CN103782231B

CN103782231B - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: CN103782231B
Application number: CN201280043173.0A
Authority: CN
Inventors: 三木德俊; 片山雅章; 后藤耕平; 保坂和义
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2011-09-08
Filing date: 2012-09-06
Publication date: 2017-05-10
Anticipated expiration: 2032-09-06
Also published as: CN103782231A; JP6011537B2; JPWO2013035803A1; TW201323521A; KR101951501B1; WO2013035803A1; KR20190124815A; KR20140059219A; KR20180072830A; TW201726811A; JP2016194707A; KR102224531B1; JP6414145B2; CN106635061A; TWI586757B; TWI620794B; CN106635061B

Abstract

Provided is a liquid crystal aligning agent which has high wettability and spreadability over substrates and is capable of providing a liquid crystal alignment film that has excellent coating film uniformity and excellent coating film properties in the end portions, said liquid crystal alignment film enabling the achievement of pretilt angles that do not change even if left at high temperatures or irradiated with light for a long period of time. A liquid crystal aligning agent which contains N-ethyl-2-pyrrolidone and at least one polymer that is selected from the group consisting of polyimide precursors having a side chain represented by formula [1] and polyimides. (In the formula, each of X1, X2 and X3 independently represents a single bond or the like; each of X4 and X5 independently represents a benzene ring or the like; X6 represents an alkyl group having 1-18 carbon atoms, or the like; and n represents an integer of 0-4.)

Description

Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells

Technical field

The present invention relates to the aligning agent for liquid crystal used when making liquid crystal orientation film and the liquid crystal using the inorganic agent Display element.

Background technology

Now, for the liquid crystal orientation film used in liquid crystal display cells requires multifrequency nature.As characteristic therein One of, there is the control of the tilt angle of the so-called liquid crystal for making liquid crystal molecule that arbitrary value is remained relative to the orientation inclination angle of real estate System.It is well known that the size of the tilt angle can be by selecting the structure of the polyimides for constituting liquid crystal orientation film changing 's.It is sub- using the diamine compound with side chain as polyamides in the technology for controlling tilt angle by the structure of polyimides A part for amine raw material and the method that uses can also control tilt angle according to the use ratio of the diamine compound.So, It is to be relatively easy to obtain target tilt angle, is useful as the method for increase tilt angle.As the tilt angle of increase liquid crystal Diamine compound side-chain structure, it is proposed that the alkyl comprising long-chain or fluoroalkyl (referring for example to patent documentation 1), phenyl and The side-chain structure (referring for example to patent documentation 2,3) of the ring structure of cyclohexyl etc..

In recent years, the LCD TV of big picture and the mobile device of high-resolution are widely used in liquid crystal display cells Purposes (display portion of digital camera and mobile phone), compared with the past, the maximization of the substrate for being used, substrate jump (Japanese：Segment difference) concavo-convex gradually increase.In this condition, from from the perspective of display characteristic, also require that relative to large-scale Substrate and jump can be formed uniformly liquid crystal orientation film.In the manufacturing process of the liquid crystal orientation film, can by polyamic acid or solvent In the case that the aligning agent for liquid crystal (also referred to as coating solution) of dissolubility polyimides (also referred to as resin) coats substrate, Industrially generally carried out with flexographic printing process or ink-jet application method etc..Now, in the solvent of coating solution, except as tree Beyond METHYLPYRROLIDONE or gamma-butyrolacton of the excellent solvent of fat dissolubility (also referred to as good solvent) etc., in order to improve The painting film uniformity of liquid crystal orientation film, can also mix the butyl as the low solvent of resin dissolubility (also referred to as poor solvent) Cellosolve etc. (referring for example to patent documentation 4).

Prior art literature

Patent documentation

Patent documentation 1：Japanese Patent Laid-Open 2-282726 publication

Patent documentation 2：Japanese Patent Laid-Open 9-278724 publication

Patent documentation 3：No. 2004/52962 text of International Publication No.

Patent documentation 4：Japanese Patent Laid-Open 2-37324 publication

The content of the invention

Invent technical problem to be solved

Liquid crystal orientation film is also used for liquid crystalline phase for the tilt angle of the angle of substrate, i.e. liquid crystal is controlled, liquid crystal Display element high performance, its use range is also expanding year by year, is not merely singly the tilt angle for obtaining regulation, tilt angle Stability also becomes more and more important.

In the manufacturing process of liquid crystal display cells, in order to improve the orientation uniformity of liquid crystal, liquid crystal is enclosed sometimes laggard Row heat treated, by the temporary transient isotropization of liquid crystal.But, when the stability of tilt angle is low, after the isotropism is processed, Appearance can not obtain the tilt angle or tilt angle of target sizes and uneven problem occurs.Especially for acquisition high brightness And use that caloric value is big, the liquid crystal display cells of backlight more than the irradiation dose of light, such as auto-navigation system and large-scale tv In the case of, use or place in the environment of long-time is exposed to high temperature and light irradiation sometimes.In such rigor condition Under, when tilt angle slowly changes, causing cannot obtain initial stage display characteristic or show unequal problem.

Additionally, being obtained using the polyamic acid by obtained by the diamine compound with side chain or solvent-soluble polyimide Aligning agent for liquid crystal, exist liquid crystal orientation film apply film uniformity decline tendency.Particularly cannot obtain uniform In the case of film, in the case of rejecting or produce pore, when liquid crystal display cells are made, the part becomes aobvious Show defect.It is therefore desirable to increase the combined amount of the coating solution poor solvent high to the infiltration spread of substrate, poor solvent The ability of polyamic acid or solvent-soluble polyimide dissolving is made, so exist if mixing in large quantities there is resin analysis The problem for going out.

Further, in recent years, for the mobile device purposes of smart mobile phone or mobile phone etc., using liquid crystal display cells. In order to ensure display surface as much as possible in these purposes, the sealant for bonding between the substrate by liquid crystal display cells is present In the position of the end of close liquid crystal orientation film.So, in the case that the film of the end of liquid crystal orientation film is reduced, i.e. liquid crystal In the case that the end of alignment films is not the state of straight line or the end in protuberance, the adhesive effect between the substrate of sealant Decline, causing the display characteristic and reliability of liquid crystal display cells reduces.

The invention that the present invention is in view of the foregoing and completes.I.e., the technical problem to be solved is to provide i.e. Long-time is set to be exposed under high temperature and light irradiation, the liquid crystal orientation film that tilt angle is also not changed in.Even if additionally, also providing a kind of It is using polyamic acid or liquid crystal aligning obtained by solvent-soluble polyimide by obtained by the diamine compound with side chain Inorganic agent, can also obtain that coating solution is high to the infiltration spread of substrate, uniform film, and the end of liquid crystal orientation film The also excellent liquid crystal orientation film of film.Additionally, also providing the liquid crystal display cells with above-mentioned liquid crystal orientation film, carrying For the aligning agent for liquid crystal of above-mentioned liquid crystal orientation film.

Solve the technical scheme that technical problem is adopted

Present inventor has performed conscientiously studying, the solvent comprising ad hoc structure and the side chain with ad hoc structure are as a result found Polymer aligning agent for liquid crystal in terms of above-mentioned purpose is reached extremely effectively, so as to complete the present invention.

That is, the present invention has following technology contents.

(1) a kind of aligning agent for liquid crystal, it includes following compositions (A) and composition (B),

Composition (A)：N- ethyl-2-pyrrolidones；

Composition (B)：Enter selected from the polyimide precursor with the side chain represented with following formula [1] and by polyimide precursor At least one polymer of polyimides obtained by row imidizate；

[changing 1]

In formula [1], X₁It is singly-bound ,-(CH₂)_a-、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、- COO-、-OCO-、-CON(CH₃)-or-N (CH₃) CO-, wherein a is 1～15 integer；X₂It is singly-bound or-(CH₂)_b-, wherein b is 1～15 integer；X₃It is singly-bound ,-(CH₂)_c-、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-COO-、- OCO-、-CON(CH₃)-or-N (CH₃) CO-, wherein c is 1～10 integer；X₄It is the divalent selected from phenyl ring, hexamethylene ring and heterocycle Cyclic group, wherein, the arbitrary hydrogen atom on the cyclic group can be by the alkyl of carbon number 1～3, the alcoxyl of carbon number 1～3 Base, carbon number 1～3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or fluorine atom replace；X₅Be selected from phenyl ring, hexamethylene ring and The divalent cyclic group of heterocycle, wherein, the arbitrary hydrogen atom on the cyclic group can by the alkyl of carbon number 1～3, carbon number 1～ 3 alkoxyl, carbon number 1～3 replace containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or fluorine atom；X₆It is carbon number 1～18 The fluoroalkoxy containing fluoroalkyl, the alkoxyl of carbon number 1～18 or carbon number 1～18 of alkyl, carbon number 1～18, n be 0～4 it is whole Number.

(2) aligning agent for liquid crystal described in (1) as described above, wherein, the composition (B) is before following polyimides Body and polyimide precursor is carried out at least one polymer of polyimides obtained by imidizate；The polyimide precursor Be will with the diamine compound of the side chain represented using formula [1] as raw material a part of use obtained by.

(3) aligning agent for liquid crystal described in (2) as described above, wherein, the diamidogen with the side chain represented with formula [1] Compound is the diamine compound represented with following formula [1a]；

[changing 2]

In formula [1a], X₁It is singly-bound ,-(CH₂)_a-、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、- COO-、-OCO-、-CON(CH₃)-or-N (CH₃) CO-, wherein a is 1～15 integer；X₂It is singly-bound or-(CH₂)_b-, wherein b is 1～15 integer；X₃It is singly-bound ,-(CH₂)_c-、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-COO-、- OCO-、-CON(CH₃)-or-N (CH₃) CO-, wherein c is 1～10 integer；X₄It is the divalent selected from phenyl ring, hexamethylene ring and heterocycle Cyclic group, wherein, the arbitrary hydrogen atom on the cyclic group can be by the alkyl of carbon number 1～3, the alcoxyl of carbon number 1～3 Base, carbon number 1～3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or fluorine atom replace；X₅Be selected from phenyl ring, hexamethylene ring and The divalent cyclic group of heterocycle, wherein, the arbitrary hydrogen atom on the cyclic group can by the alkyl of carbon number 1～3, carbon number 1～ 3 alkoxyl, carbon number 1～3 replace containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or fluorine atom；X₆It is carbon number 1～18 The fluoroalkoxy containing fluoroalkyl, the alkoxyl of carbon number 1～18 or carbon number 1～18 of alkyl, carbon number 1～18；N be 0～4 it is whole Number, m is 1～4 integer.

(4) aligning agent for liquid crystal described in (2) or (3) as described above, wherein, 5～80 moles of % of raw material diamine component Using the diamidogen represented with the formula [1a].

(5) aligning agent for liquid crystal any one of (1)～(4) as described above, wherein, the composition (B) is to use With polymer obtained by the tetracarboxylic dianhydride that following formula [2] is represented；

[changing 3]

In formula [2], Y₁It is 4 valency organic groups of carbon number 4～13, and the non-aromatic cyclic hydrocarbon base containing carbon number 4～10.

(6) aligning agent for liquid crystal described in (5) as described above, wherein, the Y₁It is to be represented with following formula [2a]～[2j] Structure group；

[changing 4]

In formula [2a], Y₂～Y₅It is hydrogen atom, methyl, chlorine atom or phenyl ring, and each group each other can be with identical or different； In formula [2g], Y₆And Y₇It is hydrogen atom or methyl, and each group each other can be with identical or different.

(7) aligning agent for liquid crystal any one of (1)～(6) as described above, wherein, as the composition (B) Polymer is polyamic acid.

(8) aligning agent for liquid crystal any one of (1)～(6) as described above, wherein, as the composition (B) Polymer is to make polyimides obtained by polyamic acid dehydration closed-loop.

(9) aligning agent for liquid crystal any one of (1)～(8) as described above, wherein, as composition (C), containing N- N-methyl-2-2-pyrrolidone N or gamma-butyrolacton.

(10) aligning agent for liquid crystal any one of (1)～(9) as described above, wherein, as composition (D), contain Selected from 1- hexanols, Hexalin, 1,2- ethylene glycol, 1,2- Propylene Glycol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol only son Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether and third At least one of glycol monobutyl ether.

(11) aligning agent for liquid crystal any one of (1)～(10) as described above, wherein, the composition (A) accounts for liquid 10～100 mass % of contained whole organic solvents in brilliant aligning agent.

(12) aligning agent for liquid crystal any one of (9)～(11) as described above, wherein, the composition (C) accounts for liquid 0.1～50 mass % of contained whole organic solvents in brilliant aligning agent.

(13) aligning agent for liquid crystal any one of (10)～(12) as described above, wherein, the composition (D) accounts for liquid 5～80 mass % of contained whole organic solvents in brilliant aligning agent.

(14) aligning agent for liquid crystal any one of (1)～(13) as described above, wherein, in aligning agent for liquid crystal The composition (B) be 0.1～15 mass %.

(15) a kind of liquid crystal orientation film, it is processed by using the liquid crystal aligning any one of above-mentioned (1)～(14) Agent and obtain.

(16) a kind of liquid crystal orientation film, it is processed by using the liquid crystal aligning any one of above-mentioned (1)～(14) Agent is simultaneously obtained using ink-jet method.

(17) a kind of liquid crystal display cells, it has the liquid crystal orientation film described in above-mentioned (15) or (16).

(18) liquid crystal orientation film described in (15) or (16) as described above, it is used by a pair of substrates for possessing electrode Between there is liquid crystal layer and constitute, through the liquid crystal display cells of following operations manufacture, the operation is：Between the pair of substrate Liquid-crystal composition of the configuration comprising the polymerizable compound being polymerized using at least one party in active energy beam and heat, While between the electrode applied voltage, while making the polymerizable compound be polymerized.

(19) a kind of liquid crystal display cells, it has the liquid crystal orientation film described in above-mentioned (18).

(20) liquid crystal display cells described in (19) as described above, it is by possess electrode and the liquid crystal orientation film one Constitute having liquid crystal layer between substrate, and through following operations manufacturing, the operation is：The configuration bag between the pair of substrate Liquid-crystal composition containing the polymerizable compound being polymerized using at least one party in active energy beam and heat, while Applied voltage between the electrode, while making the polymerizable compound be polymerized.

(21) liquid crystal orientation film described in (15) or (16) as described above, it is used for has between a pair of substrates for possessing electrode Have a liquid crystal layer and constitute, through the liquid crystal display cells of following operations manufacture, the operation is：Configure between the pair of substrate Liquid crystal orientation film comprising the polymerizable group being polymerized using at least one party in active energy beam and heat, while Applied voltage between the electrode is while make the polymerizable group be polymerized.

(22) a kind of liquid crystal display cells, it has the liquid crystal orientation film described in above-mentioned (21).

(23) liquid crystal display cells described in (22) as described above, it between a pair of substrates for possessing electrode by having liquid crystal Layer and constitute, and through following operations manufacturing, the operation is：The configuration between the pair of substrate is included and penetrated using active-energy The liquid crystal orientation film of the polymerizable group that at least one party in line and heat is polymerized, while the applied voltage between the electrode While making the polymerizable group be polymerized.

The effect of invention

Using the aligning agent for liquid crystal of the present invention, if exposed to prolonged high temperature and light irradiation, also it is obtained pre- The liquid crystal orientation film that inclination angle is not changed in, and, be obtained solution it is high to the infiltration spread of substrate, relative to large substrate or The liquid crystal orientation film of the film excellent in uniformity of jump substrate.By using the liquid crystal orientation film, it is possible to provide display characteristic is excellent The high liquid crystal display cells of reliability.

Description of the drawings

Fig. 1 is the example for evaluating the painting film image of the linear optical microscope of the end of liquid crystal orientation film.

Fig. 2 is the protuberance (Japanese for evaluating the end of liquid crystal orientation film：Contain り on Ga り) optical microscope film The example of image.

Specific embodiment

The aligning agent for liquid crystal of the present invention is (also referred to as specific molten comprising the N- ethyl-2-pyrrolidones as composition (A) Agent) and as the sub- selected from the polyamides with the side chain (also referred to as specific side-chain structure) represented with above-mentioned formula [1] of composition (B) Amine precursor and at least one polymer that polyimide precursor is carried out into polyimides obtained by imidizate are (also referred to as specific poly- Compound).

Specific solvent in the present invention is the good solvent excellent to the dissolubility of polyamic acid and soluble polyimide.Also Have, compared with commonly used METHYLPYRROLIDONE or gamma-butyrolacton, it is low as the surface tension of solvent.Cause This, has used the aligning agent for liquid crystal of specific solvent compared with the aligning agent for liquid crystal of the specific solvent is not used, and is coated with Solution is high to the infiltration spread of substrate, even if not in a large number using the poor solvent that resin dissolubility is low, it is also possible to obtain film The liquid crystal orientation film of excellent in uniformity.Additionally, the infiltration spread by improving coating solution, makes end during liquid crystal orientation film The rectilinearity in portion is improved.

Additionally, specific solvent boiling point compared with commonly used METHYLPYRROLIDONE or gamma-butyrolacton is high, So the protuberance of end when making liquid crystal orientation film can be suppressed using the aligning agent for liquid crystal of specific solvent.

Specific side-chain structure in the present invention has phenyl ring, hexamethylene ring or heterocycle in pendant moiety.These phenyl ring, hexamethylene ring Or heterocycle shows as rigid structure compared with chain alkyl of the prior art.Thereby, side chain position to heat or ultraviolet Stability is improved, and is obtained even for the also stable liquid crystal orientation film of heat or light, tilt angle.Additionally, these phenyl ring, hexamethylene ring Or even if heterocycle shows as rigid structure, compared with the cyclic group formed by steroid skeleton of the prior art, polymer Organic solvent solubility it is also higher.Therefore, the aligning agent for liquid crystal with specific side-chain structure of the invention and existing skill The aligning agent for liquid crystal with the cyclic group formed by steroid skeleton in art is compared, and the coating homogeneity of substrate is carried It is high.

For above-mentioned reasons, the liquid crystal of the polymer comprising specific solvent and with specific side-chain structure of the invention Aligning agent, even if available long-time is exposed to the irradiation of high temperature and light, tilt angle is also unchanged and painting film uniformity is excellent Different liquid crystal orientation film, additionally, by using the liquid crystal orientation film, the high liquid crystal of the excellent reliability of display characteristic is obtained Show element.

The specific solvent of the present invention is N- ethyl-2-pyrrolidones.N- ethyl-2-pyrrolidones have raising coating solution Effect to the infiltration spread of substrate, thus preferably account for whole organic solvents contained in aligning agent for liquid crystal 10～ 100 mass %.It is preferred that 15～100 mass % of whole organic solvents, more preferably 20～100 mass % are accounted for, further preferred 25 ～100 mass %.

In whole organic solvents in aligning agent for liquid crystal, the amount of the specific solvent of the present invention is more, the effect of the present invention Really, i.e., coating solution is higher to the infiltration spread of substrate, and the liquid crystal orientation film of film excellent in uniformity is obtained.

The particular polymers of the present invention, i.e. selected from polyimide precursor and polyimide precursor being carried out into imidizate and is obtained At least one of polyimides there is the specific side-chain structure that represented with following formula [1].

[changing 5]

In formula [1], X₁It is singly-bound ,-(CH₂)_a- (a is 1～15 integer) ,-O- ,-NH- ,-N (CH₃)-、-CONH-、- NHCO-、-CH₂O-、-COO-、-OCO-、-CON(CH₃)-or-N (CH₃)CO-.Wherein, due to being readily synthesized side-chain structure, therefore It is preferred that singly-bound ,-(CH₂)_a- (a is 1～15 integer) ,-O- ,-CONH- ,-CH₂O- or-COO-.More preferably singly-bound ,-(CH₂)_a- (a is 1～10 integer) ,-O- ,-CONH- ,-CH₂O- or-COO-.Further preferred singly-bound ,-(CH₂)_a- (a be 1～10 it is whole Number) ,-O- ,-CH₂O- or-COO-.

X₂It is singly-bound or-(CH₂)_b- (b is 1～15 integer).Wherein, preferred singly-bound or-(CH₂)_b- (b be 1～10 it is whole Number).

X₃It is singly-bound ,-(CH₂)_c- (c is 1～15 integer) ,-O- ,-NH- ,-N (CH₃)-、-CONH-、-NHCO-、- CH₂O-、-COO-、-OCO-、-CON(CH₃)-or-N (CH₃)CO-.Wherein, due to being readily synthesized, therefore preferred singly-bound ,- (CH₂)_c- (c is 1～15 integer) ,-O- ,-CH₂O- ,-COO- or-OCO-.More preferably singly-bound ,-(CH₂)_c- (c is 1～10 Integer) ,-O- ,-CH₂O- ,-COO- or-OCO-.

X₄It is the divalent cyclic group selected from phenyl ring, hexamethylene ring and heterocycle.Arbitrary hydrogen atom on above-mentioned cyclic group can With by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, carbon number 1～3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or Fluorine atom replaces.Wherein, as divalent cyclic group, preferred phenyl ring or hexamethylene ring.

X₅It is the divalent cyclic group selected from phenyl ring, hexamethylene ring and heterocycle.Arbitrary hydrogen atom on the cyclic group can be with By the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, carbon number 1～3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or fluorine Atom replaces.Wherein, as divalent cyclic group, preferred phenyl ring or cyclohexane ring.

N is 0～4 integer, preferably 0～2 integer.

X₆Be the alkyl of carbon number 1～18, carbon number 1～18 containing fluoroalkyl, the alkoxyl of carbon number 1～18 or carbon number 1～18 Fluoroalkoxy.The alkyl of wherein preferred carbon number 1～18, carbon number 1～10 containing fluoroalkyl, the alkoxyl of carbon number 1～18 or The fluoroalkoxy of carbon number 1～10.The more preferably alkoxyl of the alkyl of carbon number 1～12 or carbon number 1～12.Further preferred carbon number 1～9 alkyl or the alkoxyl of carbon number 1～9.

As the X in formula [1]₁、X₂、X₃、X₄、X₅、X₆And the preferred compositions of n, can enumerate and International Publication publication WO2011/ The group of (2-1) described in the table 6～45 of page 13 of 132751 (2011.10.27 is disclosed)～page 33～(2-600) same Close.Also, the X in the present invention₁～X₆Y1～Y6 is expressed as in each table of International Publication publication, Y1～Y6 can be replaced with X₁～X₆。

Import the particular polymers of the present invention, be selected from polyimides as the specific side-chain structure that will be represented with formula [1] Precursor and polyimide precursor is carried out at least one method of polyimides obtained by imidizate, preferably will be with special The diamine compound for determining side-chain structure is used as a part for raw material.Particularly preferably using two amine compounds represented with following formula [1a] Thing (also referred to as specific side chain type diamine compound).

[changing 6]

In formula [1a], X₁It is singly-bound ,-(CH₂)_a- (a is 1～15 integer) ,-O- ,-NH- ,-N (CH₃)-、-CONH-、- NHCO-、-CH₂O-、-COO-、-OCO-、-CON(CH₃)-or-N (CH₃)CO-.Wherein, due to being readily synthesized side-chain structure, therefore It is preferred that singly-bound ,-(CH₂)_a- (a is 1～15 integer) ,-O- ,-CONH- ,-CH₂O- or-COO-.More preferably singly-bound ,-(CH₂)_a- (a is 1～10 integer) ,-O- ,-CONH- ,-CH₂O- or-COO-.Further preferred singly-bound ,-(CH₂)_a- (a be 1～10 it is whole Number) ,-O- ,-CH₂O- or-COO-.

X₄It is the divalent cyclic group selected from phenyl ring, hexamethylene ring or heterocycle.Arbitrary hydrogen atom on above-mentioned cyclic group can With by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, carbon number 1～3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or Fluorine atom replaces.Wherein, as divalent cyclic group, preferred phenyl ring or hexamethylene ring.

X₅It is the divalent cyclic group selected from phenyl ring, hexamethylene ring and heterocycle.Arbitrary hydrogen atom on the cyclic group can be with By the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, carbon number 1～3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or fluorine Atom replaces.Wherein, as divalent cyclic group, preferred phenyl ring or hexamethylene ring.

N is 0～4 integer, preferably 0～2 integer.

X in formula [1a]₁、X₂、X₃、X₄、X₅、X₆And the preferred compositions of n are identical with formula [1].

X in formula [1]₁、X₂、X₃、X₄、X₅、X₆And in the combination of n, preferred combination be 1-25～1-96,1-145～ 1-168,1-217～1-240,1-268～1-315,1-364～1-387,1-436～1-483 etc., particularly preferred combination is 1-49～1-96,1-145～1-168,1-217～1-240 etc..

In formula [1a], m is 1～4 integer, preferably 1.

It is the structure for for example being represented with following formula [1-1]～[1-13] specifically as formula [1a].

[changing 7]

(in formula [1-1]～[1-3], R₁It is-O- ,-OCH₂-、-CH₂O-、-COOCH₂- or CH₂OCO-；R₂Be straight-chain or Straight-chain, the alkyl of carbon number 1～22, the alkoxyl of carbon number 1～22, carbon number 1～22 containing containing fluoroalkyl or carbon number 1～22 Fluoroalkyloxy.)

[changing 8]

(in formula [1-4]～[1-6], R₃It is-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、-CH₂OCO-、- CH₂O-、-OCH₂- or-CH₂-；R₄It is straight-chain or straight-chain, the alkyl of carbon number 1～22, the alkoxyl of carbon number 1～22, carbon The fluoroalkoxy containing fluoroalkyl or carbon number 1～22 of number 1～22.)

[changing 9]

(in formula [1-7] and [1-8], R₅It is-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、-CH₂OCO-、- CH₂O-、-OCH₂-、-CH₂- ,-O- or-NH-；R₆Be fluorine-based, cyano group, trifluoromethyl, nitro, azo group, formoxyl, acetyl group, Acetoxyl group or hydroxyl.)

[changing 10]

(in formula [1-9] and formula [1-10], R₇For the straight-chain or branched-chain alkyl of carbon number 3～12, Isosorbide-5-Nitrae-cyclohexylidene Cis-trans isomerization is respectively transisomer.)

[changing 11]

(in formula [1-11] and formula [1-12], R₈For the straight-chain or branched-chain alkyl of carbon number 3～12, Isosorbide-5-Nitrae-cyclohexylidene Cis-trans isomerization be respectively transisomer.)

[changing 12]

(in formula [1-13], A₄Can be the straight-chain or branched-chain alkyl of the carbon number 3～20 being replaced by fluorine atoms；A₃It is 1, 4- cyclohexylidenes or 1,4- phenylenes；A₂It is oxygen atom or COO-* (the wherein key and A of band " * "₃Connection)；A₁Be oxygen atom or COO-* (wherein key and the (CH of band " * "₂)a₂Connection.)

Additionally, a₁It is 0 or 1, a₂It is 2～10 integer, a₃It is 0 or 1.)

In above-mentioned formula [1-1]～[1-13], the diamine compound of particularly preferred structure is formula [1-1]～[1-6], formula [1-9]～[1-13] etc..

Above-mentioned specific side chain type diamine compound can be protected according to liquid crystal aligning when making liquid crystal orientation film, voltage The characteristics such as holdup, accumulated charge, are used alone, or mixing two or more.

In the present invention, as long as not damaging the effect of the present invention, it is also possible to beyond specific side chain type diamine compound Other diamine compounds (hereinafter also referred to other diamine compounds) are used as the diamine component of raw material.Its concrete example is enumerated below Son.

P-phenylenediamine, 2,3,5,6- tetramethyl-para-phenylene diamines, 2,5- dimethyl-p-phenylenediamines, m-diaminobenzene., 2,4- diformazans Base m-diaminobenzene., 2,5- diaminotoluenes, 2,6- diaminotoluenes, 2,5- diaminophenols, 2,4- diaminophenols, 3,5- bis- Amino-phenol, 3,5- diaminourea benzylalcohols, 2,4- diaminourea benzylalcohols, 4,6- diamino resorcins, 4,4 '-benzidine, 3, 3 '-dimethyl -4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxy -4,4 '-diamino Base biphenyl, 3,3 '-dicarboxyl -4,4 '-benzidine, 3,3 '-two fluoro- 4,4 '-biphenyl, '-two of 3,3 '-trifluoromethyl -4,4 Aminobphenyl, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-benzidine, 2,3 '-benzidine, 4, 4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-diaminourea two Phenylmethane, 2,3 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '- Diamino-diphenyl ether, 2,2 '-diamino-diphenyl ether, 2,3 '-diamino-diphenyl ether, 4,4 '-sulfonyl dianil, 3, 3 '-sulfonyl dianil, double (4- aminophenyls) silane, double (3- aminophenyls) silane, dimethyl-bis- (4- aminophenyls) silicon Alkane, dimethyl-bis- (3- aminophenyls) silane, 4,4 '-thio dianil, 3,3 '-thio dianil, 4,4 '-diaminourea hexichol Amine, 3,3 '-diamino-diphenylamine, 3,4 '-diamino-diphenylamine, 2,2 '-diamino-diphenylamine, 2,3 '-diamino-diphenylamine, N- Methyl (4,4 '-diamino-diphenyl) amine, N- methyl (3,3 '-diamino-diphenyl) amine, N- methyl (3,4 '-diaminourea hexichol Base) amine, N- methyl (2,2 '-diamino-diphenyl) amine, N- methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diaminourea hexichol Ketone, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 1,4- diaminonaphthalenes, 2,2 '-diaminourea hexichol first Ketone, 2,3 '-diaminobenzophenone, 1,5- diaminonaphthalenes, 1,6- diaminonaphthalenes, 1,7- diaminonaphthalenes, 1,8- diaminonaphthalenes, 2, 5- diaminonaphthalenes, 2,6 diaminonaphthalenes, 2,7- diaminonaphthalenes, 2,8- diaminonaphthalenes, 1,2- double (4- aminophenyls) ethane, 1,2- Double (4- aminophenyls) propane of double (3- aminophenyls) ethane, 1,3-, double (3- aminophenyls) propane of 1,3-, double (the 4- ammonia of 1,4- Base phenyl) butane, double (3- aminophenyls) butane of 1,4-, double (3,5- diethyl -4- aminophenyls) methane, double (the 4- ammonia of 1,4- Phenoxyl) benzene, double (4- amino-benzene oxygens) benzene of 1,3-, double (4- aminophenyls) benzene of 1,4-, double (4- aminophenyls) benzene of 1,3-, Double (4- aminobenzyls) benzene of 1,4-, double (4- amino-benzene oxygens) benzene of 1,3-, 4,4 '-[1,4- phenylenes are double (methylene)] double benzene Amine, 4,4 '-[1,3- phenylenes double (methylene)] dianils, 3,4 '-[1,4- phenylenes are double (methylene)] dianils, 3,4 '- [1,3- phenylenes are double (methylene)] dianil, 3,3 '-[1,4- phenylenes are double (methylene)] dianils, 3,3 '-[1,3- Asias benzene Base double (methylene)] dianil, 1,4- phenylenes double [(4- aminophenyls) ketones], 1,4- phenylenes be double [(3- aminophenyls) Ketone], 1,3- phenylenes double [(4- aminophenyls) ketone], 1,3- phenylenes double [(3- aminophenyls) ketones], 1,4- Asias benzene Base double (PABA esters), 1,4- phenylenes double (3- Aminobenzoates), the double (PABAs of 1,3- phenylenes Ester), 1,3- phenylenes double (3- Aminobenzoates), double (4- aminophenyls) terephthalate, double (3- aminophenyls) it is right Phthalic acid ester, double (4- aminophenyls) isophthalic acid esters, double (3- aminophenyls) isophthalic acid esters, N, N '-(1,4- is sub- Phenyl) double (4- aminobenzamides), N, N '-(1,3- phenylenes) double (4- aminobenzamides), N, N '-(1,4- phenylenes) Double (3-ABs), N, N '-(1,3- phenylenes) double (3-ABs), N, N '-bis- (4- aminophenyls) is right Benzenedicarboxamide, N, N '-bis- (3- aminophenyls) terephthalamide, N, N '-bis- (4- aminophenyls) isophtalamide, N, N '-bis- (3- aminophenyls) isophtalamide, 9,10- double (4- aminophenyls) anthracene, 4,4 '-bis- (4- amino-benzene oxygens) hexichol Sulfone, 2,2 '-bis- [4- (4- amino-benzene oxygens) phenyl] propane, 2,2 '-bis- [4- (4- amino-benzene oxygens) phenyl] HFC-236fa, 2, 2 '-bis- (4- aminophenyls) HFC-236fa, 2,2 '-bis- (3- aminophenyls) HFC-236fa, 2,2 '-bis- (3- amino -4- methylbenzene Base) HFC-236fa, 2,2 '-bis- (4- aminophenyls) propane, 2,2 '-bis- (3- aminophenyls) propane, 2,2 '-bis- (3- amino -4- Aminomethyl phenyl) propane, 3,5- diaminobenzoic acids, 2,5- diaminobenzoic acids, 1,3- double (4- amino-benzene oxygens) propane, 1,3- Double (4- amino-benzene oxygens) butane of double (3- amino-benzene oxygens) propane, 1,4-, double (3- amino-benzene oxygens) butane of 1,4-, 1,5- are double Double (3- amino-benzene oxygens) pentanes of (4- amino-benzene oxygens) pentane, 1,5-, double (4- amino-benzene oxygens) hexanes of 1,6-, 1,6- are double Double (4- amino-benzene oxygens) heptane of (3- amino-benzene oxygens) hexane, 1,7-, 1,7- (3- amino-benzene oxygens) heptane, the double (4- of 1,8- Amino-benzene oxygen) octane, double (3- amino-benzene oxygens) octanes of 1,8-, double (4- amino-benzene oxygens) nonanes of 1,9-, double (the 3- ammonia of 1,9- Phenoxyl) nonane, 1,10- (4- amino-benzene oxygens) decane, 1,10- (3- amino-benzene oxygens) decane, 1,11- (4- aminobenzenes Epoxide) hendecane, 1,11- (3- amino-benzene oxygens) hendecane, 1,12- (4- amino-benzene oxygens) dodecane, 1,12- (3- amino Phenoxy group) aromatic diamine compound such as dodecane；Double (4- aminocyclohexyls) methane, double (4- amino -3- methylcyclohexyls) The ester ring type diamine compound such as methane；1,3- diaminopropanes, 1,4- diaminobutanes, 1,5- 1,5-DAPs, 1,6- diaminos Base hexane, 1,7- diaminoheptanes, 1,8- diamino-octanes, 1,9- diamino nonanes, 1,10- diamino decanes, 1,11- diaminos The aliphatic diamine compounds such as base hendecane, 1,12- diamino dodecanes.

As long as additionally, not damaging the effect of the present invention, it is also possible to using having alkyl or containing fluoroalkyl on two amine side chains Diamine compound.

Specifically, the diamine compound for for example representing with following formula [DA1]～formula [DA12] can be illustrated.

[changing 13]

(in formula [DA1]～[DA5], A₁It is the straight of the straight-chain of carbon number 1～22 or the alkyl of branched or carbon number 1～22 Chain or branched containing fluoroalkyl.)

[changing 14]

(in formula [DA6]～[DA11], A₂Represent-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂- ,-O- ,-CO- or- NH-；A₃Represent carbon number 1～22 straight-chain or the alkyl of branched or the straight-chain of carbon number 1～22 or branched containing halothane Base.)

[changing 15]

(in formula [DA12], p is 1～10 integer.)

As long as not damaging the effect of the present invention, it is also possible to using two aminations represented with following formula [DA13]～formula [DA20] Compound.

[changing 16]

(in formula [DA17], m is 0～3 integer.In formula [DA20], n is 1～5 integer.)

Further, as long as not damaging the effect of the present invention, it is also possible to use and represented with following formula [DA21]～formula [DA24] There is the diamine compound of carboxyl in intramolecular.

[changing 17]

(in formula [DA21], m₁It is 1～4 integer.

In formula [DA22], A₄It is singly-bound ,-CH₂-、-C₂H₄-、-C(CH₃)₂-、-CF₂-、-C(CF₃)₂-、-O-、-CO-、- NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CON(CH₃)-or-N (CH₃)CO-；m₂ And m₃It is respectively 0～4 integer, and m₂+m₃For 1～4 integer.

In formula [DA23], m₄And m₅Respectively 1～5 integer.In formula [DA24], A₅Be carbon number 1～5 straight-chain or Chain-like alkyl；m₆It is 1～5 integer.

In formula [DA25], A₆It is singly-bound ,-CH₂-、-C₂H₄-、-C(CH₃)₂-、-CF₂-、-C(CF₃)₂-、-O-、-CO-、- NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CON(CH₃)-or-N (CH₃)CO-；m₇ It is 1～4 integer.)

Further, as long as not damaging the effect of the present invention, it is also possible to using the diamine compound represented with following formula [DA26].

[changing 18]

(in formula [DA26], A₁It is selected from-O- ,-NH- ,-N (CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCO-、-CON (CH₃)-or-N (CH₃) CO- divalent organic group；A₂It is singly-bound, the aliphatic alkyl of carbon number 1～20, non-aromatic, cyclic moiety Or aromatic hydrocarbyl.A₃It is singly-bound ,-O- ,-NH- ,-N (CH₃)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH₃)-、- N(CH₃) CO- or-O (CH₂)_m- (m is 1～5 integer)；A₄It is nitrogenous heteroaromatic；N is 1～4 integer.)

Further, as long as not damaging the effect of the present invention, it is also possible to use and represented with following formula [DA27]～formula [DA46] Diamine compound with steroid skeleton.

[changing 19]

[changing 20]

[changing 21]

[changing 22]

[changing 24]

Other above-mentioned diamine compounds can according to liquid crystal aligning when making liquid crystal orientation film, voltage retention, The characteristics such as accumulated charge, are used alone, or mixing two or more.

In order to obtain the particular polymers of the present invention, the tetracarboxylic dianhydride represented with following formula [2] is preferably used (also referred to as Specific tetracarboxylic dianhydride) as a part for raw material.

[changing 25]

Y in formula [2]₁The 4 valency groups for specifically for example being represented with following formula [2a]～[2j].

[changing 34]

In formula [2a], Y₂～Y₅It is hydrogen atom, methyl, chlorine atom or phenyl ring, and each group each other can be with identical or different.

Additionally, in formula [2g], Y₆And Y₇It is hydrogen atom or methyl, and each group each other can be with identical or different.

In formula [2], from from the viewpoint of polymerisation reactivity and the complexity of synthesis, Y₁Particularly preferred structure be formula [2a], formula [2c], formula [2d], formula [2e], formula [2f] or formula [2g].Wherein, preferred formula [2a], formula [2e], formula [2f] or formula [2g]。

In the present invention, as long as not damaging the effect of the present invention, it is possible to use the others four beyond specific tetracarboxylic dianhydride Carboxylic acid dianhydride (also referred to as other tetracarboxylic dianhydrides).As other tetracarboxylic dianhydrides, the four of tetrabasic carboxylic acid shown below can be enumerated Carboxylic acid dianhydride.

Pyromellitic Acid, 2,3,6,7- naphthalenetetracarbacidic acidics, 1,2,5,6- naphthalenetetracarbacidic acidics, 1,4,5,8 naphthalenetetracarboxylic acid, 2,3,6, 7- anthracene tetracarboxylic acids, 1,2,5,6- anthracene tetracarboxylic acids, 3,3 ', 4,4 '-bibenzene tetracarboxylic, 2,3,3 ', 4- bibenzene tetracarboxylics, double (3,4- Dicarboxyphenyi) ether, 3,3 ', 4,4 '-benzophenone tetracarboxylic, double (3,4- dicarboxyphenyis) sulfones, double (3,4- dicarboxyphenyis) Double (3,4- dicarboxyphenyis) propane of double (3,4- dicarboxyphenyis) propane of methane, 2,2-, 1,1,1,3,3,3- hexafluoros -2,2-, Double (3,4- dicarboxyphenyis) dimethylsilanes, double (3,4- dicarboxyphenyis) diphenyl silanes, 2,3,4,5- pyridine tetracarboxylic acids, 2,6- double (3,4- dicarboxyphenyis) pyridine, 3,3 ', 4,4 '-diphenyl sulfone tetraformic acid, 3,4,9,10- perylenes tetracarboxylic acid or 1,3- hexichol Base -1,2,3,4- cyclobutanetetracarboxylics.

Above-mentioned specific tetracarboxylic dianhydride and other tetracarboxylic dianhydrides can take according to liquid crystal when making liquid crystal orientation film The characteristics such as tropism, voltage retention, accumulated charge, are used alone, or mixing two or more.

The particular polymers of the present invention are selected from the polyimide precursor with the side chain represented with above-mentioned formula [1] and will be gathered Imide precursor carries out at least one polymer of polyimides obtained by imidizate.

Polyimide precursor is the structure represented with following formula [A].

[changing 27]

(in formula [A], R₁It is 4 valency organic groups, R₂It is divalent organic group, A₁And A₂It is the alkane of hydrogen atom or carbon number 1～8 Base, each group each other can be with identical or different, and n represents positive integer.)

By the tetracarboxylic dianhydride that adopts the diamine component represented with following formula [B] and represented using following formula [C] as original Material, can more easily obtain the particular polymers of the present invention, consider from the reason, preferably by being represented with following formula [D] Polyamic acid or make the polyamic acid carry out polyimides obtained by imidizate that the structural formula of repetitives is constituted.

[changing 28]

(in formula [B] and [C], R₁And R₂With with formula [A] in definition identical meaning.)

[changing 29]

(in formula [D], R₁And R₂With with formula [A] in definition identical meaning.)

In the present invention, the method to synthesizing particular polymers is not particularly limited.Generally, can be by making diamine component and tetracarboxylic acid Sour composition reacts and obtains.In general, the tetrabasic carboxylic acid composition that can pass through to make at least one selected from tetrabasic carboxylic acid and its derivant and The diamine component being made up of one or more diamine compounds reacts to obtain polyamic acid.Specifically, following sides can be used Method：The method for making tetracarboxylic dianhydride and diamine component polycondensation and obtaining polyamic acid, is dehydrated tetrabasic carboxylic acid and diamine component Polycondensation reaction and the method that obtains polyamic acid, or make the carboxylic acid halides of tetrabasic carboxylic acid two and diamine component polycondensation and obtain polyamic acid Method.

In order to obtain polyamic acid Arrcostab, following methods can be used：Carboxylic acid group is set to carry out four obtained by dialkyl group esterification Carboxylic acid and the method for diamine component polycondensation, make carboxylic acid group carry out the carboxylic acid halides of tetrabasic carboxylic acid two obtained by dialkyl group esterification and diamine component contracting Poly- method, or by the converting carboxylate groups of polyamic acid into ester method.

In order to obtain polyimides, above-mentioned polyamic acid or polyamic acid Arrcostab closed loop can be made to make polyamides sub- The method of amine.

Using the present invention particular polymers obtained by liquid crystal orientation film, in above-mentioned diamine component with above-mentioned formula [1] The containing ratio of the specific side-chain structure for representing is higher, and the tilt angle of hydrophobicity and liquid crystal when making liquid crystal orientation film is bigger. Now, diamine component preferably uses the specific side chain type diamine compound represented with above-mentioned formula [1a].Particularly preferably use and be selected from At least one of the specific side chain type diamine compound represented with above-mentioned formula [1-1]～[1-6] and formula [1-9]～[1-13].Its In, preferably use selected from the specific side chain type diamine compound represented with formula [1-1]～[1-6] or formula [1-9]～[1-12] It is at least one.For the purpose for improving above-mentioned characteristic, it is generally desirable to which 5～80 moles of % of diamine component are specific side chain type diamine Compound.Wherein, it is more excellent from the point of view of the electrical characteristics from the coating of aligning agent for liquid crystal and when making liquid crystal orientation film 5～60 moles of % for selecting diamine component are specific side chain type diamine compounds.More preferably the 10～60 of diamine component are rubbed Your % is specific side chain type diamine compound.

In order to obtain the particular polymers of the present invention, preferably use the specific tetracarboxylic dianhydride represented with above-mentioned formula [2] and make For tetrabasic carboxylic acid composition.Particularly preferably using the Y in formula [2]₁Be the structure represented with above-mentioned formula [2a]～[2j] group four Carboxylic acid dianhydride.Now, 1 mole of more than % of preferred tetrabasic carboxylic acid composition is specific tetracarboxylic dianhydride, more preferably 5 moles more than %, Further preferred 10 moles of more than %.In addition it is also possible to 100 moles of % of tetrabasic carboxylic acid composition are specific tetracarboxylic dianhydrides.

The reaction of diamine component and tetrabasic carboxylic acid composition is generally carried out in organic solvent.It is organic molten as what is now used Agent, can be the specific solvent of the present invention, as long as the polyimide precursor of generation can be dissolved, there is no particular limitation. Its specific example is enumerated below.

E.g. N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, dimethyl sulfoxide, Gamma-butyrolacton, 1,3- dimethyl-2-imidazolidinones, methyl ethyl ketone, Ketohexamethylene, Ketocyclopentane, 4- hydroxy-4-methyl-2-pentanones Deng.

These solvents can be used alone, it is also possible to be used in mixed way.Even also, polyimide precursor can not be dissolved Solvent, it is also possible in the range of the polyimide precursor for generating is not separated out, used in being blended in above-mentioned solvent.In addition, because Moisture in organic solvent hinders polyreaction, and becomes the reason for hydrolyzing the polyimide precursor of generation, so preferable Be use Jing dehydrate organic solvent.

When diamine component and tetrabasic carboxylic acid composition is reacted in organic solvent, following methods can be enumerated：Stirring make diamidogen into Be dispersed or dissolved in solution obtained by organic solvent, then directly add tetrabasic carboxylic acid composition or make tetrabasic carboxylic acid composition disperse or It is dissolved in the method added again after organic solvent；On the contrary tetracarboxylic dianhydride is dispersed or dissolved in it is molten obtained by organic solvent The method for adding diamine component in liquid；Alternately add method of tetrabasic carboxylic acid composition and diamine component etc., it is possible to use therein A kind of method.Additionally, in the case of being made up of multiple compounds respectively in diamine component or tetrabasic carboxylic acid composition and being reacted, can So that it reacts in the state of being pre-mixed, it is also possible to it is reacted successively respectively, can also make to react respectively obtained by it is low Polydispersity polymer hybrid reaction is obtaining particular polymers.Polymerization temperature now can select -20～150 DEG C of any temperature Degree, preferably -5～100 DEG C of scope.Additionally, reaction can be carried out with arbitrary concentration, but if concentration is too low, it is difficult to obtain The particular polymers of high molecular, the viscosity of reactant liquor is too high if excessive concentration, it is difficult to uniformly stirred.Therefore, Concentration is preferably 1～50 mass %, more preferably 5～30 mass %.Can in higher concentrations carry out in initial reaction stage, add afterwards Organic solvent.

In the polyreaction of polyimide precursor, the ratio of the total mole number of diamine component and the total mole number of tetrabasic carboxylic acid composition Preferably 0.8～1.2.Identical with common polycondensation reaction, the mol ratio is closer to 1.0, the polyimide precursor of generation Molecular weight is bigger.

The polyimides of the present invention are to make polyimides obtained by above-mentioned polyimide precursor closed loop, used as obtaining liquid The polymer of brilliant alignment films is useful.

In the polyimides of the present invention, the closed loop rate (also referred to as acid imide rate) of amide acidic group does not need one to be set to 100%, can arbitrarily be adjusted according to purposes or purpose.

Method as making polyimide precursor carry out imidizate, can enumerate the solution for directly heating polyimide precursor Hot-imide, or in the solution of polyimide precursor add catalyst catalysis imidizate.

Temperature when making polyimide precursor carry out hot-imide in the solution is 100～400 DEG C, preferably 120～250 ℃。

Hot imide reaction is preferably while the water of generation is excluded to outside system while carrying out.

The catalysis imidizate of polyimide precursor can by polyimide precursor solution add base catalyst and Anhydride, and stir at -20～250 DEG C, preferably at 0～180 DEG C and carry out.The amount of base catalyst is the 0.5 of amide acidic group ～30 moles times, preferably 2～20 moles times, the amount of anhydride is 1～50 mole times of amide acidic group, preferably 3～30 moles times.

As base catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine etc. can be enumerated, wherein pyridine has The alkalescence of appropriateness for reaction is carried out, therefore preferably.

As anhydride, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride etc. can be enumerated, wherein, it is easy to during using acetic anhydride Carry out reacting the purification after terminating, therefore preferably.Can be by adjusting catalyst using the acid imide rate of catalysis imidizate Amount and reaction temperature, response time control.

The polyimide precursor or polyimides of generation are reclaimed from the reaction solution of polyimide precursor or polyimides When, reaction solution is put in solvent and it is precipitated.As the solvent for precipitation, methanol, ethanol, different can be enumerated Propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, benzene, water etc..Put into molten The polymer precipitated in agent can under normal or reduced pressure, in room temperature or heat be dried after being recovered by filtration. In addition, if the polymer for repeating to reclaim precipitation is re-dissolved in organic solvent and the operation 2～10 of reprecipitation and recovery It is secondary, then can reduce the impurity in polymer.As solvent now, such as alcohols, ketone, hydro carbons etc. can be enumerated, if made With the solvent selected from more than 3 kinds of above-mentioned solvent, then purification efficiency is further improved, therefore preferably.

For the molecular weight of the particular polymers of the present invention, it is contemplated that the polymer of gained is by film strength, polymer quilt Operability, the uniformity of polymer envelope when film is formed, with the weight average molecular weight measured using GPC (gel permeation chromatography) method Meter is preferably 5000～1000000, more preferably 10000～150000.

It, for forming the coating solution of liquid crystal orientation film, and is containing specific solvent that the aligning agent for liquid crystal of the present invention is With the coating fluid for forming resin coating of particular polymers.

Component of polymer in the aligning agent for liquid crystal of the present invention can be entirely the particular polymers of the present invention, also may be used To mix the other polymers in addition to it in the particular polymers of the present invention.Now, in component of polymer except the present invention Particular polymers beyond the content of other polymers be 0.5～15 mass %, preferably 1～10 mass %.

As the other polymers in addition to the particular polymers of the present invention, can enumerate selected from without specific side chain type two The diamine component of amines and polyimide precursor obtained by the tetrabasic carboxylic acid composition without specific tetracarboxylic dianhydride and by polyamides Imines precursor carries out at least one polymer of polyimides obtained by imidizate.Further, as polyimide precursor and Polymer beyond polyimides, specifically can enumerate acrylate copolymer, methacrylate polymer, polystyrene, polyamide, Siloxane type polymers etc..

For the organic solvent in the aligning agent for liquid crystal of the present invention, from the viewpoint that uniform envelope is formed by coating Consider, the content of the organic solvent in aligning agent for liquid crystal is preferably 70～99 mass %.The content of organic solvent can basis The thickness of Object LC alignment films is suitably changed.

As organic solvent, the specific solvent of the present invention is preferably used.Now, as long as having for particular polymers can be dissolved Machine solvent, then in addition to specific solvent, it is also possible to using following solvents.Specifically N,N-dimethylformamide, N, N- diformazans Yl acetamide, METHYLPYRROLIDONE, dimethyl sulfoxide, gamma-butyrolacton, 1,3- dimethyl-2-imidazolidinones, methyl ethyl ketone, Ketohexamethylene, Ketocyclopentane or 4- hydroxy-4-methyl-2-pentanones.

Wherein, METHYLPYRROLIDONE, gamma-butyrolacton etc. (also referred to as composition (C)) are preferably used.

The usage amount of composition (C) preferably accounts for 0.1～70 matter of whole organic solvents contained in aligning agent for liquid crystal Amount %.Wherein, preferably 1～60 mass %.More preferably 1～50 mass %, further preferred 3～40 mass %.

The aligning agent for liquid crystal of the present invention, in the range of the effect for not damaging the present invention coating of liquid crystalline can be made The organic solvent, the poor solvent that apply film uniformity and surface smoothness raising of liquid crystal orientation film during aligning agent.Make For the concrete example of the poor solvent for applying film uniformity and surface smoothness of liquid crystal orientation film can be improved, following solvent can be enumerated.

Such as ethanol, isopropanol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- amylalcohols, 2- amylalcohols, 3- amylalcohols, 2- first Base-n-butyl alcohol, isoamyl alcohol, tert-pentyl alcohol, 3- methyl -2- butanol, neopentyl alcohol, 1- hexanols, 2- methyl-1-pentene alcohol, 2- methyl -2- penta Alcohol, 2- ethyls-n-butyl alcohol, 1-heptanol, 2- enanthol, 3- enanthol, 1- capryl alcohol, sec-n-octyl alcohol, 2- ethyl -1- hexanols, Hexalin, 1- first Cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1,2- ethylene glycol, 1,2- Propylene Glycol, 1,3- Propylene Glycol, 1,2- fourths two Alcohol, 1,3 butylene glycol, 1,4- butanediols, 2,3- butanediols, 1,5- pentanediols, 2- methyl -2,4-PD, 2- ethyl -1,3- Hexanediol, propyl ether, butyl ether, hexyl ether, twoAlkane, glycol dimethyl ether, ethylene glycol diethyl ether, butyl cellosolve, 1,2- fourth oxygen Base ethanol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dibutyl ethylene glycol ether, 2- penta Ketone, propione, methyl-n-butyl ketone, 2-heptanone, dipropyl ketone, 3- ethoxybutyl acetass, 1- methyl amyl acetass, 2- ethyl-butyls Acetass, 2- ethylhexyl acetates, ethylene monoacetate, ethylene acetate, propylene carbonate, carbonic acid Asia second Ester, glycol monoethyl ether, ethylene glycol monoethyl ether, 2- (methoxymethoxy) ethanol, glycol isopropyl ether, ethylene glycol monobutyl ether, Ethylene glycol list isoamyl oxide, ethylene glycol monohexylether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethyl 2-ethoxyethanol, diethylene glycol monobutyl ether, Propylene Glycol, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, 1- (fourths Epoxide ethyoxyl) propanol, propylene glycol methyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, DPE, three Propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol Monoacetate, ethylene acetate, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, 2- (2- ethyoxyls Ethyoxyl) ethylhexoate, diethylene glycol acetass, triethylene glycol, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, lactic acid Methyl ester, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate list ether, methyl pyruvate, acetone acid Ethyl ester, 3- methoxy methyl propionates, 3- ethoxy-propionic acid Methylethyls, 3- methoxypropionates, 3- ethoxy-propionic acids, 3- first Epoxide propanoic acid, 3- methoxy propyl propyl propionates, 3- methoxy propyl acid butyl esters, methyl lactate, ethyl lactate, lactic acid n-propyl ester, lactic acid The little organic solvent of the surface tensions such as N-butyl, isoamyl lactate.

Wherein, 1- hexanols, Hexalin, 1，2-ethandiol, 1,2-PD, glycol monoethyl ether, ethylene glycol are preferably used Single ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene Glycol list first Ether, dihydroxypropane single-ether, propylene glycol monobutyl ether etc. (also referred to as composition (D)).

The usage amount of poor solvent (composition (D)) preferably accounts for the 1 of whole organic solvents contained in aligning agent for liquid crystal ～80 mass %.Wherein, preferably 5～70 mass %.More preferably 10～70 mass %.

The preferred compositions of the organic solvent in the aligning agent for liquid crystal of the present invention are as shown in table 1～3.

[table 1]

[table 2]

[table 3]

In table 1～3, NEP represents N- ethyl-2-pyrrolidones, and NMP represents METHYLPYRROLIDONE, and γ-BL are represented Gamma-butyrolacton, BCS represents ethylene glycol monobutyl ether, and ECS represents ethylene glycol monoethyl ether, and MC represents diethylene glycol monomethyl ether, and EC is represented Diethylene glycol monoethyl ether, PGME represents propylene glycol monomethyl ether.

In the combination of these organic solvents, preferred 2-1～2-10,2-14～2-17,2-19～2-25,2-29～2-32, The combination of 2-34～2-40 or 2-44～2-46.More preferably 2-1～2-10,2-14～2-17,2-19～2-2-25,2-32 or 2- The combination of 38-2-40.The particularly preferably combination of 2-2,2-8～2-10,2-17,2-23～2-25,2-32 or 2-38～2-40.

In the aligning agent for liquid crystal of the present invention, in the range of the effect for not damaging the present invention, can import with ring The cross-linked compound of epoxide, NCO, oxetanyl or cyclocarbonate radical, with selected from hydroxyl, hydroxyalkyl and The cross-linked compound of at least one substituent group of low-grade alkoxy alkyl, or the bridging property chemical combination with polymerism unsaturated bond Thing.Preferably there is plural above-mentioned substituent group or polymerism unsaturated bond in cross-linked compound.

As the cross-linked compound with epoxy radicals or NCO, such as bisphenol acetone (+)-2,3-Epoxy-1-propanol can be enumerated Ether, novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, four glycidyl group ammonia Base diphenylene, four glycidyl group m-xylene diamine, four glycidyl group -1,3- double (amino-ethyl) hexamethylene, four benzene Base glycidyl ether ethane, trisphenyl glycidyl ether ethane, bis-phenol hexafluoro acetyl group diglycidyl ether, 1,3- pair (1- (2, 3- glycidoxies) -1- trifluoromethyl -2,2,2- trifluoromethyls) benzene, double (2,3- glycidoxies) octafluorobiphenyls of 4,4-, three Glycidyl para-aminophenol, four glycidyl group m-xylene diamine, 2- (4- (2,3- glycidoxies) phenyl) -2- (4- (double (4- (2,3- glycidoxies) phenyl) ethyls of 1,1-) phenyl) propane, the double (4- (1- (4- (oxygen of 2,3- epoxies third of 1,3- Base) phenyl) -1- (4- (1- (4- (2,3- glycidoxies) phenyl) -1- Methylethyls) phenyl) ethyl) phenoxy group) -2- propanol Deng.

It is that there are at least two oxygen represented with following formula [3] as the cross-linked compound with oxetanyl The cross-linked compound of azetidinyl.

[changing 30]

Specifically, it is the cross-linked compound that represents with following formula [3-1]～formula [3-11].

[changing 31]

[changing 32]

[changing 33]

It is that there are at least two ring carbon acid represented with following formula [4] as the cross-linked compound with cyclocarbonate radical The cross-linked compound of ester group.

[changing 34]

Specifically, it is the cross-linked compound that represents with following formula [4-1]～formula [4-37].

[changing 35]

[changing 36]

[changing 37]

[changing 38]

[changing 39]

[changing 40]

[changing 41]

[changing 42]

(in formula [4-24], n is 1～5 integer.In formula [4-25], n is 1～5 integer.In formula [4-36], n is 1～ 100 integer.In formula [4-37], n is 1～10 integer.)

The polysiloxanes with least one structure represented with following formula [4-38]～[4-40] can also be enumerated.

[changing 43]

(in formula [4-38]～[4-40], R₁、R₂、R₃、R₄And R₅Structure separately represented by formula [4], hydrogen are former Son, hydroxyl, the alkyl of carbon number 1～10, alkoxyl, aliphatic ring or aromatic ring, at least one is the knot represented by formula [4] Structure.)

More specifically, the compound of following formula [4-41] and formula [4-42] can be enumerated.

[changing 44]

(in formula [4-42], n is 1～10 integer.)

As with the cross-linked compound selected from hydroxyl and at least one substituent group of alkoxyl, for example, can enumerate and have The amino resins of hydroxyl or alkoxyl, such as melmac, Lauxite, guanamine resin, glycolurilformaldehyde resins, succinum Amide-formaldehyde resin, ethylene urea-formaldehyde resin etc..Specifically, it is possible to use the hydrogen atom of amino by methylol and/or Melamine derivative, benzoguanamine derivant or glycoluril that alkoxy methyl instead of.Melamine derivative and benzocarbamidine Amine derivative is likely in the form of dimer or trimer.They are preferably relative to averagely having 3 per 1 triazine ring The methylol of less than 6 or alkoxy methyl more than individual.

As such melamine derivative or the example of benzoguanamine derivant, can enumerate as commercially available product per 1 MX-750 that individual triazine ring averagely instead of by 3.7 methoxies, per 1 triazine ring averagely by 5.8 methoxies The MW-30 (above be Sanwa Chemical Co., Ltd's (three and ケミカ Le) system) that instead of, サイメ Le 300,301,303,350, 370th, the methoxymethylated tripolycyanamide such as 771,325,327,703,712, サイメ Le 235,236,238,212,253,254 Etc. butoxymethyl tripolycyanamide, サイ such as methoxymethylated butoxymethyl tripolycyanamide, サイメ Le 506,508 The first of carboxylic methoxymethylated isobutoxymethyl tripolycyanamide, the サイメ Le 1123 of メ Le 1141 etc etc Epoxide methylates the methoxymethylated butoxymethyl of ethoxyl methyl benzoguanamine, サイメ Le 1123-10 etc Butoxymethyl benzoguanamine, the サイメ Le 1125-80's of benzoguanamine, サイメ Le 1128 etc etc is carboxylic Methoxymethylated ethoxyl methyl benzoguanamine (being above three well cyanamide Co., Ltd. (three well サイア Na ミ De) system) Deng.As the example of glycoluril, butoxymethyl glycoluril, the サイメ Le 1172 of サイメ Le 1170 etc etc can be enumerated Methoxyl group methylolation glycoluril of methylolation glycoluril, パウダーリ Application Network 1174 etc etc..

As the benzene with hydroxyl or alkoxyl or benzene phenoloid, can enumerate such as 1,3,5- tri- (methoxy) Benzene, 1,2,4- tri- (i-propoxymethyl) benzene, 1,4- double (sec-butoxymethyl) benzene, 2,6- dihydroxymethyl p-t-butyl phenols Deng.

Specifically, can enumerate and be recorded in the 62nd of International Publication publication WO2011/132751 (2011.10.27 is disclosed) Cross-linked compound represented by page～formula [6-1]～[6-48] of page 66.

As the cross-linked compound with polymerism unsaturated bond, for example, can enumerate trimethylolpropane tris (methyl) third Olefin(e) acid ester, tetramethylolmethane three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three (methyl) acryloxies The intramolecular of poly- (methyl) acrylate of ethyoxyl trimethylolpropane, glycerine polyglycidyl ether etc. has 3 polymerisms not The cross-linked compound of saturated group；Ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, tetrem two Alcohol two (methyl) acrylate, Polyethylene Glycol two (methyl) acrylate, Propylene Glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, oxirane bisphenol-A Type two (methyl) acrylate, expoxy propane bisphenol type two (methyl) acrylate, 1,6-HD two (methyl) acrylate, Glycerol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, Ethylene glycol diglycidyl ether two (methyl) propylene Acid esters, diethylene glycol diglycidyl glycerin ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) propylene The intramolecular of acid esters, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate etc. has the friendship of 2 polymerism unsaturated groups Connection property compound；And (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid- 2- hydroxybutyls, (methyl) acrylic acid -2- phenoxy group -2- hydroxy propyl esters, phthalic acid -2- (methyl) acryloxy -2- Hydroxy propyl ester, (methyl) acrylic acid -3- chlorine-2-hydroxyl propyl ester, glycerol list (methyl) acrylate, 2- (methyl) acryloxy The intramolecular of ethyl phosphonic acid ester, N- methylols (methyl) acrylamide etc. has the bridging property of 1 polymerism unsaturated group Compound；Deng.

The compound represented with following formula [6] can also be used.

[changing 45]

In formula [6], E₁It is selected from cyclohexane ring, bis cyclohexane ring, phenyl ring, cyclohexyl biphenyl, ter phenyl ring, naphthalene nucleus, fluorenes ring, anthracene The group of ring and phenanthrene ring, E₂It is the group selected from following formula [6a] and formula [6b], n is 1～4 integer.

[changing 46]

Above-claimed cpd is of cross-linked compound, is not limited to this.

Additionally, cross-linked compound contained in the aligning agent for liquid crystal of the present invention both can be it is a kind of, or Two or more combinations.

The content of the cross-linked compound in the aligning agent for liquid crystal of the present invention is relative to the matter of whole component of polymer 100 Amount part is preferably 0.1～150 mass parts.In order that cross-linking reaction carries out and shows target effect and make the orientation of liquid crystal Do not decline, relative to the mass parts of whole component of polymer 100 0.1～100 mass parts, most preferably 1～50 mass parts are more preferably.

As the electric charge movement in the liquid crystal orientation film for promoting to be formed using the aligning agent for liquid crystal of the present invention, promote Using the compound of the electric charge release of the liquid crystal cell of the liquid crystal orientation film, International Publication publication WO2011/ can also be added The nitrogen heterocyclic ring represented by formula [M1]～[M156] described in page 69 of 132751 (2011.10.27 is disclosed)～page 73 Amines.These amines can also be directly appended in the solution of particular polymers, but preferably with suitable solvent system It is 0.1～10 mass %, preferably adds again after the solution of 1～7 mass % into concentration.As the solvent, as long as on dissolving The organic solvent of particular polymers is stated, is not particularly limited.

The aligning agent for liquid crystal of the present invention, in the range of the effect for not damaging the present invention coating of liquid crystalline can be made The compound that the film thickness uniformity of polymer envelope during aligning agent and surface smoothness are improved.Further, it is also possible to use energy Improve compound of adaptation of liquid crystal orientation film and substrate etc..

As the compound that can improve film thickness uniformity and surface smoothness, fluorine class surfactant, siloxanes can be enumerated Class surfactant, nonionic surfactant etc..

More specifically, such as エ Off トップ EF301, EF303, EF352 (Tuo Kaimu products Co., Ltd. (トー can be enumerated ケ system プロダクツ societies) system), メガ Off ァッ Network F171, F173, R-30 ((big Japan of Dainippon Ink and Chemicals, Inc イ Application キ societies) system), Off ロラー De FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo スリーエ system society) system), アサヒガー De AG710, サー Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass strain formula meetings Society (Asahi Glass society) makes) etc..The use ratio of these surfactants is poly- relative to whole contained in aligning agent for liquid crystal The mass parts of polymer component 100, preferably 0.01～2 mass parts, more preferably 0.01～1 mass parts.

As the concrete example of the compound of the adaptation that can improve liquid crystal orientation film and substrate, shown below containing can be enumerated The compound of functional silanes and the compound containing epoxy radicals.

For example, 3- TSL 8330s, APTES, 2- aminopropyls three can be enumerated Methoxy silane, 2- aminopropyltriethoxywerene werenes, N- (2- amino-ethyls) -3- TSL 8330s, N- (2- Amino-ethyl) -3- amino propyl methyl dimethoxysilanes, 3- ureido-propyl trimethoxy silanes, the ethoxy of 3- ureido-propyls three Base silane, N- ethoxy carbonyl -3- TSL 8330s, N- ethoxy carbonyl -3- aminopropyl triethoxysilicanes Alkane, N- triethoxysilylpropyltetrasulfide diethylenetriamines, N- trimethoxy-silylpropyl diethylenetriamines, 10- The azepine decane of trimethoxysilyl -1,4,7- three, the azepine decane of 10- triethoxysilyls -1,4,7- three, 9- front threes Epoxide silicyl -3,6- diaza nonyl acetass, 9- triethoxysilyl -3,6- diaza nonyl acetass, N- Benzyl -3- TSL 8330s, N- benzyls-APTES, N- phenyl -3- aminopropyls three Double (the oxyethylene group) -3- aminopropyl trimethoxy silicon of methoxy silane, N- phenyl-APTES, N- Double (the oxyethylene group)-APTESs of alkane, N-, Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl are sweet Oily ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol two Glycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- dibromoneopentyl glycol 2-glycidyls Ether, 1,3,5,6- four glycidyl group -2,4- hexanediol, N, N, N ', N ',-four glycidyl group-m-xylene diamine, 1,3- Double (N, N- diglycidyl amino methyl) hexamethylene, N, N, N ', N ',-four glycidyl group -4,4 '-diamino-diphenyl Methane etc..

During using the compound with the adaptation of substrate can be improved, relative to the whole contained in aligning agent for liquid crystal The mass parts of component of polymer 100, its content is preferably 0.1～30 mass parts, more preferably 1～20 mass parts.If less than 0.1 matter Amount part, then cannot expect the effect that adaptation is improved, if being more than 30 mass parts, sometimes the orientation of liquid crystal is deteriorated.

In the aligning agent for liquid crystal of the present invention, except above-mentioned poor solvent, cross-linked compound, to improve thickness equal The compound of even property and surface smoothness and can improve with the adaptation of substrate compound beyond, as long as do not damaging this In the range of bright effect, then can add for reaching the electrical characteristics such as the dielectric constant, the electric conductivity that change liquid crystal orientation film Purpose electrolyte and conductive materials.

The aligning agent for liquid crystal of the present invention can carry out friction treatment or light irradiation on substrate is coated and after burning till Etc. orientation process, so as to be used as liquid crystal orientation film.Additionally, when being used for vertical orientated purposes etc., even if not carrying out orientation process Can serve as liquid crystal orientation film.Now, as long as the high substrate of the substrate transparency for using, is not particularly limited, except glass Outside substrate, it is also possible to using plastic bases such as acrylic acid substrate, polycarbonate substrate etc..From the viewpoint of simplifying from technique, compared with Good use is formed with for the substrate of the ITO electrode of liquid crystal drive etc..In addition, in reflection type liquid crystal display element, it is also possible to make With the opaque substrate such as silicon wafer, but the substrate of one side is only limitted to, electrode now can also use the material of the reflected lights such as aluminum Material.

The coating process of aligning agent for liquid crystal is not particularly limited, industrially typically silk screen printing, hectographic printing, The methods such as flexographic printing, ink-jet method.As other coating processes, also dip coating, rolling method, slot coated method, spin-coating method, spray Coating etc., can use these methods according to purpose.

After aligning agent for liquid crystal is coated on substrate, heating plate, heat-circulation type stove or IR (infrared ray) can be passed through The heaters such as type stove 50～300 DEG C, preferably evaporate solvent at 80～250 DEG C, so as to form polymer envelope.If The thickness of the polymer envelope after burning till is blocked up, then unfavorable in terms of the consumption electric power of liquid crystal display cells, if excessively thin, has When liquid crystal display cells reliability reduce, therefore preferably 5～300nm, more preferably 10～100nm.

When making liquid crystal horizontal alignment or tilted alignment, by friction or polarisation ultraviolet irradiation etc. to burning till after polymer Envelope is processed.

The liquid crystal display cells of the present invention are to obtain band liquid crystal by the aligning agent for liquid crystal of the present invention by said method After the substrate of alignment films, the liquid crystal display cells of liquid crystal cell are manufactured by known method.

As the manufacture method of liquid crystal cell, following method can be illustrated：Preparation is formed with a pair of substrates of liquid crystal orientation film, Sept is spread on the liquid crystal orientation film of one piece of substrate, pastes another piece of substrate in the way of liquid crystal aligning face is in inner side Close, the method for decompression injection liquid crystal and sealing；After Deca liquid crystal on the liquid crystal aligning face for being scattered with sept, by substrate Method fitted and sealed etc..

Further, aligning agent for liquid crystal of the invention is applied to by having liquid crystal layer between a pair of substrates for possessing electrode Liquid crystal display cells constituting, through the manufacture of following operations, the operation is：Configuration is comprising using active energy between a pair of substrates The liquid-crystal composition of the polymerizable compound that at least one party in amount ray and heat is polymerized, while applying electricity between electrode Pressure is while passing through the irradiation of active energy beam and adding at least one party for hankering to make polymerizable compound be polymerized.Here, active energy The preferred ultraviolet of amount ray.

Above-mentioned liquid crystal display cells pass through PSA (Polymer Sustained Alignment：Polymer stabilizing is orientated) side Formula is controlling the tilt angle of liquid crystal molecule.In PSA modes, be mixed in advance in liquid crystal material a small amount of photopolymerizable compound, Such as photopolymerization monomer, after assembling liquid crystal cell, to optical polymerism in the state of the voltage for applying regulation to liquid crystal layer Compound irradiation ultraviolet radiation etc., the tilt angle of liquid crystal molecule is controlled using the polymer for generating.Liquid crystal when polymer is generated The state of orientation of molecule also can be memorized after removal of the voltage, so electric field formed in by controlling liquid crystal layer etc., energy Enough adjust the tilt angle of liquid crystal molecule.Additionally, during using PSA modes, it is not necessary to friction treatment, so being adapted to be difficult to by friction Process to control the formation of the liquid crystal layer of the vertical orientating type of tilt angle.

That is, the liquid crystal display cells that liquid crystal display cells of the invention can be discussed further below：By said method by this The aligning agent for liquid crystal of invention is obtained after the substrate with liquid crystal orientation film, manufactures liquid crystal cell, by ultraviolet irradiation and Plus at least one party for hankering makes polymerizable compound be polymerized, so as to control the orientation of liquid crystal molecule.

If enumerating of the liquid crystal cell of manufacture PSA modes, following method can be enumerated：Preparation is formed with liquid crystal orientation film A pair of substrates, spread sept on the liquid crystal orientation film of one piece of substrate, by liquid crystal aligning face be in inner side in the way of will Another piece of baseplate-laminating, decompression injection liquid crystal and the method for sealing；Or on the liquid crystal aligning face for be scattered with sept Deca After liquid crystal, method that baseplate-laminating is sealed etc..

The polymerizable compound being polymerized by heating or irradiation ultraviolet radiation can be mixed in liquid crystal.As polymerism chemical combination Thing, can enumerate change of the intramolecular with polymerism unsaturated groups such as the acrylate-based or methacrylic acid ester groups of more than 1 Compound.Now, polymerizable compound is preferably 0.01～10 mass parts relative to the mass parts of liquid crystal composition 100, more preferably 0.1～ 5 mass parts.If polymerizable compound is not polymerized less than 0.01 mass parts, polymerizable compound, it is impossible to carry out taking for liquid crystal To control, if being more than 10 mass parts, unreacted polymerizable compound increases, the burn-in characteristic (day of liquid crystal display cells Text：Baked I pays I characteristic) decline.

After making liquid crystal cell, while the voltage of AC or DC is applied to liquid crystal cell, while heating or irradiating ultraviolet Line, makes polymerizable compound be polymerized, thereby controlling the orientation of liquid crystal molecule.

Further, aligning agent for liquid crystal of the invention is preferred for following liquid crystal display cells, the liquid crystal display cells by There is liquid crystal layer between a pair of substrates for possessing electrode and constitute and be obtained through following operations, the operation is：In a pair of substrates Between configuration comprising the liquid crystal orientation film of polymerizable group being polymerized using at least one party in active energy beam and heat Afterwards between electrode applied voltage here, the preferred ultraviolet of active energy beam.

In order to obtain at least one polymerizable group being polymerized in including using active energy beam and heat Liquid crystal orientation film, the method that compound of the addition containing the polymerizable group can be enumerated in aligning agent for liquid crystal, and using containing The method of the component of polymer of polymerizable group.The aligning agent for liquid crystal of the present invention contains with using heat or ultraviolet Irradiation and the specific compound at double bond position that reacts, it is possible to by ultraviolet irradiation and add at least one party that hankers come The orientation of control liquid crystal molecule.

If enumerating of manufacture liquid crystal cell, following method can be enumerated：Preparation is formed with a pair of bases of liquid crystal orientation film Plate, on the liquid crystal orientation film of one piece of substrate sept is spread, by another piece of base in the way of liquid crystal aligning face is in inner side Plate is fitted, the method for decompression injection liquid crystal and sealing；Or after Deca liquid crystal on the liquid crystal aligning face for being scattered with sept, Method that baseplate-laminating is sealed etc..

After making liquid crystal cell, the voltage of AC or DC is applied to liquid crystal cell by one side, while heating or irradiation Ultraviolet, so as to controlling the orientation of liquid crystal molecule.

As described above, the reliability of obtained liquid crystal display cells is good using the aligning agent for liquid crystal of the present invention, LCD TV of big picture and high-resolution etc. can be performed well in.

Embodiment

Hereinafter, embodiment is enumerated to more specific description of the present invention, but the present invention should not be construed as being limited to this.This Outward, the abbreviation of the compound used in embodiment and comparative example is as follows.

(tetracarboxylic dianhydride)

CBDA：1,2,3,4- Tetramethylene. tetracarboxylic dianhydrides

BODA：Bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydrides

TCA：The tetracarboxylic dianhydride represented with following formula

TDA：The tetracarboxylic dianhydride represented with following formula

[changing 47]

(specific side chain type diamine compound)

PCH7DAB：1,3- diaminourea -4- [4- (trans -4- n-heptyls cyclohexyl) phenoxy group] benzene

PBCH5DAB：1,3- diaminourea -4- { 4- [trans -4- (trans -4- pentyl cyclohexyls) cyclohexyl] phenoxy group } Benzene

m-PBCH5DABz：1,3- diaminourea -5- { 4- [4- (trans -4- pentyl cyclohexyls) phenyl] phenoxymethyl } Benzene

[changing 48]

(other diamine compounds)

p-PDA：P-phenylenediamine

m-PDA：M-diaminobenzene.

DBA：3,5- diaminobenzoic acids

AP18：1,3- diaminourea -4- octadecane epoxide benzene

ColDAB：The diamine compound represented with following formula

[changing 49]

(organic solvent)

NEP：N- ethyl-2-pyrrolidones

NMP：METHYLPYRROLIDONE

γ-BL：Gamma-butyrolacton

BCS：Ethylene glycol monobutyl ether

ECS：Ethylene glycol monoethyl ether

MC：Diethylene glycol monomethyl ether

EC：Diethylene glycol monoethyl ether

PGME：Propylene glycol monomethyl ether

The physical property such as the molecular weight and acid imide rate of polyimide precursor and polyimides proceed as follows measure or comment Valency.

(molecular weight determinations of polyimide precursor and polyimides)

The molecular weight of the polyimides in synthesis example is to use room temperature gel permeation chromatography (GPC) device (GPC-101) (clear With electrician Co., Ltd. (Showa Electricity work society) system) and post (KD-803, KD-805) (Xiao Deshi Co., Ltd. (Shodex societies) system) Determine in accordance with the following methods.

Column temperature：50℃

Eluent：N, N'- dimethylformamide is (as additive, lithium bromide hydrate (LiBrH₂O) it is 30 mmoles You/liter, phosphoric anhydride crystallization (o- phosphoric acid) be 30 mM/ls, tetrahydrofuran (THF) be 10ml/L (ml l)).

Flow velocity：1.0ml/ minute

Calibration trace making standard specimen：(East ソー societies of TOSOH Co., Ltd) system TSK standard poly(ethylene oxide) (point Son amount about 900000,150000,100000 and 30000), and Polymer Laboratory company (Port リマーラボラトリー societies) The Polyethylene Glycol (molecular weight is about 12000,4000 and 1000) of system.

(measure of acid imide rate)

The acid imide rate of the polyimides in synthesis example is carried out as follows measure.The polyimide powder of 20mg is added to NMR probe tubes (specification φ 5 of wasteland's science Co. Ltd. system NMR probe tube), add 0.53ml deuterated dimethyl sulfoxide (DMSO- D6,0.05 mass %TMS (tetramethylsilane) mixture), applying ultrasound wave is completely dissolved it.For the solution, surveyed with NMR Determine the matter that instrument (JNW-ECA500) (NEC Dan Ding Co., Ltd. (Japanese Electricity データ system society) system) determines 500MHz Sub- NMR.Acid imide rate is as described below to try to achieve：Made using the proton for coming from the structure not changed before and after imidizate For standard proton, using the NH bases for coming from amic acid of the neighbouring appearance of the integrated value and 9.5 to 10.0ppm of the proton peak Proton peak integrated value, tried to achieve by following formula.

Acid imide rate (%)=(1- α x/y) × 100

In above-mentioned formula, x comes from the Proton integration value of the NH bases of amic acid, and y is the integrated value at standard proton peak, and α is For polyamic acid (acid imide rate Ga 0%) when NH substrate relative to 1 amic acid standard proton number ratio.

[synthesis of polyimides and polyimide acid]

By CBDA (5.50g, 28.0 mMs), PCH7DAB (3.20g, 8.41 mMs) and p-PDA (2.13g, 19.7 MM) mixing in NEP (32.5g) so as to react 6 hours in 40 DEG C, so as to obtain resin solid content concentration for 25.0 The polyamic acid solution (1) of quality %.The number-average molecular weight of the polyamic acid is 25100, and weight average molecular weight is 74800.

By BODA (10.2g, 40.8 mMs), PCH7DAB (9.70g, 25.5 mMs) and DBA (3.88g, 25.5 millis Mole) mixing in NEP (42.6g) so as to react 5 hours in 80 DEG C.Then, add CBDA (2.00g, 10.2 mMs) and NEP (34.8g) so as to react 6 hours in 40 DEG C, so as to obtain the polyamic acid that resin solid content concentration is 25.0 mass % Solution (2).The number-average molecular weight of the polyamic acid is 24200, and weight average molecular weight is 64000.

In the polyamic acid solution (2) for being 25.0 mass % by the resin solid content concentration of the gained of synthesis example 2 (90.0g) Middle addition NEP, it is diluted to after 6 mass %, is added the acetic anhydride (11.6g) and pyridine as imidization catalyst (8.56g) so as to react 4 hours in 80 DEG C.The reaction solution is put in methanol (1800ml), is separated by filtration what is obtained Precipitate.The precipitate is cleaned with methanol, the drying under reduced pressure at 100 DEG C and obtain polyimide powder (3).The polyimides Acid imide rate be 57%, number-average molecular weight is 21300, and weight average molecular weight is 51500.

By BODA (6.89g, 27.5 mMs), PBCH5DAB (5.21g, 12.0 mMs) and DBA (3.42g, 22.5 MM) mixing in NEP (28.1g) so as to react 5 hours in 80 DEG C.Then, CBDA (1.35g, 6.88 mMs) is added With NEP (22.4g) so as to react 6 hours in 40 DEG C, the polyamic acid that resin solid content concentration is 25.0 mass % is obtained molten Liquid.

In the polyamic acid solution (60.0g) of gained addition NEP, be diluted to 6 mass % after, add sub- as acyl The acetic anhydride (13.5g) and pyridine (9.80g) of amination catalysis so as to react 3 hours in 90 DEG C.The reaction solution is put into In methanol (1500ml), obtained precipitate is separated by filtration.The precipitate is cleaned with methanol, the drying under reduced pressure at 100 DEG C And obtain polyimide powder (4).The acid imide rate of the polyimides is 79%, and number-average molecular weight is 19200, Weight-average molecular Measure as 48200.

By BODA (5.95g, 23.8 mMs), m-PBCH5DABz (4.56g, 10.2 mMs) and p-PDA (2.57g, 23.8 mMs) mixing in NEP (25.0g) so as to react 5 hours in 80 DEG C.Then, CBDA (2.00g, 10.2 millis are added Mole) and NEP (20.3g) so as to react 6 hours in 40 DEG C, be 25.0 mass % so as to obtain resin solid content concentration Polyamic acid solution.

In the polyamic acid solution (55.0g) of gained addition NEP, be diluted to 6 mass % after, add sub- as acyl The acetic anhydride (12.3g) and pyridine (9.11g) of amination catalysis so as to react 3 hours in 90 DEG C.The reaction solution is put into In methanol (1500ml), obtained precipitate is separated by filtration.The precipitate is cleaned with methanol, the drying under reduced pressure at 100 DEG C And obtain polyimide powder (5).The acid imide rate of the polyimides is 80%, and number-average molecular weight is 21500, Weight-average molecular Measure as 53800.

By TCA (4.50g, 20.1 mMs), PCH7DAB (2.29g, 6.02 mMs) and m-PDA (1.52g, 14.1 MM) mixing in NEP (24.9g) so as to react 6 hours in 40 DEG C, so as to obtain resin solid content concentration for 25.0 The polyamic acid solution (6) of quality %.The number-average molecular weight of the polyamic acid is 25100, and weight average molecular weight is 71900.

By TCA (7.25g, 32.3 mMs), PBCH5DAB (4.20g, 9.71 mMs) and DBA (3.44g, 22.6 millis Mole) mixing in NEP (44.7g) so as to react 6 hours in 40 DEG C, so as to obtain resin solid content concentration for 25.0 matter The polyamic acid solution of amount %.

In the polyamic acid solution (50.0g) of gained addition NEP, be diluted to 6 mass % after, add sub- as acyl The acetic anhydride (6.05g) and pyridine (4.73g) of amination catalysis so as to react 4 hours in 80 DEG C.The reaction solution is put into In methanol (900ml), obtained precipitate is separated by filtration.The precipitate is cleaned with methanol, the drying under reduced pressure at 100 DEG C and Obtain polyimide powder (7).The acid imide rate of the polyimides is 54%, and number-average molecular weight is 21800, weight average molecular weight For 56200.

By TDA (2.98g, 9.92 mMs), PCH7DAB (3.78g, 9.93 mMs) and DBA (3.53g, 23.2 millis Mole) mixing in NEP (24.5g) so as to react 5 hours in 80 DEG C.Then, add CBDA (4.55g, 23.2 mMs) and NEP (20.1g) so as to react 6 hours in 40 DEG C, obtains the polyamic acid that resin solid content concentration is 25.0 mass % molten Liquid.

In the polyamic acid solution (50.0g) of gained addition NEP, be diluted to 6 mass % after, add sub- as acyl The acetic anhydride (11.1g) and pyridine (8.05g) of amination catalysis so as to react 3 hours in 90 DEG C.The reaction solution is put into In methanol (1500ml), obtained precipitate is separated by filtration.The precipitate is cleaned with methanol, the drying under reduced pressure at 100 DEG C And obtain polyimide powder (8).The acid imide rate of the polyimides is 76%, and number-average molecular weight is 20700, Weight-average molecular Measure as 52500.

By TDA (3.29g, 11.0 mMs), PBCH5DAB (4.74g, 11.0 mMs) and p-PDA (2.76g, 25.5 MM) mixing in NEP (26.1g) so as to react 5 hours in 80 DEG C.Then, CBDA (5.01g, 25.5 mMs) is added With NEP (21.3g) so as to react 6 hours in 40 DEG C, the polyamic acid that resin solid content concentration is 25.0 mass % is obtained molten Liquid.

In the polyamic acid solution (50.5g) of gained addition NEP, be diluted to 6 mass % after, add sub- as acyl The acetic anhydride (11.2g) and pyridine (8.21g) of amination catalysis so as to react 3 hours in 90 DEG C.The reaction solution is put into In methanol (1500ml), obtained precipitate is separated by filtration.The precipitate is cleaned with methanol, the drying under reduced pressure at 100 DEG C And obtain polyimide powder (9).The acid imide rate of the polyimides is 80%, and number-average molecular weight is 20100, Weight-average molecular Measure as 50200.

By TDA (3.05g, 10.2 mMs), m-PBCH5DABz (4.54g, 10.2 mMs) and DBA (3.61g, 23.7 mMs) mixing in NEP (26.2g) so as to react 5 hours in 80 DEG C.Then, CBDA (4.65g, 23.7 millis are added Mole) and NEP (21.4g) so as to react 6 hours in 40 DEG C, obtain the polyamides that resin solid content concentration is 25.0 mass % Amino acid solution.

In the polyamic acid solution (50.0g) of gained addition NEP, be diluted to 6 mass % after, add sub- as acyl The acetic anhydride (11.2g) and pyridine (8.24g) of amination catalysis so as to react 3 hours in 90 DEG C.The reaction solution is put into In methanol (1500ml), obtained precipitate is separated by filtration.The precipitate is cleaned with methanol, the drying under reduced pressure at 100 DEG C And obtain polyimide powder (10).The acid imide rate of the polyimides is 80%, and number-average molecular weight is 20500, is divided equally again Son amount is 52900.

By BODA (5.21g, 20.8 mMs), PCH7DAB (4.95g, 13.0 mMs) and DBA (1.98g, 13.0 millis Mole) mixing in NMP (21.7g) so as to react 5 hours in 80 DEG C.Then, add CBDA (1.02g, 5.20 mMs) and NMP (17.8g) so as to react 6 hours in 40 DEG C, obtains the polyamic acid solution that resin solid content concentration is 25.0 mass % (11).The number-average molecular weight of the polyamic acid is 25100, and weight average molecular weight is 65900.

By BODA (6.38g, 25.5 mMs), AP18 (6.00g, 15.9 mMs) and DBA (2.45g, 16.1 mmoles You) mixing in NMP (26.5g) so as to react 5 hours in 80 DEG C.Then, add CBDA (1.25g, 6.37 mMs) and NMP (21.7g) so as to react 6 hours in 40 DEG C, obtains the polyamic acid solution that resin solid content concentration is 25.0 mass % (12).The number-average molecular weight of the polyamic acid is 18900, and weight average molecular weight is 54800.

In the polyamic acid solution (12) that the resin solid content concentration obtained by synthesis example 12 is 25.0 mass % (50.0g) in addition NMP, be diluted to after 6 mass %, add as imidization catalyst acetic anhydride (6.23g) and Pyridine (4.65g) so as to react 4 hours in 80 DEG C.The reaction solution is put in methanol (1000ml), is separated by filtration and is obtained The precipitate for obtaining.The precipitate is cleaned with methanol, the drying under reduced pressure at 100 DEG C and obtain polyimide powder (13).This gathers Imido acid imide rate is 58%, and number-average molecular weight is 16900, and weight average molecular weight is 43800.

By BODA (6.89g, 27.5 mMs), ColDAB (5.40g, 10.3 mMs) and DBA (3.68g, 24.2 millis Mole) mixing in NEP (28.6g) so as to react 5.5 hours in 80 DEG C.Then, CBDA (1.35g, 6.88 mMs) is added With NEP (23.4g) so as to react 7 hours in 40 DEG C, the polyamic acid that resin solid content concentration is 25.0 mass % is obtained molten Liquid (14).The number-average molecular weight of the polyamic acid is 20100, and weight average molecular weight is 59800.

By BODA (6.74g, 26.9 mMs), ColDAB (5.28g, 10.1 mMs) and DBA (3.60g, 23.7 millis Mole) mixing in NMP (27.9g) so as to react 5.5 hours in 80 DEG C.Then, CBDA (1.32g, 6.73 mMs) is added With NMP (22.9g) so as to react 7 hours in 40 DEG C, the polyamic acid that resin solid content concentration is 25.0 mass % is obtained molten Liquid (15).The number-average molecular weight of the polyamic acid is 19900, and weight average molecular weight is 59100.

In the polyamic acid solution (15) that the resin solid content concentration obtained by synthesis example 15 is 25.0 mass % (55.0g) in addition NMP, be diluted to after 6 mass %, add as imidization catalyst acetic anhydride (6.81g) and Pyridine (5.07g) so as to react 4 hours in 80 DEG C.The reaction solution is put in methanol (1100ml), is separated by filtration and is obtained The precipitate for obtaining.The precipitate is cleaned with methanol, the drying under reduced pressure at 100 DEG C and obtain polyimide powder (16).This gathers Imido acid imide rate is 57%, and number-average molecular weight is 15900, and weight average molecular weight is 45100.

The polyamic acid and polyimides of the present invention collects and is shown in table 4.

[table 4]

*1：Polyamic acid is, and does not determine acid imide rate.

[preparation of aligning agent for liquid crystal]

Following embodiments 1～34 and comparative example 1～12 are the preparation examples of aligning agent for liquid crystal, and contribute to liquid crystal The evaluation of aligning agent.

Using the aligning agent for liquid crystal obtained by embodiment and comparative example, implement " the printing of aligning agent for liquid crystal Evaluation ", " ink-jet application of aligning agent for liquid crystal is evaluated ", " making (common structure cell) of liquid crystal cell ", " liquid crystal aligning And the evaluation (common structure cell) of tilt angle ", " making (PSA structure cells) of liquid crystal cell " and " (PSA is brilliant for the evaluation of liquid crystal aligning Born of the same parents) ".

(the printing evaluation of aligning agent for liquid crystal)

Printing evaluation is carried out using the aligning agent for liquid crystal obtained by embodiment and comparative example.As printer, Using Simple printing press S15 types (Nissha Printing Co., Ltd (description printing society of Japan) system).Printing is by cleaning On chromium evaporation substrate afterwards, with printing area as 80mm × 80mm, coining as 0.2mm, give up 5 pieces of substrate, predrying from being printed onto Till time be 90 seconds, predrying carry out in 70 DEG C of heating conditions of 5 minutes on hot plate.

Carry out the evaluation of pore, the linear evaluation of liquid crystal orientation film end and the liquid crystal orientation film end of the film of gained The evaluation of the protuberance in portion.

The evaluation of pore is carried out by the perusal film under sodium vapor lamp.Specifically, institute on liquid crystal orientation film is calculated The stomatal number for confirming, stomatal number is fewer, is regarded as coating more excellent.

The linear evaluation of the end of liquid crystal orientation film is by with optical microscope (Nikon Corp. (ニコン societies) System, ECLIPSE E600WPOL) observation relative to the right-hand end of print direction film carrying out.Specifically, using light Learn microscope, multiplying power is set to 25 times is observed, determine in the Fig. 1 as the painting film image of gained 3 and 4 difference, i.e., scheme The length of the A in 1.All of painting film image is all obtained under same multiplying power.The length of A is shorter, is regarded as liquid crystal and takes Rectilinearity to the end of film is more excellent.

The evaluation of the protuberance of the end of liquid crystal orientation film by with observation by light microscope relative to print direction right side The film of end is carrying out.Specifically, 25 times are set to using optical microscope, by multiplying power to be observed, the painting obtained by measure The length of the B in film image (Fig. 2).All of painting film image is all obtained under same multiplying power.The length of the B is shorter, will The protuberance 5 that it is considered as the end of liquid crystal orientation film is more excellent.

The stomatal number of the liquid crystal orientation film obtained by embodiment and comparative example, the length of A and B are shown in 8～table of table 10 Length.

(ink-jet application of aligning agent for liquid crystal is evaluated)

The aligning agent for liquid crystal obtained using the aligning agent for liquid crystal (7) and embodiment 12 that are obtained by embodiment 7 (12) ink-jet application evaluation is carried out.As ink-jet application machine, using HIS-200 (device technique Co., Ltd. of Hitachi (Hitachi プラ Application トテ Network ノロジー societies) system).Coating is deposited with substrate, with coated face by ITO (tin indium oxide) after cleaning Product is 70mm × 70mm, injector spacing is 0.423mm, sweep span (Japanese:スキャ Application ピッチ) it is 0.5mm, coating speed For the 40mm/ seconds, from be applied to it is predrying till time be 60 seconds and it is predrying on hot plate in 70 DEG C heat 5 minutes Under the conditions of carry out.

The pore for carrying out under the conditions of with " the printing evaluation of aligning agent for liquid crystal " identical the film of gained is commented Valency.The evaluation result of the pore of embodiment 7,12 is shown in Table 8.

(making (common structure cell) of liquid crystal cell)

By the aligning agent for liquid crystal obtained by embodiment and comparative example be spun on 30mm × 40mm with ITO electrode The ito surface of substrate, on hot plate with 80 DEG C of heat treated 5 minutes, with 220 DEG C of heat treated in thermal cycle type cleaning oven 30 minutes, obtain the ito substrate for the polyimide liquid crystal direct action membrane of 100nm with thickness.For the coated surface of the ito substrate Rubbing device with roll neck as 120mm simultaneously uses rayon cloth, roller rotating speed be 1000rpm, roller gait of march be the 50mm/ seconds, And intrusion is to carry out friction treatment under conditions of 0.1mm.

Prepare the ito substrate with liquid crystal orientation film of two pieces of gained, so that liquid crystal aligning face is in inner side and clips 6 μm the mode of sept ito substrate is assembled, with sealant will around bonding making negative crystal born of the same parents.Using decompression injection Method, the MLC-6608 of Merck Japanese firm (メ Le Network ジャパ Application society) system is injected in negative crystal born of the same parents, and inlet is sealed, Obtain liquid crystal cell (common structure cell).

(evaluation (common structure cell) of liquid crystal aligning and tilt angle)

Using the liquid crystal cell of above-mentioned gained, the evaluation of liquid crystal aligning and tilt angle is carried out.Liquid crystal aligning is to use Polarizing microscope (Nikon Corp.'s system, ECLIPSE E600WPOL) observes liquid crystal cell, and confirmation has No yield point defect.

Additionally, tilt angle is after liquid crystal injection, with 95 DEG C of heat treated 5 minutes after, further with 120 DEG C of heat treated It is measured after 5 hours.Further, after liquid crystal injection, for the liquid crystal cell irradiation after 95 DEG C of heat treated 5 minutes with 365nm conversions are calculated as 10J/cm²Ultraviolet after, determine tilt angle.

Relative to the tilt angle after 95 DEG C of heat treated 5 minutes, after 120 DEG C of Overheating Treatments 5 hours or to irradiate ultraviolet The change of the tilt angle after line is less, and the stability for being regarded as tilt angle relative to heat or ultraviolet is high.

In addition, tilt angle is surveyed at room temperature by using PAS-301 (Ai Lisi Kanggong department (ELSICON societies) system) It is fixed.In addition, ultraviolet irradiation is by using desk-top UV solidification equipments (HCT3B28HEX-1) (Sen Laite companies (セ Application ライト) make) come carry out.

The liquid crystal aligning of the liquid crystal cell obtained by embodiment and comparative example and the result of tilt angle are shown in 11～table of table In 13.

(making (PSA structure cells) of liquid crystal cell)

The aligning agent for liquid crystal (6) that obtains by the aligning agent for liquid crystal (5) obtained by embodiment 5, by embodiment 6, The aligning agent for liquid crystal (11) that obtained by embodiment 11, the aligning agent for liquid crystal (17) obtained by embodiment 17 and by implementing Aligning agent for liquid crystal (30) center of being spun on that example 30 is obtained have 20 μm of the pattern spacing of 10mm × 10mm with ITO electrode Substrate and center 10mm × 40mm the substrate with ITO electrode ito surface, on hot plate with 80 DEG C of 5 points of heat treated Clock, with 220 DEG C of heat treated 30 minutes in thermal cycle type cleaning oven, obtains the polyimide coating film that thickness is 100nm.With Pure water cleans coated surface, is then obtained with liquid crystal aligning with 100 DEG C of heat treated 15 minutes in thermal cycle type cleaning oven The substrate of film.

By the base with liquid crystal orientation film in the way of making liquid crystal aligning face be in inner side and clip 6 μm of sept Plate is assembled, and bonding around is made into negative crystal born of the same parents with sealant.Using decompression injection method, in the negative crystal born of the same parents liquid is injected Crystalline substance, inlet is sealed, and obtains liquid crystal cell；The liquid crystal is mixed with following in MLC-6608 (Merck Japanese firm system) Liquid crystal obtained by the polymerizable compound (1) that formula is represented, relative to the MLC-6608 of 100 mass %, polymerizable compound is 0.3 Quality %.

[changing 50]

For the liquid crystal cell of gained, while apply the voltage of exchange 5V, while using the metal halide that illumination is 60mW Thing lamp, shields the wavelength of below 350nm, irradiates and is calculated as 20J/cm with 365nm conversions²Ultraviolet, obtain liquid crystal orientation side To the liquid crystal cell (PSA structure cells) being under control.It is 50 to the temperature in irradiation unit during liquid crystal cell irradiation ultraviolet radiation ℃。

(evaluation (PSA structure cells) of liquid crystal aligning)

The response speed of the liquid crystal before the irradiation ultraviolet radiation of the liquid crystal cell of gained and after irradiation ultraviolet radiation is surveyed It is fixed.For response speed, the T90 → T10 from absorbance 90% to absorbance 10% is determined.By embodiment and comparative example gained PSA structure cells in, compared with the liquid crystal cell before irradiation ultraviolet radiation, the fast response time of the liquid crystal cell after irradiation ultraviolet radiation, So the differently- oriented directivity for confirming liquid crystal is under control.

Additionally, for any one liquid crystal cell, all confirming liquid crystal by polarized light microscope observing and being equably orientated.

Embodiment 1～34 and comparative example 1～12 are described in detail below, by the system of the aligning agent for liquid crystal of each example Collect for condition and be shown in table 5～7.

Additionally, using the aligning agent for liquid crystal obtained by embodiment 1～34 and comparative example 1～12, implement that " liquid crystal takes To the printing evaluation of inorganic agent ", the ink-jet application of aligning agent for liquid crystal " evaluate ", " making of liquid crystal cell is (common brilliant Born of the same parents) ", " evaluation (common structure cell) of liquid crystal aligning and tilt angle ", " making (PSA structure cells) of liquid crystal cell ", " liquid crystal aligning Evaluation (PSA structure cells) of property " etc..Its result is collected and is shown in table 8～13.

In the polyamic acid solution (1) that the resin solid content concentration obtained by synthesis example 1 is 25.0 mass % (10.1g) Middle addition NEP (32.0g), stirs 2 hours in 25 DEG C, obtains aligning agent for liquid crystal (1).In confirming the aligning agent for liquid crystal Do not find that muddiness or precipitation etc. are abnormal, be uniform solution.

Aligning agent for liquid crystal (1) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

In the polyamic acid solution (1) for being 25.0 mass % by the resin solid content concentration of the gained of synthesis example 1 (10.0g) Middle addition NEP (12.1g), BCS (11.8g) and EC (7.84g), stir 2 hours in 25 DEG C, obtain aligning agent for liquid crystal (2). Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (2) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

In the polyamic acid solution (2) that the resin solid content concentration obtained by synthesis example 2 is 25.0 mass % (10.0g) Middle addition NEP (31.7g), stirs 2 hours in 25 DEG C, obtains aligning agent for liquid crystal (3).In confirming the aligning agent for liquid crystal Do not find that muddiness or precipitation etc. are abnormal, be uniform solution.

Aligning agent for liquid crystal (3) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

In the polyamic acid solution (2) for being 25.0 mass % by the resin solid content concentration of the gained of synthesis example 2 (10.0g) Middle addition NEP (14.0g) and BCS (17.6g), stir 2 hours in 25 DEG C, obtain aligning agent for liquid crystal (4).Confirm the liquid crystal Do not find that muddiness or precipitation etc. are abnormal in aligning agent, be uniform solution.

Aligning agent for liquid crystal (4) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (3) by the gained of synthesis example 3 (2.55g) in addition NEP (40.0g), stir 24 in 70 DEG C Hour, obtain aligning agent for liquid crystal (5).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be Uniform solution.

Aligning agent for liquid crystal (5) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (3) by the gained of synthesis example 3 (2.54g) in addition NEP (14.6g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NEP (7.30g) and BCS (17.9g) in the solution, stir 10 hours in 50 DEG C, obtain liquid crystal Aligning agent (6).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (6) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (3) by the gained of synthesis example 3 (2.50g) in addition NEP (29.7g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NEP (14.8g) and BCS (36.4g) in the solution, stir 10 hours in 50 DEG C, obtain liquid crystal Aligning agent (7).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (7) obtained by use, carries out under the conditions described above " the ink-jet painting of aligning agent for liquid crystal Cloth is evaluated ".

The polyimide powder (3) by the gained of synthesis example 3 (2.55g) in addition NEP (17.3g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NEP (8.71g), BCS (8.01g) and MC (6.00g) in the solution, it is little in 50 DEG C of stirrings 10 When, obtain aligning agent for liquid crystal (8).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be equal Even solution.

Aligning agent for liquid crystal (8) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (3) by the gained of synthesis example 3 (2.56g) in addition NEP (18.7g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NEP (9.40g), BCS (6.00g) and EC (6.00g) in the solution, it is little in 50 DEG C of stirrings 10 When, obtain aligning agent for liquid crystal (9).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be equal Even solution.

Aligning agent for liquid crystal (9) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (3) by the gained of synthesis example 3 (2.55g) in addition NEP (17.3g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NEP (8.70g) and PGME (14.0g) in the solution, stir 10 hours in 50 DEG C, obtain liquid Brilliant aligning agent (10).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (10) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (3) by the gained of synthesis example 3 (2.55g) in addition NEP (16.0g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NMP (6.02g) and BCS (18.0g) in the solution, stir 10 hours in 50 DEG C, obtain liquid crystal Aligning agent (11).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (11) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (3) by the gained of synthesis example 3 (2.50g) in addition NEP (27.6g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NMP (10.3g) and BCS (31.0g) in the solution, stir 10 hours in 50 DEG C, obtain liquid crystal Aligning agent (12).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (12) obtained by use, carries out under the conditions described above " the ink-jet of aligning agent for liquid crystal Coating is evaluated ".

The polyimide powder (3) by the gained of synthesis example 3 (2.55g) in addition NEP (16.0g), stir 24 in 70 DEG C Hour is so that its dissolving.Add γ-BL (4.02g) and BCS (20.0g) in the solution, stir 10 hours in 50 DEG C, obtain liquid Brilliant aligning agent (13).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (13) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (4) by the gained of synthesis example 4 (2.55g) in addition NEP (12.0g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NEP (6.02g) and BCS (22.0g) in the solution, stir 10 hours in 50 DEG C, obtain liquid crystal Aligning agent (14).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (14) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (4) by the gained of synthesis example 4 (2.57g) in addition NEP (16.1g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NEP (8.10g) and ECS (16.1g) in the solution, stir 10 hours in 50 DEG C, obtain liquid crystal Aligning agent (15).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (15) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (4) by the gained of synthesis example 4 (2.53g) in addition NEP (18.5g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NEP (9.20g), BCS (7.93g) and MC (3.97g) in the solution, it is little in 50 DEG C of stirrings 10 When, obtain aligning agent for liquid crystal (16).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be equal Even solution.

Aligning agent for liquid crystal (16) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (4) by the gained of synthesis example 4 (2.55g) in addition NEP (16.0g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NMP (10.0g) and BCS (14.1g) in the solution, stir 10 hours in 50 DEG C, obtain liquid crystal Aligning agent (17).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (17) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (4) by the gained of synthesis example 4 (2.55g) in addition NEP (20.0g), stir 24 in 70 DEG C Hour is so that its dissolving.Add γ-BL (4.00g) and BCS (16.0g) in the solution, stir 10 hours in 50 DEG C, obtain liquid Brilliant aligning agent (18).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (18) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (5) by the gained of synthesis example 5 (2.55g) in addition NEP (12.5g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NEP (3.54g) and BCS (24.0g) in the solution, stir 10 hours in 50 DEG C, obtain liquid crystal Aligning agent (19).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (19) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (5) by the gained of synthesis example 5 (2.56g) in addition NEP (13.4g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NEP (6.70g), BCS (16.1g) and MC (4.02g) in the solution, it is little in 50 DEG C of stirrings 10 When, obtain aligning agent for liquid crystal (20).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be equal Even solution.

Aligning agent for liquid crystal (20) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (5) by the gained of synthesis example 5 (2.55g) in addition NEP (12.0g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NMP (10.0g) and BCS (18.1g) in the solution, stir 10 hours in 50 DEG C, obtain liquid crystal Aligning agent (21).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (21) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (5) by the gained of synthesis example 5 (2.55g) in addition NEP (17.8g), stir 24 in 70 DEG C Hour is so that its dissolving.Add γ-BL (2.00g) and BCS (20.0g) in the solution, stir 10 hours in 50 DEG C, obtain liquid Brilliant aligning agent (22).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (22) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

In the polyamic acid solution (6) for being 25.0 mass % by the resin solid content concentration of the gained of synthesis example 6 (10.0g) Middle addition NEP (6.21g) and BCS (25.5g), stir 2 hours in 25 DEG C, obtain aligning agent for liquid crystal (23).Confirm the liquid Do not find that muddiness or precipitation etc. are abnormal in brilliant aligning agent, be uniform solution.

Aligning agent for liquid crystal (23) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

In the polyamic acid solution (6) for being 25.0 mass % by the resin solid content concentration of the gained of synthesis example 6 (10.0g) Middle addition NEP (16.0g), BCS (7.87g) and PGME (7.84g), stir 2 hours in 25 DEG C, obtain aligning agent for liquid crystal (24).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (24) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (7) by the gained of synthesis example 7 (2.54g) in addition NEP (15.9g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NEP (8.00g) and ECS (15.9g) in the solution, stir 10 hours in 50 DEG C, obtain liquid crystal Aligning agent (25).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (25) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (7) by the gained of synthesis example 7 (2.55g) in addition NEP (17.3g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NEP (8.71g), BCS (8.01g) and PGME (6.00g) in the solution, in 50 DEG C 10 are stirred Hour, obtain aligning agent for liquid crystal (26).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be Uniform solution.

Aligning agent for liquid crystal (26) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (7) by the gained of synthesis example 7 (2.55g) in addition NEP (20.0g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NMP (8.00g), BCS (10.1g) and EC (2.02g) in the solution, it is little in 50 DEG C of stirrings 10 When, obtain aligning agent for liquid crystal (27).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be equal Even solution.

Aligning agent for liquid crystal (27) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (7) by the gained of synthesis example 7 (2.55g) in addition NEP (18.1g), stir 24 in 70 DEG C Hour is so that its dissolving.Add γ-BL (2.00g), BCS (12.0g) and ECS (8.00g) in the solution, in 50 DEG C 10 are stirred Hour, obtain aligning agent for liquid crystal (28).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be Uniform solution.

Aligning agent for liquid crystal (28) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (8) by the gained of synthesis example 8 (2.55g) in addition NEP (21.3g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NEP (10.7g) and BCS (8.01g) in the solution, stir 10 hours in 50 DEG C, obtain liquid crystal Aligning agent (29).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (29) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (8) by the gained of synthesis example 8 (2.56g) in addition NEP (26.1g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NMP (8.00g), BCS (4.00g) and MC (2.00g) in the solution, it is little in 50 DEG C of stirrings 10 When, obtain aligning agent for liquid crystal (30).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be equal Even solution.

Aligning agent for liquid crystal (30) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (9) by the gained of synthesis example 9 (2.55g) in addition NEP (16.0g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NMP (12.0g) and BCS (12.1g) in the solution, stir 10 hours in 50 DEG C, obtain liquid crystal Aligning agent (31).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (31) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (9) by the gained of synthesis example 9 (2.55g) in addition NEP (20.0g), stir 24 in 70 DEG C Hour is so that its dissolving.Add γ-BL (4.00g) and BCS (15.8g) in the solution, stir 10 hours in 50 DEG C, obtain liquid Brilliant aligning agent (32).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (32) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (10) by the gained of synthesis example 10 (2.55g) in addition NEP (32.2g), in 70 DEG C of stirrings 24 hours so that its dissolving.Add NMP (4.00g), BCS (2.00g) and EC (2.00g) in the solution, in 50 DEG C 10 are stirred Hour, obtain aligning agent for liquid crystal (33).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be Uniform solution.

Aligning agent for liquid crystal (33) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (10) by the gained of synthesis example 10 (2.55g) in addition NEP (16.0g), in 70 DEG C of stirrings 24 hours so that its dissolving.Add γ-BL (2.01g), BCS (16.0g) and MC (6.00g) in the solution, in 50 DEG C of stirrings 10 hours, obtain aligning agent for liquid crystal (34).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, For uniform solution.

Aligning agent for liquid crystal (34) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (3) by the gained of synthesis example 3 (2.52g) in addition NMP (14.5g), stir 24 in 70 DEG C Hour is so that its dissolving.Add NMP (7.21g) and BCS (17.8g) in the solution, stir 10 hours in 50 DEG C, obtain liquid crystal Aligning agent (35).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (35) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

By the polyamic acid solution (11) that the resin solid content concentration of the gained of synthesis example 11 is 25.0 mass % (10.1g) addition NMP (32.0g) in, stirs 2 hours in 25 DEG C, obtains aligning agent for liquid crystal (36).Confirm the liquid crystal aligning Do not find that muddiness or precipitation etc. are abnormal in inorganic agent, be uniform solution.

Aligning agent for liquid crystal (36) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

By the polyamic acid solution (11) that the resin solid content concentration of the gained of synthesis example 11 is 25.0 mass % (10.0g) addition NMP (14.0g) and BCS (17.6g) in, stir 2 hours in 25 DEG C, obtain aligning agent for liquid crystal (37).Really Recognize in the aligning agent for liquid crystal and do not find that muddiness or precipitation etc. are abnormal, be uniform solution.

Aligning agent for liquid crystal (37) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

By the polyamic acid solution (12) that the resin solid content concentration of the gained of synthesis example 12 is 25.0 mass % (10.0g) addition NMP (14.0g) and BCS (17.4g) in, stir 2 hours in 25 DEG C, obtain aligning agent for liquid crystal (38).Really Recognize in the aligning agent for liquid crystal and do not find that muddiness or precipitation etc. are abnormal, be uniform solution.

Aligning agent for liquid crystal (38) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (13) by the gained of synthesis example 13 (2.55g) in addition NMP (14.7g), in 70 DEG C of stirrings 24 hours so that its dissolving.Add NMP (7.28g) and BCS (18.0g) in the solution, stir 10 hours in 50 DEG C, obtain liquid Brilliant aligning agent (39).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (39) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (13) by the gained of synthesis example 13 (2.55g) in addition NEP (14.7g), in 70 DEG C of stirrings 24 hours so that its dissolving.Add NEP (7.30g) and BCS (18.0g) in the solution, stir 10 hours in 50 DEG C, obtain liquid Brilliant aligning agent (40).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (40) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

In the polyamic acid solution (14) that the resin solid content concentration obtained by synthesis example 14 is 25.0 mass % (10.0g) addition NEP (31.7g) in, stirs 2 hours in 25 DEG C, obtains aligning agent for liquid crystal (41).Confirm the liquid crystal aligning Do not find that muddiness or precipitation etc. are abnormal in inorganic agent, be uniform solution.

Aligning agent for liquid crystal (41) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

By the polyamic acid solution (14) that the resin solid content concentration of the gained of synthesis example 14 is 25.0 mass % (10.0g) addition NEP (14.1g) and BCS (17.6g) in, stir 2 hours in 25 DEG C, obtain aligning agent for liquid crystal (42).Really Recognize in the aligning agent for liquid crystal and do not find that muddiness or precipitation etc. are abnormal, be uniform solution.

Aligning agent for liquid crystal (42) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

By the polyamic acid solution (15) that the resin solid content concentration of the gained of synthesis example 15 is 25.0 mass % (10.0g) addition NMP (31.7g) in, stirs 2 hours in 25 DEG C, obtains aligning agent for liquid crystal (43).Confirm the liquid crystal aligning Do not find that muddiness or precipitation etc. are abnormal in inorganic agent, be uniform solution.

Aligning agent for liquid crystal (43) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

By the polyamic acid solution (15) that the resin solid content concentration of the gained of synthesis example 15 is 25.0 mass % (10.0g) addition NMP (14.0g) and BCS (17.6g) in, stir 2 hours in 25 DEG C, obtain aligning agent for liquid crystal (44).Really Recognize in the aligning agent for liquid crystal and do not find that muddiness or precipitation etc. are abnormal, be uniform solution.

Aligning agent for liquid crystal (44) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (16) by the gained of synthesis example 16 (2.55g) in addition NMP (14.7g), in 70 DEG C of stirrings 24 hours so that its dissolving.Add NMP (7.30g) and BCS (18.2g) in the solution, stir 10 hours in 50 DEG C, obtain liquid Brilliant aligning agent (45).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (45) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

The polyimide powder (16) by the gained of synthesis example 16 (2.52g) in addition NEP (14.5g), in 70 DEG C of stirrings 24 hours so that its dissolving.Add NEP (7.21g) and BCS (17.8g) in the solution, stir 10 hours in 50 DEG C, obtain liquid Brilliant aligning agent (46).Confirm not finding that muddiness or precipitation etc. are abnormal in the aligning agent for liquid crystal, be uniform solution.

Aligning agent for liquid crystal (46) obtained by use, carries out under the conditions described above the making and various evaluations of structure cell.

[table 5]

*1：Ratio in aligning agent for liquid crystal shared by polymer.

[table 6]

*2：Ratio in aligning agent for liquid crystal shared by polymer.

[table 7]

*3：Ratio in aligning agent for liquid crystal shared by polymer.

[table 8]

[table 9]

[table 10]

[table 11]

[table 12]

[table 13]

*4：It was observed that the orientation defect based on pore of more than 10.

It can be seen from above-mentioned result, the liquid crystal orientation film obtained by the aligning agent for liquid crystal of embodiment with by comparative example The liquid crystal orientation film that obtains of aligning agent for liquid crystal compare, even if the irradiation that long-time is exposed to high temperature and light can be obtained Under, the also little liquid crystal orientation film of change of tilt angle.

Further, the aligning agent for liquid crystal of embodiment is in the same of the little liquid crystal orientation film of the change that can obtain above-mentioned tilt angle When, moreover it is possible to obtain uniform film.

Additionally, using identical polyamic acid or polyimides, the embodiment comprising specific solvent of the present invention with not In the comparison of the comparative example containing specific solvent, the change of the above-mentioned tilt angle in the comparative example without specific solvent is little, but produces Substantial amounts of pore, the film lack of homogeneity of liquid crystal orientation film end.Specifically, the ratio of embodiment 3 and comparative example 2 can be passed through Compared with, embodiment 4 and comparative example 3 comparison and embodiment 6 and comparative example 1 relatively confirming.

Further, it is specific with using not containing in the embodiment of the diamine compound comprising specific side-chain structure using the present invention In the comparison of the comparative example of the diamine compound of side-chain structure, using the comparative example of the diamine compound without specific side-chain structure In above-mentioned tilt angle change it is big, produce substantial amounts of pore, the film lack of homogeneity of liquid crystal orientation film end.Specifically, Comparison, the comparison of embodiment 4 and comparative example 5 and the comparison of embodiment 4 and comparative example 6 of embodiment 4 and comparative example 4 can be passed through To confirm.Particularly in comparative example 6, although having used specific solvent, substantial amounts of pore is also generated, liquid crystal orientation film end Film lack of homogeneity.

Additionally, the embodiment in the diamine compound comprising specific side-chain structure using the present invention is specific with using not containing In the comparison of the comparative example of the diamine compound of side-chain structure, using the comparative example of the diamine compound without specific side-chain structure In above-mentioned tilt angle change it is although little, but produce substantial amounts of pore, the film lack of homogeneity of liquid crystal orientation film end.Specifically For, the ratio of comparison, the comparison of embodiment 3 and comparative example 9, embodiment 4 and the comparative example 8 of embodiment 3 and comparative example 7 can be passed through Compared with comparison, the comparison of embodiment 4 and comparative example 11 and the comparison of embodiment 4 and comparative example 12 of, embodiment 4 and comparative example 10 To confirm.

Particularly in comparative example 7, comparative example 8 and comparative example 12, although having used specific solvent, substantial amounts of gas is also generated Hole, the film lack of homogeneity of liquid crystal orientation film end.

The probability utilized in industry

The aligning agent for liquid crystal of the present invention can provide coating solution to the infiltration spread height of substrate, with uniform painting Even if film, long-time are exposed to the liquid that tilt angle under the irradiation of high temperature and light also will not change, the film of end is also excellent Brilliant alignment films, the liquid crystal display cells with such liquid crystal orientation film it is excellent in reliability, can perform well in big picture and LCD TV of high-resolution etc., can be used for the liquid crystal of TN elements, STN elements, TFT liquid crystal cells etc., particularly vertical orientating type Display element.

In addition, quoting the explanation of the Japanese patent application 2011-196320 that September in 2011 is filed an application on the 8th here Announcement of all the elements of book, claims, accompanying drawing and summary as description of the invention.

The explanation of symbol

1 liquid crystal orientation film

2 chromium are deposited with substrate

The end of 3 liquid crystal orientation films

The end of 4 liquid crystal orientation films

The protuberance of the end of 5 liquid crystal orientation films

Claims

1. a kind of aligning agent for liquid crystal, it is characterised in that comprising following composition (A) and composition (B),

Composition (A)：N- ethyl-2-pyrrolidones；

Composition (B)：Polyimides obtained by imidizate are carried out selected from polyimide precursor and by polyimide precursor at least A kind of polymer, the polyimide precursor by containing the diamine component with the diamidogen of side chain represented with following formula [1] with The tetracarboxylic dianhydride represented with following formula [2] is reacted and is obtained；

[changing 1]

In formula [1], X₁It is singly-bound ,-(CH₂)_a-、-O-、-CH₂O- or-COO-, wherein a are 1～15 integers；X₂Be singly-bound or (CH₂)_b-, wherein b is 1～10 integer；X₃It is singly-bound ,-(CH₂)_c-、-O-、-CH₂O- ,-COO- or-OCO-, wherein c be 1～ 10 integer；X₄It is the divalent cyclic group selected from phenyl ring and hexamethylene ring, wherein, the arbitrary hydrogen atom on the cyclic group can With by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, carbon number 1～3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or Fluorine atom replaces；X₅It is the divalent cyclic group selected from phenyl ring and hexamethylene ring, wherein, the arbitrary hydrogen atom on the cyclic group Can by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, carbon number 1～3 the fluoroalkoxy containing fluoroalkyl, carbon number 1～3 Or fluorine atom replaces；X₆It is the alkyl of carbon number 1～12 or the alkoxyl of carbon number 1～12, n is 0～2 integer；

[changing 2]

In formula [2], Y₁It is the group of the structure represented with following formula [2b]～formula [2f] and formula [2h]～formula [2j]；

[changing 3]

2. aligning agent for liquid crystal as claimed in claim 1, it is characterised in that with the side chain represented with formula [1] Diamidogen is the diamine compound represented with following formula [1a]；

[changing 4]

In formula [1a], X₁It is singly-bound ,-(CH₂)_a-、-O-、-CH₂O- or-COO-, wherein a are 1～15 integers；X₂Be singly-bound or (CH₂)_b-, wherein b is 1～10 integer；X₃It is singly-bound ,-(CH₂)_c-、-O-、-CH₂O- ,-COO- or-OCO-, wherein c be 1～ 10 integer；X₄It is the divalent cyclic group selected from phenyl ring and hexamethylene ring, wherein, the arbitrary hydrogen atom on the cyclic group can With by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, carbon number 1～3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 or Fluorine atom replaces；X₅It is the divalent cyclic group selected from phenyl ring and hexamethylene ring, wherein, the arbitrary hydrogen atom on the cyclic group Can by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, carbon number 1～3 the fluoroalkoxy containing fluoroalkyl, carbon number 1～3 Or fluorine atom replaces；X₆It is the alkyl of carbon number 1～12 or the alkoxyl of carbon number 1～12；N is 0～2 integer, and m is 1.

3. aligning agent for liquid crystal as claimed in claim 2, it is characterised in that 5～80 moles of % of raw material diamine component make To the diamidogen that the formula [1a] is represented.

4. the aligning agent for liquid crystal as any one of claims 1 to 3, it is characterised in that as the composition (B) Polymer is polyamic acid.

5. the aligning agent for liquid crystal as any one of claims 1 to 3, it is characterised in that as the composition (B) Polymer is to make polyimides obtained by polyamic acid dehydration closed-loop.

6. the aligning agent for liquid crystal as any one of claims 1 to 3, it is characterised in that as composition (C), contain METHYLPYRROLIDONE or gamma-butyrolacton.

7. the aligning agent for liquid crystal as any one of claims 1 to 3, it is characterised in that as composition (D), contain Selected from 1- hexanols, Hexalin, 1,2- ethylene glycol, 1,2- Propylene Glycol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol only son Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether and third At least one of glycol monobutyl ether.

8. the aligning agent for liquid crystal as any one of claims 1 to 3, it is characterised in that the composition (A) accounts for liquid crystal 10～100 mass % of contained whole organic solvents in aligning agent.

9. aligning agent for liquid crystal as claimed in claim 6, it is characterised in that the composition (C) accounts for aligning agent for liquid crystal In contained whole organic solvents 0.1～70 mass %.

10. aligning agent for liquid crystal as claimed in claim 7, it is characterised in that the composition (D) accounts for aligning agent for liquid crystal In contained whole organic solvents 5～80 mass %.

11. aligning agent for liquid crystal as any one of claims 1 to 3, it is characterised in that in aligning agent for liquid crystal The composition (B) be 0.1～15 mass %.

12. a kind of liquid crystal orientation films, it is characterised in that by using the liquid crystal aligning any one of claim 1～11 Inorganic agent and obtain.

13. a kind of liquid crystal orientation films, it is characterised in that by using the liquid crystal aligning any one of claim 1～11 Inorganic agent is simultaneously obtained using ink-jet method.

14. a kind of liquid crystal display cells, it is characterised in that with the liquid crystal orientation film described in claim 12 or 13.

15. liquid crystal orientation films as described in claim 12 or 13, it is characterised in that be used by possess electrode a pair There is liquid crystal layer between substrate and constitute, through the liquid crystal display cells of following operations manufacture, the operation is：In the pair of base Liquid crystal group of the configuration comprising the polymerizable compound being polymerized using at least one party in active energy beam and heat between plate Compound, while the applied voltage between the electrode, while making the polymerizable compound be polymerized.

16. a kind of liquid crystal display cells, it is characterised in that with the liquid crystal orientation film described in claim 15.

17. liquid crystal display cells as claimed in claim 16, it is characterised in that by possessing electrode and the liquid crystal aligning There is liquid crystal layer between a pair of substrates of film and constitute, and through following operations manufacturing, the operation is：Between the pair of substrate Liquid-crystal composition of the configuration comprising the polymerizable compound being polymerized using at least one party in active energy beam and heat, While between the electrode applied voltage, while making the polymerizable compound be polymerized.

18. liquid crystal orientation films as described in claim 12 or 13, it is characterised in that be used in a pair of substrates for possessing electrode Between there is liquid crystal layer and constitute, through the liquid crystal display cells of following operations manufacture, the operation is：Between the pair of substrate Liquid crystal orientation film of the configuration comprising the polymerizable group being polymerized using at least one party in active energy beam and heat, one While applied voltage is while make the polymerizable group be polymerized between the electrode.

19. a kind of liquid crystal display cells, it is characterised in that with the liquid crystal orientation film described in claim 18.

20. liquid crystal display cells as claimed in claim 19, it is characterised in that by having between a pair of substrates for possessing electrode There is liquid crystal layer and constitute, and through following operations manufacturing, the operation is：Configuration is comprising using activity between the pair of substrate The liquid crystal orientation film of the polymerizable group that at least one party in energy-ray and heat is polymerized, while applying between the electrode Making alive is while make the polymerizable group be polymerized.