CN105579897B

CN105579897B - Aligning agent for liquid crystal and the liquid crystal orientation film for having used it

Info

Publication number: CN105579897B
Application number: CN201480052496.5A
Authority: CN
Inventors: 万代淳彦; 堀隆夫; 野口勇步
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2013-07-24
Filing date: 2014-07-23
Publication date: 2019-03-15
Anticipated expiration: 2034-07-23
Also published as: WO2015012316A1; TW201518408A; KR102266366B1; TWI643905B; KR20160034391A; JP6354759B2; CN105579897A; JPWO2015012316A1

Abstract

The present invention provides the aligning agent for liquid crystal for being capable of forming liquid crystal orientation film that is big with the adaptation of the sealant, substrate that use when production liquid crystal expression element and being improved with the interfacial characteristics of liquid crystal.Aligning agent for liquid crystal containing following (A) ingredients, (B) ingredient and (C) ingredient.(A) ingredient: the tetracarboxylic acid acid dialkyl ester derivative of tetracarboxylic acid acid dialkyl ester derivative shown in the formula (1) by the inclusion of 60mol% or more and poly amic acid ester obtained from the diamines polycondensation reaction comprising at least one kind of diamines in the group that the diamines shown in following formula (2)~(5) forms.(R₁: alkyl, the R of carbon number 1~5₂: hydroxyl etc., Me: methyl etc., A₁: key etc., A₂: halogen atom etc., a:1~4 integer) (B) ingredient: the polyamic acid as obtained from the polycondensation reaction of tetracarboxylic dianhydride and diamines.(C) ingredient: 2 functions or polyfunctional (methyl) acrylic acid or derivatives thereof.

Description

Aligning agent for liquid crystal and the liquid crystal orientation film for having used it

Technical field

It is taken the present invention relates to the aligning agent for liquid crystal containing poly amic acid ester for making liquid crystal orientation film and by the liquid crystal The liquid crystal orientation film obtained to agent.

Background technique

Liquid crystal used in LCD TV, liquid crystal display etc. indicates that element is usually provided in element for controlling liquid The liquid crystal orientation film of brilliant ordered state.As liquid crystal orientation film, cut-off mainly uses the liquid crystal orientation film of polyimides system so far, The liquid crystal orientation film of the polyimides system is by will be with polyimide precursors, soluble poly such as polyamic acids (poly- AMIC acid) Obtained from imido solution is coated on glass substrate etc. and is burnt into as the aligning agent for liquid crystal of principal component.

As liquid crystal indicates the high-definition of element, indicate that the contrast reduction of element, reduction afterimage are existing from inhibition liquid crystal As etc requirement set out, for liquid crystal orientation film, in the base for showing excellent liquid crystal aligning, stable pre-tilt angle On plinth, voltage retention is high, inhibit the residual charge when exchanging the afterimage generated due to driving, application DC voltage few and/ Or the characteristic that the residual charge accumulated by DC voltage quickly mitigates etc gradually becomes important.

Various motions have been carried out in order to make the liquid crystal orientation film of polyimides system meet requirement as described above.For example, It proposes: has been used in polyamides as the time short liquid crystal orientation film until the afterimage generated due to DC voltage disappears The also liquid crystal orientation film of the aligning agent for liquid crystal of the tertiary amine containing specific structure on the basis of amino acid, the polyamic acid containing imide (referring for example to patent document 1)；The liquid crystal orientation film of the aligning agent for liquid crystal containing soluble polyimide has been used, it is described solvable Property polyimides raw material use the specific diamine compound (referring for example to patent document 2) etc. with pyridine skeleton etc..In addition, Short liquid crystal orientation film of high as voltage retention and until disappearing to the afterimage generated by DC voltage time, proposition Using the liquid crystal orientation film of following aligning agent for liquid crystal, the aligning agent for liquid crystal polymerize containing polyamic acid, its imidizate On the basis of object etc., also there is 1 carboxylic acid containing the minimal amount of compound selected from intramolecular with 1 carboxylic acid group, intramolecular The compound and intramolecular of anhydride group have the compound in the compound of 1 tertiary amino (referring for example to patent document 3).

In addition, it is excellent as liquid crystal aligning, voltage retention is high, afterimage is few, the excellent in reliability and high pre-tilt angle of display Liquid crystal orientation film, it is also known to use liquid crystal containing polyamic acid, the aligning agent for liquid crystal of its imide amination polymer takes To film, tetracarboxylic dianhydride of the polyamic acid by specific structure and the tetracarboxylic dianhydride with cyclobutane and specific two amination Object is closed to obtain (referring for example to patent document 4).In addition, as occurring in the liquid crystal expression element of transverse electric field driving method because handing over The suppressing method of afterimage caused by stream drives proposes good using liquid crystal aligning and big with the interaction of liquid crystal molecule Specific liquid crystal orientation film method (referring to patent document 5).

But in recent years, big picture and the LCD TV of high-resolution become mainstream, and the requirement for afterimage becomes tighter Lattice, and require can tolerate the characteristic of the long-time service under harsh use environment.Concomitantly, liquid crystal orientation film used is reliable Property needs to be higher than previous, about each characteristic of liquid crystal orientation film, it is good not to require nothing more than initial stage characteristic, even if such as also requiring in height Good characteristic is also maintained after the lower exposure for a long time of temperature.

On the other hand, report claims: as the component of polymer for constituting polyimides system aligning agent for liquid crystal, poly amic acid ester Molecular weight reduction will not occur due to heat treatment when carrying out imidizate to it, therefore, the orientation stability of liquid crystal can It is excellent (referring to patent document 6) by property.Usually there is residual electricity when high volume resistivity, application DC voltage in poly amic acid ester The problems such as lotus is more, the liquid crystal aligning that excellent polyamic acid is blended in terms of thus disclosing poly amic acid ester and electrical characteristics Agent (referring to patent document 7).

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 9-316200 bulletin

Patent document 2: Japanese Unexamined Patent Publication 10-104633 bulletin

Patent document 3: Japanese Unexamined Patent Publication 8-76128 bulletin

Patent document 4: Japanese Unexamined Patent Publication 9-138414 bulletin

Patent document 5: Japanese Unexamined Patent Publication 11-38415 bulletin

Patent document 6: Japanese Unexamined Patent Publication 2003-26918 bulletin

Patent document 7:WO2011/15080 bulletin

Summary of the invention

Problems to be solved by the invention

As described above, have report claim: as it is described poly amic acid ester is blended with polyamic acid made of aligning agent for liquid crystal obtain To liquid crystal orientation film can obtain the excellent characteristic of liquid crystal aligning, electrical characteristics.That is, by containing poly amic acid ester and polyamide The obtained liquid crystal orientation film of aligning agent for liquid crystal of acid can obtain after image characteristic in ac/dc driving, long-term reliability side The characteristic that face is improved.

However, it was found that: it is coated with sealant for the liquid crystal alignment film surface on the substrate for being formed with liquid crystal orientation film, by two panels When substrate bonding indicates element to make liquid crystal, obtained by the aligning agent for liquid crystal containing poly amic acid ester and polyamic acid The cementability (adaptation) of liquid crystal orientation film and sealant, substrate is not enough.

As described above, recently in order to expand liquid crystal indicate element in effective pixel area, it is desirable that further decrease substrate The so-called frame region for not forming pixel of surrounding outer edge is improved by by poly amic acid ester and polyamide for the purpose The liquid crystal orientation film that aligning agent for liquid crystal made of acid is blended obtains becomes project for the cementability of sealant, substrate.

In turn, as described above, improving the cementability needs of liquid crystal orientation film and sealant, substrate is not reducing liquid crystal aligning It is completed under conditions of liquid crystal aligning that film has, electrical characteristics, if may, it also requires to further increase these characteristics.

The solution to the problem

The present invention is carried out to realize the above subject, has following purport.

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

(A) ingredient: the tetracarboxylic acid of tetracarboxylic acid acid dialkyl ester derivative shown in the following formula (1) by the inclusion of 60mol% or more Acid dialkyl ester derivant and two comprising at least one kind of diamines in the group that the diamines shown in following formula (2)~(5) forms Poly amic acid ester obtained from the polycondensation reaction of amine.

(R₁For the alkyl of carbon number 1~5, R₂For hydroxyl or chlorine atom, R_XFor the alkyl of carbon number 1~6.)

(A₁For the divalent organic group of singly-bound, ester bond, amido bond, thioester bond or carbon number 2~10, A₂For halogen atom, hydroxyl Base, amino, mercapto, nitro, phosphate or carbon number 1~20 1 valence organic group, the integer that a is 1~4, when a is 2 or more, A₂Structure can be the same or different.)

(B) ingredient: the polyamic acid as obtained from the polycondensation reaction of tetracarboxylic dianhydride and diamines.

(C) ingredient: 2 functions or polyfunctional (methyl) acrylic acid or derivatives thereof.

2. the aligning agent for liquid crystal according to above-mentioned 1, wherein the containing ratio of above-mentioned (A) ingredient and (B) ingredient is with quality It is calculated as 1/9~9/1 than (A/B), the content of (C) ingredient relative to the sum of (A) ingredient and (B) ingredient (100 mass %) is 0.1~ 10 mass %.

3. the aligning agent for liquid crystal according to above-mentioned 1 or 2, wherein it includes 40 that (A) ingredient, which is using relative to all diamines, The diamines of at least one kind of diamines in the group that the diamines shown in above-mentioned formula (2)~formula (5) forms of~100 moles of % and obtain The poly amic acid ester arrived.

4. the aligning agent for liquid crystal according to above-mentioned any one of 1~3, wherein (A) ingredient is using comprising selecting free style (2) diamines shown in diamines and formula shown in (3) composition group at least one kind of diamines and select diamines and formula shown in free style (4) (5) poly amic acid ester obtained from the diamines of at least one kind of diamines in the group of the composition of diamines shown in.

5. the aligning agent for liquid crystal according to above-mentioned any one of 1~4, wherein (A) ingredient is using comprising formula (2) institute Show poly amic acid ester obtained from diamines of the diamines at least one kind of diamines in the group for selecting diamines shown in free style (4) to form.

6. the aligning agent for liquid crystal according to above-mentioned any one of 1~5, wherein the A of above-mentioned formula (4)₂For following formula (6) Shown in structure.

-A₃-R₃ (6)

(the A in formula (6)₃For singly-bound ,-O- ,-S- ,-NR '₃, ester bond, amido bond, thioester bond, urea bond, carbonic acid ester bond or ammonia Carbamate key, R₃Selected from optionally with substituent group the alkyl of carbon number 1~10, alkenyl, alkynyl, aryl and by they combine and At group, they optionally have substituent group.R′₃Selected from hydrogen atom or alkyl, alkenyl, alkynyl, aryl and combine them Made of group, they optionally have substituent group.)

7. the aligning agent for liquid crystal according to above-mentioned any one of 1~6, wherein (A) ingredient is using comprising selected under State poly amic acid ester obtained from the diamines of at least one kind of diamines in the group of formula (A-1)~(A-5) diamines composition.

8. the aligning agent for liquid crystal according to above-mentioned 7, wherein (A) ingredient is using the diamines comprising above-mentioned formula (2) and choosing Freely poly amic acid ester obtained from the diamines of at least one kind of diamines in the group of above-mentioned formula (A-1)~(A-5) composition.

9. the aligning agent for liquid crystal according to above-mentioned any one of 1~8, wherein (B) ingredient is using comprising selected under State polyamic acid obtained from least one kind of tetracarboxylic dianhydride in the group of formula (B-1)~(B-9) tetracarboxylic dianhydride composition.

10. the aligning agent for liquid crystal according to above-mentioned any one of 1~9, wherein (B) ingredient is to pass through tetracarboxylic dianhydride Polyamic acid obtained from polycondensation reaction with diamines, the tetracarboxylic dianhydride contain 20 moles of % or more selected from by above-mentioned formula (B-1)~(B-9) at least one kind of tetracarboxylic dianhydride in group formed.

11. the aligning agent for liquid crystal according to above-mentioned any one of 1~10, wherein (B) ingredient be using comprising selected from by Polyamic acid obtained from least one kind of diamines in the group of following formula (B-10)~(B-14) composition.

12. the aligning agent for liquid crystal according to above-mentioned 11, wherein (B) ingredient is rubbed using 20 with all diamines Polyamides obtained from the diamines of at least one kind of diamines in the group being made of above-mentioned formula (B-10)~(B-14) of your % or more Amino acid.

13. the aligning agent for liquid crystal according to above-mentioned any one of 1~12, wherein (C) ingredient is dipentaerythritol 6 third Olefin(e) acid ester or glycerin diglycidyl ether acrylic acid adduct.

14. the aligning agent for liquid crystal according to above-mentioned any one of 1~13 also contains mixed organic solvents, described mixed Closing organic solvent includes at least one kind of organic solvent (D1) and choosing in the group being made of gamma-butyrolacton and its derivative It is at least one kind of organic in the group of free n-methyl-2-pyrrolidone, 1,3- dimethyl-imidazolinone and their derivative composition Solvent (D2), the content of organic solvent (D1) are 2~30 matter relative to the total amount of organic solvent (D1) and organic solvent (D2) Measure %.

15. the aligning agent for liquid crystal according to above-mentioned any one of 1~14 is used for the liquid crystal of light orientation processing to be carried out Alignment films.

16. a kind of liquid crystal orientation film is that aligning agent for liquid crystal described in above-mentioned any one of 1~15 is coated on substrate simultaneously Obtained from firing.

The effect of invention

Aligning agent for liquid crystal according to the present invention, being capable of forming indicates the sealant, the substrate that use when element with production liquid crystal Cementability (adaptation) sufficiently big liquid crystal orientation film.The rim area in liquid crystal expression element can also be sufficiently coped with as a result, Domain it is narrowing.

Also, the following characteristic of the liquid crystal orientation film obtained by aligning agent for liquid crystal of the invention is improved: being driven by exchange Liquid crystal and the interfacial characteristics and voltage retention of liquid crystal orientation film, ion concentration and direct current such as the reduction of afterimage caused by dynamic The electrical characteristics such as pressure residual.

Specific embodiment

[(A) ingredient]

Poly amic acid ester used in the present invention is the polyimide precursor for obtaining polyimides, is had because of heating And it is able to carry out the polymer at the position of following imidization reactions.

(A) ingredient of the invention is the polyamides as obtained from the polycondensation reaction of tetracarboxylic acid acid dialkyl ester derivative and diamines Amino acid ester, the tetracarboxylic acid acid dialkyl ester derivative include under the 60mol% or more of all tetracarboxylic acid acid dialkyl ester derivatives Tetracarboxylic acid acid dialkyl ester shown in formula (1) is stated, the diamines includes to form selected from the diamines shown in following formula (2)~formula (5) At least one kind of diamines in group.

In formula (1), R₁For the alkyl of carbon number 1~4, R₂For hydroxyl or chlorine atom.R_xFor the linear chain or branched chain alkane of carbon number 1~6 Base, the alkyl of preferably carbon number 1~3, particularly preferably methyl.

As R₁Concrete example, methyl, ethyl, propyl, butyl or tert-butyl can be enumerated.About poly amic acid ester, with The carbon number of alkyl increase, the temperature for carrying out imidizate gets higher, therefore, from the viewpoint of the easness of hot-imide, R₁Preferably methyl or ethyl, particularly preferably methyl.

R₂When for chlorine atom, bis- (chlorocarbonyl) compounds with high reactivity with diamine reactant can be become, therefore more preferable.

The diamines to carry out polycondensation with tetracarboxylic acid acid dialkyl ester derivative shown in formula (1), which preferably comprises, selects free style (2) At least one kind of diamines in the group of the composition of diamines shown in~formula (5).Wherein, comprising selecting diamines shown in free style (2) and formula (3) institute Show at least one kind of diamines in the group of diamines composition and selects in the group of the composition of diamines shown in diamines shown in free style (4) and (5) When at least one kind of diamines, the dissolubility of gamma-butyrolacton can be improved, so it is preferred that.Especially, for comprising diamines shown in formula (2) and When the diamines at least one kind of diamines in group for selecting diamines shown in free style (4) to form, the high liquid crystal of liquid crystal aligning can be obtained Alignment films, so it is preferred that.

In formula (3) and formula (5), A₁For the divalent organic group of singly-bound, ester bond, amido bond, thioester bond or carbon number 2~10.

A₁In, ester bond use-C (O) O- or-OC (O)-are indicated.

As amido bond ,-C (O) NH- ,-C (O) NR-, structure shown in-NHC (O)-or-NRC (O)-can be shown.R is Alkyl, alkenyl, alkynyl, aryl, thioester bond or the group for being composed them of carbon number 1~10.

As the concrete example of abovementioned alkyl, methyl, ethyl, propyl, butyl, tert-butyl, hexyl, octyl, ring can be enumerated Amyl, cyclohexyl, dicyclohexyl etc..

As alkenyl, can enumerate 1 or more CH present in abovementioned alkyl₂-CH₂Structure replacing is at CH=CH structure Obtained from alkenyl more specifically can enumerate vinyl, allyl, 1- acrylic, isopropenyl, 2- cyclobutenyl, 1,3- Butadienyl, 2- pentenyl, 2- hexenyl, cyclopropanyl, cyclopentenyl, cyclohexenyl group etc..

As alkynyl, can enumerate 1 or more CH present in aforesaid alkyl₂-CH₂Structure replacing at C ≡ C-structure and More specifically obtained alkynyl can enumerate acetenyl, 1- propinyl, 2-propynyl etc..

As aryl, such as phenyl can be enumerated.

As thioester bond, structure shown in-C (O) S- or-SC (O)-can be shown.

A₁For carbon number 2~10 divalent organic group when, can use following formula (6) representation.

-A₄-R₄-A₅-R₅-A₆- (6)

A in formula (6)₄、A₅And A₆It is each independently singly-bound ,-O- ,-S- ,-NR₈, ester bond, amido bond, thioester bond, urea Key, carbonic acid ester bond or urethane bond.As R₈, be the alkyl of hydrogen atom or carbon number 1~10, alkenyl, alkynyl, aryl, Or the group for being composed them, example identical with aforesaid alkyl, alkenyl, alkynyl and aryl can be enumerated.

A₄、A₅And A₆In, about ester bond, amido bond and thioester bond, can show and aforementioned ester bond, amido bond and thioester bond Identical structure.

As urea bond, structure shown in-NH-C (O) NH- or-NR-C (O) NR- can be shown.R is the alkane of carbon number 1~10 Base, alkenyl, alkynyl, aryl or the group for being composed them can enumerate and aforesaid alkyl, alkenyl, alkynyl and aryl phase Same example.

As carbonic acid ester bond, structure shown in-O-C (O)-O- can be shown.

As urethane bond ,-NH-C (O)-O- ,-O-C (O)-NH- ,-NR-C (O)-O- or-O-C can be shown (O) structure shown in-NR-.R is alkyl, alkenyl, alkynyl, aryl or the group for being composed them of carbon number 1~10, Example identical with aforesaid alkyl, alkenyl, alkynyl and aryl can be enumerated.

R in formula (6)₄And R₅Be each independently selected from the alkylidene of singly-bound or carbon number 1~10, alkenylene, alkynylene, Arlydene and the group for being composed them, they optionally have substituent group.R₄And R₅Any one of be singly-bound when, R₄ Or R₅Alkylidene, alkenylene, alkynylene, arlydene selected from carbon number 2~10 and the group for being composed them, they Optionally there is substituent group.

As above-mentioned alkylidene, can enumerate from structure made of 1 hydrogen atom of removal in aforesaid alkyl.It is more specific and Speech, can enumerate methylene, 1,1- ethylidene, 1,2- ethylidene, 1,2- propylidene, 1,3- propylidene, Isosorbide-5-Nitrae-butylidene, 1,2- Butylidene, 1,2- pentylidene, 1,2- hexylidene, 2,3- butylidene, 2,4- pentylidene, 1,2- ring propylidene, 1,2- ring butylidene, 1,3- ring butylidene, 1,2- ring pentylidene, 1,2- cyclohexylene etc..

As above-mentioned alkenylene, can enumerate from structure made of 1 hydrogen atom of removal in foregoing alkenyl.It is more specific and Speech, can enumerate 1,1- ethenylidene, 1,2- ethenylidene, 1,2- ethenylidene methylene, 1- methyl-1,2- ethenylidene, 1,2- ethenylidene -1,1- ethylidene, 1,2- ethenylidene -1,2- ethylidene, 1,2- ethenylidene -1,2- propylidene, 1,2- Ethenylidene -1,3- propylidene, 1,2- ethenylidene -1,4- butylidene, 1,2- ethenylidene -1,2- butylidene etc..

As alkynylene, can enumerate from structure made of 1 hydrogen atom of removal in aforementioned alkynyl.More specifically, may be used Enumerate ethynylene, ethynylene methylene, ethynylene -1,1- ethylidene, ethynylene -1,2- ethylidene, sub- acetylene Base -1,2- propylidene, ethynylene -1,3- propylidene, ethynylene -1,4- butylidene, ethynylene -1,2- butylidene etc..

As arlydene, can enumerate from structure made of 1 hydrogen atom of removal in aforesaid aryl.More specifically, may be used Enumerate 1,2- phenylene, 1,3- phenylene, 1,4- phenylene etc..

If above-mentioned alkylidene, alkenylene, alkynylene, arlydene and the group for being composed them total carbon number be 1~ 20, then optionally there is substituent group, and then ring structure can also be formed via substituent group.It should be noted that via substituent group shape Refer at ring structure: substituent group bonds together and forms ring structure or substituent group and be bonded with a part of female skeleton and form ring knot Structure.

Example as the substituent can enumerate halogen group, hydroxyl, mercapto, nitro, organic oxygroup, organic sulfur Base, Organosilyl, acyl group, ester group, thioester substrate, phosphate-based, amide groups, aryl, alkyl, alkenyl, alkynyl etc..

As the halogen group for belonging to substituent group, fluorine atom, chlorine atom, bromine atom or iodine atom can be enumerated.

As the organic oxygroup for belonging to substituent group, the knot that alkoxy, alkenyloxy group, aryloxy group etc. are indicated with-O-R can be shown Structure.As the R, aforesaid alkyl, alkenyl, aryl etc. can be exemplified.These R are optionally further substituted with foregoing substituents.As The concrete example of alkoxy can enumerate methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy etc..

As the organic sulfenyl for belonging to substituent group, the knot that alkylthio group, alkenylthio group, arylthio etc. are indicated with-S-R can be shown Structure.As the R, aforesaid alkyl, alkenyl, aryl etc. can be exemplified.These R are optionally further substituted with foregoing substituents.As The concrete example of alkylthio group can enumerate methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl etc..

As the Organosilyl for belonging to substituent group ,-Si- (R) can be shown₃Shown in structure.The R can be identical Can be different, aforesaid alkyl, aryl etc. can be exemplified.These R can be further substituted with foregoing substituents.As alkyl first silicon The concrete example of alkyl can enumerate trimethyl silyl, triethylsilyl, tripropylsilyl base, tributyl first silicon Alkyl etc..

As the acyl group for belonging to substituent group, structure shown in-C (O)-R can be shown.As the R, aforementioned alkane can be exemplified Base, alkenyl, aryl etc..These R can be further substituted with foregoing substituents.As the concrete example of acyl group, formyl can be enumerated Base, acetyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl, benzoyl etc..

As the ester group for belonging to substituent group, structure shown in-C (O) O-R or-OC (O)-R can be shown.It, can as the R Exemplify aforesaid alkyl, alkenyl, aryl etc..These R can be further substituted with foregoing substituents.

As the thioester substrate for belonging to substituent group, structure shown in-C (S) O-R or-OC (S)-R can be shown.As the R, Aforesaid alkyl, alkenyl, aryl etc. can be exemplified.These R can be further substituted with foregoing substituents.

As the phosphate-based of substituent group is belonged to ,-OP (O)-(OR) can be shown₂Shown in structure.The R can be identical Can be different, aforesaid alkyl, aryl etc. can be exemplified.These R can be further substituted with foregoing substituents.

As the amide groups for belonging to substituent group ,-C (O) NH can be shown₂Or-C (O) NHR ,-NHC (O) R ,-C (O) N (R)₂ Or structure shown in-NRC (O) R.The R can be the same or different, and can exemplify aforesaid alkyl, aryl etc..These R can be with It is further substituted with foregoing substituents.

As the aryl for belonging to substituent group, group identical with aforesaid aryl can be enumerated.The aryl optionally further takes , there are aforementioned other substituent groups in generation.

As the alkyl for belonging to substituent group, group identical with aforesaid alkyl can be enumerated.The alkyl optionally further takes , there are aforementioned other substituent groups in generation.

As the alkenyl for belonging to substituent group, group identical with foregoing alkenyl can be enumerated.The alkenyl optionally further takes , there are aforementioned other substituent groups in generation.

As the alkynyl for belonging to substituent group, group identical with aforementioned alkynyl can be enumerated.The alkynyl optionally further takes , there are aforementioned other substituent groups in generation.

When using diamines with High Linear structure, upright and outspoken structure, the liquid crystal with good liquid crystal aligning can be obtained Alignment films, therefore, as A₁Structure, more preferably singly-bound or following formula (A1-1)~(A1-25) structure.

In above-mentioned formula (4) and formula (5), A₂For halogen atom, hydroxyl, amino, mercapto, nitro, phosphate or carbon number 1 ~20 1 valence organic group, the integer that a is 1~4, when a is 2 or more, A₂Structure can be the same or different.

As halogen atom, halogen atom identical with the example of aforementioned halogen atoms can be enumerated.

As amino ,-NH can be shown₂, structure shown in-NHR or-NR (R)-.R is alkyl, the alkene of carbon number 1~10 Base, alkynyl, aryl or the group for being composed them can enumerate identical as aforesaid alkyl, alkenyl, alkynyl and aryl Example.

As 1 valence organic group of carbon number 1~20, organic oxygroup, organic sulfenyl, Organosilyl, acyl can be enumerated Base, ester group, thioester substrate, phosphate-based, amide groups, alkyl, alkenyl, alkynyl or aryl.

As organic oxygroup, the structure that alkoxy, alkenyloxy group, aryloxy group etc. are indicated with-O-R can be shown.As the R, Aforesaid alkyl, alkenyl, aryl etc. can be exemplified.As the concrete example of alkoxy, can enumerate methoxyl group, ethyoxyl, propoxyl group, Butoxy, amoxy, hexyloxy etc..

As organic sulfenyl, the structure that alkylthio group, alkenylthio group, arylthio etc. are indicated with-S-R can be shown.As the R, Aforesaid alkyl, alkenyl, aryl etc. can be exemplified.As the concrete example of alkylthio group, can enumerate methyl mercapto, ethylmercapto group, rosickyite base, Butylthio, penta sulfenyl, own sulfenyl etc..

As Organosilyl ,-Si- (R) can be shown₃Shown in structure.The R can be the same or different, can Exemplify aforesaid alkyl, aryl etc..As the concrete example of aIkylsilyl groups, trimethyl silyl, triethyl group can be enumerated Silicyl, tripropylsilyl base, tributylsilyl etc..

As acyl group, structure shown in-C (O)-R can be shown.As the R, aforesaid alkyl, alkenyl, aryl can be exemplified Deng.As the concrete example of acyl group, formoxyl, acetyl group, propiono, bytyry, isobutyryl, valeryl, isoamyl can be enumerated Acyl group, benzoyl etc..

As ester group, structure shown in-C (O) O-R or-OC (O)-R can be shown.As the R, aforementioned alkane can be exemplified Base, alkenyl, aryl etc..

As thioester substrate, structure shown in-C (S) O-R or-OC (S)-R can be shown.As the R, can exemplify aforementioned Alkyl, alkenyl, aryl etc..These R can be further substituted with foregoing substituents.

As phosphate-based ,-OP (O)-(OR) can be shown₂Shown in structure.The R can be the same or different, can Exemplify aforesaid alkyl, aryl etc..

As amide groups ,-C (O) NH can be shown₂、-C(O)NHR、-NHC(O)R、-C(O)N(R)₂Or shown in-NRC (O) R Structure.The R can be the same or different, and can exemplify aforesaid alkyl, aryl etc..

As alkyl, alkenyl, alkynyl and aryl, base identical with aforesaid alkyl, alkenyl, alkynyl and aryl can be enumerated Group.

If abovementioned alkyl, alkenyl, alkynyl and aryl total carbon number be 1~20, can have substituent group, and then can also be with Ring structure is formed via substituent group.Refer to it should be noted that forming ring structure between substituent group: substituent group bonds together and shape It is bonded at ring structure or substituent group with a part of female skeleton and forms ring structure.

Example as the substituent can enumerate halogen group, hydroxyl, mercapto, nitro, organic oxygroup, organic sulfur Base, Organosilyl, acyl group, ester group, thioester substrate, phosphate-based, amide groups, carbamate groups, aryl, alkyl, alkenyl, Alkynyl etc..

As the organic oxygroup for belonging to substituent group, knot shown in the use such as alkoxy, alkenyloxy group, aryloxy group-O-R can be shown Structure.As the R, aforesaid alkyl, alkenyl, aryl etc. can be exemplified.These R can be further substituted with foregoing substituents.As The concrete example of alkoxy can enumerate methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygroup in heptan, pungent oxygen Base, nonyl epoxide, decyloxy, laurel oxygroup etc..

As the organic sulfenyl for belonging to substituent group, the knot that alkylthio group, alkenylthio group, arylthio etc. are indicated with-S-R can be shown Structure.As the R, aforesaid alkyl, alkenyl, aryl etc. can be exemplified.These R can be further substituted with foregoing substituents.As The concrete example of alkylthio group can enumerate methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl, sulfenyl in heptan, pungent sulphur Base, nonyl sulfenyl, last of the ten Heavenly stems sulfenyl, laurel sulfenyl etc..

As the Organosilyl for belonging to substituent group ,-Si- (R) can be shown₃Shown in structure.The R can be identical Can be different, aforesaid alkyl, aryl etc. can be exemplified.These R can be further substituted with foregoing substituents.As alkyl first silicon The concrete example of alkyl can enumerate trimethyl silyl, triethylsilyl, tripropylsilyl base, tributyl first silicon Alkyl, three amyl silicyls, three hexyl silicyls, amyl dimethyl silicyl, hexyl dimetylsilyl, octyl Dimetylsilyl, decyl dimethyl silicyl etc..

As the amide groups for belonging to substituent group ,-C (O) NH can be shown₂、-C(O)NHR、-NHC(O)R、-C(O)N(R)₂、 Or structure shown in-NRC (O) R.The R can be the same or different, and can exemplify aforesaid alkyl, aryl etc..These R can be with It is further substituted with foregoing substituents.

As the carbamate groups for belonging to substituent group ,-O-C (O) NH can be shown₂、-O-C(O)NHR、-NHC(O)-OR Or structure shown in-NR-C (O) OR.The R can be the same or different, and can exemplify aforesaid alkyl, aryl etc..These R can To be further substituted with foregoing substituents.

As the alkyl for belonging to substituent group, the identical group of aforesaid alkyl can be enumerated.The alkyl is optionally further substituted with There are aforementioned other substituent groups.

In formula (4) and formula (5), A₂When with alkyl, alkenyl, alkynyl, aryl or the group for being composed them, Carbon number is preferably 1~14.A₂For the alkyl of 15 or more carbon number, alkenyl, alkynyl, aryl or the group for being composed them When, with the content of diamines used, it is possible to make liquid crystal aligning reduction or uncontrollable pre-tilt angle.

A in above-mentioned formula (4) and formula (5)₂Preferably structure shown in following formula (6).

-A₃-R₃ (6)

A in formula (6)₃For singly-bound ,-O- ,-S- ,-NR '₃, ester bond, amido bond, thioester bond, urea bond, carbonic acid ester bond or ammonia Carbamate key, R₃Selected from optionally with the carbon number 1~10 of substituent group, preferably 1~5 alkyl, alkenyl, alkynyl, aryl and general The group that they are composed, they optionally have substituent group.R′₃Selected from hydrogen atom or alkyl, alkenyl, alkynyl, aryl and The group that they are composed, they optionally have substituent group.)

In turn, A₂Structure be the structure with the leaving group being detached from by heating diamines when, polymer can be improved Dissolubility, and will not influence liquid crystal aligning and pre-tilt angle.As the A with the leaving group being detached from by heating₂'s Structure shown in structure, preferably following formula (A2-1)~(A2-24).

As the ratio of diamines shown in above-mentioned formula (2)~(5), 5~100 moles of % of preferably all diamines.Above-mentioned formula (2) ratio of diamines shown in~(5) is higher, then more can obtain the liquid crystal orientation film with good liquid crystal aligning, therefore more Preferably 40~100 moles of %, further preferably 60~100 moles of %.

Wherein, it as the diamines for belonging to (A) component materials, preferably comprises and selects shown in diamines shown in free style (2) and formula (3) Diamines composition group at least one kind of diamines and select diamines shown in diamines shown in free style (4) and formula (5) form group in At least one kind of diamines.As the diamines for belonging to (A) component materials, particularly preferably comprising diamines shown in formula (2) and free style (4) are selected At least one kind of diamines in the group of shown diamines composition.It especially can be improved the dissolubility in solvent gamma-butyrolacton as a result,.

At this point, total dosage of diamines shown in diamines shown in the dosage or formula (2) of diamines shown in formula (2) and formula (3) is opposite Total dosage of diamines shown in diamines shown in the dosage or formula (4) of the diamines shown in formula (4) and formula (5) is preferred with terms of mole ratios It is 95/5~60/40, more preferably 90/10~80/20.

The more upright and outspoken structure of the structure of diamines then more can obtain the excellent liquid crystal orientation film of liquid crystal aligning, therefore, As the diamines for obtaining poly amic acid ester of the present invention, preferably containing selected from being made of following formula (A-1)~formula (A-5) The diamines of at least one kind of diamines in group, the particularly preferably diamines containing diamines shown in the diamines and above-mentioned formula (2).At this point, The dosage of diamines shown in above-mentioned formula (2) and at least one kind of diamines in the group being made of diamines formula (A-1)~formula (A-5) The molar ratio of dosage is preferably 95/5~60/40, more preferably 90/10~80/20.

In the present invention, tetracarboxylic acid acid dialkyl ester shown in above-mentioned formula (1) is preferably the 60 of all tetracarboxylic acid acid dialkyl esters to rub You are % or more, more preferably 80 moles of % or more.Wherein, further preferably 90~100 moles of %.At this point it is possible to by following Tetracarboxylic acid acid dialkyl ester derivative one shown in tetracarboxylic acid acid dialkyl ester derivative shown in formula (10)~(11) and above-mentioned formula (1) With as tetracarboxylic acid derivatives.

In above-mentioned formula (10)~(11), X is 4 valence organic groups, R₁Include the case where preference inside with formula (1) phase Together.X is not particularly limited, if enumerating its concrete example, can enumerate structure shown in following X-1~X-46.In addition, these Two or more can be used in tetracarboxylic acid derivatives.

In addition, in the present invention, diamines shown in above-mentioned formula (2)~(5) is preferably 5~100 moles of %, more of all diamines Preferably 50~100 moles of %.It can be used two shown in following formula (12) together with diamines shown in above-mentioned formula (2)~(5) Amine.

In formula (12), R₆And R₇It is each independently alkyl, the alkenyl of hydrogen atom, the optionally carbon number 1~10 with substituent group Or alkynyl.As these alkyl, the concrete example of alkenyl or alkynyl, group identical with aforementioned group can be enumerated.

If total carbon number of abovementioned alkyl, alkenyl or alkynyl is 1~10, substituent group can have, and then can also be via Substituent group forms ring structure.Refer to it should be noted that forming ring structure via substituent group: substituent group bonds together and forms ring Structure or substituent group are bonded with a part of female skeleton and form ring structure.

Example as the substituent can enumerate halogen group, hydroxyl, mercapto, nitro, aryl, organic oxygroup, have Machine sulfenyl, Organosilyl, acyl group, ester group, thioester substrate, phosphate-based, amide groups, alkyl, alkenyl, alkynyl etc..As each The concrete example of substituent group can enumerate group identical with aforementioned group.

In general, when importing bulky structure, it is possible to the reactivity of amino, liquid crystal aligning are reduced, therefore, As R₆And R₇, the more preferably alkyl of hydrogen atom or the optionally carbon number 1~5 with substituent group, particularly preferably hydrogen atom, first Base or ethyl.

In above-mentioned formula (12), Y is divalent organic group.Y is not particularly limited, if enumerating concrete example, can enumerate down State structure shown in formula Y-1~Y-113.In addition, two or more can be used in these diamines with Y.Wherein, good in order to obtain Linear high diamines is preferably directed into poly amic acid ester, as Y, more preferably Y-7, Y-10, Y- by good liquid crystal aligning 11、Y-12、Y-13、Y-21、Y-22、Y-23、Y-25、Y-26、Y-27、Y-41、Y-42、Y-43、Y-44、Y-45、Y-46、Y- 48, the diamines of Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75 or Y-98.In addition, it is desirable to when improving pre-tilt angle, It is preferred that importing side chain into poly amic acid ester has chain alkyl, aromatic ring, aliphatic ring, steroid skeleton or by their groups The diamines of structure made of conjunction, as Y, more preferably Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y- 84, the diamines of Y-85, Y-86, Y-87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96 or Y-97.It is logical It crosses and these diamines is added with the amount of 1~50 mole of % of all diamines, more preferable 5~20 moles of %, can show arbitrary Pre-tilt angle.

[(B) ingredient]

Polyamic acid used in the present invention is the polyimide precursor for obtaining polyimides, is had due to heating It is able to carry out the polymer at the position of following imidization reactions.

(B) ingredient of the invention is the polyamic acid as obtained from the polycondensation reaction of tetracarboxylic dianhydride and diamines.Tetracarboxylic acid Acid dianhydride can be indicated with following formula (13), in formula, X₁For 4 valence organic groups, structure is not particularly limited.It is provided if enumerating Body example can then enumerate above-mentioned formula (X-1)~(X-46) structure.

Diamine compound can be indicated with following formula (14), in formula, Y₁For divalent organic group, structure is not limited especially It is fixed.If enumerating concrete example, the structure of above-mentioned formula (Y-1)~(Y-99) and (Y-110)~(Y-113) can be enumerated.

(in formula, R₆And R₇It is identical as each definition of above-mentioned formula (12).)

(B) when ingredient is present in film surface with more laying particular stress on, it is possible to hinder the orientation of liquid crystal.On the other hand, if it is possible to So that (A) ingredient is present in film surface with more laying particular stress on, then can obtain excellent liquid crystal aligning and reliability, after image characteristic are also excellent Liquid crystal orientation film.Thus, as the polyamic acid of (B) ingredient, as preferably improving the surface mobility of (A) ingredient The polyamic acid that polarity is high, dissolubility is high.From this point of view, preferably by containing selected from by above-mentioned formula (B-1)~(B- 9) form group in the tetracarboxylic dianhydride of at least one kind of tetracarboxylic dianhydride and the polycondensation reaction of diamines obtained from polyamic acid.

The use ratio at least one kind of tetracarboxylic dianhydride in group for selecting free style (B-1)~(B-9) to form is relative to all Tetracarboxylic dianhydride is preferably 5~100 moles of %.The use ratio is higher, then more can be improved the polarity and dissolution of polymer Property, therefore, more preferably 20~100 moles of %, further preferably 40~100 moles of %.

In addition, from the same viewpoint, by using the diamines with highly polar substituent group, can make as (B) at The polyamic acid divided is present in more laying particular stress on inside film and substrate interface.As the diamines with highly polar substituent group, preferably Diamines containing secondary amino group or tertiary amino, hydroxyl, amide groups, urea groups or carboxyl.As concrete example, as above-mentioned formula (14) Y₁, Y-19, Y-31, Y-40, Y-45, Y-49~Y-51, Y-61, Y-98 or Y-99 can be enumerated, more preferably containing carboxyl Y-98 or Y-99.

As the dosage of the diamine compound with highly polar substituent group, rub relative to all diamines, preferably 5~100 You are %.The dosage is higher, then the polarity of polymer more improves, the film surface ratio of (A) ingredient becomes higher, therefore, more preferably For 10~100 moles of %, further preferably 30~100 moles of %.

As the tetracarboxylic dianhydride for belonging to (B) component materials, preferably comprising selected from by following formula (B-1)~(B-9) At least one kind of tetracarboxylic dianhydride in the group of tetracarboxylic dianhydride's composition.

It is preferable to use (B) component materials by least one kind of tetracarboxylic dianhydride in group for selecting free style (B-1)~(B-9) to form 20 moles of % or more of all tetracarboxylic dianhydrides used, 40 moles of % or more are more preferably used.Wherein, (B-1) is particularly preferred Use 60 moles of % or more.

On the other hand, as the diamines for belonging to (B) component materials, preferably comprising selected from by following formula (B-10)~(B- 13) at least one kind of diamines in the group formed.

It is preferable to use (B) component materials at least one kind of diamines in the group being made of above-mentioned formula (B-10)~(B-13) 20 moles of % or more of all diamines used, 40 moles of % or more are more preferably used.Wherein, (B-10) particularly preferably uses 60 Mole % or more.

Diamines as described above with photoreactive group can also be according to liquid crystal aligning when being made liquid crystal orientation film Property, the characteristics such as pre-tilt angle, voltage retention performance, accumulated charge and the liquid crystal response speed that liquid crystal is made when indicating element etc. And it using a kind or is mixed with two or more.

In addition, it is preferable to use make in the synthesis of (A) ingredient and/or (B) ingredient for this diamines with photoreactive group 5~50 moles of % of all diamine components, more preferably 10~20 moles of %.

[(C) ingredient]

(C) ingredient of the invention is 2 functions or polyfunctional (methyl) acrylic acid or derivatives thereof.(C) is at split-phase It is preferably 0.1~10 mass %, more preferably 1~5 mass % for the sum of (A) ingredient and (B) ingredient (100 mass %).

As the preferred concrete example of (C) ingredient, ARONIX M-210, ARONIX M-240, ARONIX can be enumerated M-6200 (East Asia synthetic chemical industry Co. Ltd. system), KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604, KAYARAD R-684 (Nippon Kayaku K. K's system), V260, V312, V335HP (Osaka Organic Chemical Industry Co., Ltd. System)；Light Acrylate BA-4EA, Light Acrylate BP-4PA, Light Acrylate BP-2PA (common prosperity society Oil chemical industry Co. Ltd. system) etc. 2 functions (methyl) acrylic acid derivative；ARONIX M-400,ARONIX M-405, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060 (East Asia synthetic chemical industry strain formula meeting Society's system), KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD It is more than 3 functions of DPCA-120 (Nippon Kayaku K. K's system), VGPT (Osaka Organic Chemical Industry Co., Ltd.'s system) etc. more Function (methyl) acrylic acid derivative.Wherein, dipentaerythritol hexaacrylate, glycerin diglycidyl ether propylene can be enumerated Sour addition product etc..

[organic solvent]

Aligning agent for liquid crystal of the invention contains to dissolve or disperse (A) ingredient~(C) ingredient organic solvent.Have Solvent does not limit.

As the organic solvent, can enumerate can dissolve the solvent of poly amic acid ester and polyamic acid (hereinafter referred to as Good solvent) and painting film uniformity when aligning agent for liquid crystal being applied to substrate for improving solvent (hereinafter referred to as lean solvent) this Two kinds.

As good solvent, as long as dissolving the polyamic acid as the poly amic acid ester of (A) ingredient and as (B) ingredient Solvent is just not particularly limited.If enumerating its concrete example, n,N-Dimethylformamide, N, N- diethyl formyl can be enumerated Amine, DMAC N,N' dimethyl acetamide, N- ethyl-2-pyrrolidone, N- methyl caprolactam, 2-Pyrrolidone, N- ethyl pyrrolidine Ketone, n-vinyl pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 3- methoxyl group-N, N- bis- Methyl propanamide etc..They can be used a kind or are mixed with two or more.In addition, when being used alone, even insoluble Mixing of more than two kinds can also be made as long as can also mix in the range of polymer is not precipitated in the solvent of polymer Solvent.

It is just not particularly limited as lean solvent as long as surface tension is low and makes to apply the solvent that film uniformity improves.If Its concrete example is enumerated, then can enumerate ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl card must Alcohol acetic ester, ethylene glycol, 1- methoxy-2-propanol, 1- ethyoxyl -2- propyl alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- third Alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol -1- monomethyl ether -2- acetic acid esters, propylene glycol -1- list ethyl Ether -2- acetic acid esters, butyl cellosolve acetate, dipropylene glycol, 2- (2- ethoxy-c oxygroup) propyl alcohol, methyl lactate, lactic acid second Ester, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc..Two or more can be applied in combination in these solvents.

In the present invention, organic solvent is preferably following mixed solvent: comprising selected from by gamma-butyrolacton and its derivative group At group at least one kind of organic solvent (D1) and selected from by n-methyl-2-pyrrolidone, 1,3- dimethyl-imidazolinone and At least one kind of organic solvent (D2) in the group of their derivative composition, and the content of organic solvent (D2) is relative to organic molten The total amount of agent (D1) and organic solvent (D2) are preferably 2~30 mass %.The content of organic solvent (D2) is more preferably 5~20 matter Measure %.

As the example of the gamma-butyrolacton for belonging to organic solvent (D1) or derivatives thereof, as long as with lactone structure Organic solvent, there is no particular limitation, due to being suitable as dissolving the solvent of (A) ingredient poly amic acid ester of the invention, Particularly preferably gamma-butyrolacton or gamma-valerolactone.

As belong to the n-methyl-2-pyrrolidone of organic solvent (D2), 1,3- dimethyl-imidazolinone or they spread out Biology, can enumerate n-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, n-vinyl-2-pyrrolidone, N- methyl oneself Lactams, 2-Pyrrolidone or 1,3- dimethyl-imidazolinone.When boiling point is excessively high, solvent is possible to remain in film, makes conduct The characteristic of liquid crystal orientation film deteriorates, therefore preferably n-methyl-2-pyrrolidone or 1,3-Dimethyl-2-imidazolidinone, More preferably n-methyl-2-pyrrolidone.

(A) ingredient poly amic acid ester of the invention is high for the compatibility of organic solvent (D1), can be readily dissolved in this A little organic solvents.But (A) ingredient poly amic acid ester is low for the compatibility of organic solvent (D2), when more containing quantitative change, (A) Ingredient poly amic acid ester is possible to be precipitated, influence the phase-separated state of poly amic acid ester and polyamic acid.Therefore, organic solvent (D2) content is 2~30 mass %, more preferably 2~20 matter relative to the total amount of organic solvent (D1) and organic solvent (D2) Measure %, particularly preferably 5~15 mass %.

The suitable range of organic solvent (D2) content is also different because of the coating method of aligning agent for liquid crystal, in flexible printing method In the case of, solvent composition when coating is less likely to occur to change, therefore more preferably 5~30 mass %, further preferably 5~ 15 mass %.

On the other hand, in the case where carrying out ink-jet application method, aligning agent for liquid crystal when coating becomes small drop, because This, the solvent composition before coating is possible to different from the solvent composition after aligning agent for liquid crystal liquid to substrate.Specifically, steam Press high gamma-butyrolacton and its derivative coating when volatilization, liquid to substrate when gamma-butyrolacton and its derivative content It tails off.It is therefore preferable that for organic solvent (D1) more solvent compositions, the content of organic solvent (D2) is more preferably 2~15 matter Measure %, further preferably 2~10 mass %.

[manufacturing method of poly amic acid ester]

(A) ingredient, that is, poly amic acid ester of aligning agent for liquid crystal of the invention can be manufactured using well known manufacturing method.Tool For body, (a) below and (b) method can be enumerated, but not limited thereto.

(a) by the method for acyl chlorides and diamine compound manufacture poly amic acid ester

Poly amic acid ester can be manufactured by bis- (chlorocarbonyl) compounds and diamine compound.

Specifically, can be by making bis- (chlorocarbonyl) compounds and diamine compound in the presence of alkali and organic solvent 30 minutes~24 hours are reacted with -20~140 DEG C, preferably with 0~50 DEG C, preferably reacts 1~4 hour and manufactures.Aforementioned bases can To use pyridine, triethylamine or 4-dimethylaminopyridine, in order to make reacting balance progress and preferably pyridine.The additive amount mistake of alkali When more, it is difficult to remove, when the additive amount of alkali is very few, molecular weight becomes smaller, and is 2~4 times accordingly, with respect to bis- (chlorocarbonyl) compounds Mole, preferably 2~2.5 times moles.

For manufacturing the solvent of poly amic acid ester from monomer and polymer solubility preferably N- methyl -2- pyrrolidines Ketone or gamma-butyrolacton, they can be used a kind or are mixed with two or more.

When excessive concentration when manufacture, it is easy to happen the precipitation of polymer, when concentration when manufacture is too low, molecular weight will not Rise, therefore, the total amount of bis- (chlorocarbonyl) compounds and diamine compound in reaction solution is preferably 1~30 mass %, more excellent It is selected as 5~20 mass %.In addition, (chlorocarbonyl) compound hydrolysis bis- in order to prevent, the solvent for manufacturing poly amic acid ester are excellent Choosing is dehydrated as far as possible, and reaction carries out preferably in nitrogen atmosphere, and outer gas is prevented to be mixed into.

(b) by the method for dialkyl ester dicarboxylic acids and diamine compound manufacture poly amic acid ester

Poly amic acid ester can use condensing agent and is condensed by tetracarboxylic acid acid dialkyl ester and diamine compound to manufacture.

Specifically, can be by making dialkyl ester dicarboxylic acids and diamine compound in condensing agent, alkali and organic solvent In the presence of with 0~140 DEG C, preferably with 0~100 DEG C react 30 minutes~24 hours, preferably react 3~15 hours and manufacture.

Triphenyl phosphite, dicyclohexylcarbodiimide, 1- ethyl -3- (3- dimethylamino can be used in aforementioned condensation agent Propyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-cyanuro 1,3,5 methyl morpholine, O- (benzo three Azoles -1- base)-N, N, N ', N '-tetramethylurea tetrafluoro boric acid ester, O- (benzotriazole -1- base)-N, N, N ', N '-tetramethylurea six Fluorophosphoric acid ester, (2,3- dihydro -2- thia -3- benzoxazolyl) phosphonic acid diphenyl ester etc..The additive amount of condensing agent is relative to dioxane Base ester dicarboxylic acids is preferably 2~3 times moles, more preferably 2~2.5 times moles.

The tertiary amines such as pyridine, triethylamine can be used in aforementioned bases.It is difficult to remove when the additive amount of alkali is excessive, the additive amount mistake of alkali When few, molecular weight becomes smaller, and is preferably 2~4 times moles, more preferably 2.5~3 times moles accordingly, with respect to diamine component.

It is special since the poly amic acid ester of high molecular weight can be obtained among the manufacturing method of above two poly amic acid ester It is not preferably (a) method.

By the way that the solution of poly amic acid ester obtained from operation as above is injected into lean solvent while stirring, Polymer can be made to be precipitated.After being precipitated and being cleaned with lean solvent for several times, air drying or heat drying are carried out, can be obtained Powder through the poly amic acid ester refined.

Aforementioned lean solvent is not particularly limited, and can enumerate water outlet, methanol, ethyl alcohol, hexane, butyl cellosolve, acetone, toluene Deng.

[manufacture of polyamic acid]

The polyamic acid of (B) ingredient of aligning agent for liquid crystal of the invention or the raw material as (A) ingredient poly amic acid ester It can be manufactured by the polycondensation of tetracarboxylic dianhydride and diamine compound.

It, can be by making tetracarboxylic dianhydride and diamine compound preferably in presence of organic solvent when manufacturing polyamic acid 30 minutes~24 hours are reacted with -20~140 DEG C, preferably with 0~50 DEG C, preferably reacts 1~12 hour and manufactures.

For manufacturing the organic solvent of polyamic acid from the dissolubility of monomer and polymer preferably N, N- dimethyl Formamide, n-methyl-2-pyrrolidone or gamma-butyrolacton, they can be used a kind or are mixed with two or more.When manufacture Excessive concentration when, be easy to happen the precipitation of polymer, when concentration when manufacture is too low, molecular weight will not become larger, therefore, tetracarboxylic acid The total amount of acid dianhydride and diamine compound in reaction solution is preferably 1~30 mass %, more preferably 5~20 mass %.

Polyamic acid obtained from operation can not wanted to make liquid crystal aligning using its reaction solution as (B) as above The case where in agent containing polymerization solvent used etc., can be used as polymer after recycling in solid form, be used as the present invention (B) ingredient.

Polymer can make it be precipitated and recycle by being injected into lean solvent while reaction solution is sufficiently stirred.Into After line number time is precipitated and is cleaned with lean solvent, air drying or heat drying are carried out, the polyamic acid through refining can be obtained Powder.

Diamine component used in polymerization reaction and tetracarboxylic acid derivatives (tetracarboxylic dianhydride, tetrabasic carboxylic acid dialkyl derivatives Deng) ratio be preferably 1:0.7~1:1.2 with molar ratio computing from the viewpoint of controlling molecular weight.The molar ratio is closer to 1: 1, then the molecular weight of gained polyimide precursor becomes bigger.The molecular weight of poly amic acid ester and polyamic acid will affect varnish When the molecular weight of the physical strength of viscosity, polyimide film, poly amic acid ester and polyamic acid is excessive, the coating operations of varnish Property, apply film uniformity be deteriorated sometimes.In addition, gained polyimides film strength becomes inadequate sometimes when molecular weight is too small.

Therefore, the molecular weight of poly amic acid ester of the invention and polyamic acid with Weight-average molecular meter be preferably 2,000~ 500,000,5,000~300,000, further preferably 10,000~100,000 are more preferably.

(aligning agent for liquid crystal)

(A) ingredient and the containing ratio of (B) ingredient in aligning agent for liquid crystal of the invention are preferably in terms of mass ratio (A/B) 1/9~9/1, it is more preferably 3/7~7/3.By making the ratio be in the range, it is capable of providing liquid crystal aligning and electrical characteristics Good aligning agent for liquid crystal.

In addition, the content of (C) ingredient in aligning agent for liquid crystal of the invention is relative to the sum of (A) ingredient and (B) ingredient (100 mass %) be preferably 0.1 mass % or more, more preferably 1.0 mass % or more, further preferably 3.0 mass % with On.(C) when the content of ingredient is few, improve bonding of the liquid crystal orientation film obtained by aligning agent for liquid crystal relative to sealant and substrate The effect of property is insufficient.On the other hand, from the viewpoint of liquid crystal aligning, the content of (C) ingredient be preferably 15 mass % with Under, particularly preferably 10 mass % or less.

On the other hand, the total content (concentration) of (A) ingredient in aligning agent for liquid crystal of the invention and (B) ingredient can be according to thinking The thickness of liquid crystal orientation film to be formed sets to suitably change, but the uniform and flawless film this point from formation, It is preferably 0.5 mass % or more relative to organic solvent, from the viewpoint of the storage stability of solution, preferably 15 mass % Below, it is particularly preferably 1~10 mass %.

Aligning agent for liquid crystal of the invention can also contain the various additives such as silane coupling agent, crosslinking agent.Silane coupling agent Be in order to further increase want coating of liquid crystalline alignment agent substrate and liquid crystal orientation film formed thereon adaptation and add 's.It is exemplified below out the concrete example of silane coupling agent, but not limited thereto.

3-aminopropyltriethoxysilane, 3- (2- amino-ethyl) TSL 8330,3- (2- amino second Base) aminopropylmethyldimethoxysilane, 3- TSL 8330,3- phenyl amino propyl trimethoxy silicon The amine such as alkane, 3- triethoxysilyl-N- (1,3- dimethylbutylene) propylamine, 3- aminopropyl diethoxymethylsilane It is silane coupling agent；Vinyltrimethoxysilane, vinyltriethoxysilane, vinyl three (2- methoxy ethoxy) silicon Alkane, vinyl methyl dimethoxysilane, vinyltriacetoxy silane, vinyl silane triisopropoxide, allyl three Methoxy silane, the ethylene base system silane coupling agent to styryltrimethoxysilane etc.；3- glycidoxypropyl group front three Oxysilane, 3- epoxy propoxy propyl triethoxysilane, 3- glycidoxypropyl diethoxy silane, 3- epoxy The epoxies base system such as propoxypropyl methyl dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane silane is even Join agent；3- methacryloxypropylmethyl dimethoxysilane, 3- methacryloxypropyl trimethoxy silane, 3- The metering systems such as methacryloxypropyl methyl diethoxysilane, 3- methacryloxypropyl Acyl group system silane coupling agent；The acryloyls base system silane coupling agent such as 3- acryloyloxypropyltrimethoxysilane；3- urea propyl The urea groups such as triethoxysilane system silane coupling agent；Bis- (3- (triethoxysilyl) propyl) disulphide, bis- (3- (three Triethoxysilyl) propyl) tetrasulfide sulfides system silane coupling agent；3- mercapto propyl methyl dimethoxy silane, The sulfydryls system silane coupling agents such as 3-mercaptopropyi trimethoxy silane, 3- decoyl sulfenyl -1- propyl-triethoxysilicane；3- isocyanide The isocyanates base system silane coupling agents such as perester radical propyl-triethoxysilicane, 3- isocyanate group propyl trimethoxy silicane； The aldehyde such as triethoxysilyl butyraldehyde system silane coupling agent；Triethoxysilylpropyltetrasulfide methyl carbamate, (3- tri- Triethoxysilyl propyl) the carbamate systems silane coupling agent such as t-butylcarbamate.

When the additive amount of above-mentioned silane coupling agent is excessive, unreacted substance causes bad shadow to liquid crystal aligning sometimes It rings, when additive amount is very few, can not embody to adaptation bring effect, the solid component accordingly, with respect to polymer is preferably 0.01~5.0 weight %, more preferably 0.1~1.0 weight %.

When adding above-mentioned silane coupling agent, the precipitation of polymer in order to prevent, preferably in addition for improving aforementioned film Silane coupling agent is added before the solvent of uniformity.In addition, addition silane coupling agent when, can by polyamic acid ester solution with Before polyamic acid solution is mixed, it is added to polyamic acid ester solution, polyamic acid solution or polyamic acid ester solution In polyamic acid solution the two.Furthermore it is possible to be added in poly amic acid ester-polyamic acid mixed solution.Silane is even Joining agent is added to improve the adaptation of polymer and substrate, as the adding method of silane coupling agent, more preferably It is following method, is added to more to lay particular stress on and is present in inside film and in the polyamic acid solution of substrate interface, makes in solution Polymer sufficiently reacted with silane coupling agent after, then mix with polyamic acid ester solution.

When being burnt into film, in order to efficiently promote the imidizate of poly amic acid ester, imidizate can be added Promotor.It is exemplified below out the concrete example of the imidizate promotor of poly amic acid ester, but not limited thereto.

D in above-mentioned formula (D-1)~(D-17) is each independently tert-butoxycarbonyl or 9- fluorenylmethoxycarbonyl groups. It should be noted that in a formula of (D-14)~(D-17), there are multiple D, but they each other can be identical or different.

As long as promoting in the range of can obtain the effect for promoting the hot-imide of poly amic acid ester to imidizate Content into agent is not particularly limited, the amide for the following formula (12) for being included relative to the poly amic acid ester in aligning agent for liquid crystal 1 mole of acid esters position, preferably 0.01 mole or more, more preferably 0.05 mole or more, be more preferably 0.1 mole with On.In addition, in film after it will be burnt into remaining imidizate promotor itself caused by each characteristic of liquid crystal orientation film not Good influence detention to minimum limit this point is set out, the following formula for being included relative to the poly amic acid ester in aligning agent for liquid crystal (12) 1 mole of amic acid esters position, imidizate promotor is preferably 2 moles or less, more preferably 1 mole or less, into one Preferably 0.5 mole or less of step.

When adding imidizate promotor, it is possible to promote imidizate because of heating, therefore preferably with good solvent and poor It is added again after solvent dilution.

Aligning agent for liquid crystal of the invention can also use the various additives such as crosslinking agent needless to say.In addition, of the invention (A) ingredient poly amic acid ester and (B) ingredient polyamic acid can respectively be two or more.

Gathering comprising poly amic acid ester ((A) ingredient) and polyamic acid ((B) ingredient) in aligning agent for liquid crystal of the invention The concentration (content) for closing object can be set according to the thickness of polyimide film to be formed suitably change, relative to organic solvent, It is preferably set to 1~10 mass %, more preferably 2~8 mass %.When concentration is less than 1 mass %, it is difficult to form uniform and zero defect Film, concentration be more than 10 mass % when, sometimes solution storage stability be deteriorated.

[manufacturing method of aligning agent for liquid crystal]

Aligning agent for liquid crystal of the invention includes poly amic acid ester ((A) ingredient) and polyamic acid ((B) with specific structure Ingredient).

Ratio as (A) ingredient relative to (A) ingredient and the total amount of (B) ingredient, preferably 5~95 mass %.(A) at When the ratio divided is few, it is possible to sufficient liquid crystal aligning can not be obtained, when the ratio of (B) ingredient is few, it is possible to can not obtain Effect of the present invention.Therefore, the ratio as (A) ingredient, more preferably 20~80 mass %, further preferably 30~ 70 mass %.

As the method for mixing (A) ingredient with (B) ingredient, there are as below methods: by (A) ingredient poly amic acid ester and (B) powder of ingredient polyamic acid is mixed, and the method for being dissolved in organic solvent；By the powder of (A) ingredient poly amic acid ester The method that end is mixed with (B) ingredient polyamic acid solution；By (A) ingredient polyamic acid ester solution and (B) ingredient polyamide The method that the powder of acid is mixed；(A) ingredient polyamic acid ester solution is mixed with (B) ingredient polyamic acid solution Method.Even if also can in the case where dissolution (A) ingredient poly amic acid ester is different with the good solvent of (B) ingredient polyamic acid Uniform (A) ingredient poly amic acid ester-(B) ingredient polyamic acid mixed solution is obtained, it is therefore, more preferably that (A) ingredient is poly- The method that amic acid esters solution is mixed with (B) ingredient polyamic acid solution.

As the method for preparation (A) ingredient polyamic acid ester solution, more preferably with gamma-butyrolacton or derivatives thereof, its The method that its good solvent dissolves the powder of (A) ingredient poly amic acid ester, further preferably with gamma-butyrolacton or derivatives thereof into The method of row dissolution.At this point, polymer concentration is preferably 10~30%, particularly preferably 10~15%.In addition, dissolution (A) at When dividing the powder of poly amic acid ester, it can be heated.Heating temperature is preferably 20~150 DEG C, 20~80 DEG C particularly preferred.

As the method for preparation (B) ingredient polyamic acid solution, there are as below methods: the powder of polyamic acid being made to be dissolved in N- N-methyl-2-2-pyrrolidone N, 1,3- dimethyl pyrrolidone or aforementioned good solvent and the method that polyamic acid solution is made；Directly The method using polymeric reaction solution is connect, the method for polymeric reaction solution is more preferably directly used.It may further be preferable that will gather Gamma-butyrolacton or derivatives thereof and n-methyl-2-pyrrolidone, 1,3- dimethyl pyrrolidine is made in solvent when closing polyamic acid The mixed solvent of ketone or derivatives thereof, thus the method for obtaining polyamic acid solution.When polyamic acid powder is redissolved, Polymer concentration is preferably 10~30%, particularly preferably 10~15%.In addition, can be heated when the powder of dissolution polymer. Heating temperature is preferably 20~150 DEG C, particularly preferably 20~80 DEG C.

It, can be mixed by (A) ingredient polyamic acid ester solution and (B) ingredient polyamic acid solution when adding silane coupling agent Before conjunction, (A) ingredient polyamic acid ester solution, (B) ingredient polyamic acid solution or (A) ingredient poly amic acid ester are added to In solution and (B) ingredient polyamic acid solution the two.Furthermore it is possible to which it is poly- to be added to (A) ingredient poly amic acid ester-(B) ingredient In the mixed solution of amic acid.Silane coupling agent is added to improve the adaptation of polymer and substrate, as silane The adding method of coupling agent, more preferably following method are added to more to lay particular stress on and are present in inside film and substrate interface (B) ingredient polyamic acid solution in, after reacting polymer sufficiently with silane coupling agent, then with (A) ingredient poly amic acid ester Solution mixing.When the additive amount of silane coupling agent is excessive, unreacted silane coupling agent sometimes causes liquid crystal aligning bad It influences, when very few, can not embody to adaptation bring effect, accordingly, with respect to the solid component of polymer, preferably 0.01 ~5.0 mass %, more preferably 0.1~1.0 mass %.

When (A) ingredient polyamic acid ester solution is mixed with (B) ingredient polyamic acid solution, polymer concentration is preferred It is 10~30%, particularly preferably 10~15%.In addition, can heat when mixing, heating temperature is preferably 20~100 DEG C, spy It You Xuanwei not be 20~60 DEG C.

When adding silane coupling agent, crosslinking agent, the precipitation of polymer in order to prevent is preferably carried out before adding lean solvent Addition.In addition, when film is burnt into, in order to efficiently promote the imidizate of poly amic acid ester, acid imide can be added Change promotor.When adding imidizate promotor, it is possible to imidizate is promoted because of heating, it is therefore preferable that with good solvent and It is added again after lean solvent dilution.

It is aforementioned good molten as being added in (A) the ingredient poly amic acid ester obtained by and the mixed solution of (B) ingredient polyamic acid Agent and aforementioned lean solvent are diluted in the form of reaching defined polymer concentration, can obtain liquid crystal aligning of the invention Agent.

[liquid crystal orientation film]

Liquid crystal orientation film of the invention can by being coated on substrate after preferably filtering above-mentioned aligning agent for liquid crystal, it is dry, Firing is to be made film.As the substrate that be coated with aligning agent for liquid crystal of the present invention, without spy as long as the high substrate of the transparency It does not limit, glass substrate, silicon nitride board, the plastic bases such as acrylic compounds substrate, polycarbonate substrate etc. can be used, conform to the principle of simplicity , it is preferable to use being formed with ITO (tin indium oxide, the Indium Tin Oxide) electricity for driving liquid crystal from the perspective of chemical industry skill Extremely equal substrate.In addition, the liquid crystal of reflection-type indicates, if being only single sided substrate, silicon wafer etc. also to can be used no in element The material of the meeting reflected light such as aluminium also can be used in transparency material, electrode at this time.

As the coating method of aligning agent for liquid crystal of the invention, spin-coating method, print process, ink-jet method etc. can be enumerated.Coating After aligning agent for liquid crystal of the invention, film is preferably through drying, firing.In order to sufficiently remove contain in aligning agent for liquid crystal it is organic molten Agent, it is preferably preferably 1~10 minute dry with 50~120 DEG C.Then, preferably with 150~300 DEG C, more preferably with 150~250 DEG C It is burnt into.Firing time is different because of firing temperature, preferably carries out 5~120 minutes, more preferably carries out 5~60 minutes.

The thickness of liquid crystal orientation film of the invention is not particularly limited, and when thickness is excessively thin, liquid crystal indicates the reliability of element Sometimes it reduces, therefore is 5~300nm, preferably 10~200nm.It, can by carrying out the orientation process such as brushing to the coated surface As liquid crystal orientation film.The method for carrying out orientation process to the film can enumerate brushing method, light orientation position logos etc..

Liquid crystal orientation film of the invention is the liquid crystal aligning that liquid crystal aligning ability is endowed by irradiation polarization radioactive ray Film.In turn, the light irradiation range for showing liquid crystal aligning is wider than previous light orientation liquid crystal orientation film, even if in exposure intensity In generation real estate in the case where unevenness, uniform and good liquid crystal aligning can be also obtained.

As the concrete example of light orientation position logos, following method can be enumerated: aforementioned film coated surface is irradiated along one The radioactive ray for determining direction polarization are according to circumstances further heated with 150~250 DEG C of temperature, to assign liquid crystal Alignment capability.As radioactive ray, ultraviolet light and luminous ray with 100~800nm wavelength can be used.Wherein, preferably Ultraviolet light with 100~400nm wavelength, particularly preferably with the ultraviolet light of 200~400nm wavelength.In addition, in order to improve Liquid crystal aligning can will apply ilm substrate and be heated with 50~250 DEG C, while irradiate radioactive ray.The irradiation of aforementioned radioactive ray Amount is preferably in 1~10,000mJ/cm²Range, particularly preferably be in 100~5,000mJ/cm²Range.

[liquid crystal aligning element]

It operates as above, production two panels is formed with the substrate of liquid crystal orientation film, with the orientation position of each liquid crystal orientation film Managing direction is vertical or antiparallel mode across gap (cell gap) oppositely disposed two plate base, uses sealant fitting two The peripheral portion of plate base injects filling liquid crystal into the cell gap demarcated by substrate surface and sealant, seals injection hole And constitute liquid crystal cells.Also, in the outer surface of liquid crystal cells, i.e. on another surface side of each substrate of composition liquid crystal cells, with The polarization direction of the polarizing film mode consistent or vertical with the brushing direction of the liquid crystal orientation film for the one side for being formed in the substrate is pasted Polarizing film is closed, indicates element so as to obtain liquid crystal.

In the present invention, as sealant, such as it is preferable to use with both reactions of epoxy group and (methyl) acryloyl group The solidified resin system of property group.Wherein, it as long as the pollution caused by liquid crystal is low, is not limited completely.Sealing of the invention In agent, inorganic filler can be compounded for the purpose for improving cementability, moisture-proof.As workable inorganic filler, Be not particularly limited, specifically, can enumerate spherical silicon dioxide, fused silica, crystalline silica, titanium oxide, Titanium is black, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talcum, clay, aluminium oxide, Magnesia, zirconium oxide, aluminium hydroxide, calcium silicates, alumina silicate, lithium aluminium silicate, zirconium silicate, barium titanate, glass fibre, carbon fiber, Molybdenum disulfide, asbestos etc., preferably spherical silicon dioxide, fused silica, crystalline silica, titanium oxide, titanium is black, nitrogenizes Silicon, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talcum, clay, aluminium oxide, aluminium hydroxide, calcium silicates or alumina silicate. Aforementioned inorganic filler can be mixed with two or more.

Embodiment

It is exemplified below out embodiment, is further elaborated with the present invention.Wherein, the present invention is not limited to the examples Property explain.It should be noted that the measuring method of the abbreviation of following compound and each characteristic is as follows.

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

GBL: gamma-butyrolacton

BCS: butyl cellosolve

IPA:2- propyl alcohol

DE-1: referring to following formula (DE-1)；

DA-1: referring to following formula (DA-1)；

DA-2: referring to following formula (DA-2)；

DA-3: referring to following formula (DA-3)；

DA-4: referring to following formula (DA-4)；

Me: methyl, Bu: normal-butyl, Boc: tert-butoxy

Additive A: dipentaerythritol hexaacrylate (DAICEL-ALLNEX LTD. system)

Additive B: glycerin diglycidyl ether acrylic acid adduct (trade name: EPOXY ESTER 80MFA, common prosperity society Chemical Co., Ltd. system)

[viscosity]

The viscosity of poly amic acid ester and polyamic acid solution uses TVE-22H (Toki Sangyo Co., Ltd. of E type viscosimeter System), it is measured at sample size 1.1ml, cone rotor TE-1 (1 ° 34 ', R24), 25 DEG C of temperature.

[molecular weight]

The molecular weight of poly amic acid ester and polyamic acid is measured using GPC (room temperature gel is impregnated with chromatography) device, with Polyethylene glycol (polyethylene oxide) scaled value meter calculates number-average molecular weight (hereinafter also referred to Mn) and weight average molecular weight (below Referred to as Mw).

GPC device: Shodex corporation (GPC-101)

Column: Shodex corporation (series connection of KD803 and KD805)

Column temperature: 50 DEG C

Eluent: n,N-Dimethylformamide (as additive, one water of lithium bromide and object (LiBrH₂It O) is 30mmol/ L (liter), phosphoric acid anhydrous crystal (orthophosphoric acid) are 30mmol/L, tetrahydrofuran (THF) is 10ml/L)

Flow velocity: 1.0ml/ minutes

Standard curve making standard sample: (weight is equal for the TSK standard polyethylene oxide for having used TOSOH Co., Ltd to manufacture Molecular weight (Mw) is about 900,000,150,000,100,000 and 30,000) and Polymer Laboratories Ltd. manufacture Polyethylene glycol (peak molecular weight (Mp) is about 12,000,4,000 and 1,000).In order to avoid the overlapping at peak, respectively for Lower two kinds of samples implement measurement: by 900,000,100,000,12,000 and 1,000 these four samples for mixing；And By 150,000,30,000 and 4,000 these three samples for mixing.

[production of FFS driving liquid crystal cells]

Prepare electroded substrate first.Substrate is having a size of 30mm × 35mm and with a thickness of the glass substrate of 0.7mm.? It is formed on substrate and constitutes counter electrode and have the IZO electrode of solid shape pattern as the 1st layer.In the 1st layer of counter electrode SiN (silicon nitride) film that upper formation is formed a film with CVD method is as the 2nd layer.The film thickness of 2nd layer of SiN film is 500nm, conduct Interlayer dielectric and function.Configured with the comb teeth-shaped picture for being patterned and being formed to IZO film on the 2nd layer of SiN film Plain electrode is as the 3rd layer, so as to form the 1st pixel and the 2nd pixel the two pixels.The size of each pixel be vertical 10mm and Horizontal about 5mm.At this point, the 1st layer of counter electrode is electrically insulated with the 3rd layer of pixel electrode by the effect of the 2nd layer of SiN film.

" < " font electrode element that there is 3rd layer of pixel electrode center portion to bend is constituted through multiple arrangements Comb teeth-shaped shape.The width of the width direction of each electrode element is 3 μm, between electrode element between be divided into 6 μm.Form each pixel " < " font electrode element for being bent by center portion of pixel electrode constituted through multiple arrangements, therefore the shape of each pixel Shape not instead of oblong-shaped has bending in the same manner as electrode element in center portion, " < " similar to runic The shape of word.Also, each pixel is divided using the bending part in its center as boundary up and down, and the 1st of the upside with bending part the 2nd region in region and downside.

When comparing the 1st region and 2 region of each pixel, the formation direction of the electrode element of their pixel electrode is constituted It is different.That is, using the liquid crystal aligning direction of aftermentioned liquid crystal orientation film as when benchmark, in the 1st region of pixel, to be presented+10 ° The mode of angle form the electrode element of pixel electrode, in the 2nd region of pixel, the shape in a manner of -10 ° of angle is presented The electrode element of pixel electrode.That is, the 1st region of each pixel is constituted as follows with the 2nd region: by pixel electrode and opposite direction Apply voltage between electrode and the liquid crystal that induces, spinning movement (plane switching) in real estate direction phase negative side each other To.

Then, by after 1.0 μm of filter filtering of aligning agent for liquid crystal, aligning agent for liquid crystal is coated on by rotary coating On the above-mentioned electroded substrate prepared.On 80 DEG C of hot plate after drying 2 minutes, with 230 DEG C of heated air circulation type baking oven Firing 14 minutes, to form the film that film thickness is 100nm.Across polarizing film with 500mJ/cm²254nm is irradiated to the coated surface Ultraviolet light, to obtain the substrate with liquid crystal orientation film.In addition, in not formed electrode and there are 4 μm of height as opposite substrate Column spacer glass substrate on similarly form film, and implement orientation process.

As described above, with two plate bases for one group, the printing and sealing agent on substrate, by another substrate with liquid crystal orientation film Face-to-face, after the mode that differently- oriented directivity reaches 0 ° is pasted, make sealant cures and make dummy cell.By depressurizing injection method Liquid crystal MLC-2041 (MERCK CORPORATION system) is injected into the dummy cell, seals inlet, to obtain FFS driving Liquid crystal cells.

[exchange of liquid crystal cells drives ghost]

Using the liquid crystal cells of above-mentioned production, under 60 DEG C of isoperibol with the frequency of 30Hz apply 144 hours ± 10V alternating voltage.Thereafter, make that short-circuit condition is presented between the pixel electrode of liquid crystal cells and counter electrode, directly at room temperature It places one day.

After placement, liquid crystal cells are arranged between the two panels polarizing film configured in the vertical mode of polarizing axis, not Backlight is lighted in the state of application voltage, adjusts the arrangement angles of liquid crystal cells so that the brightness of transmitted light reaches minimum.And And rotation angle when will rotate liquid crystal cells to the most dark angle in the 1st region from the most dark angle in the 2nd region of the 1st pixel Degree is calculated as angle delta.2nd pixel similarly operates, and compares the 2nd region and the 1st region, calculates same angle delta.And And the average value of the 1st pixel and the angle delta value of the 2nd pixel is calculated as the angle delta of liquid crystal cells.Exchange driving is residual It is denoted as when shadow Δ is less than 0.1 well, exchange driving ghost Δ is denoted as bad when being 0.1 or more.

500mL four-neck flask with agitating device is made nitrogen atmosphere, addition p-phenylenediamine 4.58g (42.4mmol), DA-1 1.79g (4.71mmol), NMP 84.7g, GBL 254g and the pyridine 8.40g (106mmol) as alkali, stirring make it Dissolution.Then, which is added to DE-1 14.4g (44.2mmol), while stirring with 15 DEG C of one nights of reaction.It stirs It after mixing a night, adds acryloyl chloride 1.23g (13.6mmol), is reacted 4 hours with 15 DEG C.By the solution one of gained poly amic acid ester Side stirring is put on one side into 1477g IPA, and the white precipitate that leaching is precipitated then cleans 5 times with 738g IPA and carries out It is dry, to obtain the poly amic acid ester toner 17.3g of white.Yield is 96.9%.In addition, point of the poly amic acid ester Son amount is Mn=14,288, Mw=29,956.

Gained poly amic acid ester toner 3.69g is placed in 100mL conical flask, adds GBL 33.2g, at room temperature It stirs 24 hours and makes it dissolve, to obtain polyamic acid ester solution PAE-1.

To addition 3,5- diaminobenzoic acid 0.91g in the 100mL four-neck flask with agitating device and with nitrogen ingress pipe (5.98mmol), 4,4 '-diamino-diphenylamine 4.78g (23.9mmol), NMP 13.3g and GBL 6.66g, one side supplying nitrogen It stirs and makes it dissolve on one side.The diamine solution is added to 1,2,3,4- butane tetracarboxylic acid dianhydride 4.76g while stirring (24.0mmol) adds GBL 9.99g, and is stirred at room temperature 2 hours.Then, after adding GBL 20.0g and stirring, addition Benzenetetracarboxylic dianhydride 1.31g (6.00mmol) adds GBL 4.80g, is stirred at room temperature 24 hours, to obtain polyamic acid Solution (PAA-1).Viscosity at 25 DEG C of gained polyamic acid solution is 4,147mPas.In addition, the molecular weight of polyamic acid Mn=24,333, Mw=60,010.

To addition 3,5- diaminobenzoic acid 0.30g in the 100mL four-neck flask with agitating device and with nitrogen ingress pipe (1.98mmol), 4,4 '-diamino-diphenyl methylamine 1.71g (8.02mmol), NMP 2.25g and GBL 11.3g, convey on one side Nitrogen is stirred on one side and is made it dissolve.The diamine solution is added to 1,2,3,4- butane tetracarboxylic acid dianhydride while stirring 1.72g (8.68mmol) adds GBL 4.50g, and is stirred at room temperature 2 hours.Then, benzenetetracarboxylic dianhydride 0.22g is added (1.01mmol) adds GBL 4.50g, is stirred at room temperature 24 hours, to obtain polyamic acid solution (PAA-2).Gained Viscosity at 25 DEG C of polyamic acid solution is 232mPas.In addition, the molecular weight Mn=9 of polyamic acid, 870, Mw=20, 054。

500mL four-neck flask with agitating device is made nitrogen atmosphere, addition p-phenylenediamine 2.50g (23.1mmol), DA-3 0.59g (1.22mmol), NMP 42.8g, GBL 129g and the pyridine 4.34g (54.9mmol) as alkali, stirring make it Dissolution.Then, which is added to DE-1 7.44g (22.9mmol), while stirring with 15 DEG C of one nights of reaction.It stirs It after mixing a night, adds acryloyl chloride 0.63g (7.01mmol), is reacted 4 hours with 15 DEG C.By the solution one of gained poly amic acid ester Side stirring is put on one side into 574g IPA, and the white precipitate that leaching is precipitated then is cleaned 5 times with 382g IPA, and carried out It is dry, to obtain the poly amic acid ester toner 8.82g of white.Yield is 97.8%.In addition, point of the poly amic acid ester Son amount is Mn=16,617, Mw=37,387.

Gained poly amic acid ester toner 0.80g is placed in 100mL conical flask, GBL 7.20g is added, stirs at room temperature It mixes 24 hours and makes it dissolve, to obtain polyamic acid ester solution PAE-2.

500mL four-neck flask with agitating device is made nitrogen atmosphere, addition p-phenylenediamine 1.23g (11.3mmol), 4,4 '-ethylene aniline 0.80g (3.77mmol), NMP 27.0g, GBL 91.2g and the pyridine 2.69g as alkali (34.0mmol), stirs to dissolve.Then, which is added into DE-1 4.61g while stirring (14.2mmol), with 15 DEG C of one nights of reaction.It after being stirred overnight, adds acryloyl chloride 0.39g (4.34mmol), with 15 DEG C of reactions 4 Hour.The solution of gained poly amic acid ester is put into while stirring into 384g IPA, the white precipitate that leaching is precipitated, Then, 5 times are cleaned with 256g IPA and be dried, to obtain the poly amic acid ester toner 5.11g of white.Yield is 89.6%.In addition, the molecular weight of the poly amic acid ester be Mn=14,806, Mw=32,719.

Gained poly amic acid ester toner 0.80g is placed in 100mL conical flask, GBL 7.20g is added, stirs at room temperature It mixes 24 hours and makes it dissolve, to obtain polyamic acid ester solution PAE-3.

500mL four-neck flask with agitating device is made nitrogen atmosphere, addition p-phenylenediamine 2.80g (25.9mmol), DA-2 1.45g (6.47mmol), NMP 111g and pyridine 6.18g (78.1mmol) as alkali, stir to dissolve.Then, The diamine solution is added while stirring DE-1 9.89g (30.4mmol), with 15 DEG C of one nights of reaction.After being stirred overnight, add Add acryloyl chloride 0.38g (4.21mmol), is reacted 4 hours with 15 DEG C.The solution of gained poly amic acid ester is .ed while stirring Into 1230g water, the white precipitate that leaching is precipitated then cleans 5 times with the IPA of 1230g and is dried investment, thus Obtain the poly amic acid ester toner 10.2g of white.Yield is 83.0%.In addition, the molecular weight of the poly amic acid ester is Mn =20,786, Mw=40,973.

Gained poly amic acid ester toner 0.798g is placed in 100mL conical flask, adds GBL 7.18g, at room temperature It stirs 24 hours and makes it dissolve, to obtain polyamic acid ester solution PAE-4.

Nitrogen atmosphere is made in 500mL four-neck flask with agitating device, adds DA-4 14.4g (58.8mmol), DA-1 2.48g (6.53mmol), NMP 622g and pyridine 11.6g (147mmol) as alkali, stir to dissolve.Then, by this two Amine aqueous solution is added in DE-1 20.0g (61.4mmol) while stirring, with 15 DEG C of one nights of reaction.After being stirred overnight, addition Acryloyl chloride 1.70g (18.8mmol) is reacted 4 hours with 15 DEG C.The solution of gained poly amic acid ester is thrown while stirring Enter into 2691g IPA, the white precipitate that leaching is precipitated, then, cleans 5 times with 1345g IPA and be dried, thus To the poly amic acid ester toner 31.4g of white.Yield is 95.9%.In addition, the molecular weight of the poly amic acid ester is Mn= 13,012, Mw=25,594.

Gained poly amic acid ester toner 3.70g is placed in 100mL conical flask, NMP 33.3g is added, stirs at room temperature It mixes 24 hours and makes it dissolve, to obtain polyamic acid ester solution PAE-5.

[preparation of aligning agent for liquid crystal]

(embodiment 1)

Weigh polyamic acid ester solution PAE-1 4.40g obtained in synthesis example 1, polyamic acid obtained in synthesis example 2 Solution PAA-1 5.50g adds NMP 0.52g, GBL 5.58g, BCS 4.01g, N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ- Tert-butoxycarbonyl-L-Histidine 0.15g and additive A 0.11g is stirred at room temperature 3 hours, to obtain liquid crystal aligning Agent A1.

Using aligning agent for liquid crystal A1, according to following such step production adaptation evaluation substrates and liquid crystal cells.

<<sample making>>

The sample of adaptation evaluation makes as follows.It is applied on the ito substrate of 30mm × 40mm by rotary coating Cloth aligning agent for liquid crystal A1.On 80 DEG C of hot plate after drying 2 minutes, it is burnt into 14 minutes using 230 DEG C of heated air circulation type baking ovens, To form the film that film thickness is 100nm.Across polarizing film with 500mJ/cm²The ultraviolet light that 254nm is irradiated to the coated surface, from And obtain the substrate with liquid crystal orientation film.

Prepare two plate bases obtained from operation in this way, 4 μm of pearl intervals are coated in the liquid crystal alignment film surface of a substrate After object, sealant (XN-1500T for assisting vertical Chemical Co., Ltd. manufacture) is added dropwise.Then, with the liquid crystal orientation film of another substrate Face be inside and substrate overlapping widths be 1cm mode be bonded.At this point, adjustment sealant dripping quantity, so that after fitting The diameter of sealant reach 3mm.After two plate bases being bonded are fixed with clip, with 150 DEG C heat cure 1 hour, thus Make the sample of adaptation evaluation.

<<measurement of adaptation>>

Thereafter, sample substrate is fixed with the desktop precision universal testing machine (AGS-X 500N) that Shimadzu Seisakusho Ltd. manufactures It behind the end of upper and lower base plate, is pressed from the top in substrate center portion, the pressure (N) when measuring peeling-off.For being surveyed The removing position of fixed substrate is observed, and not peeling-off between sealing/film or between film/substrate, sealant is whole or sealing A part of agent is determined as zero when being broken.When peeling-off between sealing/film, the adaptation between sealing/film is determined as ×, When film/substrate is peeling-off, the adaptation between film/substrate is determined as ×.

Weigh polyamic acid ester solution PAE-1 4.42g obtained in synthesis example 1, polyamic acid obtained in synthesis example 2 Solution PAA-1 5.48g adds NMP 0.50g, GBL 5.60g, BCS 3.99g, N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ- Tert-butoxycarbonyl-L-Histidine 0.15g and additive B 0.11g is stirred at room temperature 3 hours, to obtain liquid crystal aligning Agent A2.

Weigh polyamic acid ester solution PAE-1 4.40g obtained in synthesis example 1, polyamic acid obtained in synthesis example 3 Solution PAA-2 4.07g adds NMP 0.06g, GBL 7.46g, BCS 3.98g and N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.15g, additive A 0.11g are stirred at room temperature 3 hours, to obtain liquid crystal aligning Agent A3.

Weigh polyamic acid ester solution PAE-1 4.41g obtained in synthesis example 1, polyamic acid obtained in synthesis example 3 Solution PAA-2 4.04g adds NMP 0.06g, GBL 7.48g, BCS 4.00g and N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.15g, additive B 0.11g are stirred at room temperature 3 hours, to obtain liquid crystal aligning Agent A4.

Weigh polyamic acid ester solution PAE-2 4.41g obtained in synthesis example 4, polyamic acid obtained in synthesis example 2 Solution PAA-1 5.49g adds NMP 0.50g, GBL 5.60g, BCS 4.00g, N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ- Tert-butoxycarbonyl-L-Histidine 0.15g and additive A 0.11g is stirred at room temperature 3 hours, to obtain liquid crystal aligning Agent A5.

Weigh polyamic acid ester solution PAE-2 4.42g obtained in synthesis example 4, polyamic acid obtained in synthesis example 2 Solution PAA-1 5.48g adds NMP 0.50g, GBL 5.60g, BCS 4.00g, N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ- Tert-butoxycarbonyl-L-Histidine 0.15g and additive B 0.11g is stirred at room temperature 3 hours, to obtain liquid crystal aligning Agent A6.

Weigh polyamic acid ester solution PAE-3 4.42g obtained in synthesis example 5, polyamic acid obtained in synthesis example 2 Solution PAA-1 5.49g adds NMP 0.50g, GBL 5.60g, BCS 4.00g, N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ- Tert-butoxycarbonyl-L-Histidine 0.15g and additive A 0.11g is stirred at room temperature 3 hours, to obtain liquid crystal aligning Agent A7.

Weigh polyamic acid ester solution PAE-3 4.42g obtained in synthesis example 5, polyamic acid obtained in synthesis example 2 Solution PAA-1 5.49g adds NMP 0.50g, GBL 5.60g, BCS 4.00g, N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ- Tert-butoxycarbonyl-L-Histidine 0.15g and additive B 0.11g is stirred at room temperature 3 hours, to obtain liquid crystal aligning Agent A8.

Weigh polyamic acid ester solution PAE-4 4.42g obtained in synthesis example 6, polyamic acid obtained in synthesis example 2 Solution PAA-1 5.50g adds NMP 0.50g, GBL 5.60g, BCS 4.00g, N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ- Tert-butoxycarbonyl-L-Histidine 0.15g and additive A 0.11g is stirred at room temperature 3 hours, to obtain liquid crystal aligning Agent A9.

Weigh polyamic acid ester solution PAE-4 4.40g obtained in synthesis example 6, polyamic acid obtained in synthesis example 2 Solution PAA-1 5.49g adds NMP 0.50g, GBL 5.60g, BCS 4.00g, N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ- Tert-butoxycarbonyl-L-Histidine 0.15g and additive B 0.11g is stirred at room temperature 3 hours, to obtain liquid crystal aligning Agent A10.

Weigh polyamic acid ester solution PAE-5 4.42g obtained in synthesis example 7, polyamic acid obtained in synthesis example 2 Solution PAA-1 5.49g adds NMP 0.50g, GBL 5.60g, BCS 4.00g, N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ- Tert-butoxycarbonyl-L-Histidine 0.15g and additive A 0.11g is stirred at room temperature 3 hours, to obtain liquid crystal aligning Agent A11.

Weigh polyamic acid ester solution PAE-5 4.42g obtained in synthesis example 7, polyamic acid obtained in synthesis example 2 Solution PAA-1 5.48g adds NMP 0.50g, GBL 5.60g, BCS 4.00g, N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ- Tert-butoxycarbonyl-L-Histidine 0.15g and additive B 0.11g is stirred at room temperature 3 hours, to obtain liquid crystal aligning Agent A12.

Weigh polyamic acid ester solution PAE-1 4.39g obtained in synthesis example 1, polyamic acid obtained in synthesis example 2 Solution PAA-1 5.52g adds NMP 0.50g, GBL 5.57g, BCS 4.02g and N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.15g is stirred at room temperature 3 hours, to obtain aligning agent for liquid crystal B1.

Weigh polyamic acid ester solution PAE-1 4.42g obtained in synthesis example 1, polyamic acid obtained in synthesis example 3 Solution PAA-2 4.07g adds NMP 0.06g, GBL 7.50g, BCS 4.01g and N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.15g is stirred at room temperature 3 hours, to obtain aligning agent for liquid crystal B2.

Add polyamic acid ester solution PAE-1 11.0g, GBL 4.99g, BCS 4.02g and N- obtained in synthesis example 1 α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.15g, additive A 0.11g, are stirred at room temperature It mixes 3 hours, to obtain aligning agent for liquid crystal B3.

Add polyamic acid ester solution PAE-1 11.0g, GBL 5.00g, BCS 4.01g and N- obtained in synthesis example 1 α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.15g, is stirred at room temperature 3 hours, thus To aligning agent for liquid crystal B4.

Weigh synthesis example 2 obtained in polyamic acid solution PAA-1 9.17g, addition NMP 1.37g, GBL 5.47g, BCS 3.99g and N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.13g, is stirred at room temperature 3 hours, to obtain aligning agent for liquid crystal B5.

Weigh synthesis example 3 obtained in polyamic acid solution PAA-2 6.79g, addition NMP 1.84g, GBL 7.37g, BCS 4.00g and N- α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.15g, is stirred at room temperature 3 hours, to obtain aligning agent for liquid crystal B6.

Add polyamic acid ester solution PAE-2 11.0g, GBL 4.99g, BCS 4.01g and N- obtained in synthesis example 4 α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.15g, additive A 0.11g, are stirred at room temperature It mixes 3 hours, to obtain aligning agent for liquid crystal B7.

Add polyamic acid ester solution PAE-2 11.0g, GBL 5.00g, BCS 4.01g and N- obtained in synthesis example 4 α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.15g, is stirred at room temperature 3 hours, thus To aligning agent for liquid crystal B8.

Add polyamic acid ester solution PAE-3 11.0g, GBL 5.00g, BCS 4.00g and N- obtained in synthesis example 5 α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.15g, additive A 0.11g, are stirred at room temperature It mixes 3 hours, to obtain aligning agent for liquid crystal B9.

Add polyamic acid ester solution PAE-3 11.0g, GBL 5.00g, BCS 4.01g and N- obtained in synthesis example 5 α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.15g, is stirred at room temperature 3 hours, thus To aligning agent for liquid crystal B10.

Add polyamic acid ester solution PAE-4 11.1g, GBL 4.98g, BCS 4.02g and N- obtained in synthesis example 6 α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.15g, additive A 0.11g, are stirred at room temperature It mixes 3 hours, to obtain aligning agent for liquid crystal B11.

Add polyamic acid ester solution PAE-4 11.0g, GBL 5.00g, BCS 4.01g and N- obtained in synthesis example 6 α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.15g, is stirred at room temperature 3 hours, thus To aligning agent for liquid crystal B12.

Add polyamic acid ester solution PAE-5 11.0g, GBL 4.98g, BCS 4.02g and N- obtained in synthesis example 7 α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.15g, additive A 0.11g, are stirred at room temperature It mixes 3 hours, to obtain aligning agent for liquid crystal B13.

Add polyamic acid ester solution PAE-5 11.0g, GBL 5.00g, BCS 4.01g and N- obtained in synthesis example 7 α-(9- fluorenylmethoxycarbonyl groups)-N- τ-tert-butoxycarbonyl-L-Histidine 0.15g, is stirred at room temperature 3 hours, thus To aligning agent for liquid crystal B14.

Other than using aligning agent for liquid crystal B14, by method same as Example 1, carry out adaptation evaluation and Exchange driving ghost evaluation.

Using the aligning agent for liquid crystal respectively obtained in above-described embodiment 1~4 and comparative example 1~6, for utilization and embodiment The liquid crystal cells that 1 identical method obtains carry out adaptation evaluation and evaluate with driving ghost is exchanged, as a result summarize shown in table 1.

Similarly, using the aligning agent for liquid crystal respectively obtained in above-described embodiment 5~12 and comparative example 7~14, for benefit The liquid crystal cells obtained with method same as Example 1 carry out adaptation evaluation and evaluate with driving ghost is exchanged, as a result summarize It is shown in table 2.

[table 1]

[table 2]

Industrial availability

By using aligning agent for liquid crystal of the invention, can obtain with excellent liquid crystal aligning, electrical characteristics, Yi Jigao Seal adaptation liquid crystal orientation film, with the liquid crystal orientation film liquid crystal indicate element in because exchange driving due to generate more than As, because DC voltage residual charge caused by indicate that ghost etc. is suppressed, can be applied to require high indicate quality, big draw In the images expression such as LCD TV of face and high-resolution field.

Claims

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

(A) ingredient: the tetrabasic carboxylic acid two of tetracarboxylic acid acid dialkyl ester derivative shown in the following formula (1) by the inclusion of 60mol% or more Alkyl derivative and the diamines comprising at least one kind of diamines in the group that the diamines shown in following formula (2)~(5) forms Poly amic acid ester obtained from polycondensation reaction,

R₁For the alkyl of carbon number 1~5, R₂For hydroxyl or chlorine atom, R_xFor the alkyl of carbon number 1~6,

A₁For the divalent organic group of singly-bound, ester bond, amido bond, thioester bond or carbon number 2~10, A₂For halogen atom, hydroxyl, ammonia Base, mercapto, nitro, phosphate or carbon number 1~20 1 valence organic group, the integer that a is 1~4, when a is 2 or more, A₂Knot Structure is optionally identical or different；

(B) ingredient: the polyamic acid as obtained from the polycondensation reaction of tetracarboxylic dianhydride and diamines；

(C) ingredient: 2 functions or polyfunctional (methyl) acrylic acid or derivatives thereof,

(C) component content is 0.1 mass % or more and 15 matter relative to the sum of (A) ingredient and (B) ingredient Measure % or less.

2. aligning agent for liquid crystal according to claim 1, wherein the containing ratio of above-mentioned (A) ingredient and (B) ingredient is with quality It is calculated as 1/9~9/1 than A/B, the content of (C) ingredient is 0.1~10 mass % relative to the sum of (A) ingredient and (B) ingredient.

3. aligning agent for liquid crystal according to claim 1 or 2, wherein it includes 40 that (A) ingredient, which is using relative to all diamines, The diamines of at least one kind of diamines in the group that the diamines shown in above-mentioned formula (2)~formula (5) forms of~100 moles of % and obtain The poly amic acid ester arrived.

4. aligning agent for liquid crystal according to claim 1 or 2, wherein (A) ingredient is using comprising selecting shown in free style (2) It at least one kind of diamines in the group of the composition of diamines shown in diamines and formula (3) and selects shown in diamines shown in free style (4) and formula (5) Poly amic acid ester obtained from the diamines of at least one kind of diamines in the group of diamines composition.

5. aligning agent for liquid crystal according to claim 1 or 2, wherein (A) ingredient be using comprising diamines shown in formula (2) and Poly amic acid ester obtained from the diamines at least one kind of diamines in group for selecting diamines shown in free style (4) to form.

6. aligning agent for liquid crystal according to claim 1 or 2, wherein the A of above-mentioned formula (4)₂To be tied shown in following formula (6) Structure,

-A₃-R₃ (6)

A₃For singly-bound ,-O- ,-S- ,-NR '₃, ester bond, amido bond, thioester bond, urea bond, carbonic acid ester bond or urethane bond；R₃ Alkyl, alkenyl, alkynyl, aryl and the group for being composed them selected from the carbon number 1~10 optionally with substituent group, they Optionally there is substituent group；R′₃Selected from hydrogen atom or alkyl, alkenyl, alkynyl, aryl and the group for being composed them, it Optionally have substituent group.

7. aligning agent for liquid crystal according to claim 1 or 2, wherein (A) ingredient is using comprising selected from by following formula (A- 1) poly amic acid ester obtained from the diamines of at least one kind of diamines in the group of~(A-5) diamines composition,

8. aligning agent for liquid crystal according to claim 7, wherein (A) ingredient is using the diamines comprising above-mentioned formula (2) and choosing Freely poly amic acid ester obtained from the diamines of at least one kind of diamines in the group of above-mentioned formula (A-1)~(A-5) composition.

9. aligning agent for liquid crystal according to claim 1 or 2, wherein (B) ingredient is using comprising selected from by following formula (B- 1) polyamic acid obtained from least one kind of tetracarboxylic dianhydride in the group of~(B-9) tetracarboxylic dianhydride composition,

10. aligning agent for liquid crystal according to claim 1 or 2, wherein (B) ingredient is by tetracarboxylic dianhydride and diamines Polyamic acid obtained from polycondensation reaction, the tetracarboxylic dianhydride have being selected from for 20 moles of % or more of all tetracarboxylic dianhydrides At least one kind of tetracarboxylic dianhydride in group be made of above-mentioned formula (B-1)~(B-9).

11. aligning agent for liquid crystal according to claim 1 or 2, wherein (B) ingredient is using comprising selected from by following formula (B- 10) polyamic acid obtained from least one kind of diamines in group~(B-14) formed,

12. aligning agent for liquid crystal according to claim 11, wherein (B) ingredient is rubbed using 20 with all diamines Polyamides obtained from the diamines of at least one kind of diamines in the group being made of above-mentioned formula (B-10)~(B-14) of your % or more Amino acid.

13. aligning agent for liquid crystal according to claim 1 or 2, wherein (C) ingredient be dipentaerythritol hexaacrylate or Glycerin diglycidyl ether acrylic acid adduct.

14. aligning agent for liquid crystal according to claim 1 or 2 also contains mixed organic solvents, the mixed organic solvents Comprising at least one kind of organic solvent (D1) in the group being made of gamma-butyrolacton and its derivative and selected from by N- methyl- At least one kind of organic solvent (D2) in the group of 2-Pyrrolidone, 1,3- dimethyl-imidazolinone and their derivative composition, has The content of solvent (D1) is 2~30 mass % relative to the total amount of organic solvent (D1) and organic solvent (D2).

15. aligning agent for liquid crystal according to claim 1 or 2 is used for the liquid crystal orientation film of light orientation processing to be carried out.

16. a kind of liquid crystal orientation film is that aligning agent for liquid crystal described in any one of claim 1~15 is coated on substrate simultaneously Obtained from firing.