CN104718492B

CN104718492B - Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display element

Info

Publication number: CN104718492B
Application number: CN201380052996.4A
Authority: CN
Inventors: 根木隆之; 樱井宏之; 筒井皇晶
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2012-08-10
Filing date: 2013-08-06
Publication date: 2018-09-18
Anticipated expiration: 2033-08-06
Also published as: KR20150043360A; JP6217937B2; CN104718492A; JPWO2014024893A1; TW201422677A; KR102146140B1; WO2014024893A1

Abstract

The present invention is a kind of aligning agent for liquid crystal, and solvent-soluble polyimide and solvent obtained by polyamic acid imidizate obtained by polymerisation are carried out with diamine component it includes that will make the tetracarboxylic dianhydride that following formula (1) indicates.[changing 1](in formula (1), W is the structure that following formula indicates.) [changing 2](in formula, R¹It is hydrogen atom, COOH, N (CH₂CH=CH₂)₂Or (CH₂)_n1CH₃；The integer that n1 is 0~20；R²It is C (=O), SO₂‑、‑C(CH₃)₂‑、‑O‑、‑CH₂‑、‑NH‑、‑C₂H₄‑NH‑CONH‑C₂H₄Or O (CH₂)_m1O‑；The integer that m1 is 1~5.).

Description

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

Technical field

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

Background technology

The liquid crystal display element used in LCD TV, liquid crystal display etc. is as slim and light weight the display of realization Nowadays part is widely used.As the liquid crystal orientation film for making liquid crystal aligning, the liquid of so-called polyimide is mainly used Brilliant alignment films, the liquid crystal orientation film with polyamic acid in the upper coating such as glass substrate by (being also referred to as polyamic acid (polyamide acid)), the solution of the polyimide precursors such as poly amic acid ester or polyimides takes as the liquid crystal of principal component To agent, it is burnt into and is obtained.

In order to improve the display characteristic of this liquid crystal display element, by changing polyamic acid, poly amic acid ester and polyamides The structure of imines, the method for the different polyamic acid of blending rating, poly amic acid ester and polyimides, or addition additive etc., To carry out the improvement of liquid crystal aligning and electrical characteristics etc., control of pre-tilt angle etc. (referring to patent document 1 etc.).

Existing technical literature

Patent document

Patent document 1：Japanese Patent Laid-Open 2011-100099 bulletins

Invention content

The technical problems to be solved by the invention

In above-mentioned aligning agent for liquid crystal, the aligning agent for liquid crystal containing polyimides has the following problems：If being coated on base Plate is first-class, then in the end of coated surface, there is a phenomenon where generating the agglutinator of polymer (polyimides), (also referred to as albefaction is solidifying Collection), it is difficult to obtain uniform film.

Problem of the present invention is that solving above-mentioned problem of the prior art, the liquid crystal for providing albefaction agglutination excellent takes To agent, liquid crystal orientation film and liquid crystal display element.

Technical scheme applied to solve the technical problem

Present inventor has performed conscientiously studying, as a result, it has been found that comprising using the tetracarboxylic dianhydride of specific structure as the solvent of raw material The aligning agent for liquid crystal of soluble polyimide and solvent is extremely effective in terms of reaching the above subject, so as to complete this hair It is bright.

That is, the present invention has main points below.

1. a kind of aligning agent for liquid crystal, which is characterized in that include the tetracarboxylic dianhydride and diamine component that following formula (1) will be made to indicate Carry out solvent-soluble polyimide and solvent obtained by polyamic acid imidizate obtained by polymerisation.

[changing 1]

(in formula (1), W is the structure that following formula indicates.)

[changing 2]

(in formula, R¹It is hydrogen atom ,-COOH ,-N (CH₂CH=CH₂)₂Or-(CH₂)_n1CH₃；The integer that n1 is 0~20；R² It is-C (=O)-,-SO₂-、-C(CH₃)₂-、-O-、-CH₂-、-NH-、-C₂H₄-NH-CONH-C₂H₄Or-O (CH₂)_m1O-；M1 is 1 ~5 integer.)

2. a kind of liquid crystal orientation film, which is characterized in that obtained using the aligning agent for liquid crystal described in 1.

3. a kind of liquid crystal display element, which is characterized in that have the liquid crystal orientation film described in 2.

The effect of invention

The albefaction of the aligning agent for liquid crystal of the present invention is aggregated excellent, therefore can for example be made even if being coated on substrate Standing time Deng after is long, uniformity also good liquid crystal orientation film.

Specific implementation mode

Hereinafter, the present invention is described in detail.

The aligning agent for liquid crystal of the present invention includes that the tetracarboxylic dianhydride that above formula (1) will be made to indicate with diamine component polymerize instead Solvent-soluble polyimide and solvent obtained by polyamic acid imidizate obtained by answering.Aligning agent for liquid crystal refers to for making Make the solution of liquid crystal orientation film；Liquid crystal orientation film refers to the film for making liquid crystal be orientated along defined direction.

As described above, formula (1), W is the divalent group that following formula indicates.In following formula, R¹It is hydrogen atom ,-COOH ,-N (CH₂CH= CH₂)₂Or-(CH₂)_n1CH₃, preferably hydrogen atom ,-COOH or-N (CH₂CH=CH₂)₂.In addition, R¹Binding site without special limit It is fixed, it is preferably ortho position or contraposition relative to the-NH- combined with phenyl ring.The integer that n1 is 0~20；R²It is-C (=O)-,-SO₂-、- C(CH₃)₂-、-O-、-CH₂-、-NH-、-C₂H₄-NH-CONH-C₂H₄Or-O (CH₂)_m1O-, preferably-SO₂-、-O-、-CH₂-、-NH- Or-C₂H₄-NH-CONH-C₂H₄-.The integer that m1 is 1~5.

[changing 3]

In formula (1) ,-NH- combined with the phenyl ring of W is preferably present in contraposition or meta position each other.

By making the tetracarboxylic dianhydride that the formula (1) indicates carry out polymerisation with diamine component, polyamic acid is can get, is led to It crosses the polyamic acid imidizate of gained, can get polyimides.Polyimides obtained by this is dissolved in the liquid of the present invention The polyimides of solvent contained by brilliant alignment agent, i.e. solvent-soluble polyimide.

The aligning agent for liquid crystal of the present invention includes that the tetracarboxylic dianhydride that the formula (1) will be made to indicate with diamine component polymerize instead Solvent-soluble polyimide and solvent obtained by polyamic acid imidizate obtained by answering.In addition, the solvent soluble is poly- Acid imide can be a kind of, can also be two or more.Include the tetracarboxylic dianhydride indicated with formula (1) by being made as described above For the solvent-soluble polyimide of raw material and the aligning agent for liquid crystal of solvent, as shown in following embodiments, albefaction agglutination is special Property is excellent.That is, when the aligning agent for liquid crystal of the present invention is coated on substrate etc. above, in the generation polymer that the end of coated surface occurs The phenomenon that agglutinator of (polyimides) (also referred to as albefaction agglutination), is inhibited, therefore can get uniform film.Therefore, Such as good liquid crystal orientation film the long standing time after being coated on substrate etc., uniformity can be made.By as above Described be made takes comprising the tetracarboxylic dianhydride indicated using formula (1) as the liquid crystal of the solvent-soluble polyimide of raw material and solvent To agent, it is not susceptible to albefaction agglutination, the detailed reason of film high uniformity is not known, but speculates it is because as raw material The tetracarboxylic dianhydride that indicates of formula (1) possessed by under the influence of the amido bond that combines in specific structure, with mixing for solvent Property improves.In addition, the tetracarboxylic dianhydride indicated using formula (1) is the solvent-soluble polyimide of raw material in N- methyl -2- pyrroles The dissolubility in the solvent of aligning agent for liquid crystal such as alkanone or butoxy ethanol is high, even if aligning agent for liquid crystal is put for a long time Setting will not be precipitated, and storage stability is high.

In addition, the manufacturing method for the tetracarboxylic dianhydride that formula (1) indicates is not particularly limited, such as can be by making 1,2,4- hexamethylenes Alkane tricarboxylic acids -1,2- acid anhydride 4- acyl chlorides and H₂N-W-NH₂(W is identical as the W in formula (1)) reacts to manufacture.It can specifically enumerate Japanese special Manufacturing method described in sharp special open 2012-72121 bulletins.In addition, for example there is R in manufacture²For-C₂H₄-NH-CONH- C₂H₄W formula (1) indicate tetracarboxylic dianhydride when, such as can be by making 1,2,4- cyclohexanetricarboxylic acid -1,2- acid anhydride 4- acyl chlorides It is manufactured with the diamine reactant described in WO2010/053128 texts.

In addition it is also possible to which the tetracarboxylic dianhydride other than the tetracarboxylic dianhydride that formula (1) indicates (is also denoted as other tetracarboxylic acids below Acid dianhydride) and formula (1) indicate tetracarboxylic dianhydride reacted together with diamine component.At this point, formula (1) indicate tetracarboxylic dianhydride compared with Be well with the 60 of the tetracarboxylic dianhydride's ingredient total amount used in the synthesis of polyamic acid (and solvent-soluble polyimide)~ The amount of 95 moles of % uses, and more preferably the 70~90 of tetracarboxylic dianhydride's ingredient mole % is the tetracarboxylic dianhydride that formula (1) indicates.It will The tetracarboxylic dianhydride and other tetracarboxylic dianhydrides of formula (1) expression and referred to as tetracarboxylic dianhydride's ingredient.

As other tetracarboxylic dianhydrides, the tetracarboxylic dianhydride of following formula (2) expression can be enumerated.

[changing 4]

(in formula (2), Z₁It is 4 valence organic groups of the carbon number 4~13 of the non-aromatic cyclic hydrocarbon base containing carbon number 4~6.)

In formula (2), as Z₁Concrete example, the 4 valence organic groups that following formula (2a)~formula (2j) indicates can be enumerated.

[changing 5]

(in formula (2a), Z₂~Z₅It is hydrogen atom, methyl, chlorine atom or phenyl ring, they can be the same or different each other； In formula (2g), Z₆And Z₇It is hydrogen atom or methyl, they can be the same or different each other.)

In formula (2), from the viewpoint of polymerisation reactivity and the complexity of synthesis, Z₁Particularly preferred structure be formula (2a), formula (2c), formula (2d), formula (2e), formula (2f) or formula (2g).Wherein, preferred formula (2a), formula (2e), formula (2f) or formula (2g)。

In addition, the tetracarboxylic dianhydride that formula (2) indicates is not particularly limited relative to the ratio of tetracarboxylic dianhydride's ingredient total amount, example Such as be preferably tetracarboxylic dianhydride's ingredient total amount 5~40 moles of % be above formula (2) indicate tetracarboxylic dianhydride, more preferably 10~30 Mole %.

Other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride indicated as above formula (2), can enumerate Pyromellitic Acid, 2, and 3, 6,7- naphthalenetetracarbacidic acidics, 1,2,5,6- naphthalenetetracarbacidic acidics, 1,4,5,8 naphthalenetetracarboxylic acid, 2,3,6,7- anthracenes tetracarboxylic acid, 1,2,5,6- anthracenes four Formic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylics, 2,3,3 ', 4- bibenzene tetracarboxylics, bis- (3,4- dicarboxyphenyis) ethers, 3,3 ', 4,4 '- Benzophenone tetracarboxylic, bis- (3,4- dicarboxyphenyis) sulfones, bis- (3,4- dicarboxyphenyis) methane, bis- (the 3,4- dicarboxyl benzene of 2,2- Base) propane, bis- (3,4- dicarboxyphenyis) propane of 1,1,1,3,3,3- hexafluoros -2,2-, bis- (3,4- dicarboxyphenyis) dimethyl Silane, bis- (3,4- dicarboxyphenyis) diphenyl silanes, 2,3,4,5- pyridines tetracarboxylic acid, bis- (3,4- dicarboxyphenyis) pyrroles of 2,6- Pyridine, 3,3 ', 4,4 '-diphenyl sulfone tetraformic acids, 3,4,9,10- tetracarboxylic acids or 1,3- diphenyl -1,2,3,4- cyclobutanetetracarboxylics Dianhydride.

In addition, the tetracarboxylic dianhydride of above formula (1) expression of the raw material as solvent-soluble polyimide, other tetrabasic carboxylic acids Dianhydride can be a kind of respectively, can also be two or more.

The diamine component reacted with tetracarboxylic dianhydrides' ingredients such as the tetracarboxylic dianhydrides of formula (1) expression is not particularly limited, and can be made With common diamines in aligning agent for liquid crystal.As general diamines, general diamines can be enumerated, with the side for making liquid crystal vertical-tropism The diamines of chain makes liquid crystal show the diamines of high pre-tilt angle, the diamines etc. with photoreactive group.

As general diamines, such as p-phenylenediamine, 2 can be enumerated, 3,5,6- tetramethyl-para-phenylene diamines, 2,5- dimethyl are to benzene Diamines, m-phenylene diamine (MPD), 2,4- dimethyl-m-phenylenediamines, 2,5- diaminotoluenes, 2,6- diaminotoluenes, 2,5- diaminobenzenes Phenol, 2,4- diaminophenols, 3,5- diaminophenols, 3,5- diamino benzylalcohol, 2,4- diamino benzylalcohol, 4,6- diamino isophthalic Diphenol, 4,4 '-benzidines, 3,3 '-dimethyl -4,4 '-benzidine, 3,3 '-dimethoxy-4 's, 4 '-diamino connection Benzene, 3,3 '-dihydroxy -4,4 '-benzidine, 3,3 '-dicarboxyls -4,4 '-benzidine, 3,3 '-two fluoro- 4,4 '-connection Benzene, 3,3 '-trifluoromethyls -4,4 '-benzidine, 3,4 '-benzidines, 3,3 '-benzidines, 2,2 '-diamino Biphenyl, 2,3 '-benzidines, 4,4 '-diaminodiphenyl-methanes, 3,3 '-diaminodiphenyl-methanes, 3,4 '-diamino Diphenyl methane, 2,2 '-diaminodiphenyl-methanes, 2,3 '-diaminodiphenyl-methanes, 4,4 '-diamino-diphenyl ethers, 3, 3 '-diamino-diphenyl ethers, 3,4 '-diamino-diphenyl ethers, 2,2 '-diamino-diphenyl ethers, 2,3 '-diamino-diphenyls Ether, 4,4 '-sulfonyldianilines, 3,3 '-sulfonyldianilines, bis- (4- aminophenyls) silane, bis- (3- aminophenyls) silane, diformazan Bis- (4- aminophenyls) silane of base-, bis- (3- aminophenyls) silane of dimethyl-, 4,4 '-diaminodiphenyl sulfides, 3,3 '-diaminos Base diphenyl sulfide, 4,4 '-diamino-diphenylamines, 3,3 '-diamino-diphenylamines, 3,4 '-diamino-diphenylamines, 2,2 '-diamino Diphenylamines, 2,3 '-diamino-diphenylamines, N- methyl (4,4 '-diamino-diphenyl) amine, N- methyl (3,3 '-diamino hexichol Base) amine, N- methyl (3,4 '-diamino-diphenyl) amine, N- methyl (2,2 '-diamino-diphenyl) amine, N- methyl (2,3 '-two Aminodiphenyl base) amine, 4,4 '-diamino benzophenone, 3,3 '-diamino benzophenone, 3,4 '-diamino benzophenone, 1,4- diaminos Base naphthalene, 2,2 '-diamino benzophenone, 2,3 '-diamino benzophenone, 1,5- diaminonaphthalenes, 1,6- diaminonaphthalenes, 1,7- diamino Naphthalene, 1,8- diaminonaphthalenes, 2,5- diaminonaphthalenes, 2,6 diaminonaphthalenes, 2,7- diaminonaphthalenes, 2,8- diaminonaphthalenes, the bis- (4- of 1,2- Aminophenyl) ethane, bis- (3- aminophenyls) ethane of 1,2-, bis- (4- aminophenyls) propane of 1,3-, bis- (the 3- aminobenzenes of 1,3- Base) propane, bis- (4- aminophenyls) butane of 1,4-, bis- (3- aminophenyls) butane of 1,4-, bis- (3,5- diethyl -4- aminobenzenes Base) methane, bis- (4- amino-benzene oxygens) benzene of 1,4-, bis- (4- amino-benzene oxygens) benzene of 1,3-, bis- (4- aminophenyls) benzene of 1,4-, 1, Bis- (the 4- aminobenzenes methyl) benzene of bis- (4- aminophenyls) benzene of 3-, 1,4-, bis- (4- amino-benzene oxygens) benzene of 1,3-, 4,4 '-[Asias 1,4- Phenyl is bis- (methylene)] diphenylamines, 4,4 '-[1,3- phenylenes are bis- (methylene)] diphenylamines, 3,4 '-[1,4- phenylenes are bis- (sub- Methyl)] diphenylamines, 3,4 '-[1,3- phenylenes are bis- (methylene)] diphenylamines, 3,3 '-[1,4- phenylenes are bis- (methylene)] two Aniline, 3,3 '-[1,3- phenylenes are bis- (methylene)] diphenylamines, 1,4- phenylenes bis- [(4- aminophenyls) ketones], 1,4- are sub- Phenyl bis- [(3- aminophenyls) ketones], 1,3- phenylenes bis- [(4- aminophenyls) ketones], bis- [(the 3- amino of 1,3- phenylenes Phenyl) ketone], 1,4- phenylenes bis- (4-aminobenzoic acid esters), 1,4- phenylenes bis- (3- Aminobenzoates), the Asias 1,3- benzene Base bis- (4-aminobenzoic acid esters), 1,3- phenylenes bis- (3- Aminobenzoates), bis- (4- aminophenyls) terephthalates, Bis- (3- aminophenyls) terephthalates, bis- (4- aminophenyls) isophthalic acid esters, bis- (3- aminophenyls) isophthalic diformazans Acid esters, N, N '-(1,4- phenylenes) bis- (4- aminobenzamides), N, N '-(1,3- phenylenes) bis- (4- aminobenzamides), N, N '-(1,4- phenylenes) bis- (3-ABs), N, N '-(1,3- phenylenes) bis- (3-ABs), N, N '- Bis- (4- aminophenyls) terephthalamides, N, bis- (3- aminophenyls) terephthalamides of N '-, N, bis- (the 4- aminobenzenes of N '- Base) isophtalamide, N, it is bis- (3- aminophenyls) isophtalamides of N '-, bis- (4- aminophenyls) anthracenes of 9,10-, 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS), 2,2 '-bis- [4- (4- amino-benzene oxygens) phenyl] propane, 2,2 '-bis- [4- (4- aminobenzene oxygen Base) phenyl] hexafluoropropane, 2,2 '-bis- (4- aminophenyls) hexafluoropropane, 2,2 '-bis- (3- aminophenyls) hexafluoropropane, 2, 2 '-bis- (3- amino -4- aminomethyl phenyls) hexafluoropropane, 2,2 '-bis- (4- aminophenyls) propane, 2,2 '-bis- (3- aminophenyls) Propane, 2,2 '-bis- (3- amino -4- aminomethyl phenyls) propane, 3,5- diaminobenzoic acids, 2,5- diaminobenzoic acids, 1,3- are bis- Bis- (3- amino-benzene oxygens) propane of (4- amino-benzene oxygens) propane, 1,3-, bis- (4- amino-benzene oxygens) butane of 1,4-, 1,4- are bis- Bis- (4- amino-benzene oxygens) pentanes of (3- amino-benzene oxygens) butane, 1,5-, bis- (3- amino-benzene oxygens) pentanes of 1,5-, 1,6- are bis- Bis- (3- amino-benzene oxygens) hexanes of (4- amino-benzene oxygens) hexane, 1,6-, bis- (4- amino-benzene oxygens) heptane of 1,7-, 1,7- (3- Amino-benzene oxygen) heptane, bis- (4- amino-benzene oxygens) octanes of 1,8-, bis- (3- amino-benzene oxygens) octanes of 1,8-, bis- (the 4- ammonia of 1,9- Phenoxyl) nonane, bis- (3- amino-benzene oxygens) nonanes of 1,9-, 1,10- (4- amino-benzene oxygens) decane, 1,10- (3- aminobenzenes Oxygroup) decane, 1,11- (4- amino-benzene oxygens) hendecane, 1,11- (3- amino-benzene oxygens) hendecane, 1,12- (4- aminobenzenes Oxygroup) aromatic diamines such as dodecane, 1,12- (3- amino-benzene oxygens) dodecane, bis- (4- aminocyclohexyls) methane, bis- (4- Amino -3- methylcyclohexyls) alicyclic diamines such as methane, 1,3- diaminopropanes, 1,4-Diaminobutane, 1,5- diamino penta Alkane, 1,6- diamino hexanes, 1,7- diaminoheptanes, 1,8- diamino-octanes, 1,9- diamino nonanes, the 1,10- diamino last of the ten Heavenly stems The aliphatic diamines such as alkane, 1,11- diamino undecanes, 1,12- diamino dodecanes.

This general diamines be preferably with used in the synthesis of polyamic acid (and solvent-soluble polyimide) two The amount of 50~95 moles of % of amine component uses, more preferably the 70~90 of diamine component mole %.

As with the side chain for making liquid crystal vertical-tropism diamines, so that liquid crystal is shown the diamines of high pre-tilt angle, can enumerate With chain alkyl, midway circular structure or the group of branched structure in chain alkyl, steroid radical, by the hydrogen of these groups Atomic component or diamines of the group as side chain for being all substituted by fluorine atom.Can specifically enumerate for example following formula (3), (4), (5), (6) diamines indicated, but not limited thereto.

[changing 6]

(in formula (3), l, m and n separately indicate 0 or 1 integer, R³Indicate the alkylidene of carbon number 2~6 ,-O- ,- The alkylidene ether of COO- ,-OCO- ,-NHCO- ,-CONH- or carbon number 1~3, R⁴、R⁵And R⁶Separately indicate phenylene or Cycloalkylidene, R⁷Indicate hydrogen atom, the alkyl of carbon number 2~24 or containing fluoroalkyl, monovalence aromatic rings, univalent aliphatic series ring, monovalence Heterocycle or the big cyclic annular substitution body of monovalence being made of them.)

In addition, from the viewpoint of the complexity of synthesis, the R in above formula (3)³It is preferred that-O- ,-COO- ,-CONH-, carbon The alkylidene ether of number 1~3.

In addition, from the complexity of synthesis and from the viewpoint of making the ability of liquid crystal vertical-tropism, the R in formula (3)⁴、R⁵With R⁶It is preferred that l, m, n, R shown in the following table 1⁴、R⁵And R⁶Combination.

[table 1]

l	m	n	R⁴	R⁵	R⁶
						1	1	1	Phenylene	Phenylene	Cyclohexylidene
1	1	1	Phenylene	Cyclohexylidene	Cyclohexylidene
						1	1	1	Cyclohexylidene	Cyclohexylidene	Cyclohexylidene
1	1	0	Phenylene	Phenylene
						1	1	0	Phenylene	Cyclohexylidene
1	1	0	Cyclohexylidene	Cyclohexylidene

Moreover, l, m, n it is at least one be 1 in the case of, the R in formula (3)⁷It is preferred that hydrogen atom or carbon number 2~14 Alkyl contains fluoroalkyl, the alkyl of more preferable hydrogen atom or carbon number 2~12 or contains fluoroalkyl.In addition, l, m, n are 0 feelings Under condition, R⁷It is preferred that the alkyl of carbon number 12~22 or containing fluoroalkyl, monovalence aromatic rings, univalent aliphatic series ring, monovalence heterocycle, by them The big cyclic annular substitution body of the monovalence of composition, the alkyl of more preferable carbon number 12~20 or contains fluoroalkyl.

In addition, with making the polymer of the side chain of liquid crystal vertical-tropism make the ability of liquid crystal vertical-tropism according to keeping liquid crystal vertical The structure for the side chain being directly orientated and it is different, but in general, if keeping the amount of the side chain of liquid crystal vertical-tropism more, i.e. diamine component Contained in have keep the diamine contents of the side chain of liquid crystal vertical-tropism more, then so that the ability of liquid crystal vertical-tropism is improved, if Above-mentioned amount is few, then aforementioned capabilities reduce.In addition, if having cyclic structure, then with without cyclic structure the case where compared with, deposit In the high tendency of the ability for making liquid crystal vertical-tropism.

[changing 7]

(in formula (4) and formula (5), A₁₀Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂,-O- ,-CO- or-NH-, A₁₁Indicate singly-bound or phenylene, a expressions-R³-(R⁴)_l-(R⁵)_m-(R⁶)_n-R⁷(R³、R⁴、R⁵、R⁶、R⁷, in l, m, n and above formula (3) Definition it is identical), a ' indicates the bivalent group of the structure after removing the elements such as hydrogen in structure identical with above-mentioned a.)

[changing 8]

(in formula (6), A₁₄It is the alkyl for the carbon number 3~20 that can be replaced by fluorine atoms, A₁₅It is 1,4- cyclohexylidenes or 1, 4- phenylenes, A₁₆It is that oxygen atom or-COO-* (here, indicate the key and A of " * "₁₅In conjunction with), A₁₇It is oxygen atom or-COO-* (these In, indicate the key and (CH of " * "₂)a₂In conjunction with).In addition, a₁It is 0 or 1, a₂For 2~10 integer, a₃It is 0 or 1.)

To two amino (- NH in formula (3)₂) binding site do not limit.It can specifically enumerate：Relative to side chain (- R³- (R⁴)_l-(R⁵)_m-(R⁶)_n-R⁷), 2,3,2,4,2,5,2,6,3,4,3,5 on phenyl ring.Wherein, poly- from synthesis From the viewpoint of reactivity when amic acid, preferably 2,4,2,5 or 3,5.If also considering difficulty or ease when synthesis diamines Degree, then more preferable 2,4 or 3,5.

As the concrete structure of formula (3), the diamines that following formula [A-1]~formula [A-24] indicates can be enumerated, but not limited thereto.

[changing 9]

(in formula [A-1]~formula [A-5], A₁Be carbon number 2~24 alkyl or contain fluoroalkyl.)

[changing 10]

(in formula [A-6] and formula [A-7], A₂Expression-O- ,-OCH₂-、-CH₂O-、-COOCH₂Or-CH₂OCO-, A₃It is carbon number 1~22 alkyl, contains fluoroalkyl or fluoroalkoxy at alkoxy.)

[changing 11]

(in formula [A-8]~formula [A-10], A₄Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、- CH₂OCO-、-CH₂O-、-OCH₂Or-CH₂, A₅It is the alkyl of carbon number 1~22, alkoxy, contains fluoroalkyl or fluoroalkoxy.)

[changing 12]

(in formula [A-11] and formula [A-12], A₆Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-COOCH₂-、- CH₂OCO-、-CH₂O-、-OCH₂-、-CH₂,-O- or-NH-, A₇It is fluorine-based, cyano, trifluoromethyl, nitro, azo group, formyl Base, acetyl group, acetoxyl group or hydroxyl.)

[changing 13]

(in formula [A-13] and formula [A-14], A₈It is the alkyl of carbon number 3~12, the cis-trans isomerism point of 1 or 4 cyclohexylidene It Wei not transisomer.)

[changing 14]

(in formula [A-15] and formula [A-16], A₉It is the alkyl of carbon number 3~12, the cis-trans isomerism point of 1 or 4 cyclohexylidene It Wei not transisomer.)

[changing 15]

As the concrete example for the diamines that formula (4) indicates, the diamines that following formula [A-25]~formula [A-30] indicates can be enumerated, but not It is defined in this.

[changing 16]

(in formula [A-25]~formula [A-30], A₁₂Expression-COO- ,-OCO- ,-CONH- ,-NHCO- ,-CH₂-、-O-、-CO- Or-NH-, A₁₃It indicates the alkyl of carbon number 1~22 or contains fluoroalkyl.)

As the concrete example for the diamines that formula (5) indicates, the diamines that following formula [A-31]~formula [A-32] indicates can be enumerated, but not It is defined in this.

[changing 17]

Wherein, from the viewpoint of making the ability of liquid crystal vertical-tropism, the response speed of liquid crystal, preferably [A-1], [A-2], The diamines of [A-3], [A-4], [A-5], [A-25], [A-26], [A-27], [A-28], [A-29], [A-30].

It is this that there is the diamines for the side chain for making liquid crystal vertical-tropism and the diamines that makes liquid crystal show high pre-tilt angle to be preferably Made with the amount of 0~50 mole of % of the diamine component used in the synthesis of polyamic acid (and solvent-soluble polyimide) With more preferably the 10~40 of diamine component mole %.

As the diamines with photoreactive group, can enumerate with vinyl, acryloyl group, methylacryloyl, alkene The photoreactive groups such as propyl, styryl, cinnamoyl, chalcone base, cumarin base, dimaleoyl imino are as side chain Diamines, for example, the following general formula (7) indicate diamines, but not limited thereto.

[changing 18]

(in formula (7), R⁸Indicate singly-bound or-CH₂-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH₂O-、- N(CH₃)-、-CON(CH₃)-、-N(CH₃Any one of) CO-, R⁹Indicate singly-bound or carbon that is non-substituted or being replaced by fluorine atoms The alkylidene of number 1~the 20 ,-CH of alkylidene₂It can be by-CF₂Or-CH=CH- arbitrarily replaces, arbitrary base exemplified below In the case that group is not adjacent to each other, it can also be replaced by these groups：-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、 Divalent carbocyclic ring, bivalent heterocyclic.R¹⁰Indicate vinyl, acryloyl group, methylacryloyl, allyl, styryl ,-N (CH₂CHCH₂)₂Or the structure that following formula indicates.)

[changing 19]

In addition, the R in above formula (7)⁸Although can be formed by conventional organic synthesis technology, from the difficulty or ease journey of synthesis From the viewpoint of degree, preferably-CH₂-、-O-、-COO-、-NHCO-、-NH-、-CH₂O-。

In addition, as substitution R⁹Arbitrary-CH₂Divalent carbocyclic ring or bivalent heterocyclic carbocyclic ring or heterocycle, specifically can example It lifts with lower structure, but not limited thereto.

[changing 20]

From the viewpoint of photoreactivity, R¹⁰Preferred vinyl, acryloyl group, methylacryloyl, allyl, styrene Base ,-N (CH₂CHCH₂)₂Or the structure that following formula indicates.

[changing 21]

In addition,-the R of above formula (7)⁸-R⁹-R¹⁰More preferable following structures.

[changing 22]

To two amino (- NH in formula (7)₂) binding site do not limit.It can specifically enumerate：Relative to side chain (- R⁸- R⁹-R¹⁰), 2,3,2,4,2,5,2,6,3,4,3,5 on phenyl ring.Wherein, from synthesizing polyamides acid when it is anti- From the viewpoint of answering property, preferably 2,4,2,5 or 3,5.If also considering complexity when synthesis diamines, more preferably 2,4 or 3,5.

As the diamines with photoreactive group, following compound can be specifically enumerated, but not limited thereto.

[changing 23]

(in formula, X indicates that singly-bound or the conjugated group selected from-O- ,-COO- ,-NHCO- ,-NH-, Y indicate singly-bound or non- The alkylidene of carbon number 1~20 for replacing or being replaced by fluorine atoms.)

In addition, this diamines with photoreactive group is preferably with polyamic acid, (and solvent soluble polyamides is sub- Amine) synthesis in the amount of 0~70 mole of % of diamine component that uses use, more preferably 0~60 mole of %.

Above-mentioned diamines can be according to liquid crystal aligning when being made liquid crystal orientation film, pre-tilt angle, voltage retention performance, accumulation The characteristics such as charge, the response speed of liquid crystal when being made liquid crystal display element, are used alone, or mixing two or more.

The polymerisation of diamine component and tetracarboxylic dianhydride's ingredient usually carries out in organic solvent.As what is used at this time Organic solvent is not particularly limited as long as the polyamic acid of generation can be dissolved.As concrete example, N, N- diformazans can be enumerated Base formamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- methyl caprolactams, dimethyl sulfoxide, tetramethylurea, Pyridine, dimethyl sulfone, gamma-butyrolacton, isopropanol, methoxy amylalcohol, cinene, ethylpentyl ketone, methyl nonyl ketone, first Base ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, second Base cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, Ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, dipropylene glycol list Methyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, two Propylene glycol monomethyl ether, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethylether, dipropylene glycol list propyl ether, two Propylene glycol monoacetate list propyl ether, 3- methyl -3- methoxybutyls acetic acid esters, tripropylene glycol methyl ether, 3- methyl -3- methoxies Base butanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl Cyclohexene, propyl ether, two hexyl ether, dioxanes, n-hexane, normal heptane, normal octane, diethyl ether, cyclohexanone, ethylene carbonate, carbonic acid Sub- propyl ester, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethylether, third Ketone acid methyl esters, ethyl pyruvate, 3- methoxy methyl propionates, 3- ethoxy-propionic acids methyl ethyl ester, 3- methoxypropionates, 3- second Oxygroup propionic acid, 3- methoxypropionic acids, 3- methoxy propyls propyl propionate, 3- methoxy propyls acid butyl ester, diethylene glycol dimethyl ether or 4- hydroxyls- 4-methyl-2 pentanone etc..These organic solvents can be used alone, and can also be used in mixed way.Even also, cannot dissolve poly- The solvent of amic acid may be combined in above-mentioned solvent and use in the range of the polyamic acid of generation is not precipitated.In addition, having Moisture in solvent hinders polymerisation, and the polyamic acid of generation can be made to hydrolyze, therefore it is preferable to use warps for organic solvent The organic solvent of dehydration and drying.

When diamine component and tetracarboxylic dianhydride's ingredient being made to react in organic solvent, following methods can be enumerated：Stirring makes two Amine component is dispersed or dissolved in solution obtained by organic solvent, then directly adds tetracarboxylic dianhydride's ingredient or makes tetrabasic carboxylic acid two Anhydride component is dispersed or dissolved in the method added again after organic solvent；Tetracarboxylic dianhydride's ingredient is set to be dispersed or dissolved on the contrary The method that diamine component is added in solution obtained by organic solvent；The method for alternately adding tetracarboxylic dianhydride's ingredient and diamine component Deng any method therein can be used.In addition, being carried out instead using a variety of respectively in diamine component or tetracarboxylic dianhydride's ingredient In the case of answering, it can be made to be reacted in the state of being pre-mixed, it can also be made to react successively respectively, difference can also be made Low-molecular weight hybrid reaction obtained by reaction.Polymerization temperature at this time can select -20 DEG C~150 DEG C of arbitrary temp, excellent The range of -5 DEG C~100 DEG C of choosing.In addition, reaction can be carried out with arbitrary concentration, but if concentration is too low, it is difficult to obtain high score The polyamic acid (and solvent-soluble polyimide) of son amount, the viscosity of reaction solution is excessively high if excessive concentration, it is difficult into The uniform stirring of row.Therefore, the concentration of the total amount of diamine component and tetracarboxylic dianhydride's ingredient is preferably 1~50 matter in reaction solution Measure %, more preferable 5~30 mass %.It can be carried out with high concentration in initial reaction stage, then add organic solvent again.

In the polymerisation of polyamic acid, the total mole number of diamine component and the ratio between the total mole number of tetracarboxylic dianhydride's ingredient Preferably 0.8~1.2.Identical as common polycondensation reaction, the molar ratio is closer to 1.0, the molecule of the polyamic acid of generation Amount is bigger.

Thus polyamic acid obtained by polymerizeing, the polymer of the repetitive unit e.g. indicated with following formula [a].

[changing 24]

(in formula [a], R₁₁It is derived from tetracarboxylic dianhydrides' ingredients such as the tetracarboxylic dianhydride of above formula (1) expression as raw material 4 valence organic groups, R₁₂It is derived from the diamine component H as raw material₂N-R₁₂-NH₂Divalent organic group, j indicate it is just whole Number.)

Above formula [a] can be R₁₁And R₁₂The respectively a kind of, polymer with same repetitive unit, or can also be R₁₁Or R₁₂For the polymer of repetitive unit a variety of, with different structure.

Then, by making such polyamic acid dehydration closed-loop, it can get solvent-soluble polyimide.

As the method for making polyamic acid imidizate, the hot acid imide for the solution for directly heating polyamic acid can be enumerated Change or added in the solution of polyamic acid the catalysis imidizate of catalyst.

Temperature when making polyamic acid hot-imide in the solution is 100~400 DEG C, preferably 120~250 DEG C, preferably Using the method for carrying out imidizate while the water generated by imidization reaction is expelled to outside system.

The catalysis imidizate of polyamic acid can by adding basic catalyst and acid anhydrides in polyamic acid solution, At -20~250 DEG C, preferably stirs and carry out at 0~180 DEG C.The amount of basic catalyst is 0.5~30 mole of amide acidic group Times, preferably 2~20 moles times, acid anhydrides amount is 1~50 mole times of amide acidic group, and preferably 3~30 moles are again.As alkalinity Catalyst, can enumerate pyridine, triethylamine, trimethylamine, tri-n-butylamine or trioctylamine etc., wherein pyridine have for making reaction carry out and Say the alkalinity of appropriateness, therefore preferably.As acid anhydrides, acetic anhydride, trimellitic anhydride or pyromellitic dianhydride etc. can be enumerated, wherein It is easy to carry out purifying after reaction when using acetic anhydride, therefore preferably.Acid imide rate based on catalysis imidizate can To be controlled by adjusting catalytic amount and reaction temperature, reaction time.

The polymer that generation is recycled from the reaction solution of polymer (solvent-soluble polyimide or polyamic acid) is (molten Agent soluble polyimide or polyamic acid) when, reaction solution, which is put into solvent, makes it precipitate.As for precipitating Solvent, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethyl alcohol, first can be enumerated Benzene, benzene or water etc..Putting into the polymer precipitated in solvent can be after being recovered by filtration, under normal or reduced pressure, normal It is dried under temperature or heating.In addition, if repeating the polymer that 2~10 times make precipitation recycle is re-dissolved in organic solvent And the operation of reprecipitation recycling, then it can reduce the impurity in polymer.As the solvent at this point, such as alcohols, ketone can be enumerated Class or hydro carbons etc., if using 3 kinds or more of the solvent selected from above-mentioned solvent, purification efficiency further increases, therefore preferably.

(acyl is sub- for the dehydration closed-loop rate of the amide acidic group of solvent-soluble polyimide contained by the aligning agent for liquid crystal of the present invention Amination rate) 100% is need not be, it can arbitrarily be selected according to purposes and purpose in the range of 0% to 100%, preferably 50%~90%, more preferable 82%~86%.

In addition, for the molecular weight of polyamic acid or solvent-soluble polyimide, it is contemplated that the polymer envelope of gained Operability, the uniformity of polymer envelope when the intensity of (liquid crystal orientation film), polymer envelope are formed, to utilize GPC (gels Permeation chromatography) the Weight-average molecular gauge that measures of method is preferably 5000~1000000, and more preferable 10000~150000.

In addition, as long as the solvent contained by the aligning agent for liquid crystal of the present invention can dissolve above-mentioned solvent-soluble polyimide and be Can, it is not particularly limited, n,N-Dimethylformamide, n,N-dimethylacetamide, n-methyl-2-pyrrolidone, N- first can be enumerated Base caprolactam, 2-Pyrrolidone, N- ethyl-2-pyrrolidones, n-vinyl pyrrolidone, dimethyl sulfoxide, tetramethylurea, pyrrole Pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 1,3- dimethyl-2-imidazolidinones, ethylpentyl ketone, methyl nonyl ketone, first Base ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether And the organic solvents such as 4- hydroxy-4-methyl-2-pentanones.These organic solvents can be used alone, and can also be used in mixed way.

For the solvent in the aligning agent for liquid crystal of the present invention, examined from the viewpoint for forming uniform polymer envelope by coating Consider, the content of solvent is preferably 70~99 mass %.Its content can suitably be changed according to the film thickness of Object LC alignment films.

Component of polymer contained by the aligning agent for liquid crystal of the present invention can only be the tetracarboxylic dianhydride that above formula (1) will be made to indicate Solvent-soluble polyimide obtained by polyamic acid imidizate obtained by polymerisation is carried out with diamine component, can also be incited somebody to action The tetracarboxylic dianhydride that above formula (1) indicates is set to be carried out with diamine component molten obtained by polyamic acid imidizate obtained by polymerisation Agent soluble polyimide and other mixed with polymers in addition to this.At this point, relative to the tetrabasic carboxylic acid that above formula (1) will be made to indicate Dianhydride carries out the total of solvent-soluble polyimide obtained by polyamic acid imidizate obtained by polymerisation with diamine component The content of amount, other polymer in addition to this is 0.5~90 mass %, preferably 1.0~80 mass %.As in addition to this Other polymer, in addition to making the tetracarboxylic dianhydride that above formula (1) indicates carry out polyamic acid obtained by polymerisation with diamine component In addition, obtained by the tetracarboxylic dianhydride's ingredient and diamine component that can also enumerate the tetracarboxylic dianhydride by not including above formula (1) expression Polyamic acid or solvent-soluble polyimide.In addition, as the polymerization other than polyamic acid and solvent-soluble polyimide Object, specifically, poly amic acid ester, acrylate copolymer, methacrylate polymer, polystyrene or polyamide can be enumerated Deng.

In the aligning agent for liquid crystal of the present invention, within the scope of the effect of the invention, can contain further to carry The film thickness uniformity of polymer envelope when high coating of liquid crystalline alignment agent and the organic solvent of surface smoothness are (also referred to as bad molten Agent) or compound.The compound etc. for the adaptation that can improve liquid crystal orientation film and substrate can also be contained.

As the concrete example for the poor solvent for improving film thickness uniformity and surface smoothness, such as isopropanol, first can be enumerated Oxygroup methyl anyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetic acid Ester, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol acetate, ethylene glycol list isopropyl Base ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, dipropyl Glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl Ether, dipropylene glycol monomethyl ether, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethylether, dipropylene glycol list propyl Ether, dipropylene glycol monoacetate list propyl ether, 3- methyl -3- methoxybutyls acetic acid esters, tripropylene glycol methyl ether, 3- methyl - 3- methoxybutanols, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl Ketone, methylcyclohexene, propyl ether, two hexyl ethers, n-hexane, pentane, normal octane, diethyl ether, methyl lactate, ethyl lactate, acetic acid Methyl esters, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethylether, methyl pyruvate, ethyl pyruvate, 3- methoxyl groups Methyl propionate, 3- ethoxy-propionic acids methyl ethyl ester, 3- methoxypropionates, 3- ethoxy-propionic acids, 3- methoxypropionic acids, 3- methoxies Base propyl propionate, 3- methoxy propyls acid butyl ester, 1- methoxy-2-propanols, 1- ethyoxyl -2- propyl alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol -1- monomethyl ether -2- acetic acid esters, the third two Alcohol -1- list ethylether -2- acetic acid esters, dipropylene glycol, 2- (2- ethoxy-cs oxygroup) propyl alcohol, methyl lactate, ethyl lactate, lactic acid N-propyl, n-butyl lactate or isoamyl lactate etc. have the organic solvent etc. of low surface tension.

These poor solvents can use one kind, a variety of can also be used in mixed way.When using poor solvent as described above, Preferably account for 5~80 mass % of organic solvent total amount contained in aligning agent for liquid crystal, more preferably 20~60 mass %.

As the compound for further increasing film thickness uniformity and surface smoothness, fluorine class surfactant, silicon can be enumerated Oxygen alkanes surfactant, nonionic surface active agent etc..More specifically, can enumerate such as エ Off トップ EF301, EF303, EF352 (illuminating product Co., Ltd. (トーケ system プロダクツ societies) system), メガ Off ァッ Network F171, F173, R-30 (big days This ink Co., Ltd. (big Japan イ Application キ societies) makes), Off ロラー De FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo スリーエ system society) system), アサヒガー De AG710, サー Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd (Asahi Glass society) system) etc..The use ratio of these surfactants is relative to liquid crystal 100 mass parts of component of polymer contained in alignment agent, preferably 0.01~2 mass parts, more preferable 0.01~1 mass parts.

As the compound for the adaptation for improving liquid crystal orientation film and substrate, can enumerate compound containing functional silanes or Compound containing epoxy group can enumerate such as 3- TSL 8330s, 3-aminopropyltriethoxysilane, 2- ammonia Base propyl trimethoxy silicane, 2- aminopropyltriethoxywerene werenes, N- (2- amino-ethyls) -3- aminopropyl trimethoxy silicon Alkane, N- (2- amino-ethyls) -3- aminopropylmethyldimethoxysilanes, 3- ureido-propyl trimethoxy silanes, 3- urea groups third Ethyl triethoxy silicane alkane, N- ethoxy carbonyl -3- TSL 8330s, N- ethoxy carbonyl -3- aminopropyls three Ethoxysilane, N- triethoxysilylpropyltetrasulfides diethylenetriamine, N- trimethoxy-silylpropyl triethylenes Triamine, three azepine decane of 10- trimethoxysilyls -1,4,7-, the three azepine last of the ten Heavenly stems of 10- triethoxysilyls -1,4,7- Alkane, 9- trimethoxysilyl -3,6- diaza nonyls acetic acid esters, 9- triethoxysilyl -3,6- diaza nonyls Acetic acid esters, N- benzyl -3- TSL 8330s, N- benzyls -3-aminopropyltriethoxysilane, N- phenyl -3- Bis- (the oxyethylene group) -3- aminopropyls of TSL 8330, N- phenyl -3-aminopropyltriethoxysilane, N- Bis- (the oxyethylene group) -3-aminopropyltriethoxysilane of trimethoxy silane, N-, ethylene glycol diglycidylether, poly- second two Alcohol diglycidyl ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentylglycol diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- dibromoneopentyl glycols Diglycidyl ether, 1,3,5,6- four glycidyl group -2,4- hexylene glycols, N, N, N ', N '-four glycidyl groups-meta-xylene Bis- (N, the N- diglycidyl amino methyl) hexamethylenes of diamines, 1,3-, N, N, N ', N '-four glycidyl groups -4,4 '-diamino Base diphenyl methane etc..

When using these raisings and the compound of the adaptation of substrate, relative to polymer contained in aligning agent for liquid crystal at Divide 100 mass parts, content is preferably 0.1~30 mass parts, more preferably 1~20 mass parts.If less than 0.1 mass parts, It can not expect the effect that adaptation improves, if being more than 30 mass parts, the orientation of liquid crystal is deteriorated sometimes.

In the aligning agent for liquid crystal of the present invention other than above-mentioned poor solvent and compound, as long as not damaging the present invention Effect in the range of, then can add the mesh for reaching the electrical characteristics such as dielectric constant, electric conductivity for changing liquid crystal orientation film Dielectric and conductive materials.

The aligning agent for liquid crystal of the present invention can carry out friction treatment or light irradiation etc. and take on being coated on substrate and after being burnt into To processing, to be used as liquid crystal orientation film.In addition, whens for vertical orientation purposes etc., without orientation process As liquid crystal orientation film.As substrate used at this time, as long as the substrate that the transparency is high, is not particularly limited, glass is removed Outside substrate, plastic bases such as acrylic acid substrate and polycarbonate substrate etc. can also be used.It is excellent from the viewpoint of technique simplification Choosing uses the substrate for being formed with ITO (tin indium oxide (Indium Tin Oxide)) electrode for liquid crystal drive etc..In addition, anti- In emitting liquid crystal display element, the opaque substrates such as silicon wafer can also be used, but be only limitted to unilateral substrate, electricity at this time Pole can also use the material of the reflected lights such as aluminium.

The coating method of aligning agent for liquid crystal is not particularly limited, industrial generally use passes through silk-screen printing, graph The method that brush, flexographic printing or ink-jet method etc. are coated.As other coating methods, there are infusion process, rolling method, slot coated Method, spin-coating method or spray coating method etc. can use these methods according to purpose.The albefaction of the above-mentioned aligning agent for liquid crystal of the present invention is solidifying Collect excellent, so the end for the coated surface for hardly generating the coating of liquid crystalline alignment agent on substrate and being formed easy tos produce Solvent-soluble polyimide agglutinator, therefore uniformity and the excellent liquid crystal orientation film of the transparency can be made.

Although drying process after aligning agent for liquid crystal is coated on substrate is not required in that, but be extremely burnt into after coating This period be all not fixed or be coated with for each piece of substrate after be not burnt into immediately in the case of, preferably include dry Drying process.As long as solvent is removed the degree that will not be deformed to film shape by reasons such as the transports of substrate by the drying, The drying means is not particularly limited.For example, can enumerate in the heating plate of 40 DEG C~150 DEG C, preferably 60 DEG C~100 DEG C of temperature Dry 0.5~30 minute, preferably 1~5 minute method.

It is burnt by being formed by film to coating of liquid crystalline alignment agent in aforementioned manners, can be made into liquid crystal orientation film (polymer envelope).At this point, firing temperature can be 100 DEG C~350 DEG C of arbitrary temp, it is preferably 140 DEG C~300 DEG C, more excellent Select 150 DEG C~230 DEG C, more preferred 160 DEG C~220 DEG C.As firing time, when can be 5 minutes~240 minutes arbitrary Between.It is preferred that 10~90 minutes, more preferable 20~80 minutes.Conventional known method, such as heating plate, thermal cycle can be used in heating Formula stove or IR (infrared ray) types stove, band oven etc..If the thickness of the liquid crystal orientation film after firing is blocked up, in liquid crystal display member Unfavorable in terms of the power consumption of part, if excessively thin, the reliability of liquid crystal display element reduces sometimes, therefore preferably 5~300nm, more It is preferred that 10~100nm.So that liquid crystal is horizontally oriented or when tilted alignment, by friction or polarized UV rays irradiation etc. to firing after Liquid crystal orientation film implementation is handled.

The liquid crystal display element of the present invention is to obtain band liquid crystal aligning by the aligning agent for liquid crystal of the present invention by the above method After the substrate of film, liquid crystal display element made of liquid crystal cell is manufactured by well known method.It is to enumerate an example, then of the invention Liquid crystal display element be the liquid crystal display element for having following liquid crystal cells, which includes the two pieces of bases configured in opposite directions What plate, the liquid crystal layer being arranged between substrate and the aligning agent for liquid crystal by the present invention being arranged between substrate and liquid crystal layer were formed Above-mentioned liquid crystal orientation film.As the liquid crystal display element of such present invention, twisted-nematic (TN can be enumerated:Twisted Nematic) mode, vertical orientation (VA:Vertical Alignment) mode, horizontal alignment (IPS:In-Plane Switching) mode, OCB are orientated (OCB:Optically Compensated Bend) etc. various liquid crystal display elements.

As the manufacturing method of liquid crystal cell, following method can be illustrated：Prepare a pair for being formed with above-mentioned liquid crystal orientation film Substrate spreads spacer on the liquid crystal orientation film of one piece of substrate, by another piece in such a way that liquid crystal alignment film surface is in inside Substrate is bonded, the method for decompression injection liquid crystal and sealing；Or liquid crystal is added dropwise in the liquid crystal alignment film surface for be scattered with spacer Later, the method etc. for substrate being bonded and being sealed.

In addition, the mode that manufacture makes the liquid crystal molecule relative to substrate vertical orientation be responded under the action of electric field is (vertical It is aligned) liquid crystal display element in, in advance in a liquid crystal composition add photopolymerizable compound PSA (Polymer Sustained Al ignment) type liquid crystal display or optical polymerism is added in the liquid crystal orientation film (aligning agent for liquid crystal) When closing the SC-PVA type liquid crystal displays of object, liquid crystal etc. can be injected simultaneously between a pair of of the substrate for being formed with above-mentioned liquid crystal orientation film After sealing, ultraviolet light is irradiated while to liquid crystal orientation film and liquid crystal applied voltages, to make polymerizable compound polymerize.

As liquid crystal, the positive type liquid crystal or each with negative dielectric constant with positive dielectric constant anisotropy can be used The negative type liquid crystal of anisotropy, specifically, MLC-2003, MLC-6608 of for example usable Merck ＆ Co., Inc. (メルク societies) system, MLC-6609 etc..

As described above, liquid crystal display element is due to having uniform liquid crystal aligning made of aligning agent for liquid crystal of the invention Film, thus it is excellent in reliability.

[embodiment]

Hereinafter, enumerate embodiment carries out more specific description to the present invention.In addition, the present invention should not be construed as being limited to This.Abbreviation used in embodiment and comparative example is as described below.

PPHT：The N that following formula indicates, bis- (the 1,2- cyclohexane dicarboxylic acid acid anhydride -4- bases) carbonyl -1,4- phenylenediamines of N ' -

PSHT：The N that following formula indicates, bis- (1,2- cyclohexane dicarboxylic acid acid anhydride -4- bases) carbonyl-the 3,3 '-diaminodiphenylsulfones of N ' -

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

TDA：3,4- dicarboxyl -1,2,3,4- tetrahydrochysene -1- naphthalene succinic dianhydrides

[changing 25]

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

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

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

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

p-PDA：P-phenylenediamine

NMP：N-methyl-2-pyrrolidone

BCS：Butoxy ethanol

The assay method implemented in the present embodiment described below.

The molecular weight of polyamic acid and polyimides is to measure the polyamide by GPC (room temperature gel permeation chromatography) device Acid or polyimides calculate number-average molecular weight and weight average molecular weight as polyethylene glycol, polyethylene oxide scaled value.

GPC devices：Shodex (Showa Denko K. K) corporation (GPC-101)

Column：Showa Denko K. K's system (series connection of KD803, KD805)

Column temperature：50℃

Eluent：N, N'- dimethylformamide are (as additive, lithium bromide-hydrate (LiBrH₂O) it is 30 mmoles That/L, phosphoric acid anhydrous crystal (o- phosphoric acid) are 30 mMs/L, tetrahydrofuran (THF) is 10mL/L)

Flow velocity：1.0ml/ minute

Calibration curve making standard sample：(East ソー societies of TOSOH Co., Ltd) TSK standards polyethylene oxide (molecule processed Amount about 900000,150000,100000,30000) and Polymer Laboratory company (Port リマーラボラトリー societies) system it is poly- Ethylene glycol (molecular weight about 12000,4000,1000).

The acid imide rate of polyimides measures as follows.

The polyimide powder of 20mg is added to NMR probe tubes, addition deuterated dimethyl sulfoxide (DMSO-d₆, 0.05% TMS (tetramethylsilane) mixture) 0.53ml, it makes it completely dissolved.For the solution, with Japan Electronics data Co., Ltd. The NMR analyzers (JNM-ECA500) of (Japanese Electricity データ system society) system determine the proton NMR of 500MHz.Acid imide rate It acquires as follows：The proton for coming from unconverted structure before and after imidizate is set to standard proton, the peak of the proton is used to accumulate The proton peak integrated value of score value and the NH bases from polyamic acid occurred near 9.5ppm~10.0ppm is asked by following formula .

Acid imide rate (%)=(1- α x/y) × 100

In above formula, x is the proton peak integrated value of the NH bases from polyamic acid, and y is the peak integrated value of standard proton, and α is The number ratio of the reference proton of NH matrix relative to polyamic acid when polyamic acid (acid imide rate is 0%) Example.

(synthesis example 1)

Using the PPHT of 1.33g as tetracarboxylic dianhydride's ingredient, using the p-PDA of 0.32g as diamine component, In the NMP of 14.93g, at room temperature react 18 hours, obtain the molten of the solid component concentration 10wt% of polyamic acid (PAA-1) Liquid.

(synthesis example 2~8)

Other than using being formed shown in table 2, synthesis example 2~8 is obtained using method same as above-mentioned synthesis example 1 The solution of polyamic acid (PAA-2~PAA-8).

[table 2]

(synthesis example 9)

The NMP that 12.59g is added in the solution 15.1g of the polyamic acid (PAA-1) obtained in synthesis example 1 is diluted, It is modulated into the polyamic acid solution of solid component concentration 6wt%.Acetic anhydride 2.95g and pyridine are added in the polyamic acid solution 1.37g reacts 3 hours at 50 DEG C, carries out imidizate.After obtained polyimide solution is cooled to room temperature left and right, throw Enter into 150g methanol, recycles the solid matter of precipitation.Further, after cleaning the solid matter 2 times with methanol, subtract in 100 DEG C It press dry dry, obtains the khaki powder of polyimides (SPI-1).The acid imide rate of polyimides (SPI-1) is measured, result is 79%.

(synthesis example 10~16)

Other than using being formed shown in table 3, synthesis example 10~16 is obtained using method same as above-mentioned synthesis example 9 Polyimides (SPI-2~SPI-8) powder.

[table 3]

(embodiment 1)

The NMP of 7.53g is added in polymer (polyimides SPI-1) 0.50g obtained in above-mentioned synthesis example 9, in room The lower stirring of temperature 3 hours.Polyimides is completely dissolved at the end of stirring.The BCS of 2.01g is further added in the solution, in room The lower stirring of temperature 1 hour, obtains the polymer solution (A1) that solid component concentration is 5.0wt%.The polymer solution is directly made To be used to form the aligning agent for liquid crystal of liquid crystal orientation film.

(embodiment 2~7, comparative example 1)

Other than using being formed shown in table 4, the polymerization of embodiment 2~7 is obtained using method similarly to Example 1 The polymer solution (B1) of object solution (A2~A7) and comparative example 1.In addition, each embodiment 2~7 also similarly to Example 1, is stirred Polyimides is completely dissolved at the end of mixing.

[table 4]

[making of liquid crystal cell]

After the polymer solution (A1) obtained in embodiment 1, i.e. aligning agent for liquid crystal (A1) is filtered with 1.0 μm of filters, rotation It is applied on the glass substrate with transparent electrode, after 80 seconds dry in 80 DEG C of heating plate, be burnt into 10 minutes, obtain in 230 DEG C To the film (polyimide film) of film thickness 100nm.It is rubbed (roller diameter 120mm, rotating speed to the polyimide film with rayon cloth 1000rpm, movement speed 50mm/sec, intrusion 0.3mm) after, 1 minute ultrasonic irradiation is carried out in pure water, in 80 DEG C It is 10 minutes dry, form liquid crystal orientation film.Prepare two pieces of substrates for carrying above-mentioned liquid crystal orientation film, is taken in the liquid crystal of one piece of substrate It is arranged after 6 μm of spacer on film surface, it, will be all with the orthogonal condition of the frictional direction of two pieces of substrates by two pieces of substrate in combination Sealing is enclosed, but leaves liquid crystal injecting port, the negative crystal born of the same parents that structure cell interval (cel l gap) is 6 μm are made.In room temperature in the structure cell Lower vacuum injection liquid crystal (MLC-2003 (C080), Merck Japanese firm (メ Le Network ジャパ Application society) system), seals inlet, Obtain the liquid crystal cell of 90 degree of orientations of liquid crystal torsion.

In addition, being taken about the liquid crystal obtained in the aligning agent for liquid crystal (A2~A7) and comparative example 1 obtained in embodiment 2~7 To agent (B1), also liquid crystal cell is manufactured using with the same method of aligning agent for liquid crystal (A1) obtained in embodiment 1.

[evaluation of pre-tilt angle]

After being heated 1 hour at 120 DEG C to the liquid crystal cell of gained, the measurement of pre-tilt angle is carried out.Pre-tilt angle Axo " the Axo Scan " of Metrix companies is measured using Muller matrix method.As a result it is shown in table 5.

[albefaction is aggregated the evaluation of characteristic]

Be added dropwise respectively on Cr substrates about 0.1ml Examples 1 to 7 and comparative example 1 in obtained each aligning agent for liquid crystal it is (poly- Polymer solution), it is placed in the environment of 23 DEG C of temperature, humidity 55%.The every 10 minutes ends with the micro- sem observation drop are attached Closely.In addition, observation is carried out with 100 times of multiplying power.Generate agglutinator time it is below at 10 minutes be evaluated as ×, more than 10 points Clock and it was evaluated as △ less than 1 hour, zero is evaluated as at 1 hour or more and less than 3 hours, in 3 hours or more be evaluated as ◎.Evaluation result is shown in table 5.

[table 5]

As shown in table 5, it is known that containing the tetracarboxylic dianhydride indicated using formula (1) as the Examples 1 to 7 of the polyimides of raw material Aligning agent for liquid crystal (polymer solution) in the evaluation that albefaction is aggregated characteristic, do not produced completely placing 3 hours or more Raw agglutinator, there is excellent albefaction to be aggregated characteristic.On the other hand, comparative example 1 generates agglutinator within 10 minutes, in vain It is poor to change agglutination characteristic.In addition, also confirming that the aligning agent for liquid crystal of Examples 1 to 7 realizes the good of liquid crystal by orientation process Orientation (pre-tilt angle).

Claims

1. a kind of aligning agent for liquid crystal, which is characterized in that carried out with diamine component comprising the tetracarboxylic dianhydride that following formula (1) indicates will be made Solvent-soluble polyimide and solvent obtained by polyamic acid imidizate obtained by polymerisation；

In formula (1), W is the structure that following formula indicates；

In formula, R¹It is hydrogen atom ,-COOH ,-N (CH₂CH=CH₂)₂Or-(CH₂)_n1CH₃；The integer that n1 is 0~20；R²Be-C (= O)-、-SO₂-、-C(CH₃)₂-、-O-、-CH₂-、-NH-、-C₂H₄-NH-CONH-C₂H₄Or-O (CH₂)_m1O-；M1 be 1~5 it is whole Number.

2. a kind of liquid crystal orientation film, which is characterized in that obtained using aligning agent for liquid crystal described in claim 1.

3. a kind of liquid crystal display element, which is characterized in that have the liquid crystal orientation film described in claim 2.