CN104364296B

CN104364296B - Polymer, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells and diamidogen

Info

Publication number: CN104364296B
Application number: CN201380031830.4A
Authority: CN
Inventors: 芦泽亮; 芦泽亮一; 南悟志; 星野稔
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2012-04-17
Filing date: 2013-04-09
Publication date: 2016-12-28
Anticipated expiration: 2033-04-09
Also published as: JPWO2013157450A1; KR20150001820A; TW201402654A; TWI494348B; KR102073437B1; CN104364296A; JP6143014B2; WO2013157450A1

Abstract

The present invention relates to a kind of polyimide precursor selected from the structure having represented by following formula [I] as side chain, by polyimides obtained by this polyimide precursor imidizate and at least one polymer of polyamide.(in formula, Y¹For the ring class selected from the ring class of the dicyclic that 2 adjacent monocyclic rings that the monocyclic ring that atomic number is 5 or 6, atomic number are 5 or 6, atomic number are 8～10 or three-ring type that atomic number is 13 or 14, non-substituted or substituted, carbon-ring type or the divalent aromatic group of hetero ring type；Y²For singly-bound or selected from ehter bond, ester bond, amido link and the divalent linking group of amino-formate bond；Y³That can be replaced by fluorine atoms for hydrogen atom, the straight-chain alkyl of carbon number 3～20 or there is the 1 valency organic group of alicyclic skeleton of carbon number 4～40).

Description

Polymer, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells and diamidogen

Technical field

The present invention relates to polyimide precursor, polyimides and polyamide, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal Show element and diamidogen.

Background technology

In liquid crystal display cells, liquid crystal orientation film carries the effect making liquid crystal be upwardly oriented in certain side.Now, work The main liquid crystal orientation film used in industry is by using by polyamic acid, poly amic acid ester or the polyamides as polyimide precursor The aligning agent for liquid crystal of the polyimide that the solution of imines is constituted is coated on substrate and carries out film forming and prepare.Additionally, make liquid crystal During or tilted alignment parallel-oriented relative to real estate, after film forming, the surface carrying out using friction further is prolonged treatment.This Outward, it is proposed that utilize the method for the anisotropy photochemical reaction using polarisation ultraviolet irradiation etc. to be used as replacing of friction treatment In generation, carry out in recent years towards industrialized research.

In order to improve the display characteristic of this liquid crystal display cells, by changing polyamic acid, poly amic acid ester and polyamides The structure of imines, polyamic acid, poly amic acid ester and the polyimides that blending rating is different, or the method adding additive etc., Carry out the control etc. of the improvement of liquid crystal aligning and electrical characteristics etc., tilt angle.Such as, in order to obtain providing good electric performance Even if the excellent liquid of the printing of liquid crystal orientation film using liquid crystal aligning performance not deteriorate the most for a long time Brilliant alignment agent, it is proposed that use the polymer (with reference to patent documentation 1 etc.) of the group with ad hoc structure.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 2011-100099 publication

Summary of the invention

Invent technical problem to be solved

But, along with the high performance of liquid crystal display cells, large area, the energy-saving technology etc. of display device, liquid crystal is taken Also become harsh to the characteristic required by film, also require the patience that backlight is exposed to the open air by liquid crystal display cells.Especially with Past aligning agent for liquid crystal, the method utilizing anisotropy photochemical reaction by polarized UV rays irradiation etc., i.e. irradiate with light Carry out the liquid crystal orientation film that the method for orientation process is formed, owing to liquid crystal orientation film existing unreacted photoreactive group, Therefore there is the problem that liquid crystal display cells is exposed to the liquid crystal aligning performance degradation caused in backlight.

Present invention aim to address above-mentioned problem of the prior art point, it is provided that inhibit the liquid crystal aligning that backlight causes The liquid crystal orientation film of performance degradation.That is, it is an object of the invention to provide that to have the polyimide precursor of above-mentioned characteristic, polyamides sub- Amine or polyamide, it is further provided use the aligning agent for liquid crystal of these compounds and liquid crystal display cells and diamidogen.

Solve the technical scheme that technical problem is used

Present inventor has performed and conscientiously study, it was found that comprise side chain there is the polyamides of the structure represented by following formula [I] The aligning agent for liquid crystal of imines precursor, polyimides or polyamide is extremely effective to realizing above-mentioned purpose, thus completes the present invention.

That is, the present invention has techniques below content.

1. a polymer, it is characterised in that sub-for the polyamides selected from the structure having as side chain represented by following formula [I] Amine precursor, by least one of polyimides obtained by this polyimide precursor imidizate and polyamide.

(in formula, Y¹For selected from 2 adjacent monocyclic rings that the monocyclic ring that atomic number is 5 or 6, atomic number are 5 or 6, Atomic number be the ring class of the ring class of the dicyclic of 8～10 or three-ring type that atomic number is 13 or 14, non-substituted or substituted, The divalent aromatic group of carbon-ring type or hetero ring type；Y²For singly-bound or selected from ehter bond, ester bond, amido link and the 2 of amino-formate bond Valency linking group；Y³That can be replaced by fluorine atoms for hydrogen atom, the straight-chain alkyl of carbon number 3～20 or there is carbon number 4～40 1 valency organic group of alicyclic skeleton.)

2. the polymer as described in 1, it is characterised in that use the diamidogen represented by following formula (1) to obtain.

(in formula, Y¹For selected from 2 adjacent monocyclic rings that the monocyclic ring that atomic number is 5 or 6, atomic number are 5 or 6, Atomic number be the ring class of the ring class of the dicyclic of 8～10 or three-ring type that atomic number is 13 or 14, non-substituted or substituted, The divalent aromatic group of carbon-ring type or hetero ring type；Y²For singly-bound or selected from ehter bond, ester bond, amido link and the 2 of amino-formate bond Valency linking group；Y³That can be replaced by fluorine atoms for hydrogen atom, the straight-chain alkyl of carbon number 3～20 or there is carbon number 4～40 1 valency organic group of alicyclic skeleton；Y⁴For singly-bound, methylene or the alkylidene of carbon number 2～6；Y⁵For singly-bound, oxygen atom, *- OCO-or-CH₂O-* is (wherein, with key and the Y of " * "⁴In conjunction with.).Wherein, Y is worked as⁴For Y during singly-bound⁵For singly-bound.)

3. an aligning agent for liquid crystal, it is characterised in that containing the polymer described in 1 or 2.

4. a liquid crystal orientation film, it is characterised in that use the aligning agent for liquid crystal described in 3 to obtain.

5. a liquid crystal display cells, it is characterised in that possess the liquid crystal orientation film described in 4.

6. a diamidogen, it is characterised in that represent with following formula (1).

Invention effect

If the employing present invention, then can provide the liquid of the liquid crystal aligning performance degradation that can obtain inhibiting backlight to cause The brilliant novel polyimide precursor of alignment films, polyimides and polyamide.Even if being additionally, since this liquid crystal orientation film to be exposed to the back of the body Light source is also difficult to liquid crystal aligning performance degradation, thus the liquid crystal display cells with this liquid crystal orientation film achieves for a long time The effect that display characteristic is excellent.Additionally, this liquid crystal orientation film further suppress AC drives the deterioration of the liquid crystal aligning performance caused, no Easily there is sintering attachment.

Detailed description of the invention

Hereinafter, the present invention is described in detail.

The polymer of the present invention is to have the polyimide precursor of structure represented by above formula [I], as side as side chain Chain has the polyimides of the structure represented by above formula [I] and has the polyamides of structure represented by above formula [I] as side chain Amine.It addition, polyimide precursor refers to polyamic acid or poly amic acid ester etc..Structure represented by above formula [I] can be with polyamides The main chain of the polyimide precursor such as amino acid or poly amic acid ester, polyimides or polyamide, i.e. polyamic acid skeleton, polyimides Skeleton or polyimide backbone directly in conjunction with, in addition it is also possible to combined by suitable linking group.

In formula [I], Y¹As mentioned above for adjacent selected from 2 that the monocyclic ring that atomic number is 5 or 6, atomic number are 5 or 6 Monocyclic ring, atomic number be 8～10 dicyclic ring class, or the ring class of the three-ring type that atomic number is 13 or 14 is non-substituted Or the divalent aromatic group of substituted, carbon-ring type or hetero ring type.As the monocyclic ring that atomic number is 5 or 6, phenyl ring can be enumerated Or pyridine ring etc..As 2 adjacent monocyclic rings that atomic number is 5 or 6, biphenyl etc. can be enumerated.It is 8～10 as atomic number Dicyclic ring class, naphthalene etc. can be enumerated.Additionally, as the three-ring type ring class that atomic number is 13 or 14, anthracene or fluorenes etc. can be enumerated.And And, as it has been described above, the hydrogen atom of these compounds can be replaced by the such as alkyl of carbon number 1～4, alkoxy or halogen etc..Y²It is Singly-bound or selected from ehter bond (-O-), ester bond (-COO-or-OCO-), amido link (-CONH-or-NHCO-) and amino-formate bond The divalent linking group of (-NHCOO-or-OCONH-).Y³It it is hydrogen atom can be replaced by fluorine atoms, the straight-chain of carbon number 3～20 Alkyl or there is the 1 valency organic group of alicyclic skeleton of carbon number 4～40.Y¹It is preferably phenylene or divalent naphthalene (-C₁₀H₆-), Y² It is preferably singly-bound or ehter bond, Y³It is preferably cyclohexyl or dicyclohexyl.

Use and as side chain, there are the polyamic acid of structure represented by above formula [I], poly amic acid ester etc. containing such The aligning agent for liquid crystal of polyimide precursor, polyimides or polyamide and the liquid crystal orientation film that formed inhibit the irradiation of backlight The deterioration of the liquid crystal aligning performance caused.Specifically, use has the structure represented by formula [I] containing such as side chain Polyamic acid, the aligning agent for liquid crystal of polyimide precursor, polyimides or the polyamide such as poly amic acid ester utilizing by partially Shake ultraviolet irradiation etc. anisotropy photochemical reaction method, i.e., use the method shape injecting row orientation process with illumination The liquid crystal orientation film (also referred to as " optical alignment film ") become inhibits the liquid crystal aligning performance degradation that the irradiation of backlight causes.Cause This, is even if the liquid crystal display cells with this liquid crystal orientation film uses liquid crystal aligning performance also good due to long-time, thus real Show the effect that long-time display characteristic is excellent.Even if additionally, there is structure represented by above formula [I] to using as side chain Polyimide precursor, polyimides or polyamide and the liquid crystal orientation film that formed applies long-time AC (exchange) and is driven, also The deterioration of liquid crystal aligning performance can be suppressed.Therefore, even if drive the liquid crystal display unit with this liquid crystal orientation film with long-time AC Part, is not easy to produce sintering attachment.

Speculate that the effect of the liquid crystal aligning performance degradation that the irradiation of such suppression backlight causes is due to the present invention It is acrylate-based and do not have the cinnamoyl near 313nm with absorption maximum that structure represented by above formula [I] has oxo Bases etc. have the group of absorption maximum in the ultraviolet range of longer wavelength.On the other hand, if using conventional liquid crystal to take To agent, the aligning agent for liquid crystal of the structure with cinnamoyl such as replacing the acrylate-based patent documentation 1 of oxo, then due to The unreacted photoreactive group cinnamoyl that liquid crystal orientation film is had can take at liquid crystal due to the light from backlight React in film, upset the orientation of liquid crystal, thus make the deterioration of the liquid crystal aligning performance that the irradiation of backlight causes serious.

Even if additionally, speculating that the effect that long-time AC drives the deterioration that also can suppress liquid crystal aligning performance is due to above formula Structure represented by [I] has longer chain alkyl or ring structure, has the reason of high vertical orientated performance.

The present invention as side chain have the polyimide precursor of structure represented by above formula [I] such as can by make containing Diamine component and the tetrabasic carboxylic acid composition as side chain with the diamidogen of structure represented by above formula [I] carry out reacting and obtain.It addition, Poly amic acid ester can obtain by the carboxyl of polyamic acid is converted to the method for ester.Additionally, the polyimide precursor of the present invention Also can be by making, as side chain, there is the tetrabasic carboxylic acid composition of structure represented by above formula [I] and diamine component carries out reacting and obtains. Then, by these polyimide precursors such as polyamic acid or poly amic acid ester are carried out imidizate, the available present invention's There is the polyimides of structure represented by above formula [I] as side chain.Additionally, the present invention's has above formula [I] institute as side chain The polyamide of the structure represented by make the diamine component of diamidogen containing the structure having as side chain represented by above formula [I] with The halogenide of dicarboxylic acids reacts in the presence of base, or makes containing having the structure represented by above formula [I] as side chain Diamine component and the dicarboxylic acids of diamidogen carry out reacting and obtaining in the presence of suitable condensing agent, alkali.Additionally, the present invention's is poly- Amide is also by making to have the halogenide of dicarboxylic acids of structure represented by above formula [I] and diamine component at alkali as side chain In the presence of react, or make there is the dicarboxylic acids of structure represented by above formula [I] and diamine component suitably as side chain Condensing agent, carry out reacting and obtaining in the presence of alkali.The polyimide precursors such as described polyamic acid, poly amic acid ester, polyamides are sub- Any one of amine and polyamide is as the most useful for obtaining the polymer of liquid crystal orientation film.It addition, the work contained by diamine component The diamidogen for side chain with the structure represented by formula [I] can be a kind, it is also possible to is two or more；Additionally, diamine component also may be used Other diamidogen beyond the diamidogen containing the one kind or two or more structure having as side chain represented by formula [I].Additionally, make It can be a kind for side chain tetrabasic carboxylic acid composition or the dicarboxylic acids with structure represented by formula [I] etc., it is also possible to be two or more；This Outward, it is also possible to the tetrabasic carboxylic acid composition containing the one kind or two or more structure having as side chain represented by formula [I] or dicarboxylic acids Other tetrabasic carboxylic acid beyond Deng or dicarboxylic acids.

The diamidogen as side chain with the structure represented by above formula [I] can enumerate the diamidogen represented by above formula (1).It addition, Diamidogen represented by above formula (1) is the new compound that document is not yet recorded.In formula (1), Y¹、Y²、Y³Respectively with in formula [I] Y¹、Y²、Y³Identical.Additionally, Y⁴For singly-bound, methylene or the alkylidene of carbon number 2～6.Further, Y⁵For singly-bound, oxygen atom, *-OCO- Or-CH₂O-* is (wherein, with key and the Y of " * "⁴In conjunction with).It addition, Y⁴For Y during singly-bound⁵For singly-bound.In formula (1), Y¹It is preferably Asia Phenyl or divalent naphthalene (-C₁₀H₆-), Y²It is preferably singly-bound or ehter bond, Y³It is preferably cyclohexyl or dicyclohexyl, Y⁴It is preferably singly-bound, Y⁵It is preferably singly-bound or-CH₂O-。

Additionally, in formula (1), there is no particular limitation in the position of amino, although as long as then there is no particular limitation for diamidogen, But from the viewpoint of the difficulty of liquid crystal aligning or synthesis, such as, it is respectively relative to oxo acrylate-based, can be exemplified by Prosposition on phenyl ring, 2,4,2,5,2,6,3,4 or 3,5.Wherein, the reactive sight when synthetic polymer Point considers, preferably 2,4,2,5 or 3,5.

As the concrete example of the diamidogen represented by formula (1), following diamidogen can be enumerated.

The synthetic method of the diamine compound that above formula (1) as above represents is not particularly limited, such as can basis Synthesis example described later manufactures.Such as, the diamidogen represented by formula (1) can be by two represented by the following formula (1 ') of synthesis correspondence Restoring nitro after nitro compound makes it be converted into amino and obtain.The method of reduction dinitro compound is the most particularly limited System, generally can be using palladium-carbon, platinum oxide, Raney nickel, ferrum, stannic chloride, platinum black, rhodium-aluminium oxide, platinum sulfide carbon etc. as catalysis Agent uses, but never reduction alkene and retain and the most only reduce from the viewpoint of nitro with high yield, utilize use ferrum Or the chemical reduction method of stannic chloride is effective.Have use ethyl acetate, toluene, oxolane, twoThe alcohols such as alkane, methanol Solvent, as solvent, uses the method that hydrogen, hydrazine, hydrogen chloride, ammonium chloride etc. carry out reacting as reducing agent.

(in formula, Y¹、Y²、Y³、Y⁴、Y⁵Respectively with the Y in formula (1)¹、Y²、Y³、Y⁴、Y⁵Identical)

The synthetic method of the dinitro compound represented by formula (1 ') is not particularly limited, and can be synthesized by any means, As its object lesson, such as, can be synthesized by the method shown in following reaction.

In the reaction, by making dinitro compound A and can have the compound B of hydroxyl in such as ethyl acetate, first Benzene, oxolane, twoIn the organic solvents such as alkane, chloroform, dichloromethane, use DABCO (Isosorbide-5-Nitrae-diazabicyclo [2.2.2] Octane) or the base catalyst such as DMAP (DMAP) carry out reacting synthesizing.

In above-mentioned dinitro compound A, Y⁴、Y⁵Respectively with the Y in formula (1)⁴、Y⁵Identical, as long as having in side chain terminal In alkynes structure then structure, there is no particular limitation.Additionally, in the above-mentioned compound B with hydroxyl, Y¹、Y²、Y³Respectively with formula (1) Y in¹、Y²、Y³Identical, such as can enumerate phenol and its derivatives, be not particularly limited.

By making the diamidogen represented by above formula (1) relative to diamine component total amount at 10 moles of more than %, it is possible to achieve this The effect of invention, preferably 30～100 moles %, further preferred 50～100 moles of %.It addition, in this specification, without Recording especially, ratio refers to the ratio on the basis of molal quantity.

Additionally, as other diamidogen beyond the diamidogen represented by formula (1), the diamidogen represented by following formula (2) can be enumerated.

(in formula (2), R²For singly-bound ,-O-or divalent organic group, X²、X³、X⁴It is separately divalent phenyl ring or hexamethylene Ring, p, q, r are separately the integer of 0 or 1, R³For hydrogen atom, the alkyl of carbon number 1～22 or the carbon with steroid skeleton The 1 valency organic group of several 12～25.)

In formula (2), R²It is preferably ehter bond, ester bond, amido link or amino-formate bond.R³It is preferably the alkane of carbon number 12～18 Base.The alkyl of carbon number 1～22 can be straight-chain, it is also possible to be branched.

Diamidogen represented by formula (2) contributes to increase tilt angle (the inclining of liquid crystal relative to liquid crystal orientation film of liquid crystal Rake angle) compound, preferably have chain alkyl, perfluoroalkyl, aromatic cyclic base, aliphatic cyclic base and these The diamidogen of the substituent group of moiety combinations, steroid skeleton base etc..

Diamidogen represented by formula (2) relative to diamine component total amount, preferably 5～50 moles %, further preferred 10～30 Mole %.

Additionally, as other diamidogen beyond the diamidogen represented by above formula (1), can enumerate p-phenylenediamine, 2,3,5,6-tetra- Dimethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-diaminobenzene., 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2, 6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminourea benzylalcohol, 2,4- Diaminourea benzylalcohol, 4,6-diamino resorcin, 4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3, 3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxy-4,4 '-benzidine, 3,3 '-dicarboxyl-4,4 '-diamino Base biphenyl, 3,3 '-two fluoro-4,4 '-biphenyl, 3,3 '-trifluoromethyl-4,4 '-benzidine, 3,4 '-benzidine, 3, 3 '-benzidine, 2,2 '-benzidine, 2,3 '-benzidine, 4,4 '-diaminodiphenyl-methane, 3,3 '-diamino Base diphenyl methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methane, 2,3 '-diamino-diphenyl first Alkane, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 2,2 '-diaminourea two Phenyl ether, 2,3 '-diamino-diphenyl ether, 4,4 '-sulfonyl dianil, 3,3 '-sulfonyl dianil, double (4-aminophenyls) Silane, double (3-aminophenyl) silane, dimethyl-bis-(4-aminophenyl) silane, dimethyl-bis-(3-aminophenyl) silane, 4,4 '-thiobis aniline, 3,3 '-thiobis aniline, 4,4 '-diamino-diphenylamine, 3,3 '-diamino-diphenylamine, 3,4 '-diamino Base diphenylamines, 2,2 '-diamino-diphenylamine, 2,3 '-diamino-diphenylamine, N-methyl (4,4 '-diamino-diphenyl) amine, N-first Base (3,3 '-diamino-diphenyl) amine, N-methyl (3,4 '-diamino-diphenyl) amine, N-methyl (2,2 '-diamino-diphenyl) Amine, N-methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 3,4 '- Diaminobenzophenone, 1,4-diaminonaphthalene, 2,2 '-diaminobenzophenone, 2,3 '-diaminobenzophenone, 1,5-diamino Base naphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-bis- Double (4-aminophenyl) ethane of amino naphthalenes, 2,8-diaminonaphthalene, 1,2-, double (3-aminophenyl) ethane of 1,2-, double (the 4-ammonia of 1,3- Base phenyl) propane, double (3-aminophenyl) propane of 1,3-, double (4-aminophenyl) butane of 1,4-, 1,4-be double (3-aminophenyl) Double (4-amino-benzene oxygen) benzene of butane, double (3,5-diethyl-4-aminophenyl) methane, 1,4-, double (the 4-aminobenzene oxygen of 1,3- Base) benzene, double (4-aminophenyl) benzene of 1,4-, double (4-aminophenyl) benzene of 1,3-, double (4-aminobenzyl) benzene of 1,4-, 1,3-be double (4-amino-benzene oxygen) benzene, 4,4 '-[1,4-phenylene is double (methylene)] dianils, the 4,4 '-[double (methylene of 1,3-phenylene Base)] dianil, 3,4 '-[1,4-phenylene double (methylene)] dianils, 3,4 '-[1,3-phenylene is double (methylene)] double benzene Amine, 3,3 '-[1,4-phenylene is double (methylene)] dianils, 3,3 '-[1,3-phenylene is double (methylene)] dianils, 1,4-are sub- Phenyl double [(4-aminophenyl) ketone], 1,4-phenylene double [(3-aminophenyl) ketone], double [(the 4-amino of 1,3-phenylene Phenyl) ketone], 1,3-phenylene double [(3-aminophenyl) ketone], 1,4-phenylene double (PABA ester), 1,4-sub- Phenyl double (3-Aminobenzoate), 1,3-phenylene double (PABA ester), double (the 3-amino benzoic Acid of 1,3-phenylene Ester), double (4-aminophenyl) terephthalate, double (3-aminophenyl) terephthalate, double (4-aminophenyl) isophthalic Dicarboxylic acid esters, double (3-aminophenyl) isophthalic acid ester, N, N '-(1,4-phenylene) double (4-aminobenzamide), N, N '- (1,3-phenylene) double (4-aminobenzamide), N, N '-(1,4-phenylene) double (3-AB), N, N '-(1,3- Phenylene) double (3-ABs), N, N '-bis-(4-aminophenyl) terephthalamide, N, N '-bis-(3-aminophenyls) Terephthalamide, N, N '-bis-(4-aminophenyl) isophtalamide, N, N '-bis-(3-aminophenyl) isophtalamide, 9,10-double (4-aminophenyl) anthracene, 4,4 '-bis-(4-amino-benzene oxygen) diphenyl sulphone (DPS)s, 2,2 '-bis-[4-(4-amino-benzene oxygen) benzene Base] propane, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2 '-bis-(4-aminophenyl) HFC-236fa, 2, 2 '-bis-(3-aminophenyl) HFC-236fa, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) HFC-236fa, 2,2 '-bis-(4-aminobenzenes Base) propane, 2,2 '-bis-(3-aminophenyl) propane, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) propane, double (the 4-amino of 1,3- Phenoxy group) propane, double (3-amino-benzene oxygen) propane of 1,3-, double (4-amino-benzene oxygen) butane of 1,4-, double (the 3-aminobenzene of 1,4- Epoxide) butane, double (4-amino-benzene oxygen) pentane of 1,5-, double (3-amino-benzene oxygen) pentane of 1,5-, double (the 4-aminobenzene oxygen of 1,6- Base) hexane, double (3-amino-benzene oxygen) hexane of 1,6-, 1,7-double (4-amino-benzene oxygen) heptane, 1,7-(3-amino-benzene oxygen) Double (4-amino-benzene oxygen) octane of heptane, 1,8-, double (3-amino-benzene oxygen) octane of 1,8-, double (4-amino-benzene oxygen) nonyl of 1,9- Double (3-amino-benzene oxygen) nonane of alkane, 1,9-, 1,10-(4-amino-benzene oxygen) decane, 1,10-(3-amino-benzene oxygen) decane, 1,11-(4-amino-benzene oxygen) hendecane, 1,11-(3-amino-benzene oxygen) hendecane, 1,12-(4-amino-benzene oxygen) 12 Alkane, 1,12-(3-amino-benzene oxygen) dodecane, 4-(amino methyl) aniline, 3-(amino methyl) aniline, 3-((amino methyl) Methyl) aniline, the aromatic diamine such as 4-(2-amino-ethyl) aniline or 3-(2-amino-ethyl aniline)；Double (4-aminocyclohexyl) The ester ring type diamidogen such as methane or double (4-amino-3-methylcyclohexyl) methane；1,3-diaminopropanes, 1,4-diaminobutane, 1,5-1,5-DAP, 1,6-diamino hexane, 1,7-diaminoheptane, 1,8-diamino-octane, 1,9-diamino nonane, 1, The aliphatic diamines such as 10-diamino decane, 1,11-diamino undecane or 1,12-diamino dodecane.

Other diamidogen above-mentioned can be according to liquid crystal aligning when making liquid crystal orientation film, voltage retention, accumulated charge Etc. characteristic, it is used alone, or mixing two or more.

Tetrabasic carboxylic acid composition refers at least one selected from tetrabasic carboxylic acid and tetracarboxylic acid derivatives.As tetracarboxylic acid derivatives, can example Lift tetrabasic carboxylic acid two carboxylic acid halides, tetracarboxylic dianhydride, tetrabasic carboxylic acid diester diacid chloride, tetrabasic carboxylic acid diester etc..Such as, can be by making tetrabasic carboxylic acid two Carboxylic acid halides, tetracarboxylic dianhydride etc. react with diamine component, obtain polyamic acid.Additionally, tetrabasic carboxylic acid diester diacid chloride can be passed through Reaction with diamine component or make tetrabasic carboxylic acid diester react in the presence of suitable condensing agent, alkali with diamine component, To poly amic acid ester.It addition, tetrabasic carboxylic acid composition can be a kind, it is also possible to be two or more.

As tetrabasic carboxylic acid composition, the tetracarboxylic dianhydride shown in following formula (3) can be enumerated.

(in formula (3), Z₁It is 4 valency organic groups of the carbon number 4～13 of non aromatic cyclic alkyl containing carbon number 4～6.)

In formula (3), as Z₁Concrete example, following formula (3a) can be enumerated～4 valency organic groups that formula (3j) represents.

(in formula (3a), Z₂～Z₅Being hydrogen atom, methyl, chlorine atom or phenyl ring, they each other can be identical or different；Formula (3g) in, Z₆And Z₇Being hydrogen atom or methyl, they each other can be identical or different.)

In formula (3), consider from the easness of polymerisation reactivity and synthesis, Z₁Particularly preferred structure be formula (3a), formula (3c), formula (3d), formula (3e), formula (3f) or formula (3g).Wherein, preferred formula (3a), formula (3e), formula (3f) or formula (3g).

Additionally, relative to tetrabasic carboxylic acid composition total amount, the ratio of the tetracarboxylic dianhydride shown in above formula (3) is not particularly limited, Such as, tetrabasic carboxylic acid composition can simply be the tetracarboxylic dianhydride that above formula (3) represents.Certainly, the effect of the present invention is not being damaged In the range of, tetrabasic carboxylic acid composition can also comprise the tetrabasic carboxylic acid beyond the tetracarboxylic dianhydride shown in above formula (3) and tetracarboxylic acid derivatives. Now, preferably 1 mole of % of tetrabasic carboxylic acid composition total amount is above the tetracarboxylic dianhydride shown in above formula (3), more preferably 5 moles % with On, further preferred 10 moles of more than %.

As other tetracarboxylic dianhydride in addition to the tetracarboxylic dianhydride that above-mentioned formula (3) represents, can enumerate Pyromellitic Acid, 2,3,6,7-naphthalenetetracarbacidic acidic, 1,2,5,6-naphthalenetetracarbacidic acidic, 1,4,5,8 naphthalenetetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6- Anthracene tetracarboxylic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic, 2,3,3 ', 4-bibenzene tetracarboxylic, double (3,4-dicarboxyphenyi) ether, 3,3 ', Double (the 3,4-dicarboxyl of 4,4 '-benzophenone tetracarboxylic, double (3,4-dicarboxyphenyi) sulfone, double (3,4-dicarboxyphenyi) methane, 2,2- Base phenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-double (3,4-dicarboxyphenyi) propane, double (3,4-dicarboxyphenyi) two Double (the 3,4-dicarboxyl benzene of methyl-monosilane, double (3,4-dicarboxyphenyi) diphenyl silane, 2,3,4,5-pyridine tetracarboxylic acid, 2,6- Base) pyridine, 3,3 ', 4,4 '-diphenyl sulfone tetraformic acid, 3,4,9,10-tetracarboxylic acid or 1,3-diphenyl-1,2,3,4-Tetramethylene. Tetracarboxylic acid.

Tetrabasic carboxylic acid diester is also not particularly limited.Enumerate its concrete example below.

As the object lesson of aliphatic tetrabasic carboxylic acid diester, can enumerate 1,2,3,4-Tetramethylene. tetrabasic carboxylic acid dialkyls, 1, 2-dimethyl-1,2,3,4-Tetramethylene. tetrabasic carboxylic acid dialkyl, 1,3-dimethyl-1,2,3,4-Tetramethylene. tetrabasic carboxylic acid dialkyl group Ester, 1,2,3,4-tetramethyl-1,2,3,4-Tetramethylene. tetrabasic carboxylic acid dialkyl, 1,2,3,4-Pentamethylene. tetrabasic carboxylic acid dialkyl, 2,3,4,5-oxolane tetrabasic carboxylic acid dialkyl, 1,2,4,5-cyclopentanetetracarboxylic's dialkyl, 3,4-dicarboxyl-1-hexamethylene Base dialkyl succinate, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dialkyl, 1,2,3,4-butane tetracarboxylic Acid dialkyl ester, bicyclo-[3,3,0] octane-2,4,6,8-tetrabasic carboxylic acid dialkyl, 3,3 ', 4,4 ' dicyclohexyl tetrabasic carboxylic acid dioxanes Base ester, 2,3,5-tricarboxylic cyclopentyl dialkyl acetates, cis-3,7-dibutyl ring octyl-1,5-diene-1,2,5,6-tetrabasic carboxylic acid Dialkyl, three ring [4.2.1.0^2,5] nonane-3,4,7,8-tetrabasic carboxylic acid-3,4:7,8-dialkyl, six ring [6.6.0.1^2, ⁷.0^3,6.1^9,14.0^10,13] hexadecane-4,5,11,12-tetrabasic carboxylic acid-4,5:11,12-dialkyl, 4-(2,5-dioxotetrahydro Furan-3-base)-1,2,3,4-tetralin-1,2-dicarboxylic acid dialkyl esters etc..

As aromatic tetracarboxylic acid's dialkyl, can enumerate Pyromellitic Acid dialkyl, 3,3 ', 4,4 '-biphenyl tetracarboxylic acid Acid dialkyl ester, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid dialkyl, 2,3,3 ', 4-biphenyltetracarboxyacid acid dialkyl, 3,3 ', 4, 4 '-benzophenone tetrabasic carboxylic acid dialkyl, 2,3,3 ', 4-benzophenone tetrabasic carboxylic acid dialkyl, double (3,4-dicarboxyphenyi) ether two Arrcostab, double (3,4-dicarboxyphenyi) sulfone dialkyl, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl, 2,3,6,7-naphthalene tetracarboxylic acid Dialkyl etc..

Dicarboxylic acids etc. for reacting with diamine component for obtaining the polyamide of the present invention is not particularly limited.As for The concrete example of the aliphatic dicarboxylic acid of the dicarboxylic acids or derivatives thereof obtaining polyamide and react with diamine component, can enumerate third Diacid, oxalic acid, dimethyl malonic acid, succinic acid, fumaric acid, 1,3-propanedicarboxylic acid, adipic acid, muconic acid, 2-methyl adipic acid, trimethyl The dicarboxyls such as adipic acid, 1,5-pentanedicarboxylic acid., 2,2-dimethylated pentanedioic acid, 3,3-diethyl succinic acid, Azelaic Acid, decanedioic acid and suberic acid Acid.

As the dicarboxylic acids of ester ring type class, 1 can be enumerated, 1-cyclopropane dicarboxylic acid, 1,2-cyclopropane dicarboxylic acid, 1,1-ring fourth Alkane dicarboxylic acids, 1,2-cyclobutane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 3,4-diphenyl-1,2-cyclobutane dicarboxylic acid, 2,4-bis- Phenyl-1,3-cyclobutane dicarboxylic acid, 1-cyclobutane-1,2-dicarboxylic acids, 1-cyclobutane-3,4-dicarboxylic acids, 1,1-Pentamethylene. dicarboxyl Acid, 1,2-cyclopentane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,1-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-ring Hexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,4-(2-norborene) dicarboxylic acids, norborene-2,3-dicarboxylic acids, bicyclo- [2.2.2] octane-1,4-dicarboxylic acid, bicyclo-[2.2.2] octane-2,3-dicarboxylic acids, 2,5-dioxo-1,4-bicyclo-[2.2.2] Octane dicarboxylic acid, 1,3-diamantane (obsolete) dicarboxylic acids, 4,8-dioxo-1,3-diamantane (obsolete) dicarboxylic acids, 2,6-spiral shell [3.3] heptane dicarboxyl Acid, 1,3-diamantane (obsolete) oxalic acid, dextrocamphoric acid. etc..

As aromatic dicarboxylic acid, phthalic acid, M-phthalic acid, p-phthalic acid, oreinol two can be enumerated Formic acid, 5-tert-butyl isophthalic acid, 5-amino isophthalic acid, 5-Hydroxy M Phthalic Acid, 2,5-dimethyl terephthaldehyde Acid, tetramethyl p-phthalic acid, 1,4-naphthalene dicarboxylic acids, 2,5-naphthalene dicarboxylic acids, 2,6 naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acids, 1,4- Anthracene dicarboxylic acids, 1,4-anthraquinone dicarboxylic acids, 2,5-diphenyl dicarboxylic acid, 4,4 '-diphenyl dicarboxylic acid, 1,5-diphenylene dicarboxylic acids, 4, 4 "-terphenyl dicarboxylic acids, 4,4 '-diphenyl methane dicarboxylic acids, 4,4 '-diphenylethane dicarboxylic acids, 4,4 '-diphenyl propane two Carboxylic acid, 4,4 '-diphenyl HFC-236fa dicarboxylic acids, 4,4 '-diphenyl ether dicarboxylic acids, 4,4 '-dibenzyl dicarboxylic acids, 4,4 '- Dicarboxylic acids, 4,4 '-tolan dioctyl phthalate, 4,4 '-carbonyl diurethane benzoic acid, 4,4 '-sulfonyl dibenzoic acid, 4,4 '-dithio Dibenzoic acid, to phenylenediacetic Acid, 3,3 '-to benzene dipropionic acid, 4-o-carboxy cinnamic acid, to benzene diacrylate, 3,3 '-[4,4 '-(sub- Methyl two is to phenylene)] dipropionic acid, 4,4 '-[4,4 '-(oxo two is to phenylene)] dipropionic acids, 4,4 '-[4,4 '-(oxo two To phenylene)] two butanoic acid, (isopropylidene two is to phenylene dioxy) two butanoic acid, double (to carboxyl phenyl) dimethylsilane etc. two Carboxylic acid.

As the dicarboxylic acids containing heterocycle, 1 can be enumerated, 5-(9-oxo fluorenes) dicarboxylic acids, 3,4-furan dicarboxylic acid, 4,5-thiazole Dicarboxylic acids, 2-phenyl-4,5-thiazole dicarboxylic acids, 1,2,5-thiadiazoles-3,4-dicarboxylic acids, 1,2,5-Diazole-3,4-dicarboxylic acids, 2,3-dipicolinic acid, 2,4 pyridine dicarboxylic acid, 2,5-dipicolinic acid, 2,6-dipicolinic acid, 3,4-dipicolinic acid, 3, 5-dipicolinic acid etc..

Above-mentioned various dicarboxylic acids can also be sour two carboxylic acid halides or the structure of anhydride.Wherein, be preferably used p-phthalic acid, Phthalic acid, 1,4-cyclohexane dicarboxylic acid, 4,4 '-diphenyl dicarboxylic acid, 4,4 '-diphenyl methane dicarboxylic acids, 4,4 '-diphenyl second Alkane dicarboxylic acids, 4,4 '-diphenyl propane dicarboxylic acids, 4,4 '-diphenyl HFC-236fa dicarboxylic acids, 2,2-bis-(phenyl) propane dicarboxyl Acid, 4,4 "-terphenyl dicarboxylic acids, 2,6 naphthalene dicarboxylic acid, 2,5-dipicolinic acid or their acid two carboxylic acid halides etc..These compounds In sometimes there is also isomer, it is also possible to be the mixture comprising isomer.In addition it is also possible to and use compound of more than two kinds.

Tetracarboxylic dianhydride shown in above formula (3), other tetrabasic carboxylic acid and tetracarboxylic acid derivatives, dicarboxylic acids etc., it is also possible to according to The required characteristic of liquid crystal aligning, voltage retention and accumulated charge etc. when making liquid crystal orientation film use a kind or by 2 kinds with On be used in mixed way.

The reaction of diamine component and tetrabasic carboxylic acid composition is carried out the most in organic solvent.Organic molten as now use Agent, as long as the polyimide precursors such as the polyamic acid of generation can be dissolved, there is no particular limitation.As object lesson, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N-methyl caprolactam, diformazan can be enumerated Sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, isopropanol, methoxy amylalcohol, diamyl Alkene, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl Cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol Monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl Ether, propylene glycol t-butyl ether, DPGME, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl Ether, dipropylene glycol monoacetate monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol list acetic acid Ester list ethylether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic acid Ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, acetic acid penta Ester, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, twoAlkane, normal hexane, normal heptane, the most pungent Alkane, diethyl ether, Ketohexamethylene, ethylene carbonate, propylene carbonate, methyl lactate, lactic acid ethyl, methyl acetate, ethyl acetate, second Acid N-butyl, propylene glycol acetate list ethylether, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethyoxyl Propanoic acid methyl ethyl ester, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy Base butyl propionate, diethylene glycol dimethyl ether or 4-hydroxy-4-methyl-2-pentanone etc..These solvents can be used alone, it is also possible to mixed Close and use.Further, even the solvent of polyimide precursor can not be dissolved, it is also possible to do not separate out at the polyimide precursor generated In the range of, it is blended in above-mentioned solvent use.It addition, because the moisture in organic solvent hinders polyreaction, and then become Make the reason that the polyimide precursor of generation hydrolyzes, so being preferably to use the organic solvent through dehydrate.

When making diamine component and tetrabasic carboxylic acid composition react in organic solvent, following method can be enumerated: stirring makes diamidogen become Be dispersed or dissolved in solution obtained by organic solvent, the most directly add tetrabasic carboxylic acid composition or make the dispersion of tetrabasic carboxylic acid composition or The method added again after being dissolved in organic solvent；On the contrary tetracarboxylic dianhydride is dispersed or dissolved in obtained by organic solvent molten The method adding diamine component in liquid；Alternately add tetrabasic carboxylic acid composition and the method etc. of diamine component, it is possible to use therein A kind of method.Additionally, in the case of diamine component or tetrabasic carboxylic acid composition use multiple reaction respectively, it can be made in advance React under the state first mixed, it is possible to so that it reacts the most successively, then low-molecular weight mixing obtained by making to react respectively is anti- Should.Polymerization temperature now can select-20 DEG C～the arbitrary temp of 150 DEG C, preferably-5 DEG C～the scope of 100 DEG C.Additionally, it is anti- Should be able to carry out with arbitrary concentration, if but concentration is too low, it is difficult to obtain polyimide precursor (and then the polyamides of high molecular Imines), if excessive concentration, the viscosity of reactant liquor is too high, it is difficult to stir uniformly.Therefore, diamine component and tetrabasic carboxylic acid The concentration of the total amount of composition is preferably 1～50 mass %, more preferably 5～30 mass % in reactant liquor.Initial reaction stage is highly concentrated Carry out under degree, organic solvent can be added afterwards.

In the polyreaction of the polyimide precursors such as polyamic acid, the total mole number of diamine component is total with tetrabasic carboxylic acid composition The ratio of molal quantity is preferably 0.8～1.2.Identical with common polycondensation reaction, this mol ratio is closer to 1.0, the polyamides of generation The molecular weight of imines precursor is the biggest.

It addition, poly amic acid ester can be by the reaction of above-mentioned tetrabasic carboxylic acid diester diacid chloride and diamine component or make tetracarboxylic acid Acid diesters and diamine component carry out reacting obtaining in the presence of suitable condensing agent, alkali.Or, it is also possible in aforementioned manners Pre-synthesis polyamic acid, the carboxyl in polyamic acid is esterified and obtains by recycling high molecular weight reactive.

Specifically, can be by such as making tetrabasic carboxylic acid diester diacid chloride and diamine component in alkali and the existence of organic solvent Under, and react 30 minutes～24 hours, preferably 1 hour～4 hours at-20 DEG C～150 DEG C, preferably 0 DEG C～50 DEG C, synthesize Poly amic acid ester.

As alkali, pyridine, triethylamine, 4-dimethylaminopyridine can be used, in order to carry out with making reacting balance, preferably pyrrole Pyridine.The addition of alkali is from the amount easily removed and from the viewpoint of being readily available high molecular body, relative to tetrabasic carboxylic acid diester two Acyl chlorides, preferably 2～4 times moles.

Additionally, when making tetrabasic carboxylic acid diester and diamine component carry out polycondensation in the presence of condensing agent, can use as alkali Triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride, N, N '-carbonyl Base diimidazole, dimethoxy-1,3,5-triazine methyl morpholine, O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylurea four Fluoboric acid ester, O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylurea hexafluorophosphoric acid ester, (2,3-dihydro-2-sulfur generation-3-benzoOxazolyl) phosphonic acid diphenyl ester, chlorination 4-(4,6-dimethoxy-1,3,5-triazine-2-base) 4-methoxyl group morpholineN hydrate Deng.

Additionally, in the method using above-mentioned condensing agent, by interpolation lewis acid as additive, reaction can be efficiently Carry out.As lewis acid, the preferably lithium halide such as lithium chloride, lithium bromide.Lewis acidic addition is relative to carrying out reacting Preferably 0.1～1.0 times mole of diamidogen or tetrabasic carboxylic acid diester.

As the solvent used in above-mentioned reaction, can use and be used when the above-mentioned synthesizing polyamides acid illustrated The solvent that solvent phase is same, considers from the dissolubility of monomer and polymer, preferably METHYLPYRROLIDONE, gamma-butyrolacton, can To use a kind in them or two or more be used in mixed way.From being difficult to the precipitation of generation polymer and being readily available high molecular From the viewpoint of body, tetracarboxylic acid derivatives and the diamidogen such as concentration, tetrabasic carboxylic acid diester diacid chloride or tetrabasic carboxylic acid diester during synthesis Total concentration in the reaction solution of composition is preferably 1～30 mass %, more preferably 5～20 mass %.Additionally, in order to prevent tetracarboxylic acid Acid diesters diacid chloride hydrolyzes, and the solvent for the synthesis of poly amic acid ester can be the state being dehydrated as far as possible, preferably at nitrogen In atmosphere, prevent being mixed into of foreign gas.

Thus polyimide precursor obtained by polymerization e.g. has the polymer of the repetitive shown in following formula [a].

(in formula [a], R₁₁It is derived from 4 valency organic groups of the tetrabasic carboxylic acid composition of raw material；R₁₂It is derived from the two of raw material The divalent organic group of amine component；A₁₁And A₁₂Being hydrogen atom or the alkyl of carbon number 1～4, they each other can be identical or different；j Represent positive integer.)

Can be that there is R in above formula [a]₁₁And R₁₂It is the polymer of a kind of identical repetitive respectively, in addition, it is possible to Think that there is R₁₁And R₁₂It it is the polymer of the repetitive of multiple different structure.

In above formula [a], R₁₁It is derived from the group of the tetrabasic carboxylic acid composition that the following formula [c] etc. as raw material represents.Additionally, R₁₂It is derived from the group of the diamine component shown in following formula [b] as raw material etc., such as, if R₁₂For deriving from above formula (1) The group of represented diamine compound, then be the C on phenyl ring with 2 keys₆H₃-Y⁵-Y⁴-OCO-CH=CH-O-Y¹-Y²- Y³。

(in formula [b] and formula [c], R₁₁And R₁₂Identical with the definition in formula [a].)

Then, by by these polyimide precursor dehydration closed-loops, it is thus achieved that polyimides.

As the method making polyimide precursor carry out imidizate, the solution directly heating polyimide precursor can be enumerated Hot-imide, or in the solution of polyimide precursor, add the catalysis imidizate of catalyst.

Making temperature during polyimide precursor hot-imide in the solution is 100 DEG C～400 DEG C, preferably 120 DEG C～250 DEG C, preferably carry out while the water eliminating that will be generated by imidization reaction is outer to system.

The catalysis imidizate of polyimide precursor can by polyimide precursor solution add base catalyst and Anhydride, and-20～250 DEG C, preferably at 0～180 DEG C stirring and carry out.The amount of base catalyst is the 0.5 of amide acidic group ～30 moles times, preferably 2～20 moles times, the amount of anhydride is 1～50 mole times of amide acidic group, preferably 3～30 moles times.Make For base catalyst, can enumerate pyridine, triethylamine, trimethylamine, tri-n-butylamine or trioctylamine etc., wherein pyridine has for making reaction The alkalescence of appropriateness for carrying out, the most preferably.As anhydride, acetic anhydride, trimellitic anhydride or pyromellitic dianhydride etc. can be enumerated, Wherein, the purification carrying out reacting after terminating it is prone to when using acetic anhydride, the most preferably.Use the imidizate of catalysis imidizate Rate can control by adjusting catalytic amount and reaction temperature, response time.

Generate it addition, reclaim from the reaction solution of the polyimide precursor such as polyamic acid, poly amic acid ester or polyimides Polyimide precursor or during polyimides, reaction solution can be poured solvent into and make it precipitate.As the solvent for precipitation, can Enumerate methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene or water Deng.Put into the polyimide precursor precipitated in solvent or polyimides can be after being recovered by filtration, in normal pressure or decompression Under, be dried at room temperature or heat.If additionally, make polyimide precursor that precipitation reclaims or polyimides repeat into Row 2～be re-dissolved in the operation that organic solvent reprecipitation reclaim for 10 times, then can reduce polyimide precursor or polyimides In impurity.As solvent now, such as alcohols, ketone or hydro carbons etc. can be enumerated, if using 3 in these solvents Plant above solvent, then purification efficiency improves further, the most preferably.

The dehydration closed-loop rate (acid imide rate) of the amide acidic group of polyimides need not be 100%, can be 0% Arbitrarily select according to purposes and purpose in the range of 100%, preferably 30%～80%.

Polyamide can synthesize in the way of identical with poly amic acid ester.

Molecular weight for polyimide precursor, polyimides or the polyamide of the present invention, it is contemplated that the polymer of gained The operability when intensity of tunicle (liquid crystal orientation film), polymer tunicle are formed, the uniformity of polymer tunicle, to utilize GPC The Weight-average molecular gauge that (gel permeation chromatography) method records is preferably 5000～1000000, more preferably 10000～150000.

The aligning agent for liquid crystal of the present invention comprises the polyamide of the present invention as side chain with structure represented by above formula [I] Polyimide precursor, polyimides or the polyamide such as acid, poly amic acid ester.Aligning agent for liquid crystal refers to for forming liquid crystal orientation film Solution, be the solution component of polymer being used for being formed liquid crystal orientation film being dispersed or dissolved in organic solvent and being formed.Separately Outward, liquid crystal orientation film refers to for making liquid crystal along the film of the direction orientation of regulation.And, in the present invention, as above-mentioned polymer Composition, containing at least one of above-mentioned polyimide precursor, polyimides and polyamide selected from the present invention.

Component of polymer contained in the aligning agent for liquid crystal of the present invention can be entirely the above-mentioned polyimides of the present invention Precursor, polyimides or polyamide, in addition can also be in above-mentioned polyimide precursor, polyimides or the polyamide of the present invention Mix other polymer.When component of polymer contains other polymer, other the polymer in component of polymer total amount Content is 0.5 mass %～80 mass %, preferably 40 mass %～80 mass %.

As other polymer such, can enumerate such as reacting with tetracarboxylic dianhydride's composition or dicarboxylic acids etc. Diamine component, only use the diamidogen beyond the diamidogen as side chain with structure represented by above formula [I] of the present invention to obtain Polyimide precursor, polyimides or polyamide etc..Further, gathering beyond polyimide precursor, polyimides or polyamide Compound, specifically can enumerate acrylate copolymer, methacrylate polymer, polysiloxanes, polystyrene etc..

In the aligning agent for liquid crystal of the present invention, selected from the present invention polyimide precursor, polyimides and polyamide at least The content ratio of other polymer that is a kind of and that mix as required is preferably 1 mass %～20 in component of polymer total amount Quality %, more preferably 3 mass %～15 mass %, particularly preferred 3～10 mass %.

As long as the polyimide precursor of the solvent solubilized present invention that the aligning agent for liquid crystal of the present invention contains, polyimides Or the organic solvent of the component of polymer such as polyamide, it is not particularly limited.As its concrete example, N, N-dimethyl can be enumerated Methanamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrole Pyrrolidone, NVP, dimethyl sulfoxide, tetramethylurea, pyridine, dimethylsulfone, pregnancy sulfoxide, gamma-butyrolacton, 3-first Epoxide-N, N-dimethylpropionamide, 3-ethyoxyl-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1, 3-dimethyl-2-imidazolidinone, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, Ketohexamethylene, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone etc..These solvents are permissible It is used alone, but also also mix together.

In the aligning agent for liquid crystal of the present invention, in the range of the effect not damaging the present invention, can be containing improving coating The film thickness uniformity of polymer tunicle during aligning agent for liquid crystal and the organic solvent (also referred to as poor solvent) of surface smoothness or Compound.Further, it is also possible to containing the compound etc. that can improve liquid crystal orientation film and the adaptation of substrate.

As the concrete example of the poor solvent of the uniformity and surface smoothness that can improve thickness, isopropanol, first can be enumerated Epoxide 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, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethylether, dipropylene glycol list propyl group Ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetas, tripropylene glycol methyl ether, 3-methyl- 3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl Ketone, methylcyclohexene, propyl ether, two hexyl ethers, normal hexane, pentane, normal octane, diethyl ether, methyl lactate, ethyl lactate, acetic acid Methyl ester, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethylether, methyl pyruvate, ethyl pyruvate, 3-methoxyl group Methyl propionate, 3-ethoxy-propionic acid Methylethyl ester, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3- Methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 1-methoxy-2-propanol, 1-ethyoxyl-2-propanol, 1-butoxy-2-third Alcohol, 1-phenoxy group-2-propanol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetas, Propylene glycol-1-list ethylether-2-acetas, dipropylene glycol, 2-(2-ethoxy-c epoxide) propanol, methyl lactate, ethyl lactate, Lactic acid n-propyl ester, n-butyl lactate or isoamyl lactate etc. have the organic solvent etc. of low surface tension.

These poor solvents can use a kind, or is used in mixed way multiple.When using solvent as above, preferably comprise 5～80 mass % of solvent total amount contained in aligning agent for liquid crystal, more preferably 20～60 mass %.

As improving film thickness uniformity or the compound of surface smoothness, fluorine class surfactant, type siloxane can be enumerated Surfactant, nonionic surfactant etc..More specifically, such as エ Off トップ EF301, EF303, EF352 can be enumerated (Tuo Kaimu product Co., Ltd. (トケ system プロダ Network Star) system), メガ Off ァッ Network F171, F173, R-30 (big Japan oil Ink Co., Ltd. (big Japan イ Application キ) system), Off ロラ De FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo スリエ System) system), アサヒガ De AG710, サ Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd's (Asahi Glass) system) etc..The use ratio of these surfactants is relative to containing in aligning agent for liquid crystal Component of polymer 100 mass parts, preferably 0.01～2 mass parts, more preferably 0.01～1 mass parts.

As the compound of the adaptation improving liquid crystal orientation film and substrate, can enumerate the compound containing functional silanes or Compound containing epoxy radicals, such as, can enumerate 3-TSL 8330, APTES, 2- TSL 8330,2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-aminopropyl trimethoxy Silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl trimethoxy silane, 3-urea groups Propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-3-aminopropyl Triethoxysilane, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl Sanya second Base triamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three azepine Decane, 9-trimethoxysilyl-3,6-diaza nonyl acetas, 9-triethoxysilyl-3,6-diaza nonyl Yl acetate, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl- Double (the oxyethylene group)-3-aminopropan of 3-TSL 8330, N-phenyl-APTES, N- Base trimethoxy silane, N-double (oxyethylene group)-APTES, Ethylene glycol diglycidyl ether, poly-second Hexanediol diglycidyl ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl Ether, neopentylglycol diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2-dibromo new penta Hexanediol diglycidyl ether, 1,3,5,6-four glycidyl group-2,4-hexanediol, N, N, N ', N ' ,-four glycidyl group-two Double (N, the N-diglycidyl amino methyl) hexamethylene of toluenediamine, 1,3-or N, N, N ', N ' ,-four glycidyl group-4, 4 '-diaminodiphenyl-methane etc..

When use can improve with the compound of the adaptation of substrate, its usage amount is contained gathering relative in aligning agent for liquid crystal Polymer component 100 mass parts, preferably 0.1～30 mass parts, more preferably 1～20 mass parts.If usage amount is less than 0.1 mass Part, then cannot expect the effect that adaptation improves, if more than 30 mass parts, the orientation of liquid crystal is deteriorated the most sometimes.

In the aligning agent for liquid crystal of the present invention, in addition to the foregoing, in the range of the effect not damaging the present invention, Ke Yitian Electrolyte for the purpose of the electrical characteristics such as the dielectric constant or the electric conductivity that are changed liquid crystal orientation film or conductive materials, it is also possible to add Improved the hardness of film when forming liquid crystal orientation film or the cross-linked compound for the purpose of consistency.

The aligning agent for liquid crystal of the present invention can carry out orientation process with light irradiation etc. after coating on substrate and burning till, Thus it is used as liquid crystal orientation film.The liquid crystal orientation film of such present invention has represented by above formula [I] as side chain owing to comprising The polyimide precursor of structure, polyimides or polyamide, therefore, it is difficult to occur the liquid crystal aligning performance that causes of backlight bad Change, be difficult in addition occur AC to drive the liquid crystal aligning performance degradation caused.It addition, the aligning agent for liquid crystal of the present invention can be used for Above-mentioned inject row orientation process with illumination and form the purposes beyond liquid crystal orientation film (optical alignment film).Specifically, may be used for In vertical orientated purposes etc., carry out friction treatment after burning till or do not carry out orientation process and the liquid crystal orientation film that formed.

As substrate, as long as the substrate that the transparency is high, it is not particularly limited, in addition to glass substrate, it is possible to use The plastic bases etc. such as acrylic acid substrate, polycarbonate substrate.From the viewpoint of technique simplifies, it is preferably used and defines for liquid The substrate of brilliant ITO (the Indium Tin Oxide) electrode etc. driven.It addition, in reflection type liquid crystal display element, it is possible to so that With opaque substrates such as silicon wafers, but being only limitted to the substrate of one side, electrode now can also use the material of the reflection light such as aluminum Material.Additionally, in the TFT contour performance components of type element, be usable in being formed between the electrode and substrate of liquid crystal drive The component of the elements such as transistor.

Being not particularly limited the coating process of aligning agent for liquid crystal, industrial usual employing is by silk screen printing, graph The method that brush, flexographic printing or ink-jet method etc. are coated.As other coating process, also dip coating, rolling method, slit are coated with Cloth method, spin-coating method or spraying process etc., can use these methods according to purpose.

After being coated on substrate by aligning agent for liquid crystal, heating plate, heat-circulation type stove or IR (infrared ray) type stove can be passed through Deng heater 50～300 DEG C, preferably make solvent evaporate at 80～250 DEG C, thus form liquid crystal orientation film (polymer quilt Film).If the thickness of the liquid crystal orientation film after burning till is blocked up, then unfavorable in terms of the power consumption of liquid crystal display cells, if the thinnest, The most sometimes the reliability of liquid crystal display cells reduces, the most preferably 5～300nm, more preferably 10～100nm.Make liquid crystal vertical In the case of orientation, horizontal alignment or tilted alignment, the liquid crystal orientation film after burning till can be irradiated the lonizing radiation such as polarized UV rays Or carry out friction treatment.

The liquid crystal display cells of the present invention is to be obtained band liquid crystal aligning by said method by the aligning agent for liquid crystal of the present invention After the substrate of film, the liquid crystal display cells formed by known method manufacture liquid crystal cell.If example is as an example, then has and possess The liquid crystal display cells of following liquid crystal cell: this liquid crystal cell possesses the 2 pieces of substrates configured in opposite directions, the liquid crystal being arranged between substrate Layer, and the above-mentioned liquid crystal orientation film formed by the aligning agent for liquid crystal of the present invention being arranged between substrate and liquid crystal layer.As this The liquid crystal display cells of the present invention of sample, can enumerate vertical orientated (VA:Vertical Alignment) mode, stable twisted nematic (TN:Twisted Nematic) mode and horizontal alignment (IPS:In-Plane Switching, in-plane switching) mode, OCB The various liquid crystal display cells such as orientation (OCB:Optically Compensated Bend, optical compensation curved).It addition, liquid crystal Alignment films may be provided at least one piece in 2 pieces of substrates.

The substrate used as the liquid crystal display cells of the present invention, as long as the substrate that the transparency is high, does not has spy Do not limit, it is common that on substrate, be formed with the substrate of transparency electrode for driving liquid crystal.As concrete example, can enumerate with The substrate that substrate described in above-mentioned liquid crystal orientation film is same.

Additionally, liquid crystal orientation film is by burning till after being coated with the aligning agent for liquid crystal of the present invention on the substrate, then root Being formed according to needing to irradiate the lonizing radiation such as polarized UV rays, detailed content is described above.

The liquid crystal material of the liquid crystal layer of the liquid crystal display cells constituting the present invention is not particularly limited, can use and just have The positive type liquid crystal of dielectric anisotropy or there is the negative type liquid crystal of negative dielectric anisotropy.As concrete example, can use with The liquid crystal material that past vertical orientation mode is used, MLC-6608, MLC-6609 that such as Merck & Co., Inc. (メルク society) makes Deng.

If enumerating the example manufacturing liquid crystal cell, following method can be illustrated: prepare to be formed with a pair base of liquid crystal orientation film Plate, spreads pearl thing at equal intervals on the liquid crystal orientation film of a plate base, liquid crystal aligning face is become the laminating of another plate base For interior rear flank, liquid crystal the method sealed are injected in decompression；Or on the liquid crystal aligning face be scattered with sept drip liquid crystal it After, baseplate-laminating is carried out the method etc. sealed.Now, the thickness of sept preferably 1～30 μm, more preferably 2～10 μm.

The liquid crystal display cells that the aligning agent for liquid crystal of the present invention as used above is made inhibits backlight owing to having The liquid crystal orientation film of the deterioration of liquid crystal aligning performance that causes of irradiation, thus long-time display characteristic is excellent.Additionally, due to tool Even if having the long-time AC that applies to be driven also can suppressing the liquid crystal orientation film of the deterioration of liquid crystal aligning performance, even if being therefore long Time is driven the liquid crystal display cells being not easy to produce sintering attachment with AC.

Embodiment

Below, it is described in further detail based on embodiment, but the present invention is not by any restriction of this embodiment.

Breviary symbol used in the present embodiment is as follows:

(tetracarboxylic dianhydride)

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

(diamidogen)

DA-1: (E)-3 represented by following formula, 5-diaminourea benzyl 3-(4-(trans-4-heptyl cyclohexyl) phenoxy group) third Olefin(e) acid ester

DA-2: (E)-3 represented by following formula, and 5-diaminourea benzyl 3-(4-(trans-4 '-amyl group-[1,1 '-bis-(hexamethylenes Alkane)]-4-base) phenoxy group) acrylate

PCH:1,3-diaminourea-4-[4-(4-heptyl cyclohexyl) phenoxy group] benzene

(organic solvent)

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

BCS: butyl cellosolve

The molecular weight of polymer (polyamic acid etc.) uses Sen Xiu science Co., Ltd. (セ Application シュ science society) to make Room temperature gel permeation chromatography (GPC) device (SSC-7200), Showa electrician (Shodex) Co., Ltd. post (KD-803, KD-805) measure as follows.

Column temperature: 50 DEG C

Eluent: N, N'-dimethylformamide is (as additive, lithium bromide hydrate (LiBr H₂O) it is 30 mmoles You/liter, phosphoric anhydride crystallization (o-phosphoric acid) be 30 mM/ls, oxolane (THF) be 10 ml l)

Flow velocity: 1.0ml/ minute

Calibration trace making standard specimen: (molecular weight is about for Dong Cao company (ソ society) TSK processed standard poly(ethylene oxide) Be 900000,150000,100000,30000) and Polymer Laboratory company (Port リマラボラトリ society) make poly-second two Alcohol (molecular weight is about 12000,4000,1000).

<synthesis example 1>DA-1 ((E)-3,5-diaminourea benzyl 3-(4-(trans-4-heptyl cyclohexyl) phenoxy group) acrylic acid Ester) synthesis

(in above-mentioned reaction equation, the cis-trans isomerization of cyclohexylidene is respectively transisomer.)

In the four-hole boiling flask of 1L add compound [A] (11.00g, 55.5mmol), triphenylphosphine (16.02g, 61.1mmol), oxolane (80g) (being the most also denoted as THF), after carrying out nitrogen displacement, reaction solution is cooled to 0 DEG C.At it In slowly drip acetylenecarboxylic acid [B] (4.67g, 66.6mmol), azodicarboxy isopropyl propionate (12.34g, 61.1mmol), THF (120g) mixed solution.After completion of dropwise addition, reaction solution is recovered to 23 DEG C, stirs further.Use high-efficient liquid phase color Spectrometry (HPLC) carries out reactive tracing, after confirming that reaction terminates, removes solvent with vaporizer distillation and obtains the thick product of compound [C] Thing.

Then, compound obtained above [C] adds compound [D] (15.23g, 55.5mmol) and THF (140g), Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane (being the most also denoted as DABCO) (622mg, 5.55mmol) is added, 23 It is stirred at DEG C.Carry out reactive tracing with HPLC, after confirming that reaction terminates, add 10wt% sodium hydrate aqueous solution 200g, Extract with ethyl acetate (200mL)/hexane (600mL) mixed solution.After removing water layer, clear with saturated aqueous common salt (500g) Wash 3 times, make it dried with magnesium sulfate, remove solvent with vaporizer distillation, obtain the crude product of compound [E].Then, obtaining To compound [E] crude product in add 2-propanol (being the most also denoted as IPA) (200g) and after carrying out 30 minutes heated and stirred, Placement is cooled to 30 DEG C, carries out filtering, drying under reduced pressure, obtains compound [E] (15.4g, yield 53%).Measure with NMR and obtain The result of compound [E] as follows.

¹H-NMR (400MHz, CDCl₃, δ ppm): 9.01 (1H, t), 8.57-8.56 (2H, m), 7.88 (1H, d), 7.23- 7.01 (2H, m), 7.01-6.98 (2H, m), 5.58 (1H, d), 5.35 (2H, s), 2.53-2.44 (1H, m), 1.88-1.85 (4H, m), 1.49-1.00 (17m), 0.89 (3H, t).

In the four-hole boiling flask of 500mL add compound [E] (14.81g, 28.2mmol), ferrous components (9.46g, 169mmol), 10wt% aqueous ammonium chloride solution (45g), ethyl acetate (130g), at 70 DEG C, carry out heated and stirred.Chase after with HPLC Track reacts, and after reaction terminates to confirm, filters with kieselguhr and removes solid constituent, be carried out with ethyl acetate and distilled water.Point Analysis filtrate, after removing water layer, cleans organic layer 3 times with distilled water (500g), makes it dried with magnesium sulfate, distills with vaporizer Remove solvent, obtain the crude product of compound DA-1.In this crude product, add methanol (30g), 30 minute after mistake is stirred at room temperature Filter, carries out methanol and cleans and drying under reduced pressure, obtain compound DA-1 (9.9g, yield 76%).The compound obtained is measured with NMR The result of DA-1 is as follows.

¹H-NMR (400MHz, CDCl₃, δ ppm): 7.81 (1H, d), 7.20-7.18 (2H, m), 6.98-6.96 (2H, m), 6.11 (2H, d), 5.98 (1H, t), 5.54 (1H, m), 4.99 (2H, s), 3.60 (4H, brs), 2.48-2.42 (1H, m), 1.87-1.85 (4H, m), 1.42-1.20 (14H, m), 1.08-0.99 (3H, m), 0.89-0.87 (3H, m).

<synthesis example 2>DA-2 ((E)-3,5-diaminourea benzyl 3-(4-(trans-4 '-amyl group-[1,1 '-bis-(hexamethylene)]- 4-yl) phenoxy group) acrylate) and synthesis

Acetylenecarboxylic acid [B] (3.23g, 46.2mmol) and N, N '-dimethyl Methanamide is added in the four-hole boiling flask of 200mL (40g) (the most also it is denoted as DMF), stirs at 23 DEG C and gradually add sodium bicarbonate (7.76g, 92.4mmol) on a small quantity Powder, is stirred at room temperature 30 minutes.Then, solution is heated to 50 DEG C, slowly drips 3,5-dinitrobenzyl chlorine [F] DMF (60g) solution of (10.00g, 46.2mmol).Carry out reactive tracing with HPLC, after reaction terminates, add ethyl acetate (600g), hexane (200g) and distilled water (600g), carry out separatory operation, remove water layer.Clean with distilled water (500g) and have Machine layer 3 times, makes it dried with magnesium sulfate, removes solvent with vaporizer distillation, obtains compound [C] (11.05g, yield 96%).The result measuring the compound [C] obtained with NMR is as follows.

¹H-NMR (400MHz, CDCl₃, δ ppm): 9.06-9.05 (1H, m), 8.60-8.59 (2H, m), 5.41 (2H, s), 3.04 (1H, s).

In the four-hole boiling flask of 200mL add compound [C] (11.05g, 44.2mmol), compound [G] (14.51g, 44.2mmol), Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane (495mg, 4.42mmol) and oxolane (140g), at 23 DEG C It is stirred.Carry out reactive tracing with HPLC, after reaction terminates, add 10wt% sodium hydrate aqueous solution (100g), further Add ethyl acetate (200g), remove water layer by separatory operation.Clean organic layer 3 times with saturated aqueous common salt (500g), use sulfur Acid magnesium makes it dried, removes solvent with vaporizer distillation, obtains the crude product of compound [H].2-is added in this crude product Propanol (180g), after carrying out 30 minutes being heated to reflux stirring, is cooled to 40 DEG C, after filtering and carrying out IPA cleaning, carries out decompression dry Dry, obtain compound [H] (25.3g, yield 98%).The result measuring the compound [H] obtained with NMR is as follows.

¹H-NMR (400MHz, CDCl₃, δ ppm): 9.00 (1H, t), 8.57-8.56 (2H, m), 7.88 (1H, d), 7.22- 7.21 (2H, m), 7.00-6.98 (2H, m), 5.58 (1H, d), 5.36 (2H, s), 2.50-2.37 (1H, m), 1.94-0.84 (30H, m).

In the four-hole boiling flask of 500mL add compound [H] (25.3g, 44.2mmol), ferrous components (14.80g, 265mmol), 10wt% aqueous ammonium chloride solution (71g), ethyl acetate (230g), at 70 DEG C, carry out heated and stirred.Chase after with HPLC Track reacts, and after reaction terminates to confirm, filters with kieselguhr and removes solid constituent, be carried out with ethyl acetate and distilled water.Point Analysis filtrate, after removing water layer, cleans organic layer 3 times with distilled water (500g), makes it dried with magnesium sulfate, distills with vaporizer Remove solvent, obtain the crude product of compound DA-2.In this crude product, add methanol (50g), 30 minute after mistake is stirred at room temperature Filter, carries out methanol and cleans and drying under reduced pressure, obtain compound DA-2

(14.7g, yield 64%).The result measuring the compound DA-2 obtained with NMR is as follows.

¹H-NMR (400MHz, CDCl₃, δ ppm): 7.81 (1H, d), 7.20-7.18 (2H, m), 6.98-6.96 (2H, m), 6.11 (2H, d), 5.98 (1H, t), 5.54 (1H, m), 4.99 (2H, s), 3.59 (4H, brs), 2.53-2.38 (1H, m), 1.87-0.90 (30H, m).

The synthesis of<synthesis example 3>DA-3

Synthesis example 1-1 synthesis DA-3 according to patent documentation 1.

The synthesis of<synthesis example 4>DA-4

Embodiment 1 according to Japan Patent spy's table 2001-517719 publication synthesizes DA-4.

By CBDA (0.288g, 1.50mmol) and DA-1 (0.697g, 1.5mmol) mixing in NMP (5.58g), in room The lower reaction of temperature obtains polyamic acid solution in 10 hours.BCS (4.93g) and NMP (4.93g) is added in this polyamic acid solution, It is 6 mass % by polyamic acid concentration dilution, obtains aligning agent for liquid crystal A1 by being stirred at room temperature 5 hours.This polyamic acid Number-average molecular weight be 14000, weight average molecular weight is 74000.

By CBDA (0.485g, 2.50mmol) and DA-2 (1.297g, 2.5mmol) mixing in NMP (10.1g), in room The lower reaction of temperature obtains polyamic acid solution in 10 hours.BCS (8.91g) and NMP (8.91g) is added in this polyamic acid solution, It is 6 mass % by polyamic acid concentration dilution, obtains aligning agent for liquid crystal A2 by being stirred at room temperature 5 hours.This polyamic acid Number-average molecular weight be 3500, weight average molecular weight is 5300.

By CBDA (0.485g, 2.50mmol) and DA-3 (1.052g, 2.5mmol) mixing in NMP (8.71g), in room The lower reaction of temperature obtains polyamic acid solution in 10 hours.BCS (7.68g) and NMP (7.68g) is added in this polyamic acid solution, It is 6 mass % by polyamic acid concentration dilution, obtains aligning agent for liquid crystal A3 by being stirred at room temperature 5 hours.This polyamic acid Number-average molecular weight be 5500, weight average molecular weight is 13000.

By CBDA (1.537g, 7.8mmol), DA-4 (2.832g, 6.4mmol), PCH (0.609g, 1.6mmol) at NMP (19.91g) mixing in, at room temperature reaction obtains polyamic acid solution in 10 hours.NMP is added in this polyamic acid solution (33.19g) with BCS (24.89g), it is 6 mass % by polyamic acid concentration dilution, obtains liquid by being stirred at room temperature 5 hours Brilliant alignment agent A4.The number-average molecular weight of this polyamic acid is 12000, and weight average molecular weight is 24000.

Use aligning agent for liquid crystal A1, make liquid crystal orientation film according to step shown below, measure UV (ultraviolet) and absorb Spectrum.Additionally, use aligning agent for liquid crystal A1, make liquid crystal cell by step shown below, and carry out tilt angle evaluation, The evaluation of AC (exchange) sintering attachment and the evaluation of backlight patience.

[mensuration of UV absorption spectrum]

Aligning agent for liquid crystal A1 is spun on quartz base plate, after being dried 90 seconds by the heating plate of 80 DEG C, follows with the hot blast of 200 DEG C Circular furnace burns till 30 minutes, forms the liquid crystal orientation film of thickness 100nm.The substrate being formed with this liquid crystal orientation film is used Shimadzu Make institute (institute is made in Tianjin) UV-3600 processed and measure UV absorption spectrum, obtain maximum absorption wavelength (λ_max).Result is shown in table 1.

[making of liquid crystal cell]

What aligning agent for liquid crystal A1 was spun on the glass substrate with the transparency electrode being made up of ito film is formed with ito film Face, the hot plate of 80 DEG C was dried after 90 seconds, burns till in the heated air circulation type stove of 200 DEG C 30 minutes, forming thickness is The liquid crystal orientation film of 100nm.To being formed with the substrate of this liquid crystal orientation film, use exposure rate 2.0mW/cm^-2The straight line of 254nm Polarization UV, is irradiated in the way of light exposure changes between 0～1000mJ.The direction of incident ray is relative to substrate normal Direction is 40 ° of inclinations.Linear polarization UV is at the ultraviolet light of high voltage mercury lamp after the band filter of 254nm, through 254nm Polarization plates make.

Prepare 2 pieces of aforesaid substrates, after the liquid crystal orientation film of the substrate of a side spreads the pearl sept of 4 μm, thereon Printing and sealing agent (Xie Li KCC (vertical chemistry) XN-1500T processed).Then, the liquid crystal aligning face of 2 pieces of substrates is made Relatively, to be that antiparallel condition crimps to the projecting direction of the optical axis of linear polarization UV of each substrate, 150 DEG C are kept 105 minutes, make sealant heat cure.Injected by decompression and normal direction this negative crystal born of the same parents inject negative type liquid crystal (Merck & Co., Inc.'s system, MLC- 6608), the stove of 120 DEG C carries out isotropic process (reorientation using the liquid crystal of heating processes), prepares liquid crystal brilliant Born of the same parents.

[evaluation of tilt angle]

" AxoScan " that the tilt angle of liquid crystal cell uses Acker Suo Mei Tekes company (Axo Metrix society) to make passes through Muller matrix method is measured.Result is shown in table 1.

[evaluation of AC sintering attachment]

After making liquid crystal cell, the liquid crystal cell determining tilt angle is driven 240 hours under the alternating voltage of 16Vpp After, after driving stopping to start 1 hour, again measure the tilt angle of liquid crystal cell, the change of the tilt angle before and after evaluation AC driving Change.The change (tilt angle after tilt angle-AC driving before AC Δ angle=AC driving) of the tilt angle before and after AC drives is not enough Judge when 0.2 ° that AC sintering attachment characteristic is good.AC Δ angle is shown in table 1.

[evaluation of backlight patience]

After making liquid crystal cell, the liquid crystal cell determining tilt angle is placed (ripening) and uses at 40 inch type liquid crystal TVs (wavelength 400～800nm) backlight (BL), after upper 240 hour, measures the pre-of liquid crystal cell after leaving 1 hour on BL again Inclination angle, the change of the tilt angle before and after evaluation ripening.The change of the tilt angle before and after ripening (BL Δ angle=BL pre-irradiation pre- Inclination angle-BL irradiate after tilt angle) less than 0.1 ° time judge that BL patience is good.BL Δ angle is shown in table 1.

Liquid crystal is made in the way of same as in Example 1 in addition to using aligning agent for liquid crystal A2 to replace aligning agent for liquid crystal A1 Alignment films, measures the UV absorption spectrum of the liquid crystal orientation film obtained.

Additionally, system in the way of same as in Example 1 in addition to replacing aligning agent for liquid crystal A1 except use aligning agent for liquid crystal A2 Make liquid crystal cell, the liquid crystal cell obtained is carried out commenting of the evaluation of tilt angle, the evaluation of AC sintering attachment and backlight patience Valency.Result is shown in table 1.

Liquid crystal is made in the way of same as in Example 1 in addition to using aligning agent for liquid crystal A3 to replace aligning agent for liquid crystal A1 Alignment films, measures the UV absorption spectrum of the liquid crystal orientation film obtained.

Additionally, with except using aligning agent for liquid crystal A3 to replace aligning agent for liquid crystal A1 and by the irradiation ripple of linear polarization UV Length is changed to mode same as in Example 1 beyond 313nm and makes liquid crystal cell, and the liquid crystal cell obtained is carried out tilt angle Evaluate, AC sinters the evaluation and the evaluation of backlight patience adhered to.Result is shown in table 1.

Liquid crystal is made in the way of same as in Example 1 in addition to using aligning agent for liquid crystal A4 to replace aligning agent for liquid crystal A1 Alignment films, measures the UV absorption spectrum of the liquid crystal orientation film obtained.

Additionally, with except using aligning agent for liquid crystal A4 to replace aligning agent for liquid crystal A1 and by the irradiation ripple of linear polarization UV Length is changed to mode same as in Example 1 beyond 313nm and makes liquid crystal cell, and the liquid crystal cell obtained is carried out tilt angle Evaluate, AC sinters the evaluation and the evaluation of backlight patience adhered to.Result is shown in table 1.

[table 1]

By the results verification of above-mentioned table 1, employ the side chain of the present invention and there is the polymer of structure represented by formula [I] The liquid crystal display cells of embodiment 1 and embodiment 2 is owing to tilt angle is high, i.e. have high vertical orientated ability, thus before AC drives After the change of tilt angle little, demonstrate that good AC sinters attachment characteristic.Additionally, confirm formula [I] institute due to the present invention The structure represented has UV absorption band near the 254nm as low wavelength region, thus embodiment 1 and the liquid crystal of embodiment 2 Display element is susceptible to the impact of backlight, even if being exposed to backlight for a long time the change of tilt angle occurs the most hardly. On the other hand, it is known that use the comparative example 1 of the conventional diamidogen with cinnamoyl and comparative example 2 owing to having near 300nm Absorbing, thus easily affected by backlight, if being exposed to backlight for a long time, the change of tilt angle can slowly occur.

Claims

1. a polymer, it is characterised in that for before the polyimides of the structure having as side chain represented by following formula [I] Body, using obtained by this polyimide precursor imidizate as the polyimides of the structure represented by side chain has following formula [I], with And there is at least one of polyamide of structure represented by following formula [I] as side chain；

[changing 1]

In formula, Y¹For selected from 2 adjacent monocyclic rings, the atomic numbeies that the monocyclic ring that atomic number is 5 or 6, atomic number are 5 or 6 It is ring class or the ring class of three-ring type that atomic number is 13 or 14, the non-substituted or substituted carbon-ring type or miscellaneous of the dicyclic of 8～10 The divalent aromatic group of ring type；Y²For singly-bound or selected from ehter bond, ester bond, amido link and the divalent linker of amino-formate bond Group；Y³That can be replaced by fluorine atoms for hydrogen atom, the straight-chain alkyl of carbon number 3～20 or there is the ester ring type bone of carbon number 4～40 1 valency organic group of frame；

Wherein, except following side chain

2. polymer as claimed in claim 1, it is characterised in that use the diamidogen represented by following formula (1) to obtain；

[changing 2]

In formula, Y¹For selected from 2 adjacent monocyclic rings, the atomic numbeies that the monocyclic ring that atomic number is 5 or 6, atomic number are 5 or 6 It is ring class or the ring class of three-ring type that atomic number is 13 or 14, the non-substituted or substituted carbon-ring type or miscellaneous of the dicyclic of 8～10 The divalent aromatic group of ring type；Y²For singly-bound or selected from ehter bond, ester bond, amido link and the divalent linker of amino-formate bond Group；Y³That can be replaced by fluorine atoms for hydrogen atom, the straight-chain alkyl of carbon number 3～20 or there is the ester ring type bone of carbon number 4～40 1 valency organic group of frame；Y⁴For singly-bound, methylene or the alkylidene of carbon number 2～6；Y⁵For singly-bound, oxygen atom, *-OCO-or- CH₂O-*, wherein, with key and the Y of " * "⁴In conjunction with；Work as Y⁴For Y during singly-bound⁵For singly-bound.

3. an aligning agent for liquid crystal, it is characterised in that containing the polymer described in claim 1 or 2.

4. a liquid crystal orientation film, it is characterised in that use the aligning agent for liquid crystal described in claim 3 to obtain.

5. a liquid crystal display cells, it is characterised in that possess the liquid crystal orientation film described in claim 4.

6. a diamidogen, it is characterised in that represent with following formula (1)；

[changing 3]

In formula, Y¹For selected from 2 adjacent monocyclic rings, the atomic numbeies that the monocyclic ring that atomic number is 5 or 6, atomic number are 5 or 6 It is ring class or the ring class of three-ring type that atomic number is 13 or 14, the non-substituted or substituted carbon-ring type or miscellaneous of the dicyclic of 8～10 The divalent aromatic group of ring type；Y²For singly-bound or selected from ehter bond, ester bond, amido link and the divalent linker of amino-formate bond Group；Y³That can be replaced by fluorine atoms for hydrogen atom, the straight-chain alkyl of carbon number 3～20 or there is the ester ring type bone of carbon number 4～40 1 valency organic group of frame；Y⁴For singly-bound, methylene or the alkylidene of carbon number 2～6；Y⁵For singly-bound, oxygen atom, *-OCO-or- CH₂O-*, wherein, with key and the Y of " * "⁴In conjunction with；Work as Y⁴For Y during singly-bound⁵For singly-bound；

Wherein, except following diamidogen