CN103415583B

CN103415583B - Polyimide film is formed with coating fluid, liquid crystal aligning agent, polyimide film, liquid crystal orientation film and liquid crystal display device

Info

Publication number: CN103415583B
Application number: CN201180068575.1A
Authority: CN
Inventors: 南悟志
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2010-12-28
Filing date: 2011-12-28
Publication date: 2016-02-24
Anticipated expiration: 2031-12-28
Also published as: KR20130130033A; JPWO2012091088A1; TW201241046A; TWI519569B; WO2012091088A1; KR101856808B1; JP5831712B2; CN103415583A

Abstract

The present invention is a kind of polyimide film formation coating fluid, the liquid crystal aligning agent be made up of this coating fluid, this coating solution is carried out burning till in substrate and the polyimide film obtained, by described polymkeric substance crosslinked and polyimide film that polyimide that is that obtain is formed under the effect of the difunctional compound represented with following formula [A], the liquid crystal orientation film be made up of this polyimide film, and possess the liquid crystal display device of this liquid crystal orientation film, described polyimide film formation coating fluid contains polymkeric substance and difunctional compound, described polymkeric substance is at least one of the polyimide being selected from polyimide precursor and being obtained by this polyimide precursor imidization, described polyimide precursor carries out polyreaction by making tetracarboxylic acid composition and diamine component and obtains, described difunctional compound is the difunctional compound represented with following formula [A] introduced Michaelis acid structure respectively and obtain on two amino of diamine compound.［ changing A ］ (in formula, Y, R ₁and R ₂the group of regulation in claim 1 or 4).

Description

Polyimide film is formed with coating fluid, liquid crystal aligning agent, polyimide film, liquid crystal orientation film and liquid crystal display device

Technical field

The present invention relates to novel polyimide film formation coating fluid and liquid crystal aligning agent, use them and the polyimide film formed and liquid crystal orientation film and liquid crystal display device.

Background technology

In liquid crystal display device, liquid crystal orientation film is responsible for the effect making liquid crystal along certain direction orientation.Now, the method that the main liquid crystal orientation film of industrial use carries out film forming by the liquid crystal aligning agent of the polyimide by the solution composition as the polyamic acid of polyimide precursor, poly amic acid ester or polyimide being coated substrate manufactures.In addition, make mesomorphic phase for real estate, when parallel-oriented or tilted alignment, carries out areal stretch process further by friction after film forming.In addition, as the alternative method of friction treatment, it is also proposed and adopt based on the method for the anisotropy photochemical reaction of polarized UV rays irradiation etc., carry out towards industrialized research in recent years.

In order to improve the display characteristic of this liquid crystal display device, carry out the improvement of liquid crystal aligning and electrical characteristic etc., the control etc. of tilt angle by the change of the structure of polyamic acid, poly amic acid ester or polyimide, the method such as the doping of polyamic acid, poly amic acid ester or polyimide, the interpolation of additive that characteristic is different.

Control in the technology of tilt angle by the structure of polyimide, use the diamines with side chain can control tilt angle according to the usage ratio of this diamines as the method for a part for polyimide raw material, therefore target tilt angle is reached than being easier to, useful as the method increasing tilt angle.As the side-chain structure of diamines of tilt angle increasing liquid crystal, the combination (such as with reference to patent documentation 2), steroid skeleton (such as reference patent documentation 3) etc. of the alkyl of known long-chain or fluoroalkyl (such as with reference to patent documentation 1), cyclic group or cyclic group and alkyl.

In addition, for the diamines of the tilt angle for increasing liquid crystal described above, also the structural research for the stability and process dependency improving tilt angle has been carried out, as side-chain structure used, propose the ring structure side-chain structure of the bag such as phenyl or cyclohexyl (such as with reference to patent documentation 4,5) here.Also proposed the diamines (such as with reference to patent documentation 6) side chain with 3 ~ 4 this ring structures.

In recent years, along with extensively practical in the LCD TV of large picture and the mobile purposes (display section of digital camera and portable phone) of high-resolution of liquid crystal display device, compared with the past, the maximization of the substrate of use, the concavo-convex continuous aggravation of substrate step.In this condition, from the viewpoint of display characteristic, requiring can coating of liquid crystalline alignment films equably for large substrate and step.

In the manufacturing process of liquid crystal orientation film, by the solution of polyamic acid or the solution coat of solvent-soluble polyimide in the substrate when, industrially generally to be undertaken by offset printing etc.As the solvent of coating fluid, except solvent (hereinafter also referred to good solvent) METHYLPYRROLIDONE and the gamma-butyrolactone etc. of the solvability excellence of resin, in order to solvent (hereinafter also referred to the poor solvent) ethylene glycol butyl ether etc. that the solvability improving film homogeneity and hybrid resin is low.But the ability making polyamic acid or polyimide dissolve of poor solvent, if therefore a large amount of mixing, can separate out (such as with reference to patent documentation 7).Particularly in the solution of solvent-soluble polyimide, this problem shows clearly.In addition, use the diamines with side chain as above and tendency that coating homogeneity that the polyimide that obtain exists solution declines, therefore need the combined amount of increase poor solvent, the mixing allowance of this solvent is also the key property of polyimide.

In addition, the development such as power saving of the high performance of liquid crystal display device, big area, display device, in addition also uses under circumstances, also becomes strict for the characteristic required by liquid crystal orientation film.The problems such as the precipitation caused because pitch time extends when particularly liquid crystal aligning agent the being coated substrate generation bad with being separated caused printing, the burning screen that caused by accumulated charge (RDC) become problem, are difficult to solve this two problems by prior art simultaneously.

As mentioned above, in polyimide liquid crystal orientation film, use various diamine component as a part for raw material to improve desired characteristic, but due to the relation with other characteristic, sometimes cannot freely use desired diamine component.

Also have; due to its feature, namely higher physical strength, thermotolerance, solvent resistance; polyimide is except being used as liquid crystal orientation film; also be widely used as the protecting materials in elec-tric-electronic field, insulating material; when as this material; similarly the diamine component as polyimide raw material is improved, but freely cannot use desired diamine component this point too.So, wish the improvement easily carrying out these desired characteristics.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 2-282726 publication

Patent documentation 2: Japanese Patent Laid-Open 3-179323 publication

Patent documentation 3: Japanese Patent Laid-Open 4-281427 publication

Patent documentation 4: Japanese Patent Laid-Open 9-278724 publication

Patent documentation 5: International Publication No. 2004/52962 text

Patent documentation 6: Japanese Patent Laid-Open 2004-67589 publication

Patent documentation 7: Japanese Patent Laid-Open 2-37324 publication

Summary of the invention

Invent technical problem to be solved

Problem of the present invention is the problem solving above-mentioned prior art, provide easily can obtain the polyimide film more freely improving various characteristic polyimide film formation coating fluid and liquid crystal aligning agent, use them and the polyimide film formed and liquid crystal orientation film and liquid crystal display device.

The technical scheme that technical solution problem adopts

The feature solving the polyimide film formation coating fluid of the present invention of above-mentioned problem is, containing polymkeric substance and difunctional compound, described polymkeric substance is at least one of the polyimide being selected from polyimide precursor and being obtained by this polyimide precursor imidization, described polyimide precursor is carried out polyreaction by least one tetracarboxylic acid composition and diamine component making to be selected from tetracarboxylic acid and derivative thereof and is obtained, described difunctional compound is the difunctional compound represented with following formula [A] introduced Michaelis acid structure respectively and obtain on two amino of diamine compound.

[changing 1]

(in formula, Y represents the divalent organic group deriving from described diamine compound, R ₁and R ₂be respectively-H or can comprise at an arbitrary position phenyl ring, cyclohexane ring, heterocycle, fluorine, ehter bond, ester bond, amido linkage carbonatoms be 1 ~ 35 1 valency organic group, can be connected with a part of Y and form ring, in addition, R ₁and R ₂can be the same or different.)

The feature of liquid crystal aligning agent of the present invention is, is formed form with coating fluid by described polyimide film.

In addition, the feature of polyimide film of the present invention is, by described polyimide film formation coating solution in substrate, carries out burning till and obtaining.

In addition, the feature of polyimide film of the present invention is, crosslinked and polyimide that is that obtain is formed under the effect of difunctional compound by polymkeric substance, described polymkeric substance is at least one of the polyimide being selected from polyimide precursor and being obtained by this polyimide precursor imidization, described polyimide precursor is carried out polyreaction by least one tetracarboxylic acid composition and diamine component making to be selected from tetracarboxylic acid and derivative thereof and is obtained, described difunctional compound is the difunctional compound represented with following formula [A] introduced Michaelis acid structure respectively and obtain on two amino of diamine compound.

[changing 2]

In addition, the feature of liquid crystal orientation film of the present invention is, is made up of described polyimide film.

In addition, the feature of liquid crystal display device of the present invention is, possesses described liquid crystal orientation film.

The effect of invention

According to the present invention, by making the polyimide film formation coating fluids such as the liquid crystal aligning agent of the difunctional compound represented with above formula [A] obtained containing introducing Michaelis acid structure on two amino of diamine compound respectively, the polyimide films such as the liquid crystal orientation film more freely improving various characteristic can be obtained.And, the difunctional compound represented with above formula [A] is the compound introduced Michaelis acid structure respectively and obtain on two amino of diamine compound, as this diamine compound, can use for obtain carried out studying in the past want the diamine component of characteristic, therefore easily can improve the various characteristics of gained polyimide film.In addition, polyimide film formation of the present invention polyimide precursor contained by coating fluid or polyimide are cross-linked under the effect of the difunctional compound represented with above formula [A] by heating, therefore the polyimide film of gained has the patience to organic solvent, and plays the effect making film hardening.

The best mode carried out an invention

Below, the present invention is described in detail.

Polyimide film formation of the present invention contains with coating fluid to introduce Michaelis acid structure respectively and the difunctional compound represented with following formula [A] that obtains on two amino of diamine compound.

[changing 3]

In above formula [A], Y is the divalent organic group of the diamine compound of the raw material derived from as the difunctional compound represented with above formula [A] as mentioned above, its structure is not particularly limited, as the concrete example of Y, the divalent organic group etc. represented with following formula (Y-1) ~ (Y-120) can be exemplified.Wherein, when using the polyimide film of gained as liquid crystal orientation film, in order to obtain good liquid crystal aligning, it is better the structure that is raw material with the diamine compound that rectilinearity is high, as this Y, can exemplify (Y-7), (Y-10), (Y-11), (Y-12), (Y-13), (Y-21), (Y-22), (Y-23), (Y-25), (Y-26), (Y-27), (Y-41), (Y-42), (Y-43), (Y-44), (Y-45), (Y-46), (Y-48), (Y-61), (Y-63), (Y-64), (Y-65), (Y-66), (Y-67), (Y-68), (Y-69), (Y-70), (Y-71), (Y-78), (Y-79), (Y-80), (Y-81), or (Y-109) etc. (Y-82).In addition, using the polyimide film of gained as when being used for the liquid crystal orientation film of the tilt angle improving liquid crystal, better side chain to have chain alkyl (such as the alkyl of carbon number more than 10), aromatic ring, aliphatics ring, steroid skeleton or the diamine compound of structure they combined are the structure of raw material, as this Y, can exemplify (Y-83), (Y-84), (Y-85), (Y-86), (Y-87), (Y-88), (Y-89), (Y-90), (Y-91), (Y-92), (Y-93), (Y-94), (Y-95), (Y-96), (Y-97), (Y-98), (Y-99), (Y-100), (Y-101), (Y-102), (Y-103), (Y-104), (Y-105), (Y-106), or (Y-108) etc. (Y-107), but be not limited to this.In addition, when wish improves the electrical characteristic of liquid crystal display device, (Y-31), (Y-40), (Y-64), (Y-65), (Y-66), (Y-67), (Y-109), (Y-110) etc. can be exemplified.In addition, for giving liquid crystal orientation film with in photoreactive situation, (Y-17), (Y-18), (Y-111), (Y-112), (Y-113), (Y-114), (Y-115), (Y-116), (Y-117), (Y-118), (Y-119) etc. can be exemplified.

[changing 4]

[changing 5]

[changing 6]

[changing 7]

[changing 8]

[changing 9]

[changing 10]

[changing 11]

[changing 12]

[changing 13]

[changing 14]

[changing 15]

[changing 16]

[changing 17]

[changing 18]

Two amino of diamine compound are introduced Michaelis acid structure respectively and the difunctional compound represented with above formula [A] that obtains such as manufactures by following method: in trimethyl orthoformate, or in triethyl orthoformate, or the organic solvent used in the organic synthesis of routine (such as ethyl acetate, hexane, toluene, tetrahydrofuran (THF), acetonitrile, methyl alcohol, chloroform, 1, 4-diox, N, dinethylformamide, METHYLPYRROLIDONE) in, the diamine compound that represents with following formula [B] and Michaelis acid and trimethyl orthoformate or triethyl orthoformate one are reacted.As the diamine compound represented with following formula [B], can use for obtain carried out studying in the past want the diamine component of characteristic, namely for carrying out polyreaction to manufacture polyimide precursor or polyimide and diamine component for obtaining wanted characteristic with tetracarboxylic acid composition.Temperature of reaction and reaction times are not particularly limited, such as, in 60 ~ 120 DEG C of reaction 30 minutes ~ 2 hours.

[changing 19]

(Y, R ₁and R ₂with Y, the R in above formula [A] ₁and R ₂identical.)

Certainly, the difunctional compound represented with above formula [A] can be a kind of, or also can be two or more and use.

In addition, polyimide film formation coating fluid of the present invention contains at least one polymkeric substance of the polyimide being selected from polyimide precursor and obtained by this polyimide precursor imidization, and described polyimide precursor is carried out polyreaction by least one tetracarboxylic acid composition and diamine component making to be selected from tetracarboxylic acid and derivative thereof and obtained.Certainly, this polyimide precursor or polyimide can be a kind of, or also can be two or more and use.Polyimide precursor refers to polyamic acid and poly amic acid ester.

Polyimide precursor contained by polyimide film formation coating fluid of the present invention is described above, is carried out polyreaction by least one tetracarboxylic acid composition and diamine component making to be selected from tetracarboxylic acid and derivative thereof and is obtained.

As diamine component, can exemplify such as with the diamine compound that above formula [B] represents.In addition, diamine component used when in the past obtaining polyimide precursor making diamine component and tetracarboxylic acid composition react can be used.Diamine component as the raw material of this polyimide precursor can be partly or entirely the compound identical with the diamine compound of the raw material as the difunctional compound represented with above formula [A], or diamine component also can be the compound different from the diamine compound of the raw material as the difunctional compound represented with above formula [A].

In addition, as at least one tetracarboxylic acid composition being selected from tetracarboxylic acid and derivative thereof, tetracarboxylic acid composition used when in the past obtaining polyimide precursor making diamine component and tetracarboxylic acid composition react can be used.As tetracarboxylic acid derivatives, the tetracarboxylic dianhydride, tetracarboxylic acid diester diacid chloride, tetracarboxylic acid diester etc. that tetracarboxylic acid two carboxylic acid halides can be exemplified, represent with following formula [C].Such as, by making the tetracarboxylic acid or derivatives thereofs such as tetracarboxylic acid two carboxylic acid halides, tetracarboxylic dianhydride and diamine component reaction, polyamic acid can be obtained.In addition, by the reaction of tetracarboxylic acid diester diacid chloride and diamine component, or by make tetracarboxylic acid diester and diamine component suitable condensing agent, alkali there is inferior condition under react, can poly amic acid ester be obtained.

[changing 20]

(X is 4 valency organic groups.)

As the concrete example of the X of above formula [C], the 4 valency organic groups represented with following formula (X-1) ~ (X-46) can be exemplified.Obtain difficulty from the viewpoint of compound, X is better (X-1), (X-2), (X-3), (X-4), (X-5), (X-6), (X-8), (X-16), (X-17), (X-19), (X-21), (X-25), (X-26), (X-27), (X-28), (X-32) or (X-46).When wish improves the transparency of gained polyimide film, preferred use has the tetracarboxylic dianhydride of aliphatics and aliphatic ring structure, as X, be more preferably (X-1), (X-2) and (X-25), consider from the reactive viewpoint with diamines, be more preferably further (X-1).

[changing 21]

As the concrete example of tetracarboxylic acid diester, can 1 be exemplified, 2, 3, 4-tetramethylene tetracarboxylic acid dialkyl, 1, 2-dimethyl-1, 2, 3, 4-tetramethylene tetracarboxylic acid dialkyl, 1, 3-dimethyl-1, 2, 3, 4-tetramethylene tetracarboxylic acid dialkyl, 1, 2, 3, 4-tetramethyl--1, 2, 3, 4-tetramethylene tetracarboxylic acid dialkyl, 1, 2, 3, 4-pentamethylene tetracarboxylic acid dialkyl, 2, 3, 4, 5-tetrahydrofuran (THF) tetracarboxylic acid dialkyl, 1, 2, 4, 5-cyclopentanetetracarboxylic dialkyl, 3, 4-dicarboxyl-1-cyclohexyl dialkyl succinate, 3, 4-dicarboxyl-1, 2, 3, 4-tetrahydrochysene-1-naphthalene succinic dialkyl, 1, 2, 3, 4-butane tetracarboxylic acid dialkyl ester, dicyclo [3, 3, 0] octane-2, 4, 6, 8-tetracarboxylic acid dialkyl, 3, 3 ', 4, 4 '-dicyclohexyl tetracarboxylic acid dialkyl, 2, 3, 5-tricarboxylic cyclopentyl dialkyl acetates, cis-3, 7-dibutyl ring pungent-1, 5-diene-1, 2, 5, 6-tetracarboxylic acid dialkyl, three ring [4.2.1.0 ^2,5] nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-dialkyl, six ring [6.6.0.1 ^2,7.0 ^3,6.1 ^9,14.0 ^10,13] n-Hexadecane-4, 5, 11, 12-tetracarboxylic acid-4, 5:11, 12-dialkyl, 4-(2, 5-dioxotetrahydro furans-3-base)-1, 2, 3, 4-tetraline-1, the aliphatics tetracarboxylic acid diester such as 2-dicarboxylic acid dialkyl esters, Pyromellitic Acid dialkyl, 3, 3 ', 4, 4 '-biphenyltetracarboxyacid acid dialkyl, 2, 2 ', 3, 3 '-biphenyltetracarboxyacid acid dialkyl, 2, 3, 3 ', 4-biphenyltetracarboxyacid acid dialkyl, 3, 3 ', 4, 4 '-benzophenone tetracarboxylic acid dialkyl, 2, 3, 3 ', 4-benzophenone tetracarboxylic acid dialkyl, two (3, 4-dicarboxyphenyi) ether dialkyl, two (3, 4-dicarboxyphenyi) sulfone dialkyl, 1, 2, 5, 6-naphthalene tetracarboxylic acid dialkyl, 2, 3, 6, aromatic tetracarboxylic acid's dialkyls such as 7-naphthalene tetracarboxylic acid dialkyl.

Certainly, diamine component and tetracarboxylic acid composition can be a kind of respectively, or also can be two or more and use.

Tetracarboxylic acid composition and diamine component are carried out, and method that polyreaction carrys out synthesis of polyimides precursor is not particularly limited, and can use known synthetic method.

Such as, as the reaction of diamine component and tetracarboxylic dianhydride, the method that diamine component and tetracarboxylic dianhydride are reacted in organic solvent can be exemplified.As long as organic solvent now used dissolves the organic solvent of the polyimide precursor generated, be not particularly limited.As its concrete example, DMF can be exemplified, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-methyl caprolactam, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolactone, Virahol, methoxymethyl amylalcohol, limonene, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methylcyclohexane, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monobutyl ether, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, Diethylene Glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, tetrahydrotoluene, propyl ether, hexyl ether, two alkane, normal hexane, Skellysolve A, octane, diethyl ether, pimelinketone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate list ethyl ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, 3-methoxy 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, diglyme or 4-hydroxy-4-methyl-2-pentanone etc.These can be used alone, also can be used in combination.Further, even the solvent of polyimide precursor can not be dissolved, in the scope that the polyimide precursor generated is not separated out, may be combined in above-mentioned solvent and use.In addition, because the moisture in organic solvent hinders polyreaction, and the reason that the polyimide precursor of generation is hydrolyzed is become, so it is desirable to use the organic solvent dehydrated.

When diamine component and tetracarboxylic dianhydride are reacted in organic solvent, can exemplify: the solution that stirring makes diamine component be dispersed or dissolved in organic solvent and obtains, the method for then directly adding tetracarboxylic dianhydride or adding again after making tetracarboxylic dianhydride be dispersed or dissolved in organic solvent; The method of diamine component is added in the solution obtained making tetracarboxylic dianhydride be dispersed or dissolved in organic solvent on the contrary; Alternately add the method etc. of tetracarboxylic dianhydride and diamine component, any one method wherein can be adopted.When using multiple diamine component or tetracarboxylic dianhydride to react respectively, can it be made to react under the state be pre-mixed, it also can be made to react successively respectively, can also make to react respectively and the low-molecular weight hybrid reaction obtained and obtain polymkeric substance.Polymerization temperature now can select the arbitrary temp of-20 DEG C ~ 150 DEG C, is better the scope of-5 DEG C ~ 100 DEG C.Reaction can be carried out under any concentration, if but concentration is too low, then and be difficult to the polymkeric substance obtaining high molecular, if excessive concentration, then the viscosity of reaction solution is too high, is difficult to uniform stirring.Therefore, be preferably 1 ~ 50 quality %, be more preferably 5 ~ 30 quality %.Initial reaction stage is carried out in higher concentrations, can add organic solvent afterwards.

In the polyreaction of polyimide precursor, the total mole number of diamine component and the relatively good of the total mole number of tetracarboxylic dianhydride are 0.8 ~ 1.2.Identical with common polycondensation, this mol ratio is more close to 1.0, and the molecular weight of the polyimide precursor of generation is larger.

In addition, as mentioned above, by the reaction of tetracarboxylic acid diester diacid chloride and diamine component, or by make tetracarboxylic acid diester and diamine component suitable condensing agent, alkali there is inferior condition under react, can poly amic acid ester be obtained.Or, by the pre-synthesis polyamic acid of aforesaid method, utilize high molecular weight reactive by the carboxyl esterification of polyamic acid, also can obtain poly amic acid ester thus.

Specifically, such as, can make tetracarboxylic acid diester diacid chloride and diamine component under the existence of alkali and organic solvent, and-20 DEG C ~ 150 DEG C, preferably 0 DEG C ~ 50 DEG C at reaction 30 minutes ~ 24 hours, preferably 1 hour ~ 4 hours, thus synthesizing polyamides acid esters.

As alkali, pyridine, triethylamine, DMAP can be used, because reacting balance ground carries out, so preferred pyridine.Easily obtain high molecular body from the viewpoint of with the amount easily removed, the addition of alkali is better 2 ~ 4 times moles relative to tetracarboxylic acid diester diacid chloride.

In addition, make tetracarboxylic acid diester and diamine component under the existence of condensing agent when polycondensation, as alkali, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride, N can be used, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazine methylmorpholine, O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylurea (TMU) Tetrafluoroboric acid ester, O-(benzotriazole-1-base)-N, N, N ', N '-tetramethylurea (TMU) phosphofluoric acid ester, (2,3-dihydro-2-sulfo--3-benzo azoles) phosphonic acid diphenyl ester, 4-(4,6-dimethoxy-1,3,5-triazines-2-base) 4-methoxyl group morpholine muriate n-hydrate etc.

In addition, in the method for above-mentioned use condensing agent, by adding Lewis acid as additive, reaction is carried out efficiently.As Lewis acid, the lithium halides such as preferred lithium chloride, lithiumbromide.Lewis acidic addition is better 0.1 ~ 1.0 times of molar weight relative to the diamines carrying out reacting or tetracarboxylic acid diester.

As solvent used in above-mentioned reaction, can with the solvent same with solvent phase used during the acid of above shown synthesizing polyamides, considering from monomer and structure adaptability, is better METHYLPYRROLIDONE, gamma-butyrolactone, and they can one or more be used in combination.As concentration during synthesis, easily obtain high molecular body from the viewpoint of the precipitation that polymkeric substance not easily occurs, the tetracarboxylic acid derivatives such as tetracarboxylic acid diester diacid chloride or tetracarboxylic acid diester and the total concn of diamine component in reaction soln are better 1 ~ 30 quality %, are more preferably 5 ~ 20 quality %.In addition, in order to prevent the hydrolysis of tetracarboxylic acid diester diacid chloride, the solvent used in the synthesis of poly amic acid ester is better dewater as far as possible, is better in nitrogen atmosphere, prevent being mixed into of ambient atmos.

Polyimide contained by polyimide film formation coating fluid of the present invention obtains by making above-mentioned polyimide precursor dehydration closed-loop.In this polyimide, the dehydration closed-loop rate (imide rate) of acid amides acidic group not necessarily needs to be 100%, can adjust arbitrarily according to purposes or object.

As the method making polyimide precursor imidization, the hot-imide of the solution of direct heating polyimide precursor can be exemplified or in the solution of polyimide precursor, add the catalysis imidization of catalyzer.

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

The catalysis imidization of polyimide precursor is by adding basic catalyst and acid anhydrides in polyimide precursor solution, and at-20 ~ 250 DEG C, is better stir at 0 ~ 180 DEG C and carry out.The amount of basic catalyst is mole to count 0.5 ~ 30 times of acid amides acidic group, preferably 2 ~ 20 times, and the amount of acid anhydrides is mole to count 1 ~ 50 times of acid amides acidic group, preferably 3 ~ 30 times.As basic catalyst, pyridine, triethylamine, Trimethylamine 99, Tributylamine or trioctylamine etc. can be exemplified, wherein pyridine have for make reaction carry out for appropriateness alkalescence, therefore preferably.As acid anhydrides, diacetyl oxide, trimellitic acid 1,2-anhydride or pyromellitic dianhydride etc. can be exemplified, wherein, use during diacetyl oxide and be easy to carry out reacting the purifying after terminating, therefore preferably.Adopt the imide rate of catalysis imidization can be controlled by adjustment catalytic amount and temperature of reaction, reaction times.

When reclaiming polyimide precursor or the polyimide of generation from the reaction soln of polyimide precursor or polyimide, be better reaction soln is put in solvent make it precipitate.As the solvent for precipitating, methyl alcohol, acetone, hexane, ethylene glycol butyl ether, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene, water etc. can be exemplified.The polymkeric substance putting into precipitation in solvent after filtered and recycled, can carry out drying in normal temperature or heating under normal or reduced pressure.In addition, if the polymkeric substance repeating to make precipitation reclaim is dissolved in organic solvent and the redeposition operation 2 ~ 10 times of reclaiming again, then the impurity in polymkeric substance can be reduced.As solvent now, can exemplify such as alcohols, ketone or hydrocarbon etc., if use the solvent being selected from more than 3 kinds of these solvents, then purification efficiency improves further, therefore preferably.

Polyimide precursor contained by polyimide film formation coating fluid of the present invention or polyimide, when the homogeneity of the operability when considering that the polyimide film strength of gained, polyimide film are formed, polyimide film, the weight-average molecular weight utilizing GPC (gel permeation chromatography) method to measure is better 5000 ~ 1000000, is more preferably 10000 ~ 150000.

Polyimide film formation coating fluid of the present invention can containing the polymkeric substance beyond above-mentioned polyimide precursor or polyimide as component of polymer.As the polymkeric substance beyond polyimide precursor or polyimide, can exemplified by acrylic polymkeric substance, methacrylate polymer, polystyrene, polysiloxane or polymeric amide etc.

By containing above-mentioned polymkeric substance and difunctional compound, namely, such as by making the existing polyimide film formation for the formation of liquid crystal orientation film etc. with containing the difunctional compound represented with above formula [A] in coating fluid further, thus become the polyimide film formation coating fluid that can obtain the polyimide film more freely improving various characteristic; Described polymkeric substance is at least one of the polyimide being selected from polyimide precursor and being obtained by this polyimide precursor imidization, described polyimide precursor is carried out polyreaction by least one tetracarboxylic acid composition and diamine component making to be selected from tetracarboxylic acid and derivative thereof and is obtained, and described difunctional compound is the difunctional compound represented with above formula [A] introduced Michaelis acid structure respectively and obtain on two amino of diamine compound.

If described in detail, the difunctional compound then represented with above formula [A] has 2 Michaelis acid structures at two ends, namely the structure of Michaelis acid is derived from, this Michaelis acid structure is by heating (such as more than 180 ~ 250 DEG C), ketenes (namely there is the carbonyl compound of divalent group >C=C=O) is become along with carbonic acid gas and leaving away of acetone, the independent dimerization of ketenes, or the carboxyl to have with polyimide precursor or polyimide, hydroxyl, amino, sulfydryl, aldehyde, ketone, unsaturated link(age) (such as carbon-to-carbon double bond, carbon-to-carbon triple bond, imines (carbon-nitrogen double bond), carbodiimide, Sulfur ylide, phosphonium ylide), amido linkage and ester bond, the carbonyl of imide bond, the reactions such as active methylene group.Therefore, the difunctional compound represented with above formula [A] does not react with polyimide precursor or polyimide under the state of polyimide film formation coating fluid not being heated to high temperature (such as less than 100 DEG C), but by heating, be introduced into polyimide precursor or polyimide via Michaelis acid structure.The difunctional compound represented with above formula [A] because have 2 Michaelis acid structures, so infer be formed as after the heating polyimide by the difunctional compound represented with above formula [A] crosslinked structure.

Thus, polyimide film formation coating solution of the present invention is carried out burning till in substrate and in the polyimide film obtained, in polyimide, introduce the Y structure that the difunctional compound that represents with above formula [A] has, namely derive from the Y structure of the diamine compound of the raw material as the difunctional compound represented with formula [A].

In the past; polyimide film is due to its feature, namely higher physical strength, thermotolerance, solvent resistance and the protecting materials, the insulating material that are widely used as in liquid crystal orientation film, elec-tric-electronic field; use various diamine component as a part for raw material to improve desired characteristic, but sometimes cannot freely use desired diamine component.Such as, in liquid crystal orientation film, in order to carry out raising of liquid crystal aligning and tilt angle etc., namely use various diamine component as a part for raw material to improve desired characteristic, but according to the difference of the kind in order to obtain the diamine component that desired characteristic uses, combination and amount, the polymerisation reactivity of diamine component and tetracarboxylic acid composition is deteriorated, and is therefore restricted sometimes for obtaining the kind of the diamine component of wanted characteristic, combination and amount.In addition, for various kind and the combination of the diamine component for obtaining wanted characteristic, the polymeric reaction condition studying diamine component and tetracarboxylic acid composition is respectively needed.In addition, in order to make the polyimide film formation coating fluid that can form uniform polyimide film, it must be the solution state being dissolved in solvent containing composition, but according to the difference of the kind of the diamine component for obtaining wanted characteristic, combination and amount, the problem that the solvability that there is polyimide precursor contained by polyimide film formation coating fluid or polyimide is deteriorated.

In the present invention, in the stage of polyimide film formation coating fluid, as different compounds respectively containing polyimide precursor or polyimide and the difunctional compound represented with above formula [A] as the compound for obtaining wanted characteristic, polyimide film formation coating fluid is being heated to the stage of (burning till), the difunctional compound represented with above formula [A] as the compound being used for obtaining wanted characteristic is being introduced polyimide precursor or polyimide.Therefore, polyimide precursor contained by polyimide film formation coating fluid or polyimide without the need to for acquisition want the diamine component of characteristic to be raw material, therefore can not producing the problem of the polymerisation reactivity difference of diamine component and tetracarboxylic acid composition, the various kind of the diamine component for obtaining wanted characteristic and combination being needed to the poorly soluble problem of polyimide precursor contained by the problem of the polymeric reaction condition studying diamine component and tetracarboxylic acid composition respectively, polyimide film formation coating fluid or polyimide.Thus, polyimide film formation coating fluid of the present invention can use the diamine compound for obtaining wanted characteristic, and the solvability of the Necessity of Study of the polymerisation reactivity of diamine component and tetracarboxylic acid composition, polymeric reaction condition, polyimide precursor or polyimide need not be considered, compared with existing polyimide film formation coating fluid, more freely can improve the various characteristics of gained polyimide film.

In addition, in the difunctional compound represented with above formula [A], two amino of diamine compound are introduced Michaelis acid structure respectively, as this diamine compound, can use for obtain carried out studying in the past want the diamine component of characteristic, namely for carrying out polyreaction to manufacture polyimide precursor or polyimide and diamine component for obtaining wanted characteristic with tetracarboxylic acid composition.Therefore, the various characteristics of gained polyimide film can easily be improved.

Also have, polyimide film formation of the present invention polyimide precursor contained by coating fluid or polyimide are cross-linked under the effect of the difunctional compound represented with above formula [A] by heating, therefore the polyimide film of gained has the patience to organic solvent, and becomes dura mater.

The manufacture method of polyimide film formation coating fluid of the present invention is not particularly limited, as long as make polymkeric substance and difunctional compound be dissolved in solvent, described polymkeric substance is at least one of the polyimide being selected from polyimide precursor and being obtained by this polyimide precursor imidization, described polyimide precursor is carried out polyreaction by least one tetracarboxylic acid composition and diamine component making to be selected from tetracarboxylic acid and derivative thereof and is obtained, described difunctional compound is the difunctional compound represented with above formula [A] introduced Michaelis acid structure respectively and obtain on two amino of diamine compound.

As long as the solvent energy dissolve polymer of polyimide film formation coating fluid of the present invention and difunctional compound, can exemplify such as DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl-2-pyrrolidone, NVP, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, pregnancy sulfoxide, gamma-butyrolactone, 1,3-dimethyl-imidazolinone, ethyl pentyl group ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, pimelinketone, ethylene carbonate, propylene carbonate, the organic solvents such as diglyme and 4-hydroxy-4-methyl-2-pentanone, described polymkeric substance is at least one of the polyimide being selected from above-mentioned polyimide precursor and being obtained by this polyimide precursor imidization, described polyimide precursor is carried out polyreaction by least one tetracarboxylic acid composition and diamine component making to be selected from tetracarboxylic acid and derivative thereof and is obtained, and described difunctional compound is the difunctional compound represented with above formula [A] introduced Michaelis acid structure respectively and obtain on two amino of diamine compound.These solvents can be used alone, also can be used in combination.

Uniform polyimide film is formed, content preferably 70 ~ 97 quality % of the organic solvent in polyimide film formation coating fluid of the present invention from the viewpoint of by coating.This content can according to the thickness of the polyimide films such as Object LC alignment films appropriate change.

In addition, the polyimide precursor in polyimide film formation coating fluid of the present invention and content preferably 3 ~ 30 quality % of polyimide.This content also can according to the thickness of the polyimide films such as Object LC alignment films appropriate change.

The polyimide film formation of the present invention content of the difunctional compound represented with above formula [A] in coating fluid total amount 100 mass parts preferably 1 ~ 200 mass parts relative to polyimide precursor and polyimide, in order to carry out crosslinking reaction to embody desired film solidified nature and the orientation of liquid crystal can not be made to decline, more preferably 1 ~ 100 mass parts, particularly preferably 1 ~ 50 mass parts.

In polyimide film formation coating fluid of the present invention, in the scope not damaging effect of the present invention, can containing the homogeneity of thickness of polyimide film when being improved coating polyimide film formation coating fluid of the present invention and the organic solvent (also referred to as Weak solvent) of surface smoothness or compound.The compound etc. of the adaptation improving polyimide film and substrate can also be used.

As the concrete example improving the homogeneity of thickness and the Weak solvent of surface smoothness, such as Virahol can be exemplified, methoxymethyl amylalcohol, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monobutyl ether, ethyl carbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, Diethylene Glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, tetrahydrotoluene, propyl ether, hexyl ether, normal hexane, Skellysolve A, octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycolmethyletheracetate list ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, 3-methoxy 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-oxyethyl group-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 ester, propylene glycol-1-single ether-2-acetic ester, dipropylene glycol, 2-(2-oxyethyl group propoxy-) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, the organic solvent etc. with low surface tension of n-butyl lactate or isoamyl lactate etc.These Weak solvents can one or more be used in combination.When using Weak solvent as above, be better 1 ~ 50 quality % of the organic solvent total amount comprised in polyimide film formation coating fluid, be more preferably 5 ~ 30 quality %.

As the raising homogeneity of thickness and the compound of surface smoothness, fluorine class tensio-active agent can be exemplified, siloxane type surfactants, nonionic class tensio-active agent etc., specifically can exemplify such as エ Off トップ EF301, EF303, EF352 (illuminating product Co., Ltd. (トーケ system プロダクツ society) system), メガ Off ァッ Network F171, F173, R-30 (large Japanese ink Co., Ltd. (large Japanese イ Application キ) system), 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 usage ratio of these tensio-active agents, relative to total amount 100 mass parts of the component of polymer comprised in polyimide film formation coating fluid, is better 0.01 ~ 2 mass parts, is more preferably 0.01 ~ 1 mass parts.

As the concrete example of compound of adaptation improving polyimide film and substrate, 3-TSL 8330 can be exemplified, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl Trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae 4-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae 4-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (the oxyethylene group)-3-TSL 8330 of N-, two (the oxyethylene group)-APTES of N-, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2-dibromoneopentyl glycol diglycidylether, 1,3,5,6-four glycidyl group-2,4-hexylene glycol, N, N, N ', N ' ,-four glycidyl group-m-xylene diamine, two (N, the N-diglycidyl amino methyl) hexanaphthene of 1-or N, N, N ', N ' ,-four glycidyl group-4, the compound containing functional silanes such as 4 '-diaminodiphenyl-methane or the compound containing epoxy group(ing).

During the compound using these and substrate closely sealed, relative to component of polymer total amount 100 mass parts contained in polyimide film formation coating fluid of the present invention, be better 0.1 ~ 30 mass parts, be more preferably 1 ~ 20 mass parts.If less than 0.1 mass parts, then cannot expect the effect that adaptation improves, if more than 30 mass parts, then the orientation of liquid crystal is deteriorated sometimes.

In addition, as long as in the scope not damaging effect of the present invention, then dielectric medium and the conducting material of the electrical characteristic such as specific inductivity and electroconductibility for changing polyimide film can be added in polyimide film formation coating fluid of the present invention.

In addition, in polyimide film formation coating fluid of the present invention, only otherwise damage effect of the present invention, then can mix the cross-linked compound with epoxy group(ing), isocyanate group or oxetanyl, the cross-linked compound that there is the substituent cross-linked compound of at least one being selected from hydroxyl or alkoxyl group, there is polymerizability unsaturated link(age) can also be mixed.

This polyimide film formation coating fluid of the present invention can be used as the liquid crystal aligning agent forming liquid crystal orientation film.Liquid crystal orientation film refers to for making liquid crystal along the film of the direction orientation of regulation.

By being burnt till in substrate by polyimide film formation coating solution of the present invention, polyimide film can be formed.In addition, when using polyimide film formation coating fluid of the present invention as liquid crystal aligning agent, can be coated on substrate, after burning till, carry out the orientation process such as friction treatment or rayed, or do not carry out orientation process in vertical orientated purposes etc., thus form liquid crystal orientation film.

As substrate, as long as can be coated with polyimide film formation coating fluid, being not particularly limited, is better the substrate that the transparency is high when forming liquid crystal orientation film.As concrete example, glass substrate or the plastic base etc. such as vinylformic acid substrate and polycarbonate substrate can be exemplified.In addition, from the viewpoint of work simplification, the substrate of the ITO electrode etc. be formed for liquid crystal drive is preferably used.In addition, in reflection type liquid crystal display element, can use the opaque materials such as silicon wafer, but be only limitted to the substrate of side, electrode now can use the light reflecting materials such as aluminium.In addition, in the high functional element of element of TFT type and so on, the substrate of the element being formed with transistor and so between the electrode of liquid crystal drive and substrate can be used in.

The coating process of polyimide film formation coating fluid on substrate is not particularly limited, and the method be coated with is carried out in industrial usual employing by silk screen printing, offset printing, flexographic printing, ink-jet etc.As other coating process, there are dip coating, rolling method, slot coated, spin-coating method etc., these methods can be used according to object.

By polyimide film formation coating solution on substrate, after making solvent content or whole drying as required, burn till.During this burns till, as long as the temperature that the Michaelis acid structure being heated to the difunctional compound represented with above formula [A] can become ketenes etc. and react with the carboxyl etc. that polyimide precursor or polyimide have.The heating installations such as hot-plate, recirculation furnace, infrared heating heating furnace are such as utilized to heat at 180 ~ 250 DEG C, solvent is evaporated, and Michaelis acid structure and polyimide precursor or polyimide are reacted, thus the difunctional compound represented with above formula [A] can be introduced in polyimide precursor or polyimide, form polyimide film of the present invention.The polyimide film obtained as mentioned above because have polyimide by the difunctional compound represented with above formula [A] crosslinked structure, so become dura mater, resistance to excellent in machinability.

During for liquid crystal orientation film, if the thickness burning till the polyimide film of rear formation is blocked up, then unfavorable in the power consumption of liquid crystal display device, if cross thin, then the reliability of liquid crystal display device reduces sometimes, therefore preferably 5 ~ 300nm, more preferably 10 ~ 200nm.When making liquid crystal horizontal alignment or tilted alignment, by friction or polarized UV rays irradiation etc., the film after burning till is processed.

Liquid crystal display device of the present invention is after obtaining the substrate of band liquid crystal orientation film by aforesaid method, the liquid crystal display device formed by known method manufacture liquid crystal cells.If exemplify an example, it is then the liquid crystal display device possessing liquid crystal cells, this liquid crystal cells comprises: the two pieces of substrates configured in opposite directions, be arranged at liquid crystal layer between substrate, be arranged at above-mentioned liquid crystal orientation film between substrate and liquid crystal layer, and the liquid crystal aligning agent that this liquid crystal orientation film is formed with coating fluid is formed by polyimide film of the present invention is formed.As this liquid crystal display device of the present invention, the various liquid crystal display device such as twisted-nematic (TN:TwistedNematic) mode, vertical orientated (VA:VerticalAlignment) mode, horizontal alignment (IPS:In-PlaneSwitching) mode can be exemplified.

As the substrate that liquid crystal display device of the present invention is used, as long as the substrate that the transparency is high, be not particularly limited, on substrate, be normally formed with the substrate of the transparency electrode for driving liquid crystal.As concrete example, the substrate identical with the substrate recorded in above-mentioned polyimide film can be exemplified.

In addition, liquid crystal orientation film carries out burning till and being formed after being coated with liquid crystal aligning agent of the present invention on the substrate, and details are described above.

The liquid crystal material forming the liquid crystal layer of liquid crystal display device of the present invention is not particularly limited, and can use existing liquid crystal material, MLC-2003, MLC-6608, MLC-6609 etc. that such as Merck & Co., Inc. (メルク society) makes.

If exemplify an example of liquid crystal cells manufacture method, following method can be exemplified: a pair substrate preparing to be formed with liquid crystal orientation film, the liquid crystal orientation film of a substrate scatters pearl thing at equal intervals, make liquid crystal aligning face become interior rear flank another baseplate-laminating, decompression injects liquid crystal and the method for sealing; Or drip liquid crystal on the liquid crystal aligning face being scattered with spacer after, baseplate-laminating is carried out the method etc. sealed.The thickness of spacer now preferably 1 ~ 30 μm, more preferably 2 ~ 10 μm.

The liquid crystal display device made as mentioned above is the liquid crystal display device using the liquid crystal aligning agent containing at least one party that can introduce in the difunctional compound represented with above formula [A] of desired characteristic and polyimide precursor and polyimide and make, and therefore various characteristic can be improved.

Embodiment

Below, the present invention will be described in more detail to exemplify embodiment and comparative example, but explanation of the present invention is not limited to these embodiments.

[synthesis of the difunctional compound represented with above formula [A]]

< synthesis example 1>

The synthesis of the compound 5,5'-(Isosorbide-5-Nitrae-phenylene two (azane two base)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) represented with following formula [4]

[changing 22]

Add in 300mL four-hole boiling flask Michaelis acid [1] (14.7g, l02mmol) and trimethyl orthoformate [2] (147g), carry out 1 hour reflux.Then add Ursol D [3] (5.09,46mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 15.8g compound [4] (yield 82%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.29(2H,d),8.56(2H,d),7.64(4H,s),1.68(12H,s).

< synthesis example 2>

The synthesis of the compound 5,5'-(1,3-phenylene two (azane two base)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) represented with following formula [6]

[changing 23]

Add in 300mL four-hole boiling flask Michaelis acid [1] (14.R, 102mmol) and trimethyl orthoformate [2] (1479), carry out 1 hour reflux.Then add mphenylenediamine [5] (5.09,46mmo1), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 14.1g compound [6] (yield 72%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.28(2H,s),8.74(2H,s),7.98(1H,s),7.44(3H,s),1.68(12H,s).

< synthesis example 3>

The synthesis of the compound 5,5'-(pyridine-2,6-bis-base two (azane two base)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) represented with following formula [8]

[changing 24]

In 300mL four-hole boiling flask, add Michaelis acid [1] (16.09,11lmmol) and trimethyl orthoformate [2] (1609), carry out 1 hour reflux.Then add DAP [7] (5.5g, 50mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 16.7g compound [8] (yield 80%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.42(2H,d),9.15(2H,d),7.96(1H,t),7.52(2H,d),1.67(12H,s).

< synthesis example 4>

Compound 5,5'-(4, the 4'-methylene-bis (4 represented with following formula [10], 1-phenylene) two (azane two base)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthesis

[changing 25]

Add in 300mL four-hole boiling flask Michaelis acid [1] (14.7g, 102mmol) and trimethyl orthoformate [2] (147g), carry out 1 hour reflux.Then add 4,4 '-diaminodiphenyl-methane [9] (5.0g, 46mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 14.1g compound [10] (yield 72%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.23(2H,d),8.54(2H,d),7.50-7.48(4H,m),7.31-7.29(4H,m),3.96(2H,m),1.66(12H,s).

< synthesis example 5>

Compound 5,5'-(4, the 4'-oxygen base two (4 represented with following formula [12], 1-phenylene) two (azane two base)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthesis

[changing 26]

Add in 200mL four-hole boiling flask Michaelis acid [1] (7.92g, 54.9mmol) and trimethyl orthoformate [2] (78g), carry out 1 hour reflux.Then add 4,4 '-diamino-diphenyl ether [11] (5.0g, 25.0mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 11.7g compound [12] (yield 92%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.30(2H,d),8.51(2H,d),7.62(4H,d),7.08(4H,d),1.67(12H,s).

< synthesis example 6>

Compound 5,5'-(4,4'-azane two base two (4 represented with following formula [14], 1-phenylene) two (azane two base)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthesis

[changing 27]

Add in 200mL four-hole boiling flask Michaelis acid [1] (7.96g, 55.2mmol) and trimethyl orthoformate [2] (79g), carry out 1 hour reflux.Then add 4,4 '-diamino-diphenyl amine [13] (5.0g, 25.1mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 10.1g compound [14] (yield 79%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.29(2H,d),8.51(2H,d),7.62(4H,d),7.08(4H,d),4.97(1H,s),1.67(12H,s).

< synthesis example 7>

With the compound 5 that following formula [16] represents, 5'-(4,4'-(methyl azane two base) two (4,1-phenylene) two (azane two base)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthesis

[changing 28]

Add in 500mL four-hole boiling flask Michaelis acid [1] (14.9g, 103mmol) and trimethyl orthoformate [2] (100g), carry out 1 hour reflux.Then add 4,4 '-diamino-diphenyl methylamine [15] (10.0g, 46.9mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 21.7g compound [16] (yield 86%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.21(2H,d),8.44(2H,d),7.45-7.42(4H,m),7.03-7.01(4H,m),3.24(3H,s),1.62(12H,s).

< synthesis example 8>

With the compound 5 that following formula [18] represents, 5'-(4,4'-(pentane-1,5-bis-base two (oxygen base)) two (4,1-phenylene) two (azane two base)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthesis

[changing 29]

Add in 300mL four-hole boiling flask Michaelis acid [1] (16.6g, 115mmol) and trimethyl orthoformate [2] (111g), carry out 1 hour reflux.Then add compound [17] (15.0g, 52.4mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 20.8g compound [18] (yield 67%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.23(2H,s),8.45(2H,s),7.51-7.47(4H,m),7.00-6.94(4H,m),4.01(4H,t),1.82-1.72(4H,m),1.67(12H,s),1.62-1.54(2H,m).

< synthesis example 9>

The synthesis of two (4-((2,2-dimethyl-4,6-dioxo-1, the 3-diox-5-subunit) methylamino) styroyl) urea of compound 1,3-represented with following formula [20]

[changing 30]

Add in 200mL four-hole boiling flask Michaelis acid [1] (28.6g, 147mmol) and trimethyl orthoformate [2] (200g), carry out 1 hour reflux.Then add compound [19] (20.0g, 67.0mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 40.3g compound [20] (yield 99%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.17(2H,d),8.48(2H,d),7.40(4H,d),7.21(4H,d),5.89(2H,t),3.18-3.14(4H,m),2.62(4H,t),1.62(12H,s).

< synthesis example 10>

The compound 5,5'-(6,7,9 represented with following formula [22], 10,17,18,20,21-octahydro dibenzo [b, k] [1,4,7,10,13,16] six oxa-ring octadecyne-2,13-bis-bases) two (azane two base) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthesis

[changing 31]

Add in 200mL four-hole boiling flask Michaelis acid [1] (7.38g, 51.2mmol) and trimethyl orthoformate [2] (100g), carry out 1 hour reflux.Then add compound [21] (10.0g, 25.6mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 17.9g compound [22] (yield 96%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.16(2H,d),8.50(2H,d),7.19(2H,d),7.01-6.98(2H,m),6.93(2H,m),4.09-4.08(4H,m),4.04-4.02(4H,m),3.79(8H,m),1.61(12H,s).

< synthesis example 11>

Compound 5-((3-((2,2-dimethyl-4, the 6-dioxo-1 represented with following formula [24], 3-diox-5-subunit) methylamino) benzylamino) methylene radical)-2, the synthesis of 2-dimethyl-1,3-diox-4,6-diketone

[changing 32]

Add in 300mL four-hole boiling flask Michaelis acid [1] (23.6g, 164mmol) and trimethyl orthoformate [2] (100g), carry out 1 hour reflux.Then add 3-amino-benzylamine [23] (10.0g, 81.9mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 36.2g compound [24] (yield 100%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.21(1H,s),10.04-9.97(1H,m),8.55(1H,s),8.30(1H,d),7.57(1H,s),7.48-7.38(2H,m),7.23(1H,d),4.65(2H,d),1.63(6H,s),1.55(6H,s).

< synthesis example 12>

Compound 5,5'-(4, the 4'-(propane-1 represented with following formula [26], 3-bis-base) two (piperidines-4,1-bis-base)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthesis

[changing 33]

Add in 200mL four-hole boiling flask Michaelis acid [1] (11.7g, 81.0mmol) and trimethyl orthoformate [2] (128g), carry out 1 hour reflux.Then add 1,3-bis--4-piperidyl propane [25] (8.52g, 40.5mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 20.2g compound [26] (yield 99%).

¹H-NMR(400MHz,DMSO-d6,δppm):8.09(2H,s),4.06-3.97(4H,m),3.56-3.49(2H,m),3.28-3.25(2H,m),1.84-1.81(4H,m),1.61-1.56(12H,m),1.32-1.23(12H,m).

< synthesis example 13>

The synthesis of the compound 5,5'-(propane-1,3-bis-base two (azane two base)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) represented with following formula [28]

[changing 34]

Add in 500mL four-hole boiling flask Michaelis acid [1] (42.8g, 297mmol) and trimethyl orthoformate [2] (150g), carry out 1 hour reflux.Then add 1,3-diaminopropanes [27] (10.0g, 135mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 24.8g compound [28] (yield 48%).

¹H-NMR(400MHz,CDCl3,δppm):9.57-9.54(2H,m),8.16(2H,d),3.59(4H,q),2.11(2H,quin),1.71(12H,s).

< synthesis example 14>

With the compound 5 that following formula [30] represents, 5'-(hexanaphthene-1,3-bis-base two (methylene radical)) two (2, the 2-dimethyl-1 of two (azane two base) two (methane-1-base-1-subunit), 3-diox-4,6-diketone) synthesis

[changing 35]

Add in 500mL four-hole boiling flask Michaelis acid [1] (44.6g, 309mmol) and trimethyl orthoformate [2] (200g), carry out 1 hour reflux.Then add 1,3-bis aminomethyl hexanaphthene (cis/trans mixture) [29] (20.0g, 141mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 58.3g compound [30] (cis/trans mixture) (yield 92%).

¹H-NMR(400MHz,DMSO-d6,δppm):9.63-9.60(2H,m),8.11-7.97(2H,m),3.51-3.12(4H,m),1.87-0.54(22H,m).

< synthesis example 15>

Two ((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methylamino) the benzoic synthesis of compound 3,5-represented with following formula [32]

[changing 36]

Add in 200mL four-hole boiling flask Michaelis acid [1] (10.4g, 72.3mmol) and trimethyl orthoformate [2] (105g), carry out 1 hour reflux.Then add 3,5-diaminobenzoic acid [31] (5.0g, 32.9mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 9.0g compound [32] (yield 59%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.34(2H,d),8.74(2H,d),7.92(2H,d),1.69(12H,s).

< synthesis example 16>

The synthesis of two ((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methylamino)-N-(pyridin-3-yl methyl) benzamide of compound 3,5-represented with following formula [34]

[changing 37]

Add in 200mL four-hole boiling flask Michaelis acid [1] (6.5g, 45.4mmol) and trimethyl orthoformate [2] (66g), carry out 1 hour reflux.Then add compound [33] (5.0g, 20.6mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 11.3g compound [34] (yield 98%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.35(2H,d),9.27(1H,t),8.78(2H,d),8.59(1H,d),8.49-8.47(1H,m),8.16-8.15(1H,m),7.84(2H,d),7.77-7.74(1H,m),7.40-7.36(1H,m),4.55(2H,d),1.69(12H,s).

< synthesis example 17>

The synthesis of two ((2,2-dimethyl-4,6-dioxo-1, the 3-diox-5-subunit) methylamino) benzamide of the compound N represented with following formula [36]-(3-(1H-imidazoles-1-base) propyl group)-3,5-

[changing 38]

Add in 200mL four-hole boiling flask Michaelis acid [1] (10.1g, 52.1mmol) and trimethyl orthoformate [2] (50g), carry out 1 hour reflux.Then add compound [35] (5.0g, 23.7mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 13.4g compound [36] (yield 100%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.27(2H,s),8.71-8.65(3H,m),8.01(1H,t),7.99(1H,t),7.75(2H,d),7.32(1H,t),7.05(1H,t),4.07-4.03(2H,m),3.25-3.18(2H,m),1.97(2H,t),1.64(12H,s).

< synthesis example 18>

The synthesis of two ((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methylamino) the benzyl ester of compound furans-2-carboxylic acid-3,5-represented with following formula [38]

[changing 39]

Add in 200mL four-hole boiling flask Michaelis acid [1] (13.7g, 94.7mmol) and trimethyl orthoformate [2] (100g), carry out 1 hour reflux.Then add compound [37] (10.0g, 43.1mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 21.1g compound [38] (yield 90%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.22(2H,d),8.67(2H,d),7.94-7.93(1H,m),7.87-7.86(1H,m),7.46-7.45(2H,m),7.38(1H,dd),6.68-6.66(1H,m),5.28(2H,s),1.63(12H,s).

< synthesis example 19>

With the compound 5 that following formula [40] represents, two (2, the 2-dimethyl-1 of 5'-(4-(dodecyloxy)-1,3-phenylene) two (azane two base) two (methane-1-base-1-subunit), 3-diox-4,6-diketone) synthesis

[changing 40]

Add in 300mL four-hole boiling flask Michaelis acid [1] (10.8g, 75.2mmol) and trimethyl orthoformate [2] (100g), carry out 1 hour reflux.Then add compound [39] (10.0g, 34.2mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 29.7g compound [40] (yield 99%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.57(1H,d),11.20(1H,d),8.90(1H,d),8.64(1H,d),8.09(1H,d),7.31(1H,dd),7.13(1H,d),4.06(2H,t),1.74-1.68(2H,m),1.63(12H,s),1.46-1.40(2H,m),1.25-1.16(16H,m),0.79(3H,t).

< synthesis example 20>

With the compound 5 that following formula [42] represents, 5'-(4-(octadecane oxygen base)-1,3-phenylene) two (azane two base) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthesis

[changing 41]

Add in 100mL four-hole boiling flask Michaelis acid [1] (4.2g, 29.2mmol) and trimethyl orthoformate [2] (42g), carry out 1 hour reflux.Then add compound [41] (5.0g, 13.3mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 6.4g compound [42] (yield 71%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.63(1H,d),11.26(1H,d),8.99(1H,d),8.72(1H,d),8.19(1H,d),7.40(1H,dd),7.20(1H,d),4.13(2H,t),1.80-1.74(2H,m),1.68(12H,s),1.49-1.45(2H,m),1.25-1.22(28H,m),0.85(3H,t).

< synthesis example 21>

With the compound 5 that following formula [44] represents, 5'-(4-(4-(trans-4-heptyl cyclohexyl) phenoxy group)-1,3-phenylene) two (azane two base) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthesis

[changing 42]

Add in 100mL four-hole boiling flask Michaelis acid [1] (4.2g, 28.9mmol) and trimethyl orthoformate [2] (41g), carry out 1 hour reflux.Then add compound [43] (5.0g, 13.1mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 9.0g compound [44] (yield 98%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.64(1H,d),11.30(1H,d),9.03(1H,d),8.76(1H,d),8.31(1H,d),7.40(1H,dd),7.28(2H,d),7.03(2H,d),6.97(1H,d),1.81(2H,d),1.69(10H,d),1.44-1.34(1H,m),1.26-1.78(10H,m),1.07-1.01(1H,m),0.86(3H,t).

< synthesis example 22>

With the compound 5 that following formula [46] represents, 5'-(4-(trans-4-(two (the hexanaphthene)-4-base of trans-4'-amyl group) phenoxy group)-1,3-phenylene) two (azane two base) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthesis

[changing 43]

Add in 300mL four-hole boiling flask Michaelis acid [1] (9.0g, 62.1mmol) and trimethyl orthoformate [2] (120g), carry out 1 hour reflux.Then add compound [45] (12.3g, 28.2mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 20.68g compound [46] (yield 98%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.64(1H,d),11.30(1H,d),9.03(1H,d),8.76(1H,d),8.31(1H,d),7.39(1H,dd),7.27(1H,d),7.02(2H,d),6.97(2H,d),1.88-1.03(43H,m),0.86(3H,t).

< synthesis example 23>

With the compound 5 that following formula [48] represents, 5'-(5-((trans-4-(two (the hexanaphthene)-4-base of trans-4'-amyl group) phenoxy group) methyl)-1,3-phenylene) two (azane two base) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthesis

[changing 44]

Add in 500mL four-hole boiling flask Michaelis acid [1] (19.0g, 98.6mmol) and trimethyl orthoformate [2] (200g), carry out 1 hour reflux.Then add compound [47] (20.0g, 44.6mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 33.4g compound [48] (yield 99%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.29(2H,d),8.74(2H,d),7.94(1H,s),7.53(2H,d),7.12(2H,d),6.92(2H,d),5.09(2H,s),1.81-1.68(20H,m),1.36-0.84(23H,m).

< synthesis example 24>

The synthesis of two (trans-the hexanaphthene)-4-base ester of two ((2,2-dimethyl-4,6-dioxo-1, the 3-diox-5-subunit) methylamino) phenylformic acid-4'-amyl group of compound 3,5-represented with following formula [50]

[changing 45]

Add in 500mL four-hole boiling flask Michaelis acid [1] (13.3g, 92.0mmol) and trimethyl orthoformate [2] (150g), carry out 1 hour reflux.Then add compound [49] (15.0g, 41.8mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 28.8g compound [50] (yield 99%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.28(2H,s),8.67(2H,s),8.17(1H,t),7.86(2H,d),4.79-4.73(1H,m),2.02(2H,d),1.74-1.64(18H,m),1.44-1.32(2H,m),1.29-0.76(20H,m).

< synthesis example 25>

With the compound N-(2 that following formula [52] represents, 4-two ((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methylamino) phenyl) synthesis of-4-(trans-4-pentylcyclohexyl) benzamide

[changing 46]

Add in 300mL four-hole boiling flask Michaelis acid [1] (8.2g, 56.7mmol) and trimethyl orthoformate [2] (80g), carry out 1 hour reflux.Then add compound [51] (10.0g, 25.8mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 16.0g compound [52] (yield 92%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.36-11.27(2H,m),10.38(1H,s),8.80-8.74(2H,m),8.09(1H,s),7.87(2H,d),7.44(1H,dd),7.34(2H,d),2.51-2.46(3H,m),1.77(2H,d),1.66(6H,s),1.59(6H,s),1.50-1.37(3H,m),1.29-1.14(8H,m),0.99(2H,q),0.82(3H,t).

< synthesis example 26>

With the compound N-(2 that following formula [54] represents, 4-two ((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methylamino) phenyl) synthesis of-4-(trans-4-heptyl cyclohexyl) benzamide

[changing 47]

Add in 300mL four-hole boiling flask Michaelis acid [1] (11.7g, 81.0mmol) and trimethyl orthoformate [2] (150g), carry out 1 hour reflux.Then add compound [53] (15.0g, 36.8mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 26.1g compound [54] (yield 99%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.36-11.27(2H,m),10.38(1H,s),8.78(2H,t),8.10(1H,s),7.88(2H,d),7.44(1H,dd),7.35(3H,d),2.52(2H,t),1.78(2H,d),1.65(6H,s),1.60(6H,s),1.50-1.37(2H,m),1.29-1.12(14H,m),0.99(2H,q),0.82(3H,t).

< synthesis example 27>

The compound 5,5'-(4-((3S, the 8S that represent with following formula [56], 9S, 10R, 13R, 14S, 17R)-10,13-dimethyl-17-(own-2-base of (R)-5-methyl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-ten tetrahydrochysene-1H-ring penta [a] phenanthrene-3-base oxygen base)-1,3-phenylene) two (azane two base) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthesis

[changing 48]

Add in 100mL four-hole boiling flask Michaelis acid [1] (4.1g, 29mmol) and trimethyl orthoformate [2] (50g), carry out 1 hour reflux.Then add compound [55] (10.0g, 13mmol), then carry out 2 hours reflux.After reaction terminates, reaction soln is cooled to room temperature, filters the solid of separating out, with hexanes wash, then make solid drying, obtain 9.9g compound [56] (yield 99%).

< synthesis example 28>

Compound 3-(4-(oxygen base in the last of the ten Heavenly stems) phenyl) vinylformic acid (E)-2 represented with following formula [58], 4-two ((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methylamino) synthesis of styroyl ester

[changing 49]

Add in 200mL four-hole boiling flask Michaelis acid [1] (7.3g, 37mmol) and trimethyl orthoformate [2] (75g), carry out 1 hour reflux.Then add compound [57] (7.46g, 17mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 12.5g compound [58] (yield 99%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.57(1H,d),11.29(1H,s),8.82(1H,dd),8.23(1H,dd),8.04(1H,s),7.57-7.46(5H,m),6.92(2H,d),6.35(1H,d),4.34(2H,t),3.99(2H,t),1.74-1.65(15H,m),1.43-1.21(15H,m),0.85(3H,t).

< synthesis example 29>

Compound 3-(4-(oxygen base in the last of the ten Heavenly stems) phenyl) vinylformic acid (E)-3 represented with following formula [60], 5-two ((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methylamino) synthesis of benzyl ester

[changing 50]

Add in 200mL four-hole boiling flask Michaelis acid [1] (6.3g, 33mmol) and trimethyl orthoformate [2] (63g), carry out 1 hour reflux.Then add compound [59] (6.3g, 15mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 10.7g compound [60] (yield 99%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.25(1H,d),8.71(1H,d),7.93(1H,s),7.67-7.62(3H,m),7.48(2H,d),6.91(2H,d),6.52(1H,d),5.19(2H,s),3.96(2H,t),3.62-3.60(2H,m),1.68-1.63(15H,m),1.38-1.20(15H,m),0.81(3H,t).

< synthesis example 30>

Represent with following formula [62] 5,5'-(((6,7,9,10,17,18,20,21-octahydro dibenzo [b, k] [1,4,7,10,13,16] six oxa-ring octadecyne-2,14-bis-bases) two (azane two base)) two (methyl subunit)) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthesis

[changing 51]

Add in 200mL four-hole boiling flask Michaelis acid [1] (4.87g, 33.8mmol) and trimethyl orthoformate [2] (60g), carry out 1 hour reflux.Then add compound [61] (6.00g, 15.4mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 10.4g compound [62] (yield 97%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.21(2H,d),8.54(2H,d),7.26(2H,d),7.05(2H,dd),6.96(2H,d),4.15-4.06(8H,m),3.88-3.80(6H,m),3.17(2H,d),1.67(12H,s).

< synthesis example 31>

5,5'-((Isosorbide-5-Nitrae, 10 represented with following formula [64], 13-tetra-oxa--7,16-diazacyclo octadecane-7,16-bis-base) two (methyl subunit)) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthesis

[changing 52]

Add in 500mL four-hole boiling flask Michaelis acid [1] (24.17g, 167.7mmol) and trimethyl orthoformate [2] (200g), carry out 1 hour reflux.Then add compound [63] (20.00g, 76.2mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 43.2g compound [64] (yield 100%).

< synthesis example 32>

Represent with following formula [66] 5,5'-(((((two (the ethane-2 of oxygen base, 1-bis-base)) two (oxygen base)) two (4,1-phenylene)) two (azane two base)) two (methyl subunit)) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthesis

[changing 53]

Add in 500mL four-hole boiling flask Michaelis acid [1] (22.00g, 153mmol) and trimethyl orthoformate [2] (200g), carry out 1 hour reflux.Then add compound [65] (20.00g, 69.4mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 40.2g compound [66] (yield 97%).

¹H-NMR(400MHz,DMSO-d6,δppm):11.23(2H,d),8.44(2H,d),7.50-7.48(2H,m),7.01-6.99(4H,m),4.42-4.12(4H,m),3.89-3.78(4H,m),1.67(12H,s).

< synthesis example 33>

The synthesis of represent with following formula [68] 3,5-two (((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methyl) is amino) phenylformic acid-2-(methacryloxy) ethyl ester

[changing 54]

Add in 500mL four-hole boiling flask Michaelis acid [1] (24.18g, 168mmol) and trimethyl orthoformate [2] (300g), carry out 1 hour reflux.Then add compound [67] (20.00g, 76.3mmol), then carry out 2 hours reflux.After reaction terminates, after interpolation hexane filters, carry out drying, obtain 43.7g compound [68] (yield 100%).

¹H-NMR(400MHz,CDCl3,δppm):11.36(2H,d),8.72(2H,d),7.80(2H,d),7.37(1H,t),6.17(1H,t),5.64-5.62(1H,m),4.67-4.65(2H,m),4.55-4.52(2H,m),3.79(1H,s),3.47(1H,s),3.34(2H,s),1.97-1.96(3H,m),1.78-1.76(13H,m).

< synthesis example 34>

3-(4'-butoxy-[1 represented with following formula [70], 1'-phenylbenzene]-4-base) vinylformic acid (E)-2,4-two (((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methyl) amino) synthesis of styroyl ester

[changing 55]

Add in 100mL four-hole boiling flask Michaelis acid [1] (4.00g, 20.4mmol) and trimethyl orthoformate [2] (40g), carry out 1 hour reflux.Then add compound [69] (4.00g, 9.3mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 6.8g compound [70] (yield 99%).

¹H-NMR(400MHz,CDCl3,δppm):11.59(1H,d),11.29(1H,d),8.84(1H,d),8.78(1H,d),8.23(1H,s),8.04(1H,s),7.70-7.64(7H,m),7.62(1H,d),7.48(2H,s),7.03(2H,d),6.53(1H,d),4.41(2H,t),4.01(2H,t),3.66-3.63(6H,m),1.68-1.57(10H,m),1.56(1H,s),1.44-1.39(1H,m),0.94(3H,t).

< synthesis example 35>

The 3-(4-cyclohexyl phenyl) vinylformic acid (E)-2 represented with following formula [72], 4-two (((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methyl) amino) synthesis of styroyl ester

[changing 56]

Add in 200mL four-hole boiling flask Michaelis acid [1] (4.35g, 30mmol) and trimethyl orthoformate [2] (50g), carry out 1 hour reflux.Then add compound [71] (5.00g, 14mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 9.63g compound [72] (yield 99%).

¹H-NMR(400MHz,CDCl3,δppm):11.63(1H,d),11.30(1H,d),8.64-8.63(2H,m),7.60(1H,d),7.42-7.39(3H,m),7.29-7.27(2H,m),7.21-7.15(3H,m),6.37(1H,d),4.49-4.46(2H,m),3.33-3.11(2H,m),2.59-2.42(1H,m),1.86-1.45(2H,m),1.76-1.70(14H,m),1.42-1.20(6H,m).

< synthesis example 36>

3-(the 4-([trans-1 represented with following formula [74], 1'-two (hexanaphthene)]-4-base) phenyl) vinylformic acid (E)-2,4-two (((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methyl) amino) synthesis of styroyl ester

[changing 57]

Add in 200mL four-hole boiling flask Michaelis acid [1] (2.84g, 20mmol) and trimethyl orthoformate [2] (40g), carry out 1 hour reflux.Then add compound [73] (4.00g, 9.0mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 6.6g compound [74] (yield 99%).

¹H-NMR(400MHz,CDCl3,δppm):11.63(1H,d),11.30(1H,d),8.67-8.60(2H,m),7.60(1H,d),7.41-7.39(3H,m),7.26-7.14(4H,m),6.36(1H,d),4.48(2H,t),3.12(2H,t),2.52-2.45(1H,m),1.91-1.70(24H,m),1.52-1.01(8H,m).

< synthesis example 37>

3-(4-(the trans-4-pentylcyclohexyl) phenyl) vinylformic acid (E)-2 represented with following formula [76], 4-two (((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methyl) amino) synthesis of styroyl ester

[changing 58]

Add in 300mL four-hole boiling flask Michaelis acid [1] (13.55g, 69.8mmol) and trimethyl orthoformate [2] (140g), carry out 1 hour reflux.Then add compound [75] (13.79g, 31.7mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 22.4g compound [76] (yield 95%).

¹H-NMR(400MHz,CDCl3,δppm):11.63(1H,d),11.27(1H,d),8.68-8.57(2H,m),7.41-7.39(3H,m),7.26-7.14(4H,m),6.36(1H,d),4.48(2H,t),3.80-3.76(3H,m),3.48(2H,d),3.34(1H,s),3.12(2H,d),2.47(2H,t),1.86(6H,d),1.77-1.68(10H,m),1.47-1.20(10H,m),1.06-0.90(5H,m).

< synthesis example 38>

3-(4-(the trans-4-heptyl cyclohexyl) phenyl) vinylformic acid (E)-2 represented with following formula [78], 4-two (((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methyl) amino) synthesis of styroyl ester

[changing 59]

Add in 100mL four-hole boiling flask Michaelis acid [1] (3.43g, 23.8mmol) and trimethyl orthoformate [2] (50g), carry out 1 hour reflux.Then add compound [77] (5.00g, 10.8mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 8.3g compound [78] (yield 100%).

¹H-NMR(400MHz,CDCl3,δppm):11.64(1H,d),11.28(1H,d),8.70-8.63(2H,m),7.61(1H,d),7.45-7.40(3H,m),7.27-7.15(3H,m),6.37(1H,d),4.46(2H,t),3.60(2H,d),3.12(2H,t),2.34(1H,t),1.87(4H,d),1.85-1.75(15H,m),1.42-1.38(2H,m),1.33-1.26(10H,m),1.07-1.02(2H,m),0.89(3H,t).

< synthesis example 39>

3-(4-(the trans-4-pentylcyclohexyl) phenyl) vinylformic acid (E)-3 represented with following formula [80], 5-two (((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methyl) amino) synthesis of benzyl ester

[changing 60]

Add in 300mL four-hole boiling flask Michaelis acid [1] (11.31g, 78.5mmol) and trimethyl orthoformate [2] (150g), carry out 1 hour reflux.Then add compound [79] (15.00g, 35.7mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 25.3g compound [80] (yield 99%).

¹H-NMR(400MHz,CDCl3,δppm):11.30(2H,d),8.66(2H,d),7.74(1H,d),7.49(2H,d),7.26-7.19(4H,m),7.08(1H,d),6.49(1H,d),5.27(2H,s),2.49(1H,t),1.93-1.77(18H,m),1.65-0.87(14H,m).

< synthesis example 40>

3-(4-(the trans-4'-amyl group-[1 represented with following formula [82], 1'-two (hexanaphthene)]-4-base) phenoxy group) vinylformic acid (E)-3,5-two (((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methyl) amino) synthesis of benzyl ester

[changing 61]

Add in 200mL four-hole boiling flask Michaelis acid [1] (1.83g, 12.7mmol) and trimethyl orthoformate [2] (45g), carry out 1 hour reflux.Then add compound [81] (3.00g, 5.8mmol), then carry out 2 hours reflux.After reaction terminates, with vaporizer except desolventizing, carry out drying, obtain 4.8g compound [82] (yield 100%).

¹H-NMR(400MHz,CDCl3,δppm):11.27(2H,d),8.64(2H,d),7.85(1H,d),7.21(2H,d),7.14(2H,d),7.10-7.09(1H,m),7.00-6.98(2H,m),5.57(1H,d),5.19(2H,s),3.81(1H,s),3.47-3.46(1H,m),3.33(4H,s),1.91-1.72(20H,m),1.41-0.84(13H,m).

[synthesis of polyamic acid or polyimide and the preparation of solution thereof]

Abbreviation hereinafter used is as described below.

(tetracarboxylic dianhydride)

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

BODA: dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

[changing 62]

(diamines)

P-PDA: Ursol D

DDM:4,4 '-diaminodiphenyl-methane

PCH7AB:1,3-diamino-4-(4-(trans-4-n-heptyl cyclohexyl) phenoxy group) benzene

[changing 63]

(organic solvent)

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

BCS: ethylene glycol butyl ether

(mensuration of molecular weight)

In the present embodiment, the molecular weight of polymkeric substance (polyamic acid, polyimide) uses normal temperature gel permeation chromatography (GPC) device (GPC-101) of Showa electrician (Shodex) Co., Ltd., the post (KD-803 of Showa Denko K. K, KD-805), measure as follows.

Column temperature: 50 DEG C

Elutriant: DMF (as additive, lithiumbromide-hydrate (LiBrH ₂o) for 30mmol/L, phosphoric acid anhydrous crystal (o-phosphoric acid) be 30mmol/L, tetrahydrofuran (THF) (THF) is 10ml/L)

Flow velocity: 1.0ml/ minute

Calibration curve making standard test specimen: Dong Cao company (East ソー society) TSK standard polyethylene oxide processed (molecular weight about 900000,150000,100000,30000) and Polymer Laboratory company (Port リマーラボラトリー society) polyoxyethylene glycol processed (molecular weight about 12000,4000,1000).

(mensuration of imide rate)

In the present embodiment, the imide rate of polyimide measures as follows.

The polyimide powder of about 20mg is added NMR stopple coupon, adds the deuterated dimethylsulfoxide (DMSO-d of about 0.53ml ₆, 0.05%TMS melange), make it dissolve completely by ultrasonic wave.This solution is measured the proton N MR of 500MHz with NMR determinator.Imide rate is as described below tries to achieve: the proton coming from the structure do not changed before and after imidization is decided to be standard proton, utilize the accumulated value coming from the proton peak of the NH base of amido acid occurred near the accumulated value of this proton peak and 10.0ppm, tried to achieve by following formula.In following formula, x is the accumulated value of the proton peak of the NH base coming from amido acid, and y is the accumulated value at standard proton peak, and α is the number ratio relative to the standard proton of 1 NH matrix of amido acid time polyamic acid (imide rate is 0%).

Imide rate (%)=(1-α x/y) × 100

The synthesis of < polyamic acid (PAA-1) and the preparation > of solution thereof

DDM7.93g (40mmol), NMP (20g) is added and after making it dissolve in 100mL four-hole boiling flask, be cooled to about 10 DEG C, add NMP (67g) pulp solution of CBDA7.46g (38mmol), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-1) is the solution of 15 quality %.

The solution 88g being 15 quality % by the concentration of this polyamic acid (PAA-1) moves in 200mL Erlenmeyer flask, add NMP87.6g, BCS43.8g to dilute, polyamic acid (PAA-1) solution of to make polyamic acid (PAA-1) be 6 quality %, NMP to be 74 quality %, BCS be 20 quality %.The number-average molecular weight of this polyamic acid (PAA-1) is 12081, and weight-average molecular weight is 30449.

The synthesis of < polyamic acid (PAA-2) and the preparation > of solution thereof

P-PDA8.65g (80mmol), NMP (49g) is added and after making it dissolve in 200mL four-hole boiling flask, be cooled to about 10 DEG C, add NMP (80g) pulp solution of CBDA14.1g (72mmol), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-2) is the solution of 15 quality %.

The solution 125g being 15 quality % by the concentration of this polyamic acid (PAA-2) moves in 300mL Erlenmeyer flask, add NMP118.5g, BCS60.9g to dilute, polyamic acid (PAA-2) solution of to make polyamic acid (PAA-2) be 6 quality %, NMP to be 74 quality %, BCS be 20 quality %.The number-average molecular weight of this polyamic acid (PAA-2) is 7609, and weight-average molecular weight is 15837.

The synthesis of < polyamic acid (PAA-3) and the preparation > of solution thereof

P-PDA8.05g (74mmol), PCH7AB2.13g (5.6mmol), NMP (118g) after making it dissolve is added in 200mL four-hole boiling flask, be cooled to about 10 DEG C, add NMP (100g) pulp solution of CBDA14.1g (72mmol), return to room temperature, react 6 hours under nitrogen atmosphere, the concentration obtaining polyamic acid (PAA-3) is the solution of 10 quality %.

The solution 234g being 10 quality % by the concentration of this polyamic acid (PAA-3) moves in 300mL Erlenmeyer flask, add NMP70.8g, BCS76.2g to dilute, polyamic acid (PAA-3) solution of to make polyamic acid (PAA-3) be 6 quality %, NMP to be 74 quality %, BCS be 20 quality %.The number-average molecular weight of this polyamic acid (PAA-3) is 6092, and weight-average molecular weight is 12002.

The synthesis of < soluble polyimide (SPI-1) and the preparation > of solution thereof

By BODA (16.9g in 300mL four-hole boiling flask, 68mmol), p-PDA (6.8g, 63mmol), PCH7AB (10.3g, 27mmol) mixing in NMP (100g), react at 40 DEG C after 3 hours, add CBDA (4.1g, 21mmol) and NMP (52g), react 3 hours at 40 DEG C, obtain polyamic acid solution.After interpolation NMP is diluted to 6 quality % in this polyamic acid solution (130g), add diacetyl oxide (16g), the pyridine (12g) as imidization catalyst, react 3 hours at 80 DEG C.This reaction soln is put in methyl alcohol (1.6L), the throw out that filtering separation obtains.By this throw out methanol wash, drying under reduced pressure at 100 DEG C, obtains polyimide powder (SPI-1).The imide rate of this polyimide is 54%, and number-average molecular weight is 18300, and weight-average molecular weight is 45300.The amount of the carboxyl in this polyimide is 0.92 relative to repeating unit.

NMP (98g), BCS (90g) is added in the polyimide powder obtained as mentioned above (SPI-1) (12.0g), stirring at 80 DEG C makes it dissolve in 40 hours, makes soluble polyimide (SPI-1) solution.

[polyimide film forms the preparation with coating fluid (liquid crystal aligning agent)]

< embodiment 1 ~ 9>

The compound recorded in following table 1 obtained in as the above-mentioned synthesis example of the compound represented with above formula [A] is added in polyamic acid (PAA-1) solution (10.0g) obtained as mentioned above, them are made to reach 10mol% relative to the solids component (i.e. polyamic acid (PAA-1)) of polyamic acid (PAA-1) solution respectively, stir under room temperature (25 DEG C), until become homogeneous solution, make the polyimide film formation coating fluid (functional polymer film formation coating fluid) of embodiment 1 ~ 9.

[table 1]

< embodiment 10 ~ 34>

The compound recorded in following table 2 obtained in as the above-mentioned synthesis example of the compound represented with above formula [A] is added in polyamic acid (PAA-1) solution (10.0g) obtained as mentioned above, them are made to reach the ratio recorded in following table 2 respectively relative to the solids component (i.e. polyamic acid (PAA-1)) of polyamic acid (PAA-1) solution, at room temperature stir, until become homogeneous solution, make the polyimide film formation coating fluid of embodiment 10 ~ 34.

[table 2]

< embodiment 35 ~ 45>

The compound recorded in following table 3 obtained in as the above-mentioned synthesis example of the compound represented with above formula [A] is added in polyamic acid (PAA-2) solution (10.0g) obtained as mentioned above, them are made to reach 10mol% relative to the solids component (i.e. polyamic acid (PAA-2)) of polyamic acid (PAA-2) solution respectively, at room temperature stir, until become homogeneous solution, make the polyimide film formation coating fluid of embodiment 35 ~ 45.

[table 3]

< embodiment 46 ~ 59>

The compound recorded in following table 4 obtained in as the above-mentioned synthesis example of the compound represented with above formula [A] is added in polyamic acid (PAA-3) solution (40.0g) obtained as mentioned above, them are made to reach the quality % recorded in table 4 respectively relative to the solids component (i.e. polyamic acid (PAA-3)) of polyamic acid (PAA-3) solution, at room temperature stir, until become homogeneous solution, make the polyimide film formation coating fluid of embodiment 46 ~ 59.

[table 4]

< embodiment 60 ~ 62>

The compound recorded in following table 5 obtained in as the above-mentioned synthesis example of the compound represented with above formula [A] is added in polyamic acid (PAA-2) solution (70.0g) obtained as mentioned above, them are made to reach the ratio recorded in following table 5 respectively relative to the solids component (i.e. polyamic acid (PAA-2)) of polyamic acid (PAA-2) solution, at room temperature stir, until become homogeneous solution, make the polyimide film formation coating fluid of embodiment 60 ~ 62.

[table 5]

< embodiment 63 ~ 76>

The compound recorded in following table 6 obtained in as the above-mentioned synthesis example of the compound represented with above formula [A] is added in soluble polyimide (SPI-1) solution (10.0g) obtained as mentioned above, them are made to reach the ratio recorded in following table 6 respectively relative to the solids component (i.e. soluble polyimide (SPI-1)) of soluble polyimide (SPI-1) solution, at room temperature stir, until become homogeneous solution, make the polyimide film formation coating fluid of embodiment 63 ~ 76.

[table 6]

< embodiment 77 ~ 86 and comparative example 1> [validation test (stripping test) of cross-linking effect]

The polyimide film formation coating fluid of above-described embodiment 63 ~ 72 is spun on silicon wafer (2500rpm/30 second), the hot-plate of 230 DEG C carries out 30 minutes burn till, form film [a1].The thickness of the film [a1] of gained is measured with Kosaka Laboratory Ltd. SurfcorderET4000M.Then, the silicon wafer being formed with film [a1] is arranged at spin coater again, drip NMP, until the whole surface of silicon wafer is all capped, leave standstill after 60 seconds, by NMP Rotary drying (1500rpm/30 second), the hot-plate of 100 DEG C carries out burning till of 30 seconds, using residual film as film [a2].Again measure the thickness of this film [a2], calculate residual film ratio based on following formula.As comparative example 1, also same operation is carried out for as mentioned above obtained soluble polyimide (SPI-1) solution, soluble polyimide solution namely containing the compound represented with above formula [A], calculates residual film ratio.Result is shown in table 7.

Thickness × 100 of the thickness/film [a1] of residual film ratio (%)=film [a2]

Consequently, confirm, by using the polyimide film formation coating fluid (aligning agent for liquid crystal) being added with the compound represented with above formula [A], the solvent resistance of film (polyimide film) can be improved.Therefore infer, soluble polyimide is crosslinked under the effect of the compound represented with above formula [A].Also confirming, by suitably selecting the added difunctional compound represented with above formula [A], more freely can control the solvability of film.

Similarly form film with the polyimide film formation coating fluid of embodiment 1 ~ 62 and embodiment 73 ~ 76, carry out stripping test, consequently, compared with not adding the example of the compound represented with above formula [A], their residual film ratio is higher, confirm, by using the polyimide film formation coating fluid being added with the compound represented with above formula [A], the solvent resistance of polyimide film can be improved.

[table 7]

[preparation of liquid crystal orientation film and liquid crystal cells]

Use the polyimide film formation coating fluid (liquid crystal aligning agent) prepared in the various embodiments described above, manufacture liquid crystal cells as described below.

Polyimide film formation coating fluid (liquid crystal aligning agent) is spun on the glass substrate of glass substrate or band ito transparent electrode, on the hot-plate of 80 DEG C after dry 70 seconds, under the firing condition of regulation, forms the film of thickness 100nm.

Then, for the liquid crystal aligning process adopting friction, use the friction gear of roller diameter 120mm, under the friction condition of regulation, this coated surface is rubbed with Artificial Fibers cloth, obtain the substrate being with liquid crystal orientation film.For the liquid crystal aligning process adopting light, make linear polarization UV light (UV wavelength 313nm, exposure intensity 8.0mW/cm ^-2) exposure change between 0mJ ~ 1000mJ, relative to the normal slope 40 ° of plate, this coated surface is irradiated.Linear polarization UV preparation as described below: make the UV-light of high voltage mercury lamp by after the bandpass filter of 313nm, make it by the polaroid of 313nm.

Prepare the substrate that two pieces have been carried out the band liquid crystal orientation film of liquid crystal aligning process as mentioned above, after the liquid crystal aligning face of a piece scattering the spacer of 6 μm wherein, printing and sealing agent from the upper side, by another block baseplate-laminating, make liquid crystal aligning face toward each other, frictional direction is parallel to each other (antiparallel type liquid crystal cells, embodiment 87 ~ 116) or orthogonal (twisted nematic liquid crystals unit, embodiment 155 ~ 179, embodiment 296 ~ 315, embodiment 316 ~ 321), or for the substrate irradiated through UV, to fit (vertical alignment mode antiparallel type liquid crystal cells in the mode parallel with the direction of polarized light irradiated, embodiment 180 ~ 182, 183 ~ 294), make sealant cures, make dummy cell.For antiparallel type liquid crystal cells, in this dummy cell, liquid crystal MLC-2003 (Merck & Co., Inc.'s system) is injected by decompression injection method, for twisted nematic liquid crystals unit, in this dummy cell, the liquid crystal MLC-2003 (Merck & Co., Inc.'s system) being added with chiral agent is injected by decompression injection method, for vertical alignment mode antiparallel type liquid crystal cells, in this dummy cell, liquid crystal MLC-6608 (Merck & Co., Inc.'s system) is injected by decompression injection method, inlet is sealed, obtains each liquid crystal cells.

[evaluation of liquid crystal cells]

The mensuration of physical property of obtained each liquid crystal cells and the method for the evaluation of characteristic as described below.The liquid crystal orientation film obtained in each mensuration, evaluation and the substrate of liquid crystal cells, firing condition and friction condition illustrate in the lump.

< embodiment 87 ~ 116 and comparative example 2 ~ 4>< liquid crystal aligning evaluate >

The liquid crystal cells polaroid that the polyimide film formation coating fluid prepared in each embodiment shown in use table 8 is obtained is clamped, under the state of irradiating backlight from rear portion, liquid crystal cells is rotated, to detect by an unaided eye liquid crystal whether orientation according to the change of light and shade and the presence or absence of flow orientation.Now, evaluate according to following standard.In order to evaluate and obtained liquid crystal cells preparation as described below for liquid crystal aligning: use glass substrate as substrate, the firing condition of the film of polyimide film formation coating fluid is set on the hot-plate being heated to 230 DEG C, burns till 30 minutes, friction condition is set to roller rotating speed 300rpm, roller gait of march 50mm/sec, intrusion 0.15mm.In addition, preparation is not added the coating fluid (comparative example 2) of compound and the linking agent represented using above formula [A] and is added with the coating fluid (comparative example 3 or comparative example 4) of the following linking agent as common commercially available linking agent, comparative effectiveness in the lump.Result is shown in table 8.

Judgement criteria

◎: the orientation that can confirm liquid crystal, and without flow orientation

Zero: although liquid crystal orientation, observe some flow orientation

×: although liquid crystal orientation, observe much flow orientation

[changing 64]

Consequently, when confirming to use commercially available linking agent as shown in comparative example 3 and comparative example 4, usually the easy affected tendency of the orientation of liquid crystal is had, and use of the present invention when being added with the polyimide film formation coating fluid of the compound represented with formula [A], the orientation of liquid crystal can not be affected, according to circumstances also can improve orientation.

[table 8]

< embodiment 117 ~ 154 and comparative example 5 ~ 6>< rub evaluate >

The surface of the liquid crystal orientation film obtained with the polyimide film formation coating fluid prepared in each embodiment shown in confocal laser microscopic examination use table 9-1 ~ table 9-2, evaluates according to following standard.Use the glass substrate of band ito transparent electrode as substrate, the firing condition of the film of polyimide film formation coating fluid is set on the hot-plate being heated to 230 DEG C, burns till 30 minutes, friction condition is set to roller rotating speed 1000rpm, roller gait of march 50mm/sec, intrusion 0.5mm, thus makes.In addition, the coating fluid (comparative example 5 and comparative example 6) of the compound represented with above formula [A] is not added in preparation, comparative effectiveness in the lump.Result is shown in table 9-1 ~ table 9-2.

Zero: do not observe grinding and friction scar.

△: observe grinding and friction scar.

×: film is peeled off or is observed with the naked eye friction scar.

Consequently, confirm to compare with comparative example 6 with the comparative example 5 not adding the compound represented with above formula [A], use of the present invention when being added with the polyimide film formation coating fluid of the compound represented with above formula [A], resistance to machinability can be improved with any one polymkeric substance.

[table 9-1]

[table 9-2]

The tilt angle of < embodiment 155 ~ 179 and comparative example 7>< twisted nematic liquid crystals unit measures >

For the liquid crystal cells that the polyimide film formation coating fluid prepared in each embodiment shown in use table 10 is obtained, heat after 5 minutes at 105 DEG C, carry out the mensuration of tilt angle." AxoScan " of tilt angle AxoMetrix company adopts Muller matrix method to measure.The obtained liquid crystal cells preparation as described below in order to the tilt angle for measuring twisted nematic liquid crystals unit: use the glass substrate of band ito transparent electrode as substrate, the firing condition of the film of polyimide film formation coating fluid is set on the hot-plate being heated to 230 DEG C, burns till 30 minutes, friction condition is set to roller rotating speed 1000rpm, roller gait of march 50mm/sec, intrusion 0.3mm.In addition, the coating fluid (comparative example 7) of the compound represented with above formula [A] is not added in preparation, comparative effectiveness in the lump.Result is shown in table 10.

Consequently, confirming kind and the addition by suitably selecting the compound represented with above formula [A], can at random obtain desired tilt angle.

[table 10]

The tilt angle of < embodiment 180 ~ 182 and comparative example 8>< antiparallel type liquid crystal cells measures >

For the liquid crystal cells that the polyimide film formation coating fluid prepared in each embodiment shown in use table 11 is obtained, heat after 1 hour at 120 DEG C, carry out the mensuration of tilt angle." AxoScan " of tilt angle AxoMetrix company adopts Muller matrix method to measure.As the obtained liquid crystal cells in order to the tilt angle for measuring antiparallel type liquid crystal cells, use the glass substrate of band ito transparent electrode as substrate, the firing condition of the film of polyimide formation coating fluid is set in the heated air circulation type stove being heated to 200 DEG C, burns till 30 minutes, do not carry out orientation process, carry out above-mentioned liquid crystal cells preparation.In addition, the coating fluid (comparative example 8) of the compound represented with above formula [A] is not added in preparation, comparative effectiveness in the lump.Result is shown in table 11.

Consequently, confirm compared with not adding the comparative example 8 of the compound represented with above formula [A], when use is added with the polyimide film formation coating fluid of the compound represented with above formula [A], tilt angle can be increased significantly.Therefore, by adding the compound represented with above formula [A], even if do not introduce the side chain moiety making liquid crystal erect in matrix polymer, polyimide precursor namely contained by polyimide film formation coating fluid or polyimide, also liquid crystal vertical-tropism can be made.

[table 11]

< embodiment 183 ~ 294>< liquid crystal aligning is evaluated and the tilt angle of antiparallel type liquid crystal cells measures >

The liquid crystal cells polaroid that polyimide film formation coating fluid use being shown to prepare in each embodiment shown in 12-1 ~ 12-4 obtains is clamped, under the state of irradiating backlight from rear portion, liquid crystal cells is rotated, whether to detect by an unaided eye liquid crystal orientation according to the change of light and shade and the presence or absence of flow orientation, result demonstrates good orientation.Then, liquid crystal cells is applied to the voltage of alternating current of 3V, whether the liquid crystal that detects by an unaided eye orientation.Now, evaluate according to following standard.In order to evaluate and obtained liquid crystal cells preparation as described below for liquid crystal aligning: use glass substrate as substrate, the firing condition of the film of polyimide film formation coating fluid is set in the heated air circulation type stove being heated to 200 DEG C, burns till 30 minutes, be prepared after above-mentioned smooth orientation process is carried out to the glass substrate of the band film of gained.

Judgement criteria

Good: the orientation that can confirm liquid crystal, and without flow orientation

Bad: although liquid crystal orientation, to observe much flow orientation

In addition, for the liquid crystal cells that the polyimide film formation coating fluid prepared in each embodiment shown in use table 12-1 ~ 12-4 is obtained, heat after 1 hour at 120 DEG C, carry out the mensuration of tilt angle." AxoScan " of tilt angle AxoMetrix company adopts Muller matrix method to measure.

Consequently, confirm by using the polyimide film formation coating fluid (aligning agent for liquid crystal) being added with the compound represented with above formula [A] with photoreactivity side chain, even if also can obtain good vertical orientated property when having carried out light orientation process.In addition also confirm, by irradiating the ultraviolet of polarization to polyimide film formation coating fluid (aligning agent for liquid crystal) of the present invention, it has makes liquid crystal with the ability of the state orientation slightly tilted relative to vertical direction.Can also confirming, by controlling addition and irradiation dose, can finely tune tilt angle.It can thus be appreciated that polyimide film formation coating fluid (aligning agent for liquid crystal) of the present invention may be used for the liquid crystal orientation film used for liquid crystal display element of vertical orientation mode, and also can as the liquid crystal orientation film used in optical alignment method.

[table 12-1]

[table 12-2]

[table 12-3]

[table 12-4]

The mensuration > of < embodiment 295 ~ 315 and comparative example 9>< voltage retention (VHR)

For the liquid crystal cells that the polyimide film formation coating fluid prepared in each embodiment shown in use table 13 is obtained, the voltage retention of carrying out original state measures.The mensuration of voltage retention is the voltage 60 μ s applying 4V at the temperature of 90 DEG C, measures the voltage after 16.67ms, calculates voltage and can remain to which kind of degree, as voltage retention.The mensuration of voltage retention uses scientific & technical corporation of Japan (East Yang テ Network ニカ society) the VHR-1 voltage retention determinator made.Liquid crystal cells preparation as described below in order to obtain for measuring voltage retention (VHR): use the glass substrate of band ito transparent electrode as substrate, the firing condition of the film of polyimide film formation coating fluid is set on the hot-plate being heated to 230 DEG C, burns till 30 minutes, friction condition is set to roller rotating speed 1000rpm, roller gait of march 50mm/sec, intrusion 0.3mm.In addition, the coating fluid (comparative example 9) of the compound represented with above formula [A] is not added in preparation, comparative effectiveness in the lump.Result is shown in table 13.

Consequently, confirm, by using the polyimide film formation coating fluid being added with the compound represented with above formula [A], voltage retention characteristic more good compared with when not adding can be obtained.

[table 13]

The estimation > of < embodiment 316 ~ 321 and comparative example 10>< accumulated charge (RDC)

For the twisted nematic liquid crystals unit that the polyimide film formation coating fluid prepared in each embodiment shown in use table 14 is obtained, the voltage from 0V to 1.0V is applied with the interval of 0.1V at the temperature of 23 DEG C, measure the flickering level under each voltage, make calibration curve.Ground connection, after 5 minutes, applies voltage of alternating current 3.0V, volts DS 5.0V, measuring the flickering level after 1 hour, estimating RDC (flicker reference entry) by contrasting ready-made calibration curve.Liquid crystal cells preparation as described below in order to obtain for estimating accumulated charge (RDC): use the glass substrate of band ito transparent electrode as substrate, the firing condition of the film of polyimide film formation coating fluid is set on the hot-plate being heated to 230 DEG C, burns till 30 minutes, friction condition is set to roller rotating speed 1000rpm, roller gait of march 50mm/sec, intrusion 0.3mm.In addition, the coating fluid (comparative example 10) of the compound represented with above formula [A] is not added in preparation, comparative effectiveness in the lump.Result is shown in table 14.

Consequently, confirm, by using the polyimide film formation coating fluid being added with the compound represented with above formula [A], the liquid crystal cells that RDC is little can be obtained.

[table 14]

* by optical flicker reference entry, the value of the RDC after volts DS (DC) has just been stopped

* has just stopped the value of the residual RDC after volts DS (DC) after 30 minutes

The mensuration of the ion density before and after < embodiment 322 ~ 329 and comparative example 11> weathering test

The compound shown in table 15 obtained in as the synthesis example of modification compound is added in above-mentioned polyamic acid (PAA-1) solution (10.0g), them are made to reach the ratio recorded in following table 15 respectively relative to the solids component (i.e. polyamic acid (PAA-1)) of polyamic acid (PAA-1) solution, at room temperature stir, until become homogeneous solution, make polyimide film formation coating fluid.

Then, for the twisted nematic liquid crystals unit using these polymeric film formation coating fluids (liquid crystal aligning agent) to make respectively, measure the ion density of original state (23 DEG C), and carry out the ion density mensuration keep 30 hours (aging) at 60 DEG C after.During ion density measures, measure the ion density during choppy sea to liquid crystal cells applying voltage ± 10V, frequency 0.01Hz.Measure temperature to carry out at 80 DEG C.Determinator all uses scientific & technical corporation of Japan system 6245 type liquid crystal evaluation of physical property device in each mensuration.Result is shown in table 15.

In addition, firing condition except the film by polyimide film formation coating fluid is set to and burns till except 30 minutes on the hot-plate being heated to 200 DEG C, carry out the operation same with above-mentioned twisted nematic liquid crystals unit (embodiment 155 ~ 179), make twisted nematic liquid crystals unit.In addition, also same operation is carried out for the coating fluid not adding modification compound, comparative result in the lump.

Consequently, confirm kind and the addition by suitably selecting modification compound, compared with when not adding, the ionic impurity in liquid crystal cells significantly reduces.

[table 15]

< embodiment 330 ~ 342>

The compound recorded in following table 16 obtained in as the above-mentioned synthesis example of modification compound is added in polyamic acid (PAA-1) solution (10.0g) obtained as mentioned above, them are made to reach the ratio recorded in following table 16 respectively relative to the solids component (i.e. polyamic acid (PAA-1)) of polyamic acid (PAA-1) solution, at room temperature stir, until become homogeneous solution, make the polyimide film formation coating fluid of embodiment 330 ~ 342.

[table 16]

< embodiment 343 ~ 344>

The compound recorded in following table 17 obtained in as the above-mentioned synthesis example of modification compound is added in polyamic acid (PAA-3) solution (40.0g) obtained as mentioned above, them are made to reach the quality % recorded in table 17 respectively relative to the solids component (i.e. polyamic acid (PAA-3)) of polyamic acid (PAA-3) solution, at room temperature stir, until become homogeneous solution, make the polyimide film formation coating fluid of embodiment 343 ~ 344.

[table 17]

	Polyamic acid	Modification compound	Add (wt%)
				Embodiment 343	PAA-3	[70]	70
Embodiment 344	PAA-3	[70]	100

< embodiment 345 ~ 447>< liquid crystal aligning is evaluated and the tilt angle of vertical alignment mode antiparallel type liquid crystal cells measures >

[preparation of liquid crystal orientation film and liquid crystal cells]

The polyimide film of preparation in the various embodiments described above 330 ~ 344 is used to be formed with coating fluid (liquid crystal aligning agent), manufacture liquid crystal cells as described below.

Polyimide film formation coating fluid (liquid crystal aligning agent) is spun on glass substrate, on the hot-plate of 80 DEG C after dry 70 seconds, in the heated air circulation type stove being heated to 200 DEG C, burns till 30 minutes, form the film of thickness 100nm.

Then, linear polarization UV light (UV wavelength 313nm, exposure intensity 8.0mW/cm is made ^-2) exposure change between 0mJ ~ 1000mJ, relative to the normal slope 40 ° of plate, this coated surface is irradiated.Linear polarization UV preparation as described below: make the UV-light of high voltage mercury lamp by after the bandpass filter of 313nm, make it by the polaroid of 313nm.

Prepare the substrate that two pieces have been carried out the band liquid crystal orientation film of liquid crystal aligning process as mentioned above, after the liquid crystal aligning face of a piece scattering the spacer of 6 μm wherein, printing and sealing agent from the upper side, by another block baseplate-laminating, make liquid crystal aligning face toward each other, the direction of polarized light irradiated is parallel, make sealant cures, make dummy cell.Adopt decompression injection method, in this dummy cell, inject liquid crystal MLC-6608 (Merck & Co., Inc.'s system), inlet is sealed, obtains each vertical alignment mode antiparallel type liquid crystal cells.

Then, clamped by obtained above-mentioned liquid crystal cells polaroid, under the state of irradiating backlight from rear portion, liquid crystal cells is rotated, whether to detect by an unaided eye liquid crystal orientation according to the change of light and shade and the presence or absence of flow orientation, result demonstrates good orientation.Then, liquid crystal cells is applied to the voltage of alternating current of 3V, whether the liquid crystal that detects by an unaided eye orientation.Now, evaluate according to following standard.Result is shown in table 18-1 ~ 18-4.

Judgement criteria

Bad: although liquid crystal orientation, to observe much flow orientation

In addition, for obtained above-mentioned liquid crystal cells, heat after 1 hour at 120 DEG C, carry out the mensuration of tilt angle." AxoScan " of tilt angle AxoMetrix company adopts Muller matrix method to measure.Result is shown in table 18-1 ~ table 18-4.

Consequently, as shown shown in 18-1 ~ 18-4, confirm by using the polyimide film formation coating fluid (aligning agent for liquid crystal) being added with the modification compound with photoreactivity side chain, even if also can obtain good vertical orientated property when having carried out light orientation process.In addition also confirm, by irradiating the ultraviolet of polarization to polyimide film formation coating fluid (aligning agent for liquid crystal) of the present invention, it has makes liquid crystal with the ability of the state orientation slightly tilted relative to vertical direction.Can also confirming, by controlling addition and irradiation dose, can finely tune tilt angle.It can thus be appreciated that polyimide film formation coating fluid (aligning agent for liquid crystal) of the present invention may be used for the liquid crystal orientation film used for liquid crystal display element of vertical orientation mode, and also can as the liquid crystal orientation film used in optical alignment method.

[table 18-1]

[table 18-2]

[table 18-3]

[table 18-4]

< embodiment 448 ~ 471>

The compound recorded in following table 19 obtained in as the above-mentioned synthesis example of modification compound is added in polyamic acid (PAA-1) solution (10.0g) obtained as mentioned above, them are made to reach the ratio recorded in following table 19 respectively relative to the solids component (i.e. polyamic acid (PAA-1)) of polyamic acid (PAA-1) solution, at room temperature stir, until become homogeneous solution, make the polyimide film formation coating fluid of embodiment 448 ~ 471.

[table 19]

< embodiment 472 ~ 495>< horizontal alignment pattern liquid crystal aligning of antiparallel type unit evaluates >

[preparation of liquid crystal orientation film and liquid crystal cells]

The polyimide film of preparation in the various embodiments described above 448 ~ 471 is used to be formed with coating fluid (liquid crystal aligning agent), manufacture liquid crystal cells as described below.

Then, linear polarization UV light (UV wavelength 313nm, exposure intensity 8.0mW/cm is made ^-2) exposure change between 0mJ ~ 1000mJ, relative to substrate from directly over this coated surface is irradiated.Linear polarization UV preparation as described below: make the UV-light of high voltage mercury lamp by after the bandpass filter of 313nm, make it by the polaroid of 313nm.

Prepare the substrate that two pieces have been carried out the band liquid crystal orientation film of liquid crystal aligning process as mentioned above, after the liquid crystal aligning face of a piece scattering the spacer of 6 μm wherein, printing and sealing agent from the upper side, by another block baseplate-laminating, make liquid crystal aligning face toward each other, the direction of polarized light irradiated is parallel, make sealant cures, make dummy cell.Adopt decompression injection method, in this dummy cell, inject liquid crystal MLC-2041 (Merck & Co., Inc.'s system), inlet is sealed, obtains horizontal alignment pattern antiparallel type liquid crystal cells.

Then, obtained above-mentioned horizontal alignment pattern antiparallel type liquid crystal cells polaroid is clamped, under the state of irradiating backlight from rear portion, liquid crystal cells is rotated, to detect by an unaided eye liquid crystal whether orientation according to the change of light and shade and the presence or absence of flow orientation.Now, evaluate according to following standard.Result is shown in table 20.

Judgement criteria

Zero: although liquid crystal orientation, observe some flow orientation

△: although liquid crystal orientation, observe much flow orientation

×: liquid crystal is completely non-oriented

Consequently, confirm, in each liquid crystal cells, not carry out light-struck liquid crystal cells and do not demonstrate orientation completely, and carried out in light-struck liquid crystal cells, liquid crystal is orientation according to the addition of modification compound and rayed amount.In addition, even if when carrying out the isotropy process of 30 minutes to each liquid crystal cells confirming orientation at 130 DEG C, also unconfirmedly to have significant change to orientation.That is, kind and the addition by suitably selecting additive is confirmed, can easily manufacture level orientation unit.

[table 20]

Claims

1. polyimide film formation coating fluid, it is characterized in that, containing polymkeric substance and difunctional compound, described polymkeric substance is at least one being selected from the polyimide precursor selected from polyamic acid and poly amic acid ester and the polyimide obtained by this polyimide precursor imidization, described polyimide precursor is by making to be selected from tetracarboxylic acid and from tetracarboxylic acid two carboxylic acid halides, tetracarboxylic dianhydride, tetracarboxylic acid diester diacid chloride, the at least one tetracarboxylic acid composition of the tetracarboxylic acid derivatives selected in tetracarboxylic acid diester and diamine component carry out polyreaction and obtain, described difunctional compound is the difunctional compound represented with following formula [A] introduced Michaelis acid structure respectively and obtain on two amino of diamine compound,

In formula, Y represents the divalent organic group deriving from described diamine compound, R ₁and R ₂be respectively-H or can comprise at an arbitrary position phenyl ring, cyclohexane ring, heterocycle, fluorine, ehter bond, ester bond, amido linkage carbonatoms be 1 ~ 35 1 valency organic group, can be connected with a part of Y and form ring, in addition, R ₁and R ₂can be the same or different.

2. liquid crystal aligning agent, is characterized in that, is formed form with coating fluid by polyimide film according to claim 1.

3. polyimide film, is characterized in that, polyimide film formation coating solution according to claim 1 is carried out burning till in substrate and obtained.

4. polyimide film, it is characterized in that, crosslinked and polyimide that is that obtain is formed under the effect of difunctional compound by polymkeric substance, described polymkeric substance is at least one being selected from the polyimide precursor selected from polyamic acid and poly amic acid ester and the polyimide obtained by this polyimide precursor imidization, described polyimide precursor is by making to be selected from tetracarboxylic acid and from tetracarboxylic acid two carboxylic acid halides, tetracarboxylic dianhydride, tetracarboxylic acid diester diacid chloride, the at least one tetracarboxylic acid composition of the tetracarboxylic acid derivatives selected in tetracarboxylic acid diester and diamine component carry out polyreaction and obtain, described difunctional compound is the difunctional compound represented with following formula [A] introduced Michaelis acid structure respectively and obtain on two amino of diamine compound,

5. liquid crystal orientation film, is characterized in that, is made up of the polyimide film described in claim 3 or 4.

6. liquid crystal display device, is characterized in that, possesses liquid crystal orientation film according to claim 5.