CN105579897A

CN105579897A - Liquid crystal aligning agent and liquid crystal aligning film using same

Info

Publication number: CN105579897A
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: 2016-05-11
Anticipated expiration: 2034-07-23
Also published as: TW201518408A; CN105579897B; KR20160034391A; KR102266366B1; TWI643905B; WO2015012316A1; JP6354759B2; JPWO2015012316A1

Abstract

Provided is a liquid crystal aligning agent capable of forming a liquid crystal aligning film which exhibits high adhesion to a sealing agent and a substrate that are used in making a liquid crystal display element and which exhibits improved interface characteristics between the aligning film and a liquid crystal. A liquid crystal aligning agent comprising components (A), (B) and (C): (A) a polyamic acid ester obtained by polycondensation of a tetracarboxylic acid dialkyl ester derivative which comprises at least 60mol% of a tetracarboxylic acid dialkyl ester derivative represented by formula (1) with at least one diamine selected from the group consisting of diamines represented by formulae (2) to (5) [wherein R1 is C1-5 alkyl, R2 is hydroxyl or the like, Me is methyl or the like, A1 is a bond or the like, A2 is a halogen atom or the like, and a is an integer of 1 to 4]; (B) a polyamic acid obtained by polycondensation of a tetracarboxylic dianhydride with a diamine; and (C) a bi- or poly-functional (meth)acrylic acid or a derivative thereof.

Description

Aligning agent for liquid crystal and the liquid crystal orientation film employing it

Technical field

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

Background technology

The liquid crystal used in LCD TV, liquid crystal display etc. represents that element is provided with the liquid crystal orientation film for controlling liquid crystal arrangement state usually in element.As liquid crystal orientation film, cut-off mainly uses the liquid crystal orientation film of polyimide system so far, and the liquid crystal orientation film of described polyimide system is by obtaining coating glass substrate etc. using the solution of the polyimide precursors such as polyamic acid (poly-AMIC acid), soluble polyimide as the aligning agent for liquid crystal of major component and burn till.

Along with liquid crystal represents the high-definition of element, represent that from suppressing liquid crystal the contrast of element reduces, reduces the requirement of persistence of vision and so on, for liquid crystal orientation film, on the basis showing excellent liquid crystal aligning, stable tilt angle, voltage retention is high, suppress because exchange drive and produces after image, applying DC voltage time residual charge few and/or, the characteristic to relax fast and so on of the residual charge accumulated because of DC voltage becomes important gradually.

Various motion has been carried out in order to make the liquid crystal orientation film of polyimide system meet requirement as described above.Such as, propose as the short liquid crystal orientation film of the time disappearing to the after image that produces because of DC voltage: employ at polyamic acid, liquid crystal orientation film (such as with reference to patent documentation 1) containing the aligning agent for liquid crystal of the tertiary amine also containing ad hoc structure on the basis of the polyamic acid of imide; Employ the liquid crystal orientation film of the aligning agent for liquid crystal containing soluble polyimide, the raw material of described soluble polyimide uses the specific diamine compound (such as with reference to patent documentation 2) etc. with pyridine skeleton etc.In addition, and liquid crystal orientation film that time of to the after image that because of DC voltage produce disappear short high as voltage retention, propose the liquid crystal orientation film using following aligning agent for liquid crystal, described aligning agent for liquid crystal, on the basis containing polyamic acid, its imide amination polymer etc., is selected from molecule in the compound with 1 carboxylic acid group, the compound in molecule with 1 acid anhydride and molecule also containing minute quantity the compound (such as with reference to patent documentation 3) had in the compound of 1 tertiary amino.

In addition, excellent as liquid crystal aligning, voltage retention is high, after image is few, excellent in reliability and show the liquid crystal orientation film of high tilt angle, it is known that, employ the liquid crystal orientation film of the aligning agent for liquid crystal containing polyamic acid, its imide amination polymer, described polyamic acid is obtained (such as with reference to patent documentation 4) with the tetracarboxylic dianhydride and specific diamine compound with cyclo-butane by the tetracarboxylic dianhydride of ad hoc structure.In addition, liquid crystal as transverse electric field type of drive represents the suppressing method because exchanging the after image that driving causes occurred in element, proposes and uses liquid crystal aligning well and the method for the specific liquid crystal orientation film large with the interaction of liquid crystal molecule (with reference to patent documentation 5).

But in recent years, large picture and the LCD TV of high-resolution becomes main flow, the requirement for after image becomes stricter, and requirement can tolerate the characteristic of the Long-Time Service under harsh environment for use.Concomitantly, the reliability of liquid crystal orientation film used needs higher than in the past, about each characteristic of liquid crystal orientation film, not only requires that initial stage characteristic is good, even if also maintain good characteristic after such as also requiring at high temperature long-time exposure.

On the other hand, report is had to claim: as the component of polymer forming polyimide system aligning agent for liquid crystal, poly amic acid ester molecular weight can not occur to be reduced because of heating when it being carried out to imidizate, and therefore, the orientation stability of liquid crystal is excellent in reliability (with reference to patent documentation 6).Poly amic acid ester exists that specific insulation is high, problems such as residual charge is many when applying DC voltage usually, thus discloses the blended aligning agent for liquid crystal (with reference to patent documentation 7) obtained of polyamic acid by poly amic acid ester and electrical characteristics aspect excellence.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 9-316200 publication

Patent documentation 2: Japanese Unexamined Patent Publication 10-104633 publication

Patent documentation 3: Japanese Unexamined Patent Publication 8-76128 publication

Patent documentation 4: Japanese Unexamined Patent Publication 9-138414 publication

Patent documentation 5: Japanese Unexamined Patent Publication 11-38415 publication

Patent documentation 6: Japanese Unexamined Patent Publication 2003-26918 publication

Patent documentation 7:WO2011/15080 publication

Summary of the invention

the problem that invention will solve

As mentioned above, report is had to claim: by the described characteristic that the liquid crystal orientation film that poly amic acid ester and the blended aligning agent for liquid crystal of polyamic acid obtain can be obtained liquid crystal aligning, electrical characteristics excellence.That is, the liquid crystal orientation film obtained by the aligning agent for liquid crystal containing poly amic acid ester and polyamic acid can obtain after image characteristic, the improved characteristic in long-term reliability aspect in ac/dc driving.

But find: for the liquid crystal aligning face coating sealant be formed on the substrate of liquid crystal orientation film, two panels substrate bonding is made liquid crystal when representing element, the cementability (adaptation) of the liquid crystal orientation film obtained by the described aligning agent for liquid crystal containing poly amic acid ester and polyamic acid and sealant, substrate is not enough.

As mentioned above, recently effective pixel area in element is represented in order to expand liquid crystal, require the so-called frame region not forming pixel reducing outer edge around substrate further, for described object, improve, by liquid crystal orientation film poly amic acid ester and the blended aligning agent for liquid crystal of polyamic acid obtained, problem is become for the cementability of sealant, substrate.

And then, as mentioned above, improve liquid crystal orientation film and sealant, the cementability of substrate needs to complete under the condition not reducing liquid crystal aligning that liquid crystal orientation film possesses, electrical characteristics, if may, also require to improve these characteristics further.

for the scheme of dealing with problems

The present invention carries out to realize above-mentioned problem, has following purport.

1. an aligning agent for liquid crystal, is characterized in that, it contains following (A) composition, (B) composition and (C) composition.

(A) composition: the poly amic acid ester obtained by the tetrabasic carboxylic acid dialkyl derivant of tetrabasic carboxylic acid dialkyl derivant shown in the following formula (1) that comprises more than 60mol% and the polycondensation reaction of the diamines of at least a kind of diamines comprised in the group that is selected from and is made up of diamines following formula (2) ~ (5) Suo Shi.

(R ₁for the alkyl of carbon number 1 ~ 5, R ₂for hydroxyl or chlorine atom, R _xfor the alkyl of carbon number 1 ~ 6.)

(A ₁for the divalent organic group of singly-bound, ester bond, amido link, thioester bond or carbon number 2 ~ 10, A ₂for 1 valency organic group of halogen atom, hydroxyl, amino, mercapto, nitro, phosphate or carbon number 1 ~ 20, a is the integer of 1 ~ 4, when a is more than 2, and A ₂structure can be the same or different.)

(B) composition: by the polycondensation reaction of tetracarboxylic dianhydride and diamines and the polyamic acid obtained.

(C) composition: 2 officials can or polyfunctional (methyl) acrylic acid or derivatives thereof.

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

3. the aligning agent for liquid crystal according to above-mentioned 1 or 2, wherein, (A) composition uses to comprise the diamines being selected from least a kind of diamines in the group be made up of diamines above-mentioned formula (2) ~ formula (5) Suo Shi of 40 ~ 100 % by mole and the poly amic acid ester that obtains relative to all diamines.

4. the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 3, wherein, (A) composition uses at least a kind of diamines comprised in the group selecting the composition of diamines shown in diamines and formula (3) shown in free style (2) and the poly amic acid ester selecting the diamines of at least a kind of diamines in the group of the composition of diamines shown in diamines and formula (5) shown in free style (4) and obtain.

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

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

-A ₃-R ₃(6)

(the A in formula (6) ₃for singly-bound ,-O-,-S-,-NR ' ₃-, ester bond, amido link, thioester bond, urea key, carbonic acid ester bond or amino-formate bond, R ₃be selected from alkyl, thiazolinyl, alkynyl, aryl and the group that they combined optionally with substituent carbon number 1 ~ 10, they optionally have substituting group.R ' ₃the group being selected from hydrogen atom or alkyl, thiazolinyl, alkynyl, aryl and they being combined, they optionally have substituting group.)

7. the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 6, wherein, (A) composition is the poly amic acid ester using the diamines of at least a kind of diamines comprised in the group being selected from and being made up of the diamines of following formula (A-1) ~ (A-5) and obtain.

8. the aligning agent for liquid crystal according to above-mentioned 7, wherein, (A) composition is the diamines of at least a kind of diamines in the group using the diamines and being selected from comprising above-mentioned formula (2) to be made up of above-mentioned formula (A-1) ~ (A-5) and the poly amic acid ester that obtains.

9. the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 8, wherein, (B) composition is the polyamic acid using the tetracarboxylic dianhydride of at least a kind that comprises in the group being selected from and being made up of the tetracarboxylic dianhydride of following formula (B-1) ~ (B-9) and obtain.

10. the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 9, wherein, (B) composition is polycondensation reaction by tetracarboxylic dianhydride and diamines and the polyamic acid obtained, and described tetracarboxylic dianhydride contains at least a kind of tetracarboxylic dianhydride be selected from the group be made up of above-mentioned formula (B-1) ~ (B-9) of more than 20 % by mole.

11. aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 10, wherein, (B) composition uses the diamines of at least a kind comprised in the group being selected from and being made up of following formula (B-10) ~ (B-14) and the polyamic acid obtained.

12. aligning agent for liquid crystal according to above-mentioned 11, wherein, (B) composition uses the diamines being selected from least a kind of diamines in the group be made up of above-mentioned formula (B-10) ~ (B-14) and the polyamic acid that obtains with more than 20 % by mole of all diamines.

13. aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 12, wherein, (C) composition is dipentaerythritol acrylate or glycerin diglycidyl ether acrylic acid adduct.

14. aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 13, it is also containing mixed organic solvents, described mixed organic solvents comprises at least a kind of organic solvent (D1) in the group being selected from and being made up of gamma-butyrolacton and derivant thereof and is selected from by METHYLPYRROLIDONE, 1, at least a kind of organic solvent (D2) in the group of 3-dimethyl-imidazolinone and their derivant composition, the content of organic solvent (D1) is 2 ~ 30 quality % relative to organic solvent (D1) and the total amount of organic solvent (D2).

15. aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 14, it is for carrying out the liquid crystal orientation film of light orientation process.

16. 1 kinds of liquid crystal orientation films, the aligning agent for liquid crystal according to any one of above-mentioned 1 ~ 15 is coated substrate and is burnt till and obtains by it.

the effect of invention

According to aligning agent for liquid crystal of the present invention, can be formed with make use when liquid crystal represents element sealant, substrate the fully large liquid crystal orientation film of cementability (adaptation).Thus, fully can also tackle liquid crystal and represent the narrowing of frame region in element.

And, the following characteristic of the liquid crystal orientation film obtained by aligning agent for liquid crystal of the present invention improves: by exchanging the interfacial characteristics with liquid crystal orientation film such as the liquid crystal that drives the after image reduction that causes, and voltage retention, ion concentration and DC voltage such as to remain at the electrical characteristics.

Embodiment

[(A) composition]

The poly amic acid ester used in the present invention is the polyimide precursor for obtaining polyimide, is to have the polymkeric substance that can carry out the position of following imidization reaction because of heating.

(A) of the present invention composition is polycondensation reaction by tetrabasic carboxylic acid dialkyl derivant and diamines and the poly amic acid ester obtained, described tetrabasic carboxylic acid dialkyl derivant comprises the tetrabasic carboxylic acid dialkyl shown in following formula (1) of more than the 60mol% of all tetrabasic carboxylic acid dialkyl derivants, and described diamines comprises at least a kind of diamines in the group being selected from and being made up of diamines following formula (2) ~ formula (5) Suo Shi.

In formula (1), R ₁for the alkyl of carbon number 1 ~ 4, R ₂for hydroxyl or chlorine atom.R _xfor carbon number 1 ~ 6 straight or branched alkyl, be preferably carbon number 1 ~ 3 alkyl, be particularly preferably methyl.

As R ₁concrete example, methyl, ethyl, propyl group, butyl or the tert-butyl group can be listed.About poly amic acid ester, along with the carbon number of alkyl increases, the temperature of carrying out imidizate uprises, therefore, from the view point of the easness of hot-imide, and R ₁be preferably methyl or ethyl, be particularly preferably methyl.

R ₂for the chlorine atomic time, two (chlorocarbonyl) compounds high with the reactivity of diamine reactant can be become, therefore more preferably.

The diamines that will carry out polycondensation with the tetrabasic carboxylic acid dialkyl derivant shown in formula (1) preferably comprises at least a kind of diamines selected in group that shown in free style (2) ~ formula (5), diamines forms.Wherein, when comprising at least a kind of diamines in the group selecting the composition of diamines shown in diamines and formula (3) shown in free style (2) and select at least a kind of diamines in the group of the composition of diamines shown in diamines and (5) shown in free style (4), the dissolubility of gamma-butyrolacton can be improved, so preferably.Especially, for diamines contained (2) Suo Shi with when selecting the diamines of at least a kind of diamines in the group of the composition of diamines shown in free style (4), the liquid crystal orientation film that liquid crystal aligning is high can be obtained, so preferably.

In formula (3) and formula (5), A ₁for the divalent organic group of singly-bound, ester bond, amido link, thioester bond or carbon number 2 ~ 10.

A ₁in, ester bond-C (O) O-or-OC (O)-represent.

As amido link, the structure of-C (O) NH-,-C (O) NR-,-NHC (O)-or-NRC (O)-shown can be shown.R is the alkyl of carbon number 1 ~ 10, thiazolinyl, alkynyl, aryl, thioester bond or the group that they combined.

As the concrete example of abovementioned alkyl, methyl, ethyl, propyl group, butyl, the tert-butyl group, hexyl, octyl group, cyclopentyl, cyclohexyl, dicyclohexyl etc. can be listed.

As thiazolinyl, more than 1 CH will existed in abovementioned alkyl can be listed ₂-CH ₂the thiazolinyl that structure replacing becomes CH=CH structure and obtains, more specifically, vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl group, 1,3-butadiene base, 2-pentenyl, 2-hexenyl, cyclopropanyl, cyclopentenyl, cyclohexenyl group etc. can be listed.

As alkynyl, more than 1 CH will existed in aforesaid alkyl can be listed ₂-CH ₂the alkynyl that structure replacing becomes C ≡ C-structure and obtains, more specifically, can list ethinyl, 1-propinyl, 2-propynyl etc.

As aryl, include, for example out phenyl.

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

A ₁during divalent organic group for carbon number 2 ~ 10, the representation of following formula (6) can be used.

-A ₄-R ₄-A ₅-R ₅-A ₆-(6)

A in formula (6) ₄, A ₅and A ₆be singly-bound ,-O-,-S-,-NR independently of one another ₈-, ester bond, amido link, thioester bond, urea key, carbonic acid ester bond or amino-formate bond.As R ₈, be the alkyl of hydrogen atom or carbon number 1 ~ 10, thiazolinyl, alkynyl, aryl or group that they are combined, can list and aforesaid alkyl, thiazolinyl, example that alkynyl is identical with aryl.

A ₄, A ₅and A ₆in, about ester bond, amido link and thioester bond, can illustrate and aforementioned ester bond, structure that amido link is identical with thioester bond.

As urea key, the structure shown in-NH-C (O) NH-or-NR-C (O) NR-can be shown.R is the alkyl of carbon number 1 ~ 10, thiazolinyl, alkynyl, aryl or the group that they combined, can list and aforesaid alkyl, thiazolinyl, example that alkynyl is identical with aryl.

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

As amino-formate bond, the structure shown in-NH-C (O)-O-,-O-C (O)-NH-,-NR-C (O)-O-or-O-C (O)-NR-can be shown.R is the alkyl of carbon number 1 ~ 10, thiazolinyl, alkynyl, aryl or the group that they combined, can list and aforesaid alkyl, thiazolinyl, example that alkynyl is identical with aryl.

R in formula (6) ₄and R ₅the group being selected from the alkylidene of singly-bound or carbon number 1 ~ 10, alkenylene, alkynylene, arlydene independently of one another and they being combined, they optionally have substituting group.R ₄and R ₅in any one when being singly-bound, R ₄or R ₅the group being selected from the alkylidene of carbon number 2 ~ 10, alkenylene, alkynylene, arlydene and they being combined, they optionally have substituting group.

As above-mentioned alkylidene, the structure removing 1 hydrogen atom from aforesaid alkyl can be listed.More specifically, methylene, 1,1-ethylidene, 1 can be listed, 2-ethylidene, 1,2-propylidene, 1,3-propylidene, 1,4-butylidene, 1,2-butylidene, 1,2-pentylidene, 1,2-hexylidene, 2,3-butylidenes, 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, the structure removing 1 hydrogen atom from foregoing alkenyl can be listed.More specifically, 1,1-ethenylidene, 1 can be listed, 2-ethenylidene, 1,2-ethenylidene methylene, 1-methyl isophthalic acid, 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, the structure removing 1 hydrogen atom from aforementioned alkynyl can be listed.More specifically, ethynylene, ethynylene methylene, ethynylene-1,1-ethylidene, ethynylene-1 can be listed, 2-ethylidene, ethynylene-1,2-propylidene, ethynylene-1,3-propylidene, ethynylene-1,4-butylidene, ethynylene-1,2-butylidene etc.

As arlydene, the structure removing 1 hydrogen atom from aforesaid aryl can be listed.More specifically, 1,2-phenylene, 1,3-phenylene, Isosorbide-5-Nitrae-phenylene etc. can be listed.

If above-mentioned alkylidene, alkenylene, alkynylene, arlydene and the total carbon number of group they combined are 1 ~ 20, then optionally there is substituting group, and then also can form ring structure via substituting group.It should be noted that, form ring structure via substituting group and refer to: substituting group bonds together and forms the female skeleton bonding of ring structure or substituting group and a part and form ring structure.

As this substituent example, halogen group, hydroxyl, mercapto, nitro, organic oxygen base, organic sulfenyl, Organosilyl, acyl group, ester group, thioester substrate, phosphate-based, amide group, aryl, alkyl, thiazolinyl, alkynyl etc. can be listed.

As belonging to substituent halogen group, fluorine atom, chlorine atom, bromine atoms or atomic iodine can be listed.

As belonging to substituent organic oxygen base, the structure that alkoxy, alkene oxygen base, aryloxy group etc. represent with-O-R can be shown.As this R, aforesaid alkyl, thiazolinyl, aryl etc. can be exemplified.These R optionally replace further foregoing substituents.As the concrete example of alkoxy, methoxyl, ethoxy, propoxyl group, butoxy, amoxy, own oxygen base etc. can be listed.

As belonging to substituent organic sulfenyl, the structure that alkylthio group, alkenylthio group, arylthio etc. represent with-S-R can be shown.As this R, aforesaid alkyl, thiazolinyl, aryl etc. can be exemplified.These R optionally replace further foregoing substituents.As the concrete example of alkylthio group, methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl etc. can be listed.

As belonging to substituent Organosilyl ,-Si-(R) can be shown ₃shown structure.This R can be the same or different, and can exemplify aforesaid alkyl, aryl etc.These R can replace further foregoing substituents.As the concrete example of aIkylsilyl groups, trimethyl silyl, triethylsilyl, tripropylsilyl base, tributylsilyl etc. can be listed.

As belonging to substituent acyl group, the structure shown in-C (O)-R can be shown.As this R, aforesaid alkyl, thiazolinyl, aryl etc. can be exemplified.These R can replace further foregoing substituents.As the concrete example of acyl group, formoxyl, acetyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl, benzoyl etc. can be listed.

As belonging to substituent ester group, the structure shown in-C (O) O-R or-OC (O)-R can be shown.As this R, aforesaid alkyl, thiazolinyl, aryl etc. can be exemplified.These R can replace further foregoing substituents.

As belonging to substituent thioester substrate, the structure shown in-C (S) O-R or-OC (S)-R can be shown.As this R, aforesaid alkyl, thiazolinyl, aryl etc. can be exemplified.These R can replace further foregoing substituents.

As belonging to substituent phosphate-based ,-OP (O)-(OR) can be shown ₂shown structure.This R can be the same or different, and can exemplify aforesaid alkyl, aryl etc.These R can replace further foregoing substituents.

As belonging to substituent amide group ,-C (O) NH can be shown ₂or-C (O) NHR ,-NHC (O) R ,-C (O) N (R) ₂or the structure shown in-NRC (O) R.This R can be the same or different, and can exemplify aforesaid alkyl, aryl etc.These R can replace further foregoing substituents.

As belonging to substituent aryl, the group identical with aforesaid aryl can be listed.This aryl optionally replaces further other substituting group aforementioned.

As belonging to substituent alkyl, the group identical with aforesaid alkyl can be listed.This alkyl optionally replaces further other substituting group aforementioned.

As belonging to substituent thiazolinyl, the group identical with foregoing alkenyl can be listed.This thiazolinyl optionally replaces further other substituting group aforementioned.

As belonging to substituent alkynyl, the group identical with aforementioned alkynyl can be listed.This alkynyl optionally replaces further other substituting group aforementioned.

Use have High Linear structure, upright and outspoken structure diamines time, the liquid crystal orientation film with good liquid crystal aligning can be obtained, therefore, as A ₁structure, be more preferably the structure of singly-bound or following formula (A1-1) ~ (A1-25).

In above-mentioned formula (4) and formula (5), A ₂for 1 valency organic group of halogen atom, hydroxyl, amino, mercapto, nitro, phosphate or carbon number 1 ~ 20, a is the integer of 1 ~ 4, when a is more than 2, and A ₂structure can be the same or different.

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

As amino ,-NH can be shown ₂,-NHR or-NR (R)-shown structure.R is the alkyl of carbon number 1 ~ 10, thiazolinyl, alkynyl, aryl or the group that they combined, can list and aforesaid alkyl, thiazolinyl, example that alkynyl is identical with aryl.

As 1 valency organic group of carbon number 1 ~ 20, organic oxygen base, organic sulfenyl, Organosilyl, acyl group, ester group, thioester substrate, phosphate-based, amide group, alkyl, thiazolinyl, alkynyl or aryl can be listed.

As organic oxygen base, the structure that alkoxy, alkene oxygen base, aryloxy group etc. represent with-O-R can be shown.As this R, aforesaid alkyl, thiazolinyl, aryl etc. can be exemplified.As the concrete example of alkoxy, methoxyl, ethoxy, propoxyl group, butoxy, amoxy, own oxygen base etc. can be listed.

As organic sulfenyl, the structure that alkylthio group, alkenylthio group, arylthio etc. represent with-S-R can be shown.As this R, aforesaid alkyl, thiazolinyl, aryl etc. can be exemplified.As the concrete example of alkylthio group, methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl etc. can be listed.

As Organosilyl ,-Si-(R) can be shown ₃shown structure.This R can be the same or different, and can exemplify aforesaid alkyl, aryl etc.As the concrete example of aIkylsilyl groups, trimethyl silyl, triethylsilyl, tripropylsilyl base, tributylsilyl etc. can be listed.

As acyl group, the structure shown in-C (O)-R can be shown.As this R, aforesaid alkyl, thiazolinyl, aryl etc. can be exemplified.As the concrete example of acyl group, formoxyl, acetyl group, propiono, bytyry, isobutyryl, valeryl, isovaleryl, benzoyl etc. can be listed.

As ester group, the structure shown in-C (O) O-R or-OC (O)-R can be shown.As this R, aforesaid alkyl, thiazolinyl, aryl etc. can be exemplified.

As thioester substrate, the structure shown in-C (S) O-R or-OC (S)-R can be shown.As this R, aforesaid alkyl, thiazolinyl, aryl etc. can be exemplified.These R can replace further foregoing substituents.

As phosphate-based ,-OP (O)-(OR) can be shown ₂shown structure.This R can be the same or different, and can exemplify aforesaid alkyl, aryl etc.

As amide group ,-C (O) NH can be shown ₂,-C (O) NHR ,-NHC (O) R ,-C (O) N (R) ₂or the structure shown in-NRC (O) R.This R can be the same or different, and can exemplify aforesaid alkyl, aryl etc.

As alkyl, thiazolinyl, alkynyl and aryl, can list and aforesaid alkyl, thiazolinyl, group that alkynyl is identical with aryl.

If total carbon number of abovementioned alkyl, thiazolinyl, alkynyl and aryl is 1 ~ 20, then can have substituting group, and then also can form ring structure via substituting group.It should be noted that, form ring structure between substituting group and refer to: substituting group bonds together and forms the female skeleton bonding of ring structure or substituting group and a part and form ring structure.

As this substituent example, halogen group, hydroxyl, mercapto, nitro, organic oxygen base, organic sulfenyl, Organosilyl, acyl group, ester group, thioester substrate, phosphate-based, amide group, carbamate groups, aryl, alkyl, thiazolinyl, alkynyl etc. can be listed.

As belonging to substituent organic oxygen base, the structure shown in-O-R such as alkoxy, alkene oxygen base, aryloxy group can be shown.As this R, aforesaid alkyl, thiazolinyl, aryl etc. can be exemplified.These R can replace further foregoing substituents.As the concrete example of alkoxy, can list methoxyl, ethoxy, propoxyl group, butoxy, amoxy, own oxygen base, heptan oxygen base, octyloxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, bay oxygen base etc.

As belonging to substituent organic sulfenyl, the structure that alkylthio group, alkenylthio group, arylthio etc. represent with-S-R can be shown.As this R, aforesaid alkyl, thiazolinyl, aryl etc. can be exemplified.These R can replace further foregoing substituents.As the concrete example of alkylthio group, can list methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl, own sulfenyl, heptan sulfenyl, pungent sulfenyl, the ninth of the ten Heavenly Stems sulfenyl, the last of the ten Heavenly stems sulfenyl, bay sulfenyl etc.

As belonging to substituent Organosilyl ,-Si-(R) can be shown ₃shown structure.This R can be the same or different, and can exemplify aforesaid alkyl, aryl etc.These R can replace further foregoing substituents.As the concrete example of aIkylsilyl groups, trimethyl silyl, triethylsilyl, tripropylsilyl base, tributylsilyl, three amyl group silicyls, three hexyl silicyls, amyl dimethyl silicyl, hexyl dimetylsilyl, octyldimethyl silicyl, decyl dimethyl silicyl etc. can be listed.

As belonging to substituent amide group ,-C (O) NH can be shown ₂,-C (O) NHR ,-NHC (O) R ,-C (O) N (R) ₂, or the structure shown in-NRC (O) R.This R can be the same or different, and can exemplify aforesaid alkyl, aryl etc.These R can replace further foregoing substituents.

As belonging to substituent carbamate groups ,-O-C (O) NH can be shown ₂, the structure shown in-O-C (O) NHR ,-NHC (O)-OR or-NR-C (O) OR.This R can be the same or different, and can exemplify aforesaid alkyl, aryl etc.These R can replace further foregoing substituents.

As belonging to substituent alkyl, the group that aforesaid alkyl is identical can be listed.This alkyl optionally replaces further other substituting group aforementioned.

In formula (4) and formula (5), A ₂have alkyl, thiazolinyl, alkynyl, aryl or they are combined group time, carbon number is preferably 1 ~ 14.A ₂for the alkyl of carbon number more than 15, thiazolinyl, alkynyl, aryl or they are combined group time, along with the content of diamines used, likely make liquid crystal aligning reduce or be difficult to control tilt angle.

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

-A ₃-R ₃(6)

A in formula (6) ₃for singly-bound ,-O-,-S-,-NR ' ₃-, ester bond, amido link, thioester bond, urea key, carbonic acid ester bond or amino-formate bond, R ₃be selected from optionally have substituent carbon number 1 ~ 10, preferably 1 ~ 5 alkyl, thiazolinyl, alkynyl, aryl and group that they are combined, they optionally have substituting group.R ' ₃the group being selected from hydrogen atom or alkyl, thiazolinyl, alkynyl, aryl and they being combined, they optionally have substituting group.)

And then, A ₂structure when being the diamines of the structure with the leaving group departed from because of heating, can structure adaptability be improved, and liquid crystal aligning and tilt angle can not be affected.As the A with the leaving group departed from because of heating ₂structure, be preferably the structure shown in following formula (A2-1) ~ (A2-24).

As the ratio of diamines above-mentioned formula (2) ~ (5) Suo Shi, be preferably 5 ~ 100 % by mole of all diamines.Shown in above-mentioned formula (2) ~ (5), the ratio of diamines is higher, then more can obtain the liquid crystal orientation film with good liquid crystal aligning, therefore be more preferably 40 ~ 100 % by mole, more preferably 60 ~ 100 % by mole.

Wherein, as the diamines belonging to (A) component materials, preferably comprise at least a kind of diamines in the group selecting the composition of diamines shown in diamines and formula (3) shown in free style (2) and select at least a kind of diamines in the group of the composition of diamines shown in diamines and formula (5) shown in free style (4).As the diamines belonging to (A) component materials, particularly preferably diamines shown in contained (2) and at least a kind of diamines selected in the group of the composition of diamines shown in free style (4).Thus, the dissolubility in solvent gamma-butyrolacton can especially be improved.

Now, the consumption of diamines shown in formula (2) or total consumption of the shown diamines of formula (2) and the shown diamines of formula (3) are preferably 95/5 ~ 60/40 relative to the consumption of diamines formula (4) Suo Shi or total consumption of the shown diamines of formula (4) and the shown diamines of formula (5) with terms of mole ratios, are more preferably 90/10 ~ 80/20.

The structure of diamines is more upright and outspoken structure, then more can obtain the liquid crystal orientation film of liquid crystal aligning excellence, therefore, as the diamines for obtaining poly amic acid ester of the present invention, be preferably the diamines containing at least a kind of diamines be selected from the group that is made up of following formula (A-1) ~ formula (A-5), be particularly preferably the diamines containing diamines shown in described diamines and above-mentioned formula (2).Now, the consumption of diamines shown in above-mentioned formula (2) is preferably 95/5 ~ 60/40 with the molar ratio of the consumption of at least a kind of diamines be selected from the group that is made up of diamines formula (A-1) ~ formula (A-5), is more preferably 90/10 ~ 80/20.

In the present invention, the tetrabasic carboxylic acid dialkyl shown in above-mentioned formula (1) is preferably more than 60 % by mole of all tetrabasic carboxylic acid dialkyls, is more preferably more than 80 % by mole.Wherein, more preferably 90 ~ 100 % by mole.Now, the tetrabasic carboxylic acid dialkyl derivant shown in the tetrabasic carboxylic acid dialkyl derivant shown in following formula (10) ~ (11) and above-mentioned formula (1) together can be used as tetracarboxylic acid derivatives.

In above-mentioned formula (10) ~ (11), X is 4 valency organic groups, R ₁comprise preference all identical with the situation of formula (1).X is not particularly limited, if list its concrete example, then can list the structure shown in following X-1 ~ X-46.In addition, these tetracarboxylic acid derivatives can use two or more.

In addition, in the present invention, the diamines shown in above-mentioned formula (2) ~ (5) is preferably 5 ~ 100 % by mole of all diamines, is more preferably 50 ~ 100 % by mole.The diamines shown in following formula (12) can be used in the lump with the diamines shown in above-mentioned formula (2) ~ (5).

In formula (12), R ₆and R ₇be hydrogen atom, alkyl, the alkenyl or alkynyl optionally with substituent carbon number 1 ~ 10 independently of one another.As the concrete example of these alkyl, alkenyl or alkynyl, the group identical with aforementioned group can be listed.

If total carbon number of abovementioned alkyl, alkenyl or alkynyl is 1 ~ 10, then can have substituting group, and then also can form ring structure via substituting group.It should be noted that, form ring structure via substituting group and refer to: substituting group bonds together and forms the female skeleton bonding of ring structure or substituting group and a part and form ring structure.

As this substituent example, halogen group, hydroxyl, mercapto, nitro, aryl, organic oxygen base, organic sulfenyl, Organosilyl, acyl group, ester group, thioester substrate, phosphate-based, amide group, alkyl, thiazolinyl, alkynyl etc. can be listed.As each substituent concrete example, the group identical with aforementioned group can be listed.

In general, when importing bulky structure, likely make amino reactivity, liquid crystal aligning reduce, therefore, as R ₆and R ₇, be more preferably hydrogen atom or optionally there is the alkyl of substituent carbon number 1 ~ 5, be particularly preferably hydrogen atom, methyl or ethyl.

In above-mentioned formula (12), Y is divalent organic group.Y is not particularly limited, if list concrete example, then can list the structure shown in following formula Y-1 ~ Y-113.In addition, these diamines with Y can use two or more.Wherein, in order to obtain good liquid crystal aligning, preferably linearly high diamines is directed into poly amic acid ester, as Y, be more preferably the diamines of Y-7, Y-10, Y-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, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75 or Y-98.In addition, when wanting to improve tilt angle, in poly amic acid ester, preferably import the diamines of structure that side chain has chain alkyl, aromatic ring, aliphatics ring, steroid skeleton or they combined, as Y, be more preferably the diamines of Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, 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.By adding these diamines with the amount of 1 ~ 50 of all diamines % by mole, more preferably 5 ~ 20 % by mole, arbitrary tilt angle can be shown.

[(B) composition]

The polyamic acid used in the present invention is the polyimide precursor for obtaining polyimide, is to have the polymkeric substance that can carry out the position of following imidization reaction because of heating.

(B) of the present invention composition is polycondensation reaction by tetracarboxylic dianhydride and diamines and the polyamic acid obtained.Tetracarboxylic dianhydride can represent with following formula (13), in formula, and X ₁be 4 valency organic groups, its structure is not particularly limited.If list concrete example, then can list the structure of above-mentioned formula (X-1) ~ (X-46).

Diamine compound can represent with following formula (14), in formula, and Y ₁for divalent organic group, its structure is not particularly limited.If list concrete example, then can list the structure of above-mentioned formula (Y-1) ~ (Y-99) and (Y-110) ~ (Y-113).

(in formula, R ₆and R ₇define identical with each of above-mentioned formula (12).)

(B), when composition more with laying particular stress on is present in film surface, the orientation of liquid crystal is likely hindered.On the other hand, if (A) composition can be made more with laying particular stress on to be present in film surface, then can obtain the excellent and liquid crystal orientation film that reliability, after image characteristic are also excellent of liquid crystal aligning.Thus, the surperficial movability of (A) composition as the polyamic acid of (B) composition, is preferably made to improve the polyamic acid that such polarity is high, dissolubility is high.From this point of view, preferably by containing the tetracarboxylic dianhydride of at least a kind of tetracarboxylic dianhydride be selected from the group that is made up of above-mentioned formula (B-1) ~ (B-9) and the polycondensation reaction of diamines and the polyamic acid obtained.

The usage ratio of at least a kind of tetracarboxylic dianhydride in the group selecting free style (B-1) ~ (B-9) to form is preferably 5 ~ 100 % by mole relative to all tetracarboxylic dianhydrides.Described usage ratio is higher, then more can improve polarity and the dissolubility of polymkeric substance, therefore, is more preferably 20 ~ 100 % by mole, more preferably 40 ~ 100 % by mole.

In addition, from the same viewpoint, by using the diamines with high polar substituent, the polyamic acid as (B) composition can be made more with laying particular stress on to be present in film inside and substrate interface.As the diamines with high polar substituent, be preferably the diamines containing secondary amino group or uncle's amino, hydroxyl, amide group, urea groups or carboxyl.As concrete example, as the Y of above-mentioned formula (14) ₁, Y-19, Y-31, Y-40, Y-45, Y-49 ~ Y-51, Y-61, Y-98 or Y-99 can be listed, be more preferably Y-98 or Y-99 containing carboxyl.

As the consumption of diamine compound with high polar substituent, relative to all diamines, be preferably 5 ~ 100 % by mole.This consumption is higher, then the polarity of polymkeric substance more improves, the film surface proportion of (A) composition becomes higher, therefore, is more preferably 10 ~ 100 % by mole, more preferably 30 ~ 100 % by mole.

As the tetracarboxylic dianhydride belonging to (B) component materials, preferably comprise the tetracarboxylic dianhydride of at least a kind in the group being selected from and being made up of the tetracarboxylic dianhydride of following formula (B-1) ~ (B-9).

More than 20 % by mole, the more preferably use more than 40 % by mole of all tetracarboxylic dianhydrides that at least a kind of tetracarboxylic dianhydride in the group selecting free style (B-1) ~ (B-9) to form preferably uses (B) component materials used.Wherein, (B-1) particularly preferably uses more than 60 % by mole.

On the other hand, as the diamines belonging to (B) component materials, preferably comprise the diamines of at least a kind in the group being selected from and being made up of following formula (B-10) ~ (B-13).

More than 20 % by mole, more preferably use more than 40 % by mole of all diamines that at least a kind of diamines be selected from the group be made up of above-mentioned formula (B-10) ~ (B-13) preferably uses (B) component materials used.Wherein, (B-10) particularly preferably uses more than 60 % by mole.

The diamines with photoreactive group as described above also and can be made liquid crystal response speed when liquid crystal represents element etc. and use a kind or be mixed with two or more according to the characteristic such as liquid crystal aligning, tilt angle, voltage retention performance, accumulated charge when making liquid crystal orientation film.

In addition, this diamines with photoreactive group preferably uses 5 ~ 50 % by mole of all diamine component used in the synthesis of (A) composition and/or (B) composition, is more preferably 10 ~ 20 % by mole.

[(C) composition]

(C) of the present invention composition be 2 officials can or polyfunctional (methyl) acrylic acid or derivatives thereof.Described (C) composition is preferably 0.1 ~ 10 quality % relative to (A) composition and (B) composition sum (100 quality %), is more preferably 1 ~ 5 quality %.

As the preferred concrete example of described (C) composition, ARONIXM-210, ARONIXM-240, ARONIXM-6200 (East Asia synthetic chemical industry Co., Ltd. system) can be listed, KAYARADHDDA, KAYARADHX-220, KAYARADR-604, KAYARADR-684 (Nippon Kayaku K. K's system), V260, V312, V335HP (Osaka Organic Chemical Industry Co., Ltd.'s system); LightAcrylateBA-4EA, LightAcrylateBP-4PA, LightAcrylateBP-2PA (oil chemical industry Co., Ltd. of common prosperity society system) etc. 2 official can (methyl) acrylic acid derivative; ARONIXM-400, ARONIXM-405, ARONIXM-450, ARONIXM-7100, ARONIXM-8030, ARONIXM-8060 (East Asia synthetic chemical industry Co., Ltd. system), KAYARADTMPTA, KAYARADDPCA-20, KAYARADDPCA-30, KAYARADDPCA-60, KAYARADDPCA-120 (Nippon Kayaku K. K's system), 3 officials such as VGPT (Osaka Organic Chemical Industry Co., Ltd.'s system) can above multifunctional (methyl) acrylic acid derivative.Wherein, dipentaerythritol acrylate, glycerin diglycidyl ether acrylic acid adduct etc. can be listed.

[organic solvent]

Aligning agent for liquid crystal of the present invention contains the organic solvent being generally used for dissolving or disperse (A) composition ~ (C) composition.Organic solvent does not limit.

As described organic solvent, the solvent (being denoted as good solvent below) that can dissolve poly amic acid ester and polyamic acid and the solvent (being denoted as lean solvent below) these two kinds for improving painting film uniformity when aligning agent for liquid crystal being applied to substrate can be listed.

As good solvent, as long as dissolve as the poly amic acid ester of (A) composition and be just not particularly limited as the solvent of the polyamic acid of (B) composition.If list its concrete example, then N can be listed, dinethylformamide, N, N-diethylformamide, N, N-dimethyl acetamide, N-ethyl-2-pyrrolidone, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrolidone, NVP, dimethyl sulfoxide (DMSO), dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 3-methoxyl-N, N-dimethylpropionamide etc.They can use a kind or be mixed with two or more.In addition, when being used alone, even the solvent of not dissolve polymer, as long as in the scope that polymkeric substance is not separated out, then also can mixing, mixed solvent of more than two kinds can also be made.

As lean solvent, as long as the low and solvent making painting film uniformity improve of surface tension, be just not particularly limited.If list its concrete example, then ethyl cellosolve can be listed, butyl cellosolve, ethyl carbitol, butyl carbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic acid esters, propylene glycol-1-single ethylether-2-acetic acid esters, butyl cellosolve acetate, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc.These solvents can combinationally use two or more.

In the present invention, organic solvent is preferably following mixed solvent: comprise at least a kind of organic solvent (D1) in the group being selected from and being made up of gamma-butyrolacton and derivant thereof and be selected from by METHYLPYRROLIDONE, 1, at least a kind of organic solvent (D2) in the group of 3-dimethyl-imidazolinone and their derivant composition, and the content of organic solvent (D2) is preferably 2 ~ 30 quality % relative to organic solvent (D1) and the total amount of organic solvent (D2).The content of organic solvent (D2) is more preferably 5 ~ 20 quality %.

As the example of gamma-butyrolacton or derivatives thereof belonging to organic solvent (D1), as long as have the organic solvent of lactone structure, just be not particularly limited, owing to being suitable as the solvent dissolving (A) of the present invention composition poly amic acid ester, therefore, gamma-butyrolacton or gamma-valerolactone is particularly preferably.

As the METHYLPYRROLIDONE, 1 belonging to organic solvent (D2), 3-dimethyl-imidazolinone or their derivant, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, NVP, N-methyl caprolactam, 2-Pyrrolidone or 1,3-dimethyl-imidazolinone can be listed.When boiling point is too high, solvent likely remains in film, and the characteristic as liquid crystal orientation film is worsened, and is therefore preferably METHYLPYRROLIDONE or DMI, is more preferably METHYLPYRROLIDONE.

(A) of the present invention composition poly amic acid ester is high for the compatibility of organic solvent (D1), can easily be dissolved in these organic solvents.But (A) composition poly amic acid ester is low for the compatibility of organic solvent (D2), when they are many containing quantitative change, the phase-separated state of poly amic acid ester and polyamic acid is likely separated out, affected to (A) composition poly amic acid ester.Therefore, the content of organic solvent (D2) is 2 ~ 30 quality % relative to the total amount of organic solvent (D1) with organic solvent (D2), is more preferably 2 ~ 20 quality %, is particularly preferably 5 ~ 15 quality %.

The applicable scope of organic solvent (D2) content is also different because of the coating process of aligning agent for liquid crystal, when flexible printing method, change is less likely to occur solvent composition during coating, is therefore more preferably 5 ~ 30 quality %, more preferably 5 ~ 15 quality %.

On the other hand, when carrying out ink-jet application method, aligning agent for liquid crystal during coating becomes small drop, and therefore, it is likely different that the solvent composition before coating and aligning agent for liquid crystal the solvent composition after liquid to substrate.Specifically, the gamma-butyrolacton that vapor pressure is high and derivant thereof be volatilization when being coated with, and liquid to the content of gamma-butyrolacton during substrate and derivant thereof and tails off.Therefore, be preferably the more solvent composition of organic solvent (D1), the content of organic solvent (D2) is more preferably 2 ~ 15 quality %, more preferably 2 ~ 10 quality %.

[manufacture method of poly amic acid ester]

(A) composition of aligning agent for liquid crystal of the present invention and poly amic acid ester can utilize known manufacture method to manufacture.Specifically, following (a) and (b) method can be listed, but be not limited to this.

A () manufactures the method for poly amic acid ester by acyl chlorides and diamine compound

Poly amic acid ester can be manufactured by two (chlorocarbonyl) compound and diamine compound.

Specifically, can by make two (chlorocarbonyl) compound and diamine compound under the existence of alkali and organic solvent with-20 ~ 140 DEG C, preferably with 0 ~ 50 DEG C react 30 minutes ~ 24 hours, preferred reaction manufactures for 1 ~ 4 hour.Aforementioned bases can use pyridine, triethylamine or DMAP, is preferably pyridine to make reacting balance carry out.When the addition of alkali is too much, be difficult to remove, when the addition of alkali is very few, molecular weight diminishes, and therefore, is 2 ~ 4 times moles relative to two (chlorocarbonyl) compound, is preferably 2 ~ 2.5 times moles.

Solvent for the manufacture of poly amic acid ester is preferably METHYLPYRROLIDONE or gamma-butyrolacton from monomer and polymer solubility, and they can use a kind or be mixed with two or more.

During excessive concentration during manufacture, the precipitation of easy generation polymkeric substance, when concentration during manufacture is too low, molecular weight can not rise, therefore, two (chlorocarbonyl) compound and the total amount of diamine compound in reactant liquor are preferably 1 ~ 30 quality %, are more preferably 5 ~ 20 quality %.In addition, in order to prevent two (chlorocarbonyl) compound hydrolysis, the solvent for the manufacture of poly amic acid ester preferably dewaters as far as possible, and reaction is preferably carried out in nitrogen atmosphere, prevents outer gas to be mixed into.

B () manufactures the method for poly amic acid ester by dialkyl dicarboxylic acid and diamine compound

Poly amic acid ester can utilize condensation agent to be carried out condensation to manufacture by tetrabasic carboxylic acid dialkyl and diamine compound.

Specifically, can by make dialkyl dicarboxylic acid and diamine compound under the existence of condensation agent, alkali and organic solvent with 0 ~ 140 DEG C, preferably with 0 ~ 100 DEG C react 30 minutes ~ 24 hours, preferred reaction manufactures for 3 ~ 15 hours.

Aforementioned condensation agent can use triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazinyl methyl morpholine, O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylurea tetrafluoro boric acid ester, O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylurea hexafluorophosphoric acid ester, (2,3-dihydro-2-thia-3-benzoxazolyl) phosphonic acid diphenyl ester etc.The addition of condensation agent is preferably 2 ~ 3 times moles relative to dialkyl dicarboxylic acid, is more preferably 2 ~ 2.5 times moles.

Aforementioned bases can use the tertiary amine such as pyridine, triethylamine.Be difficult to when the addition of alkali is too much remove, when the addition of alkali is very few, molecular weight diminishes, and therefore, is preferably 2 ~ 4 times moles relative to diamine component, is more preferably 2.5 ~ 3 times moles.

Among the manufacture method of above-mentioned two kinds of poly amic acid esters, due to the poly amic acid ester of high molecular can be obtained, be particularly preferably (a) method.

Being stirred by the solution of the poly amic acid ester obtained operating as above while be injected in lean solvent, polymkeric substance can be made to separate out.Carry out several separate out and with after lean solvent cleaning, carry out air drying or heat drying, the powder through refining poly amic acid ester can be obtained.

Aforementioned lean solvent is not particularly limited, and can enumerate water outlet, methyl alcohol, ethanol, hexane, butyl cellosolve, acetone, toluene etc.

[manufacture of polyamic acid]

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

When manufacturing polyamic acid, can by make tetracarboxylic dianhydride and diamine compound preferred in presence of organic solvent with-20 ~ 140 DEG C, preferably with 0 ~ 50 DEG C react 30 minutes ~ 24 hours, preferred reaction manufactures for 1 ~ 12 hour.

Organic solvent for the manufacture of polyamic acid is preferably DMF, METHYLPYRROLIDONE or gamma-butyrolacton from monomer and structure adaptability, and they can use a kind or be mixed with two or more.During excessive concentration during manufacture, the precipitation of polymkeric substance easily occurs, and when concentration during manufacture is too low, molecular weight can not become large, and therefore, tetracarboxylic dianhydride and the diamine compound total amount in reactant liquor is preferably 1 ~ 30 quality %, is more preferably 5 ~ 20 quality %.

To operate as above and the polyamic acid obtained can using its reaction solution as (B), do not wanting the situation etc. making solvent used containing polymerization in aligning agent for liquid crystal, after can reclaiming in solid form as polymkeric substance, as (B) of the present invention composition.

Polymkeric substance can by the abundant stirring reaction solution in one side while be injected into lean solvent and make it separate out and reclaim.Carry out several separate out and with after lean solvent cleaning, carry out air drying or heat drying, the powder through refining polyamic acid can be obtained.

The ratio of the diamine component used in polyreaction and tetracarboxylic acid derivatives (tetracarboxylic dianhydride, tetrabasic carboxylic acid dialkyl derivatives etc.) is preferably 1:0.7 ~ 1:1.2 from the viewpoint controlling molecular weight with molar ratio computing.This mol ratio is more close to 1:1, then the molecular weight of gained polyimide precursor becomes larger.The molecular weight of poly amic acid ester and polyamic acid can affect the viscosity of varnish, the physical strength of polyimide film, and when the molecular weight of poly amic acid ester and polyamic acid is excessive, coating operations, the painting film uniformity of varnish are deteriorated sometimes.In addition, when molecular weight is too small, gained polyimide film strength becomes insufficient sometimes.

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

(aligning agent for liquid crystal)

(A) composition in aligning agent for liquid crystal of the present invention is preferably 1/9 ~ 9/1, is more preferably 3/7 ~ 7/3 containing ratio in mass ratio (A/B) with (B) composition.By making described ratio be in this scope, the aligning agent for liquid crystal that liquid crystal aligning and electrical characteristics are all good can be provided.

In addition, the content of (C) composition in aligning agent for liquid crystal of the present invention is preferably more than 0.1 quality % relative to (A) composition and (B) composition sum (100 quality %), is more preferably more than 1.0 quality %, more preferably more than 3.0 quality %.(C), when the content of composition is few, the liquid crystal orientation film that obtained by aligning agent for liquid crystal is improved insufficient relative to the effect of the cementability of sealant and substrate.On the other hand, from the view point of liquid crystal aligning, the content of (C) composition is preferably below 15 quality %, is particularly preferably below 10 quality %.

On the other hand, (A) composition in aligning agent for liquid crystal of the present invention suitably can change according to wanting the thickness of the liquid crystal orientation film formed to set with the total content (concentration) of (B) composition, but from the even and flawless film this point of formation, more than 0.5 quality % is preferably relative to organic solvent, from the view point of the storage stability of solution, be preferably below 15 quality %, be particularly preferably 1 ~ 10 quality %.

Aligning agent for liquid crystal of the present invention can also contain the various adjuvant such as silane coupling agent, crosslinking chemical.Silane coupling agent wants the adaptation of the substrate of coating of liquid crystalline alignment agent and liquid crystal orientation film formed thereon to add to improve further.Below list the concrete example of silane coupling agent, but be not limited to this.

The amine system silane coupling agents such as APTES, 3-(2-amino-ethyl) TSL 8330,3-(2-amino-ethyl) amino propyl methyl dimethoxysilane, 3-TSL 8330,3-phenyl amino propyl trimethoxy silane, 3-triethoxysilyl-N-(1,3-dimethylbutylene) propylamine, 3-aminopropyl diethoxymethylsilane; Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, vinyl methyl dimethoxysilane, vinyltriacetoxy silane, vinyl silane triisopropoxide, allyltrimethoxysilanis, ethene base system silane coupling agent to styryl trimethoxy silane etc.; The epoxy base system silane coupling agents such as 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl group triethoxysilane, 3-glycidoxypropyl diethoxy silane, 3-glycidoxypropyl dimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane; The methacryl base system silane coupling agents such as 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloyloxypropyl methyl diethoxy silane, 3-methacryloxypropyl; The acryloyl base system silane coupling agents such as 3-acryloxypropyl trimethoxy silane; The urea groups system silane coupling agents such as 3-urea propyl-triethoxysilicane; Two (3-(triethoxysilyl) propyl group) disulfide, two (3-(triethoxysilyl) propyl group) tetrasulfide sulfides system silane coupling agent; The sulfydryl system silane coupling agents such as 3-mercaptopropyi methyl dimethoxysilane, 3-mercaptopropyi trimethoxy silane, 3-decoyl sulfenyl-1-propyl-triethoxysilicane; The isocyanates base system silane coupling agents such as 3-isocyanate group propyl-triethoxysilicane, 3-isocyanate group propyl trimethoxy silicane; The aldehyde system silane coupling agents such as triethoxysilyl butyraldehyde; The carbamate system silane coupling agents such as triethoxysilylpropyltetrasulfide methyl carbamate, (3-triethoxysilylpropyltetrasulfide) t-butylcarbamate.

When the addition of above-mentioned silane coupling agent is too much, unreacted material causes harmful effect to liquid crystal aligning sometimes, when addition is very few, can not embody the effect that adaptation is brought, therefore, be preferably 0.01 ~ 5.0 % by weight relative to the solid constituent of polymkeric substance, be more preferably 0.1 ~ 1.0 % by weight.

When adding above-mentioned silane coupling agent, in order to prevent the precipitation of polymkeric substance, preferably before adding the solvent for improving aforementioned painting film uniformity, add silane coupling agent.In addition, when adding silane coupling agent, before polyamic acid ester solution is mixed with polyamic acid solution, can be added in both polyamic acid ester solution, polyamic acid solution or polyamic acid ester solution and polyamic acid solution.In addition, can be added in the mixed solution of poly amic acid ester-polyamic acid.Silane coupling agent adds in order to the adaptation improving polymkeric substance and substrate, as the adding method of silane coupling agent, more preferably following method, be added in the polyamic acid solution more can laid particular stress on and be present in film inside and substrate interface, after polymkeric substance in solution and silane coupling agent are fully reacted, then mix with polyamic acid ester solution.

When film is burnt till, in order to advance the imidizate of poly amic acid ester efficiently, imidizate promoter can be added.Below list the concrete example of the imidizate promoter of poly amic acid ester, but be not limited to this.

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

As long as in the scope of effect that can obtain the hot-imide promoting poly amic acid ester, then the content of imidizate promoter is not particularly limited, relative to 1 mole, the amic acid esters position of the following formula (12) that the poly amic acid ester in aligning agent for liquid crystal comprises, be preferably more than 0.01 mole, be more preferably more than 0.05 mole, more preferably more than 0.1 mole.In addition, from the harmful effect detention that each characteristic of imidizate promoter self to liquid crystal orientation film residual in the film after burning till is caused to Min. this point, relative to 1 mole, the amic acid esters position of the following formula (12) that the poly amic acid ester in aligning agent for liquid crystal comprises, imidizate promoter is preferably less than 2 moles, is more preferably less than 1 mole, more preferably less than 0.5 mole.

When adding imidizate promoter, likely advance imidizate because of heating, therefore preferably add again with after good solvent and lean solvent dilution.

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

The concentration (content) comprising the polymkeric substance of poly amic acid ester ((A) composition) and polyamic acid ((B) composition) in aligning agent for liquid crystal of the present invention suitably can change according to the thickness setting of the polyimide film that will be formed, relative to organic solvent, be preferably set to 1 ~ 10 quality %, be more preferably 2 ~ 8 quality %.When concentration is less than 1 quality %, be difficult to form even and flawless film, when concentration is more than 10 quality %, the storage stability of solution is deteriorated sometimes.

[manufacture method of aligning agent for liquid crystal]

Aligning agent for liquid crystal of the present invention comprises the poly amic acid ester ((A) composition) and polyamic acid ((B) composition) with ad hoc structure.

As (A) composition relative to the ratio of (A) composition with the total amount of (B) composition, be preferably 5 ~ 95 quality %.(A) when the ratio of composition is few, likely sufficient liquid crystal aligning cannot be obtained, when the ratio of (B) composition is few, likely effect of the present invention cannot be obtained.Therefore, as the ratio of (A) composition, be more preferably 20 ~ 80 quality %, more preferably 30 ~ 70 quality %.

As the method that (A) composition and (B) composition are carried out mixing, there is following method: mixed by the powder of (A) composition poly amic acid ester and (B) composition polyamic acid, and be dissolved in the method for organic solvent; The powder of (A) composition poly amic acid ester and (B) composition polyamic acid solution are carried out the method mixed; (A) composition polyamic acid ester solution and the powder of (B) composition polyamic acid are carried out the method mixed; (A) composition polyamic acid ester solution and (B) composition polyamic acid solution are carried out the method mixed.Even if when dissolving (A) composition poly amic acid ester and being different with the good solvent of (B) composition polyamic acid, also uniform (A) composition poly amic acid ester-(B) composition polyamic acid mixed solution can be obtained, therefore, the method (A) composition polyamic acid ester solution and (B) composition polyamic acid solution being carried out mixing is more preferably.

As the method for preparation (A) composition polyamic acid ester solution, be more preferably the method for dissolving the powder of (A) composition poly amic acid ester with gamma-butyrolacton or derivatives thereof, other good solvent, more preferably carry out the method for dissolving with gamma-butyrolacton or derivatives thereof.Now, polymer concentration is preferably 10 ~ 30%, is particularly preferably 10 ~ 15%.In addition, when dissolving the powder of (A) composition poly amic acid ester, can heat.Heating-up temperature is preferably 20 ~ 150 DEG C, particularly preferably 20 ~ 80 DEG C.

As the method for preparation (B) composition polyamic acid solution, there is following method: make the powder dissolution of polyamic acid make the method for polyamic acid solution in METHYLPYRROLIDONE, 1,3-dimethyl pyrrolidone or aforementioned good solvent; The method of direct use polymeric reaction solution, more preferably directly uses the method for polymeric reaction solution.Further preferably, solvent during polymeric polyamide acid is made the mixed solvent of gamma-butyrolacton or derivatives thereof and METHYLPYRROLIDONE, 1,3-dimethyl pyrrolidone or derivatives thereof, thus obtain the method for polyamic acid solution.When being dissolved by polyamic acid powder, polymer concentration is preferably 10 ~ 30%, is particularly preferably 10 ~ 15% again.In addition, can heat during the powder of dissolve polymer.Heating-up temperature is preferably 20 ~ 150 DEG C, is particularly preferably 20 ~ 80 DEG C.

When adding silane coupling agent, before being mixed with (B) composition polyamic acid solution by (A) composition polyamic acid ester solution, (A) composition polyamic acid ester solution, (B) composition polyamic acid solution or (A) composition polyamic acid ester solution can be added into both (B) composition polyamic acid solutions.In addition, can be added in the mixed solution of (A) composition poly amic acid ester-(B) composition polyamic acid.Silane coupling agent adds in order to the adaptation improving polymkeric substance and substrate, as the adding method of silane coupling agent, more preferably following method, be added in (B) composition polyamic acid solution more can laid particular stress on and be present in film inside and substrate interface, after polymkeric substance and silane coupling agent are fully reacted, then mix with (A) composition polyamic acid ester solution.When the addition of silane coupling agent is too much, unreacted silane coupling agent causes harmful effect to liquid crystal aligning sometimes, time very few, can not embody the effect that adaptation is brought, therefore, relative to the solid constituent of polymkeric substance, be preferably 0.01 ~ 5.0 quality %, be more preferably 0.1 ~ 1.0 quality %.

When being mixed with (B) composition polyamic acid solution by (A) composition polyamic acid ester solution, polymer concentration is preferably 10 ~ 30%, is particularly preferably 10 ~ 15%.In addition, can heat during mixing, heating-up temperature is preferably 20 ~ 100 DEG C, is particularly preferably 20 ~ 60 DEG C.

When adding silane coupling agent, crosslinking chemical, in order to prevent the precipitation of polymkeric substance, preferably added before interpolation lean solvent.In addition, when being burnt till by film, in order to advance the imidizate of poly amic acid ester efficiently, imidizate promoter can be added.When adding imidizate promoter, likely advance imidizate because of heating, therefore, preferably add again with after good solvent and lean solvent dilution.

By adding aforementioned good solvent and aforementioned lean solvent in the mixed solution to gained (A) composition poly amic acid ester and (B) composition polyamic acid, dilute with the form of the polymer concentration reaching regulation, aligning agent for liquid crystal of the present invention can be obtained.

[liquid crystal orientation film]

Liquid crystal orientation film of the present invention is coated on substrate after preferably being filtered by above-mentioned aligning agent for liquid crystal, dry, burn till to make film.As the substrate that will be coated with aligning agent for liquid crystal of the present invention, as long as the high substrate of the transparency is just not particularly limited, glass substrate, silicon nitride board can be used, the plastic bases etc. such as acrylic compounds substrate, polycarbonate substrate, from the view point of Simplified flowsheet, preferred use is formed with the substrate of ITO (tin indium oxide, IndiumTinOxide) electrode for driving liquid crystal etc.In addition, the liquid crystal of reflection-type represents in element, if be only single sided substrate, then also can use the opaque materials such as silicon wafer, and electrode now also can use the material of the meeting reflected light such as aluminium.

As the coating process of aligning agent for liquid crystal of the present invention, spin-coating method, print process, ink-jet method etc. can be listed.After being coated with aligning agent for liquid crystal of the present invention, the preferred drying of film, to burn till.In order to fully remove the organic solvent contained in aligning agent for liquid crystal, preferably with 50 ~ 120 DEG C of dryings preferably 1 ~ 10 minute.Then, preferably with 150 ~ 300 DEG C, more preferably burn till with 150 ~ 250 DEG C.Firing time is different because of firing temperature, preferably carry out 5 ~ 120 minutes, more preferably carry out 5 ~ 60 minutes.

The thickness of liquid crystal orientation film of the present invention is not particularly limited, and when thickness is crossed thin, liquid crystal represents that the reliability of element reduces sometimes, is therefore 5 ~ 300nm, is preferably 10 ~ 200nm.By carrying out the orientation process such as brushing to this coated surface, liquid crystal orientation film can be used as.The method of this film being carried out to orientation process can list brushing method, light orientation process method etc.

Liquid crystal orientation film of the present invention is the liquid crystal orientation film being endowed liquid crystal aligning ability by irradiating polarization radioactive ray.And then the illumination showing liquid crystal aligning penetrates scope wider than light aligned liquid-crystal alignment films in the past, even if in exposure intensity generation real estate when inequality, also homogeneous and good liquid crystal aligning can be obtained.

As the concrete example of light orientation process method, following method can be listed: the radioactive ray along certain orientation polarization are irradiated to aforementioned film coated surface, according to circumstances, heats with the temperature of 150 ~ 250 DEG C further, thus give liquid crystal aligning ability.As radioactive ray, the ultraviolet and luminous ray with 100 ~ 800nm wavelength can be used.Wherein, preferably there is the ultraviolet of 100 ~ 400nm wavelength, be particularly preferably the ultraviolet with 200 ~ 400nm wavelength.In addition, in order to improve liquid crystal aligning, film substrate can be heated with 50 ~ 250 DEG C, irradiating radioactive ray simultaneously.The exposure of aforementioned radioactive ray is preferably in 1 ~ 10,000mJ/cm ²scope, be particularly preferably in 100 ~ 5,000mJ/cm ²scope.

[liquid crystal aligning element]

Operate as above, make the substrate that two panels is formed with liquid crystal orientation film, be that vertical or antiparallel mode configures two plate bases across gap (cell gap) subtend with the orientation process direction of each liquid crystal orientation film, sealant is used to fit the periphery of two plate bases, in the cell gap demarcated by substrate surface and sealant, inject filling liquid crystal, seal filling orifice and form liquid crystal cells.And, liquid crystal cells outside surface, namely form on the another side side of each substrate of liquid crystal cells, to fit polaroid in the mode that the polarization direction of polaroid is consistent or vertical with the brushing direction of liquid crystal orientation film of the one side being formed at this substrate, thus liquid crystal can be obtained represent element.

In the present invention, as sealant, such as, preferably use the cured resin system with epoxy radicals and these two kinds of reactive groups of (methyl) acryloyl group.Wherein, as long as the contaminative caused liquid crystal is low, then not circumscribed completely.In sealant of the present invention, can compounding inorganic filler for the object of raising cementability, moisture-proof.As spendable inorganic filler, be not particularly limited, specifically, spherical silicon dioxide can be listed, fused silica, crystalline silica, titanium dioxide, titanium is black, silit, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulphate, calcium sulphate, mica, talcum, clay, aluminium oxide, magnesium oxide, zirconia, aluminium hydroxide, calcium silicate, alumina silicate, lithium aluminium silicate, zirconium silicate, barium titanate, glass fibre, carbon fiber, molybdenum disulfide, asbestos etc., be preferably spherical silicon dioxide, fused silica, crystalline silica, titanium dioxide, titanium is black, silicon nitride, boron nitride, calcium carbonate, barium sulphate, calcium sulphate, mica, talcum, clay, aluminium oxide, aluminium hydroxide, calcium silicate or alumina silicate.Aforementioned inorganic filling agent can be mixed with two or more.

Embodiment

Below list embodiment, illustrate the present invention further.Wherein, being not limited to the examples property of the present invention is explained.It should be noted that, the abbreviation of following compound and the assay method of each characteristic as follows.

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

GBL: gamma-butyrolacton

BCS: butyl cellosolve

IPA:2-propyl alcohol

DE-1: with reference to following formula (DE-1);

DA-1: with reference to following formula (DA-1);

DA-2: with reference to following formula (DA-2);

DA-3: with reference to following formula (DA-3);

DA-4: with reference to following formula (DA-4);

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

Additive A: dipentaerythritol acrylate (DAICEL-ALLNEXLTD. system)

Additive B: glycerin diglycidyl ether acrylic acid adduct (trade name: EPOXYESTER80MFA, Kyoeisha Chemical Co., Ltd.'s system)

[viscosity]

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

[molecular weight]

The molecular weight of poly amic acid ester and polyamic acid utilizes GPC (normal temperature gel soaks into chromatogram) device to measure, in polyglycol (polyethylene oxide) scaled value, calculate number-average molecular weight (hereinafter also referred to Mn) and weight-average molecular weight (hereinafter also referred to Mw).

GPC device: Shodex Inc. (GPC-101)

Post: Shodex Inc. (series connection of KD803 and KD805)

Column temperature: 50 DEG C

Eluent: DMF (as adjuvant, lithium bromide one water and thing (LiBrH ₂o) for 30mmol/L (liter), phosphoric acid anhydrous crystal (orthophosphoric acid) be 30mmol/L, tetrahydrofuran (THF) is 10ml/L)

Flow velocity: 1.0ml/ minute

Standard curve making standard model: employ TOSOH Co., Ltd manufacture TSK standard polyethylene oxide (weight-average molecular weight (Mw) is about 900,000,150,000,100,000 and 30,000) and PolymerLaboratoriesLtd. manufacture polyglycol (peak molecular weight (Mp) is about 12,000,4,000 and 1,000).In order to avoid the overlap at peak, implement to measure for following two kinds of samples respectively: by 900,000,100,000,12,000 and 1,000 these four kinds of samples mixed; And, by 150,000,30,000 and 4,000 these three kinds of samples mixed.

[FFS drives the making of liquid crystal cells]

First electroded substrate is prepared.Substrate is of a size of 30mm × 35mm and thickness is the glass substrate of 0.7mm.Substrate is formed and forms counter electrode and the IZO electrode possessing solid shape pattern is used as the 1st layer.On the counter electrode of the 1st layer, SiN (silicon nitride) film of formation CVD film forming is used as the 2nd layer.The thickness of the SiN film of the 2nd layer is 500nm, and it plays function as interlayer dielectric.The SiN film of the 2nd layer is configured with and patterning is carried out to IZO film and the comb teeth-shaped pixel electrode formed is used as the 3rd layer, thus define the 1st pixel and these two pixels of the 2nd pixel.Each pixel is of a size of vertical 10mm and horizontal about 5mm.Now, the pixel electrode of the counter electrode of the 1st layer and the 3rd layer by the effect of the SiN film of the 2nd layer electrical isolation.

The pixel electrode of the 3rd layer has the comb teeth-shaped shape that " < " font electrode key element that middle body bends is formed through multiple arrangement.The width of the Width of each electrode key element is 3 μm, is spaced apart 6 μm between electrode key element." < " font electrode key element that the pixel electrode forming each pixel is bent by middle body is formed through multiple arrangement, therefore the shape of each pixel is not oblong-shaped, but possess in the same manner as electrode key element middle body bend, the shape of " < " word of being similar to runic.Further, each pixel for boundary is split up and down, has the 1st region of the upside of sweep and the 2nd region of downside with the sweep of its central authorities.

When contrasting the 1st region and the 2nd region of each pixel, the formation direction forming the electrode key element of their pixel electrode is different.Namely, during using the liquid crystal aligning direction of aftermentioned liquid crystal orientation film as benchmark, in the 1st region of pixel, form the electrode key element of pixel electrode in the mode of the angle presenting+10 °, in the 2nd region of pixel, form the electrode key element of pixel electrode in the mode of the angle presenting-10 °.That is, the 1st region of each pixel and the 2nd region are formed as follows: the liquid crystal brought out by applying voltage between pixel electrode and counter electrode, the direction reverse direction each other of spinning movement (plane switches) in real estate.

Then, by aligning agent for liquid crystal with after the metre filter of 1.0 μm, by rotary coating, aligning agent for liquid crystal is coated on prepared above-mentioned electroded substrate.On the hot plate of 80 DEG C after dry 2 minutes, burn till 14 minutes with the heated air circulation type baking oven of 230 DEG C, thus formation thickness is the film of 100nm.Across polaroid with 500mJ/cm ²this coated surface is irradiated to the ultraviolet of 254nm, thus obtain the substrate being with liquid crystal orientation film.In addition, as subtend substrate, do not forming electrode and the glass substrate with the column spacer of 4 μm high is forming film similarly, and implementation orientation process.

As mentioned above, be one group with two plate bases, printing and sealing agent on substrate, by another substrate with liquid crystal orientation film face-to-face, after the direction of orientation mode that reaches 0 ° pastes, make sealant cures and make dummy cell.In this dummy cell, inject liquid crystal MLC-2041 (MERCKCORPORATION system) by decompression injection method, sealing inlet, thus obtain FFS driving liquid crystal cells.

[interchange of liquid crystal cells drives ghost]

Use the liquid crystal cells of above-mentioned making, under the isoperibol of 60 DEG C with the frequency of 30Hz apply 144 hours ± 10V alternating voltage.Thereafter, make to present short-circuit condition between the pixel electrode of liquid crystal cells and counter electrode, directly at room temperature place one day.

After placement, be arranged on by liquid crystal cells between the two panels polaroid that configures in the mode that polarizing axis is vertical, light backlight not executing under alive state, the arrangement angles of adjustment liquid crystal cells reaches minimum to make the brightness of transmitted light.Further, will the rotation of the liquid crystal cells angle the darkest from the 2nd region of the 1st pixel be calculated as angle delta to the anglec of rotation during angle that the 1st region is the darkest.2nd pixel operates too, and contrast the 2nd region and the 1st region, calculate same angle delta.Further, the mean value of the angle delta value of the 1st pixel and the 2nd pixel is calculated as the angle delta of liquid crystal cells.Exchanging when driving ghost Δ less than 0.1 is denoted as well, is denoted as bad when interchange drives ghost Δ to be more than 0.1.

< synthesis example 1>

The 500mL tetra-neck flask of band stirring apparatus is made nitrogen atmosphere, add p-phenylenediamine (PPD) 4.58g (42.4mmol), DA-11.79g (4.71mmol), NMP84.7g, GBL254g and the pyridine 8.40g (106mmol) as alkali, stir and make it dissolve.Then, this two amine aqueous solution is stirred and adds DE-114.4g (44.2mmol), react a night with 15 DEG C.After stirring a night, add acryloyl chloride 1.23g (13.6mmol), with 15 DEG C of reactions 4 hours.The solution of gained poly amic acid ester is stirred while be fed in 1477gIPA, the white precipitate that leaching is separated out, then clean 5 times with 738gIPA and carry out drying, thus obtain the poly amic acid ester toner 17.3g of white.Yield is 96.9%.In addition, the molecular weight of this poly amic acid ester is Mn=14,288, Mw=29,956.

Gained poly amic acid ester toner 3.69g is placed in 100mL conical flask, adds GBL33.2g, at room temperature stir 24 hours and make it dissolve, thus obtaining polyamic acid ester solution PAE-1.

< synthesis example 2>

To band stirring apparatus and interpolation 3 in the 100mL tetra-neck flask of band nitrogen ingress pipe, 5-diaminobenzoic acid 0.91g (5.98mmol), 4,4 '-diamino-diphenylamine 4.78g (23.9mmol), NMP13.3g and GBL6.66g, supplying nitrogen is while stir and make it dissolve.This two amine aqueous solution is stirred while add 1,2,3,4-butane tetracarboxylic acid dianhydride 4.76g (24.0mmol), add GBL9.99g, and at room temperature stir 2 hours.Then, add GBL20.0g and after stirring, add pyromellitic dianhydride 1.31g (6.00mmol), adding GBL4.80g, at room temperature stir 24 hours, thus obtain polyamic acid solution (PAA-1).Viscosity at 25 DEG C of gained polyamic acid solution is 4,147mPas.In addition, the molecular weight Mn=24 of polyamic acid, 333, Mw=60,010.

< synthesis example 3>

To band stirring apparatus and interpolation 3 in the 100mL tetra-neck flask of band nitrogen ingress pipe, 5-diaminobenzoic acid 0.30g (1.98mmol), 4,4 '-diamino-diphenyl methylamine 1.71g (8.02mmol), NMP2.25g and GBL11.3g, supplying nitrogen is while stir and make it dissolve.This two amine aqueous solution is stirred while add 1,2,3,4-butane tetracarboxylic acid dianhydride 1.72g (8.68mmol), add GBL4.50g, and at room temperature stir 2 hours.Then, add pyromellitic dianhydride 0.22g (1.01mmol), add GBL4.50g, at room temperature stir 24 hours, thus obtain polyamic acid solution (PAA-2).Viscosity at 25 DEG C of gained polyamic acid solution is 232mPas.In addition, the molecular weight Mn=9 of polyamic acid, 870, Mw=20,054.

< synthesis example 4>

The 500mL tetra-neck flask of band stirring apparatus is made nitrogen atmosphere, add p-phenylenediamine (PPD) 2.50g (23.1mmol), DA-30.59g (1.22mmol), NMP42.8g, GBL129g and the pyridine 4.34g (54.9mmol) as alkali, stir and make it dissolve.Then, this two amine aqueous solution is stirred and adds DE-17.44g (22.9mmol), react a night with 15 DEG C.After stirring a night, add acryloyl chloride 0.63g (7.01mmol), with 15 DEG C of reactions 4 hours.The solution of gained poly amic acid ester is stirred while be fed in 574gIPA, the white precipitate that leaching is separated out, then clean 5 times with 382gIPA, and carry out drying, thus obtain the poly amic acid ester toner 8.82g of white.Yield is 97.8%.In addition, the molecular weight of this poly amic acid ester is Mn=16,617, Mw=37,387.

Gained poly amic acid ester toner 0.80g is placed in 100mL conical flask, adds GBL7.20g, at room temperature stir 24 hours and make it dissolve, thus obtaining polyamic acid ester solution PAE-2.

< synthesis example 5>

The 500mL tetra-neck flask of band stirring apparatus is made nitrogen atmosphere, add p-phenylenediamine (PPD) 1.23g (11.3mmol), 4,4 '-ethylene aniline 0.80g (3.77mmol), NMP27.0g, GBL91.2g and the pyridine 2.69g (34.0mmol) as alkali, stir and make it dissolve.Then, this two amine aqueous solution is stirred and adds DE-14.61g (14.2mmol), react a night with 15 DEG C.After stirring a night, add acryloyl chloride 0.39g (4.34mmol), with 15 DEG C of reactions 4 hours.The solution of gained poly amic acid ester is stirred while be fed in 384gIPA, the white precipitate that leaching is separated out, then, clean 5 times with 256gIPA and carry out drying, thus obtain the poly amic acid ester toner 5.11g of white.Yield is 89.6%.In addition, the molecular weight of this poly amic acid ester is Mn=14,806, Mw=32,719.

Gained poly amic acid ester toner 0.80g is placed in 100mL conical flask, adds GBL7.20g, at room temperature stir 24 hours and make it dissolve, thus obtaining polyamic acid ester solution PAE-3.

< synthesis example 6>

The 500mL tetra-neck flask of band stirring apparatus is made nitrogen atmosphere, add p-phenylenediamine (PPD) 2.80g (25.9mmol), DA-21.45g (6.47mmol), NMP111g and the pyridine 6.18g (78.1mmol) as alkali, stir and make it dissolve.Then, this two amine aqueous solution is stirred and adds DE-19.89g (30.4mmol), react a night with 15 DEG C.After stirring a night, add acryloyl chloride 0.38g (4.21mmol), with 15 DEG C of reactions 4 hours.The solution of gained poly amic acid ester is stirred while be fed in 1230g water, the white precipitate that leaching is separated out, then, clean 5 times with the IPA of 1230g and carry out drying, thus obtain the poly amic acid ester toner 10.2g of white.Yield is 83.0%.In addition, the molecular weight of this 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 GBL7.18g, at room temperature stir 24 hours and make it dissolve, thus obtaining polyamic acid ester solution PAE-4.

< synthesis example 7>

The 500mL tetra-neck flask of band stirring apparatus is made nitrogen atmosphere, add DA-414.4g (58.8mmol), DA-12.48g (6.53mmol), NMP622g and the pyridine 11.6g (147mmol) as alkali, stir and make it dissolve.Then, this two amine aqueous solution is stirred and is added in DE-120.0g (61.4mmol), react a night with 15 DEG C.After stirring a night, add acryloyl chloride 1.70g (18.8mmol), with 15 DEG C of reactions 4 hours.The solution of gained poly amic acid ester is stirred while be fed in 2691gIPA, the white precipitate that leaching is separated out, then, clean 5 times with 1345gIPA and carry out drying, thus obtain the poly amic acid ester toner 31.4g of white.Yield is 95.9%.In addition, the molecular weight of this 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, adds NMP33.3g, at room temperature stir 24 hours and make it dissolve, thus obtaining polyamic acid ester solution PAE-5.

[preparation of aligning agent for liquid crystal]

(embodiment 1)

The polyamic acid solution PAA-15.50g obtained in the polyamic acid ester solution PAE-14.40g obtained in weighing synthesis example 1, synthesis example 2, add NMP0.52g, GBL5.58g, BCS4.01g, N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g and additive A 0.11g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal A1.

Use this aligning agent for liquid crystal A1, make adaptation evaluation substrate and liquid crystal cells according to following such step.

< adaptation evaluates >

<< sample making >>

The sample of adaptation evaluation makes as follows.By rotary coating coating of liquid crystalline alignment agent A1 on the ito substrate of 30mm × 40mm.On the hot plate of 80 DEG C after dry 2 minutes, utilize the heated air circulation type baking oven of 230 DEG C to burn till 14 minutes, thus formation thickness is the film of 100nm.Across polaroid with 500mJ/cm ²this coated surface is irradiated to the ultraviolet of 254nm, thus obtain the substrate being with liquid crystal orientation film.

Two plate bases that preparation operates like this and obtains, after the liquid crystal aligning face of a substrate is coated with 4 μm of pearl septs, drip sealant (XN-1500T of Xie Li KCC manufacture).Then, with the liquid crystal aligning face of another substrate for inner side and the mode that the overlapping widths of substrate is 1cm fit.Now, adjustment sealant dripping quantity, reaches 3mm to make the diameter of the sealant after laminating.After being fixed by the two plate base clips of having fitted, with 150 DEG C of heat curings 1 hour, thus make the sample of adaptation evaluation.

The mensuration >> of << adaptation

Thereafter, behind the end of the fixing upper and lower base plate of the accurate universal testing machine (AGS-X500N) of desktop that sample substrate is manufactured with Shimadzu Seisakusho Ltd., press from the top in substrate center portion, measure the pressure (N) occurred when peeling off.Stripping position for measured substrate is observed, and does not peel off, a sealant part that is overall or sealant is judged to be zero when there is fracture between sealing/intermembranous or film/substrate.When sealing/intermembranous generation is peeled off, sealing/intermembranous adaptation is judged to be ×, when film/substrate occurs to peel off, the adaptation between film/substrate is judged to be ×.

< embodiment 2>

The polyamic acid solution PAA-15.48g obtained in the polyamic acid ester solution PAE-14.42g obtained in weighing synthesis example 1, synthesis example 2, add NMP0.50g, GBL5.60g, BCS3.99g, N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g and additive B 0.11g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal A2.

< embodiment 3>

The polyamic acid solution PAA-24.07g obtained in the polyamic acid ester solution PAE-14.40g obtained in weighing synthesis example 1, synthesis example 3, add NMP0.06g, GBL7.46g, BCS3.98g and N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g, additive A 0.11g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal A3.

< embodiment 4>

The polyamic acid solution PAA-24.04g obtained in the polyamic acid ester solution PAE-14.41g obtained in weighing synthesis example 1, synthesis example 3, add NMP0.06g, GBL7.48g, BCS4.00g and N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g, additive B 0.11g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal A4.

< embodiment 5>

The polyamic acid solution PAA-15.49g obtained in the polyamic acid ester solution PAE-24.41g obtained in weighing synthesis example 4, synthesis example 2, add NMP0.50g, GBL5.60g, BCS4.00g, N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g and additive A 0.11g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal A5.

< embodiment 6>

The polyamic acid solution PAA-15.48g obtained in the polyamic acid ester solution PAE-24.42g obtained in weighing synthesis example 4, synthesis example 2, add NMP0.50g, GBL5.60g, BCS4.00g, N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g and additive B 0.11g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal A6.

< embodiment 7>

The polyamic acid solution PAA-15.49g obtained in the polyamic acid ester solution PAE-34.42g obtained in weighing synthesis example 5, synthesis example 2, add NMP0.50g, GBL5.60g, BCS4.00g, N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g and additive A 0.11g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal A7.

< embodiment 8>

The polyamic acid solution PAA-15.49g obtained in the polyamic acid ester solution PAE-34.42g obtained in weighing synthesis example 5, synthesis example 2, add NMP0.50g, GBL5.60g, BCS4.00g, N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g and additive B 0.11g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal A8.

< embodiment 9>

The polyamic acid solution PAA-15.50g obtained in the polyamic acid ester solution PAE-44.42g obtained in weighing synthesis example 6, synthesis example 2, add NMP0.50g, GBL5.60g, BCS4.00g, N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g and additive A 0.11g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal A9.

< embodiment 10>

The polyamic acid solution PAA-15.49g obtained in the polyamic acid ester solution PAE-44.40g obtained in weighing synthesis example 6, synthesis example 2, add NMP0.50g, GBL5.60g, BCS4.00g, N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g and additive B 0.11g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal A10.

< embodiment 11>

The polyamic acid solution PAA-15.49g obtained in the polyamic acid ester solution PAE-54.42g obtained in weighing synthesis example 7, synthesis example 2, add NMP0.50g, GBL5.60g, BCS4.00g, N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g and additive A 0.11g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal A11.

< embodiment 12>

The polyamic acid solution PAA-15.48g obtained in the polyamic acid ester solution PAE-54.42g obtained in weighing synthesis example 7, synthesis example 2, add NMP0.50g, GBL5.60g, BCS4.00g, N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g and additive B 0.11g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal A12.

< comparative example 1>

The polyamic acid solution PAA-15.52g obtained in the polyamic acid ester solution PAE-14.39g obtained in weighing synthesis example 1, synthesis example 2, add NMP0.50g, GBL5.57g, BCS4.02g and N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal B1.

< comparative example 2>

The polyamic acid solution PAA-24.07g obtained in the polyamic acid ester solution PAE-14.42g obtained in weighing synthesis example 1, synthesis example 3, add NMP0.06g, GBL7.50g, BCS4.01g and N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal B2.

< comparative example 3>

Add polyamic acid ester solution PAE-111.0g, GBL4.99g, BCS4.02g and N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g, the additive A 0.11g obtained in synthesis example 1, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal B3.

< comparative example 4>

Add polyamic acid ester solution PAE-111.0g, GBL5.00g, BCS4.01g and N-α-(9-the fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g obtained in synthesis example 1, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal B4.

< comparative example 5>

Weigh the polyamic acid solution PAA-19.17g obtained in synthesis example 2, add NMP1.37g, GBL5.47g, BCS3.99g and N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.13g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal B5.

< comparative example 6>

Weigh the polyamic acid solution PAA-26.79g obtained in synthesis example 3, add NMP1.84g, GBL7.37g, BCS4.00g and N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal B6.

< comparative example 7>

Add polyamic acid ester solution PAE-211.0g, GBL4.99g, BCS4.01g and N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g, the additive A 0.11g obtained in synthesis example 4, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal B7.

< comparative example 8>

Add polyamic acid ester solution PAE-211.0g, GBL5.00g, BCS4.01g and N-α-(9-the fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g obtained in synthesis example 4, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal B8.

< comparative example 9>

Add polyamic acid ester solution PAE-311.0g, GBL5.00g, BCS4.00g and N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g, the additive A 0.11g obtained in synthesis example 5, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal B9.

< comparative example 10>

Add polyamic acid ester solution PAE-311.0g, GBL5.00g, BCS4.01g and N-α-(9-the fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g obtained in synthesis example 5, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal B10.

< comparative example 11>

Add polyamic acid ester solution PAE-411.1g, GBL4.98g, BCS4.02g and N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g, the additive A 0.11g obtained in synthesis example 6, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal B11.

< comparative example 12>

Add polyamic acid ester solution PAE-411.0g, GBL5.00g, BCS4.01g and N-α-(9-the fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g obtained in synthesis example 6, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal B12.

< comparative example 13>

Add polyamic acid ester solution PAE-511.0g, GBL4.98g, BCS4.02g and N-α-(9-fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g, the additive A 0.11g obtained in synthesis example 7, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal B13.

< comparative example 14>

Add polyamic acid ester solution PAE-511.0g, GBL5.00g, BCS4.01g and N-α-(9-the fluorenylmethoxycarbonyl groups)-N-τ-tert-butoxycarbonyl-L-Histidine 0.15g obtained in synthesis example 7, at room temperature stir 3 hours, thus obtain aligning agent for liquid crystal B14.

Except using this aligning agent for liquid crystal B14, by the method identical with embodiment 1, carry out adaptation evaluation and drive ghost evaluation with exchanging.

Use the aligning agent for liquid crystal obtained respectively in above-described embodiment 1 ~ 4 and comparative example 1 ~ 6, for the liquid crystal cells utilizing the method identical with embodiment 1 to obtain, carry out adaptation evaluation and drive ghost evaluation with exchanging, result is summed up and is shown in table 1.

Similarly, use the aligning agent for liquid crystal obtained respectively in above-described embodiment 5 ~ 12 and comparative example 7 ~ 14, for the liquid crystal cells utilizing the method identical with embodiment 1 to obtain, carry out adaptation evaluation and drive ghost evaluation with exchanging, result is summed up and is shown in table 2.

[table 1]

[table 2]

utilizability in industry

The aligning agent for liquid crystal of the application of the invention, the liquid crystal orientation film with excellent liquid crystal aligning, electrical characteristics and high sealing adaptation can be obtained, the liquid crystal with this liquid crystal orientation film represents to drive and the after image produced, the expression ghost etc. that causes because of the residual charge of DC voltage are suppressed because exchanging in element, can be applicable to require highly represent quality, greatly picture and in the image expression fields such as the LCD TV of high-resolution.

Claims

1. an aligning agent for liquid crystal, is characterized in that, it contains following (A) composition, (B) composition and (C) composition,

(A) composition: the poly amic acid ester obtained by the tetrabasic carboxylic acid dialkyl derivant of tetrabasic carboxylic acid dialkyl derivant shown in the following formula (1) that comprises more than 60mol% and the polycondensation reaction of the diamines of at least a kind of diamines comprised in the group that is selected from and is made up of diamines following formula (2) ~ (5) Suo Shi

R ₁for the alkyl of carbon number 1 ~ 5, R ₂for hydroxyl or chlorine atom, R _xfor the alkyl of carbon number 1 ~ 6,

A ₁for the divalent organic group of singly-bound, ester bond, amido link, thioester bond or carbon number 2 ~ 10, A ₂for 1 valency organic group of halogen atom, hydroxyl, amino, mercapto, nitro, phosphate or carbon number 1 ~ 20, a is the integer of 1 ~ 4, when a is more than 2, and A ₂structure optionally identical or different;

(B) composition: by the polycondensation reaction of tetracarboxylic dianhydride and diamines and the polyamic acid obtained;

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

3. aligning agent for liquid crystal according to claim 1 and 2, wherein, (A) composition uses to comprise the diamines being selected from least a kind of diamines in the group be made up of diamines above-mentioned formula (2) ~ formula (5) Suo Shi of 40 ~ 100 % by mole and the poly amic acid ester that obtains relative to all diamines.

4. the aligning agent for liquid crystal according to any one of claims 1 to 3, wherein, (A) composition uses at least a kind of diamines comprised in the group selecting the composition of diamines shown in diamines and formula (3) shown in free style (2) and the poly amic acid ester selecting the diamines of at least a kind of diamines in the group of the composition of diamines shown in diamines and formula (5) shown in free style (4) and obtain.

5. the aligning agent for liquid crystal according to any one of Claims 1 to 4, wherein, (A) composition is the poly amic acid ester using diamines shown in contained (2) and select the diamines of at least a kind of diamines in the group of the composition of diamines shown in free style (4) and obtain.

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

-A ₃-R ₃(6)

A ₃for singly-bound ,-O-,-S-,-NR ' ₃-, ester bond, amido link, thioester bond, urea key, carbonic acid ester bond or amino-formate bond; R ₃be selected from alkyl, thiazolinyl, alkynyl, aryl and the group that they combined optionally with substituent carbon number 1 ~ 10, they optionally have substituting group; R ' ₃the group being selected from hydrogen atom or alkyl, thiazolinyl, alkynyl, aryl and they being combined, they optionally have substituting group.

7. the aligning agent for liquid crystal according to any one of claim 1 ~ 6, wherein, (A) composition is the poly amic acid ester using the diamines of at least a kind of diamines comprised in the group being selected from and being made up of the diamines of following formula (A-1) ~ (A-5) and obtain

8. aligning agent for liquid crystal according to claim 7, wherein, (A) composition is the diamines of at least a kind of diamines in the group using the diamines and being selected from comprising above-mentioned formula (2) to be made up of above-mentioned formula (A-1) ~ (A-5) and the poly amic acid ester that obtains.

9. the aligning agent for liquid crystal according to any one of claim 1 ~ 8, wherein, (B) composition is the polyamic acid using the tetracarboxylic dianhydride of at least a kind that comprises in the group being selected from and being made up of the tetracarboxylic dianhydride of following formula (B-1) ~ (B-9) and obtain

10. the aligning agent for liquid crystal according to any one of claim 1 ~ 9, wherein, (B) composition is polycondensation reaction by tetracarboxylic dianhydride and diamines and the polyamic acid obtained, and described tetracarboxylic dianhydride has at least a kind of tetracarboxylic dianhydride be selected from the group be made up of above-mentioned formula (B-1) ~ (B-9) of more than 20 % by mole of all tetracarboxylic dianhydrides.

11. aligning agent for liquid crystal according to any one of claim 1 ~ 10, wherein, (B) composition is the polyamic acid using the diamines of at least a kind that comprises in the group being selected from and being made up of following formula (B-10) ~ (B-14) and obtain

12. aligning agent for liquid crystal according to claim 11, wherein, (B) composition uses the diamines being selected from least a kind of diamines in the group be made up of above-mentioned formula (B-10) ~ (B-14) and the polyamic acid that obtains with more than 20 % by mole of all diamines.

13. aligning agent for liquid crystal according to any one of claim 1 ~ 12, wherein, (C) composition is dipentaerythritol acrylate or glycerin diglycidyl ether acrylic acid adduct.

14. aligning agent for liquid crystal according to any one of claim 1 ~ 13, it is also containing mixed organic solvents, described mixed organic solvents comprises at least a kind of organic solvent (D1) in the group being selected from and being made up of gamma-butyrolacton and derivant thereof and is selected from by METHYLPYRROLIDONE, 1, at least a kind of organic solvent (D2) in the group of 3-dimethyl-imidazolinone and their derivant composition, the content of organic solvent (D1) is 2 ~ 30 quality % relative to organic solvent (D1) and the total amount of organic solvent (D2).

15. aligning agent for liquid crystal according to any one of claim 1 ~ 14, it is for carrying out the liquid crystal orientation film of light orientation process.

16. 1 kinds of liquid crystal orientation films, the aligning agent for liquid crystal according to any one of claim 1 ~ 15 is coated substrate and is burnt till and obtains by it.