CN105038817A - Liquid crystal aligning agent, liquid crystal alignment film and manufacturing method therefor, liquid crystal display device, polymer and compound - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent, a liquid crystal alignment film and a manufacturing method therefor, a liquid crystal display device, a polymer and a compound. The invention is capable for allowing a polymer (P) of a partial structure expressed by the formula (I) to be contained into the liquid crystal aligning agent. *-X1-Y1-X2-* (1) (X1 is a dibasic organic group, Y1 is a dibasic concatenating group or single bond; wherein at least one of two X1 is a dibasic aromatic heterocyclic radical, in the case that one of two X1 is a dibasic aromatic heterocyclic radical, and Y1 has a dibasic concatenating bond having more than one nitrogen-atoms, and the two X1 are bonded on the same and different nitrogen-atoms in the Y1; and two X1 may be same or different, and * represents an associative key.)

Description

Liquid crystal aligning agent, liquid crystal orientation film and manufacture method thereof, liquid crystal display device, polymkeric substance and compound

Technical field

The present invention relates to a kind of liquid crystal aligning agent, liquid crystal orientation film and manufacture method thereof, liquid crystal display device, polymkeric substance and compound.

Background technology

In recent years, liquid crystal display device not only for as in the past for display terminals such as Personal Computers, and for multiple uses such as such as LCD TV, auto-navigation system, mobile telephone, smart mobile phone, information displays.In addition, liquid crystal display device requires the further high-quality of display quality along with multi-usage, provides plurality of liquid crystals alignment agent (such as with reference to patent documentation 1 ~ patent documentation 3) to meet this requirement.

Patent documentation 1 ~ Patent Document 3 discloses: make to have the diamines of piperazine ring, carry out reacting with tetracarboxylic dianhydride and the polyamic acid or derivatives thereof that obtains is used as the component of polymer of liquid crystal aligning agent.Specifically, Patent Document 1 discloses: the aromatic diamine will with the part-structure of "-phenyl ring-piperazine ring-phenyl ring-" is used for monomer, Patent Document 3 discloses: the diamines will with the part-structure of "-alkylidene chain-piperazine ring-alkylidene chain-" is used for monomer.By using described diamines, attempt obtaining ion density suitably and there is the liquid crystal orientation film of long-term reliability.In addition, Patent Document 2 discloses: by make by the polymerization diamines with piperazine ring being used for monomer and the polyimide obtained is contained in liquid crystal aligning agent, improve thermotolerance and charging voltage (chargedvoltage) leaks of liquid crystal orientation film.

[prior art document]

[patent documentation]

[patent documentation 1] Japanese Patent Laid-Open 2009-175684 publication

[patent documentation 2] Japanese Patent Laid-Open 2010-2501 publication

[patent documentation 3] Japanese Patent Laid-Open 2011-28223 publication

Summary of the invention

[invention institute for solution problem]

In order to improve display quality, various characteristic is required to liquid crystal orientation film, include, for example liquid crystal aligning, image retention generation difficulty (image retention characteristic), reliability etc. as key property one example.Particularly reliability, along with the multi-usage of liquid crystal display device, imagine and use under long continuous drive or the harsh and unforgiving environments such as thermal stresses, photostress, in order to stand the use under described harsh and unforgiving environments, described reliability is very important.Liquid crystal display device improves to realize further quality, and requires to improve these various characteristics further.

The present invention is formed in view of described problem, and main purpose is to provide a kind of liquid crystal aligning agent, and it can form the good film of liquid crystal aligning, and can obtain reliability and the good liquid crystal display device of image retention characteristic.

[technique means of dealing with problems]

The people such as the present inventor have carried out active research to reach the problem of prior art as above, found that, by containing the component of polymer of polymkeric substance as liquid crystal aligning agent of the specific part structure on main chain with nitrogen atom, described problem can be solved, thus complete the present invention.Specifically, manufacture method and the liquid crystal display device of following liquid crystal aligning agent, liquid crystal orientation film, liquid crystal orientation film are provided by the present invention.

Of the present invention wherein on the one hand for providing a kind of liquid crystal aligning agent, it contains the polymkeric substance (P) on main chain with the part-structure represented by following formula (1).

[changing 1]

*-X ¹-Y ¹-X ¹-*(1)

(in formula (1), X ¹for divalent organic radical, Y ¹for divalent concatenating group or singly-bound; Wherein, 2 X ¹at least one be divalent aromatic heterocycle, at 2 X ¹only one of them is divalent aromatic heterocycle when, Y ¹for having the divalent concatenating group of more than 1 nitrogen-atoms, and 2 X ¹be binding on Y ¹in identical or different nitrogen-atoms on; 2 X ¹can identical also can be different; " * " represents associative key (bondinghand))

Of the present invention wherein on the one hand for providing: a kind of manufacture method of liquid crystal orientation film, it comprises: described liquid crystal aligning agent is coated step substrate being formed film and carry out rayed to give the step of liquid crystal aligning ability to this film; And the manufacture method of another kind of liquid crystal orientation film, it comprises: use described liquid crystal aligning agent to form the step of film; And friction treatment is carried out to give the step of liquid crystal aligning ability to this film.In addition, the present invention also provides the liquid crystal orientation film formed by described liquid crystal aligning agent and the liquid crystal display device comprising this liquid crystal orientation film.

Another aspect of the invention is and provide a kind of polymkeric substance, it for being selected from least one in the cohort that is made up of polyamic acid, poly amic acid ester and polyimide, and has the part-structure represented by described formula (1) on main chain.

In addition, the compound provided represented by a kind of following formula (3) is provided.

[changing 2]

(in formula (3), X ¹for divalent organic radical, wherein, 2 X ¹at least one be divalent aromatic heterocycle; Z ¹for one-level is amino or following formula (z-1)

[changing 3]

(in formula (z-1), " * " represents and X ¹associative key)

Represented group; R ¹for alkane two base or the cyclohexylidene of singly-bound, carbon number 1 ~ 6, R ²for the alkyl of hydrogen atom or carbon number 1 ~ 6, or 2 R ²mutual bond and with 2 nitrogen-atoms and R ¹form the divalent ester ring type heterocyclic radical of carbon number 2 ~ 10 together; 2 X ¹can identical also can be different, 2 R ²can identical also can be different; P is 0 or 1)

[effect of invention]

According to liquid crystal aligning agent of the present invention, can by component of polymer at least partially in comprise the polymkeric substance with ad hoc structure and form the good film of liquid crystal aligning, and reliability and the good liquid crystal display device of image retention characteristic can be obtained.

Embodiment

Below, each composition contained in liquid crystal aligning agent of the present invention and other compositions of optionally and arbitrarily allocating are described.

< polymkeric substance (P) >

Liquid crystal aligning agent of the present invention contains at least one composition of polymkeric substance (P) as component of polymer on main chain with the structure represented by following formula (1).

[changing 4]

*-X ¹-Y ¹-X ¹-*(1)

(in formula (1), X ¹for divalent organic radical, Y ¹for divalent concatenating group or singly-bound; Wherein, 2 X ¹at least one be divalent aromatic heterocycle, at 2 X ¹only one of them is divalent aromatic heterocycle when, Y ¹for having the divalent concatenating group of more than 1 nitrogen-atoms, and 2 X ¹be binding on Y ¹in identical or different nitrogen-atoms on; 2 X ¹can identical also can be different; " * " represents associative key)

X in described formula (1) ¹divalent aromatic heterocycle be remove the group of 2 hydrogen atoms in the atom of the formation ring of heteroaromatic, also can import substituting group in loop section.X ¹loop section be preferably the heteroaromatic of nitrogen atom, its concrete example include, for example: pyrroles, imidazoles, pyrazoles, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indoles, benzoglyoxaline, purine, quinoline, isoquinoline 99.9, naphthyridines, quinoxaline, phthalazines, triazine, nitrogen Boom, phenodiazine Boom, acridine, azophenlyene, phenanthroline, oxazole, thiazole, carbazole, thiadiazoles, benzothiazole, thiodiphenylamine, oxadiazoles etc.

X can be directed into ¹aromatic heterocycle loop section in substituting group include, for example: the halogen atoms such as fluorine atom, chlorine atom, bromine atoms, atomic iodine; The alkyl of the carbon number 1 ~ 6 of the chains such as methyl, ethyl, propyl group or branch-like; The alkoxyl group etc. of the carbon numbers 1 ~ 6 such as methoxyl group, oxyethyl group, propoxy-.

Reduce with regard to the image retention (imagesticking) of the synthesis easness of monomer, liquid crystal display device and reliability viewpoint with regard to, in described heteroaromatic, described X ¹the ring skeleton that has of aromatic heterocycle be preferably pyrroles, imidazoles, pyrazoles, pyridine, pyrimidine, pyridazine, pyrazine or triazine, be more preferably pyridine, pyrimidine or pyrazine.X ¹in 2 associative keys be preferably positioned at Isosorbide-5-Nitrae-position relative to other groups.

X ¹divalent organic radical include, for example: divalent chain alkyl, divalent ester ring type alkyl and divalent aromatic hydrocarbyl etc.In these groups, with regard to the viewpoint of the reliability of liquid crystal display device and the improvement effect of image retention characteristic, be preferably divalent aromatic hydrocarbyl, concrete example include, for example: phenylene, biphenylene (biphenylenegroup), naphthylidene etc.Be preferably phenylene or biphenylene.

With regard to the aspect that image retention reduces and the improvement effect of reliability is high of liquid crystal display device, 2 X in described formula (1) ¹be preferably two and be divalent aromatic heterocycle.

Y ¹the concrete example of divalent concatenating group include, for example :-O-,-CO-,-COO-,-NR ^a-,-CONR ^a-,-NR ^acONR ^a-(wherein, R ^aalkyl for hydrogen atom or carbon number 1 ~ 6), the divalent functional group such as-N=N-,-COS-,-S-; The divalent alkyl such as divalent chain alkyl, divalent ester ring type alkyl and divalent aromatic hydrocarbyl; By the group that at least 1 methylene radical in divalent alkyl replaces with described divalent functional group; There is the divalent base etc. of heterocycle.

Herein, the what is called " chain alkyl " in this specification sheets, refers to not containing ring texture on main chain, but the straight-chain alkyl be only made up of chain-like structure and branch-like alkyl.Wherein, can be saturated, also can be unsaturated.So-called " ester ring type alkyl ", refers to that the structure only comprising ester ring type hydrocarbon is used as ring structure, and not containing the alkyl of aromatic ring structure.Wherein, be not necessarily only made up of the structure of ester ring type hydrocarbon, be also contained in the alkyl in its part with chain-like structure.So-called " aromatic hydrocarbyl ", refers to and comprises the alkyl that aromatic ring structure is used as ring structure.Wherein, be not necessarily only made up of aromatic ring structure, also can comprise the structure of chain-like structure or ester ring type hydrocarbon in its part.

With regard to the image retention minimizing of liquid crystal display device and the viewpoint of reliability, Y ¹divalent concatenating group preferably there is the group of at least 1 nitrogen-atoms, be more preferably the group with more than 2 nitrogen-atoms.Y ¹there is no particular restriction for the upper limit of the nitrogen-atoms number had, and is preferably less than 4, is more preferably less than 3.

At Y ¹when for having the divalent organic radical of more than 1 nitrogen-atoms, be preferably 2 X ¹be binding on Y respectively ¹in nitrogen-atoms on.At Y ¹when for having the divalent concatenating group of more than 2 nitrogen-atoms, 2 X ¹y can be binding on ¹in identical nitrogen-atoms on, also can be binding on different nitrogen-atoms, preferably be binding on Y ¹in different nitrogen-atoms on.In addition, at 2 X ¹in only wherein 1 when being divalent aromatic heterocycle, Y ¹become the divalent concatenating group with more than 1 nitrogen-atoms.In this situation, 2 X in described formula (1) ¹be binding on Y ¹in identical or different nitrogen-atoms on.

Particularly preferred Y ¹concrete example include, for example group etc. represented by following formula (Y-1).

[changing 5]

(in formula (Y-1), R ¹for alkane two base or the cyclohexylidene of singly-bound, carbon number 1 ~ 6, R ²for the alkyl of hydrogen atom or carbon number 1 ~ 6, or 2 R ²mutual bond and with 2 nitrogen-atoms and R ¹form the divalent ester ring type heterocyclic radical of carbon number 2 ~ 10 together; 2 R ²can identical also can be different; P is 0 or 1; " * " represents and X ¹associative key)

R in described formula (Y-1) ¹alkane two base of carbon number 1 ~ 6 include, for example: methylene radical, ethylidene, glyceryl, Ding Erji, penta 2 bases, dihexyl etc., these alkane two bases can be straight-chain, also can be branch-like.R ¹be preferably alkane two base of carbon number 1 ~ 6, be more preferably carbon number 1 ~ 4.At R ¹when for cyclohexylidene, be preferably Isosorbide-5-Nitrae-cyclohexylidene.

R ²the alkyl of carbon number 1 ~ 6 include, for example methyl, ethyl, propyl group, butyl, amyl group, hexyl etc., these alkyl can be straight-chain, also can be branch-like.This alkyl is preferably carbon number 1 ~ 4, is more preferably carbon number 1 ~ 3.

P is 0 or 1, with regard to the reliability of liquid crystal display device and the good viewpoint of image retention characteristic, is preferably p=1 with regard to making.

When p=1, in formula (Y-1), there are 2 R ².By these 2 R ²mutual bond and the divalent ester ring type heterocyclic radical that formed is the group removing 2 hydrogen atoms in the atom of the formation ring of ester ring type heterocycle, specifically, can represented by following formula (Y-1-1).

[changing 6]

(in formula (Y-1-1), R ¹¹be 1 valency substituting group, k is the integer of 0 ~ (a+b); A and b be meet a+b>=2 more than 0 integer; " * " represents associative key)

The R of described formula (Y-1-1) ¹¹include, for example: the alkyl of halogen atom, carbon number 1 ~ 6, the alkoxyl group etc. of carbon number 1 ~ 6.K is preferably 0.

Ester ring type heterocyclic radical represented by described formula (Y-1-1) is preferably ring element number 5 ~ 12, is more preferably 5 ~ 7.Mitigation speed with regard to accumulated charge is fast, the aspect that the minimizing effect of image retention is high, is particularly preferably Isosorbide-5-Nitrae-piperazine two base.

The structure of structure optimization represented by described formula (1) represented by following formula (2).

[changing 7]

(in formula (2), X ¹for divalent organic radical, wherein, 2 X ¹at least one be divalent aromatic heterocycle; R ¹, R ²and p is identical with described formula (Y-1) implication; " * " represents associative key)

The preferred concrete example of the structure represented by described formula (1) include, for example: following formula (2-1-1) ~ formula (2-1-8), formula (2-2-1) ~ formula (2-2-5), formula (2-3-1) ~ formula (2-3-3), formula (2-4-1) ~ formula (2-4-5), formula (2-5-1) ~ formula (2-5-6) and the structure etc. represented by formula (2-6-1) difference.

[changing 8]

(in formula, " * " represents associative key).

[changing 9]

(in formula, " * " represents associative key).

The main chain of described polymkeric substance (P) include, for example the skeleton comprising polyamic acid, polyimide, poly amic acid ester, polyester, polymeric amide etc.In addition, " main chain " of so-called polymkeric substance in this specification sheets, is by a kind or the above monomers of 2 profits bond and the structure that formed repeatedly, refers to the part of " doing " the longest in polymkeric substance.Therefore, so-called " on main chain, having the part-structure represented by described formula (1) ", refers to the part of " doing " of this Structure composing polymkeric substance.Wherein, in described polymkeric substance (P), the structure do not got rid of represented by described formula (1) is also present in the part beyond main chain, such as, situation on side chain (part of " doing " top set of autohemagglutination compound).

Polymkeric substance (P) such as can utilize and the compound of the structure had represented by described formula (1) is used for monomer carries out the method for being polymerized and obtain.

Described polymkeric substance (P) suitably can be selected to be selected from the one kind or two or more of the polymkeric substance in these and use.Wherein, preferably described polymkeric substance (P) is set at least one in the cohort being selected from and being made up of polyamic acid, polyimide and poly amic acid ester.

[polyamic acid (P)]

When described polymkeric substance (P) is for polyamic acid (hereinafter also referred to " polyamic acid (P) "), this polyamic acid (P) such as obtains by making tetracarboxylic dianhydride and diamines carry out reacting.Specifically, such as can utilize following methods to obtain: the tetracarboxylic dianhydride (hereinafter also referred to " specific tetracarboxylic dianhydride ") of the part-structure had represented by described formula (1) is carried out the method for being polymerized by (i) for monomer; (ii) diamines (hereinafter also referred to " specific diamines ") of the part-structure had represented by described formula (1) is carried out the method for being polymerized for monomer; (iii) specific tetracarboxylic dianhydride and described specific diamines are used for monomer to carry out the method for being polymerized.

[tetracarboxylic dianhydride]

(specific tetracarboxylic dianhydride)

Specific tetracarboxylic dianhydride for the synthesis of described polyamic acid (P) include, for example the compound etc. represented by following formula (3-1b).

[changing 10]

(in formula (3-1b), X ¹and Y ¹implication identical with described formula (1) respectively)

About the X of described formula (3-1b) ¹and Y ¹, the X of described formula (1) can be applied respectively ¹and Y ¹explanation.

The concrete example of the compound represented by described formula (3-1b) include, for example the compound etc. represented by following formula (4-1) ~ formula (4-8) difference.In addition, specific tetracarboxylic dianhydride can be used alone a kind or two or more combinationally used.

[changing 11]

Described specific tetracarboxylic dianhydride is preferably the Y in described formula (3-1b) ¹the group represented by described formula (Y-1), the compound specifically represented by following formula (3-B).

[changing 12]

(in formula (3-B), R ¹, R ²and the implication of p is identical with described formula (Y-1), X ¹implication identical with described formula (2))

About the X of described formula (3-B) ¹, the X of described formula (1) can be applied ¹explanation.In addition, about R ¹and R ², the R of described formula (Y-1) can be applied respectively ¹and R ²explanation.P is preferably 1.

The concrete example of the compound represented by described formula (3-B) include, for example the compound etc. represented by described formula (4-1) ~ formula (4-4), formula (4-7) and formula (4-8) difference.

In addition, the compound represented by described formula (3-B) can synthesize appropriately combined for vitochemical well-established law.If enumerate a wherein example, then by have the structure represented by described formula (2) diamines (compound represented by following formula (3-A)), with carboxylic halid reaction, synthesizing the tetracarboxylic acid of the structure had represented by described formula (2), then obtaining compound represented by described formula (3-B) by carrying out intramolecular dehydration condensation.

(other tetracarboxylic dianhydrides)

Described specific tetracarboxylic dianhydride can be used alone by the tetracarboxylic dianhydride for the synthesis of polymkeric substance (P), also other tetracarboxylic dianhydrides and specific tetracarboxylic dianhydride can be used simultaneously.

Other tetracarboxylic dianhydrides described include, for example: aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.As the concrete example of these tetracarboxylic dianhydrides, aliphatics tetracarboxylic dianhydride include, for example: 1,2,3,4-butane tetracarboxylic acid dianhydride etc.;

Ester ring type tetracarboxylic dianhydride include, for example: 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-volution-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl group norbornane-2:3, 5:6-dianhydride, 2, 4, 6, 8-tetracarboxylic dicyclo [3.3.0] octane-2:4, 6:8-dianhydride, 4, 9-dioxa three ring [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, TOPOT 2,2′ p phenylenebis (trimellitic acid monoesters acid anhydride) (p-phenylenebis (trimelliticacidmonoesteranhydride)) etc.,

Aromatic tetracarboxylic acid's dianhydride include, for example: pyromellitic acid anhydride etc.;

In addition, the tetracarboxylic dianhydride etc. recorded in Japanese Patent Laid-Open 2010-97188 publication can be used.In addition, tetracarboxylic dianhydride can be used alone a kind or two or more combinationally used.

The preferred usage ratio of described specific tetracarboxylic dianhydride is different according to the synthetic method of polyamic acid (P).Such as when the method for described (i), relative to the total amount of the tetracarboxylic dianhydride for the synthesis of polyamic acid (P), preferably the usage ratio of specific tetracarboxylic dianhydride is set to more than 5 % by mole, be more preferably and be set to more than 10 % by mole, be especially preferably set to more than 20 % by mole.There is no particular restriction for the higher limit of this usage ratio, suitably can select in the scope below 100 % by mole.

[diamines]

(specific diamines)

Specific diamines for the synthesis of described polyamic acid (P) can be any one of aliphatie diamine, ester ring type diamines, aromatic diamine etc., specifically, is preferably the compound represented by following formula (3-1a).

[changing 13]

H ₂N-X ¹-Y ¹-X ¹-NH ₂(3-1a)

(in formula (3-1a), X ¹and Y ¹implication identical with described formula (1))

About the X of described formula (3-1a) ¹and Y ¹, the X of described formula (1) can be applied ¹and Y ¹explanation.Specific diamines is preferably aromatic diamine.

The concrete example of specific diamines include, for example the compound etc. represented by following formula (3-1) ~ formula (3-83) difference.

[changing 14]

[changing 15]

[changing 16]

[changing 17]

[changing 18]

[changing 19]

[changing 20]

The preferred concrete example of described specific diamines is the Y in described formula (3-1a) ¹the compound of the group represented by described formula (Y-1), specifically, can represented by following formula (3-A).

[changing 21]

(in formula (3-A), R ¹, R ²and the implication of p is identical with described formula (Y-1), described formula X ¹implication identical with described formula (2))

About the X of described formula (3-A) ¹, the X of described formula (1) can be applied ¹explanation.In addition, about R ¹and R ², the R of described formula (Y-1) can be applied respectively ¹and R ²explanation.P is preferably 1.

The concrete example of the compound represented by described formula (3-A) include, for example: the compound etc. represented by described formula (3-1) ~ formula (3-13), formula (3-16), formula (3-19), formula (3-64), formula (3-65) and formula (3-68) ~ formula (3-83) difference.

In addition, the compound represented by described formula (3-A) is by synthesizing appropriately combined for vitochemical well-established law.As one example, method can be listed below: synthesis has nitro to replace the dinitrobenzene intermediate of 2 one-level amino in described formula (3-A), then, uses suitable reduction system, carries out amination to the nitro of the dinitrobenzene intermediate of gained.The method of synthesis dinitrobenzene intermediate suitably can be selected according to the compound as target.

1 of these compounds kind can be used alone or suitably select two or more to use by the specific diamines for the synthesis of described polyamic acid.

(other diamines)

Diamines for the synthesis of polymkeric substance (P) can be used alone described specific diamines, also other diamines and specific diamines can be used simultaneously.

Other diamines described include, for example: aliphatie diamine, ester ring type diamines, aromatic diamine, diamino organo-siloxane etc.As the concrete example of these diamines, aliphatie diamine include, for example: m-xylene diamine, 1,3-propylene diamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine etc.;

Ester ring type diamines include, for example: Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene-bis (cyclo-hexylamine), 1,3-two (amino methyl) hexanaphthenes etc.;

Aromatic diamine include, for example: O-Phenylene Diamine, mphenylenediamine, Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfide, 4,4 '-diamino-diphenyl amine, 4-aminophenyl-4 '-Aminobenzoate, two (4-amino-benzene oxygen) heptane of 1,7-, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 4,4 '-diamino-diphenyl ether, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two (4-aminophenyl) fluorenes of 9,9-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-(to phenylenediisopropylidene) dianiline, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, DAP, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, 3,5-diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, cholestane oxygen base-3,5-diaminobenzene, cholestane oxygen base-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base ester, two (the 4-amino benzoyl oxygen base) cholestane of 3,6-, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 2,4-diamino-N, N-diallyl aniline, 4-aminobenzyl amine, 1-(2,4-diamino-phenyl) piperazine-4-carboxylic acid, two (N-(4-aminophenyl) piperidyl) propane of 1,3-, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethylammonium-1H-indenes-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethylammonium-1H-indenes-6-amine, 4-aminophenyl-4 '-Aminobenzoate, 4,4 '-[4,4 '-propane-1,3-bis-base two (piperidines-Isosorbide-5-Nitrae-two base)] pentanoic, and following formula (A-1)

[changing 22]

(in formula (A-1), X ⁱand X ^iIbe separately singly-bound ,-O-,-COO-or-OCO-, R ⁱfor alkane two base of carbon number 1 ~ 3, R ^iIfor alkane two base of singly-bound or carbon number 1 ~ 3; A be 0 or 1, b be the integer of 0 ~ 2, c is the integer of 1 ~ 20, and d is 0 or 1; Wherein, a and b can not be 0 simultaneously)

Represented compound etc.;

Diamino organo-siloxane include, for example: two (3-aminopropyl)-tetramethyl disiloxanes of 1,3-etc., in addition, can use the diamines recorded in Japanese Patent Laid-Open 2010-97188 publication.

"-X in described formula (A-1) ¹-(R ¹-X ¹¹) _d-" represented by divalent base be preferably alkane two base ,-O-, the *-COO-or-O-C of carbon number 1 ~ 3 ₂h ₄-O-(wherein, with associative key and the diamino-phenyl bond of " * ").Base "-C _ch _2c+1" concrete example include, for example: methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base etc.2 amino in diamino-phenyl are preferably positioned at 2 relative to other groups, 4-position or 3,5-position.

The concrete example of the compound represented by described formula (A-1) include, for example the compound etc. represented by following formula (A-1-1) ~ formula (A-1-4) difference.

[changing 23]

In addition, 1 of these compounds kind can be used alone by other diamines for the synthesis of described polyamic acid, or suitably selects two or more to use.

The preferred usage ratio of described specific diamines is different according to the synthetic method of polyamic acid (P).Such as in the method for described (ii) when, relative to the total amount of the diamines for the synthesis of polyamic acid (P), preferably the usage ratio of described specific diamines is set to more than 5 % by mole, be more preferably and be set to more than 10 % by mole, be especially preferably set to more than 20 % by mole.There is no particular restriction for the higher limit of this usage ratio, can according to the various characteristics of giving polymkeric substance (such as tilt angle characteristic etc.), and at random set in scope below 100 % by mole.

By liquid crystal aligning agent of the present invention for the manufacture of twisted nematic (twistednematic, TN) type, STN Super TN (supertwistednematic, when the liquid crystal display device of STN) type or vertical orientating type, polymkeric substance (P) contained in this liquid crystal aligning agent can be set to the polymkeric substance having and can give the group (hereinafter also referred to as " tilt angle expression power base ") of tilt angle expressive ability to film at least partially.Tilt angle expression power base include, for example the alkyl of carbon number 4 ~ 20, the fluoroalkyl of carbon number 4 ~ 20, the alkoxyl group of carbon number 4 ~ 20, the having the group of steroid skeleton, have the group etc. of polynuclear plane of carbon number 17 ~ 51.

Such as, the polyamic acid (P) with tilt angle expression power base obtains by comprising the diamines with tilt angle expression power base be used as the polymerization of other diamines described in monomer composition.When use has the diamines of tilt angle expression power base, as long as its usage quantity suitably sets according to the size of target tilt angle, relative to for the synthesis of whole diamines, such as can be set to more than 1 % by mole, preferably be set to 3 % by mole ~ 70 % by mole.

Utilizing optical alignment method, when giving liquid crystal aligning ability to the film using liquid crystal aligning agent of the present invention to make, also at least one of polymkeric substance (P) contained in this liquid crystal aligning agent can be set to the polymkeric substance with light orientation structure.

Herein, so-called light orientation structure comprises light orientation base and the concept both decomposition type light orientation section.Specifically, light orientation structure can adopt by photoisomerization or photodimerization, photolysis etc. and show the group of bright dipping orientation, include, for example: containing the group containing nitrogen benzide of nitrogen benzide or derivatives thereof as basic framework, containing the group with cinnamic acid structure of styracin or derivatives thereof as basic framework, containing the group containing phenyl styryl ketone of phenyl styryl ketone or derivatives thereof as basic framework, containing the group containing benzophenone of benzophenone or derivatives thereof as basic framework, containing the group containing tonka bean camphor of tonka bean camphor or derivatives thereof as basic framework, containing the structure containing polyimide of polyimide or derivatives thereof as basic framework, the main chain of polymkeric substance is imported with the structure containing unsaturated link(age) of carbon-to-carbon unsaturated bond, following formula (p-1)

[changing 24]

(in formula (p-1), X ³for sulphur atom, Sauerstoffatom or-NH-; " * " represents associative key respectively; Wherein, in 2 " * ", at least one is binding on aromatic nucleus)

Represented part-structure is directed into the structure etc. containing aromatic nucleus-CO on the main chain of polymkeric substance.

In described formula (p-1), with X ³and the aromatic nucleus of at least any one bond of carbonyl include, for example phenyl ring, naphthalene nucleus, anthracene nucleus etc.In these aromatic nucleus, with regard to the viewpoint of liquid crystal aligning and the transparency, be preferably phenyl ring.In 2 " * " in described formula (p-1), be not particularly limited with the structure of the side of aromatic nucleus bond, include, for example chain hydrocarbon structure, aliphatics ring, aromatic nucleus (comprising aromatic hydrocarbons ring and heteroaromatic), ester ring type heterocycle etc.In these structures, with regard to the aspect of the sensitivity to light, be preferably 2 " * " and be all binding on aromatic nucleus, be more preferably and be binding on aromatic hydrocarbons ring.With regard to the aspect of the sensitivity to light, X ³be preferably sulphur atom, with regard to the options of the aspect that easily obtains and spendable monomer widely with regard to aspect, X ³be preferably Sauerstoffatom.

When liquid crystal aligning agent of the present invention being used for light orientation purposes, the polymkeric substance preferably on main chain at least partially with light orientation structure of polymkeric substance (P), is more preferably the polymkeric substance with the structure containing polyimide or the structure containing aromatic nucleus-CO.

When polymkeric substance (P) has the structure containing polyimide, this polymkeric substance preferably has dicyclo [2.2.2] octene skeleton or tetramethylene skeleton.Described polymkeric substance such as by make to comprise in tetramethylene tetracarboxylic dianhydride and dicyclo [2.2.2] pungent-7-alkene-2,3,5,6-tetracarboxylic dianhydride at least any one tetracarboxylic dianhydride, carry out reacting and obtaining with the diamine compound comprising specific diamines.

In addition, when polymkeric substance (P) has the structure containing aromatic nucleus-CO, this polymkeric substance preferably has "-phenyl ring-COO-" or the part-structure represented by "-phenyl ring-OCO-" on main chain.At least any one the polymerization of described polymkeric substance such as by comprising the tetracarboxylic dianhydride with this part-structure and the diamines with this part-structure in monomer obtains.The concrete example of this monomer include, for example the compound etc. represented by following formula (p-1-1) ~ formula (p-1-6) difference.

[changing 25]

Synthesis main chain has the polymkeric substance of light orientation structure, with regard to photoreactive viewpoint, relative to the total amount of the monomer for the synthesis of polymkeric substance, the usage ratio with the monomer of light orientation structure is preferably established as more than 20 % by mole, is more preferably and is set to 30 % by mole ~ 80 % by mole.

[synthesis of polyamic acid (P)]

The usage ratio of the tetracarboxylic dianhydride and diamines that are supplied to the building-up reactions of polyamic acid (P) is preferably amino 1 equivalent relative to diamines, the anhydride group of tetracarboxylic dianhydride becomes the ratio of 0.2 equivalent ~ 2 equivalent, is more preferably the ratio becoming 0.3 equivalent ~ 1.2 equivalent.

Time synthesizing polyamides acid (P), also can use suitable molecular weight regulator with tetracarboxylic dianhydride as above and diamines simultaneously, synthesize the polymkeric substance of end modified type.By making the polymkeric substance of described end modified type, the coating (printing) of liquid crystal aligning agent can be improved further when not undermining effect of the present invention.

Molecular weight regulator include, for example: sour single acid anhydrides such as MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, itaconic anhydride, the monoamine compounds such as aniline, cyclo-hexylamine, n-butylamine, the monoisocyanate compound such as phenylcarbimide, naphthyl isocyanate etc.Relative to total 100 weight part of used tetracarboxylic dianhydride and diamines, the usage ratio of molecular weight regulator is preferably set to below 20 weight parts, is more preferably and is set to below 10 weight parts.

The building-up reactions of polyamic acid is preferably carried out in organic solvent.The organic solvent used in reaction include, for example aprotic polar solvent, phenol series solvent, alcohol, ketone, ester, ether, halon, hydrocarbon etc.In these organic solvents, preferably use more than a kind that is selected from the cohort (organic solvent of the first cohort) be made up of aprotic polar solvent and phenol series solvent, or be selected from the organic solvent of the first cohort more than a kind with the mixture of more than a kind be selected from the cohort (organic solvent of the second cohort) that is made up of alcohol, ketone, ester, ether, halon and hydrocarbon.In the latter case, relative to the total amount of the organic solvent of the first cohort and the organic solvent of the second cohort, the usage ratio of the organic solvent of the second cohort is preferably less than 50 % by weight, is more preferably less than 40 % by weight, is especially preferably less than 30 % by weight.

Being particularly preferably use is selected from by METHYLPYRROLIDONE, N, N-N,N-DIMETHYLACETAMIDE, N, more than a kind in the cohort that dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA, meta-cresol, xylenol and halogenation phenol form as solvent, or preferably use in the scope of described ratio more than a kind of these solvents with the mixture of other organic solvents.

The usage quantity (a) of organic solvent is preferably set to the total amount (a+b) relative to reaction soln, and the total amount (b) of tetracarboxylic dianhydride and diamines becomes the amount of 0.1 % by weight ~ 50 % by weight.Temperature of reaction in the building-up reactions of polyamic acid is preferably-20 DEG C ~ 150 DEG C, is more preferably 0 DEG C ~ 100 DEG C.In addition, the reaction times is preferably 0.1 hour ~ 24 hours, is more preferably 0.5 hour ~ 12 hours.

Carry out as described above, obtain the reaction soln dissolved by polyamic acid (P).This reaction soln directly can be supplied to the preparation of liquid crystal aligning agent, also reoffer to the preparation of liquid crystal aligning agent after polyamic acid (P) contained in reaction soln can being separated, or reoffer after polyamic acid (P) purifying be separated to the preparation of liquid crystal aligning agent.When making polyimide when polyamic acid (P) is carried out dehydration closed-loop, described reaction soln directly can be supplied to dehydration closed-loop reaction, also reoffer to dehydration closed-loop reaction after polyamic acid (P) contained in reaction soln can being separated, or also can react reoffering after polyamic acid (P) purifying be separated to dehydration closed-loop.The separation of polyamic acid and purifying can carry out according to known method.

[poly amic acid ester (P)]

Poly amic acid ester (hereinafter also referred to poly amic acid ester (P)) as described polymkeric substance (P) such as can utilize following methods to obtain: [I] makes the compound of polyamic acid (P) and the hydroxyl obtained by described building-up reactions and esterifying agent carry out the method for reacting; [II] makes tetracarboxylic acid diester and diamines carry out the method for reacting; [III] makes tetracarboxylic acid diester dihalide and diamines carry out the method etc. of reacting.

Herein, the esterifying agent used in method [I] include, for example acetal based compound, halogenide, compound etc. containing epoxy group(ing).As the concrete example of these compounds, the compound of hydroxyl include, for example: the alcohols such as methyl alcohol, ethanol, propyl alcohol, the phenols such as phenol, cresols etc.; Acetal based compound include, for example: DMF diethyl acetal, N, N-diethylformamide diethyl acetal etc.; Halogenide include, for example: methyl bromide, bromic ether, bromo-octadecane, methyl chloride, chlorooctadecane, 1,1,1-tri-fluoro-2-iodoethane etc.; Compound containing epoxy group(ing) include, for example: propylene oxide etc.

The tetracarboxylic acid diester used in method [II], by using described alcohols, carries out open loop to tetracarboxylic dianhydride and obtains.In addition, the tetracarboxylic acid diester dihalide used in method [III] obtains by making the suitable chlorizating agent such as the tetracarboxylic acid diester that obtains in this way and thionyl chloride carry out reacting.Method [II] and the middle diamines used of method [III] preferably comprise described specific diamines, also optionally can use other diamines described.In addition, poly amic acid ester (P) can only have amic acid esters structure, also can be amido acid structure and amic acid esters structure and the partial esterification thing deposited.

[polyimide (P)]

Polyimide (hereinafter also referred to polyimide (the P)) polyamic acid (P) such as by synthesizing in this way as described polymkeric substance (P) carries out dehydration closed-loop, in addition imidization and obtaining.

Described polyimide (P) can be the complete imide compound of the amido acid structure had as the polyamic acid (P) of its precursor all being carried out dehydration closed-loop, also can be only a part for amido acid structure carried out dehydration closed-loop and make amido acid structure and imide ring structure and the part imide compound of depositing.The imide rate of polyimide contained in liquid crystal aligning agent of the present invention is preferably more than 30%, is more preferably 40% ~ 99%, is especially preferably 50% ~ 99%.This imide rate is the total relative to the quantity of the amido acid structure of polyimide and the quantity of imide ring structure, represents the ratio shared by quantity of imide ring structure with percentage.Herein, a part for imide ring also can be different imide ring.

The dehydration closed-loop of polyamic acid preferably utilizes following methods to carry out: the method heated polyamic acid; Or polyamic acid is dissolved in organic solvent, in this solution, adds dewatering agent and dehydration closed-loop catalyzer, optionally carry out the method heated.Wherein, the method for the latter is preferably utilized.

Add in the solution of described polyamic acid in the method for dewatering agent and dehydration closed-loop catalyzer, dewatering agent such as can use the acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.Relative to 1 mole of the amido acid structure of polyamic acid, the usage quantity of dewatering agent is preferably set to 0.01 mole ~ 20 moles.Dehydration closed-loop catalyzer such as can use the tertiary amine such as pyridine, collidine, two picolins, triethylamine.Relative to used dewatering agent 1 mole, the usage quantity of dehydration closed-loop catalyzer is preferably set to 0.01 mole ~ 10 moles.Dehydration closed-loop reaction in use organic solvent can enumerate as the synthesis of polyamic acid and illustrative organic solvent.The temperature of reaction of dehydration closed-loop reaction is preferably 0 DEG C ~ 180 DEG C, is more preferably 10 DEG C ~ 150 DEG C.Reaction times is preferably 1.0 hours ~ 120 hours, is more preferably 2.0 hours ~ 30 hours.

Obtain the reaction soln containing polyimide (P) in this way.This reaction soln directly can be supplied to the preparation of liquid crystal aligning agent, also reoffer to the preparation of liquid crystal aligning agent after can removing dewatering agent and dehydration closed-loop catalyzer in autoreaction solution, also reoffer to the preparation of liquid crystal aligning agent after polyimide can being separated, or can also reoffer after the polyimide purifying of separation to the preparation of liquid crystal aligning agent.These purification process can be carried out according to known method.In addition, polyimide (P) also can pass through the imidization of poly amic acid ester (P) and obtain.

The polyamic acid (P) obtained in this way, poly amic acid ester (P) and polyimide (P) are preferably when being made into concentration and being the solution of 10 % by weight, there is the soltion viscosity of 10mPas ~ 800mPas, be more preferably the soltion viscosity with 15mPas ~ 500mPas.In addition, the soltion viscosity (mPas) of described polymkeric substance be to the concentration using the good solvent (such as gamma-butyrolactone, METHYLPYRROLIDONE etc.) of this polymkeric substance to prepare be 10 % by weight polymers soln, use E type rotational viscosimeter to measure at 25 DEG C and the value that obtains.

Described polyamic acid, poly amic acid ester and polyimide utilize gel permeation chromatography (GelPermeationChromatography, the weight average molecular weight (Mw) of the polystyrene conversion GPC) measured is preferably 1,000 ~ 500,000, be more preferably 2,000 ~ 300,000.In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw and the severals molecular-weight average (Mn) of polystyrene conversion utilizing GPC to measure preferably less than 15, is more preferably less than 10.By in described molecular weight ranges, good orientation and the stability of liquid crystal display device can be guaranteed.

Other compositions of < >

Liquid crystal aligning agent of the present invention contains described polymkeric substance (P), also optionally can contain other compositions.Other compositions that can make an addition in this liquid crystal aligning agent include, for example: the compound (hereinafter referred to as " compound containing epoxy group(ing) "), functional silanes compound etc. in other polymkeric substance beyond described polymkeric substance (P), molecule with at least one epoxy group(ing).

[other polymkeric substance]

Other polymkeric substance described can be used for improving solution properties or electrical characteristic.Other polymkeric substance described are the polymkeric substance of the part-structure do not had represented by described formula (1), are not particularly limited its main framing.Specifically, include, for example the polymkeric substance as main framing such as polyamic acid, polyimide, poly amic acid ester, organopolysiloxane, polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenylmaleimide) derivative, poly-(methyl) acrylate.In these polymkeric substance, be preferably selected from least one polymkeric substance in the cohort be made up of polyamic acid, poly amic acid ester, polyimide and organopolysiloxane.

When other polymkeric substance are made an addition in liquid crystal aligning agent, relative to total 100 weight part of polymkeric substance contained in liquid crystal aligning agent, the allotment ratio of other polymkeric substance described is preferably set to below 50 weight parts, be more preferably and be set to 0.1 weight part ~ 40 weight part, be especially preferably set to below 0.1 weight part ~ 30 weight part.

[compound containing epoxy group(ing)]

Compound containing epoxy group(ing) can be used for improving liquid crystal orientation film with the cementability of substrate surface or electrical characteristic.The described compound containing epoxy group(ing) include, for example following compound as preferably: ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2, 2-dibromoneopentyl glycol diglycidylether, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzyl amine, N, N-diglycidyl-aminomethyl cyclohexane, N, N-diglycidyl-cyclo-hexylamine etc.In addition, containing the organopolysiloxane containing epoxy group(ing) that the example of the compound of epoxy group(ing) can use No. 2009/096598th, International Publication to record.

When these epoxy compoundss are made an addition in liquid crystal aligning agent, relative to total 100 weight part of polymkeric substance contained in liquid crystal aligning agent, the allotment ratio of described epoxy compounds is preferably set to below 40 weight parts, is more preferably and is set to 0.1 weight part ~ 30 weight part.

[functional silanes compound]

Described functional silanes compound can use for the object of the printing improving liquid crystal aligning agent.Described functional silanes compound include, for example: 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl Trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-tri-ethoxy silylpropyl diethylenetriamine, 10-Trimethoxy silane base-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-Trimethoxy silane base-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-phenyl-3-TSL 8330, glycidoxypropyl methyltrimethoxy silane, 2-glycidoxypropyl ethyl trimethoxy silane, 3-glycidoxypropyltrimewasxysilane etc.

When these functional silanes compounds are made an addition in liquid crystal aligning agent, relative to total 100 weight part of polymkeric substance contained in liquid crystal aligning agent, the allotment ratio of described functional silanes compound is preferably set to below 2 weight parts, is more preferably and is set to 0.02 weight part ~ 0.2 weight part.

In addition, the additive being generally used for preparing liquid crystal aligning agent can be used as other compositions.Additive beyond described include, for example in molecule the compound, antioxidant, tensio-active agent etc. with at least one oxetanylmethoxy.

< solvent >

Liquid crystal aligning agent of the present invention is prepared into and described polymkeric substance (P) and other compositions of optionally using preferably is disperseed or are dissolved in the liquid composition in suitable solvent.

The organic solvent used include, for example: METHYLPYRROLIDONE, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, methyl methoxypropionate, ethyl ethoxy-c acid esters, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (ethylene glycol butyl ether), glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, ethylene carbonate, Texacar PC etc.These organic solvents can be used alone or two or more is used in combination.

Solid component concentration (ratio of total weight shared by the gross weight of liquid crystal aligning agent of the composition beyond the solvent of liquid crystal aligning agent) in liquid crystal aligning agent of the present invention can consider that viscosity, volatility etc. are suitably selected, and is preferably the scope of 1 % by weight ~ 10 % by weight.That is, liquid crystal aligning agent of the present invention is by coating substrate surface in aftermentioned mode, preferably heating, thus formed as liquid crystal orientation film film or become the film of liquid crystal orientation film.Now, when solid component concentration is less than 1 % by weight, the thickness of film becomes too small and is difficult to obtain good liquid crystal orientation film.On the other hand, when solid component concentration is more than 10 % by weight, the thickness of film becomes excessive and is difficult to obtain good liquid crystal orientation film, and in addition, the viscosity that there is liquid crystal aligning agent increases, the tendency that coating declines.

The scope of particularly preferred solid component concentration is different according to the method used during coating of liquid crystalline alignment agent on substrate.Such as when utilizing turner method, solid component concentration (ratios of total weight shared by the gross weight of liquid crystal aligning agent of the whole compositions beyond the solvent in liquid crystal aligning agent) is particularly preferably the scope of 1.5 % by weight ~ 4.5 % by weight.When utilizing print process, being particularly preferably scope solid component concentration being set to 3 % by weight ~ 9 % by weight, whereby soltion viscosity being set to the scope of 12mPas ~ 50mPas.When utilizing ink jet method, being particularly preferably scope solid component concentration being set to 1 % by weight ~ 5 % by weight, whereby soltion viscosity being set to the scope of 3mPas ~ 15mPas.Temperature when preparing liquid crystal aligning agent of the present invention is preferably 10 DEG C ~ 50 DEG C, is more preferably 20 DEG C ~ 30 DEG C.

[liquid crystal orientation film and liquid crystal display device]

Liquid crystal aligning agent of the present invention by described explanation manufactures liquid crystal orientation film.Liquid crystal display device of the present invention comprises the liquid crystal orientation film using described liquid crystal aligning agent to be formed.The operating mode of liquid crystal display device of the present invention is not particularly limited, such as can be applicable to TN type, STN type, vertical orientated (VerticalAlignment, VA) type (comprises vertical orientated-multidomain vertical orientation (VerticalAlignment-MultidomainVerticalAlignment, VA-MVA) type, vertical orientated (the VerticalAlignment-PatternedVerticalAlignment of vertical orientated-pattern, VA-PVA) type etc.), coplanar switching (In-PlaneSwitching, IPS) type, fringing field switches (FringeFieldSwitching, FFS) type, optical compensation curved (OpticallyCompensatoryBend, OCB) multiple operation mode such as type.

The step of liquid crystal display device of the present invention such as by comprising following step (1-1) ~ step (1-3) manufactures.Step (1-1) uses different substrates according to required operating mode.Step (1-2) and step (1-3) share in each operating mode.

[step (1-1): the formation of film]

First, substrate is coated with liquid crystal aligning agent of the present invention, then coated face is heated, on substrate, form film thus.

(1-1A) when the liquid crystal display device of Production Example as TN type, STN type or VA type, first, to two pieces of substrates of patterned nesa coating be provided with as a pair, in described each transparent conductive film forming surface, flexographic printing process, method of spin coating, roll-coater method or ink jet printing method is preferably utilized to be coated with liquid crystal aligning agent of the present invention respectively.Substrate such as can use: the glass such as float glass, soda glass; Comprise the transparency carrier of the plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-(ester ring type alkene).The wherein nesa coating of one side being arranged at substrate can use and comprise stannic oxide (SnO ₂) nesa (NESA) film (PPG register of company of U.S. trade mark), comprise indium oxide-tin oxide (In ₂o ₃-SnO ₂) tin indium oxide (IndiumTinOxide, ITO) film etc.In order to obtain patterned nesa coating, such as, can utilize following methods: after forming patternless nesa coating, being formed the method for pattern by photoetch; The method etc. with the mask of required pattern is used when forming nesa coating.During coating of liquid crystalline alignment agent, in order to make the cementability of substrate surface and nesa coating and film better, also to the face forming film in substrate surface, the pre-treatment being coated with functional silanes compound, functionality titanium compound etc. in advance can be implemented.

After coating of liquid crystalline alignment agent, for the object such as sagging preventing be coated with liquid crystal aligning agent, be preferably enforcement and preheat (prebake conditions).Prebake conditions temperature is preferably 30 DEG C ~ 200 DEG C, is more preferably 40 DEG C ~ 150 DEG C, is particularly preferably 40 DEG C ~ 100 DEG C.The prebake conditions time is preferably 0.25 minute ~ 10 minutes, is more preferably 0.5 minute ~ 5 minutes.Then, remove completely for by solvent, optionally the amido acid structure be present in polymkeric substance is carried out the object of hot-imide, and implement to burn till (toasting afterwards) step.Firing temperature (rear storing temperature) is now preferably 80 DEG C ~ 300 DEG C, is more preferably 120 DEG C ~ 250 DEG C.Post-bake times is preferably 5 minutes ~ 200 minutes, is more preferably 10 minutes ~ 100 minutes.The thickness of the film formed in this way is preferably 0.001 μm ~ 1 μm, is more preferably 0.005 μm ~ 0.5 μm.

(1-1B) when manufacturing the liquid crystal display device of IPS type or FFS type, be provided with electrode (comprising patterned nesa coating for interdigitated electrode structure or metallic membrane) substrate electrode forming surface, with do not arrange in the one side of subtend substrate of electrode, be coated with liquid crystal aligning agent of the present invention respectively, then each coated face is heated, form film thus.About the patterning method of heating condition, nesa coating or metallic membrane after the material of the substrate now used and nesa coating, coating process, coating, the pre-treatment of substrate and the preferred thickness of film that formed, identical with described (1-1A).Metallic membrane can use the film such as comprising the metals such as chromium.

In any one situation of described (1-1A) and (1-1B), all by after coating of liquid crystalline alignment agent on substrate, organic solvent is removed and forms liquid crystal orientation film or become the film of liquid crystal orientation film.Now, also can by heating further after film is formed, and make the polyamic acid of allotment in liquid crystal aligning agent of the present invention, poly amic acid ester and polyimide carry out dehydration closed-loop reaction, thus make further through the film of imidization.

[step (1-2): alignment capability gives process]

When manufacturing the liquid crystal display device of TN type, STN type, IPS type or FFS type, implement the process of the film formed in described step (1-1) being given to liquid crystal aligning ability.Whereby, the alignment capability of liquid crystal molecule is imparted on film becomes liquid crystal orientation film.Alignment capability gives process can enumerate following process etc.: friction treatment, utilizes the roller being wound with the cloth comprising the fibers such as such as nylon, artificial silk, cotton, by film to certain orientation wiping; And light orientation process, film is irradiated to the radioactive rays of polarisation or non-polarized.On the other hand, when manufacturing VA type liquid crystal display device, the film formed directly can be used as liquid crystal orientation film, also can give process to this film implementation orientation ability in described step (1-1).

When giving liquid crystal aligning ability by light orientation process to film, ultraviolet and the visible rays of the light comprising 150nm ~ 800nm wavelength such as can be used to the radioactive rays of film irradiation.When radioactive rays are polarisation, can be linear polarization, also can be part polarisation.In addition, when used radioactive rays are for linear polarization or part polarisation, can irradiate from the direction vertical with real estate, also can irradiate from vergence direction, or these irradiation combinations are carried out.When irradiating the radioactive rays of non-polarized, the direction of irradiation is set to vergence direction.

The light source used such as can use: Cooper-Hewitt lamp, high pressure mercury vapour lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer laser etc.The ultraviolet of preferred wavelength region may can utilize light source and method also such as such as spectral filter, diffraction grating etc. etc. and obtain.The irradiation dose of radioactive rays is preferably 100J/m ²~ 50,000J/m ², be more preferably 300J/m ²~ 20,000J/m ².In addition, in order to improve reactivity, can heat to film while carry out rayed to film.Temperature when heating is generally 30 DEG C ~ 250 DEG C, is preferably 40 DEG C ~ 200 DEG C, is more preferably 50 DEG C ~ 150 DEG C.

In addition, also can carry out following process further to the liquid crystal orientation film after friction treatment and make liquid crystal orientation film have different liquid crystal aligning abilities in each region: make by a part of irradiation ultraviolet radiation to liquid crystal orientation film the process that the tilt angle in a part of region of liquid crystal orientation film changes; Or after a part on liquid crystal orientation film surface forms resist film, after friction treatment is carried out in the direction different from friction treatment just now, by the process that resist film is removed.In this situation, the visual field characteristic of the liquid crystal display device of gained can be improved.The liquid crystal orientation film being suitable for VA type liquid crystal display device also can be suitable for the liquid crystal display device of polymer stabilizing orientation (Polymersustainedalignment, PSA) type.

[step (1-3): constructing of liquid crystal cells]

Prepare the 2 pieces of substrates being formed with liquid crystal orientation film in this way, between 2 pieces of substrates of subtend configuration, configure liquid crystal, manufacture liquid crystal cells whereby.In order to manufacture liquid crystal cells, include, for example following 2 kinds of methods.First method is in the past known method.First, 2 pieces of substrate subtends are configured via gap (cell gap) in the mode of each liquid crystal orientation film subtend, sealing agent is used to be fitted by the periphery of 2 pieces of substrates, inject filling liquid crystal in the cell gap divided by substrate surface and sealing agent after, filling orifice is sealed, manufactures liquid crystal cells whereby.Second method is for being called the method for liquid crystal drip-injection (OneDropFill, ODF) mode.Specified location on wherein one piece of substrate in the 2 pieces of substrates being formed with liquid crystal orientation film, the such as sealing agent of coated UV photo-hardening, and then after the set several positions on liquid crystal aligning face drip liquid crystal, to fit another block substrate in the mode of liquid crystal orientation film subtend, and liquid crystal is spread out on whole of substrate, then, whole irradiating ultraviolet light of substrate is cured the sealant, manufactures liquid crystal cells whereby.When utilizing any one method, all it is desirable to the liquid crystal cells to manufacturing in this way, and then be heated to till used liquid crystal obtains the temperature of isotropic phase, then slowly be cooled to room temperature, remove flow orientation when liquid crystal is filled whereby.

As sealing agent, such as, can use the epoxy resin etc. containing stiffening agent and the alumina balls as spacer.

Liquid crystal can enumerate nematic liquid crystal (nematicliquidcrystal) and stratose liquid crystal (smecticliquidcrystal), wherein be preferably nematic liquid crystal, such as, can use: schiff bases (Schiffbase) is liquid crystal, azoxy (azoxy) is liquid crystal, biphenyl system liquid crystal, Santosol 360 system liquid crystal, ester system liquid crystal, terphenyl (terphenyl) are liquid crystal, xenyl hexamethylene methane series liquid crystal, pyrimidine system liquid crystal, dioxan system liquid crystal, double-octane system liquid crystal, cubane (cubane) are liquid crystal etc.In addition, also can add following material to use in these liquid crystal: the cholesteryl liquid crystals (cholestericliquidcrystal) such as such as cholesteryl chloride (cholesterylchloride), cholesteryl nonanoate (cholesterylnonanoate), cholesteryl carbonate (cholesterylcarbonate); As the chiral agent (chiralagent) that trade(brand)name " C-15 ", " CB-15 " (manufacture of Merck (Merck) company) are sold; To oxygen base α-tolylene-to ferroelectric liquid crystals (ferroelectricliquidcrystal) etc. such as amino-2-methyl butyl laurates (p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate) in the last of the ten Heavenly stems.

Then, liquid crystal display device of the present invention is obtained by the outer surface laminating Polarizer at liquid crystal cells.The Polarizer fitting in the outside surface of liquid crystal cells can be enumerated: be called as the Polarizer of the light polarizing film of " H film " with the clamping of rhodia protective membrane or comprise itself Polarizer of H film, described " H film " polyvinyl alcohol is extended film that orientation absorbs iodine.

Liquid crystal display device of the present invention can be effectively applied to multiple device, such as can be used for: the various display unit such as clock and watch, pocket game machine, word processor, notes type Personal Computer, auto-navigation system, video camera, personal digital assistant (PersonalDigitalAssistant, PDA), digital camera, mobile telephone, smart mobile phone, various watch-dog, LCD TV, information display.

[embodiment]

Below, by embodiment, the present invention is specifically described further, but the present invention is not limited to these embodiments.

In following example, utilize following methods to measure the soltion viscosity of polymers soln.In addition, below, sometimes by the compound represented by formula X referred to as " compounds X ".

[soltion viscosity of polymers soln]

The soltion viscosity [mPas] of polymers soln is the solution being prepared into polymer concentration 10 % by weight to using set solvent, uses E type rotational viscosimeter to measure at 25 DEG C.

The synthesis > of < compound

[embodiment 1-1: the synthesis of compound (DA-1)]

The compound represented by following formula (DA-1) is synthesized according to following flow process 1.

[changing 26]

Make 2-chloro-5-nitropyridine 2.5g be suspended in toluene 25ml, add triethylamine 1.88g wherein.The solution that piperazine 0.5g is dissolved in chloroform 2ml is slowly dripped in its container.At room temperature stir after 30 minutes, stir 12 hours at 80 DEG C.Now, along with reaction is carried out, yellow solid is separated out.After cooling, solid is filtered, after fully washing with water, utilize ethyl acetate to remove toluene.Make the solid drying of gained, obtain compound (DA-1-1) 1.94g that purity is 99%.

Then, to dividing the there-necked flask having got the Pd/C of 0.3g to carry out nitrogen replacement, adding wherein through the degassed ethanol 40ml of oxygen, stirring.Compound (DA-1-1) 1.94g is made an addition in this container, is cooled to 0 DEG C, stir 5 minutes.After stirring, in reaction soln, slowly drip hydrazine monohydrate 5ml.

Stir 3 hours at 0 DEG C, at room temperature stir 6 hours, reaction is finished.Add ethyl acetate 100ml and THF80ml, then add pure water 60ml, carried out separatory.After again carrying out separatory with pure water, concentrated, obtained with the form of yellow ~ white solid compound (DA-1) 1.5g that purity is 99%.

[embodiment 1-2: the synthesis of compound (DA-2)]

The compound represented by following formula (DA-2) is synthesized according to following flow process 2.

[changing 27]

Make 2-chloro-5-nitropyridine 2.68g be suspended in toluene 25ml, add triethylamine 1.99g wherein.To make N, the solution that N '-dimethyl-ethylenediamine 0.51g is dissolved in chloroform 2ml slowly drips in its container.At room temperature stir after 30 minutes, stir 12 hours at 80 DEG C.Now, along with reaction is carried out, yellow solid is separated out.After cooling, this solid is filtered, after fully washing with water, utilize ethyl acetate to remove toluene.Make this solid drying, obtain compound (DA-2-1) 1.69g that purity is 96%.

Then, to dividing the there-necked flask having got the Pd/C of 0.3g to carry out nitrogen replacement, adding wherein through the degassed ethanol 40ml of oxygen, stirring.Compound (DA-2-1) 1.69g is made an addition in this container, is cooled to 0 DEG C, stir 5 minutes.After stirring, in reaction soln, slowly drip hydrazine monohydrate 5ml.

Stir 3 hours at 0 DEG C, at room temperature stir 6 hours, reaction is finished.Add ethyl acetate 100ml and THF80ml, then add pure water 60ml, carried out separatory.After again carrying out separatory with pure water, concentrated, obtained with the form of yellow solid compound (DA-2) 1.18g that purity is 97%.

[embodiment 1-3: the synthesis of compound (DA-3)]

The compound represented by following formula (DA-3) is synthesized according to following flow process 3.

[changing 28]

Make 2-chloro-5-nitro-pyrimidine 2.82g be suspended in toluene 25ml, add triethylamine 1.99g wherein.The solution that piperazine 0.5g is dissolved in chloroform 2ml is slowly dripped in its container.At room temperature stir after 30 minutes, stir 12 hours at 80 DEG C.Now, along with reaction is carried out, yellow solid is separated out.After cooling, this solid is filtered, after fully washing with water, utilize ethyl acetate to remove toluene.Make this solid drying, obtain compound (DA-3-1) 1.51g that purity is 98%.

Then, to dividing the there-necked flask having got the Pd/C of 0.3g to carry out nitrogen replacement, adding wherein through the degassed ethanol 40ml of oxygen, stirring.Compound (DA-3-1) 1.51g is made an addition in its container, is cooled to 0 DEG C, stir 5 minutes.After stirring, in reaction soln, slowly drip hydrazine monohydrate 5ml.

Stir 3 hours at 0 DEG C, at room temperature stir 6 hours, reaction is finished.Add ethyl acetate 100ml and THF80ml, then add pure water 60ml, carried out separatory.After again carrying out separatory with pure water, concentrated, obtained with the form of yellow solid compound (DA-3) 1.02g that purity is 98%.

[embodiment 1-4: the synthesis of compound (DA-4)]

The compound represented by following formula (DA-4) is synthesized according to following flow process 4.

[changing 29]

Make 4-chloro-2-nitropyridine 2.5g be suspended in toluene 25ml, add triethylamine 1.88g wherein.The solution that piperazine 0.5g is dissolved in chloroform 2ml is slowly dripped in its container.At room temperature stir after 30 minutes, stir 12 hours at 80 DEG C.Now, along with reaction is carried out, yellow solid is separated out.After cooling, this solid is filtered, after fully washing with water, utilize ethyl acetate to remove toluene.Make this solid drying, obtain compound (DA-4-1) 1.78g that purity is 96%.

Then, three mouthfuls that point to have got the Pd/C of 0.3g are burnt till and carries out nitrogen replacement, add wherein through the degassed ethanol 40ml of oxygen, stir.Compound (DA-4-1) 1.78g is made an addition in its container, is cooled to 0 DEG C, stir 5 minutes.After stirring, in this reaction soln, slowly drip hydrazine monohydrate 5ml.

Stir 3 hours at 0 DEG C, at room temperature stir 6 hours, reaction is finished.Add ethyl acetate 100ml and THF80ml, then add pure water 60ml, carried out separatory.After again carrying out separatory with pure water, concentrated, obtaining purity with the form of yellow ~ white solid is 98% compound (DA-4) 1.44g.

[embodiment 1-5: the synthesis of compound (DC-1)]

The compound represented by following formula (DC-1) is synthesized according to following flow process 5.

[changing 30]

Make compound (DA-1) 2.7g be suspended in pure water 25ml, after adding potassium hydroxide 5.6g, bromoacetic acid 13.9g wherein, stir 12 hours at 90 DEG C.Now, along with reaction is carried out, be changed to dark brown.After cooling, be fed in cold concentrated hydrochloric acid 100mL by this reaction solution, the solid obtained carrying out redeposition filters, and fully washs with water.Make this solid drying, obtain compound (DC-1-1) 3.6g that purity is 98%.

Then, compound (DC-1-1) 3.6g, diacetyl oxide 20mL are made an addition in container, stir 6 hours at 60 DEG C.The solid of separating out after cooling is filtered, obtains with the form of yellow ~ white solid compound (DC-1) 2.2g that purity is 98%.

The synthesis > of < polymkeric substance

[embodiment 2-1: the synthesis of polyamic acid (P1)]

Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride 50 molar part and pyromellitic acid anhydride 50 molar part, as Ursol D 50 molar part of diamines and compound (DA-1) 50 molar part, be dissolved in METHYLPYRROLIDONE (NMP), at 60 DEG C, carry out reaction in 6 hours, obtain the solution of the polyamic acid containing 20 % by weight.The polyamic acid solution of gained is divided and takes a morsel, add NMP and make the solution that polyamic acid concentration is 10 % by weight, measure and the soltion viscosity that obtains is 80mPas.

[embodiment 2-2 ~ embodiment 2-28 and synthesis example 2-29 ~ synthesis example 2-32]

Except by except the kind of used tetracarboxylic dianhydride and diamines and quantitative change are more as described in following table 1, with the mode identical with described embodiment 2-1 synthesizing polyamides acid (P2) ~ polyamic acid (P32) respectively.

[table 1]

In table 1, the usage ratio [molar part] of the numeric representation in the parantheses of tetracarboxylic dianhydride and diamines for total 100 molar part of the tetracarboxylic dianhydride for the synthesis of polymkeric substance.Abbreviation in table 1 is respectively following implication.

< tetracarboxylic dianhydride >

T-1:2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride

T-2: pyromellitic acid anhydride

T-3:1,2,3,4-tetramethylene tetracarboxylic dianhydride

T-4: TOPOT 2,2′ p phenylenebis (trimellitic acid monoesters acid anhydride)

T-5:1R, 2S, 4S, 5R-1,2,4,5-cyclopentanetetracarboxylic dianhydride

T-6: ethylenediamine tetraacetic acid (EDTA) dianhydride

< diamines >

D-1: Ursol D

D-2:4,4 '-diamino-diphenyl ether

D-3:3,5-diaminobenzoic acid

D-4:4-aminophenyl-4 '-Aminobenzoate

D-5: the compound represented by following formula (d-5)

D-6: the compound represented by following formula (d-6)

D-7: the compound represented by following formula (d-7)

DA-5: the compound represented by following formula (DA-5)

DA-6: the compound represented by following formula (DA-6)

[changing 31]

[embodiment 1A]

(1) preparation of liquid crystal aligning agent

In the polyamic acid (P1) obtained in as the described embodiment 2-1 of polymkeric substance, add NMP and ethylene glycol butyl ether (butylcellosolve, BC) as solvent, the solution that solvent composition is NMP: BC=50: 50 (weight ratios), solid component concentration is 6.0 % by weight is made.Use aperture is the strainer of 1 μm, is filtered by this solution, prepares liquid crystal aligning agent (S1) whereby.

(2) manufacture of friction orientation liquid crystal display device

Be on the glass substrate of 1mm in the thickness that one side has a chromium electrode being set to comb teeth-shaped wherein, utilize turner to be coated with the liquid crystal aligning agent (S1) of described preparation.Then, after the hot-plate of 80 DEG C carries out the prebake conditions of 1 minute, the hot-plate of 230 DEG C carries out toast after 10 minutes, form thickness and be about film.For formed coated surface, use the friction machine with the roller being wound with nylon cloth, carry out friction treatment with the translational speed 25mm/ second of the rotating speed 1,000rpm of roller, platform, hair press-in length 0.4mm, give liquid crystal aligning ability.And then, this substrate is carried out 1 minute ultrasonic washing in ultrapure water, carry out in 100 DEG C of cleaning ovens 10 minutes dry, be manufactured on there is comb teeth-shaped chromium electrode face on there is the substrate of liquid crystal orientation film.To there is the substrate of this liquid crystal orientation film as " substrate A ".

In addition, in the one side that the thickness without electrode is the glass substrate of 1mm, to form the film of liquid crystal aligning agent (S1) with described identical mode, carry out friction treatment, washing, drying, be manufactured on wherein one side and have the substrate of liquid crystal orientation film.To there is the substrate of this liquid crystal orientation film as " substrate B ".

Then, in the outer rim with the face of liquid crystal orientation film of substrate A, coating adds has diameter to be after the epoxy resin adhesive of the alumina balls of 5.5 μm, antiparallel mode is become with the frictional direction in each liquid crystal orientation film, via gap by 2 pieces of substrate A, B subtend configurations, make outer edge against each other and crimp, making adhesive hardens.Then, to between a pair substrate, nematic liquid crystal (Merck (Merck) company manufacture is filled in liquid crystal injecting port, MLC-2042) after, utilize acrylic acid series photo-hardening caking agent to be sealed by liquid crystal injecting port, manufacture IPS type liquid crystal cells whereby.

(3) evaluation of reliability

Use the liquid crystal cells manufactured in described (2) to evaluate reliability.Evaluate as follows.First, for described liquid crystal cells, after applying the voltage of 5V with the application time of 60 microseconds, the span of 167 milliseconds, measure the voltage retention (VHR1) after 167 milliseconds from applying to remove.Then, after leaving standstill 200 hours in 80 DEG C of baking ovens of liquid crystal cells under photodiode (LightEmittingDiode, LED) light irradiation, at room temperature leave standstill and naturally cool to room temperature.After cooling, after with the application time of 60 microseconds, the span of 167 milliseconds liquid crystal cells being applied to the voltage of 5V, measure the voltage retention (VHR2) after 167 milliseconds from applying to remove.In addition, determinator is " VHR-1 " that use Dongyang Te Kenika (ToyoTechnica) (stock) to manufacture.Utilize following numerical expression (2) to calculate the velocity of variation (Δ VHR) of VHR now, evaluate reliability according to Δ VHR.About evaluation, situation Δ VHR being less than 1% is judged to be reliability " good (◎) ", by more than 1% and the situation being less than 2% is judged to be reliability " can (zero) ", the situation of more than 2% is judged to be reliability " bad (×) ".Its result is, is reliability " well " in embodiment 1A.

ΔVHR[％]＝(VHR1-VHR2)/(VHR1)×100(2)

(4) evaluation of liquid crystal aligning

To the liquid crystal cells manufactured in described (2), the presence or absence of abnormal area when utilizing polarizing microscope to observe on-off (apply remove) voltage, the situation in region without exception is judged to be liquid crystal aligning " well ", even if the situation that there is 1 abnormal area is judged to be liquid crystal aligning " bad ".Its result is, the liquid crystal aligning of the liquid crystal cells of this embodiment is " well ".

(5) image retention characteristic (image retention characteristic)

Except as substrate, be used in wherein one side have the patterned metal electrode (electrode a and electrode b) comprising 2 systems of chromium for comb teeth-shaped glass substrate, with the subtend glass substrate not arranging electrode as beyond a pair, manufacture IPS type liquid crystal cells in the mode identical with described (2).Then, at the two sides, outside of the substrate of liquid crystal cells laminating Polarizer, liquid crystal display device is manufactured.This IPS type liquid crystal display device is positioned over 25 DEG C, under the environment of 1 air pressure, voltage is not applied to electrode b, electrode a is applied to the resultant voltage 2 hours of voltage of alternating current 3.5V and volts DS 5V.Then, at once the voltage exchanging 4V is applied to electrode a and electrode b these two.Measure from start to apply the moment of the voltage exchanging 4V to two electrodes, until with the visual time that cannot confirm again till the difference of the photopermeability of electrode a and electrode b.Be image retention evaluating characteristics when being less than 100 seconds by this time be " well ", the image retention evaluating characteristics by more than 100 seconds and when being less than 150 seconds is "available", and is " bad " by image retention evaluating characteristics when more than 150 seconds.Its result is, is the result of image retention characteristic " well " in the liquid crystal cells of embodiment 1A.

[embodiment 2A ~ embodiment 11A, embodiment 28A and comparative example 1, comparative example 2]

Except the kind of used polymkeric substance being changed to as described in Table 2, prepare liquid crystal aligning agent (S2) ~ liquid crystal aligning agent (S11) and liquid crystal aligning agent (S28) ~ liquid crystal aligning agent (S30) respectively with the solvent ratio identical with described embodiment 1A and solid component concentration.In addition, use each liquid crystal aligning agent, manufacture liquid crystal cells in the mode identical with embodiment 1A, and use the liquid crystal cells of gained to carry out various evaluation.The results are shown in following table 2.

[embodiment 12A]

(1) preparation of liquid crystal aligning agent

Except the kind of used polymkeric substance being changed to except polyamic acid (P12), with the solvent identical with described embodiment 1A when solid component concentration prepare liquid crystal aligning agent (S12).

(2) manufacture of optical alignment film liquid crystal display device

One side has the thickness of the chromium electrode being set to comb teeth-shaped is wherein on the glass substrate of 1mm, the mode of 0.1 μm is become with thickness, utilize turner to be coated with the liquid crystal aligning agent (S12) of described preparation, after the hot-plate of 80 DEG C carries out the prebake conditions of 1 minute, the hot-plate of 230 DEG C carries out the rear baking of 10 minutes, forms film.To there is the substrate of this film as " substrate A ".

In addition, be the one side of the glass substrate of 1mm at the thickness without electrode, to form the film of liquid crystal aligning agent (S12) with described identical mode.To there is the substrate of this film as " substrate B ".

Then, for the film coated surface of substrate A and substrate B, use Hg-Xe lamp, irradiate the polarisation ultraviolet 10,000J/m comprising the open-wire line of 254nm from substrate normal direction ², form liquid crystal orientation film.

Then, for a pair substrate carrying out described photo-irradiation treatment, liquid crystal injecting port at the margin residual in the face being formed with liquid crystal orientation film, after being coated with and adding by screen painting and have diameter to be the epoxy resin adhesive of the alumina balls of 5.5 μm, antiparallel mode is become with the projecting direction of polarizing axis during rayed on real estate, by the crimping of substrate overlap, at 150 DEG C, spend 1 hour make caking agent carry out heat embrittlement.Then, in liquid crystal injecting port, fill nematic liquid crystal (Merck (Merck) company manufactures, MLC-7028) between a pair substrate after, utilize epoxy caking agent to be sealed by liquid crystal injecting port.And then, in order to remove flow orientation during Liquid crystal pour, after it being heated at 150 DEG C, be slowly cooled to room temperature.Then, liquid crystal display device is made at the two sides, outside of substrate laminating Polarizer.

(3) evaluation of reliability

Except using the liquid crystal display device of manufacture in described (2), carrying out the evaluation of reliability in the mode identical with described embodiment 1A, result, Δ VHR=1.6% in this embodiment, is the result of reliability "available".

(4) evaluation of liquid crystal aligning

Except using the liquid crystal display device of manufacture in described (2), carrying out the evaluation of reliability in the mode identical with described embodiment 1A, result, is the result of liquid crystal aligning " well " in this embodiment.

(5) image retention characteristic (image retention characteristic)

Except using the aspect of liquid crystal aligning agent (S12), evaluating image retention characteristic in the mode identical with described embodiment 1A, result, is the evaluation of image retention characteristic "available" in this embodiment.

[embodiment 13A ~ embodiment 27A and comparative example 3, embodiment 4]

Except the kind of used polymkeric substance is changed to as described in Table 2, with the solvent identical with described embodiment 1A when solid component concentration prepare liquid crystal aligning agent (S13) ~ liquid crystal aligning agent (S27), liquid crystal aligning agent (S31), liquid crystal aligning agent (S32) respectively.In addition, use each liquid crystal aligning agent, manufacture liquid crystal cells in the mode identical with embodiment 12A, and use the liquid crystal cells of gained to carry out various evaluation.The results are shown in following table 2.

[table 2]

As shown in table 2, be in embodiment 1A ~ embodiment 28A: even if long-time (200 hours) are exposed to after under photostress and thermal stresses environment, the decline of voltage retention is still few, and reliability is good.On the other hand, in comparative example 1 ~ comparative example 4, due to the imparting of photostress and thermal stresses, voltage retention significantly declines, and is the evaluation of reliability " bad ".

In addition, about liquid crystal aligning, all do not observe orientation bad in embodiment 1A ~ embodiment 28A, about image retention characteristic, in embodiment, arbitrary sample is also the evaluation of " well " or "available".

Confirm as previously discussed: the liquid crystal orientation film with the structure used in embodiment can not upset liquid crystal aligning, there is the characteristic that reliability is high.

Claims (14)

1. a liquid crystal aligning agent, is characterized in that: the polymkeric substance (P) containing the part-structure had on main chain represented by following formula (1),

*-X ¹-Y ¹-X ¹-*(1)

In formula (1), X ¹for divalent organic radical, Y ¹for divalent concatenating group or singly-bound; Wherein, 2 X ¹at least one be divalent aromatic heterocycle, at 2 X ¹only one of them is divalent aromatic heterocycle when, Y ¹for having the divalent concatenating group of more than 1 nitrogen-atoms, and 2 X ¹be binding on Y ¹in identical or different nitrogen-atoms on; 2 X ¹can identical also can be different; " * " represents associative key.

2. liquid crystal aligning agent according to claim 1, is characterized in that: described Y ¹for having divalent concatenating group or the singly-bound of more than 1 nitrogen-atoms,

At described Y ¹when for having the divalent concatenating group of more than 1 nitrogen-atoms, 2 X in described formula (1) ¹be binding on described Y ¹in identical or different nitrogen-atoms on.

3. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: described part-structure is represented by following formula (2),

In formula (2), X ¹for divalent organic radical, wherein, 2 X ¹at least one be divalent aromatic heterocycle; R ¹for alkane two base or the cyclohexylidene of singly-bound, carbon number 1 ~ 6, R ²for the alkyl of hydrogen atom or carbon number 1 ~ 6, or 2 R ²mutual bond and with 2 nitrogen-atoms and R ¹form the divalent ester ring type heterocyclic radical of carbon number 2 ~ 10 together; 2 X ¹can identical also can be different, 2 R ²can identical also can be different; P is 0 or 1; " * " represents associative key.

4. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: described polymkeric substance (P) is for being selected from least one in the cohort that is made up of polyamic acid, poly amic acid ester and polyimide.

5. liquid crystal aligning agent according to claim 4, is characterized in that: described polymkeric substance (P) is polymerization by comprising the compound represented by following formula (3) in monomer composition and the polymkeric substance that obtains,

In formula (3), X ¹for divalent organic radical, wherein, 2 X ¹at least one be divalent aromatic heterocycle; Z ¹for the base represented by one-level amino or following formula (z-1);

In formula (z-1), " * " represents and X ¹associative key;

R ¹for alkane two base or the cyclohexylidene of singly-bound, carbon number 1 ~ 6, R ²for the alkyl of hydrogen atom or carbon number 1 ~ 6, or 2 R ²mutual bond and with 2 nitrogen-atoms and R ¹form the divalent ester ring type heterocyclic radical of carbon number 2 ~ 10 together; 2 X ¹can identical also can be different, 2 R ²can identical also can be different; P is 0 or 1.

6. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: 2 X in described formula (1) ¹for divalent aromatic heterocycle.

7. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: described Y ¹divalent concatenating group or the singly-bound with more than 2 nitrogen-atoms,

In described Y ¹when for having the divalent concatenating group of more than 2 nitrogen-atoms, described 2 X ¹be binding on described Y ¹in different nitrogen-atoms on.

8. a manufacture method for liquid crystal orientation film, is characterized in that comprising: use liquid crystal aligning agent according to any one of claim 1 to 7 to form the step of film; And rayed is carried out to give the step of liquid crystal aligning ability to described film.

9. a manufacture method for liquid crystal orientation film, is characterized in that comprising: use liquid crystal aligning agent according to any one of claim 1 to 7 to form the step of film; And friction treatment is carried out to give the step of liquid crystal aligning ability to described film.

10. a liquid crystal orientation film, is characterized in that: it utilizes liquid crystal aligning agent according to any one of claim 1 to 7 to be formed.

11. 1 kinds of liquid crystal display device, is characterized in that: comprise liquid crystal orientation film according to claim 10.

12. 1 kinds of polymkeric substance, is characterized in that: it for being selected from least one in the cohort that is made up of polyamic acid, poly amic acid ester and polyimide, and has the part-structure represented by following formula (1) on main chain,

*-X ¹-Y ¹-X ¹-*(1)

In formula (1), X ¹for divalent organic radical, Y ¹for divalent concatenating group or singly-bound; Wherein, 2 X ¹at least one be divalent aromatic heterocycle, at 2 X ¹only one of them is divalent aromatic heterocycle when, Y ¹for having the divalent concatenating group of more than 1 nitrogen-atoms, and 2 X ¹be binding on Y ¹in identical or different nitrogen-atoms on; 2 X ¹can identical also can be different; " * " represents associative key.

13. polymkeric substance according to claim 12, is characterized in that: described part-structure is represented by following formula (2),

In formula (2), X ¹for divalent organic radical, wherein, 2 X ¹at least one be divalent aromatic heterocycle; R ¹for alkane two base or the cyclohexylidene of singly-bound, carbon number 1 ~ 6, R ²for the alkyl of hydrogen atom or carbon number 1 ~ 6, or 2 R ²mutual bond and with 2 nitrogen-atoms and R ¹form the divalent ester ring type heterocyclic radical of carbon number 2 ~ 10 together; 2 X ¹can identical also can be different, 2 R ²can identical also can be different; P is 0 or 1; " * " represents associative key.

14. 1 kinds of compounds, is characterized in that, it is represented by following formula (3):

In formula (3), X ¹for divalent organic radical, wherein, 2 X ¹at least one be divalent aromatic heterocycle; Z ¹for the group represented by one-level amino or following formula (z-1);

In formula (z-1), " * " represents and X ¹associative key;

R ¹for alkane two base or the cyclohexylidene of singly-bound, carbon number 1 ~ 6, R ²for the alkyl of hydrogen atom or carbon number 1 ~ 6, or 2 R ²mutual bond and with 2 nitrogen-atoms and R ¹form the divalent ester ring type heterocyclic radical of carbon number 2 ~ 10 together; 2 X ¹can identical also can be different, 2 R ²can identical also can be different; P is 0 or 1.