CN101548228B - Liquid crystal orientation treatment agent and liquid crystal display element produced by using the same - Google Patents

Liquid crystal orientation treatment agent and liquid crystal display element produced by using the same Download PDF

Info

Publication number
CN101548228B
CN101548228B CN2007800434831A CN200780043483A CN101548228B CN 101548228 B CN101548228 B CN 101548228B CN 2007800434831 A CN2007800434831 A CN 2007800434831A CN 200780043483 A CN200780043483 A CN 200780043483A CN 101548228 B CN101548228 B CN 101548228B
Authority
CN
China
Prior art keywords
liquid crystal
formula
polyimide
diamines
aligning agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2007800434831A
Other languages
Chinese (zh)
Other versions
CN101548228A (en
Inventor
志田启文
筒井皇晶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Publication of CN101548228A publication Critical patent/CN101548228A/en
Application granted granted Critical
Publication of CN101548228B publication Critical patent/CN101548228B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Liquid Crystal (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed is a liquid crystal orientation treatment agent which enables to produce a liquid crystal orientation film having excellent rubbing resistance and a large liquid crystal pretilt angle and which can provide an excellent printing property even when the agent has a high imidization level. Also disclosed is a liquid crystal display element produced by using the liquid crystal orientation treatment agent. The liquid crystal orientation treatment agent comprises the following polyimides (A) and (B). Polyimide (A): a polyimide which is produced by the imidization of a polyamic acid produced by the reaction between a diamine component comprising a diamine represented by the formula (1) or a diamine component comprising a diamine represented by the formula (1) and at least one diamine selected from the group consisting of diamines respectively represented by the formulae (2), (3), (4) and (5) with a tetracarboxylic acid dianhydride. Polyimide (B): a polyimide which is produced by theimidization of a polyamic acid produced by the reaction between a diamine component comprising diamines respectively represented by the formulae (1) and (6) or a diamine component comprising diaminesrespectively represented by the formulae (1) and (6) and at least one diamine selected from the group consisting of diamines respectively represented by the formulae (2), (3), (4) and (5) with a tetracarboxylic acid dianhydride.

Description

Aligning agent for liquid crystal and used the liquid crystal display cells of this treating agent
Technical field
The present invention relates to aligning agent for liquid crystal and used the liquid crystal orientating membrane and the liquid crystal display cells of this treating agent.Be particularly related to the aligning agent for liquid crystal, the liquid crystal orientating membrane that has used this treating agent and the liquid crystal display cells that when the friction treatment operation is made liquid crystal display cells, use.
Background technology
Liquid crystal display cells is to have structure that liquid crystal molecule is formed on the liquid crystal orientating membrane clamping on the substrate, utilized the display element of this liquid crystal molecule according to the character of voltage responsive.Liquid crystal orientating membrane possesses the vital role that the orientation direction of liquid crystal molecule and tilt angle is controlled at free position.
Liquid crystal orientating membrane is generally by implementing with rayon or nylon cloth etc. the what is called " friction treatment " of its surperficial pressurization friction to be made to the surface that is formed at the polyimide film on the substrate.The orientation direction of liquid crystal molecule is by this friction treatment decision.
As the method for the tilt angle that strengthens liquid crystal, the known method (for example with reference to patent documentation 1) that in the structure of the polyimide that forms liquid crystal orientating membrane, imports chain alkyl.
As making polyimide film be formed at method on the substrate, comprise the solution of coating polyamic acid etc., on substrate, make the method for its imidizate; The method of the solution of coating soluble polyimide.
Wherein, even use the method for the solution of soluble polyimide to burn till the good polyimide film of characteristic that also can form when making liquid crystal orientating membrane at a lower temperature.But relatively, exist the film strength that forms low, produce the damage on film surface and the problem of peeling off of film because of friction treatment easily.
In addition, as the method for when making liquid crystal orientating membrane, polymer solution being coated substrate, use the flexible printing method widely at industrial circle at present.But this printing of the soluble polyimide solution that the imidizate rate is high is poor, therefore must mix and use polyamic acid or low (for example with reference to the patent documentations 2) such as soluble polyimides of imidizate rate.In addition, if in the structure of soluble polyimide, import chain alkyl, then there is the tendency of its printing deterioration in order to give the bigger tilt angle of liquid crystal.
As the method for improving the printing of polymer solution on substrate, the method for known adding butyl cellosolve equal solvent (for example with reference to patent documentation 3).But,, therefore can't use the butyl cellosolve equal solvent in a large number because the dissolubility of general soluble polyimide is lower than polyamic acid etc.
Patent documentation 1: Japanese patent laid-open 2-282726 communique
Patent documentation 2: Japanese patent laid-open 9-297312 communique
Patent documentation 3: Japanese patent laid-open 2-037324 communique
The announcement of invention
The purpose of this invention is to provide that the rub resistance that can obtain to film is good, the tilt angle of liquid crystal big (for example more than 4 °) though liquid crystal orientating membrane and the high printing of imidizate rate also well polyimide be aligning agent for liquid crystal.
The present inventor has finished the present invention in order to realize after described purpose is conscientiously studied.That is, the present invention has following technical characterictic.
(1) aligning agent for liquid crystal, the feature of this treating agent be, contains following polyimide (A) and following polyimide (B),
Polyimide (A):
Make the diamines of two amine components that the diamines of (i) formula (1) expression constitutes or (ii) formula (1) expression and be selected from two amine components that at least a kind of diamines of formula (2), formula (3), formula (4) and formula (5) constitutes to obtain polyamic acid, with this polyamic acid imidizate and the polyimide that gets with the reaction of tetracarboxylic dianhydride's composition;
Polyimide (B):
Make the diamines of the diamines of two amine components that the diamines of the diamines of (iii) formula (1) expression and formula (6) expression constitutes or (iv) formula (1) expression and formula (6) expression and be selected from two amine components that at least a kind of diamines of formula (2), formula (3), formula (4) and formula (5) constitutes to obtain polyamic acid, with this polyamic acid imidizate and the polyimide that gets with the reaction of tetracarboxylic dianhydride's composition;
Figure G2007800434831D00021
In the formula (2), X 1The expression singly-bound or be selected from ether, ester and acid amides in conjunction with the base, X 2The straight chain shape alkyl of expression carbon number 1～12, in the formula (3), n is 1 or 2, in the formula (5), X 3For singly-bound or be selected from-O-,-CH 2-,-NH-and-CONH-in conjunction with the base, R is hydrogen atom or methyl,
In the formula (6), X 4The expression singly-bound or be selected from ether, ester, methylene ether and acid amides in conjunction with the base, X 51 valency organic group of the straight chain shape alkyl of expression carbon number 14～20 or following formula (7) expression,
-X 6-X 7(7)
In the formula (7), X 6Be phenyl or cyclohexyl, X 7Cyclohexyl for straight chain shape alkyl with carbon number 1～12.
(2) aligning agent for liquid crystal of above-mentioned (1) record wherein, contains polyimide (A) and polyimide (B) with 50: 50～90: 10 mass ratioes.
(3) aligning agent for liquid crystal of above-mentioned (1) or (2) record, wherein, the imidizate rate of polyimide (A) and polyimide (B) all is more than 40%.
(4) aligning agent for liquid crystal of each record in above-mentioned (1)～(3), wherein, with respect to whole 100 moles of % of diamines amount in the polyimide (A), the diamines that contains 20～100 moles of % formulas (1) expression, and during 100 moles of % of the diamine contents deficiency of formula (1), remaining diamines is for being selected from least a kind of diamines of formula (2), formula (3), formula (4) and formula (5).
(5) aligning agent for liquid crystal of each record in above-mentioned (1)～(4), wherein, with respect to whole 100 moles of % of diamines amount in the polyimide (B), contain the diamines of 20～90 moles of % formulas (1) expression, the diamines of 5～40 moles of % formulas (6) expression, and when the total of the diamines of the diamines of formula (1) and formula (6) contained 100 moles of % of quantity not sufficient, remaining diamines was for being selected from least a kind of diamines of formula (2), formula (3), formula (4) and formula (5).
(6) aligning agent for liquid crystal of each record in above-mentioned (1)～(5) wherein, also contains the organic solvent composition.
(7) aligning agent for liquid crystal of above-mentioned (6) record, wherein, described organic solvent composition contains gamma-butyrolacton and butyl cellosolve and dipropylene glycol monomethyl ether or diethyl carbitol.
(8) aligning agent for liquid crystal of each record in above-mentioned (1)～(7), described aligning agent for liquid crystal is used for by the liquid crystal orientating membrane of friction treatment.
(9) liquid crystal orientating membrane that the aligning agent for liquid crystal of each record obtains in use above-mentioned (1)～(8).
(10) liquid crystal orientating membrane, the aligning agent for liquid crystal of each record in coating described (1)～(8) burns till on electroded substrate, carries out friction treatment again and gets.
(11) liquid crystal display cells wherein, has the liquid crystal orientating membrane of record in described (9) or (10).
Printing when aligning agent for liquid crystal of the present invention is coated with on substrate is good, damage and film to the film surface during friction treatment are peeled off few, can obtain the big liquid crystal orientating membrane of tilt angle of liquid crystal, therefore can obtain to possess the liquid crystal display cells of the few superperformance of display defect.In addition, aligning agent for liquid crystal of the present invention can possess described characteristic under the prerequisite that the imidizate rate that is contained in polyimide wherein improves, therefore can obtain the high liquid crystal display cells of reliability.
The best mode that carries out an invention
Below, the present invention is described in detail.
Aligning agent for liquid crystal of the present invention contains following polyimide (A) and following these 2 kinds of polyimide of polyimide (B), and contains polyimide (A) and polyimide (B) with 50: 50～90: 10 mass ratio.Aligning agent for liquid crystal of the present invention is specially adapted to by the liquid crystal orientating membrane of friction treatment.That is, aligning agent for liquid crystal of the present invention is used to it is coated on the electroded substrate, burns till, carries out friction treatment again and obtain liquid crystal orientating membrane.
＜polyimide (A) 〉
Be used for polyimide of the present invention (A) and be two amine components and the reaction of tetracarboxylic dianhydride's composition and the polyamic acid imidizate and the polyimide that forms.Polyimide (A) is a solubility in the contained organic solvent of aligning agent for liquid crystal of the present invention, also is solubility in the organic solvent that obtains to use in the reaction system of polyimide (A) in two amine components and the reaction of tetracarboxylic dianhydride's composition.
[two amine components]
The diamines of the following formula of two amine components (1) expression of using in order to obtain polyimide (A) is necessary composition.
In the diamines of formula (1) expression, each the substituent position on the phenyl ring is not particularly limited, but the position of 2 amino relation preferred between position or contraposition.Below exemplify the preferred concrete example of this diamines, but be not limited thereto.
Figure G2007800434831D00052
Damage and the film to film surface of the use of the diamines of formula (1) expression when suppressing friction treatment peeled off effectively, and the dissolubility raising of polyimide (A) in organic solvent.The diamines of formula (1) expression can use a kind separately, also can be also with multiple.
The content of the diamines of formula (1) expression is 20～100 moles of % of two amine component total amounts in the polyimide (A), is preferably 30～100 moles of %, more preferably 40～100 moles of %.The ratio of the diamines of formula (1) the expression damage and the effect that film is peeled off on the oriented film surface during many inhibition friction treatment more is high more, and polyimide dissolubility in organic solvent is also high more.
During 100 moles of % of diamines less than of formula (1) expression, remaining diamines is to be selected from following formula (2), formula (3), formula (4) and formula (5) at least a kind.The content that is selected from least a kind of diamines of formula (2), formula (3), formula (4) and formula (5) is 0 (not comprising 0)～80 moles of % of two amine component total amounts in the polyimide (A), is preferably 5～70 moles of %, more preferably 10～60 moles of %.Special good be that the content of the diamines of formula (2) expression is preferably % 0 (not comprising 0)～40 moles, more preferably 5～30 moles of %, further 10～30 moles of % more preferably, the content that is selected from least a kind of diamines of formula (3), formula (4) and formula (5) is remaining content.
Figure G2007800434831D00061
In the formula (2), X 1The expression singly-bound or be selected from ether, ester and acid amides in conjunction with the base, X 2The straight chain shape alkyl of expression carbon number 1～12.
In the formula (3), n is 1 or 2, preferred 1.
In the formula (5), X 3Expression singly-bound or be selected from-O-,-CH 2-,-NH-and-CONH-in conjunction with base, R is hydrogen atom or methyl, preferred hydrogen atom.
If the diamines of use formula (2) then has the effect of the tilt angle that improves dissolubility and liquid crystal.In addition, if the diamines of use formula (3)～formula (5) expression then has the direction-sense effect that improves liquid crystal.
Below exemplify the concrete example of the diamines of formula (2)～formula (5) expression, but be not limited thereto.
Example as the diamines of formula (2) expression can exemplify the diamines of following formula (11)～formula (14) etc.
Figure G2007800434831D00071
In formula (11)～formula (14), m is 0～11, preferred 5～11 integer.
Example as the diamines of formula (3) expression can exemplify 2-aminobenzene methyl amine, 3-aminobenzene methyl amine, 4-aminobenzene methyl amine, 2-(2-aminophenyl) ethylamine, 2-(3-aminophenyl) ethylamine, 2-(4-aminophenyl) ethylamine etc.
Example as the diamines of formula (4) expression can exemplify p-phenylenediamine (PPD), m-phenylene diamine, o-phenylenediamine etc.
Example as the diamines of formula (5) expression can exemplify 4,4 '-benzidine, 4,4 '-diamido-2,2 '-dimethyl diphenyl, 4,4 '-diamido-3,3 '-dimethyl diphenyl, 4,4 '-diamino-diphenyl ether, 3,3 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamido-3,3 '-dimethyl diphenylmethane, 4,4 '-diamino-diphenyl amine, 4,4 '-diamino-diphenyl acid amides etc.
Wherein, 3-aminobenzene methyl amine or the dissolubility height of 4-aminobenzene methyl amine when forming polyimide, therefore preferred especially.
[tetracarboxylic dianhydride's composition]
In order to obtain polyimide (A), as long as the damage on the liquid crystal orientating membrane surface that is produced in the time of can improving printing when coating substrate, friction treatment with tetracarboxylic dianhydride's composition of described two amine components reaction and the problem that film is peeled off, be not particularly limited, can do various selections according to other characteristic certainly.Among the present invention used tetracarboxylic dianhydride can be independent a kind also can be multiple and use.
For example, even the voltage retention equal angles that also obtains the higher polyimide of dissolubility easily and can improve liquid crystal cell from the polyimide of high imidizate rate better is to use the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure.
As tetracarboxylic dianhydride, can exemplify 1,2,3 with ester ring type structure or aliphatic structure, 4-cyclo-butane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclo-butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 3,4-dicarboxyl-1-cyclohexyl succinic acid dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, two rings [3,3,0] octane-2,4,6, the 8-tetracarboxylic dianhydride, 3,3 ', 4,4 '-the dicyclohexyl tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, suitable-3,7-dibutyl ring suffering-1,5-diene-1,2,5, the 6-tetracarboxylic dianhydride, three ring [4.2.1.0 2,5] nonane-3,4,7,8-tetrabasic carboxylic acid-3,4:7,8-dianhydride, six ring [6.6.0.1 2,7.0 3,6.1 9,14.0 10,13] hexadecane-4,5,11,12-tetrabasic carboxylic acid-4,5:11,12-dianhydride etc.
Particularly with aromatic tetracarboxylic acid dianhydride and time spent, the liquid crystal aligning raising, and the savings electric charge of liquid crystal cell is reduced.
As the aromatic tetracarboxylic acid dianhydride, can exemplify pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride etc.
Consider the balance of each characteristic such as directionality, voltage retention and savings charge characteristic of dissolubility, the liquid crystal of polyimide (A), have the tetracarboxylic dianhydride of ester ring type structure or aliphatic structure and aromatic tetracarboxylic acid dianhydride and with ratio with the former/latter's molar ratio computing better is 90/10～40/60, is more preferably 80/20～70/30.Special good tetracarboxylic dianhydride's combination is 1,2,3,4-cyclo-butane tetracarboxylic dianhydride and pyromellitic acid anhydride.
[manufacture method of polyamic acid]
The reaction that makes the reaction of two above-mentioned amine components and tetracarboxylic dianhydride's composition and obtain polyamic acid usually can be by mixing tetracarboxylic dianhydride's composition and two amine components be realized in organic solvent.
The method that tetracarboxylic dianhydride's composition and two amine components are mixed in organic solvent is not particularly limited.Can exemplify and for example be stirred in the solution that has dispersed or dissolved two amine components in the organic solvent, directly or be dispersed or dissolved in the method for adding in the organic solvent tetracarboxylic dianhydride's composition; Two amine components are added to the method in the solution that in organic solvent, has dispersed or dissolved tetracarboxylic dianhydride's composition; Alternately add the method for tetracarboxylic dianhydride's composition and two amine components etc.In addition, under the situation that tetracarboxylic dianhydride's composition or two amine components are made of multiple compound, polyreaction can be under the state that multiple composition with these is pre-mixed, carried out, also polyreaction can be carried out respectively successively.
Temperature when making tetracarboxylic dianhydride's composition and two amine components carry out polyreaction in organic solvent is generally 0～150 ℃, better is 5～100 ℃, is more preferably 10～80 ℃.
The fast more end of the high more polyreaction of temperature during polyreaction, if but too high, then can't obtain high molecular weight polymers sometimes.
In addition, polyreaction can be carried out under the concentration arbitrarily of the polymkeric substance that is generated, if but concentration is low excessively, then be difficult to obtain high molecular weight polymers, if excessive concentration, then the viscosity of reactant liquor is too high, is difficult to uniform stirring.Therefore, the concentration when carrying out polyreaction is preferably 1～50 weight %, more preferably 5～30 weight %.In addition, can adopt at the polyreaction initial stage and react, append the method that organic solvent reduces concentration then with high concentration.
The employed organic solvent of above-mentioned reaction so long as the polyamic acid that dissolving generates be not particularly limited.Can exemplify for example N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, N-methyl caprolactone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton etc.
These organic solvents can use a kind separately, also can multiple and usefulness.In addition, even the insoluble solvent of separating polyamic acid in the scope that the polyamic acid that generates is not separated out, also may be mixed in in the above-mentioned organic solvent and uses.
In addition, moisture in the organic solvent hinders polyreaction, and make the polyamic acid hydrolysis of generation, so the organic solvent that preferred use has dehydrated as far as possible.
Tetracarboxylic dianhydride's composition that the polyreaction of polyamic acid is used and diamines components in proportions better are 0.8: 1～1.2: 1 with molar ratio computing, more preferably 0.9: 1～1: 1.This mol ratio is more near 1: 1, and the molecular weight of the polyamic acid that then obtains is big more.By controlling the molecular weight of this polyamic acid, can adjust the molecular weight of the polyimide that obtains behind the imidizate.
Among the present invention, be not particularly limited for the molecular weight of polyamic acid, as the precursor that obtains to be particularly suitable for polyimide of the present invention (A), its weight-average molecular weight better is 2000～200000, is more preferably 5000～50000.
[manufacture method of polyimide (A)]
The imidizate of the polyamic acid that obtains as mentioned above can carry out by stirring in the presence of base catalyst and acid anhydrides in organic solvent in 1～100 hour.
As base catalyst, can exemplify pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc.Wherein, pyridine has the alkalescence that required appropriateness is carried out in the reaction of making, and is therefore preferred.
In addition, as acid anhydrides, can exemplify acetic anhydride, trimellitic anhydride, pyromellitic acid acid anhydride etc.Wherein, acetic anhydride is because the polyimide that obtains after imidizate finishes is easy to purifying, and is therefore preferred.
As the organic solvent that with the polyamic acid imidizate time, uses, the used identical organic solvent of organic solvent in the time of can using the polyreaction with aforementioned polyamic acid.
The imidizate rate of polyimide (A) can wait and control by adjusting catalytic amount, temperature of reaction, reaction time.The amount of base catalyst better is 0.2～10 times of mole of acid amides acidic group, is more preferably 0.5～5 times of mole.In addition, the amount of acid anhydrides better is 1～30 times of mole of acid amides acidic group, is more preferably 1～10 times of mole.Temperature of reaction better is-20～250 ℃, is more preferably 0～180 ℃.Reaction time is 1～100 hour, is more preferably 1～10 hour.
Imidizate rate for polyimide (A) is not particularly limited, and better is more than 40%, in order to obtain high voltage holding ratio, is more preferably more than 60%, and the spy is well more than 80%.
The remaining catalyzer that interpolation is arranged in the solution of resulting polyimide (A) is so be used for aligning agent for liquid crystal of the present invention after preferably polyimide being reclaimed cleaning.
The recovery of polyimide (A) can make polyimide separate out the back filtration and realize by the solution behind the imidizate being put in the Weak solvent in the stirring.As Weak solvent, can exemplify methyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene etc.The cleaning of the polyimide that recovery obtains also can be undertaken by this Weak solvent.The polyimide that reclaims after cleaning can carry out normal temperature or heat drying formation powder under normal pressure or decompression.
Molecular weight for the contained polyimide of aligning agent for liquid crystal of the present invention (A) is not particularly limited, from the intensity of filming with as the processing difficulty or ease consideration of aligning agent for liquid crystal, be preferably 2000～200000 in weight-average molecular weight, more preferably 5000～50000.
＜polyimide (B) 〉
Polyimide (B) be with the reaction of two amine components and tetracarboxylic dianhydride's composition and the polyimide that obtains of polyamic acid imidizate.Polyimide (B) is a solubility in the contained organic solvent of aligning agent for liquid crystal of the present invention, also is solubility in the organic solvent that obtains to use in the reaction system of polyimide (B) in two amine components and the reaction of tetracarboxylic dianhydride's composition.
[two amine components]
Two amine components that use in order to obtain polyimide (B) are must composition with the diamines of formula (1) expression and the diamines of formula (6) expression.
Figure G2007800434831D00111
In the formula (6), X 4The expression singly-bound or be selected from ether, ester, methylene ether and acid amides in conjunction with the base, X 51 valency organic group of the straight chain shape alkyl of expression carbon number 14～20 or following formula (7) expression,
-X 6-X 7(7)
In the formula (7), X 6Be phenyl or cyclohexyl, X 7Cyclohexyl for straight chain shape alkyl with carbon number 1～12.
The diamines of formula (1) expression can use two amine components of record in the above polyimide (A), and its effect is also identical with preferred concrete example.
In the polyimide (B), not only the diamines of formula (1) expression is necessary composition, and the diamines of formula (6) expression also is two necessary amine components.The content of the diamines of formula (1) expression is 20～90 moles of % of two amine component total amounts in the polyimide (B), is preferably 30～60 moles of %, more preferably 30～50 moles of %.
On the other hand, the content of the diamines by making formula (6) expression is 5～40 moles of % of two amine component total amounts in the polyimide (B), can strengthen the tilt angle of liquid crystal, and is therefore preferred.The content of the diamines of formula (6) expression is 10～40 moles of % more preferably, further 10～30 moles of % more preferably.The tilt angle of the high more liquid crystal of ratio of the diamines of formula (6) expression becomes big more, and is therefore preferred especially.The diamines of formula (6) expression can use separately a kind also can be multiple and use.
In addition, when the total of the diamines of the formula (1) in the two amine component total amounts in the polyimide (B) and the diamines of formula (6) contained 100 moles of % of quantity not sufficient, remaining diamines was for being selected from described formula (2), formula (3), formula (4) and formula (5) at least a kind.Better be at least a kind of diamines that is selected from formula (3), formula (4) and formula (5), these diamines play the direction-sense effect that keeps liquid crystal well.The content of these diamines is 0 (the not comprising 0)～75 moles of % in two amine components in the polyimide (B), is preferably 5～75 moles of %, more preferably 10～60 moles of %.
Below, exemplify the concrete example of the diamines of formula (6) expression, but be not limited thereto.
Figure G2007800434831D00121
In formula (15)～formula (19), p is 13～19 integer, is preferably 13～17 integer.
Figure G2007800434831D00131
In formula (20)～formula (24), q is 0～11 integer, is preferably 2～6 integer.
Figure G2007800434831D00132
In formula (25)～formula (29), h is 0～11 integer, is preferably 2～6 integer.
[tetracarboxylic dianhydride's composition]
In order to obtain polyimide (B), as long as the damage on the liquid crystal orientating membrane surface that is produced in the time of can improving printing when coating substrate, friction treatment with tetracarboxylic dianhydride's composition of described two amine components reaction and the problem that film is peeled off, be not particularly limited, can do various selections according to other characteristic certainly.Used tetracarboxylic dianhydride can be independent a kind also can be multiple and use.As preferred concrete example, can exemplify illustrated tetracarboxylic dianhydride in tetracarboxylic dianhydride's composition of polyimide (A).
[manufacture method of polyamic acid and polyimide (B)]
Make the reaction of described two amine components and tetracarboxylic dianhydride's composition and obtain the imidizate of polyamic acid of operation, gained of polyamic acid and the reclaimer operation of polyimide etc. and can carry out equally with operating described in the manufacture method of the manufacture method of the polyamic acid of described polyimide (A) and polyimide (A).
Molecular weight as the polyamic acid of the precursor of polyimide (B) is not particularly limited, and as the precursor that obtains to be particularly suitable for polyimide of the present invention (B), its weight-average molecular weight is preferably 2000～200000, and more preferably 5000～50000.
In addition, also be not particularly limited, consider, be preferably 2000～200000, more preferably 5000～50000 in weight-average molecular weight from the intensity of filming with as the angle of the processing difficulty or ease of aligning agent for liquid crystal for the molecular weight of polyimide (B).
Imidizate rate for polyimide (B) is not particularly limited, and is same with polyimide (A), is preferably more than 40%, in order to obtain high voltage holding ratio, more preferably more than 60%, particularly preferably more than 80%.
＜aligning agent for liquid crystal 〉
Aligning agent for liquid crystal of the present invention is the solution that contains polyimide (A) and polyimide (B) with suitable ratio.For example, with the powder of polyimide (A) and polyimide (B) be dissolved in respectively organic solvent form polyimide solution, be diluted to institute's concentration of wanting after these solution are mixed and solution, or the solution dilution of each polyimide extremely mixed after the desired concentration again and the solution that gets.In the described dilution operation, can adjust the organic solvent composition, can also append additive etc. in order to improve the characteristic of filming in order to be controlled at the coating on the substrate.
The polyimide (A) that aligning agent for liquid crystal of the present invention is contained and the ratio of polyimide (B) are, total content with respect to polyimide (A) and polyimide (B), the content of polyimide (A) is 50～90 quality %, printing and big tilt angle that so easy acquisition is good.The content of polyimide (A) is 60～80 quality % more preferably.
That is, polyimide (A) and polyimide (B) with the former and the latter's mass ratio count 50: 50～90: 10, more preferably 60: 40～80: 20.
The organic solvent that dissolves again as the powder that is used to make polyimide (A) and/or polyimide (B), can exemplify N, dinethylformamide, N, N-dimethyl acetamide, N-N-methyl-2-2-pyrrolidone N-, N-methyl caprolactone, 2-Pyrrolidone, N-ethyl pyrrolidone, N-vinyl pyrrolidone, dimethyl sulfoxide, tetramethylurea, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 1,3-dimethyl-imidazolinone etc.Wherein, gamma-butyrolacton is difficult for moisture absorption, and is therefore preferred.
As in order to control and the solvent that adds can exemplify ethyl cellosolve to the coating of substrate, butyl cellosolve, ethyl carbitol, butyl carbitol, the ethyl carbitol acetic acid esters, ethylene glycol, diethylene glycol diethyl ether, 1-methoxyl-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, propylene-glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, the single ether of propylene glycol-1--2-acetic acid esters, dipropylene glycol, dipropylene glycol monomethyl ether, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc.
Also comprise the solvent that can't make polyimide (A) or polyimide (B) dissolving individually in these solvents, but so long as in the scope that polyimide is not separated out, just may be mixed in in the aligning agent for liquid crystal of the present invention.Particularly known to moderately mixing solvent with low surface tension, be coated with film uniformity in the time of on being applied to substrate and improve, this also is suitable for for aligning agent for liquid crystal of the present invention.
In the combination of above-described solvent, except gamma-butyrolacton and butyl cellosolve, better be to comprise dipropylene glycol monomethyl ether or diethyl carbitol, the spy is well the combination of gamma-butyrolacton and butyl cellosolve and dipropylene glycol monomethyl ether.Ratio as each solvent, in the solvent total amount, gamma-butyrolacton is 40～80 quality %, be preferably 40～70 quality %, butyl cellosolve is 10～30 quality %, be preferably 10～20 quality %, dipropylene glycol monomethyl ether or diethyl carbitol are 10～30 quality %, are preferably 10～20 quality %.Adopted the aligning agent for liquid crystal of the present invention of this composition more not to be prone to inequality and the pore that causes because of Thickness Variation when printing.
As the additive that is used to improve the characteristic of filming, can exemplify silane coupling agents such as 3-aminopropyl methyldiethoxysilane, 3-phenyl amino propyl trimethoxy silicane, 3-aminopropyltriethoxywerene werene, (aminoethylamino methyl) phenethyl trimethoxy silane.By adding these silane coupling agents, the adaptation of filming for substrate is further improved.
The content of the polyimide that aligning agent for liquid crystal of the present invention is contained (concentration) can be according to the setting of the thickness of liquid crystal orientating membrane to be formed and appropriate change.Usually the total content of polyimide (A) and polyimide (B) better is 1～10 weight %, and the spy is well 2～6 quality %, in this case, easily forms homogeneous and flawless filming, and the storage stability of aligning agent for liquid crystal further improves.In addition, aligning agent for liquid crystal of the present invention preferably filtered before coating substrate.
＜liquid crystal orientating membrane 〉
Liquid crystal orientating membrane of the present invention can be by coating substrate with described aligning agent for liquid crystal, and drying is burnt till, and is solidified to form to filming, and this coated surface carried out directional process such as friction treatment again and make.
As used substrate, so long as the high substrate of the transparency gets final product, be not particularly limited, can use glass substrate or plastic bases such as acrylic acid substrate, polycarbonate substrate.From the angle of work simplification, better be to use the substrate that has formed ITO electrode of being used for liquid crystal drive etc.In addition, for reflection type liquid crystal display element, also can only use opaque substrates such as silicon chip on one-sided substrate, electrode also can use catoptrical materials such as aluminium.
As the coating process of aligning agent for liquid crystal, can exemplify spin-coating method, print process, ink-jet method etc.Consider the productivity aspect, the flexible printing method is widely used at industrial circle, also is applicable to aligning agent for liquid crystal of the present invention.
Drying steps behind the coating of liquid crystalline aligning agent is optional.But,, better be to comprise drying steps under the inconsistent situation of time till burn till after the every base plate coating or under the situation of not burning till immediately after the coating.Degree of drying reach with solvent evaporation to the shape of filming not because of the degree that carrying of substrate etc. is out of shape gets final product, be not particularly limited for this drying means.For example can exemplify 50～150 ℃ of temperature, better be on 80～120 ℃ the heating plate dry 0.5～30 minute, better be 1～5 minute method.
The burning till of substrate that has been coated with aligning agent for liquid crystal can be carried out under 100～350 ℃ arbitrary temp, better is 150 ℃～300 ℃, is more preferably 180 ℃～250 ℃.Exist in the polyimide under the situation of acid amides acidic group, cause the imidizate rate of the polyimide film of gained to change because of this firing temperature, among the present invention, the imidizate rate must not be 100%.
Filming as if blocked up after burning till is being disadvantageous aspect the power consumption of liquid crystal display cells then, if thin excessively, then the reliability of liquid crystal display cells descends sometimes, better is 10～200nm therefore, is more preferably 50～100nm.
The friction treatment that is formed at the coated surface on the substrate that obtains as mentioned above can be used existing rubbing device.Material as friction cloth at this moment can exemplify cotton, rayon, nylon etc.
Liquid crystal orientating membrane of the present invention can obtain by above method.
＜liquid crystal display cells 〉
Liquid crystal display cells of the present invention is after obtaining substrate with liquid crystal orientating membrane by above-mentioned method by aligning agent for liquid crystal of the present invention, makes liquid crystal cell and the liquid crystal display cells that obtains with known method.
The method for making of liquid crystal cell generally for example is that to clip better be 1～30 μ m, the sept that is more preferably 2～10 μ m is 0～270 ° condition setting at any angle with frictional direction for 1 pair of substrate will having formed liquid crystal orientating membrane, fix with sealant on every side, inject the method that seals behind the liquid crystal.The method of enclosing for liquid crystal is not particularly limited, but the dripping method that illustration seals the laggard row of vacuum method, dropping liquid crystal that injects liquid crystal after reducing pressure in the liquid crystal cell that makes etc.
Embodiment
Below, exemplify embodiment, the present invention will be described in more detail, but the present invention is not limited to these embodiment.
Being described as follows of the dummy suffix notation that uses in embodiment or the comparative example is described.
＜tetracarboxylic dianhydride 〉
CBDA:1,2,3,4-cyclo-butane tetracarboxylic dianhydride
PMDA: pyromellitic acid dianhydride
TDA:3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride
＜diamines 〉
2,4-DAA:2,4-diamino-N, N-diallyl aniline
PCH7AB:4-{4-(4-heptyl cyclohexyl) phenoxy group }-1, the 3-diaminobenzene
C12DAB:4-dodecyloxy-1, the 3-diaminobenzene
C14DAB:4-tetradecyloxyaniline-1, the 3-diaminobenzene
C16DAB:4-hexadecane Oxy-1, the 3-diaminobenzene
The 4-ABA:4-amino-benzylamine
The 3-ABA:3-amino-benzylamine
＜organic solvent 〉
The NMP:N-N-methyl-2-2-pyrrolidone N-
γ BL: gamma-butyrolacton
BS: butyl cellosolve
DPM: dipropylene glycol monomethyl ether
＜structural formula 〉
Figure G2007800434831D00181
The mensuration of＜molecular weight 〉
For the molecular weight of polyimide, this polyimide is measured by GPC (normal temperature gel permeation chromatography) device, calculate number-average molecular weight and weight-average molecular weight as polyglycol, polyethylene oxide scaled value.
GPC device: Xiao De (Shodex) corporate system (GPC-101)
Post: Xiao De corporate system (series connection of KD803, KD805)
Column temperature: 50 ℃
Eluent: N, and dinethylformamide (as adjuvant, lithium bromide monohydrate (LiBrH 2O) be 30mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) is 30mmol/L, and tetrahydrofuran (THF) is 10ml/L)
Flow velocity: 1.0ml/ minute
Calibration curve is made and is used standard model: eastern Cao (East ソ-) Co., Ltd.'s system TSK standard polyethylene oxide (molecular weight about 900000,150000,100000,30000) and polymkeric substance laboratory (PolymerLaboratories) corporate system polyglycol (molecular weight about 12000,4000,1000)
The mensuration of＜imidizate rate 〉
The following mensuration of imidizate rate of polyimide.The 20mg polyimide powder is packed in the NMR test tube, add 0.53ml deuterate dimethyl sulfoxide (DMSO-d 6, the 0.05%TMS melange), it is dissolved fully.Measure the proton N MR of the 500MHz of this solution with NEC Dai Temu (デ-タ system) Co., Ltd. system NMR analyzer (JNM-ECA500).The imidizate rate is that the benchmark proton is determined with the proton from unconverted structure before and after the imidizate, obtains according to following formula with the peak integrated value of this proton and near occur 9.5～10.0ppm the proton peak integrated value from the NH base of amic acid.
Imidizate rate (%)=(1-α x/y) * 100
In the following formula, x is the proton peak integrated value from the NH base of amic acid, and y is the peak integrated value of benchmark proton, α be polyamic acid (imidizate rate 0%) with respect to 1 number ratio from the benchmark proton of the proton of the NH base of amic acid.
(synthesis example 1)
As tetracarboxylic dianhydride's composition, use 13.53g (0.069 mole) CBDA, 6.54g (0.030 mole) PMDA, as two amine components, use 8.13g (0.040 mole) 2,4-DAA, 3.67g (0.030 mole) 4-ABA, 8.77g (0.030 mole) C12DAB, in the NMP of 161.8g,, obtain polyamic acid solution in room temperature reaction 24 hours.
The NMP that adds 62.65g in this polyamic acid solution of 34.81g dilutes, and adds 5.15g acetic anhydride and 2.19g pyridine, carries out imidizate in 3 hours in 50 ℃ of reactions of temperature.
After being cooled to this reaction solution about room temperature, it is dropped in the 366.8ml methyl alcohol, reclaim the solid content of precipitation.Then, with this solid content of methanol wash for several times, drying under reduced pressure under 100 ℃ temperature again obtains the white powder of polyimide (SPI-1).The number-average molecular weight of this polyimide is 12016, and weight-average molecular weight is 35126.In addition, the imidizate rate is 90%.
The γ BL that adds 17.91g more than 1.99g in the polyimide that obtains stirred 24 hours for 50 ℃ in temperature.Polyimide dissolves fully when stirring end.After being cooled to this solution about room temperature, the BS of γ BL, the 4.82g of adding 7.53g and the DPM of 4.82g fully stir, and obtain the solution of homogeneous.
(synthesis example 2)
As tetracarboxylic dianhydride's composition, use 13.43g (0.0685 mole) CBDA, 6.54g (0.030 mole) PMDA, as two amine components, use 8.13g (0.040 mole) 2,4-DAA, 5.50g (0.045 mole) 4-ABA, 4.39g (0.015 mole) C12DAB, in the NMP of 152.0g,, obtain polyamic acid solution in room temperature reaction 24 hours.
The NMP that adds 72.88g in this polyamic acid solution of 32.39g dilutes, and adds 5.09g acetic anhydride and 2.17g pyridine, carries out imidizate in 3 hours in 50 ℃ of reactions of temperature.
After being cooled to this reaction solution about room temperature, it is dropped in the 393.9ml methyl alcohol, reclaim the solid content of precipitation.Then, with this solid content of methanol wash for several times, drying under reduced pressure under 100 ℃ temperature again obtains the white powder of polyimide (SPI-2).The number-average molecular weight of this polyimide is 12616, and weight-average molecular weight is 39703.In addition, the imidizate rate is 90%.
The γ BL that adds 27.09g more than 3.01g in the polyimide that obtains stirred 24 hours for 50 ℃ in temperature.Polyimide dissolves fully when stirring end.After being cooled to this solution about room temperature, the BS of γ BL, the 8.21g of adding 10.09g and the DPM of 8.21g fully stir, and obtain the solution of homogeneous.
(synthesis example 3)
As tetracarboxylic dianhydride's composition, use 13.33g (0.068 mole) CBDA, 6.54g (0.030 mole) PMDA, as two amine components, use 8.13g (0.040 mole) 2,4-DAA, 7.33g (0.060 mole) 4-ABA, in the NMP of 141.4g,, obtain polyamic acid solution in room temperature reaction 24 hours.
The NMP that adds 67.84g in this polyamic acid solution of 30.15g dilutes, and adds 5.11g acetic anhydride and 2.18g pyridine, carries out imidizate in 3 hours in 50 ℃ of reactions of temperature.
After being cooled to this reaction solution about room temperature, it is dropped in the 368.5ml methyl alcohol, reclaim the solid content of precipitation.Then, with this solid content of methanol wash for several times, drying under reduced pressure under 100 ℃ temperature again obtains the white powder of polyimide (SPI-3).The number-average molecular weight of this polyimide is 12899, and weight-average molecular weight is 39984.In addition, the imidizate rate is 85%.
The γ BL that adds 27.54g more than 3.06g in the polyimide that obtains stirred 24 hours for 50 ℃ in temperature.Polyimide dissolves fully when stirring end.After being cooled to this solution about room temperature, the BS of γ BL, the 8.24g of adding 10.14g and the DPM of 8.24g fully stir, and obtain the solution of homogeneous.
(synthesis example 4)
As tetracarboxylic dianhydride's composition, use 13.53g (0.069 mole) CBDA, 6.54g (0.030 mole) PMDA, as two amine components, use 6.10g (0.030 mole) 2,4-DAA, 4.89g (0.040 mole) 3-ABA, 9.62g (0.030 mole) C14DAB, in the NMP of 162.7g,, obtain polyamic acid solution in room temperature reaction 24 hours.
The NMP that adds 63.91g in this polyamic acid solution of 35.79g dilutes, and adds 5.16g acetic anhydride and 2.20g pyridine, carries out imidizate in 3 hours in 50 ℃ of reactions of temperature.
After being cooled to this reaction solution about room temperature, it is dropped in the 374.7ml methyl alcohol, reclaim the solid content of precipitation.Then, with this solid content of methanol wash for several times, drying under reduced pressure under 100 ℃ temperature again obtains the white powder of polyimide (SPI-4).The number-average molecular weight of this polyimide is 13472, and weight-average molecular weight is 35859.In addition, the imidizate rate is 89%.
The γ BL that adds 15.91g more than 2.17g in the polyimide that obtains stirred 24 hours for 50 ℃ in temperature.Polyimide dissolves fully when stirring end.After being cooled to this solution about room temperature, the BS of γ BL, the 7.38g of adding 6.37g and the DPM of 7.38g fully stir, and obtain the solution of homogeneous.
(synthesis example 5)
As tetracarboxylic dianhydride's composition, use 13.53g (0.069 mole) CBDA, 6.54g (0.030 mole) PMDA, as two amine components, use 6.10g (0.030 mole) 2,4-DAA, 6.11g (0.050 mole) 3-ABA, 6.97g (0.020 mole) C16DAB, in the NMP of 157.0g,, obtain polyamic acid solution in room temperature reaction 24 hours.
The NMP that adds 32.77g in this polyamic acid solution of 23.20g dilutes, and adds 3.49g acetic anhydride and 1.49g pyridine, carries out imidizate in 3 hours in 50 ℃ of reactions of temperature.
After being cooled to this reaction solution about room temperature, it is dropped in the 213.3ml methyl alcohol, reclaim the solid content of precipitation.Then, with this solid content of methanol wash for several times, drying under reduced pressure under 100 ℃ temperature again obtains the white powder of polyimide (SPI-5).The number-average molecular weight of this polyimide is 12498, and weight-average molecular weight is 34121.In addition, the imidizate rate is 89%.
The γ BL that adds 11.66g more than 1.59g in the polyimide that obtains stirred 24 hours for 50 ℃ in temperature.Polyimide dissolves fully when stirring end.After being cooled to this solution about room temperature, the BS of γ BL, the 5.78g of adding 4.99g and the DPM of 5.78g fully stir, and obtain the solution of homogeneous.
(synthesis example 6)
As tetracarboxylic dianhydride's composition, use 13.33g (0.068 mole) CBDA, 6.54g (0.030 mole) PMDA, as two amine components, use 8.13g (0.040 mole) 2,4-DAA, 6.11g (0.040 mole) 4-ABA, 3.81g (0.010 mole) PCH7AB, in the NMP of 151.7g,, obtain polyamic acid solution in room temperature reaction 24 hours.
The NMP that adds 59.61g in this polyamic acid solution of 33.38g dilutes, and adds 5.26g acetic anhydride and 2.24g pyridine, carries out imidizate in 3 hours in 50 ℃ of reactions of temperature.
After being cooled to this reaction solution about room temperature, it is dropped in the 351.7ml methyl alcohol, reclaim the solid content of precipitation.Then, with this solid content of methanol wash for several times, drying under reduced pressure under 100 ℃ temperature again obtains the white powder of polyimide (SPI-6).The number-average molecular weight of this polyimide is 10877, and weight-average molecular weight is 34898.In addition, the imidizate rate is 90%.
The γ BL that adds 17.19g more than 1.91g in the polyimide that obtains stirred 24 hours for 50 ℃ in temperature.Polyimide dissolves fully when stirring end.After being cooled to this solution about room temperature, the BS of γ BL, the 4.35g of adding 2.37g and the DPM of 4.35g fully stir, and obtain the solution of homogeneous.
(synthesis example 7)
As tetracarboxylic dianhydride's composition, use 13.53g (0.069 mole) CBDA, 6.54g (0.030 mole) PMDA, as two amine components, use 6.10g (0.030 mole) 2,4-DAA, 3.67g (0.030 mole) 3-ABA, 12.82g (0.040 mole) C14DAB, in the NMP of 170.6g,, obtain polyamic acid solution in room temperature reaction 24 hours.
The NMP that adds 102.3g in this polyamic acid solution of 58.20g dilutes, and adds 8.06g acetic anhydride and 3.44g pyridine, carries out imidizate in 3 hours in 50 ℃ of reactions of temperature.
After being cooled to this reaction solution about room temperature, it is dropped in the 601.9ml methyl alcohol, reclaim the solid content of precipitation.Then, with this solid content of methanol wash for several times, drying under reduced pressure under 100 ℃ temperature again obtains the white powder of polyimide (SPI-7).The number-average molecular weight of this polyimide is 11013, and weight-average molecular weight is 36721.In addition, the imidizate rate is 89%.
The γ BL that adds 23.98g more than 3.27g in the polyimide that obtains stirred 24 hours for 50 ℃ in temperature.Polyimide dissolves fully when stirring end.After being cooled to this solution about room temperature, the BS of γ BL, the 11.95g of adding 7.75g and the DPM of 11.95g fully stir, and obtain the solution of homogeneous.
(synthesis example 8)
As tetracarboxylic dianhydride's composition, use 19.36g (0.099 mole) CBDA, as two amine components, use 6.10g (0.030 mole) 2,4-DAA, 4.89g (0.040 mole) 3-ABA, 9.62g (0.030 mole) C14DAB, in the NMP of 159.8g,, obtain polyamic acid solution in room temperature reaction 24 hours.
The NMP that adds 131.68g in this polyamic acid solution of 74.94g dilutes, and adds 11.09g acetic anhydride and 4.73g pyridine, carries out imidizate in 3 hours in 50 ℃ of reactions of temperature.
After being cooled to this reaction solution about room temperature, it is dropped in the 778.5ml methyl alcohol, reclaim the solid content of precipitation.Then, with this solid content of methanol wash for several times, drying under reduced pressure under 100 ℃ temperature again obtains the white powder of polyimide (SPI-8).The number-average molecular weight of this polyimide is 16241, and weight-average molecular weight is 40259.In addition, the imidizate rate is 89%.
The γ BL that adds 43.20g more than 4.80g in the polyimide that obtains stirred 24 hours for 50 ℃ in temperature.Polyimide dissolves fully when stirring end.After being cooled to this solution about room temperature, the BS of γ BL, the 18.05g of adding 3.60g and the DPM of 18.05g fully stir, and obtain the solution of homogeneous.
(synthesis example 9)
As tetracarboxylic dianhydride's composition, use 9.61g (0.049 mole) CBDA, 15.02g (0.050 mole) TDA, as two amine components, use 6.10g (0.030 mole) 2,4-DAA, 4.89g (0.040 mole) 3-ABA, 9.62g (0.030 mole) C14DAB, in the NMP of 180.9g,, obtain polyamic acid solution in room temperature reaction 24 hours.
The NMP that adds 70.66g in this polyamic acid solution of 40.54g dilutes, and adds 5.27g acetic anhydride and 2.24g pyridine, carries out imidizate in 3 hours in 50 ℃ of reactions of temperature.
After being cooled to this reaction solution about room temperature, it is dropped in the 415.5ml methyl alcohol, reclaim the solid content of precipitation.Then, with this solid content of methanol wash for several times, drying under reduced pressure under 100 ℃ temperature again obtains the white powder of polyimide (SPI-9).The number-average molecular weight of this polyimide is 14756, and weight-average molecular weight is 35977.In addition, the imidizate rate is 90%.
The γ BL that adds 36.63g more than 4.07g in the polyimide that obtains stirred 24 hours for 50 ℃ in temperature.Polyimide dissolves fully when stirring end.After being cooled to this solution about room temperature, the BS of γ BL, the 14.16g of adding 2.44g and the DPM of 14.16g fully stir, and obtain the solution of homogeneous.
(synthesis example 10)
As tetracarboxylic dianhydride's composition, use 19.41g (0.099 mole) CBDA, as two amine components, use 20.33g (0.100 mole) 2,4-DAA in room temperature reaction 24 hours, obtains polyamic acid solution in the NMP of 159.00g.
The NMP that adds 38.79g in this polyamic acid solution of 25.13g dilutes, and adds 3.94g acetic anhydride and 1.68g pyridine, carries out imidizate in 3 hours in 50 ℃ of reactions of temperature.
After being cooled to this reaction solution about room temperature, it is dropped in the 243.4ml methyl alcohol, reclaim the solid content of precipitation.Then, with this solid content of methanol wash for several times, drying under reduced pressure under 100 ℃ temperature again obtains the white powder of polyimide (SPI-10).The number-average molecular weight of this polyimide is 10122, and weight-average molecular weight is 21004.In addition, the imidizate rate is 97%.
The γ BL that adds 22.50g more than 2.50g in the polyimide that obtains stirred 24 hours for 50 ℃ in temperature.Polyimide dissolves fully when stirring end.
(synthesis example 11)
As tetracarboxylic dianhydride's composition, use 13.53g (0.069 mole) CBDA, 6.54g (0.030 mole) PMDA, as two amine components, use 8.13g (0.040 mole) 2,4-DAA, 3.67g (0.030 mole) 4-ABA, 8.77g (0.030 mole) C12DAB, in the NMP of 162.6g,, obtain polyamic acid solution in room temperature reaction 24 hours.
The NMP that adds 68.99g in this polyamic acid solution of 38.33g dilutes, and adds 5.67g acetic anhydride and 2.42g pyridine, carries out imidizate in 3 hours in 45 ℃ of reactions of temperature.
After being cooled to this reaction solution about room temperature, it is dropped in the 403.9ml methyl alcohol, reclaim the solid content of precipitation.Then, with this solid content of methanol wash for several times, drying under reduced pressure under 100 ℃ temperature again obtains the white powder of polyimide (SPI-11).The number-average molecular weight of this polyimide is 13513, and weight-average molecular weight is 47948.In addition, the imidizate rate is 76%.
The γ BL that adds 46.89g more than 5.21g in the polyimide that obtains stirred 24 hours for 50 ℃ in temperature.Polyimide dissolves fully when stirring end.After being cooled to this solution about room temperature, the BS of γ BL, the 14.49g of adding 14.49g and the DPM of 14.49g fully stir, and obtain the solution of homogeneous.
(synthesis example 12)
As tetracarboxylic dianhydride's composition, use 13.53g (0.069 mole) CBDA, 6.54g (0.030 mole) PMDA, as two amine components, use 6.10g (0.030 mole) 2,4-DAA, 4.89g (0.040 mole) 3-ABA, 9.62g (0.030 mole) C14DAB, in the NMP of 162.7g,, obtain polyamic acid solution in room temperature reaction 24 hours.
The NMP that adds 69.88g in this polyamic acid solution of 39.77g dilutes, and adds 5.79g acetic anhydride and 2.47g pyridine, carries out imidizate in 1 hour in 50 ℃ of reactions of temperature.
After being cooled to this reaction solution about room temperature, it is dropped in the 412.7ml methyl alcohol, reclaim the solid content of precipitation.Then, with this solid content of methanol wash for several times, drying under reduced pressure under 100 ℃ temperature again obtains the white powder of polyimide (SPI-12).The number-average molecular weight of this polyimide is 10734, and weight-average molecular weight is 28190.In addition, the imidizate rate is 79%.
The γ BL that adds 43.2g more than 4.8g in the polyimide that obtains stirred 24 hours for 50 ℃ in temperature.Polyimide dissolves fully when stirring end.After being cooled to this solution about room temperature, the BS of γ BL, the 18.05g of adding 3.6g and the DPM of 18.05g fully stir, and obtain the solution of homogeneous.
(reference example 1)
As tetracarboxylic dianhydride's composition, use 22.59g (0.115 mole) CBDA, as two amine components, use 14.66g (0.120 mole) 4-ABA, in the NMP of 211.10g,, obtain polyamic acid solution in room temperature reaction 24 hours.
The NMP that adds 22.74g in this polyamic acid solution of 21.22g dilutes, and adds 10.12g acetic anhydride and 4.71g pyridine, reacts for 50 ℃ in temperature, and gelation in the time of 30 minutes can't obtain polyimide.
Then, temperature of reaction is reduced to 35 ℃, carry out 3 hours imidization reaction with described same solution.
After being cooled to this reaction solution about room temperature, it is dropped in the 205.7ml methyl alcohol, reclaim the solid content of precipitation.Then, with this solid content of methanol wash for several times, drying under reduced pressure under 100 ℃ temperature again obtains the white powder of polyimide.The number-average molecular weight of this polyimide is 12994, and weight-average molecular weight is 30081.In addition, the imidizate rate is 78%.
The γ BL that adds 14.76g more than 1.64g in the polyimide that obtains stirred 24 hours for 50 ℃ in temperature, but residual when finishing undissolved polyimide was arranged stirring, if confirm in two amine components, not use 2, and 4-DAA, then polyimide is poorly soluble.
Synthesis example 1～12 and reference example 1 the results are shown in table 1.
[table 1]
Figure G2007800434831D00261
(embodiment 1)
Adopt the polyimide solution of synthesis example 1 and synthesis example 4 acquisitions, they are mixed making the mass ratio of SPI-1 and SPI-4 reach 7: 3, obtain aligning agent for liquid crystal of the present invention.
The evaluation of＜printing 〉
With oriented film printing machine (Nissha Printing Co., Ltd's system " オ Application グ ス ト ロ-マ-") with described aligning agent for liquid crystal flexible printing on the Cr plate of cleaning.Substrate after the printing was placed 5 minutes the interim drying of filming on 70 ℃ hot plate.
With 50 times of surfaces of interim dried film more than the observation, do not see the inequality that has Thickness Variation to cause with optical microscope (NIKON's system " ECLIPSE ME600 "), also not seeing has pore (depression of film).
The evaluation of＜rub resistance 〉
Above-mentioned aligning agent for liquid crystal is spun on the glass substrate of band transparency electrode, after on 70 ℃ the hot plate dry 5 minutes, on 230 ℃ hot plate, carries out 15 minutes burn till, form filming of thickness 100nm.For this coated surface, the rubbing device by roller footpath 120mm rubs with the condition of rayon cloth with roller rotating speed 500rpm, roller gait of march 50mm/sec, the amount of being pressed into 0.3mm, obtains the substrate with liquid crystal orientating membrane.
Observe with 2000 times of film surfaces to this liquid crystal orientating membrane by the confocal laser microscope, the result does not find to damage or the peeling off of film.
In addition, in the observation on film surface, used laser technology (Lasertec) corporate system real time scan type laser microscope 1LM21D.
(embodiment 2)
Adopt the polyimide solution of synthesis example 1 and synthesis example 5 acquisitions, they are mixed making the mass ratio of SPI-1 and SPI-5 reach 7: 3, obtain aligning agent for liquid crystal of the present invention.
Use this aligning agent for liquid crystal, carried out the evaluation of printing and rub resistance similarly to Example 1.Consequently, do not see the inequality that has Thickness Variation to cause, do not find pore yet, do not see yet the damage and film peel off.
(embodiment 3)
Adopt the polyimide solution of synthesis example 1 and synthesis example 6 acquisitions, they are mixed making the mass ratio of SPI-1 and SPI-6 reach 7: 3, obtain aligning agent for liquid crystal of the present invention.
Use this aligning agent for liquid crystal, carried out the evaluation of printing and rub resistance similarly to Example 1.Consequently, do not see the inequality that has Thickness Variation to cause, do not find pore yet, do not see yet the damage and film peel off.
(embodiment 4)
Adopt the polyimide solution of synthesis example 2 and synthesis example 4 acquisitions, they are mixed making the mass ratio of SPI-2 and SPI-4 reach 7: 3, obtain aligning agent for liquid crystal of the present invention.
Use this aligning agent for liquid crystal, carried out the evaluation of printing and rub resistance similarly to Example 1.Consequently, do not see the inequality that has Thickness Variation to cause, do not find pore yet, do not see yet the damage and film peel off.
(embodiment 5)
Adopt the polyimide solution of synthesis example 3 and synthesis example 4 acquisitions, they are mixed making the mass ratio of SPI-3 and SPI-4 reach 7: 3, obtain aligning agent for liquid crystal of the present invention.
Use this aligning agent for liquid crystal, carried out the evaluation of printing and rub resistance similarly to Example 1.Consequently, do not see the inequality that has Thickness Variation to cause, do not find pore yet, do not see yet the damage and film peel off.
(embodiment 6)
Adopt the polyimide solution of synthesis example 1 and synthesis example 7 acquisitions, they are mixed making the mass ratio of SPI-1 and SPI-7 reach 7: 3, obtain aligning agent for liquid crystal of the present invention.
Use this aligning agent for liquid crystal, carried out the evaluation of printing and rub resistance similarly to Example 1.Consequently, do not see the inequality that has Thickness Variation to cause, do not find pore yet, do not see yet the damage and film peel off.
(embodiment 7)
Adopt the polyimide solution of synthesis example 1 and synthesis example 8 acquisitions, they are mixed making the mass ratio of SPI-1 and SPI-8 reach 7: 3, obtain aligning agent for liquid crystal of the present invention.
Use this aligning agent for liquid crystal, carried out the evaluation of printing and rub resistance similarly to Example 1.Consequently, do not see the inequality that has Thickness Variation to cause, do not find pore yet, do not see yet the damage and film peel off.
(embodiment 8)
Adopt the polyimide solution of synthesis example 1 and synthesis example 9 acquisitions, they are mixed making the mass ratio of SPI-1 and SPI-9 reach 7: 3, obtain aligning agent for liquid crystal of the present invention.
Use this aligning agent for liquid crystal, carried out the evaluation of printing and rub resistance similarly to Example 1.Consequently, do not see the inequality that has Thickness Variation to cause, do not find pore yet, do not see yet the damage and film peel off.
(embodiment 9)
Adopt the polyimide solution of synthesis example 1 and synthesis example 4 acquisitions, they are mixed making the mass ratio of SPI-1 and SPI-4 reach 6: 4, obtain aligning agent for liquid crystal of the present invention.
Use this aligning agent for liquid crystal, carried out the evaluation of printing and rub resistance similarly to Example 1.Consequently, do not see the inequality that has Thickness Variation to cause, do not find pore yet, do not see yet the damage and film peel off.
(embodiment 10)
Adopt the polyimide solution of synthesis example 1 and synthesis example 4 acquisitions, they are mixed making the mass ratio of SPI-1 and SPI-4 reach 9: 1, obtain aligning agent for liquid crystal of the present invention.
Use this aligning agent for liquid crystal, carried out the evaluation of printing and rub resistance similarly to Example 1.Consequently, do not see the inequality that has Thickness Variation to cause, do not find pore yet, do not see yet the damage and film peel off.
(embodiment 11)
Adopt the polyimide solution of synthesis example 10 and synthesis example 4 acquisitions, they are mixed making the mass ratio of SPI-10 and SPI-4 reach 7: 3, obtain aligning agent for liquid crystal of the present invention.
Use this aligning agent for liquid crystal, carried out the evaluation of printing and rub resistance similarly to Example 1.Consequently, do not see the inequality that has Thickness Variation to cause, do not find pore yet, do not see yet the damage and film peel off.
(embodiment 12)
Adopt the polyimide solution of synthesis example 1 and synthesis example 12 acquisitions, they are mixed making the mass ratio of SPI-1 and SPI-12 reach 7: 3, obtain aligning agent for liquid crystal of the present invention.
Use this aligning agent for liquid crystal, carried out the evaluation of printing and rub resistance similarly to Example 1.Consequently, do not see the inequality that has Thickness Variation to cause, do not find pore yet, do not see yet the damage and film peel off.
(embodiment 13)
Adopt the polyimide solution of synthesis example 11 and synthesis example 4 acquisitions, they are mixed making the mass ratio of SPI-11 and SPI-4 reach 7: 3, obtain aligning agent for liquid crystal of the present invention.
Use this aligning agent for liquid crystal, carried out the evaluation of printing and rub resistance similarly to Example 1.Consequently, do not see the inequality that has Thickness Variation to cause, do not find pore yet, do not see yet the damage and film peel off.
(comparative example 1)
The polyimide solution that uses synthesis example 4 acquisitions has carried out the evaluation of printing and rub resistance similarly to Example 1 as aligning agent for liquid crystal.Consequently, what Thickness Variation caused is obviously uneven, visible a large amount of pores.Do not see the damage and film peel off.
(comparative example 2)
Use the polyimide solution of synthesis example 1 and synthesis example 4 acquisitions, they are mixed making the mass ratio of SPI-1 and SPI-4 reach 4: 6, obtain aligning agent for liquid crystal.
Use this aligning agent for liquid crystal, carried out the evaluation of printing and rub resistance similarly to Example 1.Consequently, what Thickness Variation caused is obviously uneven, visible a large amount of pores.Do not see the damage and film peel off.
(comparative example 3)
The polyimide solution that uses synthesis example 1 acquisition has carried out the evaluation of printing and rub resistance similarly to Example 1 as aligning agent for liquid crystal.Consequently, do not see the inequality that has Thickness Variation to cause, do not find pore yet, do not see yet the damage and film peel off.
The evaluation of＜tilt angle 〉
For the aligning agent for liquid crystal that uses in embodiment 1～5 and the comparative example 1～3, the evaluation of carrying out the tilt angle of liquid crystal cell as described below.
Aligning agent for liquid crystal is spun on the glass substrate of band transparency electrode, after on the hot plate of 70 ℃ of temperature dry 5 minutes, on 230 ℃ hot plate, carries out 15 minutes burn till, form filming of thickness 100nm.For this coated surface, the rubbing device by roller footpath 120mm rubs with the condition of rayon cloth with roller rotating speed 1000rpm, roller gait of march 50mm/sec, the amount of being pressed into 0.3mm, obtains the substrate with liquid crystal orientating membrane.
Prepare 2 these substrates, scatter the sept of 6 μ m on 1 the liquid crystal aligning face therein after, printing and sealing agent from it behind bonding 1 substrate in addition of the condition relative with the liquid crystal aligning face, that frictional direction is opposite, makes sealant cures and makes sylphon.In this sylphon, inject liquid crystal MLC-2003 (Japanese Mai Luke (Merck) Co., Ltd. system) by the decompression injection method,, obtain antiparallel (anti-parallel) nematic crystal box the inlet sealing.
Measure tilt angle under 23 ℃ of temperature with this liquid crystal cell.Mensuration has been used Qiao Nike difficult to understand (autronic) corporate system TBA107.Evaluation result is shown in table 2.
The evaluation of＜voltage retention 〉
2 of the substrates of the band liquid crystal orientating membrane of use and described same preparation, printing and sealing agent behind the sept of distribution 6 μ m on 1 liquid crystal aligning face therein, with the liquid crystal aligning face relatively, behind bonding 1 substrate in addition of the frictional direction condition of keeping straight on, make sealant cures and make sylphon.In this sylphon, injects liquid crystal MLC-2003 (C080) (Japanese Mai Luke Co., Ltd. system) by the decompression injection method, inlet is sealed, obtain the twisted nematic liquid crystals box.
This liquid crystal cell is applied the voltage 60 μ s of 4V under 23 ℃ temperature, how much voltage behind the mensuration 16.67ms can keep calculate as voltage retention voltage.In addition, under 90 ℃ temperature, also carry out same mensuration.In addition, the mensuration of voltage retention is used the system VHR-1 of Dongyang technology company voltage retention determinator.
The evaluation result of each characteristic of embodiment 1～13 and comparative example 1～3 is shown in table 2.
In the evaluation of rub resistance, with observe do not see that damage and film peel off behind the liquid crystal orientating membrane surface be designated as zero.
[table 2]
Figure G2007800434831D00311
Can confirm that from above evaluation result the printing of aligning agent for liquid crystal of the present invention is good, the tilt angle of the liquid crystal of the liquid crystal orientating membrane of gained is big, and rub resistance is good.On the other hand, affirmation is big by the tilt angle of the liquid crystal of the liquid crystal orientating membrane of the aligning agent for liquid crystal acquisition of comparative example, printing poor (comparative example 1), though perhaps printing is out of question, but the tilt angle of the liquid crystal of the liquid crystal orientating membrane of gained little (comparative example 3).
The possibility of utilizing on the industry
Aligning agent for liquid crystal of the present invention contains the high polyimide of imidizate rate, is difficult for the liquid crystal orientating membrane that causes damage and difficult generation film to peel off on the film surface in the time of can forming friction treatment.In addition, the liquid crystal display cells that makes with aligning agent for liquid crystal of the present invention is applicable to TN liquid crystal display cells, stn liquid crystal display element, TFT liquid crystal display cells, OCB liquid crystal display cells etc. as the high liquid crystal display device of reliability.
Here quote the announcement of all the elements of Japanese patent application 2006-317529 number of filing an application on November 24th, 2006 and Japanese patent application 2006-322397 number instructions, claims and the summary of filing an application on November 29th, 2006 as instructions of the present invention.

Claims (9)

1. aligning agent for liquid crystal is characterized in that, contains following polyimide A and following polyimide B with 50: 50～90: 10 mass ratioes,
Polyimide A:
Make two amine components of the diamines formation of formula (1) expression, or the diamines of formula (1) expression obtains polyamic acid with two amine components and the reaction of tetracarboxylic dianhydride's composition that at least a kind of diamines that is selected from formula (2), formula (3), formula (4) and formula (5) constitutes, with this polyamic acid imidizate and polyimide
With respect to whole 100 moles of % of diamines amount among the polyimide A, the diamines that contains 20～100 moles of % formulas (1) expression, and during 100 moles of % of the diamine contents deficiency of formula (1), remaining diamines is for being selected from least a kind of diamines of formula (2), formula (3), formula (4) and formula (5);
Polyimide B:
Make two amine components of the diamines of formula (1) expression and the diamines formation that formula (6) is represented, or the diamines of the diamines of formula (1) expression and formula (6) expression obtains polyamic acid with two amine components and the reaction of tetracarboxylic dianhydride's composition that at least a kind of diamines that is selected from formula (2), formula (3), formula (4) and formula (5) constitutes, with this polyamic acid imidizate and polyimide
With respect to whole 100 moles of % of diamines amount among the polyimide B, contain the diamines of 20～90 moles of % formulas (1) expression, the diamines of 5～40 moles of % formulas (6) expression, and when the total of the diamines of the diamines of formula (1) and formula (6) contained 100 moles of % of quantity not sufficient, remaining diamines was for being selected from least a kind of diamines of formula (2), formula (3), formula (4) and formula (5);
Figure FSB00000275234800011
In the formula (2), X 1The expression singly-bound or be selected from ether, ester and acid amides in conjunction with the base, X 2The straight chain shape alkyl of expression carbon number 1～12, in the formula (3), n is 1 or 2, in the formula (5), X 3For singly-bound or be selected from-O-,-CH 2-,-NH-and-CONH-in conjunction with the base, R is hydrogen atom or methyl,
Figure FSB00000275234800021
In the formula (6), X 4The expression singly-bound or be selected from ether, ester, methylene ether and acid amides in conjunction with the base, X 51 valency organic group of the straight chain shape alkyl of expression carbon number 14～20 or following formula (7) expression,
-X 6-X 7 (7)
In the formula (7), X 6Be phenyl or cyclohexyl, X 7Cyclohexyl for straight chain shape alkyl with carbon number 1～12.
2. aligning agent for liquid crystal as claimed in claim 1 is characterized in that, the imidizate rate of polyimide A and polyimide B all is more than 40%.
3. aligning agent for liquid crystal as claimed in claim 1 or 2 is characterized in that, also contains the organic solvent composition.
4. aligning agent for liquid crystal as claimed in claim 3 is characterized in that, as the organic solvent composition, contains gamma-butyrolacton and butyl cellosolve and dipropylene glycol monomethyl ether or diethyl carbitol.
5. as claim 1,2 or 4 described aligning agent for liquid crystal, it is characterized in that aligning agent for liquid crystal is used for by the liquid crystal orientating membrane of friction treatment.
6. aligning agent for liquid crystal as claimed in claim 3 is characterized in that aligning agent for liquid crystal is used for by the liquid crystal orientating membrane of friction treatment.
7. liquid crystal orientating membrane is characterized in that, uses each described aligning agent for liquid crystal in the claim 1～6 and gets.
8. liquid crystal orientating membrane is characterized in that, each described aligning agent for liquid crystal in the coating claim 1～5 burns till on electroded substrate, carries out friction treatment again and gets.
9. liquid crystal display cells is characterized in that, has claim 7 or 8 described liquid crystal orientating membranes.
CN2007800434831A 2006-11-24 2007-11-22 Liquid crystal orientation treatment agent and liquid crystal display element produced by using the same Active CN101548228B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP317529/2006 2006-11-24
JP2006317529 2006-11-24
JP2006322397 2006-11-29
JP322397/2006 2006-11-29
PCT/JP2007/072681 WO2008062877A1 (en) 2006-11-24 2007-11-22 Liquid crystal orientation treatment agent and liquid crystal display element produced by using the same

Publications (2)

Publication Number Publication Date
CN101548228A CN101548228A (en) 2009-09-30
CN101548228B true CN101548228B (en) 2011-11-16

Family

ID=39429805

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2007800434831A Active CN101548228B (en) 2006-11-24 2007-11-22 Liquid crystal orientation treatment agent and liquid crystal display element produced by using the same

Country Status (5)

Country Link
JP (1) JP5109979B2 (en)
KR (1) KR101446818B1 (en)
CN (1) CN101548228B (en)
TW (1) TWI422616B (en)
WO (1) WO2008062877A1 (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5019050B2 (en) * 2007-12-13 2012-09-05 Ｊｓｒ株式会社 Liquid crystal aligning agent and liquid crystal display element
JP5083539B2 (en) * 2007-12-13 2012-11-28 Ｊｓｒ株式会社 Liquid crystal aligning agent and liquid crystal display element
JP5019049B2 (en) * 2007-12-13 2012-09-05 Ｊｓｒ株式会社 Liquid crystal aligning agent and liquid crystal display element
JP5326355B2 (en) * 2008-05-16 2013-10-30 日産化学工業株式会社 Liquid crystal alignment treatment agent and liquid crystal display element using the same
CN102084287B (en) * 2008-06-04 2014-05-07 日产化学工业株式会社 Liquid crystal aligning agent and liquid crystal display element using same
CN102209928B (en) * 2008-10-22 2014-02-26 日产化学工业株式会社 Liquid crystal aligning agent and liquid crystal element using same
KR101840484B1 (en) * 2010-02-26 2018-03-20 닛산 가가쿠 고교 가부시키 가이샤 Diamine compound, liquid crystal aligning agent and liquid crysta display element
JP5831712B2 (en) * 2010-12-28 2015-12-09 日産化学工業株式会社 Coating liquid for forming polyimide film, liquid crystal aligning agent, polyimide film, liquid crystal aligning film and liquid crystal display element
WO2013047693A1 (en) 2011-09-30 2013-04-04 日産化学工業株式会社 Liquid crystal orientation treatment agent, liquid crystal orientation membrane, and liquid crystal display element
CN102517039A (en) * 2011-10-25 2012-06-27 珠海彩珠实业有限公司 Preparation methods of liquid crystal orientation agent, liquid crystal orientation membrane, and liquid crystal cells thereof
JP6083388B2 (en) 2012-01-26 2017-02-22 日産化学工業株式会社 Method for producing liquid crystal aligning agent
CN104756002B (en) * 2012-11-21 2018-06-08 Jsr株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and its manufacturing method and liquid crystal display element
JP6447209B2 (en) * 2014-05-12 2019-01-09 Jsr株式会社 Polymer composition, liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, and method for producing liquid crystal display element
JP7078033B2 (en) 2017-03-22 2022-05-31 日産化学株式会社 Polymer and liquid crystal alignment agent using it
KR20220151604A (en) * 2020-03-06 2022-11-15 닛산 가가쿠 가부시키가이샤 Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5298590A (en) * 1991-08-13 1994-03-29 Nissan Chemical Industries Ltd. Liquid crystal alignment treating agent
CN1211743A (en) * 1997-06-26 1999-03-24 默克专利股份有限公司 Multi-domain STN LCD comprising fluorinated polyimide alignment layers

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3212162B2 (en) * 1992-10-22 2001-09-25 日産化学工業株式会社 Diaminobenzene derivative, polyimide and liquid crystal alignment film
JP4085206B2 (en) * 1996-02-15 2008-05-14 日産化学工業株式会社 Diaminobenzene derivative, polyimide and liquid crystal alignment film using the same
US6808766B1 (en) * 1998-08-26 2004-10-26 Nissan Chemical Industries, Ltd. Liquid crystal alignment agent and liquid crystal device using the liquid crystal alignment and method for alignment of liquid crystal molecules
JP4524458B2 (en) * 2002-05-31 2010-08-18 エルシコン・インコーポレーテッド Branched hybrid polymer material for optical alignment layer preparation
US6919404B2 (en) * 2002-05-31 2005-07-19 Elsicon, Inc. Hybrid polymer materials for liquid crystal alignment layers
CN100427529C (en) 2003-11-26 2008-10-22 日产化学工业株式会社 Liquid crystal alignment treating agent for vertical alignment and liquid crystal display
KR101235412B1 (en) * 2004-12-28 2013-02-20 닛산 가가쿠 고교 가부시키 가이샤 Liquid-crystal alignment material for vertical alignment, liquid-crystal alignment film, and liquid-crystal display element employing the same
KR101363224B1 (en) * 2005-05-25 2014-02-12 닛산 가가쿠 고교 가부시키 가이샤 Liquid crystal aligning agent and liquid crystal dispaly device using same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5298590A (en) * 1991-08-13 1994-03-29 Nissan Chemical Industries Ltd. Liquid crystal alignment treating agent
CN1211743A (en) * 1997-06-26 1999-03-24 默克专利股份有限公司 Multi-domain STN LCD comprising fluorinated polyimide alignment layers

Also Published As

Publication number Publication date
WO2008062877A1 (en) 2008-05-29
TWI422616B (en) 2014-01-11
JP5109979B2 (en) 2012-12-26
KR20090096428A (en) 2009-09-10
JPWO2008062877A1 (en) 2010-03-04
CN101548228A (en) 2009-09-30
TW200844139A (en) 2008-11-16
KR101446818B1 (en) 2014-10-01

Similar Documents

Publication Publication Date Title
CN101548228B (en) Liquid crystal orientation treatment agent and liquid crystal display element produced by using the same
CN100538478C (en) Aligning agent for liquid crystal and use the liquid crystal display cells of this treating agent
CN101057178B (en) Liquid-crystal alignment material for vertical alignment, liquid-crystal alignment film, and liquid-crystal display element employing the same
CN102067024B (en) Liquid-crystal alignment material, liquid-crystal display element employing same, and novel diamine
CN102084287B (en) Liquid crystal aligning agent and liquid crystal display element using same
CN101589333B (en) Liquid crystal aligning agent, liquid crystal alignment film using the same, and liquid crystal display element
JP5771948B2 (en) Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element
JP4779974B2 (en) Liquid crystal aligning agent and liquid crystal display element using the same
JP5849391B2 (en) Liquid crystal aligning agent and liquid crystal display element
CN103797408A (en) Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
JPWO2004021076A1 (en) Liquid crystal aligning agent and liquid crystal display element using the same
CN104130784B (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
CN102754020B (en) Aligning agent for liquid crystal and use the liquid crystal display cells of this treating agent
JP5773116B2 (en) Liquid crystal aligning agent and liquid crystal display element
JP6852347B2 (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element
WO2008010528A1 (en) Liquid crystal orienting agent and liquid crystal oriented film and liquid crystal display element using the same
CN105073708A (en) Novel diamine, polymer, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element using same
CN102859426B (en) Liquid crystal aligning agent, liquid crystal alignment film produced using same, and liquid crystal display element
JP6314488B2 (en) Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal display element, retardation film and method for producing retardation film
CN112602013A (en) Liquid crystal aligning agent, method for producing same, liquid crystal alignment film, and liquid crystal display element
CN102947754A (en) Liquid crystal aligning agent, liquid crystal alignment film using same, and liquid crystal display element
CN102209928B (en) Liquid crystal aligning agent and liquid crystal element using same
CN109207170A (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
JP6897791B2 (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element
CN101241274A (en) Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant