voltage retention | Agglutinating property | ||||
| Infiltration type | Reflection-type | Infiltration type | Reflection-type | |||||||
| Embodiment 1 | ??A-1 | ??B-1 | ??50/50 | Polyethyleneglycol diglycidylether | ????10 | Well | Well | Well | Well | Well |
| Embodiment 2 | ??A-2 | ??B-1 | ??40/60 | Polyethyleneglycol diglycidylether | ????20 | Well | Well | Well | Well | Well |
| Embodiment 3 | ??A-3 | ??B-3 | ??50/50 | Polyethyleneglycol diglycidylether | ????10 | Well | Well | Well | Well | Well |
| Embodiment 4 | ??A-3 | ??B-3 | ??50/50 | 1,3,5,6-four glycidyl group-2,4-hexanediol | ????10 | Well | Well | Well | Well | Well |
| Embodiment 5 | ??A-3 | ??B-2 | ??50/50 | 1,3,5,6-four glycidyl group-2,4-hexanediol | ????10 | Well | Well | Well | Well | Well |
| Embodiment 6 | ??A-2 | ??B-2 | ??40/60 | 1, two (N, the N-diglycidyl amino methyl) cyclohexanes of 3- | ????10 | Well | Well | Well | Well | Well |
| Embodiment 7 | ??A-4 | ??B-2 | ??50/50 | 1, two (N, the N-diglycidyl amino methyl) cyclohexanes of 3- | ????10 | Well | Well | Well | Well | Well |
| Embodiment 8 | ??A-4 | ??B-3 | ??50/50 | N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane | ????20 | Well | Well | Well | Well | Well |
| Embodiment 9 | ??A-1 | ??B-1 | ??50/50 | Polyethyleneglycol diglycidylether | ????5 | Well | Well | Well | Well | Well |
| Embodiment 10 | ??A-1 | ??B-1 | ??50/50 | N, N, N ', N '-four glycidyl group-4,4 '-m-xylene diamine | ????5 | Well | Well | Well | Well | Well |
| Embodiment 11 | ??A-2 | ??B-3 | ??45/55 | Polyethyleneglycol diglycidylether | ????20 | Well | Well | Well | Well | Well |
| Embodiment 12 | ??A-1 | ??B-3 | ??50/50 | Ethylene glycol diglycidylether | ????20 | Well | Well | Well | Well | Well |
| Embodiment 13 | ??C-1 | Polyethyleneglycol diglycidylether | ????20 | Well | Well | Well | Well | Well | ||
| Embodiment 14 | ??C-2 | Ethylene glycol diglycidylether | ????20 | Well | Well | Well | Well | Well | ||
| Embodiment 15 | ??C-3 | N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane | ????20 | Well | Well | Well | Well | Well | ||
| Comparative example 1 | ??A-1 | Polyethyleneglycol diglycidylether | ????10 | Well | Well | Well | Well | Bad | ||
| Comparative example 2 | ??A-1 | ??B-1 | ??50/50 | Well | Well | Well | Well | Bad | ||
| Comparative example 3 | ??B-3 | 1, two (N, the N-diglycidyl amino methyl) cyclohexanes of 3- | ????10 | Well | Well | Well | Bad | Well | ||
| Comparative example 4 | ??C-1 | Well | Well | Well | Well | Bad | ||||
| Comparative example 5 | ??C-3 | Well | Well | Well | Well | Bad | ||||
Claims (3)
1. aligning agent for liquid crystal, it is characterized in that this aligning agent for liquid crystal contains ratio that 100 weight portions have the represented recurring unit of the represented recurring unit of the represented recurring unit of following formula (I-1) and following formula (I-2) and formula (I-1) and accounts for the compound that has at least 2 epoxy radicals in the polymkeric substance of whole recurring units 40%～60% and at least 5 weight portion molecules by weight
[changing 1]
In the formula, P
1Be 4 valency organic groups, and Q
1Be the divalent organic group,
[changing 2]
In the formula, P
2Be 4 valency organic groups, and Q
2It is the divalent organic group.
2. aligning agent for liquid crystal as claimed in claim 1, the compound that wherein has at least 2 epoxy radicals in the molecule are at least a compounds that contains epoxy radicals that is selected from represented compound of following formula (1) and the represented compound of following formula (2),
[changing 3]
In the formula, R
10Expression divalent aliphatic group,
[changing 4]
In the formula, R
11Expression divalent organic group.
3. aligning agent for liquid crystal as claimed in claim 1 or 2, wherein polymkeric substance is not less than 90% in the transmitance of 300nm～700nm wavelength region may.
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| Publication number | Publication date |
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| TWI360680B (en) | 2012-03-21 |
| CN100397159C (en) | 2008-06-25 |
| TW200537180A (en) | 2005-11-16 |
| KR20060043138A (en) | 2006-05-15 |
| KR101084453B1 (en) | 2011-11-21 |
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