CN103666487A

CN103666487A - Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element

Info

Publication number: CN103666487A
Application number: CN201310395480.1A
Authority: CN
Inventors: 角谷宪一; 徳久博昭; 西川通则
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2012-09-14
Filing date: 2013-09-03
Publication date: 2014-03-26
Anticipated expiration: 2033-09-03
Also published as: KR20140035806A; KR101985261B1; CN103666487B; JP2014074886A; TW201410740A; JP6127721B2; TWI631149B

Abstract

The invention relates to a liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display element, wherein the storage stability of the long-term low-temperature storage of substrates is good and the coating property of substrate is excellent. The liquid crystal aligning agent provided by the invention comprises a polymer (A) selected from at least one out of groups formed by polyamic acid, polyimide and polyamide acid ester obtained through the reaction of tetracarboxylic acid dianhydride with diamine, with the presence of specific diamine; and a specific solvent (B).

Description

Crystal aligning agent, liquid crystal orienting film and liquid crystal display device

Technical field

The present invention relates to a kind of crystal aligning agent, liquid crystal orienting film and liquid crystal display device, specifically relate to crystal aligning agent and the liquid crystal orienting film of making of this crystal aligning agent and liquid crystal display device that a kind of storage stability is good.

Background technology

In the past, liquid crystal display device has been developed electrode structure or the liquid crystal display device of the multiple type of drive that the physical property of the liquid crystal molecule that uses etc. is different, for example known have a twisted nematic (Twisted Nematic, TN) type or STN Super TN (Super Twisted Nematic, STN) type, vertical orientation (Vertical Alignment, VA) type, coplanar switching (In-Plane Switching, IPS) type, fringing field switches (Fringe Field Switching, FFS) type, optical compensation curved (Optically Compensated Bend, OCB) the various liquid crystal display device such as type.These liquid crystal display device have for making the liquid crystal orienting film of liquid crystal alignment.With regard to thermotolerance, physical strength, with the good aspect of the various characteristicses such as affinity of liquid crystal with regard to, the material of liquid crystal orienting film is used polyamic acid or polyimide conventionally.

In crystal aligning agent, component of polymer is dissolved in solvent, by this crystal aligning agent is coated on substrate, heats and forms liquid crystal orienting film.Herein, for the object that makes polymkeric substance uniform dissolution, the solvent of crystal aligning agent is used non-proton property polar solvents such as METHYLPYRROLIDONE or gamma-butyrolactone conventionally.In addition, the coating (printing) of the crystal aligning agent when making crystal aligning agent coat on substrate is good, the solvent of crystal aligning agent conventionally by the good solvent such as the lower poor solvent of the surface tension such as ethylene glycol butyl ether and these polyamic acids etc. also for example, with (refer to Patent Document 1 or patent documentation 2).

[prior art document]

[patent documentation]

[patent documentation 1] Japanese Patent Laid-Open 2010-97188 communique

[patent documentation 2] Japanese Patent Laid-Open 2010-156934 communique

Crystal aligning agent after manufacture to during till shipment, (for example, at-15 ℃) keeping under utmost point low temperature environment in order to prevent the deteriorated of polyamic acid or polyimide conventionally.But the crystal aligning agent of taking care of at low temperatures for a long time can produce precipitate in solution.In addition, once the precipitate of separating out is difficult to dissolve again, in the manufacture processing procedure of liquid crystal display device, there are the misgivings cause the unfavorable conditions such as printing is bad.The reason that this precipitate produces is also uncertain, but is speculated as: the ethylene glycol butyl ether using usually used as the solvent composition of crystal aligning agent is a reason.Therefore, require the to get a replacement new organic solvent of ethylene glycol butyl ether is used as for making the solvent good to the coating of substrate.

Summary of the invention

The present invention forms in view of above-mentioned problem, and main purpose is to provide a kind of storage stability to long-term low temperature keeping good, and the crystal aligning agent good to the coating of substrate.

The people such as the inventor carry out active research in order to reach the problem of prior art as above, found that, by using specific polymkeric substance as the component of polymer of crystal aligning agent, and use specific solvent as at least a portion of solvent composition, can solve above-mentioned problem, thereby complete the present invention.Particularly, by the present invention, provide following crystal aligning agent, liquid crystal orienting film and liquid crystal display device.

In the 1st technical scheme of the present invention, provide a kind of crystal aligning agent, it contains: choosing freely makes tetracarboxylic dianhydride and diamine reactant and the polyamic acid that obtains, polyimide and poly amic acid ester form at least one polymkeric substance (A) in cohort, and solvent, described polymkeric substance (A) is to use diamines and the polymkeric substance that obtains, this diamines comprises freely following formula (d-1)～formula (d-4) represented at least one in cohort that compound forms respectively of choosing, and described solvent comprises specific solvent (B), this specific solvent (B) is freely following formula (b-1)～formula (b-3) represented at least one in cohort that compound forms respectively of choosing.

[changing 1]

(in formula (d-1), X ¹and X ²be independently respectively singly-bound ,-O-,-S-,-OCO-or-COO-, Y ¹for Sauerstoffatom or sulphur atom, R ¹and R ²be alkane two bases (alkanediyl) of carbon number 1～3 independently respectively; N1 be 0 or 1, n2 and n3 in the situation that of n1=0 for meeting the integer of n2+n3=2, the in the situation that of n1=1, be n2=n3=1; In formula (d-2), X ³for singly-bound ,-O-or-S-, the integer that m1 is 0～3; M2 is 1～12 integer in the situation that of m1=0, in the situation that the integer that m1 is 1～3 is m2=2; In formula (d-3), R ³for the straight chain shape of carbon number 1～12 or 1 valency alkyl of branch-like, R ⁴for the straight chain shape of hydrogen atom or carbon number 1～12 or 1 valency alkyl of branch-like, R ⁵and R ⁶be hydrogen atom or methyl independently respectively; In formula (d-4), X ⁴and X ⁵be independently respectively singly-bound ,-O-,-COO-or-OCO-, R ⁷alkane two bases for carbon number 1～3; A is 0 or 1, the b integer that is 0～2, the integer that c is 1～20, and k is 0 or 1; Wherein, a and b can not be 0 simultaneously.)

[changing 2]

(in formula (b-1), R ⁸and R ¹⁰be 1 valency alkyl of carbon number 1～3 independently respectively, R ⁹alkane two bases for carbon number 2～5; In formula (b-2), R ¹¹1 valency group, the straight chain shape of carbon number 3～5 or at least 1 hydrogen atom of branch-like alkyl between the C-C for the straight chain shape at carbon number 3～5 or branch-like alkyl with 1 " O-" replaces the 1 valency group that forms or the branch-like alkyl of carbon number 3～5 through hydroxyl; In formula (b-3), X ⁶for-C (OH) R ^a-(wherein, R ^afor methyl or ethyl) ,-CO-or-(wherein, * represents and R COO-* ¹²associative key), R ¹²alkyl for carbon number 1～4.)

The polymkeric substance (A) obtaining using the specific diamines described in utilizing is as at least a portion of the component of polymer of crystal aligning agent, and the one-tenth that comprises described specific solvent (B) is divided in the situation of solvent composition, the in the situation that of being convenient to take care of under low temperature environment for a long time, also be difficult to produce precipitate in orientation agent, storage stability is good.In addition, crystal aligning agent is also good to the coating of substrate.

The present invention is in the 2nd technical scheme, following crystal aligning agent is provided, it contains and selects free polyamic acid, polyimide and poly amic acid ester form at least one polymkeric substance in cohort, solvent, and additive, described solvent comprises specific solvent (B), this specific solvent (B) is freely described formula (b-1)～formula (b-3) represented at least one in cohort that compound forms respectively of choosing, and contain amine compound (C) as described additive, this amine compound (C) has 1 one-level amino and nitrogenous heteroaromatic in molecule, and described primary amine base is binding on chain alkyl or ester ring type alkyl.

Comprise and select free polyamic acid, polyimide and poly amic acid ester to form at least one polymkeric substance (A) in cohort crystal aligning agent as at least a portion of component of polymer, in the situation that the one-tenth that comprises described amine compound (C) is divided into additive, when crystal aligning agent is taken care of for a long time under low temperature environment, can produce the problem that described amine compound (C) is separated out in orientation agent.In this respect, crystal aligning agent according to the 2nd technical scheme of the present invention, by the one-tenth that comprises described specific solvent (B) is divided into solvent composition, the in the situation that of keeping under low temperature environment even if long-term, be also difficult to produce precipitate in orientation agent, storage stability is good.In addition, crystal aligning agent is also good to the coating of substrate.

In described the 2nd technical scheme, described amine compound (C) can be made as to the represented compound of following formula (c-1).

[changing 3]

H ₂N-A ¹-A ² (c-1)

(in formula (c-1), A ¹for thering is the divalent organic radical of chain alkyl or ester ring type alkyl, A ²for nitrogenous heteroaromatic.)

In addition, in described the 2nd technical scheme, be preferably described polymkeric substance (A) is made as to the polymkeric substance with carboxyl.In this situation, the quantity that is preferably the carboxyl that described polymkeric substance (A) is had is made as take each repeating unit of the described polymkeric substance of mean value (A) and is 0.1～3.In addition, be preferably and be made as 1 mole of the carboxyl having with respect to described polymkeric substance (A) and comprise 0.01 mole～2 moles of described amine compound (C).

The present invention in another technical scheme, the liquid crystal display device that a kind of liquid crystal orienting film being formed by described crystal aligning agent is provided and comprises this liquid crystal orienting film.Liquid crystal orienting film of the present invention is owing to being to form with the crystal aligning agent of described the 1st technical scheme or the crystal aligning agent of the 2nd technical scheme, therefore, the in the situation that of being convenient to crystal aligning agent to take care of under low temperature environment for a long time, coating (printing) is also good.In addition, in the situation that manufacturing liquid crystal display device with this liquid crystal orienting film, can in manufacturing processing procedure, reduce printing bad, the yield that result can realize goods improves.

Embodiment

Crystal aligning agent of the present invention comprises and selects free polyamic acid, polyimide and poly amic acid ester to form at least one polymkeric substance (A) in cohort as component of polymer, is prepared into this polymkeric substance (A) and disperses or be dissolved in the liquid composition forming in solvent.Below, crystal aligning agent of the present invention is described.

< < polymkeric substance (A) > >

< polyamic acid >

Polyamic acid of the present invention can be by obtaining tetracarboxylic dianhydride and diamine reactant.

[tetracarboxylic dianhydride]

For the synthesis of the tetracarboxylic dianhydride of polyamic acid of the present invention such as enumerating: aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.As these tetracarboxylic dianhydrides' concrete example,

Aliphatics tetracarboxylic dianhydride for example can enumerate: 1,2,3,4-butane tetracarboxylic acid dianhydride etc.;

Ester ring type tetracarboxylic dianhydride for example can enumerate: 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic base NSC 60134 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-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyls-2-carboxyl methyl norbornane-2: 3, 5: 6-dianhydride, 4, 9-dioxa three ring [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone, hexanaphthene tetracarboxylic dianhydride, following formula (t-1)

[change 4 ］

(in formula (t-1), X ⁷, X ⁸, X ⁹and X ¹⁰be singly-bound or methylene radical independently respectively, the integer that j is 1～3)

Represented compound etc.;

Aromatic tetracarboxylic acid's dianhydride is such as enumerating: pyromellitic acid anhydride etc., in addition, also can be used the tetracarboxylic dianhydride who records in Japanese Patent Laid-Open 2010-97188 communique.In addition, tetracarboxylic dianhydride can or be used in combination two or more a kind of the independent use of described compound.

Herein, the represented compound of described formula (t-1) for example can be enumerated: dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, dicyclo [4.3.0] nonane-2,4,7,9-tetracarboxylic dianhydride, dicyclo [4.4.0] decane-2,4,7,9-tetracarboxylic dianhydride, dicyclo [4.4.0] decane-2,4,8,10-tetracarboxylic dianhydride, three ring [6.3.0.0 (2,6)] undecane-3,5,9,11-tetracarboxylic dianhydride etc.Wherein, with regard to the viewpoint of the stability of LCD alignment, the represented compound of described formula (t-1) is preferably dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride.

In described compound, tetracarboxylic dianhydride for the synthesis of polyamic acid of the present invention is preferably the freely represented compound, 1 of described formula (t-1) of at least use choosing, 2,3,4-tetramethylene tetracarboxylic dianhydride and pyromellitic acid anhydride form at least one compound (below also referred to as specific tetracarboxylic dianhydride) in cohort.In the situation that using described specific tetracarboxylic dianhydride, with respect to the total amount of the tetracarboxylic dianhydride for the synthesis of polyamic acid, specific tetracarboxylic dianhydride's total usage quantity is preferably more than 10 % by mole, more preferably 20 % by mole～100 % by mole.

[diamines]

For the synthesis of the diamines of polyamic acid of the present invention be preferably comprise choosing freely represented represented represented compound and the represented compound of described formula (d-4) of compound, described formula (d-3) of compound, described formula (d-2) of described formula (d-1) form at least one diamines (below also referred to as " specific diamines ") in cohort.

(the represented compound of formula (d-1))

In described formula (d-1), R ¹and R ²alkane two bases of carbon number 1～3 for example can enumerate: methylene radical, ethylidene, propane-1,2-bis-bases, propane-1,3-bis-bases, propane-2,3-bis-bases etc.In these groups, be preferably methylene radical, ethylidene or propane-1,3-bis-bases.

X ¹and X ²for singly-bound ,-O-,-S-,-OCO-or-COO-.In addition X, ¹with X ²can be identical, also can be different.In these groups, be preferably singly-bound ,-O-or-S-.

Y ¹for Sauerstoffatom or sulphur atom.Be preferably Sauerstoffatom.

The in the situation that of n1=0,2 one-level amino that the represented compound of formula (d-1) has can be binding on same phenyl ring, also can be on 2 different phenyl ring 1 of each bond.On the other hand, the in the situation that of n1=1,2 one-level amino can be respectively on different phenyl ring 1 of each bond.

The bond position of the one-level amino on phenyl ring is not particularly limited.For example, in the situation that the one-level amino on phenyl ring is 1, with respect to other groups, the bond position of this one-level amino can be any of 2-position, 3-position, 4-position, is preferably 3-position or 4-position, more preferably 4-position.In addition, in the situation that the one-level amino on phenyl ring is 2, with respect to other groups, 2,4-position, 2 for example can be enumerated in the bond position of these one-level amino, and 5-position etc., are wherein preferably 2,4-position.

1 valency group or fluorine atom that hydrogen atom on the phenyl ring of the amino institute of one-level bond can be replaced by fluorine atom through 1 valency alkyl or at least 1 hydrogen atom on this alkyl of carbon number 1～10 replace.1 valency alkyl in this situation is such as enumerating: the aryl (phenyl, tolyl etc.) of the thiazolinyl of the alkyl of carbon number 1～10, carbon number 1～10, the cycloalkyl of carbon number 3～10, carbon number 5～10, the aralkyl (benzyl etc.) of carbon number 5～10 etc.

In addition, " alkyl " in this specification sheets is the implication that comprises chain alkyl, ester ring type alkyl and aromatic hydrocarbyl.In addition, so-called " chain alkyl ", refers on main chain containing ring texture, and only comprises straight chain shape alkyl and the branch-like alkyl of chain-like structure.In addition, chain-like structure can be saturated, also can be unsaturated.So-called " ester ring type alkyl ", is the structure that ring structure only comprises ester ring type hydrocarbon, and does not contain the alkyl of aromatic ring structure.But, do not need only to comprise the structure of ester ring type hydrocarbon, also comprise the alkyl that its part has chain-like structure.So-called " aromatic hydrocarbyl ", refers to and comprises aromatic ring structure as the alkyl of ring structure.Wherein, do not need only to comprise aromatic ring structure, can in its part, comprise the structure of chain-like structure or ester ring type hydrocarbon yet.

As the preferred concrete example of the represented compound of described formula (d-1), the compound of n1=0 for example can be enumerated: 4,4 '-diamino-diphenylamine, 2，4-diaminodiphenylamine etc.; the compound of n1=1 for example can be enumerated: 1, two (4-aminobenzyl) ureas of 3-, 1, two (the 4-amino-benzene ethyl) ureas of 3-, 1, two (3-aminobenzyl) ureas of 3-, 1-(4-aminobenzyl)-3-(4-amino-benzene ethyl) urea, 1, two (2-(4-amino-benzene oxygen) ethyl) ureas of 3-, 1, two (3-(4-amino-benzene oxygen) propyl group) ureas of 3-, 1, two (4-aminobenzyl) thiocarbamides of 3-, 1, two (2-aminobenzyl) ureas of 3-, 1, two (the 2-amino-benzene ethyl) ureas of 3-, 1, two (2-(the 2-amino benzoyl oxygen base) ethyl) ureas of 3-, 1, two (3-(2-amino benzoyl oxygen base) propyl group) ureas of 3-etc.In addition, the represented compound of described formula (d-1) can or be used in combination two or more a kind of the independent use of these compounds.

(the represented compound of formula (d-2))

In described formula (d-2), X ³for singly-bound ,-O-or-S-, be preferably singly-bound or-O-.

The in the situation that of m1=0, the integer that m2 is 1～12.In this situation, with regard to making the good viewpoint of the thermotolerance of resulting polymers, being preferably m2 is 1～10, more preferably 1～8.In addition, just keep good LCD alignment, and the good viewpoint of patience that makes to rub, be preferably m1=0, with regard to reducing the viewpoint of tilt angle of liquid crystal molecule, m1 is preferably 1～3 integer.

The bond position of the one-level amino on phenyl ring is not particularly limited, and with respect to other groups, each one-level amino is preferably 3-position or 4-position, more preferably 4-position.In addition 1 valency group or fluorine atom that, the hydrogen atom on the phenyl ring of the amino institute of one-level bond can be replaced by fluorine atom through 1 valency alkyl or at least 1 hydrogen atom on this alkyl of carbon number 1～10 replace.

The preferred concrete example of the compound that described formula (d-2) is represented for example can be enumerated: two (4-amino-benzene oxygen) methane, two (4-amino-benzene oxygen) ethane, two (4-amino-benzene oxygen) propane, two (4-amino-benzene oxygen) butane, two (4-amino-benzene oxygen) pentane, two (4-amino-benzene oxygen) hexane, two (4-amino-benzene oxygen) heptane, two (4-amino-benzene oxygen) octane, two (4-amino-benzene oxygen) nonane, two (4-amino-benzene oxygen) decane, two (4-aminophenyl) methane, two (4-aminophenyl) ethane, two (4-aminophenyl) propane, two (4-aminophenyl) butane, two (4-aminophenyl) pentane, two (4-aminophenyl) hexane, two (4-aminophenyl) heptane, two (4-aminophenyl) octane, two (4-aminophenyl) nonane, two (4-aminophenyl) decane, 1, two (the 4-aminophenyl alkylsulfonyl) propane of 3-, 1, two (4-aminophenyl alkylsulfonyl) butane of 4-etc.In addition, the represented compound of described formula (d-2) can or mix two or more to use a kind of the independent use of these illustrative compounds.

(the represented compound of formula (d-3))

In described formula (d-3), R ³for the straight chain shape of carbon number 1～12 or 1 valency alkyl of branch-like.R ³concrete example such as enumerating: the alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, octyl group, decyl; The thiazolinyl such as vinyl, allyl group; The cycloalkyl such as cyclopentyl, cyclohexyl; The aryl such as phenyl, tolyl; The aralkyl such as benzyl etc.R ³carbon number be preferably 1～6, more preferably 1～3.R ³be preferably chain alkyl, more preferably comprise the chain alkyl of carbon-to-carbon double bond, be especially preferably thiazolinyl.

R ⁴for the straight chain shape of hydrogen atom or carbon number 1～12 or 1 valency alkyl of branch-like.This alkyl can be enumerated: the aromatic hydrocarbyl of the chain alkyl of carbon number 1～12, the ester ring type alkyl of carbon number 3～12, carbon number 5～12, its concrete example can be enumerated described R ³explanation in illustrative group.R ⁴be preferably the chain alkyl of hydrogen atom or carbon number 1～12.In addition, R ⁴in alkyl be preferably carbon number 1～6, more preferably carbon number 1～3.

R ⁵and R ⁶be hydrogen atom or methyl independently respectively, be preferably and be hydrogen atom.

In the diamino-phenyl of described formula (d-3), the bond position of 2 one-level amino is not particularly limited, and with respect to the group with N-allylic structure being binding on phenyl ring, is preferably 2,4-position or 2,5-position, and more preferably 2,4-position.In addition 1 valency group or fluorine atom that, the hydrogen atom on the phenyl ring of the amino institute of one-level bond can be replaced by fluorine atom through 1 valency alkyl or at least 1 hydrogen atom on this alkyl of carbon number 1～10 replace.

The preferred concrete example of the compound that described formula (d-3) is represented for example can be enumerated: 2,4-diamino-N, N-diallyl aniline, 2,5-diamino-N, N-diallyl aniline, following formula (d-3-1)～formula (d-3-3) are distinguished represented compound etc.

［ changing 5 ］

(the represented compound of formula (d-4))

In formula (d-4), " X ⁴-(R ⁷-X ⁵) _k-" represented divalent group is preferably alkane two bases, *-O-, *-COO-or the *-O-C of carbon number 1～3 ₂h ₄-O-(wherein, having marked associative key and the diamino-phenyl bond of " * ").

Base " C _ch _2c+1" being preferably straight chain shape, its concrete example is such as enumerating: 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.

With respect to base " X ⁴", 2 one-level amino in diamino-phenyl are preferably 2,4-position or 3,5-position, and more preferably 2,4-position.In addition 1 valency group or fluorine atom that, the hydrogen atom on the phenyl ring of the amino institute of one-level bond can be replaced by fluorine atom through 1 valency alkyl or at least 1 hydrogen atom on this alkyl of carbon number 1～10 replace.

The preferred concrete example of the compound that described formula (d-4) is represented is such as enumerating the represented compound of following formula (d-4-1)～formula (d-4-11) difference etc.

［ changing 6 ］

During synthetic polyamic acid of the present invention, as specific diamines, can, according to the drive pattern of the liquid crystal display device of manufacturing, from described compound, suitably select to use.Particularly, by using the represented compound of described formula (d-1) as described specific diamines, can manufacture the crystal aligning agent that is suitable for fringing field switching (Fringe Field Switching, FFS) type liquid crystal display device.In addition, by use, select freely represented compound and represented at least one in cohort that compound forms of described formula (d-3) of described formula (d-2), can manufacture and be suitable for twisted nematic (Twisted Nematic, TN) crystal aligning agent of type liquid crystal display device, by using the represented compound of described formula (d-4), can manufacture the crystal aligning agent that is suitable for vertical orientation type liquid crystal display device.

(other diamines)

The diamines using for synthetic polyamic acid of the present invention can be used the compound (other diamines) beyond described specific diamines.These other diamines are such as enumerating: aliphatie diamine, ester ring type diamines, aromatic diamine, diamino organo-siloxane etc.As the concrete example of these other diamines, aliphatie diamine for example can be enumerated: m-xylene diamine, 1,3-propylene diamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine etc.;

Ester ring type diamines for example can be enumerated: Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene-bis (hexahydroaniline), 1, two (amino methyl) hexanaphthenes of 3-etc.;

Aromatic diamine for example can be enumerated: Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl thioether, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 2,7 diamin of luorene, 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 phenylene two isopropylidenes) dianiline, 4,4 '-(metaphenylene two isopropylidenes) dianiline, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-tolidine, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, 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, 3,5-diaminobenzoic acid, cholestane base oxygen base-3,5-diaminobenzene, cholesteryl oxygen base-3,5-diaminobenzene, cholestane base oxygen base-2,4-diaminobenzene, cholesteryl oxygen base-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid lanostane base ester, two (the 4-amino benzoyl oxygen base) cholestane of 3,6-, two (4-amino-benzene oxygen) cholestane of 3,6-, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethyl benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, two (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexanes of 1,1-, two (4-((aminophenyl) methyl) the phenyl)-4-heptyl hexanaphthenes of 1,1-, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptyl hexanaphthenes of 1,1-, two (4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) hexanaphthenes of 1,1-, 4-amino-benzylamine, 3-amino-benzylamine, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-etc.,

Diamino organo-siloxane for example can be enumerated: two (3-aminopropyl)-tetramethyl disiloxanes of 1,3-etc., in addition, can be used the diamines of recording in Japanese Patent Laid-Open 2010-97188 communique.In addition, these other diamines can be used alone a kind or two or more is used in combination.

In the situation that comprise following described in detail certain amines compound (C) in crystal aligning agent of the present invention as additive, be preferably to comprise and there is the diamines (below also referred to as " carboxylic diamines ") of carboxyl as at least a portion of described other diamines for the synthesis of polyamic acid.This carboxylic diamines is preferably aromatic diamine, particularly, and such as enumerating the represented compound of following formula (e1-1) and formula (e1-2) difference etc.

[changing 7]

(in formula (e1-1) and formula (e1-2), R ²⁰for the alkyl of halogen atom, carbon number 1～10 or the alkoxyl group of carbon number 1～10, Z ¹alkane two bases for singly-bound, Sauerstoffatom or carbon number 1～3; R2, r5 and r6 are respectively 1 or 2 integer independently, and r1, r3 and r4 are respectively 0～2 integer independently, and r7 and r8 are respectively independently for meeting 0～2 the integer of r7+r8=2; Wherein, r3+r5+r7≤5, r4+r6+r8≤5; In formula, there are a plurality of R ²⁰situation under, these R ²⁰there is independently described definition.)

About formula (e1-1) and formula (e1-2), R ²⁰in the alkyl of carbon number 1～10 such as enumerating: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl etc., these groups can be straight chain shapes, can be also branch-like.The alkoxyl group of carbon number 1～10 is such as enumerating: methoxyl group, oxyethyl group, propoxy-, butoxy, hexyloxy etc.

Z ¹in alkane two bases of carbon number 1～3 such as enumerating: methylene radical, ethylidene, trimethylene, propylidene etc.

R1, r3 and r4 are preferably 0 or 1, and more preferably 0.

As the concrete example of carboxylic diamines, the represented compound of following formula (e1-1) for example can be enumerated: 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid etc., the represented compound of following formula (e1-2) for example can be enumerated: 4, 4 '-benzidine-3, 3 '-dicarboxylic acid, 4, 4 '-benzidine-2, 2 '-dicarboxylic acid, 3, 3 '-benzidine-4, 4 '-dicarboxylic acid, 3, 3 '-benzidine-2, 4 '-dicarboxylic acid, 4, 4 '-diaminodiphenyl-methane-3, 3 '-dicarboxylic acid, 4, 4 '-benzidine-3-carboxylic acid, 4, 4 '-diaminodiphenyl-methane-3-carboxylic acid, 4, 4 '-diamino-diphenyl ethane-3, 3 '-dicarboxylic acid, 4, 4 '-diamino-diphenyl ethane-3-carboxylic acid, 4, 4 '-diamino-diphenyl ether-3, 3 '-dicarboxylic acid, 4, 4 '-diamino-diphenyl ether-3-carboxylic acid etc.

The usage quantity of specific diamines during synthetic polyamic acid of the present invention can at random be set according to used compound.For example, in the situation that use the represented compound of described formula (d-1), with respect to total diamines, the usage quantity of described compound is preferably and is made as more than 10 % by mole, is more preferably made as more than 30 % by mole.In addition, in the situation that use the represented compound of described formula (d-2), with regard to liquid crystal molecule being given to the viewpoint at low inclination orientation angle, with respect to total diamines, the usage quantity of described compound is preferably and is made as more than 10 % by mole, more preferably be made as more than 30 % by mole, be especially preferably and be made as more than 50 % by mole.

In the situation that use the represented compound of described formula (d-3), with regard to making the viewpoint having good stability of voltage retention, with respect to total diamines, the usage quantity of described compound is preferably and is made as more than 5 % by mole, is more preferably made as more than 10 % by mole.In addition, in the situation that use the represented compound of described formula (d-4), with regard to giving the viewpoint of good regiospecific, with respect to total diamines, the usage quantity of described compound is preferably and is made as more than 5 % by mole, is more preferably made as more than 10 % by mole.In addition, specific diamines can be used alone in above-mentioned illustrated compound a kind or two or more is used in combination.

In the situation that using carboxylic diamines as described other diamines, with respect to total diamines, the usage quantity of carboxylic diamines is preferably and is made as more than 5 % by mole, more preferably 10 % by mole～90 % by mole, is especially preferably 10 % by mole～70 % by mole.

In the situation that manufacture the crystal aligning agent of TN type used for liquid crystal display element, for the object of liquid crystal molecule being given to appropriate inclination orientation angle, as the synthetic monomer that is provided in polyamic acid of the present invention, the represented monoamine of following formula (m-1) can be used together with tetracarboxylic dianhydride and diamines.

[changing 8]

(in formula (m-1), R ²³for alkyl or the alkoxyl group of carbon number 6～20, R ²⁴for divalent organic radical, h is 0 or 1.)

In described formula (m-1), R ²³the alkyl of carbon number 6～20 such as enumerating: hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl etc., these groups can be straight chain shapes, can be also branch-like.The alkyl that the alkoxyl group of carbon number 6～20 for example can be enumerated above-mentioned illustrative carbon number 6～20 is binding on the base (OR on Sauerstoffatom ²³) etc.

R ²⁴in divalent organic radical for example can enumerate: divalent chain alkyl; The divalent alkyl such as ester ring type alkyl and aromatic hydrocarbyl; Between the C-C in alkyl, have-O-, the functional group's such as-CO-,-COO-,-S-group, containing the group of heterocycle etc.Wherein, be preferably chain alkyl, ester ring type alkyl or aromatic hydrocarbyl.

The preferred concrete example of the monoamine that described formula (m-1) is represented for example can be enumerated: normal hexyl Amine, n-octyl amine, n-Decylamine, dodecyl amine, n-hexadecyl amine, 1,3-dimethyl butylamine, 1, the aliphatics monoamines such as 5-dimethylhexylamine, 2 ethyl hexylamine; The aromatic series monoamines such as p-aminophenyl hexane, p-aminophenyl octane, p-aminophenyl dodecane, p-aminophenyl n-Hexadecane, p-aminophenyl oxygen base octane, p-aminophenyl oxygen base dodecane, p-aminophenyl oxygen base n-Hexadecane etc.

With regard to monoamine free in being suppressed at the liquid crystal cells of manufacturing, display characteristic is brought with regard to dysgenic viewpoint, the usage ratio of described monoamine is preferably used tetracarboxylic dianhydride is being made as to a mole, diamines is made as to b mole, and monoamine is made as in the situation of c mole, meets " 2 (a-b) >=c > 0 ".

In addition, the represented monoamine of described formula (m-1) can be after the reacting of tetracarboxylic dianhydride and diamines, to its resultant of reaction react, polymerization, or also can make that these three kinds of compositions of tetracarboxylic dianhydride, diamines and monoamine react simultaneously, polymerization.

[molecular weight regulator]

During synthesizing polyamides acid, suitable molecular weight regulator can be made together with tetracarboxylic dianhydride as above and diamines to the polymkeric substance for synthetic end modified type.By making the polymkeric substance of this end modified type, can not undermine effect of the present invention, and further improve the coating (printing) of crystal aligning agent.

Molecular weight regulator is such as enumerating: monoester anhydride, monoamine compound, monoisocyanates compound etc.As the concrete example of these molecular weight regulators, monoester anhydride is such as enumerating: MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinyl oxide, n-tetradecane base succinyl oxide, n-hexadecyl succinyl oxide etc.; Monoamine compound is such as enumerating: compound that aniline, hexahydroaniline, n-Butyl Amine 99, described formula (m-1) are represented etc.; Monoisocyanates compound is such as enumerating: phenylcarbimide, naphthyl isocyanate etc.

With respect to total 100 weight parts of used tetracarboxylic dianhydride and diamines, the usage ratio of molecular weight regulator is preferably and is made as below 20 weight parts, is more preferably made as below 10 weight parts.

The synthetic > of < polyamic acid

The tetracarboxylic dianhydride that the building-up reactions of polyamic acid of the present invention is provided and the usage ratio of diamines are preferably, amino 1 equivalent with respect to diamines, tetracarboxylic dianhydride's anhydride group becomes the ratio of 0.2 equivalent～2 equivalent, more preferably becomes the ratio of 0.3 equivalent～1.2 equivalent.

The building-up reactions of polyamic acid is preferably in organic solvent carries out.Temperature of reaction is now preferably-20 ℃～150 ℃, more preferably 0 ℃～100 ℃.In addition, the reaction times is preferably 0.1 hour～and 24 hours, more preferably 0.5 hour～12 hours.

Herein, organic solvent is such as enumerating: non-proton property polar solvent, phenol series solvent, alcohol, ketone, ester, ether, halohydrocarbon, hydrocarbon etc.

Concrete example as these organic solvents, described non-proton property polar solvent for example can be enumerated: METHYLPYRROLIDONE, 1,3-dimethyl-2-imidazolinone, N-ethyl-2-pyrrolidone, N, N-N,N-DIMETHYLACETAMIDE, DMF, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA etc.; Described phenol series solvent is such as enumerating: phenol, meta-cresol, xylenol, halogenated phenol etc.;

Described alcohol is such as enumerating: methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, BDO, triethylene glycol, ethylene glycol monomethyl ether etc.; Described ketone is such as enumerating: acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.; Described ester is such as enumerating: ethyl lactate, n-Butyl lactate, methyl acetate, ethyl acetate, butylacetate, methoxy methyl propionate, ethoxyl ethyl propionate, diethyl oxalate, diethyl malonate, isoamyl propionate, isoamyl isobutyrate etc.;

Described ether is such as enumerating: diethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-n-butyl ether, glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetic ester, tetrahydrofuran (THF), isoamyl ether etc.;

Described halohydrocarbon for example can be enumerated: methylene dichloride, 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene etc.; Described hydrocarbon is such as enumerating: hexane, heptane, octane, benzene,toluene,xylene etc.

In these organic solvents, be preferably use: choosing is more than one in non-proton property polar solvent and phenol cohort that series solvent forms (organic solvent A) freely, or be selected from organic solvent A more than one and select more than one the mixture in free alcohol, ketone, ester, ether, halohydrocarbon and cohort that hydrocarbon forms (organic solvent B).Under latter event, with respect to the total amount of organic solvent A and organic solvent B, the usage ratio of organic solvent B is preferably below 50 % by weight, more preferably, below 40 % by weight, is especially preferably below 30 % by weight.

The usage quantity of organic solvent (a) is preferably the total amount (a+b) being made as with respect to reaction soln, and the total amount of tetracarboxylic dianhydride and diamines (b) becomes the amount of 0.1 % by weight～50 % by weight.

Obtain in this way polyamic acid is dissolved to the reaction soln forming.This reaction soln can directly be provided in the preparation of crystal aligning agent, also can will after polyamic acid segregation contained in reaction soln, be provided in again the preparation of crystal aligning agent, or also can will after the polyamic acid purifying of segregation, be provided in again the preparation of crystal aligning agent.Polyamic acid is being carried out to dehydration closed-loop make polyimide in the situation that, described reaction soln directly can be provided in to dehydration closed-loop reaction, also can will after polyamic acid segregation contained in reaction soln, be provided in again dehydration closed-loop reaction, or also can will after the polyamic acid purifying of segregation, be provided in again dehydration closed-loop reaction.The segregation of polyamic acid and purifying can carry out according to well-known method.

< polyimide >

In crystal aligning agent of the present invention, contained polyimide can be by synthetic in this way polyamic acid is carried out to dehydration closed-loop, in addition imidization and obtaining.

Described polyimide can be amido acid structure that the polyamic acid as its precursor is had all carry out dehydration closed-loop and complete imide compound, can be also only a part for amido acid structure to be carried out to dehydration closed-loop and the part imide compound that makes amido acid structure and imide ring structure and deposit.The imide rate of polyimide of the present invention is preferably more than 30%, and more preferably 40%～99%, be especially preferably 50%～99%.This imide rate is to represent the shared ratio of imide ring number of structures for the amido acid number of structures of polyimide and the total of imide ring number of structures with percentage.Herein, a part for imide ring can be different imide (isoimide) ring.

The method that the dehydration closed-loop of polyamic acid is preferably by polyamic acid is heated is carried out, or by polyamic acid is dissolved in organic solvent, in this solution, add dewatering agent and dehydration closed-loop catalyzer, and the method optionally heating is carried out.Wherein, be preferably the method for utilizing the latter.

In the solution of described polyamic acid, add in the method for dewatering agent and dehydration closed-loop catalyzer, dewatering agent is such as using the acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.With respect to 1 mole, the amido acid structure of polyamic acid, the usage quantity of dewatering agent is preferably and is made as 0.01 mole～20 moles.Dehydration closed-loop catalyzer is such as using: the tertiary amines such as pyridine (pyridine), collidine (collidine), two picolins (1utidine), triethylamine (triethylamine).With respect to 1 mole of used dewatering agent, the usage quantity of dehydration closed-loop catalyzer is preferably and is made as 0.01 mole～10 moles.The organic solvent using in dehydration closed-loop reaction can be enumerated as the illustrative organic solvent for the synthesis of the organic solvent of polyamic acid.The temperature of reaction of dehydration closed-loop reaction is preferably 0 ℃～180 ℃, more preferably 10 ℃～150 ℃.Reaction times is preferably 1.0 hours～and 120 hours, more preferably 2.0 hours～30 hours.

Obtain in this way the reaction soln that contains polyimide.This reaction soln can directly be provided in the preparation of crystal aligning agent, also can from reaction soln, remove the preparation that is provided in again crystal aligning agent after dewatering agent and dehydration closed-loop catalyzer, also can will after polyimide segregation, be provided in again the preparation of crystal aligning agent, or can also will after the polyimide purifying of segregation, be provided in again the preparation of crystal aligning agent.These purification process can be carried out according to well-known method.

< poly amic acid ester >

Poly amic acid ester contained in crystal aligning agent of the present invention is such as utilizing following methods to obtain: [I] compound by the polyamic acid that makes to be obtained by described building-up reactions and hydroxyl, halogenide, containing the compound of epoxy group(ing) etc., react synthetic method; [II] makes the method for tetracarboxylic acid diester and diamine reactant; [III] makes the method for tetracarboxylic acid diester dihalide and diamine reactant.

The compound of the hydroxyl herein, using in method [I] is such as enumerating: the alcohols such as methyl alcohol, ethanol, propyl alcohol; The phenols such as phenol, cresols etc.In addition, halogenide for example can be enumerated: methyl bromide, bromic ether, bromo-octadecane (stearyl bromide), methyl chloride, chlorooctadecane (stearyl chloride), 1,1, the fluoro-2-iodoethane of 1-tri-etc.; Contain the compound of epoxy group(ing) such as enumerating propylene oxide etc.The tetracarboxylic acid diester using in method [II] for example can be by using described alcohols, and illustrative tetracarboxylic dianhydride in described polyamic acid synthetic is carried out to open loop and obtains.In addition, the tetracarboxylic acid diester dihalide using in method [III] can be reacted and be obtained by the suitable chlorizating agent such as the tetracarboxylic acid diester that makes to obtain in this way and thionyl chloride.The diamines using in method [II] and method [III] can be used in described polyamic acid synthetic illustrative diamines etc.In addition, poly amic acid ester can only have amic acid esters structure, can be also amido acid structure and amic acid esters structure the partial esterification thing deposited.

< soltion viscosity and weight average molecular weight >

Polyamic acid, polyimide and the poly amic acid ester obtaining is in this way preferably when being made into concentration and being the solution of 10 % by weight, the compound with the soltion viscosity of 10mPas～800mPas, more preferably has the compound of the soltion viscosity of 15mPas～500mPas.In addition, the soltion viscosity of described polymkeric substance (mPas) is to use E type rotational viscosimeter, to the concentration of using the good solvent (such as gamma-butyrolactone, METHYLPYRROLIDONE etc.) of this polymkeric substance to prepare, be the polymers soln of l0 % by weight, at 25 ℃, measure and value.

Reducing viscosity so long as can form the scope of uniform coating, is not particularly limited, and is preferably 0.05dl/g～3.0dl/g, and more preferably 0.1dl/g～2.5dl/g, is especially preferably 0.3dl/g～1.5dl/g.

About polyamic acid contained in crystal aligning agent of the present invention, polyimide and poly amic acid ester, utilize gel permeation chromatography (gel permeation chromatography, the weight average molecular weight of the polystyrene conversion of GPC) measuring is preferably 500～100,000, more preferably 1,000～50,000.

< < solvent > >

Crystal aligning agent of the present invention contains choosing, and freely the represented compound of represented compound, the described formula (b-2) of described formula (b-1) and the represented compound of described formula (b-3) form at least one organic solvent (specific solvent (B)) in cohort as solvent composition.By this specific solvent (B) is contained in crystal aligning agent, can make crystal aligning agent good to the storage stability of the coating of substrate and crystal aligning agent.

[specific solvent (B)]

(the represented compound of formula (b-1))

About the represented compound of described formula (b-1), R ⁸and R ¹⁰in 1 valency alkyl of carbon number 1～3 such as enumerating: the alkyl of the carbon numbers 1～3 such as methyl, ethyl, n-propyl, sec.-propyl; The carbon number 2 of vinyl, allyl group etc. or 1 valency unsaturated alkyl of 3 etc.In these alkyl, R ⁸and R ¹⁰be preferably methyl or ethyl.In addition R, ⁸and R ¹⁰can be mutually identical, also can be different.

R ⁹alkane two bases of carbon number 2～5 for example can enumerate: ethylidene, propane-1,2-bis-bases, propane-1,3-bis-bases, butane-1,3-bis-bases, butane-Isosorbide-5-Nitrae-bis-base, pentane-1,5-bis-bases etc.

The preferred concrete example of the compound that described formula (b-1) is represented is such as enumerating: the aklylene glycol diacetate esters such as glycol diacetate, propylene-glycol diacetate.Wherein can preferably use propylene-glycol diacetate.The represented compound of described formula (b-1) can or be used in combination two or more a kind of the independent use of described compound.

(the represented compound of formula (b-2))

The represented compound of described formula (b-2) has 2 R ¹¹be binding on respectively the structure on Sauerstoffatom.As this compound, R ¹¹between the C-C for the alkyl at carbon number 3～5, there is the concrete example of compound of 1 valency group of 1 " O-" such as enumerating: diethylene glycol dimethyl ether, diethylene glycol diethyl ether etc.; R ¹¹the concrete example of compound that replaces the 1 valency group forming through hydroxyl for the hydrogen atom of the alkyl of carbon number 3～5 is such as enumerating: dipropylene glycol etc.; R ¹¹for the concrete example of the compound of branch-like alkyl is such as enumerating: diisopropyl ether, isoamyl ether, two-secondary butyl ether (sec-buty1ether), two-secondary amyl ether (sec-amyl ether) etc.In these compounds, the represented compound of described formula (b-2) be preferably in diethylene glycol diethyl ether and isoamyl ether at least any.In addition, the represented compound of described formula (b-2) can or be used in combination two or more a kind of the independent use of described compound.

(the represented compound of formula (b-3))

X in described formula (b-3) ⁶be preferably base " C (OH) R ^a-", base " C (OH) (CH more preferably ₃)-".In addition, R ¹²the alkyl of carbon number 1～4 can be straight chain shape, can be also branch-like, be preferably methyl or ethyl.

The preferred concrete example of the compound that described formula (b-3) is represented is such as enumerating: Pyranton, Acetyl Acetone, methyl aceto acetate etc., can particularly preferably be used Pyranton.In addition, the represented compound of described formula (b-3) can or be used in combination two or more a kind of the independent use of described compound.

Wherein, specific solvent (B) is preferably choosing freely represented compound and represented at least one in cohort that compound forms of described formula (b-3) of described formula (b-1), the more preferably represented compound of described formula (b-3).

Just fully acquisition not only suppresses separating out of polymkeric substance, and make the viewpoint of the effect that coating (printing) for substrate is good, entire amount with respect to solvent contained in crystal aligning agent, the usage quantity of specific solvent (B) is preferably 1 % by weight～70 % by weight, more preferably 3 % by weight～65 % by weight, are especially preferably 5 % by weight～60 % by weight.In addition, specific solvent (B) can or be used in combination two or more a kind of the independent use of described compound.

(other solvents)

Crystal aligning agent of the present invention is preferably and contains described specific solvent (B) other solvents in addition as solvent composition.These other solvents can be enumerated: the solvent (below also referred to as " the 1st solvent ") that polymkeric substance contained in crystal aligning agent of the present invention (A) can be dissolved, as the poor solvent of this polymkeric substance (A) and for described specific solvent (B) organic solvent in addition etc.

Described the 1st solvent is so long as the good solvent of described polymkeric substance (A), its preferred concrete example for example can be enumerated: METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-amyl group-2-Pyrrolidone, 3-methoxyl group-N, N-dimethyl propylene acid amides, 3-butoxy-N, N-dimethyl propylene acid amides, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, DMI, N-ethyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), tetramethyl-urea, HMPA, meta-cresol etc.In addition, the 1st solvent can or mix two or more to use a kind of the independent use of described compound.

In addition, as the poor solvent of described polymkeric substance (A) and for example can enumerate for described specific solvent (B) organic solvent in addition: ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, methoxy methyl propionate, ethoxyl ethyl propionate, 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 monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, dipropylene glycol monomethyl ether (dipropylene glycol monomethyl ether, DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, ethylene carbonate, propylene carbonate etc.This organic solvent can or mix two or more to use a kind of the independent use of described compound.In addition,, also the poor solvent by as described polymkeric substance (A) and the cohort that forms for organic solvent in addition of described specific solvent (B) and described specific solvent (B) are called to " the 2nd solvent ".

In described other solvents, with regard to suppressing viewpoint that polymkeric substance (A) separates out, with respect to the entire amount of solvent contained in crystal aligning agent, described the 1st solvent containing proportional be preferably 5 % by weight more than, more preferably more than 10 % by weight, more than being especially preferably 20 % by weight.In addition, the proportional higher limit that contains about described the 1st solvent, with regard to the viewpoint of the effect of being brought by the interpolation of described specific solvent (B) with regard to suitable acquisition, entire amount with respect to solvent contained in crystal aligning agent, described higher limit is preferably below 95 % by weight, more preferably, below 90 % by weight, be especially preferably below 85 % by weight.

In described the 2nd solvent, entire amount with respect to solvent contained in crystal aligning agent, described specific solvent (B) organic solvent in addition containing proportional being preferably below 80 % by weight, more preferably below 70 % by weight, especially be preferably below 50 % by weight, be particularly preferably below 30 % by weight.

Just make with regard to the good viewpoint of the coating of substrate, the ratio of the 1st solvent and the 2nd solvent is preferably with respect to the usage quantity of the 1st solvent and more than the usage quantity of the 2nd solvent is made as to 0.03 times (weight), more than being more preferably made as 0.05 times (weight).In addition, with regard to suppressing viewpoint that polymkeric substance separates out, be preferably and be made as below 2.5 times (weight), be more preferably made as below 2.0 times (weight).

Crystal aligning agent of the present invention is preferably and does not contain in fact ethylene glycol butyl ether as solvent.Ethylene glycol butyl ether, as the solvent composition that crystal aligning agent is improved the coating of substrate, was used in the past conventionally when preparing crystal aligning agent.But in the situation that using ethylene glycol butyl ether, when taking care of for a long time, there is the tendency that easily produces precipitate in crystal aligning agent under the utmost point low temperature environment below for example-15 ℃.In addition, about the goods of low temperature keeping, be transported sometimes under the state with keeping in dry ice, situation about being for example exposed to, under lower temperature (-20 ℃ following) is also many.In this case, in crystal aligning agent, more easily produce precipitate.On the other hand, even if in the situation that crystal aligning agent is taken care of for a long time at low temperatures, specific solvent (B) is also difficult to produce precipitate in crystal aligning agent, can give excellent storage stability to crystal aligning agent.In addition, described specific solvent (B), owing to crystal aligning agent being given to excellent coating, therefore can be used as the substitute of ethylene glycol butyl ether.

In addition, so-called in this specification sheets " in fact containing ethylene glycol butyl ether " refer to, with respect to the entire amount of solvent contained in crystal aligning agent, ethylene glycol butyl ether containing proportional being preferably below 5 % by weight, more preferably, below 3 % by weight, be especially preferably below 0.5 % by weight.

Other compositions of < < > >

Crystal aligning agent of the present invention contains polymkeric substance as above (A) and solvent, also can optionally contain other compositions.These other compositions are such as enumerating: in other polymkeric substance in addition of described polymkeric substance (A), molecule, have the compound (hereinafter referred to as " containing the compound of epoxy group(ing) "), functional silanes compound, described amine compound (C) of at least one epoxy group(ing) etc.

[other polymkeric substance]

Described other polymkeric substance can be used for improving solution properties or electrical specification.These other polymkeric substance are such as enumerating: make not diamines containing described specific diamines react with tetracarboxylic dianhydride and the polyamic acid that obtains and this polyamic acid is carried out to dehydration closed-loop and polyimide, polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative of obtaining, gather (methyl) acrylate etc.The in the situation that of in these other polymkeric substance are made an addition to crystal aligning agent, with respect to the polymkeric substance total amount in said composition, the allotment ratio of these other polymkeric substance is preferably below 50 % by weight, and more preferably 0.1 % by weight～40 % by weight, is especially preferably 0.1 % by weight～30 % by weight.

[containing the compound of epoxy group(ing)]

Containing the compound of epoxy group(ing), can be used for improving liquid crystal orienting film and tackiness substrate surface.Herein, compound containing epoxy group(ing) for example can be enumerated: 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-benzylamine, N, N-diglycidyl-amino methyl hexanaphthene, N, N-diglycidyl-hexahydroaniline etc.

The in the situation that of in these epoxy compoundss are made an addition to crystal aligning agent, total 100 weight parts with respect to polymkeric substance contained in crystal aligning agent, the allotment ratio of these epoxy compoundss is preferably below 40 weight parts, more preferably 0.1 weight part～30 weight part.

[functional silanes compound]

Described functional silanes compound can be used for the object that improves the printing of crystal aligning agent.This functional silanes compound for example can be enumerated: 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-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.

The in the situation that of in these functional silanes compounds are made an addition to crystal aligning agent, with respect to total 100 weight parts of polymkeric substance, the allotment ratio of these functional silanes compounds is preferably below 2 weight parts, more preferably 0.02 weight part～0.2 weight part.

[amine compound (C)]

Described amine compound (C) is to have 1 one-level amino and nitrogenous heteroaromatic, and has the compound that this primary amine base is binding on the structure on chain alkyl or ester ring type alkyl.This amine compound (C) can be used for the object of improving the electrical specification (such as mitigation speed of voltage retention or residual charge etc.) etc. of liquid crystal display device.

Nitrogenous heteroaromatic in described amine compound (C) is so long as the aromatic nucleus that comprises 1 above nitrogen-atoms in ring skeleton.Therefore, in ring skeleton, can only comprise nitrogen-atoms as heteroatoms, also can comprise nitrogen-atoms and nitrogen-atoms heteroatoms (Sauerstoffatom, sulphur atom etc.) in addition.The concrete example of this nitrogenous heteroaromatic is such as enumerating: pyrrole ring, imidazole ring, pyrazole ring, triazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, indole ring, benzoglyoxaline ring, purine skeleton, quinoline ring, isoquinoline 99.9 ring, naphthyridines ring, quinoxaline ring, phthalazines ring, triazine ring, nitrogen Boom ring, phenodiazine Boom ring, acridine ring, azophenlyene ring, coffee quinoline Huan, oxazole ring, thiazole ring, carbazole ring, Thiadiazole, benzothiazole ring, thiodiphenylamine Huan, oxadiazole rings etc.In addition, this nitrogenous heteroaromatic can be to import and have substituent heterocycle on the carbon atom that forms above-mentioned illustrative ring.This substituting group is such as enumerating: halogen atom, alkyl, alkoxyl group etc.

Chain alkyl in described amine compound (C) is preferably carbon number 1～20, and more preferably carbon number 1～15, is especially preferably carbon number 1～10.In addition, this chain alkyl can be straight chain shape, can be also branch-like, can be saturated, and also can be unsaturated.In addition, the ester ring type alkyl in described amine compound (C) is preferably carbon number 3～20, and more preferably carbon number 3～15, are especially preferably carbon number 3～10.

Described amine compound (C) can preferably be used the represented compound of following formula (c-1).

[changing 9]

H ₂N-A ¹-A ² (c-1)

About described formula (c-1), A ¹in divalent organic radical for example can enumerate: divalent chain alkyl, divalent ester ring type alkyl ,-O-R ²¹-,-CO-R ²¹-(wherein, R ²¹for divalent chain alkyl or ester ring type alkyl) etc.In addition, this divalent organic radical can be: have-O-,-NH-,-CO-O-,-CO-NH-,-CO-,-S-,-S (O) between the C-C in divalent chain alkyl or divalent ester ring type alkyl ₂-,-Si (CH ₃) ₂-,-O-Si (CH ₃) ₂-,-O-Si (CH ₃) ₂the aromatic hydrocarbyl such as-O-, phenylene, the divalent groups such as heterocyclic radical such as pyridylidene; At least 1 hydrogen atom in divalent chain alkyl or divalent ester ring type alkyl is through the halogen atoms such as fluorine atom or chlorine atom, bromine atoms, iodine atom, the aromatic hydrocarbyls such as phenyl, hydroxyl, the divalent group that the replacements such as haloalkyl form etc.

Particularly, A ¹in chain alkyl such as enumerating: methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, sub-heptyl, octylene, nonamethylene, sub-decyl, sub-undecyl, sub-dodecyl, sub-tridecyl, sub-tetradecyl, sub-pentadecyl, sub-octadecyl, sub-eicosyl, vinylidene, propenylidene, crotonylidene, inferior pentenyl, ethynylene, sub-proyl etc.; Divalent ester ring type alkyl is such as enumerating: cyclopropylidene, sub-cyclobutyl, cyclopentylidene, cyclohexylidene, phenylidene, sub-suberyl, sub-ring octyl group, sub-ring nonyl, sub-ring decyl, sub-ring undecyl, sub-cyclo-dodecyl, sub-ring tridecyl, sub-ring tetradecyl, sub-cyclopentadecane base, sub-ring octadecyl, sub-ring eicosyl, two cyclohexylidene, sub-norcamphyl, sub-adamantyl etc.

In described group, A ¹be preferably the divalent organic radical with chain alkyl, more preferably divalent chain alkyl.

A ¹in divalent organic radical be preferably carbon number 1～20, more preferably carbon number 1～15, is especially preferably carbon number 1～10.

A ²nitrogenous heteroaromatic can apply described explanation.

The concrete example of described amine compound (C) is such as enumerating the represented compound of following formula (c-1-1)～formula (c-1-32) difference etc.In addition, described amine compound (C) can or be used in combination of two or more a kind of independent use in these compounds.

[changing 10]

[changing 11]

The in the situation that of in described amine compound (C) is made an addition to crystal aligning agent, with regard to the viewpoint of the effect of being brought by the interpolation of this amine compound (C) with regard to suitable acquisition, total 100 weight parts with respect to polymkeric substance, more than the allotment ratio of described amine compound (C) is preferably and is made as 1 weight part, more than being more preferably made as 2 weight parts.In addition, with regard to not undermining the viewpoint of stability of crystal aligning agent, total 100 weight parts with respect to polymkeric substance, are preferably and are made as below 20 weight parts, are more preferably made as below 15 weight parts.

In addition,, except above-mentioned, in crystal aligning agent, other contained additives can be used and in molecule, have the compound of at least one oxa-cyclobutyl or antioxidant etc.

The in the situation that of containing described amine compound (C) as additive in making crystal aligning agent of the present invention, with regard to can suitably improving the aspect of electrical specification of liquid crystal display device, be preferably described polymkeric substance (A) and there is carboxyl.In addition, the quantity of the carboxyl that this polymkeric substance (A) has is preferably the repeating unit with respect to polymkeric substance (A), in mean value, is made as 0.1～3, is more preferably made as 0.3～2, is especially preferably and is made as 0.5～1.8.

The method of the quantity of the carboxyl that adjustment polymkeric substance (A) has is not particularly limited, for example, can enumerate: the method for (i) being undertaken by adjusting the imide rate of polyimide; (ii) method of being undertaken by the carboxyl-content of adjusting for the synthesis of the diamines of polymkeric substance (A) etc.In addition, also can by by described (i) with (ii) and with carrying out.With regard to improving the aspect of degree of freedom of imide rate of polymkeric substance (A), be preferably described (ii) method of using.

In the situation that make to have polymkeric substance (A) and the described amine compound (C) of carboxyl, be contained in crystal aligning agent of the present invention, 1 mole of the carboxyl having with respect to polymkeric substance (A), amine compound (C) containing proportional be preferably to be made as comprise 0.01 mole～2 moles, more preferably be made as and comprise 0.05 mole～1 mole, be especially preferably to be made as and comprise 0.08 mole～0.8 mole.

Solid component concentration in crystal aligning agent of the present invention (the total weight of the composition beyond the solvent of crystal aligning agent in the gross weight of crystal aligning agent shared ratio) is to consider that viscosity, volatility etc. suitably select, and is preferably the scope of 1 % by weight～10 % by weight.; crystal aligning agent of the present invention is by coating substrate surface in aftermentioned mode; be preferably and heat; and formation filming or becoming filming of liquid crystal orienting film as liquid crystal orienting film; now; in the situation that solid component concentration is less than 1 % by weight, the thickness of filming becomes too small and is difficult to obtain good liquid crystal orienting film.On the other hand, in the situation that solid component concentration surpasses 10 % by weight, the thickness of filming becomes excessive and is difficult to obtain good liquid crystal orienting film, and in addition, the viscosity of crystal aligning agent increases, coating characteristics variation.

The method that the scope of particularly preferred solid component concentration is used during according to coating of liquid crystalline orientation agent on substrate and difference.For example, in the situation that utilizing method of spin coating, solid component concentration is particularly preferably the scope of 1.5 % by weight～4.5 % by weight.In the situation that utilizing offset printing method, be particularly preferably the scope that solid component concentration is made as to 3 % by weight～9 % by weight, thus soltion viscosity is made as to the scope of 12mPas～50mPas.In the situation that utilizing ink jet method, be particularly preferably the scope that solid component concentration is made as to 1 % by weight～8 % by weight, thus soltion viscosity is made as to the scope of 3mPas～20mPas.Temperature while preparing crystal aligning agent of the present invention is preferably 10 ℃～50 ℃, more preferably 20 ℃～30 ℃.

< liquid crystal orienting film and liquid crystal display device >

Liquid crystal orienting film of the present invention is to utilize the crystal aligning agent of preparation in this way to form.In addition, liquid crystal display device of the present invention comprises the liquid crystal orienting film forming with crystal aligning agent of the present invention.The drive pattern of applying liquid crystal display device of the present invention is not particularly limited, and can be applicable to the multiple drive modes such as TN type, STN type, IPS type, FFS type, VA type, MVA type.Below, the manufacture method of liquid crystal display device of the present invention is described, and the manufacture method to liquid crystal orienting film of the present invention describes in this explanation.

Liquid crystal display device of the present invention for example can be manufactured by the step of following (1)～(3).Step (1) is used different substrates according to required drive pattern.Step (2) and step (3) are common in each drive pattern.

[step (1): the formation of filming]

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

(1-1) in the situation that manufacturing TN type, STN type or VA type liquid crystal display device, using two substrates that are provided with patterned nesa coating as a pair of, on described each transparent conducting film formation face, be preferably and utilize offset printing method, method of spin coating, roll-coater method or ink jet printing method to be coated with respectively crystal aligning agent of the present invention.Herein, substrate is such as using: the glass such as float glass (float glass), soda glass (soda glass); The transparency carrier that comprises the plastic cement such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-(ester ring type alkene).The nesa coating that is arranged at the one side of substrate can be used and comprise stannic oxide (SnO ₂) NESA film (U.S. must big will (PPG) register of company trade mark), comprise Indium sesquioxide-stannic oxide (In ₂o ₃-SnO ₂) ITO film etc.In order to obtain patterned nesa coating, for example, can utilize following methods: form after patternless nesa coating, by photoetch (photo etching), form the method for pattern; While forming nesa coating, use the method for the shade with required pattern etc.During coating of liquid crystalline orientation agent, better for the tackiness that makes substrate surface and nesa coating and film, also can, to forming the face of filming in substrate surface, implement to be coated with in advance the pre-treatment of functional silanes compound, functionality titanium compound etc.

After coating of liquid crystalline orientation agent, for the objects such as sagging that prevent be coated with orientation agent, be preferably and implement to preheat (prebake conditions).Prebake conditions temperature is preferably 30 ℃～200 ℃, more preferably 40 ℃～150 ℃, is particularly preferably 40 ℃～100 ℃.The prebake conditions time is preferably 0.25 minute～and 10 minutes, more preferably 0.5 minute～5 minutes.Then, solvent is removed completely, optionally for the amido acid structure existing in polymkeric substance is carried out to the object of hot-imide, implemented calcining (rear baking (postbake)) step.This calcining (baking afterwards) temperature is preferably 80 ℃～300 ℃, more preferably 120 ℃～250 ℃.Rear baking time is preferably 5 minutes～and 200 minutes, more preferably 10 minutes～100 minutes.So, the thickness of formed film is preferably 0.001 μ m～1 μ m, more preferably 0.005 μ m～0.5 μ m.

(1-2) in the situation that manufacturing IPS type or FFS type liquid crystal display device, be provided with the electrode forming surface of the substrate that comprises the patterned electrode for the nesa coating of interdigitated electrode structure or metallic membrane and be not provided with the one side of the subtend substrate of electrode, be coated with respectively crystal aligning agent of the present invention, then each coated face is heated, form and film thus.The patterning method of heating condition, nesa coating or metallic membrane after the substrate now using and the material of nesa coating, coating process, coating is, the pre-treatment of substrate and formed preferred thickness of filming are identical with described (1-1).Metallic membrane is such as using the film that comprises the metals such as chromium.

In described (1-1) and arbitrary situation (1-2), all by after coating of liquid crystalline orientation agent on substrate, removal organic solvent forms and becomes filming of alignment film.Now, in crystal aligning agent of the present invention, contained polymkeric substance is polyamic acid, or have in the situation of imide amination polymer of imide ring structure and amido acid structure, also can, by further heating and carry out dehydration closed-loop reaction, make further filming through imidization after the formation of filming.

[step (2): friction treatment]

In the situation that manufacturing TN type, STN type, IPS type or FFS type liquid crystal display device, the friction treatment of filming and being implemented as follows to formation in described step (1): utilize the roller that is wound with the cloth that comprises fibers such as nylon, artificial silk, cotton, to certain orientation wiping.Thus, the orientation ability of liquid crystal molecule is imparted to film above becomes liquid crystal orienting film.On the other hand, in the situation that manufacturing VA type liquid crystal display device, filming of formation in described step (1) directly can be used as to liquid crystal orienting film, but also can be to this enforcement friction treatment of filming.

In addition, also can further carry out following processing to the liquid crystal orienting film after friction treatment: by the processing that makes the tilt angle in a part of region of liquid crystal orienting film change a part of irradiation ultraviolet radiation of liquid crystal orienting film; Or form after resist film in the part on liquid crystal orienting film surface, to the direction that the friction treatment from is just now different, carry out friction treatment, then remove the processing of resist film; Thereby make liquid crystal orienting film in each region, there is different LCD alignment abilities.In this situation, can improve the visual field characteristic of gained liquid crystal display device.

[step (3): liquid crystal cells construct]

By preparing two substrates that are formed with in this way liquid crystal orienting film, between two substrates of subtend configuration, configure liquid crystal and manufacture liquid crystal cells.While manufacturing liquid crystal cells, for example, can enumerate following 2 kinds of methods.

The first method is front known method for it.First, mode with each liquid crystal orienting film subtend, across gap (cell gap), two substrate subtends are configured, use sealing agent by the periphery laminating of two substrates, in substrate surface and the cell gap divided by sealing agent, inject after filling liquid crystal, by filling orifice sealing, can manufacture liquid crystal cells thus.In addition, the second method is the method that is called instillation (One Drop Fill, ODF) mode.Can be by the regulation position on the wherein substrate in being formed with two substrates of liquid crystal orienting film, be coated with for example sealing material of ultraviolet light photopolymerization, and then several positions of the regulation on LCD alignment face drip after liquid crystal, with the mode of liquid crystal orienting film subtend another piece substrate of fitting, and liquid crystal is spread out on whole of substrate, then whole the irradiating ultraviolet light to substrate, makes hardening seal, thereby manufactures liquid crystal cells.In the situation that utilizing any method, it is desirable to by the liquid crystal cells of manufacturing in this way, and then be heated to used liquid crystal and become after the temperature of isotropic phase (isotropic phase), be slowly cooled to room temperature, thus the mobile orientation when removing liquid crystal and filling.

Sealing agent contains stiffening agent and as epoxy resin of the alumina balls of spacer etc. such as using.

Liquid crystal can be enumerated nematic liquid crystal (nematic liquid crystal) and smectic liquid crystal (smectic liquid crystal), wherein be preferably nematic liquid crystal, such as using: schiff bases (Schiff base) is that liquid crystal, azoxy (azoxy) are that liquid crystal, biphenyl are that liquid crystal, Santosol 360 are that liquid crystal, ester are that liquid crystal, terphenyl (terphenyl) are that liquid crystal, xenyl hexamethylene methane series liquid crystal, pyrimidine are that liquid crystal, dioxan are that liquid crystal, double-octane are that liquid crystal, cubane (cubane) are liquid crystal etc.In addition, also can in these liquid crystal, add following material uses: cholesterol liquid crystals (cholesteric liquid crystal) such as cholesteryl chloride (cholestil chloride), cholesteryl nonanoate (cholesteryl nonanoate), cholesteryl carbonate (cholesteryl carbonate); The chirality agent of selling as trade(brand)name " C-15 ", " CB-15 " (manufacture of Merck (Merck) company); To oxygen base α-tolylene-to ferroelectric liquid crystals such as amino-2-methyl butyl laurate (p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate) (ferroelectric liquid crystal) etc. in the last of the ten Heavenly stems.

Then, the outer surface laminating Polarizer by liquid crystal cells, can obtain liquid crystal display device of the present invention.The Polarizer that fits in the outside surface of liquid crystal cells can be enumerated: with rhodia protective membrane clamping, being called as the Polarizer that the light polarizing film of " H film " forms, should " H film " be to make polyvinyl alcohol extend the film that orientation makes its absorption iodine on one side; Or comprise itself Polarizer of H film.In addition, in the situation that carrying out friction treatment to filming, two substrates are angles that frictional direction in respectively filming forms regulation mutually, for example, become the mode subtend configuration of quadrature or antiparallel (antiparallel).

Liquid crystal display device of the present invention can be effectively applied to multiple device, for example can be used in: clock and watch, portable game machine (portable video game), word processor (word processor), notes type PC (note type personal computer), auto-navigation system (car navigation system), video camera (camcorder), personal digital assistant (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, smart mobile phone (smartphone), various watch-dogs (monitor), the display unit of LCD TV etc.

[embodiment]

Below, utilize embodiment to be further specifically described the present invention, but the present invention is not subject to the restriction of these embodiment.

In following embodiment and comparative example, the imide rate of the polyimide in polymers soln and the weight average molecular weight Mw of polymkeric substance utilize following methods to measure.

[the imide rate of polyimide]

The solution of polyimide is fed in pure water, the precipitation of gained at room temperature fully after drying under reduced pressure, is dissolved in deuterate dimethyl sulfoxide (DMSO), using tetramethylsilane as primary standard, at room temperature measure ¹h-nucleus magnetic resonance ( ¹h-Nuclear Magnetic Resonance, ¹h-NMR).According to gained ¹h-NMR spectrum, utilizes following mathematical expression (x) to obtain imide rate [%].

Imide rate [%]=(1-A ¹/ A ²* α) * 100 ... (x)

(in mathematical expression (x), A ¹for near the peak area of the proton that is derived from NH base that occurs chemical shift 10ppm, A ²for being derived from the peak area of other protons, α is that other protons are with respect to the number ratio of 1 proton of the NH base in the precursor (polyamic acid) of polymkeric substance.)

[weight average molecular weight of polymkeric substance]

Weight average molecular weight Mw is the polystyrene conversion value of utilizing the gel permeation chromatography under following condition to measure.

Tubing string: eastern Cao (Tosoh) (thigh) manufactures, TSKgel GRCXLII

Solvent: tetrahydrofuran (THF)

Temperature: 40 ℃

Pressure: 68kgf/cm ²

[embodiment 1]

In the 50ml four-hole boiling flask with whipping appts and nitrogen ingress pipe, add as 1 of diamines, two (4-amino-benzene ethyl) urea (BAPU) 0.60g (2.0mmol) of 3-and Ursol D (p-PDA) 1.95g (18.0mmol), add METHYLPYRROLIDONE (NMP) 30g, on one side delivery of nitrogen stir on one side and make its dissolving.Stir this two amine aqueous solution on one side, add as tetracarboxylic dianhydride's 1 on one side, 2,3,4-tetramethylene tetracarboxylic dianhydride (CBDA) 3.70g (18.9mmol), and then add NMP in the mode that solid component concentration becomes 12 % by weight, under nitrogen environment, at room temperature stir 4 hours and obtain the solution of polyamic acid (PA-1).

In this polyamic acid solution 16.24g, add NMP9.94g and as Pyranton (DAA) 6.54g (NMP:DAA=60: 40 (weight ratios)), obtaining polyamic acid concentration is the crystal aligning agent (S1) of 6.0 % by weight of specific solvent (B).

[embodiment 2～embodiment 4 and comparative example 1]

Except the kind of the 2nd solvent for the preparation of crystal aligning agent being changed to the aspect as described in following table 1, in the mode identical with described embodiment 1, obtain crystal aligning agent (S2)～crystal aligning agent (S4), crystal aligning agent (R1).

[embodiment 5]

Using the CBDA19.2g as tetracarboxylic dianhydride (0.098mol), as 1 of diamines, two (4-amino-benzene oxygen) the pentane 24.2g (0.1mol) of 5-are dissolved in NMP343.5g, at room temperature carry out reaction in 10 hours.Polyreaction easily and is equably carried out, and obtains polyamic acid (PA-2).In the nmp solution of this polyamic acid (PA-2), interpolation is as Pyranton (DAA) 336.4g (NMP:DAA=50: 50 (weight ratios)), obtaining polyamic acid concentration is the crystal aligning agent (S5) of 6.0 % by weight of specific solvent (B).

[embodiment 6～embodiment 8 and comparative example 2]

Except the kind of the 2nd solvent for the preparation of crystal aligning agent being changed to the aspect as described in following table 1, in the mode identical with described embodiment 5, obtain crystal aligning agent (S6)～crystal aligning agent (S8), crystal aligning agent (R2).

[embodiment 9]

Using the CBDA19.61g as tetracarboxylic dianhydride (0.1mol) and as 4,4 of diamines '-diamino-diphenylamine (4,4 ' DADPA) 18.73g (0.094mol), in NMP345.1g, mix, at room temperature carry out reaction in 5 hours.Polyreaction easily and is equably carried out, and obtains polyamic acid (PA-3).In the nmp solution of this polyamic acid (PA-3), interpolation is as Pyranton (DAA) 88.89g (NMP:DAA=80: 20 (weight ratios)), obtaining polyamic acid concentration is the crystal aligning agent (S9) of 6.0 % by weight of specific solvent (B).

[embodiment 10～embodiment 12 and comparative example 3]

Except the kind of the solvent for the preparation of crystal aligning agent being changed to the aspect as described in following table 1, in the mode identical with described embodiment 9, obtain crystal aligning agent (S10)～crystal aligning agent (S12), crystal aligning agent (R3).

[embodiment 13]

Using the p-PDA6.5g as diamines (0.06mol) and 4-(4-trans-n-heptyl cyclohexyl) phenoxy group)-1,3-diaminobenzene (PCH7DAB, the represented compound of described formula (d-4-3)) 15.22g (0.04mol) is dissolved in NMP165g, add wherein the CBDA19.41g (0.099mol) as tetracarboxylic dianhydride, at room temperature carry out reaction in 24 hours, obtain the solution that comprises polyamic acid (PA-4).The weight average molecular weight (Mw) of gained polyamic acid (PA-4) is 40,000.To adding NMP50g in this solution 30g and as Pyranton (DAA) 20g (NMP:DAA=80: 20 (weight ratios)) of specific solvent (B), fully stir and make uniform solution, obtaining concentration is the crystal aligning agent (S13) of 6.0 % by weight.

[embodiment 14～embodiment 16 and comparative example 4]

Except the kind of the 2nd solvent for the preparation of crystal aligning agent being changed to the aspect as described in following table 1, in the mode identical with described embodiment 13, obtain crystal aligning agent (S14)～crystal aligning agent (S16), crystal aligning agent (R4).

[embodiment 17]

Using the p-PDA1.46g as diamines (13.5mmol) and 1,3-diamino-4-{4-[is trans-4-(trans-4-n-pentyl cyclohexyl) cyclohexyl] and phenoxy group } benzene (PBCH5DAB, the represented compound of described formula (d-4-2)) 0.65g (1.50mmol) mixes in NMP20.0g, interpolation is as tetracarboxylic dianhydride's CBDA2.85g (14.5mmol33 and interpolation NMP24.7g, at 25 ℃, carry out reaction in 5 hours, obtain the solution that comprises polyamic acid (PA-5).Then, to adding NMP10.7g in the polyamic acid solution 40.0g of gained and as Pyranton (DAA) 16.0g (NMP:DAA=75: 25 (weight ratios)) of specific solvent (B), stir 1 hour, obtain thus the crystal aligning agent that polyamic acid concentration is 6 % by weight (S17).

[embodiment 18～embodiment 20 and comparative example 5]

Except the kind of the 2nd solvent for the preparation of crystal aligning agent being changed to the aspect as described in following table 1, in the mode identical with described embodiment 17, obtain crystal aligning agent (S18)～crystal aligning agent (S20), crystal aligning agent (R5).

[embodiment 21]

Using the CBDA2.58g as tetracarboxylic dianhydride (13.1mmol), be dissolved in NMP43g as the PCH7DAB5.0g (13.1mmol) of diamines, at 20 ℃, stir and react for 4 hours, the solution that preparation comprises polyamic acid (PA-6).Then, in the nmp solution of the polyamic acid (PA-6) of gained, interpolation is as Pyranton (DAA) 75.8g (NMP:DAA=35: 65 (weight ratios)), obtaining solid component concentration is the crystal aligning agent (S21) of 6.0 % by weight of specific solvent (B).

[embodiment 22～embodiment 24 and comparative example 6]

Except the kind of the 2nd solvent for the preparation of crystal aligning agent being changed to the aspect as described in following table 1, in the mode identical with described embodiment 21, obtain crystal aligning agent (S22)～crystal aligning agent (S24), crystal aligning agent (R6).

[embodiment 25]

Make pyromellitic acid anhydride (PMDA) 8.724g (0.04mol) as tetracarboxylic dianhydride, as the p-PDA2.877g (0.0266mol) of diamines and PCH7DAB4.567g (0.012mol) in NMP91.6g, at room temperature carry out reaction in 3 hours, the solution that preparation comprises polyamic acid (PA-7).In this polyamic acid solution 25g, add NMP20g and as Pyranton (DAA) 30g (NMP:DAA=60: 40 (weight ratios)) of specific solvent (B), prepare the polyamic acid solution that solid component concentration is 5.0 % by weight, as crystal aligning agent (S25).

[embodiment 26～embodiment 28 and comparative example 7]

Except the kind of the 2nd solvent for the preparation of crystal aligning agent being changed to the aspect as described in following table 1, in the mode identical with described embodiment 25, obtain crystal aligning agent (S26)～crystal aligning agent (S28), crystal aligning agent (R7).

[embodiment 29]

Make as 2 of diamines, 4-diamino-N, N-diallyl aniline 14.64g (0.072mol), as the dodecyl amine 2.96g (0.016mol) of monoamine and as tetracarboxylic dianhydride's CBDA15.69g (0.08mol) in NMP300g, at room temperature carry out reaction in 4 hours, the solution that preparation comprises polyamic acid intermediate (PA-8).In the nmp solution of this polyamic acid intermediate, interpolation is as Pyranton (DAA) 221.5g (NMP:DAA=60: 40 (weight ratios)), obtaining solid component concentration is the crystal aligning agent (S29) of 6.0 % by weight of specific solvent (B).

[embodiment 30～embodiment 32 and comparative example 8]

Except the kind of the 2nd solvent for the preparation of crystal aligning agent being changed to the aspect as described in following table 1, in the mode identical with described embodiment 29, obtain crystal aligning agent (S30)～crystal aligning agent (S32), crystal aligning agent (R8).

[embodiment 33]

Make the dicyclo [3 as tetracarboxylic dianhydride, 3,0] octane-2,4,6,8-tetracarboxylic dianhydride (BODA) 4.50g (0.018mol), as the PCH7DAB0.68g (0.0018mol) of diamines and p-PDA1.75g (0.0162mol) in NMP39.3g, then and then at 40 ℃, carry out reaction in 43 hours at room temperature react.In this polyamic acid solution 42g, add NMP, the solution of preparation 1 % by weight, adds diacetyl oxide 4.18g, pyridine 6.48g wherein as imidization catalyst, at room temperature reacts 30 minutes, reacts 2 hours at 120 ℃.This solution is fed in a large amount of methyl alcohol, by the white precipitate filtering separation of gained and dry, obtains white polyimide powder.The imide rate of measuring gained polyimide powder (polyimide (PI-1)), result is 72%.Make this powder 0.6g be dissolved in (NMP:DAA=50: 50 (weight ratios)), obtaining solid component concentration is the crystal aligning agent (S33) of 6.0 % by weight in NMP4.7g and Pyranton (DAA) 4.7g as specific solvent (B).

[embodiment 34～embodiment 36 and comparative example 9]

Except the kind of the 2nd solvent for the preparation of crystal aligning agent being changed to the aspect as described in following table 1, in the mode identical with described embodiment 33, obtain crystal aligning agent (S34)～crystal aligning agent (S36), crystal aligning agent (R9).

[embodiment 37]

Make the dicyclo [3 as tetracarboxylic dianhydride, 3,0] octane-2,4,6,8-tetracarboxylic dianhydride (BODA) 4.50g (0.018mol), as the PBCH5DAB2.34g (0.0054mol) of diamines and 3,5-diaminobenzoic acid (35DAB) 1.92g (0.0126mol) in NMP26.3g, at room temperature react, then so that at 40 ℃, carry out 43 hours reaction.In this polyamic acid solution 30g, add NMP, the solution of preparation 6 % by weight, adds diacetyl oxide 2.4g, pyridine 1.8g wherein as imidization catalyst, at room temperature reacts 30 minutes, reacts 4 hours at 110 ℃.This solution is fed in a large amount of methyl alcohol, by the white precipitate filtering separation of gained and dry, obtains white polyimide powder.The imide rate of measuring gained polyimide powder (polyimide (PI-2)), result is 72%.Make this powder 0.6g be dissolved in NMP and the 3-methoxyl group-N as the 1st solvent, in N-dimethyl propylene acid amides (D1) and the mixed solvent as the Pyranton (DAA) of specific solvent (B), make the solution that polyamic acid concentration is 6.0 % by weight.Nmp solution 0.4g (as 3-AMP, being equivalent to 0.03g) to adding 7.5 % by weight of 3-aminomethyl pyridine (3-AMP) in this solution stirs 15 hours at 50 ℃, obtains thus crystal aligning agent (S37).In addition, the solvent composition with crystal aligning agent becomes NMP:D1:DAA=30: the mode of 20: 50 (weight ratio) is prepared crystal aligning agent.

[embodiment 38]

Except by the quantitative change of the PBCH5DAB for the synthesis of polyamic acid 3.90g (0.0090mol) more, and by 3, the quantitative change of 5-diaminobenzoic acid more beyond the aspect of 1.37g (0.0090mol), is carried out the operation identical with embodiment 37, obtains polyamic acid solution.In addition, with the polyamic acid solution of gained, carry out the operation identical with embodiment 37, obtain polyimide powder.The imide rate of measuring gained polyimide powder (polyimide (PI-3)), result is 74%.Make this powder 0.6g be dissolved in NMP and the 3-butoxy-N as the 1st solvent, in N-dimethyl propylene acid amides (D2) and the mixed solvent as the Pyranton (DAA) of specific solvent (B), make the solution that polyamic acid concentration is 6.0 % by weight.Nmp solution 0.8g (as 3-AMP, being equivalent to 0.06g) to adding 7.5 % by weight of 3-aminomethyl pyridine (3-AMP) in this solution stirs 15 hours at 50 ℃, obtains thus crystal aligning agent (S38).In addition, the solvent composition with crystal aligning agent becomes NMP:D2:DAA=30: the mode of 30: 40 (weight ratio) is prepared crystal aligning agent.

[embodiment 39]

In the mode identical with described embodiment 1, the solution that preparation comprises polyamic acid (PA-1).This solution is fed in a large amount of methyl alcohol, by the white precipitate filtering separation of gained and dry, obtains polyamic acid powder.Make this powder dissolution in the 3-methoxyl group-N as the 1st solvent, (D1: DAA=60: 40 (weight ratios)), obtaining solid component concentration is the crystal aligning agent (S39) of 6.0 % by weight in N-dimethyl propylene acid amides (D1) and the mixed solvent as the Pyranton (DAA) of specific solvent (B).

[embodiment 40]

In the mode identical with described embodiment 5, the solution that preparation comprises polyamic acid (PA-2).This solution is fed in a large amount of methyl alcohol, by the white precipitate filtering separation of gained and dry, obtains polyamic acid powder.Make this powder dissolution in the 3-butoxy-N as the 1st solvent, (D2: DEDG=50: 50 (weight ratios)), obtaining polyamic acid concentration is the crystal aligning agent (S40) of 6.0 % by weight in N-dimethyl propylene acid amides (D2) and the mixed solvent as the diethylene glycol diethyl ether (DEDG) of specific solvent (B).

[embodiment 41]

In the mode identical with described embodiment 9, the solution that preparation comprises polyamic acid (PA-3).This solution is fed in a large amount of methyl alcohol, by the white precipitate filtering separation of gained and dry, obtains polyamic acid powder.Make this powder dissolution in the NMP as the 1st solvent and 3-methoxyl group-N, N-dimethyl propylene acid amides (D1) and as in the mixed solvent of the isoamyl ether (DIPE) of specific solvent (B) (NMP: D1: DIPE=40: 40: 20 (weight ratio)), obtaining polyamic acid concentration is the crystal aligning agent (S41) of 6.0 % by weight.

[embodiment 42]

In the mode identical with described embodiment 13, the solution that preparation comprises polyamic acid (PA-4).This solution is fed in a large amount of methyl alcohol, by the white precipitate filtering separation of gained and dry, obtains polyamic acid powder.Make this powder dissolution in the NMP as the 1st solvent and 3-butoxy-N, N-dimethyl propylene acid amides (D2) and as in the mixed solvent of the propylene-glycol diacetate (PG-AC) of specific solvent (B) (NMP: D2: PG-AC=40: 40: 20 (weight ratio)), obtaining polyamic acid concentration is the crystal aligning agent (S42) of 6.0 % by weight.

[embodiment 43]

In the mode identical with described embodiment 17, the solution that preparation comprises polyamic acid (PA-5).This solution is fed in a large amount of methyl alcohol, by the white precipitate filtering separation of gained and dry, obtains polyamic acid powder.Make this powder dissolution in the 3-methoxyl group-N as the 1st solvent, (D1: DAA=75: 25 (weight ratios)), obtaining polyamic acid concentration is the crystal aligning agent (S43) of 6.0 % by weight in N-dimethyl propylene acid amides (D1) and the mixed solvent as the Pyranton (DAA) of specific solvent (B).

[embodiment 44]

In the mode identical with described embodiment 21, the solution that preparation comprises polyamic acid (PA-6).This solution is fed in a large amount of methyl alcohol, by the white precipitate filtering separation of gained and dry, obtains polyamic acid powder.Make this powder dissolution in the 3-butoxy-N as the 1st solvent, (D2: DEDG=35: 65 (weight ratios)), obtaining polyamic acid concentration is the crystal aligning agent (S44) of 6.0 % by weight in N-dimethyl propylene acid amides (D2) and the mixed solvent as the diethylene glycol diethyl ether (DEDG) of specific solvent (B).

[embodiment 45]

In the mode identical with described embodiment 25, the solution that preparation comprises polyamic acid (PA-7).This solution is fed in a large amount of methyl alcohol, by the white precipitate filtering separation of gained and dry, obtains polyamic acid powder.Make this powder dissolution in the NMP as the 1st solvent and 3-methoxyl group-N, N-dimethyl propylene acid amides (D1) and as in the mixed solvent of the isoamyl ether (DIPE) of specific solvent (B) (NMP: D1: DIPE=30: 30: 40 (weight ratio)), obtaining polyamic acid concentration is the crystal aligning agent (S45) of 6.0 % by weight.

[embodiment 46]

In the mode identical with described embodiment 29, the solution that preparation comprises polyamic acid intermediate (PA-8).This solution is fed in a large amount of methyl alcohol, by the white precipitate filtering separation of gained and dry, obtains polyamic acid powder.Make this powder dissolution in the NMP as the 1st solvent and 3-butoxy-N, N-dimethyl propylene acid amides (D2) and as in the mixed solvent of the propylene-glycol diacetate (PG-AC) of specific solvent (B) (NMP: D2: PG-AC=30: 30: 40 (weight ratio)), obtaining polyamic acid concentration is the crystal aligning agent (S46) of 6.0 % by weight.

[embodiment 47]

In the mode identical with described embodiment 33, obtain the powder of polyimide (PI-1).Make this powder dissolution in the 3-methoxyl group-N as the 1st solvent, (D1: DAA=50: 50 (weight ratios)), obtaining solid component concentration is the crystal aligning agent (S47) of 6.0 % by weight in N-dimethyl propylene acid amides (D1) and the mixed solvent as the Pyranton (DAA) of specific solvent (B).

[table 1]

[table 2]

In addition, the abbreviation in table 1 and table 2 is as described below.

(diamines)

DA-1:1, two (4-amino-benzene oxygen) pentanes of 5-

DA-2:2,4-diamino-N, N-diallyl aniline

35DAB:3,5-diaminobenzoic acid

(monoamine)

MA-1: dodecyl amine

(the 1st solvent)

D1:3-methoxyl group-N, N-dimethyl propylene acid amides

D2:3-butoxy-N, N-dimethyl propylene acid amides

(the 2nd solvent)

DAA: Pyranton

DEDG: diethylene glycol diethyl ether

DIPE: isoamyl ether

PG-AC: propylene-glycol diacetate

BC: ethylene glycol butyl ether

(additive)

3-AMP:3-aminomethyl pyridine (the represented compound of described formula (c-1-16))

Wherein, in table 2, the numerical value in the parantheses on " additive " hurdle is the allotment ratio (weight part) of the aminocompound (C) for entire amount 100 weight parts of the component of polymer for the preparation of crystal aligning agent.

The evaluation > of < storage stability

Each crystal aligning agent to above-mentioned gained, after utilizing the strainer of 1.0 μ m to filter, at-30 ℃, keeping is 1 month, then reverts to room temperature (25 ℃), observes having or not of precipitate in crystal aligning agent.The results are shown in described table 1 and table 2.In addition, in table 1 and table 2, the information slip of not observing precipitate in crystal aligning agent is shown to " zero ", the information slip of observing precipitate is shown to " * ".

The evaluation > of < printing

To above-mentioned each prepared crystal aligning agent, after utilizing the strainer of 1.0 μ m to filter, at-15 ℃, keeping is 6 months, then reverts to room temperature (25 ℃).Then, use liquid crystal orienting film printing press (Japan's description printing (thigh) is manufactured), crystal aligning agent is coated on the transparent electrical pole-face of the glass substrate with transparency electrode that comprises ITO film.Then, on the hot-plate of 80 ℃, heating (prebake conditions) is 1 minute, removes solvent, then heating on the hot-plate of 200 ℃ (baking afterwards) 10 minutes, and formation average film thickness is

film.Utilizing multiplying power is that the microscope of 20 times is observed this and filmed, and investigation printing inequality and pin hole (pin hole) have or not.Evaluation is to carry out as follows: by the average evaluation of substantially not observing printing inequality and pin hole, being printing good (zero), is printing bad (*) by least any average evaluation of observing printing inequality and pin hole.The results are shown in described table 1 and table 2.

As shown in table 1 and table 2, the storage stability that the crystal aligning agent of embodiment is in low temperature situation is certainly good, and the printing after low temperature keeping is also good.On the other hand, the printing after the storage stability of the crystal aligning agent of comparative example and low temperature keeping is bad.Therefore known, by using specific solvent (B), can guarantee the coating to substrate, and can improve storage stability.

Claims

1. a crystal aligning agent, is characterized in that containing: choosing freely makes tetracarboxylic dianhydride and diamine reactant and the polyamic acid, polyimide and the poly amic acid ester that obtain form at least one polymkeric substance (A) and the solvent in cohort;

Described polymkeric substance (A) is to use diamines and the polymkeric substance that obtains, and described diamines comprises freely following formula (d-1)～formula (d-4) represented at least one in cohort that compound forms respectively of choosing, and

Described solvent comprises specific solvent (B), and described specific solvent (B) is freely following formula (b-1)～formula (b-3) represented at least one in cohort that compound forms respectively of choosing:

In formula (d-1), X ¹and X ²be independently respectively singly-bound ,-O-,-S-,-OCO-or-COO-, Y ¹for Sauerstoffatom or sulphur atom, R ¹and R ²be alkane two bases of carbon number 1～3 independently respectively; Nl be 0 or 1, n2 and n3 in the situation that of nl=0 for meeting the integer of n2+n3=2, the in the situation that of nl=1, be n2=n3=1; In formula (d-2), X ³for singly-bound ,-O-or-S-, the integer that ml is 0～3; M2 is 1～12 integer in the situation that of ml=0, in the situation that the integer that ml is 1～3 is m2=2; In formula (d-3), R ³for the straight chain shape of carbon number 1～12 or 1 valency alkyl of branch-like, R ⁴for the straight chain shape of hydrogen atom or carbon number 1～12 or 1 valency alkyl of branch-like, R ⁵and R ⁶be hydrogen atom or methyl independently respectively; In formula (d-4), X ⁴and X ⁵be independently respectively singly-bound ,-O-,-COO-or-OCO-, R ⁷alkane two bases for carbon number 1～3; A is 0 or 1, the b integer that is 0～2, the integer that c is 1～20, and k is 0 or 1; Wherein, a and b can not be 0 simultaneously;

In formula (b-1), R ⁸and R ¹⁰be 1 valency alkyl of carbon number 1～3 independently respectively, R ⁹alkane two bases for carbon number 2～5; In formula (b-2), R ¹¹1 valency group, the straight chain shape of carbon number 3～5 or at least 1 hydrogen atom of branch-like alkyl between the C-C for the straight chain shape at carbon number 3～5 or branch-like alkyl with 1 " 0-" replaces the 1 valency group that forms or the branch-like alkyl of carbon number 3～5 through hydroxyl; In formula (b-3), X ⁶for-C (OH) R ^a-; Wherein, R ^afor methyl or ethyl;-CO-or-COO-*; Wherein, * represents and R ¹²associative key; , R ¹²alkyl for carbon number 1～4.

2. crystal aligning agent according to claim 1, is characterized in that: 1 % by weight～70 % by weight of the entire amount that the content of described specific solvent (B) is described solvent.

3. crystal aligning agent according to claim 1 and 2, it is characterized in that: described polymkeric substance (A) is to use tetracarboxylic dianhydride and the polymkeric substance that obtains, described tetracarboxylic dianhydride comprises the freely represented compound, 1 of following formula (t-1) of choosing, 2,3,4-tetramethylene tetracarboxylic dianhydride and at least one in cohort that pyromellitic acid anhydride forms:

In formula (t-1), X ⁷, X ⁸, X ⁹and X ¹⁰be singly-bound or methylene radical independently respectively, the integer that j is 1～3.

4. crystal aligning agent according to claim 1 and 2, it is characterized in that: more contain amine compound (C), described amine compound (C) has 1 one-level amino and nitrogenous heteroaromatic in molecule, and described primary amine base is binding on chain alkyl or ester ring type alkyl.

5. crystal aligning agent according to claim 4, is characterized in that: described amine compound (C) is the represented compound of following formula (c-1):

H ₂N-A ¹-A ² (c-1)

In formula (c-1), A ¹for thering is the divalent organic radical of chain alkyl or ester ring type alkyl, A ²for nitrogenous heteroaromatic.

6. crystal aligning agent according to claim 1 and 2, is characterized in that: do not contain in fact ethylene glycol butyl ether as described solvent.

7. a liquid crystal orienting film, is characterized in that: it is to use according to the crystal aligning agent described in any one in claim 1 to 6 to form.

8. a liquid crystal display device, is characterized in that: comprise liquid crystal orienting film according to claim 7.