CN101075042A - Liquid crystal orientational agent and liquid crystal display component - Google Patents

Liquid crystal orientational agent and liquid crystal display component Download PDF

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CN101075042A
CN101075042A CNA2007100973379A CN200710097337A CN101075042A CN 101075042 A CN101075042 A CN 101075042A CN A2007100973379 A CNA2007100973379 A CN A2007100973379A CN 200710097337 A CN200710097337 A CN 200710097337A CN 101075042 A CN101075042 A CN 101075042A
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liquid crystal
dicarboxylic anhydride
carboxylic acid
tetrabasic carboxylic
aligning agent
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CN101075042B (en
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宫本佳和
松本贵博
西川通则
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JSR Corp
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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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Abstract

The invention provides a liquid crystal orientational agent which has high voltage conservation rate and epitaxial film with good coating characteristic and a liquid crystal display component having good image and the epitaxial film. A liquid crystal orientational agent contains aminimide polymer aminated by daiamid acid and/or daiamid acid obtained by addition polymerization at least one of diamine compound and tetrabasic carboxylic acid anhydride in the group consisting of aliphatic tetrabasic carboxylic acid anhydride and alicyclic tetrabasic carboxylic acid anhydride; and free radical reaction compound whose molecule has at least one acrylic acid radical and/or methacrylic acid radical.

Description

Aligning agent for liquid crystal and liquid crystal display cells
Technical field
The present invention relates to novel liquid crystal alignment agent and liquid crystal display cells.More particularly, relate to the good novel liquid crystal alignment agent and liquid crystal display cells of screening characteristics when showing high voltage holding ratio and forming alignment films with graceful graph picture.
Background technology
Viewpoint from save space, low power consumption etc., the liquid crystal display cells that with the LCD is representative is since the liquid crystal counter begins volume production, be applied to wrist-watch, portable game machine, word processor, notebook computer, vehicle navigation device, field camera, PDA, digital camera, mobile phone, various watch-dog, liquid crystal TV set etc. multi-field in, and carrying out active exploitation.As liquid crystal display cells, employing has the nematic crystal of positive dielectric anisotropy, and the major axis of liquid crystal molecule is turned round TN (Twisted Nematic) the type liquid crystal display cells that turn 90 degrees and STN (Super TwistedNematic) the type liquid crystal display cells higher than TN type liquid crystal display cells contrast is widely used from a substrate continuously to another piece substrate.And in recent years, in order further to improve the display quality of LCD, developed also good optical compensation curved (OCB) type liquid crystal display cells of the high-speed response of view angle dependency little VA (VerticalAlignment) type liquid crystal display cells, IPS (In Plane Switiching) type liquid crystal display cells and the little picture of videoing simultaneously of view angle dependency etc.
In liquid crystal display cells, the orientation of liquid crystal is controlled by the liquid crystal orientation film that is formed by the aligning agent for liquid crystal that contains polymkeric substance such as polyamic acid and polyimide.Because liquid crystal orientation film is the parts that directly contact with liquid crystal molecule, known its display characteristic to above-mentioned liquid crystal panel produces very large influence.For example, usually by adopting the whole bag of tricks coated with liquid crystal alignment agents such as rolling method, spin-coating method, print process, ink-jet method, the heat drying applicator surface forms liquid crystal orientation film then, it is believed that, the coating of this alignment films is irregular bad directly related with liquid crystal aligning, and the display quality of liquid crystal panel is significantly descended.And the absorption of impurity descends voltage retention in the deterioration of liquid crystal orientation film and this alignment films, causes panel to show that the degradation display performance descends under irregular, film flicker, the contrast.So far, as the method for improving voltage retention, reported the skeleton of the raw material tetrabasic carboxylic acid dicarboxylic anhydride of attempting transforming polyamic acid and imide amination polymer and diamines example (referring to Patent Document 1 and 2), in polyamic acid, add the example (referring to Patent Document 3) of acrylate copolymer.But according to these reports, the improvement effect of voltage retention can't be said enough good, and the improved viewpoint of screening characteristics is studied when not forming with alignment films simultaneously.In recent years, liquid crystal panel is required that high-quality display performance is arranged, so, press for exploitation and screening characteristics good aligning agent for liquid crystal when forming alignment films higher than former voltage retention.
No. 3572690 communique of patent documentation 1 patent
Patent documentation 2 spies open the 2001-228481 communique
No. 3206169 communique of patent documentation 3 patents
Summary of the invention
The present invention is based on above-described situation and makes.Therefore, the purpose of this invention is to provide the demonstration high voltage holding ratio, and the good novel liquid crystal alignment agent of screening characteristics and have the liquid crystal orientation film that forms by this aligning agent for liquid crystal and have the liquid crystal display cells of graceful graph picture when forming alignment films.
Further other purpose of the present invention and advantage can be found out by the following description.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 1st, reach by a kind of aligning agent for liquid crystal, it is characterized in that containing the polyamic acid that makes at least a tetrabasic carboxylic acid dicarboxylic anhydride selected in the group that constitutes by aliphatics tetrabasic carboxylic acid dicarboxylic anhydride and alicyclic tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound addition polymerization gained and make at least a polymkeric substance of selecting in the imide amination polymer of above-mentioned polyamic acid imidizate gained; With the free radical reaction compound that has at least 1 acrylic or methacrylic acid group in the molecule.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 2nd, reach by a kind of liquid crystal display cells, it is characterized in that having the liquid crystal orientation film that forms by aligning agent for liquid crystal of the present invention.
According to the present invention, the demonstration high voltage holding ratio can be provided, and the good aligning agent for liquid crystal of oriented film coating and have this alignment films and have the liquid crystal display cells of graceful graph picture.
Embodiment
Below, the present invention will be described in detail.Aligning agent for liquid crystal of the present invention contains (1) makes at least a tetrabasic carboxylic acid dicarboxylic anhydride selected in the group that is made of aliphatics tetrabasic carboxylic acid dicarboxylic anhydride and alicyclic tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound addition polymerization and at least a polymkeric substance that synthetic polyamic acid and making is selected in the imide amination polymer of above-mentioned polyamic acid imidizate gained (below be also referred to as " principal component polymer "), (2) has the free radical reaction compound (below, be also referred to as " specific free radical reaction compound ") of at least 1 acrylic or methacrylic acid group in the molecule, (3) adjuvant of as required other.Aligning agent for liquid crystal of the present invention by at the principal component polymer first line of a couplet with above-mentioned specific low molecular compound (specific free radical reaction compound), can improve the screening characteristics when forming liquid crystal orientation film, can make does not have the homogeneous liquid crystal orientation film that applies speckle.And the polymerization and being retained in the alignment films when the alignment films roasting of this specific free radical reaction compound can be given its high voltage retention.
[polyamic acid and imide amination polymer]
The polyamic acid that uses among the present invention obtains by at least a tetrabasic carboxylic acid dicarboxylic anhydride and the diamines addition polymerization of selecting in the group that is made of aliphatics tetrabasic carboxylic acid dicarboxylic anhydride and alicyclic tetrabasic carboxylic acid dicarboxylic anhydride.In addition, the imide amination polymer that uses among the present invention obtains by making above-mentioned polyamic acid dehydration closed-loop.
[tetrabasic carboxylic acid dicarboxylic anhydride]
Used principal component polymer in the aligning agent for liquid crystal of the present invention, in order aspect voltage retention, screening characteristics when forming alignment films, to show good performance, use at least a tetrabasic carboxylic acid dicarboxylic anhydride of selecting in the group that constitutes by aliphatics tetrabasic carboxylic acid dicarboxylic anhydride and alicyclic tetrabasic carboxylic acid dicarboxylic anhydride to synthesize as the tetrabasic carboxylic acid dicarboxylic anhydride.The ratio of aliphatics tetrabasic carboxylic acid dicarboxylic anhydride and alicyclic tetrabasic carboxylic acid dicarboxylic anhydride based on whole tetrabasic carboxylic acid dicarboxylic anhydrides, is preferably 10～100 moles of %, and more preferably 20～100 moles of % are preferably 50～100 moles of % especially.
As aliphatics tetrabasic carboxylic acid dicarboxylic anhydride and alicyclic tetrabasic carboxylic acid dicarboxylic anhydride, for example, can illustration BTCA dicarboxylic anhydride, 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-two chloro-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 3,5,6-three carboxyls norbornane-2-acetic acid 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)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-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)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-7-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-ethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 5-(2,5-dioxo tetrahydrofuran methylene)-and 3-methyl-3-cyclohexene-1,2-dicarboxylic acid dicarboxylic anhydride, dicyclo [2,2,2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, two ring [3.3.0] octanes-2,4,6,8-tetrabasic carboxylic acid dicarboxylic anhydride, the compound of following formula (1) and (2) expression.
(in the formula, R 1And R 3Expression has the divalent organic group of aromatic rings, 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).
These tetrabasic carboxylic acid dicarboxylic anhydrides can a kind separately or be used in combination more than 2 kinds.
In aliphatics tetrabasic carboxylic acid dicarboxylic anhydride as implied above and the alicyclic tetrabasic carboxylic acid dicarboxylic anhydride, from showing the angle of good liquid crystal aligning, preferred 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 5-(2,5-dioxo tetrahydrofuran methylene)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-5,8-dimethyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, dicyclo [2,2,2]-Xin-7-alkene-2,3,5,6-tetrabasic carboxylic acid dicarboxylic anhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 3,5,6-three carboxyls-2-carboxyl norbornane-2:3, the 5:6-dicarboxylic anhydride, two ring [3.3.0] octanes-2,4,6,8-tetrabasic carboxylic acid dicarboxylic anhydride, the compound of following formula (6) expression in the compound of following formula (3)～(5) expression in the compound of above-mentioned formula (1) expression and the compound of above-mentioned formula (2) expression.As preferred especially, can enumerate 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-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-2 ', 5 '-diketone), 3,5,6-three carboxyls-2-carboxyl norbornane-2:3,5:6-dicarboxylic anhydride, two ring [3.3.0] octanes-2,4,6,8-tetrabasic carboxylic acid dicarboxylic anhydride, and the compound of following formula (3) expression.
Figure A20071009733700091
Used principal component polymer can also contain other tetrabasic carboxylic acid dicarboxylic anhydrides different with alicyclic tetrabasic carboxylic acid dicarboxylic anhydride with above-mentioned aliphatics tetrabasic carboxylic acid dicarboxylic anhydride among the present invention.Can enumerate aromatic tetracarboxylic acid's dicarboxylic anhydride etc. as these other tetrabasic carboxylic acid dicarboxylic anhydrides.As aromatic tetracarboxylic acid's dicarboxylic anhydride, can the following compound of illustration.
The pyromellitic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,3 ', 4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 2,2 ', 3,3 '-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 '-biphenyltetracarboxyacid acid dicarboxylic anhydride, two (phthalic acid) phosphniline oxide dicarboxylic anhydride, right-phenylene-two (triphenyl phthalic acid) dicarboxylic anhydride, between-phenylene-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), 2,2-two (4-hydroxyphenyl) propane-two (dehydration trimellitate), the compound of following formula (7)～(9) expression.
Figure A20071009733700101
Figure A20071009733700111
These aromatic tetracarboxylic acid's dicarboxylic anhydrides can a kind separately or be used in combination more than 2 kinds.
In aromatic tetracarboxylic acid's dicarboxylic anhydride as implied above, from showing the angle of good liquid crystal aligning, preferred pyromellitic acid dicarboxylic anhydride, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,3 ', 4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride, 2,2 ', 3,3 '-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.As particularly preferred, can enumerate pyromellitic acid dicarboxylic anhydride and 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid dicarboxylic anhydride.
[diamine compound]
Aligning agent for liquid crystal of the present invention preferably makes the diamine compound that contains the composition with performance tilt angle of following formula (10) or following formula (11) expression in the synthetic middle diamine compound that uses of principal component polymer when being used for TN type, STN type, OCB type, VA type.
Figure A20071009733700121
(in the formula, R 5And R 6Be hydrogen atom or methyl independently of one another, R 7For the carbon number of straight or branched is 1～20 alkyl, R 8And R 9Be the organic group of divalent independently of one another.Here, as R 8And R 9The organic group of divalent of expression, at least a group that is preferably selected from aromatic group such as phenylene, naphthalene two bases, anthracene two bases, fluorenes two bases, biphenyl two bases and cycloalkylidenes such as ring dihexyls, ring penta 2 bases be selected from carbonyl (CO-), carbonyl oxygen base (COO-), sulfonyl (SO 2-), sulfonyloxy (SO 2-O-), ehter bond (O-), thioether bond (S-), imino group (NH-), acylamino-(NHCO-), siloxane bond (Si (R 2) O-) at least a group of (here, R is alkyl such as methyl, ethyl) connects the divalent organic group that gets).
(in the formula, a is 0 or 1, R 10For by ehter bond (O-), carbonyl (CO-), carbonyl oxygen base (COO-), oxygen base carbonyl (OCO-), acylamino-(NHCO-,-CONH-), thioether bond (S-) and the divalent organic group of selecting in the group that constitutes of methylene, R 11For with R 10Different divalent organic groups.Here, as R 11The divalent organic group of expression, at least a group that is preferably selected from aromatic group such as phenylene, naphthalene two bases, anthracene two bases, fluorenes two bases, biphenyl two bases and cycloalkylidenes such as ring dihexyls, ring penta 2 bases be selected from carbonyl (CO-), carbonyl oxygen base (COO-), sulfonyl (SO 2-), sulfonyloxy (SO 2-O-), ehter bond (O-), thioether bond (S-), imino group (NH-), acylamino-(NHCO-), siloxane bond (Si (R 2) O-) at least a group of (here, R is alkyl such as methyl, ethyl) connects the divalent organic group that gets.R 12For group with steroid backbone, have the group of fluorine atom or have the group that carbon number is 1～22 straight chained alkyl).
These diamine compounds with composition of performance tilt angle can a kind be used alone or in combination of two or more.
As the object lesson of the diamine compound of above-mentioned formula (10) expression, can the following formula of illustration (12) and (13) compound of representing separately.
Figure A20071009733700131
As the object lesson of the diamine compound of above-mentioned formula (11) expression, the compound of can the following formula of illustration (14)～(18) representing separately.
Figure A20071009733700141
Aligning agent for liquid crystal of the present invention is when being used for TN type, STN type, OCB type, and the diamine compound with the composition that shows tilt angle by using above-mentioned formula (12)～(18) to represent separately can stably show 1～30 ° liquid crystal pretilt angle.At this moment, the ratio that these have the diamine compound of the composition that shows tilt angle based on whole diamines, is preferably 0.5～30 mole of %, and more preferably 0.7～20 mole of % is preferably 1～15 mole of % especially.
Aligning agent for liquid crystal of the present invention is when being used for the VA type, because show good liquid crystal vertical-tropism, so in diamine compound with above-mentioned pitch angle representative element, especially preferably adopt the diamine compound of formula (14), (15) expression, the ratio of these diamine compounds based on whole diamines, is preferably 8～60 moles of %, more preferably 9～50 moles of % are preferably 10～25 moles of % especially.
Aligning agent for liquid crystal of the present invention is when being used for IPS type or FFS type, though also can use above-mentioned diamine compound, can only use above-mentioned diamine compound diamine compound synthetic polymer in addition described later usually with composition of performance tilt angle with composition of performance tilt angle.
As the synthetic middle above-mentioned diamine compound diamine compound in addition that uses of the used polymkeric substance of aligning agent for liquid crystal of the present invention, can enumerate for example following diamines with performance tilt angle composition.
Can enumerate p-phenylenediamine, between-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ethane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino diphenyl sulfone, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diaminobenzene formailide, 4,4 '-diaminodiphenyl ether, 1, the 5-diaminonaphthalene, 3,3 '-dimethyl-4,4 '-benzidine, 5-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethyl indane, 3,4 '-diamino-diphenyl ether, 3,3 '-diamido benzophenone, 3,4 '-diamido benzophenone, 4,4 '-diamido benzophenone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 2,2-two [4-(4-amino-benzene oxygen) phenyl] sulfone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 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-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 '-(right-the phenylene isopropylidene) diphenylamine, 4,4 '-(-the phenylene isopropylidene) diphenylamine, 2,2 '-two [4-(4-amino-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-diamido-2,2 '-dimethyl diphenyl, 4,4 '-two [(4-amino-2-trifluoromethyl) phenoxy group]-octafluoro biphenyl, 1,3-two (4-amino-benzene oxygen)-2, the 2-dimethylpropane, aromatic diamines such as 4,4 '-two (4-amino-benzene oxygen) biphenyl;
2, the 3-diamino-pyridine, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 5,6-diamido-2,3-dicyano pyrazine, 5,6-diamido-2, the 4-dihydroxy-pyrimidine, 2,4-diamido-6-dimethylamino-1,3, the 5-triazine, 1,4-two (3-aminopropyl) piperazine, 2,4-diamido-6-isopropoxy-1,3, the 5-triazine, 2,4-diamido-6-methoxyl-1,3, the 5-triazine, 2,4-diamido-6-phenyl-1,3,5-triazines, 2,4-diamido-6-methyl-s-triazine, 2, the 4-diamino-1,3,5-triazines, 4,6-diamido-2-vinyl-s-triazine, 2,4-diamido-5-phenyl thiazole, 2, the 6-diaminopurine, 5, the 6-diaminostilbene, the 3-dimethyl uracil, 3, the 5-diaminostilbene, 2, the 4-triazole, 6,9-diamido-2-ethoxy acridine lactate, 3,8-diamido-6-phenylphenanthridineand, 1,4-diamido piperazine, 3, the 6-proflavin, two (4-aminophenyl) phenyl amine and following formula (19), (20) has the diamines of the nitrogen-atoms beyond 2 primary amino radicals and this primary amino radical separately in the compound equimolecular of expression;
Figure A20071009733700161
(in the formula, R 13Expression 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).
Figure A20071009733700162
(in the formula, R 14Expression is selected from the divalent organic group with nitrogen atom ring texture of pyridine, pyrimidine, triazine, piperidines and piperazine).
1,3-two (aminomethyl) cyclohexane, 1,3-propane diamine, butanediamine, pentanediamine, hexane diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, 4,4-diamido heptamethylene diamine, 1,4-diamino-cyclohexane, isophorone diamine, tetrahydrochysene bicyclopentadiene diamines, six hydrogen-4,7-methanoindene dimethylene diamines, three ring [6.2.1.0 2,7]-undecylene two methanediamines, 4,4 '-methylene two aliphatics and ester ring type diamines such as (cyclohexylamine); The diamido organosiloxane of following formula (21) expression;
Figure A20071009733700171
(in the formula, R 15The expression carbon number is 1～12 alkyl, the R of a plurality of existence 15Can be the same or different separately, p is 1～3 integer, and q is 1～20 integer).These diamine compound diamine compounds in addition with composition of performance tilt angle can be used in combination separately or more than 2 kinds.
Wherein, preferred p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl ether, 9,9-two (4-aminophenyl) fluorenes, 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, 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-diamido-2,2 '-dimethyl diphenyl, 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 (22) expression in the compound of above-mentioned formula (19) expression, the compound of following formula (23) expression in the compound of above-mentioned formula (20) expression, 1,3-two (aminomethyl) cyclohexane, 1, the 4-cyclohexane diamine, 4,4 '-methylene two (cyclo-hexylamine), 3,3 '-(tetramethyl disiloxane-1,3-two bases) two (propylamine) of following formula (24) expression in the compound of above-mentioned formula (21) expression.
Figure A20071009733700181
As particularly preferred, can enumerate p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-diphenyl ether, 2,7-diamino-fluorene, 3,3 '-(tetramethyl disiloxane-1,3-two bases) two (propylamine), 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 1,3-two (amino methyl) cyclohexane, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl.
Synthesizing of＜polyamic acid 〉
The tetrabasic carboxylic acid dicarboxylic anhydride that uses in the polyamic acid synthetic reaction of the present invention 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 tetrabasic carboxylic acid dicarboxylic anhydride is the ratio of 0.2～2 equivalent, more preferably is the ratio of 0.3～1.2 equivalent.
The synthetic reaction of polyamic acid is preferable over-20～150 ℃, more preferably carries out under 0～100 ℃ temperature conditions in organic solvent.Here, as organic solvent, as long as can dissolve synthetic polyamic acid, then it is had no particular limits, can illustration for example N-N-methyl-2-2-pyrrolidone N-, N, N-dimethyl acetamide, N, aprotic polar solvents such as dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, HMPA; Between phenol solvent such as sylvan, xylenols, phenol, halogenated phenol.And when the total amount of tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound was (b), it was the amount of 0.1～30 weight % with respect to the total amount (a+b) of reaction solution that the consumption of organic solvent (a) is preferably the value that makes (b).
In addition, in the scope that the polyamic acid that does not make generation is separated out, can also unite bad solvent alcohols, ketone, ester class, ethers, halogenated hydrocarbon and the hydro carbons etc. that use polyamic acid in the above-mentioned organic solvent.Object lesson as this bad solvent, can enumerate for example methyl alcohol, ethanol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1, the 4-butylene glycol, triethylene glycol, diacetone alcohol, glycol monoethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, propylene carbonate, diethy-aceto oxalate, diethyl malonate, ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, the ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic acid esters, the diethylene glycol monoethyl ether acetic acid esters, tetrahydrofuran, methylene chloride, 1, the 2-ethylene dichloride, 1, the 4-dichloroetane, trichloroethanes, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, dimethylbenzene etc.These bad solvents can be used in combination separately or more than 2 kinds.
As mentioned above, obtained dissolving the reaction solution of polyamic acid.Then, this reaction solution is put in a large amount of bad solvents, obtain precipitate after, can get polyamic acid by this precipitate of drying under reduced pressure.And, this polyamic acid is dissolved in the organic solvent once more, will its operation of separating out be carried out once or several times, can make with extra care polyamic acid with bad solvent then.
＜imide amination polymer 〉
Imide amination polymer used in the aligning agent for liquid crystal of the present invention can be by synthesizing above-mentioned polyamic acid dehydration closed-loop.Here so-called imide amination polymer comprises the part imide amination polymer of the above-mentioned polyamic acid of part imidizate and the polymkeric substance of 100% imidizate, below, its general name is remembered as " imide amination polymer ".
In the aligning agent for liquid crystal of the present invention in the used imide amination polymer preferred imidizate rate be 10～100%, more preferably 20～95%, be preferably 25～90% especially.Here, so-called " imidizate rate " is meant the sum with respect to repetitive 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.
Synthetic method as imide amination polymer, can adopt: (I) carry out dehydration closed-loop and synthetic method by heating above-mentioned polyamic acid, (II) by above-mentioned polyamic acid is dissolved in the organic solvent, adding dewatering agent and dehydration closed-loop catalyzer also heat as required and carry out dehydration closed-loop and synthetic method in this solution.By suitably controlling above-mentioned reaction conditions, the polymkeric substance that can obtain to have required imidizate rate.
Temperature of reaction is preferably 50～300 ℃ in the method for the heating polyamic acid of above-mentioned (I), more preferably 100～250 ℃.When 50 ℃ of temperature of reaction less thaies, then the dehydration closed-loop reaction can not be carried out fully, if temperature of reaction surpasses 300 ℃, the situation of the molecular weight and molecular weight of gained imide amination polymer then can occur.
On the other hand, in polyamic acid solution, adding in the method for dewatering agent and dehydration closed-loop catalyzer of above-mentioned (II),, can use for example acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride as dewatering agent.The consumption of dewatering agent with respect to 1 mole of polyamic acid repetitive, is preferably 0.01～20 mole.In addition, as the dehydration closed-loop catalyzer, can use for example tertiary amines such as pyridine, trimethylpyridine, lutidines, triethylamine.Dewatering agent and dehydration closed-loop catalyzer are not limited to these examples.The dehydration closed-loop catalyst consumption with respect to 1 mole of used dewatering agent, is preferably 0.01～10 mole.As the organic solvent that uses in the dehydration closed-loop reaction, can enumerate illustrative identical 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 60～150 ℃.In addition, by the reaction solution that so obtains is carried out the operation same with the polyamic acid process for purification, can make with extra care imide amination polymer.
＜end modified type polymkeric substance 〉
The polyamic acid and the imide amination polymer that constitute aligning agent for liquid crystal of the present invention can also be the end modified type polymkeric substance that has carried out molecular-weight adjusting.By using this end modified type polymkeric substance, can under the prerequisite of not damaging effect of the present invention, improve the coating characteristic of aligning agent for liquid crystal etc.This end modified type polymkeric substance can be by in synthesizing polyamides when acid, adds monobasic acid anhydrides, monoamine compound, monoisocyanates compound etc. and synthesize in reaction system.Here, as the monobasic acid anhydrides, dicarboxylic acid monobasic acid anhydrides be can enumerate, maleic anhydride, phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinic anhydride, n-tetradecane base succinic anhydride, n-hexadecyl succinic anhydride etc. for example can be enumerated.In addition, as monoamine compound, for example can enumerate aniline, cyclohexylamine, to ethylaniline, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, n-pentadecane amine, n-hexadecane amine, n-heptadecane amine, n-octadecane amine, n-eicosane amine etc.In addition, as the monoisocyanates compound, can enumerate for example phenyl isocyanate, naphthyl isocyanate etc.
The logarithm viscosity of＜polymkeric substance 〉
The as above logarithm viscosity (η of the polyamic acid of gained and imide amination polymer Ln) value is preferably 0.05～10dl/g, 0.05～5dl/g more preferably.
Logarithm viscosity (η among the present invention 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).
＜specific free radical reaction compound 〉
Aligning agent for liquid crystal of the present invention contain the free radical reaction compound that has at least 1 acrylic or methacrylic acid group in the molecule (below, be also referred to as " specific free radical reaction compound "), like this, the screening characteristics in the time of can showing high voltage holding ratio and good alignment films and form.
In the present invention, the consumption of specific free radical reaction compound with respect to the above-mentioned principal component polymer of 100 weight portions, is preferably 1～100 weight portion, and more preferably 2～50 weight portions are preferably 5～20 weight portions especially.If the amount of specific free radical reaction compound is very few, screening characteristics in the time of then can not obtaining to substantially improve voltage retention and alignment films formation, in addition, if the amount of specific free radical reaction compound is too much, the situation of the liquid crystal pretilt angle expression power of principal component polymer can appear then damaging.
The object lesson that below shows used specific free radical reaction compound among the present invention.
Have in the molecule 1 acrylic or methacrylic acid group 1 official can the example of specific free radical reaction compound:
Have in the molecule 2 acrylics or methacrylic acid group 2 officials can the example of specific free radical reaction compound:
Can enumerate glycol diacrylate, ethylene glycol bisthioglycolate (methacrylate), 1,6-hexanediyl ester, 1,6-hexanediol two (methacrylate), 1,9-nonanediol diacrylate, 1,9-nonanediol two (methacrylate), tetraethylene glycol diacrylate, tetraethylene glycol two (methacrylate), polypropyleneglycol diacrylate, polypropylene glycol two (methacrylate), two phenoxetol fluorenes diacrylates, two phenoxetol fluorenes two (methacrylate) and the described compound of following formula (25) etc.
Figure A20071009733700271
(in the formula, ring structure A and B are cyclohexane ring or phenyl ring independently of each other, these rings are optional to be replaced by alkyl, alkoxy or halogen atom, X and Z independently of each other for be selected from by singly-bound, methylene, carbon number be 2～10 alkylidene, carbon number be 2～10 alkylidene radical ,-(CH 2) nO-,-(CH 2) nCOO-and-(CH 2) nThe group's that OCO-forms key base, n is the integer more than 0 or 1, and R is hydrogen atom or methyl).
Object lesson as the compound of above-mentioned formula (25) expression, can enumerate 4,4 '-two propylene acyloxy dicyclohexyls, 4,4 '-two propylene acyloxy-2,2 '-dimethyl dicyclohexyl, 4,4 '-two propylene acyloxy-3,3 '-dimethyl dicyclohexyl, 4,4 '-two propylene acyloxy-2,2 '-diethyl dicyclohexyl, 4,4 '-two propylene acyloxy-3,3 '-diethyl dicyclohexyl, 4,4 '-two propylene acyloxy-2,2 '-dibutyl dicyclohexyl, 4,4 '-two propylene acyloxy-3,3 '-dibutyl dicyclohexyl, 4,4 '-dimethyl allene acyloxy dicyclohexyl, 4,4 '-dimethyl allene acyloxy-2,2 '-dimethyl dicyclohexyl, 4,4 '-dimethyl allene acyloxy-3,3 '-dimethyl dicyclohexyl, 4,4 '-dimethyl allene acyloxy-2,2 '-diethyl dicyclohexyl, 4,4 '-dimethyl allene acyloxy-3,3 '-diethyl dicyclohexyl, 4,4 '-dimethyl allene acyloxy-2,2 '-dibutyl dicyclohexyl, 4,4 '-dimethyl allene acyloxy-3,3 '-dibutyl dicyclohexyl, two (4-acryloxy phenyl) ether, two (4-acryloxy-2-aminomethyl phenyl) ether, two (4-acryloxy-3-aminomethyl phenyl) ether, two (4-acryloxy-2-ethylphenyl) ether, two (4-acryloxy-3-ethylphenyl) ether, two (4-acryloxy-2-butyl phenyl) ether, two (4-acryloxy-3-butyl phenyl) ether, two (4-methacryloxy phenyl) ether, two (4-methacryloxy-2-aminomethyl phenyl) ether, two (4-methacryloxy-3-aminomethyl phenyl) ether, two (4-methacryloxy-2-ethylphenyl) ether, two (4-methacryloxy-3-ethylphenyl) ether, two (4-methacryloxy-2-butyl phenyl) ether, two (4-methacryloxy-3-butyl phenyl) ether, two (4-acryloxy cyclohexyl) ether, two (4-acryloxy-2-methylcyclohexyl) ether, two (4-acryloxy-3-methylcyclohexyl) ether, two (4-acryloxy-2-ethyl cyclohexyl) ether, two (4-acryloxy-3-ethyl cyclohexyl) ether, two (4-acryloxy-2-butyl cyclohexyl) ether, two (4-acryloxy-3-butyl cyclohexyl) ether, two (4-methacryloxy cyclohexyl) ether, two (4-methacryloxy-2-methylcyclohexyl) ether, two (4-methacryloxy-3-methylcyclohexyl) ether, two (4-methacryloxy-2-ethyl cyclohexyl) ether, two (4-methacryloxy-3-ethyl cyclohexyl) ether, two (4-methacryloxy-2-butyl cyclohexyl) ether, two (4-methacryloxy-3-butyl cyclohexyl) ether, two (4-acryloxy cyclohexyl) methane, two (4-acryloxy-2-methylcyclohexyl) methane, two (4-acryloxy-3-methylcyclohexyl) methane, two (4-acryloxy-2-ethyl cyclohexyl) methane, two (4-acryloxy-3-ethyl cyclohexyl) methane, two (4-acryloxy-2-butyl cyclohexyl) methane, two (4-acryloxy-3-butyl cyclohexyl) methane, two (4-methacryloxy cyclohexyl) methane, two (4-methacryloxy-2-methylcyclohexyl) methane, two (4-methacryloxy-3-methylcyclohexyl) methane, two (4-methacryloxy-2-ethyl cyclohexyl) methane, two (4-methacryloxy-3-ethyl cyclohexyl) methane, two (4-methacryloxy-2-butyl cyclohexyl) methane, two (4-methacryloxy-3-butyl cyclohexyl) methane, two (4-acryloxy phenyl) methane, two (4-acryloxy-2-aminomethyl phenyl) methane, two (4-acryloxy-3-aminomethyl phenyl) methane, two (4-acryloxy-2-ethylphenyl) methane, two (4-acryloxy-3-ethylphenyl) methane, two (4-acryloxy-2-butyl phenyl) methane, two (4-acryloxy-3-butyl phenyl) methane, two (4-methacryloxy phenyl) methane, two (4-methacryloxy-2-aminomethyl phenyl) methane, two (4-methacryloxy-3-aminomethyl phenyl) methane, two (4-methacryloxy-2-ethylphenyl) methane, two (4-methacryloxy-3-ethylphenyl) methane, two (4-methacryloxy-2-butyl phenyl) methane, two (4-methacryloxy-3-butyl phenyl) methane, 1,1-two (4-acryloxy phenyl) ethidine, 1,1-two (4-methacryloxy phenyl) ethidine, 2,2-two (4-acryloxy phenyl) fourth fork base, 2,2-two (4-methacryloxy phenyl) fourth fork base etc.
In addition, as 2 officials can the commercially available product of (methyl) acrylate, can enumerate for example ア ロ ニ Star Network ス M-210, ア ロ ニ Star Network ス M-240, ア ロ ニ Star Network ス M-6200 (more than, produce by East Asia synthetic (strain)), KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, MU-2100, MU-4001 (more than, produce by Japanese chemical drug (strain)), PVC ス コ one ト 260, PVC ス コ one ト 312, PVC ス コ one ト 335HP (more than, produce by Osaka organic chemistry industry (strain)) etc.
The example that has the specific free radical reaction compound that 3 officials of 3 above acrylics or methacrylic acid group can be above in the molecule:
Can enumerate trimethylolpropane triacrylate, trimethylolpropane tris (methacrylate), pentaerythritol triacrylate, pentaerythrite three (methacrylate), tetramethylol methane tetraacrylate, pentaerythrite four (methacrylate), dipentaerythritol five acrylate, dipentaerythritol five (methacrylate), dipentaerythritol acrylate, dipentaerythritol six (methacrylate), three (2-acryloxy ethyl) phosphate, three (2-methacryloxyethyl) phosphate, perhaps as 9 officials can be above (methyl) acrylate, can enumerate to make and have straight-chain alkyl-sub-and ester ring type structure, and have in the compound of 2 above isocyanate group and the molecule and have 1 above hydroxyl, and have 3, the urethane acrylate compounds of the compound reaction gained of 4 and 5 acryloxies and/or methacryloxy etc.
In addition, commercially available product as the above specific free radical reaction compound of 3 officials energy, can enumerate for example ア ロ ニ Star Network ス M-309, ア ロ ニ Star Network ス M-400, ア ロ ニ Star Network ス M-402, ア ロ ニ Star Network ス M-405, ア ロ ニ Star Network ス M-450, ア ロ ニ Star Network ス M-1310, ア ロ ニ Star Network ス M-1600, ア ロ ニ Star Network ス M-1960, ア ロ ニ Star Network ス M-7100, ア ロ ニ Star Network ス M-8030, ア ロ ニ Star Network ス M-8060, ア ロ ニ Star Network ス M-8100, ア ロ ニ Star Network ス M-8530, ア ロ ニ Star Network ス M-8560, ア ロ ニ Star Network ス M-9050, ア ロ ニ Star Network ス TO-1450 (more than, produce by East Asia synthetic (strain)), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD MAX-3510 (more than, produce by Japanese chemical drug (strain)), PVC ス コ one ト 295, PVC ス コ one ト 300, PVC ス コ one ト 360, PVC ス コ one ト GPT, PVC ス コ one ト 3PA, PVC ス コ one ト 400 (more than, produce by Osaka organic chemistry industry (strain)) etc., perhaps as the urethane acrylate compounds, can enumerate ニ ュ one Off ロ Application テ イ ア R-1150 (more than, produce by the first industrial pharmacy (strain)), KAYARAD DPHA-40H (more than, produce by Japanese chemical drug (strain)) etc.
In the present invention, above-mentioned specific free radical reaction compound can separately or mix more than 2 kinds and use.
In the above-mentioned illustrative specific free radical reaction compound, the compound that contains 3 above acrylics or methacrylic acid group in the compound of more preferably above-mentioned formula (25) expression and the molecule contains the compound of 4 above acrylics or methacrylic acid group in the preferred especially molecule.The functional number of acrylic or methacrylic acid group is many more in the molecule, after then alignment films forms, specific free radical reaction compound is easy more to be retained in the alignment films, can obtain the high liquid crystal orientation film of film density, the impurity and the low molecule stripping composition that enter liquid crystal layer reduce, thereby demonstrate high voltage retention.As specific free radical reaction compound, if will enumerate preferred object lesson, in the preferred especially above-mentioned illustrative specific free radical reaction compound 4,4 '-two propylene acyloxy dicyclohexyls, 4,4 '-two propylene acyloxy-2,2 '-dimethyl dicyclohexyl, 4,4 '-two propylene acyloxy-3,3 '-dimethyl dicyclohexyl, 4,4 '-dimethyl allene acyloxy dicyclohexyl, 4,4 '-dimethyl allene acyloxy-2,2 '-dimethyl dicyclohexyl, 4,4 '-dimethyl allene acyloxy-3,3 '-dimethyl dicyclohexyl, two (4-acryloxy phenyl) ether, two (4-methacryloxy phenyl) ether, two (4-acryloxy cyclohexyl) ether, two (4-methacryloxy cyclohexyl) ether, two (4-acryloxy cyclohexyl) methane, 1,1-two (4-acryloxy phenyl) ethidine, 1,1-two (4-methacryloxy phenyl) ethidine, 2,2-two (4-acryloxy phenyl) fourth fork base, 2,2-two (4-methacryloxy phenyl) fourth fork base and ア ロ ニ Star Network ス M-450, KAYARAD DPHA, KAYARAD DPHA-40H, KAYARADDPCA-60.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention by (1) being made at least a tetrabasic carboxylic acid dicarboxylic anhydride selected in the group that constitutes by aliphatics tetrabasic carboxylic acid dicarboxylic anhydride and alicyclic tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound addition polymerization gained polyamic acid and make at least a polymkeric substance of selecting in the imide amination polymer of above-mentioned polyamic acid imidizate gained (principal component polymer), (2) has the specific free radical reaction compound of at least 1 acrylic or methacrylic acid group in the molecule, (3) the adjuvant preferred dissolution of as required other is contained in the organic solvent and constitutes.
Principal component polymer can contain separately to be made at least a tetrabasic carboxylic acid dicarboxylic anhydride selected in the group that is made of aliphatics tetrabasic carboxylic acid dicarboxylic anhydride and alicyclic tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound addition polymerization and synthetic polyamic acid, contains the imide amination polymer that makes above-mentioned polyamic acid imidizate gained or contain above-mentioned polyamic acid simultaneously and above-mentioned imide amination polymer separately.But, the balance of two kinds of performances of the screening characteristics when forming in order to make aligning agent for liquid crystal of the present invention demonstrate high voltage holding ratio and liquid crystal orientation film better, the average imidizate rate of principal component polymer is preferably 10～90% scope, is preferably 20～85% scope especially.When average imidizate rate less than 10%, the situation of sufficiently high voltage retention can appear obtaining, if average imidizate rate surpasses 90%, the situation of screening characteristics variation in the time of alignment films then can occurring and form.In addition, in order to make aligning agent for liquid crystal of the present invention obtain good anti-print and filming property, sometimes preferably contain imide amination polymer and polyamic acid simultaneously, particularly preferably make sometimes and be selected from 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), at least a tetrabasic carboxylic acid dicarboxylic anhydride of pyromellitic acid dicarboxylic anhydride be selected from p-phenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfide, 1, the 5-diaminonaphthalene, 2, the 7-diamino-fluorene, 4,4 '-diaminodiphenyl ether, 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 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-diamido-2,2 '-dimethyl diphenyl, 3, the polyamic acid of at least a diamine reactant gained of 3-(tetramethyl disiloxane-1,3-two bases) two (propylamine) and imidizate rate are the imide amination polymer more than 45%.The preferred imide amination polymer of the weight ratio of above-mentioned polyamic acid and imide amination polymer: the scope of polyamic acid=10: 90～90: 10, more preferably imide amination polymer: the scope of polyamic acid=15: 85～60: 40, preferred especially imide amination polymer: the scope of polyamic acid=20: 80～50: 50.
Temperature when preparing aligning agent for liquid crystal of the present invention is preferably 0 ℃～200 ℃, more preferably 20 ℃～60 ℃.
As the organic solvent that constitutes aligning agent for liquid crystal of the present invention, can enumerate with as the illustrated identical solvent of the solvent that uses in the polyamic acid synthetic reaction.Wherein from the angle of printing, preferred boiling point is the solvent more than 160 ℃, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, N, the N-dimethyl acetamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, HMPA, between sylvan, xylenols, phenol, cyclohexanol, ethylene glycol, propylene glycol, 1, the 4-butylene glycol, triethylene glycol, diacetone alcohol, butyl lactate, butyl acetate, ethoxyl ethyl propionate, propylene carbonate, diethy-aceto oxalate, diethyl malonate, ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monomethyl ether acetic acid esters, the diethylene glycol monoethyl ether acetic acid esters, 1, the 4-dichloroetane, o-dichlorobenzene etc., preferred N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolacton, diacetone alcohol, ethylene glycol monobutyl ether (butyl cellosolve), propylene carbonate, diethyl carbitol, particularly preferred solvent composition is the composition that above-mentioned solvent is combined, be that the polymkeric substance in the alignment agent is separated out, and making the alignment agent surface tension is the composition of the scope of 25～40mN/m.
Solids content concn is considered viscosity, volatility etc. and is selected in the aligning agent for liquid crystal of the present invention, is preferably the scope of 1～10 weight %.That is to say that aligning agent for liquid crystal of the present invention is coated on substrate surface, formation is filmed as liquid crystal orientation film, and when solids content concn less than 1 weight %, the thickness that will cause this to film is too small, thereby can not obtain good liquid crystal orientation film; When solids content concn surpasses 10 weight %, will cause coating thickness blocked up, thereby can not obtain good liquid crystal orientation film, and the viscosity of aligning agent for liquid crystal increases, coating characteristic variation.
The viscosity of aligning agent for liquid crystal of the present invention (measuring the viscosity of aligning agent for liquid crystal gained with rotary-type viscosity meter under 25 ℃) need be carried out suitable adjustment according to the alignment agent coating method, and, particularly preferred solids content concn scope used method and difference when aligning agent for liquid crystal is coated on substrate.For example, when adopting spin-coating method, special preferable solids content concentration is the scope of 1.5～4.5 weight %.When adopting print process, especially preferably making solids content concn is the scope of 3～9 weight %, can make solution viscosity drop on the scope of 10～50mPas like this.When adopting ink-jet method, especially preferably making solids content concn is the scope of 1～5 weight %, can make solution viscosity drop on the scope of 3～15mPas like this.
Aligning agent for liquid crystal of the present invention as mentioned above, can also contain other adjuvants as required.As adjuvant, for example, from the cohesive of raising to substrate surface, and the angle consideration that improves voltage retention, can enumerate compound that contains functional silanes or the compound that contains epoxy radicals.As this compound that contains functional silanes, can enumerate for example 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-carbethoxyl group-3-TSL 8330, N-carbethoxyl group-3-aminopropyltriethoxywerene werene, N-tri-ethoxy silylpropyl diethylenetriamine, N-trimethoxy silane base propyl group diethylenetriamine, 10-trimethoxy silane-1,4,7-three azepine decane, 10-triethoxysilicane alkyl-1,4,7-three azepine decane, 9-trimethoxy silane base-3,6-diaza nonyl acetic acid esters, 9-triethoxysilicane alkyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, N-two (hydroxyl ethylidene)-3-TSL 8330, N-two (hydroxyl ethylidene)-3-aminopropyltriethoxywerene werene etc.
In addition, as the compound that contains epoxy radicals, preferably can enumerate for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four glycidyl group-2, the 4-hexanediol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3-two (N, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc.These contain functional silanes compound and contain epoxy radicals compound mixture ratio, with respect to 100 weight portion principal component polymers, be preferably 0～60 weight portion, more preferably 10～50 weight portions.In addition, in order to promote the reaction of free radical reaction compound, can also add (light) free radical generating agent.The addition of (light) free radical generating agent is preferably 0～20 weight portion with respect to 100 weight portion principal component polymers, more preferably 0.1～5 weight portion.
＜liquid crystal display cells 〉
Liquid crystal display cells of the present invention can be by for example following method manufacturing.
(1) by for example methods such as rolling method, spin-coating method, print process, ink-jet method, aligning agent for liquid crystal of the present invention is coated on the substrate one side that is provided with the nesa coating that forms pattern, then,, applicator surface films by being added thermosetting.Here, as the method for coated with liquid crystal alignment agent on substrate, for the preferred spin-coating method of small-sized substrate, for the preferred print process of medium-sized substrate, for the preferred ink-jet method of large substrate.As substrate, can use for example glass such as float glass, soda-lime glass; Plastics system transparency carriers such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, ester ring type polyolefin.Simultaneously go up set nesa coating as substrate, can use tin oxide (SnO 2) system NESA film (U.S. PPG register of company trade mark), indium oxide-tin oxide (In 2O 3-SnO 2) the ITO film etc. of system.The pattern of these nesa coatings forms the method that adopts photoetch method and use mask in advance.Reflecting electrode can use metals such as Al or Ag, perhaps contains the alloy of these metals etc., as long as have enough reflectivity, then is not limited to these.When the coating of aligning agent for liquid crystal, for the cohesive of further improving substrate surface and nesa coating or reflecting electrode and filming, can also be on this surface of substrate coating in advance contain functional silanes compound, contain the compound of functionality titanium etc.Behind the coating of liquid crystalline alignment agent, the purpose for the sagging grade of alignment agent liquid that prevents to apply preheats (prebake) usually.The prebake temperature is preferably 30～300 ℃, and more preferably 40～200 ℃, preferred especially 50～150 ℃.Then, remove fully and desolvate,, carry out slaking (afterwards curing) operation for polyamic acid repetitive hot-imide being become the purpose of polyimide repetitive.This slaking (afterwards curing) temperature is preferably 80～300 ℃, more preferably 120～250 ℃.Like this, contain the aligning agent for liquid crystal of the present invention of polyamic acid repetitive, by removing organic solvent after the coating, formation is filmed as alignment films, by further carrying out the thermal dehydration closed loop, can form filming of further imidizate.The thickness of filming that forms is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(2) as required, the roller of fibrous cloth such as nylon, regenerated fiber, cotton carries out grinding process with certain direction friction with for example being tied with to formed film coated surface.Like this, give and filming, form liquid crystal orientation film with the liquid crystal molecular orientation energy.In addition, except the method that adopts grinding process, can also use method to film coated surface irradiation polarized ultraviolet control orientation energy.In addition, the micro mist (foreign matter) that produces when removing grinding process etc. makes film coated surface reach the state of cleaning, preferably the liquid crystal orientation film that forms is washed with isopropyl alcohol and/or pure water etc.In addition; to the liquid crystal orientation film that forms by aligning agent for liquid crystal of the present invention; carry out for example special open flat 6-222366 communique or the special processing of opening the part irradiation ultraviolet radiation shown in the flat 6-281937 communique and tilt angle being changed; perhaps carry out the spy and open ground, the liquid crystal orientation film top formation diaphragm after implementing grinding process shown in the flat 5-107544 communique; after carrying out grinding process with the direction different with previous grinding process; remove said protection film; the processing that the orientation of liquid crystal orientation film can be changed can improve the visual field characteristic of liquid crystal display cells like this.
(3) make 2 substrates that as above form liquid crystal orientation film, 2 substrates are staggered relatively by gap (box gap), make the vertical mutually or antiparallel of polishing direction of liquid crystal orientation film separately, fitted with sealant in 2 substrate periphery positions, in the box gap that is partitioned into by substrate surface and sealant, annotate the topping up crystalline substance, the sealing filling orifice constitutes liquid crystal cell.Then,, promptly constitute on each substrate lateral surface of liquid crystal cell polaroid is set, make liquid crystal display cells at the outside surface of liquid crystal cell.
Here, as sealant, for example can use epoxy resin as the salic ball of hardening agent and separator etc.
As liquid crystal, can enumerate nematic crystal and dish shape type liquid crystal.Wherein preferred nematic crystal can use for example schiff base class liquid crystal, azoxy base class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.In addition, also can add cholesteryl liquid crystal such as for example cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate in these liquid crystal and the chirality agent of selling with trade name " C-15 ", " CB-15 " (メ Le Network corporate system) etc. and using.And, can also use oxygen base benzylidene-in the last of the ten Heavenly stems to ferroelectric liquid crystals such as amino-2-methyl butyl cinnamates.
In addition, as the polaroid of fitting on the liquid crystal cell outside surface, can enumerate polyvinyl alcohol (PVA) is extended that the polarizing coating that is referred to as the H film that orientation absorbs the iodine gained simultaneously is clipped in the acetate fiber diaphragm and the polaroid that polaroid of making or H film itself are made.
Embodiment
Below, by embodiment the present invention is carried out more specific description, but the present invention is not limited to these embodiment.Imidizate rate, voltage retention and printing are estimated by following method in embodiment and the comparative example.
[imidizate rate]
With polymkeric substance at room temperature behind the drying under reduced pressure, adopt superconduction nuclear magnetic resonance absorption plant (NMR, Jeol Ltd. makes, trade name: EX-90A), at deuterated dimethyl sulfoxide (DMSO-d 6) in, be primary standard substance with the tetramethyl monosilane, measure 1H-NMR.In resultant data, by the ratio calculating imidizate rate of near peak area (10ppm) that comes from NH matrix in the polymkeric substance and the peak area that comes from other protons.
[voltage retention]
In 167 milliseconds time span, apply the voltage of 5V to liquid crystal display cells, the voltage application time is 60 microseconds, in the voltage retention of measuring under 60 ℃ the environment after removing to 167 milliseconds from voltage.Determinator adopts the (VHR-1 of strain) East Yang テ Network ニ カ system.When voltage retention is 99.0% when above, be judged as well, situation in addition is judged as bad.
[printing experiment]
Adopt liquid crystal orientation film printing machine (Japan's description printing machine (strain) is made), each aligning agent for liquid crystal of the present invention (the total solids content concentration adjustment is 4.5～6.5%) of preparing in following embodiment and the comparative example is coated on the transparency electrode face of glass substrate, it is 200nm that this glass substrate has by thickness, width is the bar shaped transparency electrode of the ITO film of 20 μ m with the interval formation of 100 μ m, it is being carried out 1 minute predrying under 80 ℃ on heating plate, then on heating plate in 200 ℃ of following slakings 10 minutes, after the formation thickness is about the liquid crystal orientation film of 60nm, peripheral position and central part with this liquid crystal orientation film of microscopic examination of 20 multiplying powers, be judged as " well " when not applying when irregular, be judged as when having coating irregular " bad ".Evaluation result one to each alignment agent printing is listed in the table 2.
Synthesis example 1 (polyamic acid P-1's is synthetic)
Will be as 2 of tetrabasic carboxylic acid dicarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride 38.3162g (0.1709 mole), pyromellitic acid dicarboxylic anhydride (0.0570 mole), be dissolved in the 400g N-N-methyl-2-2-pyrrolidone N-as the p-phenylenediamine 18.8610g (0.1744 mole) of diamine compound, the diamines 30.3955g (0.0581 mole) of above-mentioned formula (14) expression, reacted 4 hours down at 60 ℃.Then, reaction solution is injected in the big excessive methyl alcohol, makes the reaction product precipitation.Then, use methanol wash, in 40 ℃ of dryings 24 hours, obtain the polyamic acid that 88g logarithm viscosity is 0.70dl/g (it is as " polymer P-1 ") by under reduced pressure.
Synthesis example 2 (imide amination polymer P-2's is synthetic)
Will be as 2 of tetrabasic carboxylic acid dicarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride 20.8381g (0.0930 mole), be dissolved in the 140g N-N-methyl-2-2-pyrrolidone N-as the p-phenylenediamine 9.2129g (0.0852 mole) of diamine compound, the diamines 4.9490g (0.0095 mole) of above-mentioned formula (14) expression, reacted 5 hours down at 60 ℃.Then, reaction solution is injected in the big excessive methyl alcohol, makes the reaction product precipitation.Then, use methanol wash, in 40 ℃ of dryings 24 hours, obtaining 31g logarithm viscosity was the polyamic acid of 0.70dl/g by under reduced pressure.30g gained polyamic acid is dissolved in the 400g N-N-methyl-2-2-pyrrolidone N-, add 6.3g pyridine and 8.1g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours, carry out and above-mentioned same precipitation, washing, decompression, obtaining 26g logarithm viscosity is that 0.68dl/g, imidizate rate are 51% imide amination polymer (it is as " polymer P-2 ").
Synthesis example 5 (imide amination polymer P-5's is synthetic)
Will be as 2 of tetrabasic carboxylic acid dicarboxylic anhydride, 3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride 17.8172g (0.0795 mole), as the p-phenylenediamine 2.9223g (0.0270 mole) of diamine compound, the diamines 6.2331g (0.0119 mole), 4 of above-mentioned formula (14) expression, 4 '-diaminodiphenyl-methane 7.8793g (0.0397 mole) and be dissolved in the 140g N-N-methyl-2-2-pyrrolidone N-as end modified aniline 0.1480g with monoamine (0.0016 mole) is 60 ℃ of reactions 4 hours down.Then, reaction solution is injected in the big excessive methyl alcohol, makes the reaction product precipitation.Then, use methanol wash, in 40 ℃ of dryings 24 hours, obtaining 32g logarithm viscosity was the polyamic acid of 0.63dl/g by under reduced pressure.30g gained polyamic acid is dissolved in the 400g N-N-methyl-2-2-pyrrolidone N-, add 10.8g pyridine and 13.9g acetic anhydride, 110 ℃ of following dehydration closed-loops 4 hours, carry out and above-mentioned same precipitation, washing, decompression, obtaining 27g logarithm viscosity is that 0.60dl/g, imidizate rate are 75% imide amination polymer (it is as " polymer P-5 ").
Synthesis example 3, synthesis example 4 and synthesis example 6～13
Except tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound are replaced with in the table 1 listed, similarly operate with synthesis example 1, synthesis example 2 and synthesis example 5, obtain polyamic acid shown in the table 1 and imide amination polymer (they are as polymkeric substance " P-3 ", " P-4 ", " P-6 "～" P-13 ").Each polymkeric substance is suitably adjusted the weight ratio of employed tetrabasic carboxylic acid dicarboxylic anhydride and diamines, the polymkeric substance that can obtain to have viscosity shown in the table 1 by when this polyamic acid synthetic.In addition, the imidizate rate can obtain to have each polymkeric substance of the rate of imidizate shown in the table 1 by suitably adjusting the addition of pyridine and acetic anhydride.In addition, in table 1, acid dianhydride A～D and diamines E～K represent following compound respectively.
Acid dianhydride A:2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride
Acid dianhydride B: pyromellitic acid dicarboxylic anhydride
Acid dianhydride C:1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride
Acid dianhydride D: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,
Diamines E: the diamine compound of above-mentioned formula (14) expression
Diamines F: p-phenylenediamine
Diamines G:4,4 '-diaminodiphenyl-methane
Diamines H: the diamine compound of above-mentioned formula (12) expression
Diamines I: the diamine compound of above-mentioned formula (24) expression
Diamines J: the diamine compound of following formula (26) expression
Diamines K:2,2 '-dimethyl-4,4 '-benzidine
Figure A20071009733700411
Table 1
Polymkeric substance Expression is with respect to the mol ratio of all acid dianhydride amount in the acid dianhydride () Expression is with respect to the mol ratio of whole diamines+amine amount in diamines and the amine () Logarithm viscosity (dl/g) Imidizate rate (%)
Synthesis example 1 P-1 A(75)、B(25) E(25)、F(75) 0.70 0
Synthesis example 2 P-2 A(100) E(10)、F(90) 0.68 51
Synthesis example 3 P-3 A(100) E(20)、F(80) 0.58 50
Synthesis example 4 P-4 A(100) E(10)、F(70)、G(20) 0.65 80
Synthesis example 5 P-5 A(100) E (15), F (34), G (50), aniline (2) 0.60 75
Synthesis example 6 P-6 B(50)、C(50) G(100) 0.72 0
Synthesis example 7 P-7 A(100) F(100) 0.81 90
Synthesis example 8 P-8 A(50)、D(50) H (1.5), I (10), F (87), octadecylamine (3) 0.50 95
Synthesis example 9 P-9 A(50)、D(50) I (10), F (88.5), octadecylamine (3) 0.48 94
Synthesis example 10 P-10 A(50)、D(50) J (3), I (10), F (86.25), aniline (1,5) 0.52 89
Synthesis example 11 P-11 A(50)、D(50) J (5), I (10), F (84.25), aniline (1,5) 0.50 90
Synthesis example 12 P-12 C(100) K(100) 0.85 0
Synthesis example 13 P-13 B(50)、C(50) K(100) 0.90 0
Embodiment 1
Mixed weight with N-N-methyl-2-2-pyrrolidone N-/ethylene glycol monobutyl ether in the polymkeric substance that makes in synthesis example 1 (P-1) adds N-N-methyl-2-2-pyrrolidone N-and ethylene glycol monobutyl ether than=30/70, and add 10 weight portion dipentaerythritol acrylates with respect to polymkeric substance (P-1) respectively, the N that adds 20 weight portions with respect to polymkeric substance (P-1), N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, the aligning agent for liquid crystal of making total solids content concentration and be 3.5 weight % (still, when carrying out the printing experiment, be made into the aligning agent for liquid crystal that total solids content concentration is 6.5 weight %).After it is fully stirred, with the aperture is the filter filtration of 0.2 μ m, adopting spin coater to be coated on glass substrate simultaneously goes up on the ITO film system nesa coating that is provided with, under 80 ℃, carrying out 1 minute predrying on the heating plate, then (under the nitrogen environment) made and had the transparent electrode substrate that thickness is the liquid crystal orientation film of 60nm in 200 ℃ of following slakings 1 hour in the baking oven of cleaning.Then, on each outer rim of the substrate of the above-mentioned coated with liquid crystal alignment films of a pair of transparency electrode/transparent electrode substrate with liquid crystal orientation film, it is the epoxy adhesive of the alumina balls of 5.5 μ m that coating has added diameter, then, the liquid crystal aligning face is relatively overlapped and pressing, bonding agent is solidified.Then, by liquid crystal injecting port between substrate, fill nematic crystal (メ Le Network society system, MLC-2038) after, with the acrylic compounds Photocurable adhesive liquid crystal injecting port is sealed, make VA type liquid crystal display cells.Evaluation result to gained liquid crystal display cells voltage retention is listed in table 2.
Embodiment 2
With the polymkeric substance that makes in the synthesis example 2 (P-2) replace polymeric (P-1), and do not add N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane.And making solvent composition is the mixed weight ratio=50/50 of N-N-methyl-2-2-pyrrolidone N-/ethylene glycol monobutyl ether, in addition, makes aligning agent for liquid crystal of the present invention and VA type liquid crystal display cells similarly to Example 1.The gained liquid crystal display cells is estimated the table 2 that the results are shown in of voltage retention.
Embodiment 3
Except with the polymkeric substance that makes in the synthesis example 3 (P-3) replace polymeric (P-1), making solvent composition is beyond the mixed weight ratio=50/50 of N-N-methyl-2-2-pyrrolidone N-/ethylene glycol monobutyl ether, to make aligning agent for liquid crystal of the present invention and VA type liquid crystal display cells similarly to Example 1.Evaluation result to gained liquid crystal display cells voltage retention is listed in table 2.
Embodiment 4
Except with the polymkeric substance that makes in the synthesis example 4 (P-4) replace polymeric (P-1), use the potpourri (about 50/50 weight %) of dipentaerythritol five acrylate and dipentaerythritol acrylate to substitute dipentaerythritol acrylate, making solvent composition is beyond the mixed weight ratio=40/30/30 of gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/ethylene glycol monobutyl ether, to make aligning agent for liquid crystal of the present invention and VA type liquid crystal display cells similarly to Example 1.Evaluation result to gained liquid crystal display cells voltage retention is listed in table 2.
Embodiment 5
Except with (P-5): (P-6)=50: 50 (weight ratio) use polymkeric substance (P-6) replace polymeric (P-1) that makes in the polymkeric substance (P-5) that makes in the synthesis example 5 and the synthesis example 6, and make solvent composition be the mixed weight of gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/ethylene glycol monobutyl ether than beyond=40/35/25, make aligning agent for liquid crystal of the present invention and VA type liquid crystal display cells similarly to Example 1.Evaluation result to gained liquid crystal display cells voltage retention is listed in table 2.
Embodiment 6
Mixed weight with gamma-butyrolacton/ethylene glycol monobutyl ether in the polymkeric substance that makes in synthesis example 7 (P-7) adds gamma-butyrolacton and ethylene glycol monobutyl ether than=90/10, and add 10 weight portion dipentaerythritol acrylates with respect to polymkeric substance (P-7) respectively, the N that adds 10 weight portions with respect to polymkeric substance (P-7), N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, the aligning agent for liquid crystal of making total solids content concentration and be 3.5 weight % (still, when carrying out the printing experiment, be made into the aligning agent for liquid crystal that total solids content concentration is 4.5 weight %).After it is fully stirred, be that the filter of 0.2 μ m filters, prepare aligning agent for liquid crystal of the present invention with the aperture.It is that the glass substrate of 1mm is simultaneously gone up on the ITO film system nesa coating that is provided with the broach shape that the aligning agent for liquid crystal of the present invention that adopts spin coater as above to prepare is coated on thickness, and through 180 ℃ of dryings 1 hour down, the formation dry film thickness is the overlay film of 80nm.The sander that the roller that twines nylon cloth is equipped with in employing carries out grinding process to formed coated surface, makes liquid crystal orientation film.Here, the polishing condition is: roller rotating speed 400rpm, operator's console translational speed 3cm/ second, it is 0.4mm that fine hair is clamp-oned length.(this substrate is as substrate A).
The aligning agent for liquid crystal of the present invention that adopts spin coater as above to prepare is coated on the one side of glass substrate that thickness is 1mm, through 180 ℃ dry 1 hour down, forming dry film thickness is the overlay film of 80nm.The sander that the roller that twines nylon cloth is equipped with in employing carries out grinding process to formed coated surface, makes liquid crystal orientation film.Here, the polishing condition is: roller rotating speed 400rpm, operator's console translational speed 3cm/ second, it is 0.4mm that fine hair is clamp-oned length.(this substrate is as substrate B).
Coated surface outer rim position at substrate A, B, after containing the epoxy adhesive of alumina balls that diameter is 17 μ m by silk screen print method coating, make the mutual antiparallel of polishing direction of each liquid crystal orientation film and 2 substrates are oppositely arranged by the gap, the outer rim position is in contact with one another and pressing, bonding agent is solidified.
Then, between a pair of substrate, fill nematic crystal (メ Le Network society system by liquid crystal injecting port, MLC-2019) after, with epoxy adhesive liquid crystal injecting port is sealed, the polaroid of fitting on the two sides of outside substrate, surveying, make the polarization direction of polaroid consistent, make IPS type liquid crystal display cells with the polishing direction of substrate liquid crystal orientation film separately.Evaluation result to gained liquid crystal display cells voltage retention is listed in table 2.
Embodiment 7
With the polymkeric substance (P-12) that makes in the polymkeric substance (P-8) that makes in the synthesis example 8 and the synthesis example 12 with (P-8): (P-12)=20: 80 (weight ratio) be dissolved in the mixed solvent (weight of solvent is than 68/17/15) of gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/ethylene glycol monobutyl ether, and add 10 weight portion dipentaerythritol acrylates with respect to the principal component polymer total amount respectively, the N that adds 2 weight portions with respect to the principal component polymer total amount, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, add 1 weight portion 3-glycidoxypropyltrime,hoxysilane with respect to the principal component polymer total amount, the aligning agent for liquid crystal of making total solids content concentration and be 3.5 weight % (still, when carrying out the printing experiment, be made into the aligning agent for liquid crystal that total solids content concentration is 6.0 weight %).After it is fully stirred, be that the filter of 0.2 μ m filters, prepare aligning agent for liquid crystal of the present invention with the aperture.Adopting spin coater that above-mentioned aligning agent for liquid crystal is coated on glass substrate simultaneously goes up on the ITO film system nesa coating that is provided with, under 80 ℃, carrying out 1 minute predrying on the heating plate, then on heating plate in 210 ℃ of following slakings 10 minutes, make and have the transparent electrode substrate that thickness is the liquid crystal orientation film of 60nm.The sander of the roller that twines Artificial Fibers cloth is equipped with in employing, and with roller rotating speed 400rpm, operator's console translational speed 30mm/ second, fine hair is clamp-oned the condition that length is 0.4mm, this is filmed carry out grinding process 1 time.With above-mentioned liquid crystal orientation film coated substrate in pure water by ultrasonic washing after 1 minute, place 100 ℃ dry 10 minutes of cleaning oven.Then, on each outer rim of the above-mentioned liquid crystal orientation film coated substrate of a pair of transparency electrode/transparent electrode substrate with liquid crystal orientation film, it is the epoxy adhesive of the alumina balls of 5.5 μ m that coating has added diameter, then, the liquid crystal aligning face is relatively overlapped and pressing, bonding agent is solidified.Then, by liquid crystal injecting port between substrate, fill nematic crystal (メ Le Network society system, MLC-6221) after, with the acrylic compounds Photocurable adhesive liquid crystal injecting port is sealed, the polaroid of fitting on the two sides in the substrate outside is made TN type liquid crystal display cells.Gained TN type liquid crystal display cells is estimated the table 2 that the results are shown in of voltage retention.
Embodiment 8
With (P-9): (P-6)=50: 50 (weight ratio) use polymkeric substance (P-6) replace polymeric (P-8), (P-12) that make in the polymkeric substance (P-9) that makes in the synthesis example 9 and the synthesis example 6.And changing into the addition of dipentaerythritol acrylate with respect to the principal component polymer total amount respectively is 5 weight portions, N, N, N ', it is 20 weight portions that N '-four glycidyl group-4, the addition of 4 '-diaminodiphenyl-methane change into respect to the principal component polymer total amount.And make solvent composition be the mixed weight of gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/ethylene glycol monobutyl ether than=71/17/12, in addition, make aligning agent for liquid crystal of the present invention and TN type liquid crystal display cells similarly to Example 7.Evaluation result to gained liquid crystal display cells voltage retention is listed in table 2.
Embodiment 9
Use polymkeric substance (P-10) replace polymeric (P-8) that makes in the synthesis example 10, changing into the addition of dipentaerythritol acrylate with respect to the principal component polymer total amount respectively is 20 weight portions, N, N, N ', it is 10 weight portions that N '-four glycidyl group-4, the addition of 4 '-diaminodiphenyl-methane change into respect to the principal component polymer total amount.And, do not add the 3-glycidoxypropyltrime,hoxysilane.And make solvent composition be the mixed weight of gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/ethylene glycol monobutyl ether than=72/15/13, in addition, make aligning agent for liquid crystal of the present invention and TN type liquid crystal display cells similarly to Example 7.Evaluation result to gained liquid crystal display cells voltage retention is listed in table 2.
Embodiment 10
Use polymkeric substance (P-11) replace polymeric (P-8) that makes in the synthesis example 11, with N, N, N ', it is 10 weight portions that N '-four glycidyl group-4, the addition of 4 '-diaminodiphenyl-methane change into respect to the principal component polymer total amount.And, do not add the 3-glycidoxypropyltrime,hoxysilane.And make solvent composition be the mixed weight of gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/ethylene glycol monobutyl ether than=72/15/13, in addition, make aligning agent for liquid crystal of the present invention and TN type liquid crystal display cells similarly to Example 7.Evaluation result to gained liquid crystal display cells voltage retention is listed in table 2.
Embodiment 11
Except using polymkeric substance (P-13) replace polymeric (P-12) that makes in the synthesis example 13, and make solvent composition be the mixed weight of gamma-butyrolacton/N-N-methyl-2-2-pyrrolidone N-/ethylene glycol monobutyl ether than beyond=72/16/12, make aligning agent for liquid crystal of the present invention and TN type liquid crystal display cells similarly to Example 7.Evaluation result to gained liquid crystal display cells voltage retention is listed in table 2.
Comparative example 1
Except not adding dipentaerythritol acrylate, make aligning agent for liquid crystal and VA type liquid crystal display cells similarly to Example 1.Evaluation result to gained liquid crystal display cells voltage retention is listed in table 2.
Comparative example 2
Except not adding dipentaerythritol acrylate, make aligning agent for liquid crystal and VA type liquid crystal display cells similarly to Example 2.Evaluation result to gained liquid crystal display cells voltage retention is listed in table 2.
Comparative example 3
Except the potpourri (about 50/50 weight %) that does not add dipentaerythritol five acrylate and dipentaerythritol acrylate, make aligning agent for liquid crystal and VA type liquid crystal display cells similarly to Example 4.Evaluation result to gained liquid crystal display cells voltage retention is listed in table 2.
Comparative example 4
Except not adding dipentaerythritol acrylate, make aligning agent for liquid crystal and IPS type liquid crystal display cells similarly to Example 6.Evaluation result to gained liquid crystal display cells voltage retention is listed in table 2.
Comparative example 5
Except not adding dipentaerythritol acrylate, make aligning agent for liquid crystal and TN type liquid crystal display cells similarly to Example 8.The gained liquid crystal display cells is estimated the table 2 that the results are shown in of voltage retention.
Table 2
Polymkeric substance Be the interpolation umber in the specific free radical reaction compound bracket Voltage retention (VHR) Printing
Polyamic acid Imide amination polymer VHR(％) Judge
Embodiment 1 P-1 - KAYARAD DPHA(10) 99.1 Well Well
Embodiment 2 - P-2 KAYARAD DPHA-40H(10) 99.3 Well Well
Embodiment 3 - P-3 KAYARAD DPHA(10) 99.6 Well Well
Embodiment 4 - P-4 アロニツクスM-450(10) 99.8 Well Well
Embodiment 5 P-6 P-5 KAYARAD DPHA(10) 99.7 Well Well
Embodiment 6 - P-7 KAYARAD DPHA(10) 99.7 Well Well
Embodiment 7 P-12 P-8 KAYARAD DPHA(10) 99.3 Well Well
Embodiment 8 P-6 P-9 KAYARAD DPHA(5) 99.2 Well Well
Embodiment 9 P-12 P-10 KAYARAD DPHA(20) 99.5 Well Well
Embodiment 10 P-12 P-11 KAYARAD DPCA-60(10) 99.4 Well Well
Embodiment 11 P-13 P-8 KAYARAD DPHA(10) 99.3 Well Well
Comparative example 1 P-1 - - 98.3 Bad Well
Comparative example 2 - P-2 - 98.7 Bad Well
Comparative example 3 - P-4 - 98.9 Bad Bad
Comparative example 4 - P-7 - 98.9 Bad Bad
Comparative example 5 P-6 P-9 - 98.7 Bad Bad
By above-mentioned table 2 as can be known, the liquid crystal orientation film that the aligning agent for liquid crystal that is obtained by embodiment 1～embodiment 11 makes demonstrates the voltage retention higher than comparative example, and demonstrates the screening characteristics of good alignment films.As seen the above-mentioned characteristic of aligning agent for liquid crystal of the present invention can be adjusted by selection and addition to the specific free radical reaction compound structure that added.As mentioned above, according to the present invention, can provide to show the aligning agent for liquid crystal that high voltage holding ratio and oriented film coating are good and have this alignment films and have the liquid crystal display cells of graceful graph picture.

Claims (7)

1. aligning agent for liquid crystal is characterized in that containing:
Make the polyamic acid of at least a tetrabasic carboxylic acid dicarboxylic anhydride selected in the group that constitutes by aliphatics tetrabasic carboxylic acid dicarboxylic anhydride and alicyclic tetrabasic carboxylic acid dicarboxylic anhydride and diamine compound addition polymerization gained and make at least a polymkeric substance of selecting in the imide amination polymer of above-mentioned polyamic acid imidizate gained; With
The free radical reaction compound that has at least 1 acrylic or methacrylic acid group in the molecule.
2. aligning agent for liquid crystal according to claim 1, the average imidizate rate of wherein above-mentioned polyamic acid and imide amination polymer total amount are 10～90% scope.
3. aligning agent for liquid crystal according to claim 1 and 2 wherein has at least 3 acrylics or methacrylic acid group in the free radical reaction compound molecule.
4. according to any described aligning agent for liquid crystal of claim 1～3,, contain 1～100 weight portion free radical reaction compound wherein with respect to above-mentioned polyamic acid of 100 weight portions and imide amination polymer.
5. according to any described aligning agent for liquid crystal of claim 1～4, wherein at least a tetrabasic carboxylic acid dicarboxylic anhydride is for being selected from 2,3,5-tricarboxylic basic ring amyl group acetic acid dicarboxylic anhydride, 1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetrabasic carboxylic acid dicarboxylic anhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphthalene [1,2-c]-furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphthalene [1,2-c]-furans-1, the 3-diketone, 1,2,3,4-cyclopentane tetrabasic carboxylic acid dicarboxylic anhydride, 1,2,4,5-cyclohexane tetrabasic carboxylic acid dicarboxylic anhydride, 3-oxabicyclo [3.2.1] octane-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 3,5,6-three carboxyls-2-carboxyl norbornane-2:3,5:6-dicarboxylic anhydride and two ring [3.3.0] octanes-2,4,6, at least a alicyclic tetrabasic carboxylic acid dicarboxylic anhydride of 8-tetrabasic carboxylic acid dicarboxylic anhydride.
6. according to any described aligning agent for liquid crystal of claim 1～5, be used to form the vertical alignment-type liquid crystal aligning film.
7. a liquid crystal display cells is characterized in that having by any liquid crystal orientation film that described aligning agent for liquid crystal forms of claim 1～6.
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Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
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JP4424454B2 (en) * 2000-05-25 2010-03-03 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
JP2003049069A (en) * 2001-08-07 2003-02-21 Jsr Corp Liquid crystal-orienting agent and liquid crystal display element
KR100932410B1 (en) * 2002-05-23 2009-12-17 닛산 가가쿠 고교 가부시키 가이샤 Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element

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