CN104969123B

CN104969123B - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element

Info

Publication number: CN104969123B
Application number: CN201380072402.6A
Authority: CN
Inventors: 金尔润
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2012-12-13
Filing date: 2013-12-12
Publication date: 2019-03-15
Anticipated expiration: 2033-12-12
Also published as: TW201439288A; CN104969123A; KR102222790B1; JPWO2014092170A1; TWI596201B; WO2014092170A1; KR20150094711A

Abstract

The present invention relates to a kind of aligning agent for liquid crystal, it is selected from making tetracarboxylic acid sour component and diamine component carry out at least one of polyimide precursor and polyimides polymer obtained from polymerization reaction, the aligning agent for liquid crystal contains following (A) ingredients and following (B) ingredients, (A) a kind of ingredient: polymer, wherein, tetracarboxylic acid sour component includes to be selected from 3,4- dicarboxyl -1,2,3, at least one of 4- tetrahydro -1- naphthalene succinic dianhydride etc., and diamine component includes the diamines with side chain represented by following formula (1)；(in formula (1), P¹Indicate singly-bound etc., Q¹、Q²、Q³The phenyl ring etc. of divalent is each independently represented, p, q, r each independently represent 0 or 1 integer, P²Indicate hydrogen atom etc..) (B) ingredient: above-mentioned tetracarboxylic acid sour component and diamine component only have-CR by main chain²¹ ₂Base (herein, two R²¹Each independently represent hydrogen atom etc.) diamines constitute polymer.

Description

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

Technical field

The present invention relates to the aligning agent for liquid crystal used when making liquid crystal orientation film, the liquid crystal of the aligning agent for liquid crystal is used Alignment films and liquid crystal display element.

Background technique

Liquid crystal display element is widely used today as display device.The liquid crystal of component parts as liquid crystal display element takes To the film that film is for keeping liquid crystal evenly distributed, the orientation uniformity of liquid crystal is not only needed, it is also necessary to various characteristics.

For example, usually to carry out using cloth to wipe with wiping the friction on the surface of polymeric membrane in the production process of liquid crystal orientation film This orientation process.But the rub resistance of liquid crystal orientation film it is insufficient when, film is ground, scar or dust can be generated, or Film itself is peeling-off, reduces the display quality of liquid crystal display element.In addition, liquid crystal display element to liquid crystal applied voltages and Make its driving.Therefore, if the voltage retention (VHR) of liquid crystal orientation film is low, sufficient voltage, display can not be applied to liquid crystal Contrast reduce.In addition, by the voltage of driving liquid crystal, make charge in liquid crystal orientation film that accumulation occur or accumulated Phenomena such as charge disengaging is when needing the plenty of time, can generate image retention (baked I pays I) of afterimage and display.

As the scheme for meeting several above-mentioned requirements characteristic simultaneously, various schemes are proposed.For example, as antifriction is obtained The method of the excellent and afterimage of wiping property and the few liquid crystal orientation film of image retention, proposes scheme as patent document 1.In addition, As obtaining, liquid crystal aligning, orientation control force, rub resistance are excellent, voltage retention is high and reduces charge accumulation The method of liquid crystal orientation film proposes scheme as patent document 2.

Existing technical literature

Patent document

Patent document 1: International Publication No. WO02/33481 pamphlet

Patent document 2: International Publication No. WO2004/053583 pamphlet

Summary of the invention

Subject to be solved by the invention

In recent years, for being used to show that photo is contour in Mobyneb mobile phone (smart phone) or panel type terminal The liquid crystal display element mounted such as fine image or display animation, it is desirable that have with television set or PC etc. on an equal basis with The display performance of upper high-quality.

However, mobile phone or the display picture of tablet terminal purposes have and frequently switch on display and (or frequently switch on backlight Source) and watch attentively etc. at other with the less feature seen on the way from the moment catspaw of display.It is stored accordingly, for charge Product etc., requirement compared with the past are more stringent.

Problem of the present invention is that solving above-mentioned problem of the prior art, providing one kind can obtain maintaining rub resistance While voltage retention is high and aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal of the very small liquid crystal orientation film of charge accumulation Display element.

Solution for solving the problem

The present inventor is studied repeatedly in order to achieve the above object, is as a result completed using following the description as main points The present invention.

1. a kind of aligning agent for liquid crystal, which is characterized in that it contains following (A) ingredients and following (B) ingredients.

(A) ingredient: a kind of polymer, for selected from carrying out tetracarboxylic acid sour component and diamine component obtained from polymerization reaction Polyimide precursor and by least one of polyimides obtained from polyimide precursor imidizate polymer, it is above-mentioned Tetracarboxylic acid sour component includes to be selected from 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic dianhydride, 3,4- dicarboxyl -1,2,3,4- At least one in tetrahydro -1- naphthalene succinic diester and 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic diester dichloride Kind, and above-mentioned diamine component includes the diamines with side chain represented by following formula (1).

(in formula (1), P¹Indicate singly-bound or divalent organic group, Q¹、Q²、Q³Each independently represent the phenyl ring or hexamethylene of divalent Alkane ring, p, q, r each independently represent 0 or 1 integer, P²Expression hydrogen atom, the alkyl that carbon atom number is 1~22 have The divalent organic group that the carbon atom number of steroid skeleton is 12~25.)

(B) ingredient: a kind of polymer, for selected from carrying out tetracarboxylic acid sour component and diamine component obtained from polymerization reaction Polyimide precursor and by least one of polyimides obtained from polyimide precursor imidizate polymer, it is above-mentioned Tetracarboxylic acid sour component includes to be selected from 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic dianhydride, 3,4- dicarboxyl -1,2,3,4- At least one in tetrahydro -1- naphthalene succinic diester and 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic diester dichloride Kind, and above-mentioned diamine component only has-CR by main chain²¹ ₂Base (herein, two R²¹Each independently represent hydrogen atom or organic Group can pass through two R²¹Be combined and form cyclic structure) diamines constitute.

2. the aligning agent for liquid crystal as described in 1., which is characterized in that in (B) ingredient, above-mentioned diamine component is only by following formula (2) diamines represented by is constituted.

(in formula (2), two X each independently represent oxygen atom or singly-bound, and n indicates 1~10 integer, two R²²Respectively Independently indicate the fluoro-alkyl or fluorine atom that alkyl, carbon atom number that hydrogen atom, carbon atom number are 1~5 are 1~5, Huo Zheke To pass through two R²²It is combined and to form the alkylidene that carbon atom number is 2~7 and form cyclic structure.)

3. the aligning agent for liquid crystal as described in 1. or 2., which is characterized in that in (A) ingredient, there is side represented by formula (1) The diamines of chain is diamines represented by following formula (3).

(in formula (3), P¹Indicate singly-bound or divalent organic group, Q¹、Q²、Q³Each independently represent the phenyl ring or hexamethylene of divalent Alkane ring, p, q, r each independently represent 0 or 1 integer, P²Expression hydrogen atom, the alkyl that carbon atom number is 1~22 have The divalent organic group that the carbon atom number of steroid skeleton is 12~25.)

4. a kind of liquid crystal orientation film, which is characterized in that it is to be coated with aligning agent for liquid crystal described in any one of 1.~3. To obtained from substrate and firing.

5. a kind of liquid crystal display element, which is characterized in that it is with liquid crystal orientation film described in 4..

The effect of invention

Aligning agent for liquid crystal of the invention contains specific (A) ingredient and (B) ingredient, therefore is capable of forming following liquid crystal alignings Film, for the liquid crystal orientation film while maintaining previous required characteristic, i.e. rub resistance, voltage retention is high, and charge Accumulation is very small, can meet current strict requirements.

Specific embodiment

In the following, the present invention will be described in detail.

Aligning agent for liquid crystal of the invention contains above-mentioned (A) ingredient and above-mentioned (B) ingredient.It should be noted that liquid crystal aligning Agent refers to that the solution for making liquid crystal orientation film, liquid crystal orientation film refer to the film for being orientated liquid crystal to specific direction.It closes Each ingredient contained in aligning agent for liquid crystal of the invention, is described in detail below.

<(A) ingredient>

(A) ingredient contained by aligning agent for liquid crystal of the invention is selected from polymerizeing tetracarboxylic acid sour component with diamine component Polyimide precursor obtained from reaction and by least one in polyimides obtained from the polyimide precursor imidizate Kind polymer.As polyimide precursor, polyamic acid (also referred to as polyamic acid), poly amic acid ester etc. can be enumerated.

Also, in (A) ingredient, above-mentioned tetracarboxylic acid sour component includes to be selected from 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene ambers Amber acid dianhydride (being hereinafter also denoted as " TDA "), 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic diester (are hereinafter also remembered For " TDA diester ") and 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic diester dichloride (be hereinafter also denoted as At least one of " TDA diester dichloride ").Therefore, details is as described later, and the polymer of (A) ingredient is with next The polymer of the 4 valence structures represented by the following formula (4) of TDA, TDA diester or TDA diester dichloride.

(A) in ingredient, total amount containing relative to tetracarboxylic acid sour component total amount of TDA, TDA diester and TDA diester dichloride Amount for example, 20~100 moles of %, preferably 40~100 moles of %.

In addition, the diamine component for carrying out polymerization reaction with tetracarboxylic acid sour component includes to have above-mentioned formula (1) institute in (A) ingredient The diamines of the side chain of expression.It should be noted that the main chain of diamines refers to the structure of two amino of connection diamines, in addition, two The side chain of amine refers to the structure that the structure from two amino of connection diamines branches out.Therefore, the polymer of (A) ingredient includes original Expect that diamine component has the diamines of side chain represented by formula (1), therefore, details is as described later, the polymer of (A) ingredient For example, main chain is with phenyl ring and with the-P in conjunction with the phenyl ring¹-(Q¹)_p-(Q²)_q-(Q³)_r-P²Structure as side chain.

In the side chain represented by formula (1), it is desirable that the TN of 3~5 ° of relatively low pre-tilt angle (Twisted Nematic, Twisted nematic) it mode and requires 8~20 ° of the OCB of pre-dumping (Optically Compensated Bend, optical compensation is curved It is bent) in mode etc., relatively low the side chain (- P of preferred angled expressive ability¹-(Q¹)_p-(Q²)_q-(Q³)_r-P²)。

As the smaller structure of inclination expressive ability, in formula (1), P¹It is preferred that-O- ,-NHCO- or-CONH-, p preferably 0 ~1, q preferably 0~1, r preferably 0, in the case where p and/or q is 1, P²It is preferred that the straight chained alkyl that carbon atom number is 1~12, In the case where p=q=r=0, P²It is preferably selected from the straight chained alkyl that carbon atom number is 10~22 or the carbon original with steroid skeleton The divalent organic group in organic group that subnumber is 12~25.The specific structure for tilting the small side chain of expressive ability is illustrated in Table 1, but not limited thereto.It should be noted that in this specification, organic group for example refer to-O- ,-NHCO- ,-CONH- ,- COO- or the alkyl that can have N or O.

[table 1]

From electrology characteristic aspect, preferably there is the diamines of chain alkyl side chain as [1-1] of table 1, from liquid Brilliant orientation, pre-dumping stability in terms of set out, preferably with table 1 [1-9] represented by side chain diamines.

On the other hand, VA (Vertical Alignment, longitudinal arrangement) mode etc. can be by sharing inclination performance energy The big side chain of power and obtain vertical orientation.As the preferred structure of the formula (1) in VA mode, in formula, P¹It is preferred that-O- ,- COO- or-CH₂O-, p preferably 0~1, q preferably 0~1, r preferably 0~1, P²It is preferred that 2~22.The p=q=r=0 the case where Under, P²Preferably as carbon atom number be 18~22 straight chained alkyl or carbon atom number with steroid skeleton be 12~25 Organic group divalent organic group.The specific structure for tilting the big side chain of expressive ability is shown in table 2-1 and table 2-2.

[table 2-1]

[table 2-2]

The inclination expressive ability of these side chains is high, preferred the case where being used for VA mode.In particular, have [1-15], The inclination expressive ability of the diamines of the side chain of [1-31] etc. is high, can show vertical orientation with fewer amount of side chains, thus It is preferred that the inclination expressive ability of the diamines of the especially side chain with [1-18] or [1-34] is high, it can be with considerably less side Chain measures vertical orientation, therefore is preferred from the aspect of the printing of aligning agent for liquid crystal.

On the other hand, in the diamines with side chain represented by formula (1), P¹It is preferred that-NHCO-, P²It is preferred that carbon atom number is 1~16, preferably 3~10 alkyl.In addition, Q¹、Q²、Q³Combination appropriate is selected from p, q, r.In addition, being main chain tool in the diamines There is phenyl ring and there is the-P in conjunction with the phenyl ring¹-(Q¹)_P-(Q²)_q-(Q³)_r-P²In the case where structure as side chain, to benzene The position of each substituent group on ring is not particularly limited, the preferred meta or para position of the positional relationship of two amino.

As the example of the diamines with side chain represented by above-mentioned formula (1), for example, following [DA-1]~ [DA-26]。

(in formula [DA-1]~formula [DA-5], R₆It is the alkyl or contain fluoroalkyl that carbon atom number is 1~22.)

(in formula [DA-6]~formula [DA-9], S₅Can be the same or different respectively, expression-COO- ,-OCO- ,- CONH-、-NHCO-、-CH₂,-O- ,-CO- or-NH-, R₆Indicate the alkyl or contain fluoroalkyl that carbon atom number is 1~22.)

(in formula [DA-10] and formula [DA-11], S₆Expression-O- ,-OCH₂-、-CH₂O-、-COOCH₂Or-CH₂OCO-, R₇ It is alkyl, alkoxy that carbon atom number is 1~22, containing fluoroalkyl or fluoroalkoxy.)

(in formula [DA-12]~formula [DA-14], S₇Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、- CH₂OCO-、-CH₂O-、-OCH₂Or-CH₂, R₈It is alkyl, alkoxy that carbon atom number is 1~22, containing fluoroalkyl or containing fluothane Oxygroup.)

(in formula [DA-15] and formula [DA-16], S₈Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、- CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂,-O- or-NH-, R₉It is fluorine-based, cyano, fluoroform alkyl, nitro, azo group, first Acyl group, acetyl group, acetoxyl group or hydroxyl.)

(in formula [DA-17]~formula [DA-20], R₁₀Be carbon atom number be 3~12 alkyl, 1 or 4 cyclohexylidene it is cis- Anti- isomerism is respectively trans- body.)

Content relative to diamine component total amount, the diamines with side chain represented by above-mentioned formula (1) is preferably 5~50 Mole %, from the uniformity of pre-dumping and printing aspect, particularly preferably 5~30 moles of %.

It should be noted that in (A) ingredient, as the diamines with side chain represented by formula (1), from acquired etc. Consider, diamines, i.e. main chain represented by above-mentioned formula (3) is with phenyl ring and with the-P in conjunction with the phenyl ring¹-(Q¹)_p-(Q²)_q- (Q³)_r-P²The diamines of structure as side chain is preferred.

In diamines represented by formula (3), the position of each substituent group on phenyl ring is not particularly limited, the position of two amino Set the preferred meta or para position of relationship.

The tetracarboxylic acid sour component of raw material as (A) ingredient may include above-mentioned TDA, TDA diester or TDA diester dichloride Other tetracarboxylic acid derivatives in addition.As other tetracarboxylic acid derivatives in such (A) ingredient, for example, below Tetracarboxylic dianhydride.

As the tetracarboxylic dianhydride with ester ring type structure or aliphatic structure, 1,2,3,4- cyclobutane tetracarboxylic acids can be enumerated Acid dianhydride, 1,2- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,3- dimethyl -1,2,3,4- cyclobutane tetrabasic carboxylic acid two Acid anhydride, 1,2,3,4- tetramethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 2,3,4,5- Tetrahydrofuran tetracarboxylic dianhydride, 1,2,4,5- cyclopentanetetracarboxylic dianhydride, 3,4- dicarboxyl -1- cyclohexyl amber acid dianhydride, 1, 2,3,4- butane tetracarboxylic acid dianhydride, bicyclic [3.3.0] octane -2,4,6,8- tetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyls four Carboxylic acid dianhydride, 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride, cis- -3,7- dibutyl ring octyl- 1,5- diene -1,2,5,6- four Carboxylic acid dianhydride, tricyclic [4.2.1.0^2,5] nonane -3,4,7,8- tetrabasic carboxylic acid -3,4:7,8- dianhydride, six ring [6.6.0.1^2,7.0^3, ⁶.1^9,14.0^10,13] hexadecane -4,5,11,12- tetrabasic carboxylic acid -4,5:11,12- dianhydride etc..

As aromatic tetracarboxylic dianhydride, pyromellitic acid dianhydride, 3 can be enumerated, 3 ', 4,4 '-biphenyltetracarboxylic dianhydrides, 2,2 ', 3,3 '-biphenyltetracarboxylic dianhydrides, 2,3,3 ', 4 '-biphenyltetracarboxylic dianhydrides, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acids two Acid anhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydrides, bis- (3,4- dicarboxyphenyi) ether dianhydrides, bis- (3,4- dicarboxyphenyis) Sulfone dianhydride, 1,2,5,6- naphthalene tetracarboxylic acid dianhydride, 2,3,6,7- naphthalene tetracarboxylic acid dianhydride etc..

It is above-mentioned according to characteristics such as the liquid crystal alignings, voltage retention performance, accumulated charge for being formed by liquid crystal orientation film Tetracarboxylic dianhydride can be used one kind or share two or more.

In addition, other tetracarboxylic acid derivatives that raw material, that is, tetracarboxylic acid sour component as (A) ingredient can contain, can enumerate Tetracarboxylic acid acid dialkyl ester, tetrabasic carboxylic acid dialkyl diester dichloride.It should be noted that tetracarboxylic acid sour component contains such tetracarboxylic acid When acid dialkyl ester, tetracarboxylic acid acid dialkyl ester dichloride, polymer becomes the poly amic acid ester as polyimide precursor.It is right The tetracarboxylic acid acid dialkyl ester being able to use is not particularly limited, for example, aliphatic tetracarboxylic acid acid diesters, aromatic series tetracarboxylic acid Acid dialkyl ester etc..Its concrete example is enumerated below.

As the concrete example of aliphatic tetracarboxylic acid acid diesters, 1,2,3,4- cyclobutane tetracarboxylic acid acid dialkyl esters, 1 can be enumerated, 2- dimethyl -1,2,3,4- cyclobutane tetracarboxylic acid acid dialkyl ester, 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic acid acid dialkyl Ester, 1,2,3,4- tetramethyl -1,2,3,4- cyclobutane tetracarboxylic acid acid dialkyl ester, 1,2,3,4- pentamethylene tetracarboxylic acid acid dialkyl ester, 2,3,4,5- tetrahydrofuran tetracarboxylic acid acid dialkyl ester, 1,2,4,5- cyclopentanetetracarboxylic dialkyl ester, 3,4- dicarboxyl -1- hexamethylene Base dialkyl succinate, 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic dialkyl ester, 1,2,3,4- butane tetracarboxylic Acid dialkyl ester, bicyclic [3.3.0] octane -2,4,6,8- tetracarboxylic acid acid dialkyl ester, 3,3 ', 4,4 '-dicyclohexyl tetrabasic carboxylic acids two Arrcostab, 2,3,5- tricarboxylic cyclopentyl dialkyl acetates, cis- -3,7- dibutyl ring octyl- 1,5- diene -1,2,5,6- four Carboxylic acid dialkyl esters, tricyclic [4.2.1.0^2,5] nonane -3,4,7,8- tetrabasic carboxylic acid -3,4:7,8- dialkyl ester, six rings [6.6.0.1^2,7.0^3,6.1^9,14.0^10,13] hexadecane -4,5,11,12- tetrabasic carboxylic acid -4,5:11,12- dialkyl ester etc..

As aromatic tetracarboxylic acid's dialkyl ester, pyromellitic acid dialkyl ester, 3,3 ', 4,4 '-biphenyl tetracarboxylic acids can be enumerated Acid dialkyl ester, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid dialkyl esters, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid dialkyl esters, 3,3 ', 4, 4 '-benzophenone tetracarboxylic acid acid dialkyl esters, 2,3,3 ', 4 '-benzophenone tetracarboxylic acid acid dialkyl esters, bis- (3,4- dicarboxyl benzene Base) ether dialkyl ester, bis- (3,4- dicarboxyphenyi) sulfone dialkyl esters, 1,2,5,6- naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7- Naphthalene tetracarboxylic acid dialkyl ester etc..

In addition, other tetracarboxylic acid derivatives that raw material, that is, tetracarboxylic acid sour component as (A) ingredient can contain, tetrabasic carboxylic acid two Alkyl diester dichloride can enumerate the dichloride of above-mentioned tetracarboxylic acid acid diesters.

(A) in ingredient, the total amount phase of other tetracarboxylic acid derivatives other than TDA, TDA diester and TDA diester dichloride Content for tetracarboxylic acid sour component total amount is preferably 0~80 mole of %, more preferably 0~40 mole of %.

In addition, the diamine component of the raw material as (A) ingredient also may include with side chain represented by above-mentioned formula (1) Other diamines other than diamines.As other diamines in such (A) ingredient, for example, ester ring type below two Amine, aromatic diamine, hetero ring type diamines, aliphatic diamine or the diamines containing urea bond.

As the example of ester ring type diamines, Isosorbide-5-Nitrae-diaminocyclohexane, 1,3- diaminocyclohexane, 4 can be enumerated, 4 '- Diamino-dicyclohexyl methane, 4,4 '-diamino -3,3 '-dimethyl dicyclohexyl amine, isophorone diamine etc..

As the example of aromatic diamine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 2,4- diamino first can be enumerated Benzene, 2,5- diaminotoluene, 3,5- diaminotoluene, 1,4- diamino -2- methoxybenzene, 2,5- diamino-paraxylene, 1, 3- diamino -4- chlorobenzene, 3,5- diaminobenzoic acid, 1,4- diamino -2,5- dichloro-benzenes, 4,4 '-diaminostilbenes, 2- hexichol Base ethane, 4,4 '-diamino -2,2 '-dimethyl bibenzyl, 4,4 '-diaminodiphenyl-methanes, 3,3 '-diamino-diphenyl first Alkane, 3,4 '-diaminodiphenyl-methanes, 4,4 '-diamino -3,3 '-dimethyl diphenylmethane, 2,2 '-diamino-stilbene, 4, 4 '-diamino-stilbene, 4,4 '-diamino-diphenyl ethers, 3,4 '-diamino-diphenyl ethers, 4,4 '-diaminodiphenyl sulfides, 4, 4 '-diaminodiphenylsulfones, 3,3 '-diaminodiphenylsulfones, 4,4 '-diaminobenzophenones, 1,3- bis- (3- amino-benzene oxygens) Bis- (4- amino-benzene oxygen) benzene of benzene, 1,3-, bis- (4- amino-benzene oxygen) benzene of 1,4-, bis- (4- amino-benzene oxygen) benzoic acid of 3,5-, Bis- [(4- amino-benzene oxygen) methyl] propane of 4,4 '-bis- (4- amino-benzene oxygen) bibenzyls, 2,2-, bis- [4- (the 4- aminobenzene oxygen of 2,2- Base) phenyl] hexafluoropropane, bis- [4- (4- amino-benzene oxygen) phenyl] propane of 2,2-, bis- [4- (3- amino-benzene oxygen) phenyl] Sulfone, bis- [4- (4- amino-benzene oxygen) phenyl] sulfones, 1,1- bis- (4- aminophenyl) hexamethylenes, α, α '-bis- (4- aminophenyls)- Bis- (4- aminophenyl) fluorenes of 1,4- diisopropyl benzene, 9,9-, bis- (3- aminophenyl) hexafluoropropane of 2,2-, bis- (the 4- amino of 2,2- Phenyl) hexafluoropropane, 4,4 '-diamino-diphenyl amine, 2,4- diamino-diphenyl amine, 1,8- diaminonaphthalene, 1,5- diamino Naphthalene, 1,5- diamino-anthraquinone, 1,3- diamino pyrene, 1,6- diamino pyrene, 1,8- diamino pyrene, 2,7 diamin of luorene, 1,3- are bis- Bis- (4- aminophenyl) ethane of (4- aminophenyl) tetramethyl disiloxane, benzidine, 2,2 '-dimethylbenzidines, 1,2-, Bis- (4- aminophenyl) propane of 1,3-, bis- (4- aminophenyl) butane of 1,4-, bis- (4- aminophenyl) pentanes of 1,5-, 1,6- are bis- Bis- (4- aminophenyl) heptane of (4- aminophenyl) hexane, 1,7-, bis- (4- aminophenyl) octanes of 1,8-, bis- (the 4- amino of 1,9- Phenyl) nonane, bis- (4- aminophenyl) decane of 1,10-, bis- (4- amino-benzene oxygen) propane of 1,3-, bis- (the 4- aminobenzene oxygen of 1,4- Base) butane, bis- (4- amino-benzene oxygen) pentanes of 1,5-, bis- (4- amino-benzene oxygen) hexanes of 1,6-, bis- (the 4- aminobenzene oxygen of 1,7- Base) heptane, bis- (4- amino-benzene oxygen) octanes of 1,8-, bis- (4- amino-benzene oxygen) nonanes of 1,9-, bis- (the 4- aminobenzene oxygen of 1,10- Base) decane, two (4- aminophenyl) -1,3- malonates, two (4- aminophenyl) -1,4- succinates, two (4- aminobenzenes Base) -1,5- glutarate, two (4- aminophenyl) -1,6- adipate esters, two (4- aminophenyl) -1,7- pimelates, two (4- aminophenyl) -1,8- suberate, two (4- aminophenyl) -1,9- azelates, two (4- the aminophenyl) -1,10- last of the ten Heavenly stems Bis- [4- (4- amino-benzene oxygen) phenoxy group] propane of two acid esters, 1,3-, bis- [4- (4- amino-benzene oxygen) phenoxy group] butane of 1,4-, Bis- [4- (4- amino-benzene oxygen) phenoxy group] pentanes of 1,5-, bis- [4- (4- amino-benzene oxygen) phenoxy group] hexanes of 1,6-, 1,7- are bis- [4- (4- amino-benzene oxygen) phenoxy group] heptane, 1,8- bis- [4- (4- amino-benzene oxygen) phenoxy group] octanes, the bis- [4- (4- of 1,9- Amino-benzene oxygen) phenoxy group] nonane, bis- [4- (4- amino-benzene oxygen) phenoxy group] decane of 1,10- etc..

As the example of aromatic-aliphatic diamines, diamines represented by following formula [DAM] etc. can be enumerated.

(in formula [DAM], Ar indicates phenyl ring or naphthalene nucleus, R₁It is the alkylidene that carbon atom number is 1~5, R₂It is hydrogen atom or first Base.

As the concrete example of aromatic-aliphatic diamines, 3- aminobenzyl amine, 4- aminobenzyl amine, 3- ammonia can be enumerated Base-N- methylbenzyl amine, 4- Amino-N-methyl benzyl amine, 3- amino phenyl ethylamine, 4- amino phenyl ethylamine, 3- amino-N- methyl Phenyl ethylamine, 4- Amino-N-methyl phenyl ethylamine, 3- (3- aminopropyl) aniline, 4- (3- aminopropyl) aniline, 3- (3- methyl ammonia Base propyl) aniline, 4- (3- dimethylaminopropyl) aniline, 3- (4- aminobutyl) aniline, 4- (4- aminobutyl) aniline, 3- (4- methylamino butyl) aniline, 4- (4- methylamino butyl) aniline, 3- (5- Aminopentyl) aniline, 4- (5- amino penta Base) aniline, 3- (5- methylamino-pentyl) aniline, 4- (5- methylamino-pentyl) aniline, 2- (6- amino naphthalene) methylamine, 3- (6- amino naphthalene) methylamine, 2- (6- amino naphthalene) ethamine, 3- (6- amino naphthalene) ethamine etc..

As the example of hetero ring type diamines, 2,6-diaminopyridine, 2,4- diamino-pyridine, 2,4- diamino can be enumerated - 1,3,5- triazine, 2,7 diaminodibenz of uran, 3,6- diaminocarbazole, 2,4- diamino -6- isopropyl -1,3,5- three Bis- (4- aminophenyl) -1,3,4- oxadiazoles of piperazine, 2,5- etc..

As the example of aliphatic diamine, 1,2-Diaminoethane, 1,3- diaminopropanes, Isosorbide-5-Nitrae-diamino can be enumerated Butane, 1,5- 1,5-DAP, 1,6- diamino hexane, 1,7- diaminoheptane, 1,8- diamino-octane, 1,9- diamino nonyl Alkane, 1,10- diamino decane, 1,3- diamino -2,2- dimethylpropane, 1,6- diamino -2,5- dimethylhexane, 1,7- Diamino -2,5- dimethyl heptane, 1,7- diamino -4,4- dimethyl heptane, 1,7- diamino -3- methyl heptane, 1,9- bis- Bis- (the 3- amino propoxyl group) ethane of amino -5- methylnonane, 1,12- diamino dodecane, 1,18- diamino octadecane, 1,2- Deng.

As the example of the diamines containing urea bond, N, bis- (4- aminophenethyl) ureas of N '-etc. can be enumerated.

In addition, the diamine component in (A) ingredient can also contain diamines below.

In formula [DA-31], the integer that m is 0~3, in formula [DA-34], integer that n is 1~5.By importing [DA-27], [DA-28] can be further improved the liquid crystal display element using the liquid crystal orientation film formed by aligning agent for liquid crystal of the invention Voltage retention (also referred to as VHR).Also, [DA-29]~[DA-34] reduces the accumulated charge of this liquid crystal display element More effective fruit, is therefore preferred.

In addition, diamino represented by following formulas [DA-35] can also be enumerated as the diamine component in (A) ingredient Siloxanes etc..

(in formula [DA-35], m be 1~10 integer.)

According to the characteristics such as liquid crystal aligning, voltage retention performance, accumulated charge when being made liquid crystal orientation film, these (A) One kind can be used respectively or share two or more for diamine component in ingredient.Mixed ratio at this time is not limited.

In addition, if considering workability when obtained liquid crystal aligning film strength and liquid crystal orientation film formation, liquid crystal The uniformity of alignment films, the molecular weight of the polymer (polyimide precursor, polyimides) of (A) ingredient is preferably to utilize GPC The weight average molecular weight of (gel permeation chromatography) method measurement is calculated as 5,000~1,000,000, more preferably 10,000~150, 000。

It should be noted that the polymer of (A) ingredient is preferably polyimides.This is because: for (A) ingredient, system At having the tendency for being present in liquid crystal aligning film surface (i.e. the side opposite with substrate) when liquid crystal orientation film, it is present in liquid crystal and takes It is contacted to the polymer on the surface of film with liquid crystal, directly contributes to the value of VHR, therefore there is the acyl that reversible reaction does not occur largely Imido grpup is preferable.In addition, the acid imide rate of the polyimides is preferably 60~90%.

<(B) ingredient>

(B) ingredient contained by aligning agent for liquid crystal of the invention is selected from polymerizeing tetracarboxylic acid sour component with diamine component Polyimide precursor obtained from reaction and by least one in polyimides obtained from the polyimide precursor imidizate Kind polymer.As polyimide precursor, polyamic acid (also referred to as polyamic acid), poly amic acid ester etc. can be enumerated.

And, in (B) ingredient, above-mentioned tetracarboxylic acid sour component include 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinics Dianhydride, 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic diester and 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene amber At least one of amber acid diesters dichloride.Therefore, details is as described later, and the polymer of (B) ingredient is also with next The polymer of the 4 valence structures represented by the above-mentioned formula (4) of TDA, TDA diester or TDA diester dichloride.

(B) in ingredient, total amount containing relative to tetracarboxylic acid sour component total amount of TDA, TDA diester and TDA diester dichloride Amount is 20~100 moles of %, preferably 40~100 moles of %.

In addition, the diamine component for carrying out polymerization reaction with tetracarboxylic acid sour component only has-CR by main chain in (B) ingredient²¹ ₂- Base (herein, two R²¹Hydrogen atom or organic group are each independently represented, two R can be passed through²¹It is combined and forms ring Shape structure) diamines (be hereinafter also denoted as " and main chain have-CR²¹ ₂The diamines of base ") it constitutes.As long as main chain has-CR²¹ ₂- The diamines of base can be one kind, can also share two or more.For the polymer of (B) ingredient, due to the diamines of raw material Ingredient is only that main chain has-CR²¹ ₂The diamines of base, therefore, details is as described later, and the polymer of (B) ingredient is main chain tool There is-CR²¹ ₂Structure.It should be noted that the main chain of diamines refers to the structure of two amino of connection diamines.In addition, conduct Above-mentioned-CR²¹ ₂The R of base²¹Organic group, the fluoro that alkyl, carbon atom number that carbon atom number is 1~5 are 1~5 can be enumerated Alkyl, fluorine atom etc..In addition, passing through two R²¹It is combined, such as forms the alkylidene that carbon atom number is 2~7, so as to Form cyclic structure.

There is-CR as such main chain²¹ ₂The diamines of base, can enumerate following ester ring type diamines, aromatic diamine, Aromatic-aliphatic diamines, aliphatic diamine, diamines containing urea bond etc..

As the example of aromatic diamine, 4,4 '-diaminostilbenes, 2- diphenylethane, 4,4 '-diamino-can be enumerated 2,2 '-dimethyl bibenzyls, 4,4 '-diaminodiphenyl-methanes, 3,3 '-diaminodiphenyl-methanes, 3,4 '-diamino hexichol Methylmethane, 4,4 '-diamino -3,3 '-dimethyl diphenylmethane, 2,2- bis- [(4- amino-benzene oxygen) methyl] propane, 2,2- Bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] propane, the bis- (4- of 1,1- Aminophenyl) hexamethylene, α, bis- (4- the aminophenyl) -1,4- diisopropyl benzenes of α ' -, bis- (3- aminophenyl) hexafluoros third of 2,2- Bis- (4- aminophenyl) hexafluoropropane of alkane, 2,2-, bis- (4- aminophenyl) ethane of 1,2-, bis- (4- aminophenyl) propane of 1,3-, Bis- (4- aminophenyl) butane of 1,4-, bis- (4- aminophenyl) pentanes of 1,5-, bis- (4- aminophenyl) hexanes of 1,6-, 1,7- are bis- Bis- (4- aminophenyl) octanes of (4- aminophenyl) heptane, 1,8-, bis- (4- aminophenyl) nonanes of 1,9-, bis- (the 4- ammonia of 1,10- Base phenyl) decane, bis- (4- amino-benzene oxygen) propane of 1,3-, bis- (4- amino-benzene oxygen) butane of 1,4-, bis- (the 4- amino of 1,5- Phenoxy group) pentane, bis- (4- amino-benzene oxygen) hexanes of 1,6-, bis- (4- amino-benzene oxygen) heptane of 1,7-, bis- (the 4- amino of 1,8- Phenoxy group) octane, bis- (4- amino-benzene oxygen) nonanes of 1,9-, bis- (4- amino-benzene oxygen) decane of 1,10-, two (4- aminobenzenes Base) -1,3- malonate, two (4- aminophenyl) -1,4- succinates, two (4- aminophenyl) -1,5- glutarates, two (4- aminophenyl) -1,6- adipate ester, two (4- aminophenyl) -1,7- pimelates, two (4- aminophenyl) -1,8- pungent two Acid esters, two (4- aminophenyl) -1,9- azelates, two (4- aminophenyl) -1,10- sebacates, bis- [4- (the 4- ammonia of 1,3- Phenoxyl) phenoxy group] propane, bis- [4- (4- amino-benzene oxygen) phenoxy group] butane of 1,4-, bis- [4- (the 4- aminobenzene oxygen of 1,5- Base) phenoxy group] pentane, bis- [4- (4- amino-benzene oxygen) phenoxy group] hexanes of 1,6-, bis- [4- (4- amino-benzene oxygen) benzene of 1,7- Oxygroup] heptane, bis- [4- (4- amino-benzene oxygen) phenoxy group] octanes of 1,8-, 1,9- bis- [4- (4- amino-benzene oxygen) phenoxy groups] Bis- [4- (4- amino-benzene oxygen) phenoxy group] decane of nonane, 1,10- etc..

(in formula [DAM], Ar indicates phenyl ring or naphthalene nucleus, R₁It is the alkylidene that carbon atom number is 1~5, R₂It is hydrogen atom or first Base.)

It should be noted that there is-CR as the main chain in (B) ingredient²¹ ₂The diamines of base is examined from acquired etc. Consider, diamines represented by preferably above-mentioned formula (2).As such diamines, for example, work can be enumerated in the record of (B) ingredient The diamines etc. exemplified for aromatic diamine.

In this way, by making main chain that there is-CR²¹ ₂The diamines of base with contain TDA, TDA diester or TDA diester dichloride Polyimide precursor or polyimides and above-mentioned (A) obtained from the tetracarboxylic acid sour component polymerization of (being hereinafter also denoted as " TDA etc. ") Ingredient contains in aligning agent for liquid crystal together, thus it is speculated that the very high liquid crystal orientation film of resistance can be obtained.Also, very to the resistance For high liquid crystal orientation film, with resistance compared with low aligning agent for liquid crystal, electric current is difficult to flow when applying voltage, correspondingly, liquid Brilliant alignment films itself are difficult to accumulate voltage, therefore speculate in the present invention and obtained the very small liquid crystal orientation film of charge accumulation.It needs It is noted that accumulated charge will not occur and be detached from the cost time, generate since accumulated charge itself is very small Afterimage and this existing problem of the image retention of display.

The tetracarboxylic acid sour component of raw material as (B) ingredient also may include above-mentioned TDA, TDA diester or TDA diester dichloride Other tetracarboxylic acid derivatives other than object.As other tetracarboxylic acid derivatives in such (B) ingredient, can enumerate above-mentioned (A) other tetracarboxylic acid derivatives in ingredient.

(B) in ingredient, the total amount phase of other tetracarboxylic acid derivatives other than TDA, TDA diester and TDA diester dichloride Content for tetracarboxylic acid sour component total amount is preferably 0~80 mole of %, more preferably 0~60 mole of %.

(B) the tetracarboxylic acid sour component in ingredient can be identical as the tetracarboxylic acid sour component in (A) ingredient, can also be different.

In addition, if considering, workability when obtained liquid crystal aligning film strength and liquid crystal orientation film formation, liquid crystal are taken To the uniformity of film, then the molecular weight of the polymer (polyimide precursor, polyimides) of (A) ingredient is preferably to utilize GPC The weight average molecular weight of (gel permeation chromatography) method measurement is calculated as 5,000~1,000,000, more preferably 10,000~150, 000。

It should be noted that the polymer of (B) ingredient is preferably polyimide precursor.The reason is that: (B) ingredient is come It says, it is (i.e. opposite with liquid crystal aligning film surface with the substrate-side for being present in coating of liquid crystalline alignment agent when liquid crystal orientation film is made Side) tendency, there are a large amount of polar groups by the polymer of (B) ingredient being in contact with substrate, the adaptation with substrate Improve, printing becomes excellent.

To contained by aligning agent for liquid crystal of the invention (A) ingredient and the ratio of (B) ingredient be not particularly limited, for example, (A) ingredient by quality ratio: ingredient=5~50:95~50 (B), preferably by quality ratio (A) ingredient: ingredient=5 (B)~ 30:95~70.

In this way, aligning agent for liquid crystal of the invention is due to containing specific (A) ingredient and specific (B) ingredient, wherein specific (A) ingredient be to make the tetracarboxylic acid sour component comprising TDA etc. and the diamines comprising the diamines with side chain represented by above-mentioned formula (1) Polymer obtained from ingredient reaction, specific (B) ingredient be make the tetracarboxylic acid sour component comprising TDA etc. and only had by main chain- CR²¹ ₂Polymer obtained from the diamine component reaction that the diamines of base is constituted therefore, being capable of shape shown in embodiment as be described hereinafter While at characteristic, that is, rub resistance required for remaining previous, voltage retention is high and charge accumulation is very small, can expire The liquid crystal orientation film of the current strict requirements of foot.And hence it is also possible to frequently switch on display suitable for having and (or frequently switch on back Light source) and watch attentively etc. at other with the mobile phone of the less feature seen on the way or flat from the moment catspaw of display The display picture purposes of board terminal purposes.

This effect of the invention is by the way that the liquid crystal aligning containing specific (A) ingredient and specific (B) ingredient is made Agent is just able to the effect played, and specific (A) ingredient is to make the tetracarboxylic acid sour component comprising TDA etc. and comprising with above-mentioned formula (1) Polymer obtained from the diamine component reaction of the diamines of represented side chain, specific (B) ingredient make comprising TDA etc. Tetracarboxylic acid sour component with only by main chain have-CR²¹ ₂Polymer obtained from the diamine component reaction that the diamines of base is constituted.For example, If RDC is big, i.e., charge accumulation is big, and then rub resistance is also bad, Wu Fafa using being the polymer of raw material not with TDA etc. Wave the effect of aligning agent for liquid crystal of the invention.In addition, about (B) ingredient, if using being the polymer of raw material not with TDA etc., RDC is also big.In addition, even if with TDA etc. be raw material in the case where, if using main chain do not have-CR²¹ ₂Diamines as raw material Diamine component, then RDC is big.

It should be noted that being obtained by the tetracarboxylic acid sour component of respective raw material and the polymerization reaction of diamine component above-mentioned (A) when the polymer of the polymer of ingredient, (B) ingredient, well known synthetic method can be used.In general, to make tetrabasic carboxylic acid The method that ingredient and diamine component react in organic solvent.Tetracarboxylic acid sour component is easier with reacting for diamine component organic It is carried out in solvent, and does not generate by-product, be advantageous from this respect.

As the organic solvent reacted for tetracarboxylic acid sour component and diamine component, as long as polyamic acid generated dissolves Just it is not particularly limited.Its concrete example is enumerated below.

N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- ethyl-can be enumerated 2-Pyrrolidone, N- methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, gamma-butyrolacton, isopropanol, Methoxy amylalcohol, cinene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Base ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl Carbitol, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol list acetic acid Ester, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethyl two Diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol list acetic acid Ester list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, acetic acid -3- methyl -3- methoxybutyl, 3 third Glycol methyl ether, 3- methyl -3- methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, Butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, dioxane, n-hexane, pentane, normal octane, diethyl ether, Cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, Propyleneglycolmethyletheracetate list ether, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-propionic acid Methylethyl, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, Diethylene glycol dimethyl ether, 4- hydroxy-4-methyl-2-pentanone, 3- methoxyl group-N, N- dimethylpropane amide, 3- ethyoxyl-N, N- dimethylpropane amide, 3- butoxy-N, N- dimethylpropionamide etc..They can be used alone, and can also be used in mixed way. In addition, the solvent of even insoluble polyamic acid, can also be mixed in the range of polyamic acid generated is not precipitated to It is used in above-mentioned solvent.

In addition, the moisture in organic solvent can hinder polymerization reaction, and then cause to hydrolyze polyamic acid generated, because This organic solvent preferably uses the organic solvent through dehydrating as far as possible.

When reacting tetracarboxylic acid sour component and diamine component in organic solvent, can enumerate following methods: stirring makes diamines Solution obtained from ingredient is dispersed or dissolved in organic solvent, directly add tetracarboxylic acid sour component or tetracarboxylic acid sour component is dispersed or The method for being dissolved in organic solvent and being added；Tetracarboxylic acid sour component is dispersed or dissolved in organic solvent in turn, to The method of diamine component is added in obtained solution；Alternately add the method for tetracarboxylic acid sour component and diamine component；Etc., it can be with Use any method in these.In addition, the feelings being made of in tetracarboxylic acid sour component or diamine component two or more compounds It under condition, can be reacted, can also be successively reacted respectively with the state being pre-mixed, and then make low point reacted respectively Son amount body carries out hybrid reaction and forms high molecular weight body.

Polymerization temperature at this time can choose -20 DEG C~150 DEG C of arbitrary temp, preferably -5 DEG C~100 DEG C of range. In addition, reaction can be carried out with arbitrary concentration, if concentration is too low, it is difficult to obtain the polymer of high molecular weight, if concentration mistake Height, then the viscosity of reaction solution becomes excessively high, it is difficult to equably stirs, therefore, the reaction solution of tetracarboxylic acid sour component and diamine component In total concentration be preferably 1~50 mass %, more preferably 5~30 mass %.It can be carried out in initial reaction stage with high concentration, Organic solvent is added later.

In the polymerization reaction of polyamic acid, the ratio between total molal quantity and total molal quantity of diamine component of tetracarboxylic acid sour component Preferably 0.8~1.2.Same as common polycondensation reaction, ground, the molar ratio is closer to 1.0, then point of the polyamic acid generated Son amount is bigger.

Polyimides is obtained from making the polyimide precursors dehydration closed-loops such as above-mentioned polyamic acid or poly amic acid ester. In polyimides, the dehydration closed-loop rate (acid imide rate) of amide acidic group is not centainly to need to be 100%, can 0%~ 100% range is arbitrarily adjusted with purpose depending on the application.

It as the method for making polyimide precursor imidizate, can enumerate: by the molten of polyamic acid or poly amic acid ester The direct-fired hot-imide of liquid, the catalysis acid imide that catalyst is added into the solution of polyamic acid or poly amic acid ester Change.

Make polyamic acid or poly amic acid ester in the solution hot-imide when 100 DEG C~400 DEG C of temperature, preferably It 120 DEG C~250 DEG C, is preferably carried out while the water that will be generated by imidization reaction is in addition to going to system.

To adding basic catalyst and acid anhydrides in the solution of polyamic acid or poly amic acid ester, -20~250 DEG C, preferably 0~180 DEG C is stirred, so as to carry out the catalysis imidizate of polyamic acid or poly amic acid ester.Basic catalyst Amount is 0.5~30 mole times, preferably 2~20 moles times of amide acidic group, and the amount of acid anhydrides is 1~50 mole of amide acidic group Again, preferably 3~30 moles times.As basic catalyst, pyridine, triethylamine, trimethylamine, tri-n-butylamine, trioctylamine can be enumerated Deng, wherein pyridine has the alkalinity of appropriateness for carrying out reaction, thus preferably.As acid anhydrides, can enumerate acetic anhydride, Trimellitic anhydride or pyromellitic acid dianhydride etc., wherein if the purifying after reaction terminating is easy, thus preferred using acetic anhydride. It can be controlled by adjusting catalytic amount with reaction temperature, reaction time based on the acid imide rate of catalysis imidizate.

It should be noted that the method as synthesizing polyamides acid esters, can enumerate: making above-mentioned tetracarboxylic acid acid diesters and sulfurous Tetracarboxylic acid acid diesters dichloride and diamine component obtained from the reaction of the halogenating agents such as acyl chlorides, chlorosulfuric acid, oxalyl chloride, phosphorus oxychloride Reaction；The method for reacting tetracarboxylic acid acid diesters and diamine component in the presence of condensing agent appropriate, alkali.Alternatively, in advance Polymeric polyamide acid, using high molecular weight reactive by the carboxylic esterification in amic acid, thus also available.

Specifically, making tetracarboxylic acid acid diesters dichloride and diamines in the presence of alkali and organic solvent -20 DEG C~150 DEG C, preferably 0 DEG C~50 DEG C react 30 minutes~24 hours, preferably 1~4 hour, so as to synthesize.

Pyridine, triethylamine, 4-dimethylaminopyridine can be used in above-mentioned alkali, in order to carry out stable reaction, preferred pyridine. About the additive amount of alkali, from the aspect of to be easy the amount removed and being easy to get high molecular weight body, relative to tetrabasic carboxylic acid two Ester dichloride is preferably 2~4 times moles.

In the case where carrying out condensation polymerization in the presence of condensing agent, triphenyl phosphite, dicyclohexyl carbonization can be used Diimine, 1- ethyl -3- (3- dimethylamino-propyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy -1, Tri- azine methyl morpholine of 3,5-, O- (benzotriazole -1- base)-N, N, N ', N '-tetramethylurea tetrafluoroborate, O- (benzene And triazol-1-yl)-N, N, N ', N '-tetramethylurea hexafluorophosphate, (thio -3- benzoxazolyl of 2,3- dihydro -2-) phosphonic acids Diphenyl ester, 4- (4,6- dimethoxy -1,3,5- triazine -2- base) 4- methoxyl group morpholine chloride n- hydrate etc..

In addition, is stated in the method for condensing agent in use, lewis acid is added and is used as additive, thus react efficiently into Row.As lewis acid, the preferably lithium halides such as lithium chloride, lithium bromide.Lewis acidic additive amount is excellent relative to tetracarboxylic acid acid diesters It is selected as 0.1~1.0 times of mole.

The solvent used in above-mentioned reaction, can use it is above-mentioned shown in polymeric polyamide acid when the solvent that uses into Row, due to the dissolubility of monomer and polymer, preferably n-methyl-2-pyrrolidone, gamma-butyrolacton, they can mix a kind or Two or more is used.About synthesis when concentration, from be not susceptible to polymer precipitation and be easy to get high molecular weight body in terms of Consider, preferably 1~30 mass %, more preferable 5~20 mass %.In addition, the hydrolysis of tetracarboxylic acid acid diesters dichloride in order to prevent, Solvent used in the synthesis of poly amic acid ester is dehydrated preferably as far as possible, and the mixed of extraneous gas is preferably prevented in nitrogen atmosphere Enter.

It is generated poly- from the recycling of the reaction solution of the polyimide precursors such as polyamic acid or poly amic acid ester, polyimides In the case where the polyimide precursors such as amic acid, poly amic acid ester, polyimides, reaction solution, which is put into poor solvent, makes it Precipitating.As poor solvent used in precipitating, methanol, acetone, hexane, butyl cellosolve, heptane, methyl can be enumerated Ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, toluene, benzene, water etc..For the polymer for precipitating it in investment poor solvent, filtering And after recycling, it is made it dry under normal pressure perhaps decompression in room temperature or heating.Precipitating is recycled in addition, repeating 2~10 times Polymer be re-dissolved in organic solvent carry out reprecipitation recycling operation when, it is possible to reduce the impurity in polymer.As Poor solvent at this time, for example, alcohols, ketone, hydrocarbon etc., if using the poor solvent for being selected from 3 kinds therein or more, The efficiency then purified further increases, thus preferably.

So that such tetracarboxylic acid sour component and diamine component is carried out polyimide precursor obtained from polymerization reaction is, for example, to have There is the polymer of repetitive unit represented by following formula [a].In addition, carrying out the polyimide precursor with this repetitive unit Substance obtained from dehydration closed-loop is polyimides.

(in formula [a], R₁₁For 4 valence organic groups of the tetracarboxylic acid sour component (such as following formula (c)) from raw material, R₁₂It is next From the divalent organic group of the diamine component (such as following formula (b)) of raw material, A₁₁And A₁₂It is 1~4 for hydrogen atom or carbon atom number Alkyl, can be the same or different respectively, j indicate positive integer.)

In above-mentioned formula [a], R₁₁And R₁₂It can be respectively the polymer with a kind of identical repetitive unit, in addition, R₁₁、 R₁₂Or the polymer of the repetitive unit with two or more different structures.

In above-mentioned formula [a], R₁₁For the group from the tetracarboxylic acid sour component as raw material, therefore, (A) ingredient and (B) at In the polyimide precursor divided, R₁₁With structure represented by above-mentioned formula (4).In addition, R₁₂For from the diamines as raw material at The group divided, therefore, the R in the polyimide precursor of (A) ingredient₁₂With-P¹-(Q¹)_p-(Q²)_q-(Q³)_r-P²Represented Side chain, in addition, R in the polyimide precursor of (B) ingredient₁₂There is-CR in main chain²¹ ₂-。

(in formula [b] and formula [c], R₁₁And R₁₂It is identical as group defined in formula [a].)

Other than above-mentioned (A) ingredient and (B) ingredient, aligning agent for liquid crystal of the invention also contains organic solvent.Also, this hair Bright aligning agent for liquid crystal is the form of solution made of above-mentioned (A) ingredient and (B) ingredient are dissolved in organic solvent.

Solution made of as long as there is aligning agent for liquid crystal of the invention (A) ingredient and (B) ingredient to be dissolved in organic solvent Form, limitation is made without to it.For example, there is following methods: the powder of (A) ingredient and (B) ingredient being mixed, dissolution Method in organic solvent；The method that the solution of the powder of (A) ingredient and (B) ingredient is mixed；By the solution of (A) ingredient The method of the powder mixing of (B) ingredient；The method that the solution of the solution of (A) ingredient and (B) ingredient is mixed.Even if at (A) In the case that the good solvent that ingredient dissolves is different from the good solvent that (B) ingredient dissolves, also available uniform (A) The mixed solution of ingredient and (B) ingredient, therefore the method for more preferably mixing the solution of the solution of (A) ingredient and (B) ingredient.

Herein, the solution about the solution of (A) ingredient and (B) ingredient synthesizes (A) ingredient, (B) ingredient in organic solvent In the case where, it can be obtained reaction solution itself, alternatively, it is also possible to dilute the reaction solution with the solvent for being suitable for Obtained solution.In addition, can also be dissolved in organic in the case where obtaining (A) ingredient, (B) ingredient in the form of powder Solution is formed in solvent.

About the above-mentioned organic solvent contained in aligning agent for liquid crystal of the invention, as long as (A) ingredient, (B) ingredient are uniform Dissolution is just not particularly limited.If enumerating its concrete example, n,N-Dimethylformamide, N can be enumerated, N- diethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, N- methyl caprolactam, 2- pyrrolidines Ketone, n-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, gamma-butyrolacton, 1,3- dimethyl-2-imidazolidinone, 3- methoxy Base-N, N- dimethylpropionamide etc..They can mix one kind or two or more use.In addition, can not be uniform when even independent The solvent for dissolving (A) ingredient, (B) ingredient, as long as can also be mixed in the range of (A) ingredient, (B) ingredient are not precipitated To in above-mentioned organic solvent.

In addition to this, within the scope of the effect of the invention, can also contain in aligning agent for liquid crystal of the invention (A) ingredient and the other polymers other than (B) ingredient are as component of polymer.The other polymers will not be for example, will The polyamic acid, poly amic acid ester, polyimides of any one of TDA, TDA diester and TDA diester dichloride as raw material Or polyamide etc..

It, can also be according to wanted shape about the content (concentration) of the component of polymer contained by aligning agent for liquid crystal of the invention At liquid crystal orientation film (polyimide film) thickness and suitably change, from the aspect of forming uniform, flawless film, Relative to organic solvent, the content of component of polymer is preferably 0.5 mass % or more, is examined in terms of the storage stability of solution Consider, preferably 15 mass % or less, more preferably 1~10 mass %.It should be noted that in this case, pre-production polymerize The concentrated solution of object ingredient can be diluted when making aligning agent for liquid crystal by the concentrated solution.The concentrated solution of the component of polymer Concentration is preferably 10~30 mass %, more preferably 10~15 mass %.In addition, the powder of component of polymer is dissolved in organic When making solution in solvent, it can be heated.Heating temperature is preferably 20 DEG C~150 DEG C, particularly preferably 20 DEG C~80 DEG C. In addition, in the case where also containing the other polymers other than (A) ingredient and (B) ingredient, (A) ingredient in component of polymer and (B) content of the other polymers other than ingredient is 0.5 mass of mass %~15 %, preferably 1 mass of mass %~10 %.

In addition, aligning agent for liquid crystal of the invention can also contain the ingredient other than component of polymer.As its example, to mention The solvent and compound of film thickness uniformity and surface smoothness when high coating of liquid crystalline alignment agent improve liquid crystal orientation film and substrate Adaptation compound etc..

The concrete example of solvent (poor solvent) as the uniformity and surface smoothness for improving film thickness, can enumerate following Substance.

For example, can enumerate isopropanol, methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, Methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, second two Alcohol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol list Methyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, two Propylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate list ether, two Propylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, acetic acid -3- methyl -3- methoxybutyl, tripropylene glycol methyl ether, 3- Methyl -3- methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, two isobutyls Base ketone, methylcyclohexene, propyl ether, two hexyl ethers, 1- hexanol, n-hexane, pentane, normal octane, diethyl ether, methyl lactate, lactic acid Ethyl ester, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate list ether, methyl pyruvate, ethyl pyruvate, 3- first Oxygroup methyl propionate, 3- ethoxy-propionic acid Methylethyl, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, 1- methoxy-2-propanol, 1- ethyoxyl -2- propyl alcohol, 1- butoxy -2- Propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol -1- monomethyl ether -2- acetic acid esters, Propylene glycol -1- list ether -2- acetic acid esters, dipropylene glycol, 2- (2- ethoxy-c oxygroup) propyl alcohol, methyl lactate, ethyl lactate, cream Sour n-propyl, n-butyl lactate, isoamyl lactate etc. have the solvent etc. of low surface tension.

These poor solvents can be one kind, can also be use mixing two or more.The case where stating solvent in use Under, 5~80 mass % of the whole solvents for preferably including in aligning agent for liquid crystal, more preferably 20~60 mass %.

As the compound for the uniformity and surface smoothness for improving film thickness, fluorine system surfactant, silicone can be enumerated It is surfactant, nonionic surfactants etc..

More specifically, for example, Eftop EF301, EF303, EF352 (Tochem Products corporation Make), MEGAFACE F171, F173, R-30 (big Japanese ink company manufacture), Fluorad FC430, (Sumitomo 3M is public by FC431 Department manufacture), AashiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (rising sun The manufacture of nitre subsidiary) etc..Relative to 100 mass parts of component of polymer contained in aligning agent for liquid crystal, these surfactants Use ratio is preferably 0.01~2 mass parts, more preferably 0.01~1 mass parts.

The concrete example of compound as the adaptation for improving liquid crystal orientation film and substrate, can enumerate as shown below contain Compound, compound containing epoxy group for having functional silanes etc..

For example, 3- TSL 8330,3-aminopropyltriethoxysilane, 2- aminopropyl can be enumerated Trimethoxy silane, 2- aminopropyltriethoxywerene werene, N- (2- amino-ethyl) -3- TSL 8330, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- ureido-propyl trimethoxy silane, three second of 3- ureido-propyl Oxysilane, N- ethoxy carbonyl -3- TSL 8330, N- ethoxy carbonyl -3- aminopropyl triethoxy Silane, N- triethoxysilylpropyltetrasulfide diethylenetriamine, N- trimethoxy-silylpropyl diethylenetriamine, Three azepine decane of 10- trimethoxysilyl -1,4,7-, three azepine decane of 10- triethoxysilyl -1,4,7-, 9- Trimethoxysilyl -3,6- diaza nonyl acetic acid esters, 9- triethoxysilyl -3,6- diaza nonyl acetic acid Ester, N- benzyl -3- TSL 8330, N- benzyl -3-aminopropyltriethoxysilane, N- phenyl -3- amino Bis- (the ethylene oxide) -3- aminopropyl front threes of propyl trimethoxy silicane, N- phenyl -3-aminopropyltriethoxysilane, N- Bis- (the ethylene oxide) -3-aminopropyltriethoxysilane of oxysilane, N-, ethylene glycol diglycidylether, polyethylene glycol two Glycidol ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, new penta Hexanediol diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- dibromoneopentyl glycol two contract Water glycerin ether, 1,3,5,6- four glycidyl group -2,4- hexylene glycol, N, N, N ', N ',-four glycidyl group-meta-xylene two Amine, 1,3- bis- (N, N- diglycidyl amino methyl) hexamethylenes, N, N, N ', N ',-four glycidyl group -4,4 '-diamino Diphenyl methane etc..

In addition, other than the adaptation for improving substrate and film, for further preventing electrology characteristic caused by backlight The purpose of reduction etc. can also import the additive of phenoplasts system below in aligning agent for liquid crystal.It is illustrated below specific Phenoplasts system additive, but it is not limited to the structure.

When using the compound with the adaptation of substrate is improved, dosage is relative to the polymerization contained in aligning agent for liquid crystal 100 mass parts of object ingredient are preferably 0.1~30 mass parts, more preferably 1~20 mass parts.When dosage is less than 0.1 mass parts, nothing Method expects the effect that adaptation improves, and when being more than 30 mass parts, liquid crystal aligning is deteriorated sometimes.

In aligning agent for liquid crystal of the invention, in addition to the foregoing, within the scope of the effect of the invention, for Change the dielectric constant of liquid crystal orientation film and the purpose of the electrology characteristics such as electric conductivity, can also add dielectric or conductive materials, And film when being made liquid crystal orientation film for improving hardness and consistency cross-linked compound.

For aligning agent for liquid crystal of the invention, on being applied to substrate and after firing, irradiated using friction treatment or light etc. Orientation process is carried out, alternatively, No yield point is handled and used as liquid crystal orientation film in vertically oriented purposes etc..As making at this time Substrate is not particularly limited as long as the high substrate of the transparency, glass substrate can be used；Or acrylic compounds base The plastic bases such as plate, polycarbonate substrate；Deng.In addition, it is preferable to use being formed with for liquid crystal from the aspect of the chemical industry skill that conforms to the principle of simplicity The substrate of ITO (tin indium oxide) electrode of driving etc..In addition, in the liquid crystal display element of reflection-type, if being only unilateral The opaque substrate such as silicon wafer then also can be used in substrate, and as electrode in this case, the reflected lights such as aluminium also can be used Material.

The coating method of aligning agent for liquid crystal is not particularly limited, industrially generally by silk-screen printing, hectograph The method of the progress such as printing, aniline printing, ink-jet method.As other coating methods, have dipping, roll coater, slit coater, Spin coater etc. can use these coating methods according to purpose.In the present invention, thus it is speculated that be applied on substrate by aligning agent for liquid crystal Stage be separated into the layer of (A) ingredient and the layer of (B) ingredient.

About the firing after aligning agent for liquid crystal is applied on substrate, can use the heating units such as heating plate with 50~ 300 DEG C, preferably 80~250 DEG C progress, evaporate solvent, form film.When the thickness of the film formed after firing is blocked up, in liquid The consumption concerned power of crystal display element becomes unfavorable, and when excessively thin, the reliability of liquid crystal display element reduces sometimes, therefore, excellent It is selected as 5~300nm, more preferably 10~100nm.Making liquid crystal be horizontally oriented or in the case where tilted alignment, by friction or Polarized ultraviolet irradiation etc. handles the film after firing.Speculate that the obtained liquid crystal orientation film is separated into come from (A) layer of ingredient and come from the two layers of the layer of (B) ingredient.

About liquid crystal display element of the invention, band liquid crystal is being obtained by aligning agent for liquid crystal of the invention by the above method After the substrate of alignment films, liquid crystal cells are made using well known method, liquid crystal display element is made.If enumerating an example, to have The liquid crystal display element of following liquid crystal cells, the liquid crystal cells include 2 plate bases of relative configuration；The liquid being set between substrate Crystal layer；The above-mentioned liquid crystal orientation film for being set between substrate and liquid crystal layer, being formed by aligning agent for liquid crystal of the invention.As in this way Liquid crystal display element of the invention, can enumerate twisted-nematic (TN:Twisted Nematic) mode, vertical orientation (VA: Vertical Alignment) mode, horizontal alignment (IPS:In-Plane Switching, in-plane switching) mode, OCB orientation The liquid crystal display element of various modes such as (OCB:Optically Compensated Bend, optical compensation curved).

It as liquid crystal cells production method, may be exemplified: preparing a pair of of the substrate for being formed with liquid crystal orientation film, in a base Spacer is spread on the liquid crystal orientation film of plate, another substrate, decompression note are bonded in the way of making liquid crystal alignment film surface inside The method for entering liquid crystal and sealing；Alternatively, adhesive substrates are gone forward side by side after liquid crystal is added dropwise in the liquid crystal alignment film surface for be scattered with spacer The method of row sealing；Etc..The thickness of spacer at this time is preferably 1~30 μm, more preferably 2~10 μm.

The positive type liquid crystal with positive dielectric anisotropy and bearing with negative dielectric anisotropy can be used in liquid crystal Type liquid crystal, specifically, MLC-2003, MLC-6608, MLC-6609 etc. of for example, Merck & Co., Inc.'s manufacture.

As described above, using liquid crystal display element made by aligning agent for liquid crystal of the invention required for remaining previous Characteristic, i.e. rub resistance while, voltage retention is high, and charge accumulation is very small, can meet current strict requirements, example Mobile phone or tablet terminal can also be such as suitable for.

Embodiment

Embodiment is enumerated below illustrates the present invention in further detail.But the present invention is not limited certainly by these embodiments Qualitatively explain.It should be noted that the measuring method of following abbreviations and each characteristic used is as described below.

(tetracarboxylic dianhydride)

CBDA:1,2,3,4- cyclobutane tetracarboxylic dianhydride

TDA:3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic dianhydride

PPHT:N, N '-bis- (1,2- cyclohexane dicarboxylic acid acid anhydride -4- base carbonyl) -1,4- phenylenediamines

(diamines)

DBA:3,5- diaminobenzoic acid

P-PDA: p-phenylenediamine

DDM:4,4 '-diaminodiphenyl-methane

Bis- (4- aminophenethyl) ureas of BAPU:1,3-

APC16:1,3- diamino -4- hexadecane epoxide benzene

APC18:1,3- diamino -4- octadecane epoxide benzene

DADPA:4,4 '-diamino-diphenyl amine

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

(organic solvent)

NMP:N- N-methyl-2-2-pyrrolidone N

BCS: butyl cellosolve

GBL: gamma-butyrolacton

(additive)

LS-2450:3- aminopropyl diethoxymethylsilane

LS-3150:3- aminopropyltriethoxywerene werene

Bis- [bis- (methylol) phenyl of the 4- hydroxyl -3,5-] propane of TM-BIP:2,2 ' -

It should be noted that LS-2450, LS-3150 are respectively the trade name of Shin-Etsu Chemial Co., Ltd.

[measurement of the molecular weight of polymer]

The molecular weight of polyimides and polyamic acid in synthesis example is carried out by GPC (room temperature gel permeation chromatography) device Measurement, calculates number-average molecular weight (hereinafter also referred to as Mn) and Weight-average molecular as polyethylene glycol, polyethylene oxide scaled value It measures (hereinafter also referred to as Mw).

GPC device: (strain) Shodex company manufactures (GPC-101)

Column: Shodex company manufactures (series connection of KD803, KD805)

Column temperature: 50 DEG C

Eluent: n,N-Dimethylformamide is (as additive, lithium bromide-hydrate (LiBrH₂It O) is 30mmol/ L, phosphoric acid anhydrous crystal (o- phosphoric acid) is 30mmol/L, tetrahydrofuran (THF) is 10mL/L)

Flow velocity: 1.0mL/ minutes

Calibration curve makes standard sample: the TSK standard polyethylene oxide (weight average molecular weight that Tosoh company manufactures (Mw) about 900000,150000,100000,30000) and Polymer Laboratories company manufacture polyethylene glycol (peak molecular weight (Mp) about 12000,4000,1000).In measurement, in order to avoid overlap of peaks, determine respectively by 900000, 100000,12000,1000 this 4 kinds of samples mixed and by 150000,30000,4000 this 3 kinds mix Both samples of sample.

[measurement of acid imide rate]

The acid imide rate of polyimides measures as follows.Polyimide powder 20mg is fitted into NMR test tube, is added deuterated Dimethyl sulfoxide (DMSO-d6,0.05%TMS mixture) 0.53mL, makes it completely dissolved.For the solution, JEOL is utilized Datum company manufacture NMR analyzer (JNM-ECA500) determines the proton NMR of 500MHz.Acid imide rate is found out as follows: Determine that the proton derived from the not changed structure before and after imidizate as reference proton, uses the peak product of the proton The proton peak integrated value of score value and the NH base from the polyamic acid occurred near 9.5~10.0ppm, is found out by following formula Acid imide rate.

Acid imide rate (%)=(1- α x/y) × 100

In above-mentioned formula, x is the proton peak integrated value of the NH base from polyamic acid, and y is the peak integrated value of benchmark proton, α be relative to polyamic acid (acid imide rate be 0%) in the case where polyamic acid 1 NH matrix it is sub, reference proton Number ratio.

[production of liquid crystal cells]

Aligning agent for liquid crystal is spin-coated on the glass substrate with transparent electrode, it is dry in the heating plate that temperature is 80 DEG C After 60 seconds, carry out firing for 20 minutes in a nitrogen atmosphere using 220 DEG C of IR (infrared ray) baking oven, foring film thickness is 100nm Film.For the coated surface, the rubbing device for being 120mm using roller diameter, using cotton (Ji Chuan manufactures YA-25C), in roller Revolving speed is 1000rpm, roller travel speed is 50mm/sec, intrusion rubs under conditions of being 0.4mm, obtains band liquid crystal aligning The substrate of film.

Prepare 2 substrates, 4 μm of spacer is spread in wherein 1 liquid crystal alignment film surface, utilizes coating apparatus for sealant Printing and sealing agent (Sumitomo Chemical (strain) NX-1500T) from the upper side, it is opposite according to liquid crystal alignment film surface, frictional direction straight trip After mode pastes another plate base, make sealant cures (it is temporary fixing: 80 DEG C 10 minutes, main solidification: 150 DEG C 1 hour 45 points Clock), make dummy cell.Utilize injection liquid crystal MLC-2003 (Merck Japan corporation in decompression injection normal direction dummy cell Make), inlet is sealed, twisted nematic liquid crystals unit is obtained.It should be noted that these operate with Examples 1 to 8 and Each aligning agent for liquid crystal obtained in the Comparative Examples 1 to 5 carries out.

[evaluation of rub resistance]

The stage of the substrate with liquid crystal orientation film is obtained in [production of liquid crystal cells], passes through confocal laser microscope With the surface of visual observation liquid crystal orientation film, evaluated according to following benchmark.Show the result in table 3.

Zero: not observing chip and friction scar with laser microscope visually.

△: chip and friction scar are not observed visually, but observes chip or friction scar using laser microscope.

×: film stripping observes friction scar with visual using laser microscope.

[measurement of VHR (voltage retention)]

For utilizing twisted nematic liquid crystals unit made by the method recorded in above-mentioned [production of liquid crystal cells], 60 DEG C at a temperature of apply the 60 μ s of voltage of 4V, how long voltage is able to maintain as voltage by the voltage after measuring 166.7ms Conservation rate is calculated, and is evaluated according to following benchmark.It should be noted that the measurement of voltage retention uses The VHR-1 voltage retention measurement device of Toyo Corporation company manufacture.As a result it is shown in table 3.

◎: more than 85%

Zero: 80%~85%

△: less than 80%

[measurement of volume resistivity]

Each composition [AL-1]~[AL-10] is filtered using 0.2 μm of filter, later extremely by spin application On glass substrate with ito transparent electrode, after 1 minute dry in 80 DEG C of heating plate, fires 20 minutes, formed at 220 DEG C Film thickness is the film of 220nm.In the film coated surface, across mask using vacuum vapour deposition with 1.0 × 10^-3The vacuum degree of Pa is steamed Rate 1nm/s AM aluminum metallization is plated, the upper electrode of 1.0mm φ, the sample as volume resistivity measurement are formed.

Apply the voltage of 10V, the electricity after measurement voltage application after 180 seconds between the ITO electrode and aluminium electrode of the sample Flow valuve calculates volume resistivity by the measured value of the value and electrode area, film thickness.

It should be noted that the backlight of LED is preset below sample substrate, in a lamp bar in resistance value measurement It is measured under part.Device used in measurement is the 6517A ELECTROMETER of KEITHLEY manufacture, uses MEASURE The shielding box SM-1 with locator of Jig company manufacture, is measured in a nitrogen atmosphere.As a result it is shown in table 4.

[measurement of RDC (remanant DC voltages)]

For utilizing twisted nematic liquid crystals unit made by the method recorded in above-mentioned [production of liquid crystal cells], DC voltage is applied from 0V to 1.0V with the interval 0.1V in 23 DEG C of temperature, is turned using the flashing amplitude level photoelectricity under each voltage Changing device is measured, and flashing amplitude level is made and applies the calibration curve under voltage.Liquid crystal cells are grounded 5 minutes, are put It postpones and applies alternating voltage V50 (voltage that brightness becomes half), DC voltage 5.0V 1 hour, only make DC voltage later 0V, measurement flashing amplitude level, is compareed with the calibration curve of pre-production, to estimate RDC immediately after.It needs to illustrate , the evaluation method of the RDC referred to as flashing reference entry.In addition, RDC hours, it may be said that charge accumulation is small.As a result it is shown in table 3。

◎: less than 0.05

Zero: 0.05 more than and less than 0.08

△: 0.08 more than and less than 0.20

×: 0.20 or more

[synthesis example]

Numerical value in bracket documented by behind tetracarboxylic acid sour component, diamine component etc. indicates raw material when Macroscopic single crystal The molar fraction of monomer.

(synthesis example 1)

The polymerization of polyamic acid [PAA-1:TDA (50) CBDA (50)/DDM (100)] and composition [AL-1:TDA (50) CBDA (50)/DDM (100)] preparation

DDM 2.78g (14.01mmol) is weighed in the 50ml four-hole boiling flask for having nitrogen ingress pipe and mechanical agitator, GBL 17.40g is added and makes it dissolve, is cooled to about 10 DEG C in a nitrogen atmosphere, TDA 2.10g is added bit by bit (6.99mmol) restores to room temperature, reacts 2 hours.Later, CBDA 1.26g (6.42mmol) and NMP 17.40g is added, it is extensive Again to room temperature, reacts 4 hours, obtain the solution of the polyamic acid [PAA-1] of 15 mass %.Obtained polyamic acid [PAA- 1] number-average molecular weight is 15,200, weight average molecular weight 47,500.

The polyamic acid [PAA-1] of obtained 15 mass % is weighed in the conical flask for the 50ml for having stirrer Solution 15.02g, be added GBL 16.89g, BCS 5.64g, be stirred at room temperature 2 hours, obtain solid component concentration be 6.0 matter It is the composition [AL-1] that 20 mass %, BCS are 15 mass % that amount %, GBL, which are 59 mass %, NMP,.

(synthesis example 2)

The preparation of composition [AL-2:TDA (50) CBDA (50)/DDM (100)+LS-3150 (1)]

The polyamic acid of 15 mass % obtained in synthesis example 1 is weighed in the conical flask for the 50ml for having stirrer The solution 14.12g of [PAA-1] is added GBL 15.56g, BCS 5.56g, LS-3150 being diluted to the molten of 2 mass % with NMP Liquid 0.42g is stirred at room temperature 2 hours, and it be 59 mass %, NMP is 20 matter that obtain solid component concentration, which be 6.0 mass %, GBL, Measure the composition [AL-2] that %, BCS are 15 mass %.

(synthesis example 3)

The preparation of composition [AL-3:TDA (50) CBDA (50)/DDM (100)+LS-3150 (1)+TM-BIP (1)]

The polyamic acid of 15 mass % obtained in synthesis example 1 is weighed in the conical flask for the 50ml for having stirrer The solution 14.12g of [PAA-1] is added GBL 15.35g, BCS 5.35g, LS-3150 being diluted to the molten of 5 mass % with NMP Liquid 0.42g, the solution 0.42g that TM-BIP is diluted to 5 mass % with NMP, are stirred at room temperature 2 hours, it is dense to obtain solid component It is the composition [AL-3] that 20 mass %, BCS are 15 mass % that degree, which is 59 mass %, NMP for 6.0 mass %, GBL,.

(synthesis example 4)

The polymerization of polyamic acid [PAA-2:TDA (50) CBDA (50)/BAPU (20) DDM (80)] and composition [AL-4: TDA (50) CBDA (50)/BAPU (20) DDM (80)+LS-3150 (1)+TM-BIP (1)] preparation

Weighed in the 50ml four-hole boiling flask for having nitrogen ingress pipe and mechanical agitator BAPU 0.71g (2.38mmol), DDM 1.90g (9.58mmol) is added GBL 20.18g and makes it dissolve, is cooled to about 10 DEG C in a nitrogen atmosphere, bit by bit TDA 1.80g (6.30mmol) is added in ground, restores to room temperature, reacts 2 hours.Later, CBDA 1.08g (5.44mmol) is added With NMP 20.18g, restores to room temperature, react 4 hours, obtain the solution of the polyamic acid [PAA-2] of 12 mass %.It is acquired Polyamic acid [PAA-2] number-average molecular weight be 12,700, weight average molecular weight 38,200.

The polyamic acid [PAA-2] of obtained 12 mass % is weighed in the conical flask for the 50ml for having stirrer Solution 15.01g, be added by GBL 9.78g, BCS 4.50g, LS-3150 with NMP be diluted to 5 mass % solution 0.36g, TM-BIP is diluted to the solution 0.36g of 5 mass % with NMP, is stirred at room temperature 2 hours, obtaining solid component concentration is 6.0 matter It is the composition [AL-4] that 20 mass %, BCS are 15 mass % that amount %, GBL, which are 59 mass %, NMP,.

(synthesis example 5)

The polymerization of polyamic acid [PAA-3:TDA (30) CBDA (70)/DDM (100)] and composition [AL-5:TDA (30) CBDA (70)/DDM (100)+LS-3150 (1)+TM-BIP (1)] preparation

DDM 2.97g (14.98mmol) is weighed in the 50ml four-hole boiling flask for having nitrogen ingress pipe and mechanical agitator, GBL 18.09g is added to make it dissolve, is cooled to about 10 DEG C in a nitrogen atmosphere, TDA 1.35g is added bit by bit (4.50mmol) restores to room temperature, reacts 2 hours.Later, CBDA 2.05g (10.50mmol) and NMP 18.09g is added, it is extensive Again to room temperature, reacts 4 hours, obtain the solution of the polyamic acid [PAA-3] of 15 mass %.Obtained polyamic acid [PAA- 3] number-average molecular weight is 11,000, weight average molecular weight 41,000.

The polyamic acid [PAA-3] of obtained 15 mass % is weighed in the conical flask for the 50ml for having stirrer Solution 15.00g, be added by GBL 15.97g, BCS 5.63g, LS-3150 with NMP be diluted to 5 mass % solution 0.45g, TM-BIP is diluted to the solution 0.45g of 5 mass % with NMP, is stirred at room temperature 2 hours, obtaining solid component concentration is 6.0 matter It is the composition [AL-5] that 20 mass %, BCS are 15 mass % that amount %, GBL, which are 59 mass %, NMP,.

(synthesis example 6)

The polymerization of polyamic acid [PAA-4:TDA (70) CBDA (30)/DDM (100)] and composition [AL-6:TDA (70) CBDA (30)/DDM (100)+LS-3150 (1)+TM-BIP (1)] preparation

DDM 2.97g (14.98mmol) is weighed in the 50ml four-hole boiling flask for having nitrogen ingress pipe and mechanical agitator, GBL 19.86g is added to make it dissolve, is cooled to about 10 DEG C in a nitrogen atmosphere, TDA 3.15g is added bit by bit (10.48mmol) restores to room temperature, reacts 2 hours.Later, CBDA 0.88g (4.50mmol) and NMP 19.86g is added, it is extensive Again to room temperature, reacts 4 hours, obtain the solution of the polyamic acid [PAA-4] of 15 mass %.Obtained polyamic acid [PAA- 4] number-average molecular weight is 14,500, weight average molecular weight 45,100.

The polyamic acid [PAA-4] of obtained 15 mass % is weighed in the conical flask for the 50ml for having stirrer Solution 15.00g, be added by GBL 15.97g, BCS 5.63g, LS-3150 with NMP be diluted to 5 mass % solution 0.45g, TM-BIP is diluted to the solution 0.45g of 5 mass % with NMP, is stirred at room temperature 2 hours, obtaining solid component concentration is 6.0 matter It is the composition [AL-6] that 20 mass %, BCS are 15 mass % that amount %, GBL, which are 59 mass %, NMP,.

(synthesis example 7)

The polymerization of polyamic acid [PAA-5:TDA (100)/p-PDA (90) APC18 (10)]

In the 50ml four-hole boiling flask for having nitrogen ingress pipe and mechanical agitator, using TDA 9.00g (0.030mol), P-PDA 2.92g (0.027mol), APC181.13g (0.0030mol) react 24 hours in NMP 73.40g at 50 DEG C, Obtain the solution of polyamic acid [PAA-5].The number-average molecular weight of obtained polyamic acid [PAA-5] is 15,800, divides equally again Son amount is 49,200.

(synthesis example 8)

The preparation of polyimides [SPI-1:TDA (100)/p-PDA (90) APC18 (10)]

The solution of polyamic acid [PAA-5] obtained in synthesis example 7 is added in the 100ml conical flask for having stirrer 20.00g, NMP 30.67g, acetic anhydride 7.16g, pyridine 3.32g after being stirred at room temperature 30 minutes, are stirred 3 hours at 40 DEG C, Make its reaction.It after reaction terminating, slowly injects in the methanol of 214g, polymer (polyimides) is precipitated, stir 30 minutes Afterwards, solid is recovered by filtration.It after sufficiently cleaning obtained solid with methanol, is dried in vacuo at 100 DEG C, to obtain Polyimide powder.The acid imide rate of obtained polyimides [SPI-1] is 85%.

GBL 29.00g is added in obtained polyimide powder 2.60g, stirs 24 hours and makes it dissolve at 50 DEG C, Confirmation has been completely dissolved, and the 2 mass %GBL solution 6.15g of GBL 4.00g, LS-2450 are added, and is stirred 24 minutes at 50 DEG C, Obtaining solid component concentration is the polyimide solution [SPI-1a] that 6.0 mass %, GBL are 94 mass %.

(synthesis example 9)

The polymerization of polyamic acid [PAA-6:TDA/BAPU (30) p-PDA (60) APC18]

In the 50ml four-hole boiling flask for having nitrogen ingress pipe and mechanical agitator, using TDA 9.31g (0.031mol), BAPU 2.77g (0.0093mol), p-PDA 2.01g (0.019mol), APC181.17g (0.0031mol), in NMP It is reacted 24 hours in 86.38g in 50 DEG C, obtains the solution of polyamic acid [PAA-6].Obtained polyamic acid [PAA-6] Number-average molecular weight is 10,500, weight average molecular weight 35,900.

(synthesis example 10)

The preparation of polyimides [SPI-2:TDA/BAPU (30) p-PDA (60) APC18]

The solution of polyamic acid [PAA-6] obtained in synthesis example 9 is added in the 100ml conical flask for having stirrer 30.00g, NMP 50.50g, acetic anhydride 10.01g, pyridine 4.65g after being stirred at room temperature 30 minutes, are stirred 3 hours at 40 DEG C, Make its reaction.It after reaction terminating, is slowly injected into the methanol of 580g, polymer is precipitated, after stirring 30 minutes, by filtering back Receive solid.After sufficiently cleaning obtained solid with methanol, it is dried in vacuo at 100 DEG C, thus obtains polyimide powder. The acid imide rate of obtained polyimides [SPI-2] is 82%.

GBL 30.59g is added into obtained polyimide powder 2.66g, stirs 24 hours and makes it dissolve at 50 DEG C, Confirmation has been completely dissolved, and the 2 mass %GBL solution 6.83g of GBL 6.55g, LS-2450 are added, and is stirred 24 minutes at 50 DEG C, Thus obtaining solid component concentration is the polyimide solution [SPI-2a] that 6.0 mass %, GBL are 94 mass %.

(synthesis example 11)

The polymerization of polyamic acid [PAA-7:TDA (100)/p-PDA (90) APC16 (10)]

In the 50ml four-hole boiling flask for having nitrogen ingress pipe and mechanical agitator, using TDA 7.51g (0.025mol), P-PDA 2.43g (0.023mol), APC160.87g (0.0025mol) react 24 hours in NMP 61.26g in 50 DEG C, Obtain the solution of polyamic acid [PAA-7].The number-average molecular weight of obtained polyamic acid [PAA-7] is 13,600, divides equally again Son amount is 50,200.

(synthesis example 12)

The preparation of polyimides [SPI-3:TDA (100)/p-PDA (90) APC16 (10)]

The molten of polyamic acid [PAA-7] obtained in synthesis example 11 is added in the 100ml conical flask for having stirrer Liquid 20.00g, NMP 30.67g, acetic anhydride 7.18g, pyridine 3.33g are small in 40 DEG C of stirrings 3 after being stirred at room temperature 30 minutes When, make its reaction.It after reaction terminating, is slowly injected into the methanol of 214g, polymer is precipitated, after stirring 30 minutes, passed through Filter recycling solid.It after sufficiently cleaning obtained solid with methanol, is dried in vacuo at 100 DEG C, to obtain polyimides Powder.The acid imide rate of obtained polyimides [SPI-3] is 88%.

GBL 29.90g is added into obtained polyimide powder 2.60g, stirs 24 hours and makes it dissolve at 50 DEG C, Confirmation has been completely dissolved, and the 2 mass %GBL solution 6.15g of GBL 4.00g, LS-2450 are added, and is stirred 24 minutes at 50 DEG C, To obtain the polyimide solution [SPI-3a] that 6.0 mass %, GBL are 94 mass %.

(comparing synthesis example 1)

The polymerization of polyamic acid [PAA-8:PPHT (90) CBDA (10)/p-PDA (90) APC18 (10)]

In the 50ml four-hole boiling flask for having nitrogen ingress pipe and mechanical agitator, make PPHT 2.44g, CBDA 0.12g, P-PDA 0.58g, APC180.26g react 4 hours in NMP 19.11g, obtain the solution of polyamic acid [PAA-8].Gained To polyamic acid [PAA-8] number-average molecular weight be 13,000, weight average molecular weight 45,000.

(comparing synthesis example 2)

The preparation of polyimides [SPI-4:PPHT (90) CBDA (10)/p-PDA (90) APC18 (10)]

It is added in the 100ml conical flask for having stirrer and compares polyamic acid obtained in synthesis example 1 [PAA-8] Solution 22.49g, NMP 33.72g, acetic anhydride 5.96g, pyridine 2.77g, after being stirred at room temperature 30 minutes, 70 DEG C stir 3 Hour, make its reaction.It after reaction terminating, is slowly injected into the methanol of 250g, polymer is precipitated, after stirring 30 minutes, pass through Solid is recovered by filtration.It after sufficiently cleaning obtained solid with methanol, is dried in vacuo at 100 DEG C, to obtain polyamides Asia Amine powder.The acid imide rate of obtained polyimides [SPI-4] is 88%.

GBL 33.00g is added into obtained polyimide powder 2.60g, stirs 24 hours and makes it dissolve at 50 DEG C, Confirmation has been completely dissolved, and obtaining solid component concentration is the polyimide solution [SPI- that 6.0 mass %, GBL are 94 mass % 4a]。

(comparing synthesis example 3)

The polymerization of polyamic acid [PAA-9:TDA (50) CBDA (50)/DDM (20) p-PDA (80)] and composition [AL-7: TDA (50) CBDA (50)/DDM (20) p-PDA (80)+LS-3150 (1)] preparation

Weighed in the 100ml four-hole boiling flask for having nitrogen ingress pipe and mechanical agitator DDM 1.58g (8.00mmol), P-PDA 3.46g (32.00mmol) is added GBL 41.32g and makes it dissolve, is cooled to about 10 DEG C in a nitrogen atmosphere, and one point one TDA 6.00g (20.00mmol) is added in point ground, restores to room temperature, reacts 2 hours.Later, CBDA 3.52g is added (18.00mmol) and NMP 41.32g restores to room temperature, reacts 4 hours, obtain the polyamic acid [PAA-9] of 15 mass % Solution.The number-average molecular weight of obtained polyamic acid [PAA-9] is 7,100, weight average molecular weight 15,000.

Into the solution of the polyamic acid [PAA-9] of obtained 15 mass % be added GBL 97.2g, BCS 48.6g, LS-31500.15g is stirred at room temperature 2 hours, and it is that 59 mass %, NMP are that obtain solid component concentration, which be 6.0 mass %, GBL, 20 mass %, BCS are the composition [AL-7] of 15 mass %.

(comparing synthesis example 4)

The polymerization of polyamic acid [PAA-10:TDA (70) CBDA (30)/DDM (20) p-PDA (80)] and composition [AL- 8:TDA (70) CBDA (30)/DDM (20) p-PDA (80)+LS-3150 (1)] preparation

Weighed in the 100ml four-hole boiling flask for having nitrogen ingress pipe and mechanical agitator DDM 1.58g (8.00mmol), P-PDA 3.46g (32.00mmol) is added GBL 43.46g and makes it dissolve, is cooled to about 10 DEG C in a nitrogen atmosphere, and one point one TDA 8.40g (28.00mmol) is added in point ground, restores to room temperature, reacts 2 hours.Later, CBDA 1.88g is added (9.60mmol) and NMP 43.46g restores to room temperature, reacts 4 hours, obtain the polyamic acid [PAA-10] of 15 mass % Solution.The number-average molecular weight of the solution of obtained polyamic acid [PAA-10] is 7,100, weight average molecular weight 15,000.

GBL 97.2g, BCS 48.6g, LS-3150 are added into the solution of obtained polyamic acid [PAA-10] 0.15g is stirred at room temperature 2 hours, and it be 59 mass %, NMP is 20 matter that obtain solid component concentration, which be 6.0 mass %, GBL, Measure the composition [AL-8] that %, BCS are 15 mass %.

(comparing synthesis example 5)

The polymerization of polyamic acid [PAA-11:TDA (50) CBDA (50)/DBA (30) DDM (70)] and composition [AL-9: TDA (50) CBDA (50)/DBA (30) DDM (70)+LS-3150 (1)+TM-BIP (1)] preparation

DDM 2.08g is weighed in the 100ml four-hole boiling flask for having nitrogen ingress pipe and mechanical agitator (10.50mmol), DBA 0.68g (4.50mmol) is added GBL 18.06g and makes it dissolve, is cooled to about 10 in a nitrogen atmosphere DEG C, TDA 2.25g (7.5mmol) is added bit by bit, restores to room temperature, reacts 2 hours.Later, CBDA 1.35g is added (6.90mmol) and NMP 18.06g restores to room temperature, reacts 4 hours, obtain the polyamic acid [PAA-11] of 15 mass % Solution.The number-average molecular weight of obtained polyamic acid [PAA-11] is 9,400, weight average molecular weight 25,900.

The solution of obtained polyamic acid [PAA-11] is weighed in the conical flask for the 50ml for having stirrer 15.05g is added and GBL 16.02g, BCS 5.64g, LS-3150 is diluted to the solution 0.45g of 5 mass % with NMP, by TM- BIP is diluted to the solution 0.45g of 5 mass % with NMP, is stirred at room temperature 2 hours, obtain solid component concentration be 6.0 mass %, GBL is that 59 mass %, NMP are the composition [AL-9] that 20 mass %, BCS are 15 mass %.

(comparing synthesis example 6)

The polymerization of polyamic acid [PAA-12:TDA (20) CBDA (80)/DADPA (80) DDM (20)] and composition [AL- 10:TDA (20) CBDA (80)/DADPA (80) DDM (20)] preparation

DADPA 2.39g is weighed in the 100ml four-hole boiling flask for having nitrogen ingress pipe and mechanical agitator (12.00mmol), DDM 0.59g (3.00mmol) is added NMP 55.37g and makes it dissolve, is cooled to about 10 in a nitrogen atmosphere DEG C, TDA 0.90g (3.0mmol) and CBDA 2.26g (11.55mmol) are added bit by bit, restores to room temperature, reaction 4 is small When, obtain the solution of polyamic acid [PAA-12].

The solution of obtained polyamic acid [PAA-12] is weighed in the conical flask for the 200ml for having stirrer 61.01g is added BCS 24.60g, NMP 36.91g, is stirred at room temperature 2 hours, and obtaining solid component concentration is 5.0 matter Amount %, NMP are the composition [AL-10] that 75 mass %, BCS are 20 mass %.

(comparing synthesis example 7)

The polymerization と polyimides [SPI-5:TDA of polyamic acid [PAA-13:TDA (100)/DA-5MG (100)] (100)/DA-5MG (100)] preparation

In the 100ml four-hole boiling flask for having nitrogen ingress pipe and mechanical agitator, make DA-5MG 3.72g, TDA 3.70g reacts 4 hours in NMP 66.88g, obtains the solution of polyamic acid [PAA-13].

The solution of obtained polyamic acid [PAA-13] is added in the 200ml conical flask for having stirrer 74.31g, NMP 72.31g, acetic anhydride 15.48g, pyridine 7.19g after being stirred at room temperature 30 minutes, are stirred 3 hours at 40 DEG C, Make its reaction.It after reaction terminating, is slowly injected into the methanol of 500g, polymer is precipitated, after stirring 30 minutes, by filtering back Receive solid.It after sufficiently cleaning obtained solid with methanol, is dried in vacuo at 100 DEG C, to obtain polyimides ([SPI-5]) powder.

GBL 80.00g, BCS 15.00g are added into obtained polyimide powder 5.00g, it is small in 50 DEG C of stirrings 6 When, it is the polyimide solution [SPI- that 80 mass %, BCS are 15 mass % that obtain solid component concentration, which be 5.0 mass %, NMP, 5a]。

(embodiment 1) [AL-1]: [SPI-1a]=80:20

It is mixed in such a way that [AL-1] is 80:20 with [SPI-1a] mass ratio, is stirred at room temperature 2 hours, obtains Aligning agent for liquid crystal.

(embodiment 2) [AL-2]: [SPI-1a]=80:20

It is mixed in such a way that [AL-2] is 80:20 with [SPI-1a] mass ratio, is stirred at room temperature 2 hours, obtains Aligning agent for liquid crystal.

(embodiment 3) [AL-3]: [SPI-1a]=80:20

It is mixed in such a way that [AL-3] is 80:20 with [SPI-1a] mass ratio, is stirred at room temperature 2 hours, obtains Aligning agent for liquid crystal.

(embodiment 4) [AL-3]: [SPI-2a]=80:20

It is mixed in such a way that [AL-3] is 80:20 with [SPI-2a] mass ratio, is stirred at room temperature 2 hours, obtains Aligning agent for liquid crystal.

(embodiment 5) [AL-5]: [SPI-1a]=80:20

It is mixed in such a way that [AL-5] is 80:20 with [SPI-1a] mass ratio, is stirred at room temperature 2 hours, obtains Aligning agent for liquid crystal.

(embodiment 6) [AL-6]: [SPI-1a]=80:20

It is mixed in such a way that [AL-6] is 80:20 with [SPI-1a] mass ratio, is stirred at room temperature 2 hours, obtains Aligning agent for liquid crystal.

(embodiment 7) [AL-3]: [SPI-3a]=80:20

It is mixed in such a way that [AL-3] is 80:20 with [SPI-3a] mass ratio, is stirred at room temperature 2 hours, obtains Aligning agent for liquid crystal.

(embodiment 8) [AL-4]: [SPI-1a]=80:20

It is mixed in such a way that [AL-4] is 80:20 with [SPI-1a] mass ratio, is stirred at room temperature 2 hours, obtains Aligning agent for liquid crystal.

(comparative example 1) [AL-9]: [SPI-1a]=80:20

It is mixed in such a way that [AL-9] is 80: 20 with [SPI-1a] mass ratio, is stirred at room temperature 2 hours, obtains Aligning agent for liquid crystal.

(comparative example 2) [AL-3]: [SPI-4a]=80: 20

It is mixed in such a way that [AL-3] is 80: 20 with [SPI-4a] mass ratio, is stirred at room temperature 2 hours, obtains Aligning agent for liquid crystal.

(comparative example 3) [AL-7]: [SPI-1a]=80: 20

It is mixed in such a way that [AL-7] is 80: 20 with [SPI-1a] mass ratio, is stirred at room temperature 2 hours, obtains Aligning agent for liquid crystal.

(comparative example 4) [AL-8]: [SPI-1a]=80: 20

It is mixed in such a way that [AL-8] is 80: 20 with [SPI-1a] mass ratio, is stirred at room temperature 2 hours, obtains Aligning agent for liquid crystal.

(comparative example 5) [AL-10]: [SPI-5a]=80: 20

It is mixed in such a way that [AL-10] is 80: 20 with [SPI-5a] mass ratio, is stirred at room temperature 2 hours, obtains Aligning agent for liquid crystal.

[table 3]

	VHR	RDC(V)	Rub resistance
				Embodiment 1	◎	○	○
Embodiment 2	◎	○	○
				Embodiment 3	◎	◎	○
Embodiment 4	◎	◎	○
				Embodiment 5	◎	○	○
Embodiment 6	◎	◎	○
				Embodiment 7	◎	◎	○
Embodiment 8	◎	◎	○
				Comparative example 1	○	×	○
Comparative example 2	◎	×	△
				Comparative example 3	○	×	○
Comparative example 4	○	×	○
				Comparative example 5	○	×	○

[table 4]

Composition	Volume resistivity [Ω cm]
		AL-1	7.5×10¹⁴
AL-2	7.8×10¹⁴
		AL-3	8.9×10¹⁴
AL-4	8.0×10¹⁴
		AL-5	6.5×10¹⁴
AL-6	9.4×10¹⁴
		AL-7	7.7×10¹³
AL-8	8.3×10¹³
		AL-9	4.5×10¹³
AL-10	7.5×10¹²

As shown in table 3, in the Examples 1 to 8 as the aligning agent for liquid crystal with following polymer, VHR and rub resistance It is excellent, and RDC is also very low, the polymer are as follows: make the tetracarboxylic acid sour component comprising TDA and comprising with above-mentioned formula (1) institute Polymer obtained from the diamine component reaction of the diamines of the side chain of expression；With make the tetracarboxylic acid sour component comprising TDA with only by leading Chain has-CR²¹ ₂Diamines constitute diamine component reaction obtained from polymer.

On the other hand, it is using not using TDA as the comparative example 2 of the polymer of raw material；Raw material has been used as (B) ingredient Diamine component also include main chain do not have-CR²¹ ₂Diamines polymer comparative example 1,3 and 4；Do not make as (A) ingredient In comparative example 5 with the diamines with side chain represented by formula (1), RDC is more significantly larger than Examples 1 to 8.It needs to illustrate , can be speculated by table 4: also not have-CR comprising main chain about having used²¹ ₂Diamines polymer composition [AL-7]~[AL-10], volume resistivity is low, therefore uses composition [AL-7]~[AL-10] as fB) comparison of ingredient The RDC of example 1,3~5 is big.

Claims

1. a kind of aligning agent for liquid crystal, which is characterized in that it contains following (A) ingredients and following (B) ingredients,

(A) ingredient: a kind of polymer, for selected from making tetracarboxylic acid sour component and diamine component carry out polyamides obtained from polymerization reaction Imines precursor and by least one of polyimides obtained from polyimide precursor imidizate polymer, the tetracarboxylic acid Sour component includes to be selected from 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic dianhydride, 3,4- dicarboxyl -1,2,3,4- tetrahydro - 1- naphthalene succinic diester and 3,4- dicarboxyl -1,2, at least one of 3,4- tetrahydro -1- naphthalene succinic diester dichloride, and And the diamine component includes the diamines with side chain represented by following formula (1),

In formula (1), P¹It is expressed as follows the divalent organic group :-O- ,-NHCO- ,-CONH- ,-COO- or can have N Or the alkyl of O, Q¹Indicate the phenyl ring of divalent, Q²Indicate the cyclohexane ring of divalent, Q³Indicate the phenyl ring or cyclohexane ring of divalent, p, q, r 0 or 1 integer is each independently represented, when p=1, q=1, r=0 and P when p=q=r=0¹It is not oxygen element, P²Indicate hydrogen The alkyl that atom, carbon atom number are 1~22 or the divalent organic group that the carbon atom number with steroid skeleton is 12~25,

(B) ingredient: a kind of polymer, for selected from making tetracarboxylic acid sour component and diamine component carry out polyamides obtained from polymerization reaction Imines precursor and by least one of polyimides obtained from polyimide precursor imidizate polymer, the tetracarboxylic acid Sour component includes to be selected from 3,4- dicarboxyl -1,2,3,4- tetrahydro -1- naphthalene succinic dianhydride, 3,4- dicarboxyl -1,2,3,4- tetrahydro - 1- naphthalene succinic diester and 3,4- dicarboxyl -1,2, at least one of 3,4- tetrahydro -1- naphthalene succinic diester dichloride,

Wherein,

In (B) ingredient, the diamine component is only made of the diamines represented by following formula (2),

In formula (2), two X each independently represent oxygen atom, and n indicates 1~10 integer, two R²²Each independently represent hydrogen The fluoro-alkyl or fluorine atom that alkyl that atom, carbon atom number are 1~5, carbon atom number are 1~5, or two R can be passed through²² It is combined and to form the alkylidene that carbon atom number is 2~7 and form cyclic structure,

In (A) ingredient, the diamines with side chain represented by formula (1) is diamines represented by following formula (3),

In formula (3), P¹Indicate divalent organic group, Q¹Indicate the phenyl ring of divalent, Q²Indicate the cyclohexane ring of divalent, Q³Indicate the benzene of divalent Ring or cyclohexane ring, p, q, r each independently represent 0 or 1 integer, P when p=1, q=1, r=0¹It is not oxygen element, P²It indicates The alkyl that hydrogen atom, carbon atom number are 1~22 or the divalent organic group that the carbon atom number with steroid skeleton is 12~25, The organic group is-O- ,-NHCO- ,-CONH- ,-COO- or the alkyl that can have N or O.

2. a kind of liquid crystal orientation film, which is characterized in that it is that aligning agent for liquid crystal described in claim 1 is applied to substrate and is burnt Obtained from system.

3. a kind of liquid crystal display element, which is characterized in that it is with liquid crystal orientation film as claimed in claim 2.