CN103415583A

CN103415583A - Coating solution for forming polyimide film, liquid crystal alignment agent, polyimide film, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: CN103415583A
Application number: CN2011800685751A
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: 2013-11-27
Anticipated expiration: 2031-12-28
Also published as: TWI519569B; CN103415583B; JPWO2012091088A1; KR20130130033A; KR101856808B1; JP5831712B2; WO2012091088A1; TW201241046A

Abstract

Provided is a coating solution for forming a polyimide film, said coating solution comprising: a polymer of a polyimide precursor obtained by polymerizing a tetracarbonate component and a diamine component, and/or a polyimide formed by the imidization of the polyimide precursor; and a bifunctional compound represented by formula [A] and having a Meldrum's acid structure introduced into each of two amino groups of a diamine compound. Also provided are: a liquid crystal alignment agent comprising said coating solution; a polyimide film obtained by firing a substrate coated using said coating solution; a polyimide film comprising a polyimide in which the polymer is crosslinked using the bifunctional compound represented by formula [A]; a liquid crystal alignment film comprising the polyimide film; and a liquid crystal display element equipped with said liquid crystal alignment film. (In the formula, Y, R1 and R2 are groups specified in claims 1 and 4).

Description

Polyimide film forms 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 forms with coating fluid and liquid crystal aligning agent, uses them and the polyimide film and liquid crystal orientation film and the liquid crystal display device that form.

Background technology

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

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

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

In addition, for as mentioned above be used to the diamines of the tilt angle that increases liquid crystal, also carried out be used to the stability of improving tilt angle and the structural research of process dependency, as side-chain structure used, the side-chain structure (for example, with reference to patent documentation 4,5) that phenyl or cyclohexyl etc. comprise ring structure has been proposed here.Also proposed to have on the side chain diamines (for example, with reference to patent documentation 6) of 3～4 this ring structures.

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

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

In addition, the developments such as province's electrification of the high performance of liquid crystal display device, big area, display device, in addition also used under various environment, also become strict for the desired characteristic of liquid crystal orientation film.What while particularly liquid crystal aligning agent being coated to substrate, cause because pitch time extends separates out the generation bad with separating the printing that causes, becomes problem by accumulating the problems such as burning screen that electric charge (RDC) causes, and is difficult to solve simultaneously this two problems by prior art.

As mentioned above, in the polyimide liquid crystal orientation film, in order to improve desired characteristic, use the part of various two amine components as raw material, but, due to the relation with other characteristic, sometimes can't freely use desired two amine components.

Also have; due to its feature, i.e. higher physical strength, thermotolerance, solvent resistance; polyimide is except being used as liquid crystal orientation film; also be widely used as protecting materials, insulating material in electric-electronic applications; as in the situation of this material; similarly two amine components as the polyimide raw material are improved, but can't freely used desired two amine component this point too.So the improvement of these desired characteristics can be easily carried out in hope.

The prior art document

Patent documentation

Patent documentation 1: Japanese patent laid-open 2-282726 communique

Patent documentation 2: Japanese patent laid-open 3-179323 communique

Patent documentation 3: Japanese patent laid-open 4-281427 communique

Patent documentation 4: Japanese patent laid-open 9-278724 communique

Patent documentation 5: the international text that discloses No. 2004/52962

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

Patent documentation 7: Japanese patent laid-open 2-37324 communique

Summary of the invention

Invent technical problem to be solved

Problem of the present invention is to solve the problem of above-mentioned prior art, provides the polyimide film of the polyimide film that can easily obtain more freely having improved various characteristics to form with coating fluid and liquid crystal aligning agent, use them and the polyimide film and liquid crystal orientation film and the liquid crystal display device that form.

The technical scheme that the technical solution problem adopts

The polyimide film of the present invention that solves above-mentioned problem forms and is characterised in that with coating fluid, contain polymkeric substance and difunctional compound, described polymkeric substance be selected from polyimide precursor and by this polyimide precursor imidization and polyimide at least a, at least a tetracarboxylic acid composition and two amine components of described polyimide precursor by making to be selected from tetracarboxylic acid and derivative thereof carry out polyreaction and obtain, described difunctional compound be on two amino of diamine compound, introduce respectively Michaelis acid structure and the difunctional compound meaned with following formula [A].

[changing 1]

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

Liquid crystal aligning agent of the present invention is characterised in that, is formed with coating fluid and is formed by described polyimide film.

In addition, polyimide film of the present invention is characterised in that, described polyimide film is formed and coats substrate with coating fluid, burns till and obtains.

In addition, polyimide film of the present invention is characterised in that, by polymkeric substance under the effect of difunctional compound crosslinked and polyimide form, described polymkeric substance be selected from polyimide precursor and by this polyimide precursor imidization and polyimide at least a, at least a tetracarboxylic acid composition and two amine components of described polyimide precursor by making to be selected from tetracarboxylic acid and derivative thereof carry out polyreaction and obtain, described difunctional compound be on two amino of diamine compound, introduce respectively Michaelis acid structure and the difunctional compound meaned with following formula [A].

[changing 2]

In addition, liquid crystal orientation film of the present invention is characterised in that, consists of described polyimide film.

In addition, liquid crystal display device of the present invention is characterised in that to possess described liquid crystal orientation film.

The effect of invention

According to the present invention, by making the polyimide films such as the liquid crystal aligning agent formation that contains the difunctional compound meaned with following formula [A] of introducing respectively on two amino of diamine compound that Michaelis acid structure obtain, use coating fluid, can obtain the polyimide films such as liquid crystal orientation film that more freely improved various characteristics.And, the difunctional compound meaned with following formula [A] be on two amino of diamine compound, introduce respectively Michaelis acid structure and compound, as this diamine compound, can use for obtain two amine components of the characteristic of wanting of carrying out research in the past, therefore can easily improve the various characteristics of gained polyimide film.In addition, polyimide film of the present invention forms with the contained polyimide precursor of coating fluid or polyimide crosslinked under the effect of the difunctional compound meaned with following formula [A] by heating, therefore the polyimide film of gained has the patience to organic solvent, and plays the effect that makes the film hardening.

The best mode carried out an invention

Below, the present invention is described in detail.

Polyimide film of the present invention forms with coating fluid and contains the difunctional compound with following formula [A] expression of introducing respectively Michaelis acid structure and obtain on two amino of diamine compound.

[changing 3]

In following formula [A], Y derives from the divalent organic group of conduct with the diamine compound of the raw material of the difunctional compound of following formula [A] expression, its structure is not particularly limited, and as the concrete example of Y, can exemplify the divalent organic group that means with following formula (Y-1)～(Y-120) etc.Wherein, use in the situation of polyimide film as liquid crystal orientation film of gained, in order to obtain good liquid crystal aligning, better to take the structure of the high diamine compound of rectilinearity as raw material, 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), (Y-82) or (Y-109) etc.In addition, using the polyimide film of gained in the situation of the liquid crystal orientation film of the tilt angle be used to improving liquid crystal, for example be better, on side chain, to have chain alkyl (alkyl of carbon number more than 10), aromatic ring, the aliphatics ring, the diamine compound of steroid skeleton or structure that they are combined is 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), (Y-107) or (Y-108) etc., but be not limited to this.In addition, in the situation of the electrical characteristic of wish raising liquid crystal display device, can exemplify (Y-31), (Y-40), (Y-64), (Y-65), (Y-66), (Y-67), (Y-109), (Y-110) etc.In addition, want to give liquid crystal orientation film with in photoreactive situation, can exemplify (Y-17), (Y-18), (Y-111), (Y-112), (Y-113), (Y-114), (Y-115), (Y-116), (Y-117), (Y-118), (Y-119) etc.

[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]

The difunctional compound with following formula [A] expression of introducing respectively Michaelis acid structure and obtain on two amino of diamine compound for example can be manufactured by the following method: in trimethyl orthoformate, perhaps in triethyl orthoformate, the organic solvent perhaps used in conventional organic synthesis (ethyl acetate for example, hexane, toluene, tetrahydrofuran (THF), acetonitrile, methyl alcohol, chloroform, 1, the 4-diox, N, dinethylformamide, METHYLPYRROLIDONE) in, the diamine compound meaned with following formula [B] and Michaelis acid and trimethyl orthoformate or triethyl orthoformate one are reacted.As the diamine compound meaned with following formula [B], can use for obtain two amine components of the characteristic of wanting of carrying out research in the past, namely for the tetracarboxylic acid composition, carrying out two amine components that polyreaction is manufactured polyimide precursor or polyimide and wanted characteristic be used to obtaining.Temperature of reaction and reaction times are not particularly limited, and for example in 60～120 ℃ of reactions, get final product in about 30 minutes～2 hours.

[changing 19]

(Y, R ₁And R ₂With Y, the R in following formula [A] ₁And R ₂Identical.)

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

In addition, polyimide film of the present invention form with coating fluid contain be selected from polyimide precursor and by this polyimide precursor imidization and at least a polymkeric substance of polyimide, at least a tetracarboxylic acid composition and two amine components of described polyimide precursor by making to be selected from tetracarboxylic acid and derivative thereof carry out polyreaction and obtain.Certainly, this polyimide precursor or polyimide can be a kind of, or also can two or more and use.Polyimide precursor refers to polyamic acid and poly amic acid ester.

Polyimide film of the present invention forms with the contained polyimide precursor of coating fluid as mentioned above, and at least a tetracarboxylic acid composition by making to be selected from tetracarboxylic acid and derivative thereof and two amine components carry out polyreaction and obtain.

As two amine components, can exemplify the diamine compound for example meaned with following formula [B].In addition, can use two amine components used while in the past obtaining polyimide precursor making two amine components and the reaction of tetracarboxylic acid composition.As two amine components of the raw material of this polyimide precursor, can be partly or entirely the compound identical with the diamine compound of the raw material of difunctional compound as meaning with following formula [A], or two amine components can be also the compounds different from the diamine compound of the raw material of difunctional compound as meaning with following formula [A].

In addition, as at least a tetracarboxylic acid composition that is selected from tetracarboxylic acid and derivative thereof, can use tetracarboxylic acid composition used while in the past obtaining polyimide precursor making two amine components and the reaction of tetracarboxylic acid composition.As tetracarboxylic acid derivatives, can exemplify tetracarboxylic acid two carboxylic acid halides, the tetracarboxylic dianhydride with following formula [C] expression, tetracarboxylic acid diester diacid chloride, tetracarboxylic acid diester etc.For example, by making tetracarboxylic acid or derivatives thereof and the reactions of two amine components such as tetracarboxylic acid two carboxylic acid halides, tetracarboxylic dianhydride, can obtain polyamic acid.In addition, by the reaction of tetracarboxylic acid diester diacid chloride and two amine components, or, by tetracarboxylic acid diester and two amine components are reacted under the inferior condition of existing of suitable condensing agent, alkali, can obtain poly amic acid ester.

[changing 20]

(X is 4 valency organic groups.)

As the concrete example of the X of following formula [C], can exemplify the 4 valency organic groups that mean with following formula (X-1)～(X-46).From the viewpoint of the acquisition difficulty of compound, consider, 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).In the situation of the transparency of wish raising gained polyimide film, preferably use the tetracarboxylic dianhydride with aliphatics and aliphatics ring structure, as X, be more preferably (X-1), (X-2) and (X-25), from the reactive viewpoint with diamines, consider, further be more preferably (X-1).

[changing 21]

Concrete example as the tetracarboxylic acid diester, can exemplify 1, 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-hexanaphthene tetracarboxylic acid 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 basic ring amyl group acetic acid dialkyl, cis-3, 7-dibutyl ring hot-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, the 12-dialkyl, 4-(2, 5-dioxo tetrahydrofuran (THF)-3-yl)-1, 2, 3, 4-tetraline-1, the aliphatics tetracarboxylic acid diester such as 2-dicarboxylic acid dialkyl esters, the 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-dicarboxyl phenyl) ether dialkyl, two (3, 4-dicarboxyl phenyl) 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, two amine components and tetracarboxylic acid composition can be respectively a kind of, or also can two or more and use.

Make tetracarboxylic acid composition and two amine components carry out polyreaction and come the method for synthesis of polyimides precursor to be not particularly limited, can use known synthetic method.

For example, as two amine components and tetracarboxylic dianhydride's reaction, can exemplify two amine components and tetracarboxylic dianhydride are reacted in organic solvent method.Now organic solvent used, so long as the organic solvent of the polyimide precursor that dissolving generates gets final product, is not particularly limited.As its concrete example, can exemplify DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, the N-methyl caprolactam, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, the pregnancy sulfoxide, gamma-butyrolactone, Virahol, the 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, the glycol monomethyl isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, the propylene glycol monoacetate, propylene glycol monomethyl ether, the glycol tertiary butyl ether, dipropylene glycol monomethyl ether, Diethylene Glycol, the Diethylene Glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol monoacetate list ether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxyl group butylacetic acid ester, the tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, the 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, acetic acid propylene glycol list ethyl ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, the 3-methoxy methyl propionate, 3-ethoxy-propionic acid methylethyl ester, 3-methoxy propyl acetoacetic ester, the 3-ethoxy-propionic acid, the 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, but also also mix together.And, even can not dissolve the solvent of polyimide precursor, 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 become the reason that makes the polyimide precursor generated hydrolysis, so it is desirable to, use the organic solvent dehydrated.

When two amine components and tetracarboxylic dianhydride are reacted in organic solvent, can exemplify: stir the solution that makes two amine components be dispersed or dissolved in organic solvent and obtain, then directly add the tetracarboxylic dianhydride or make the tetracarboxylic dianhydride be dispersed or dissolved in the method for adding again after organic solvent; In the solution obtained making the tetracarboxylic dianhydride be dispersed or dissolved in organic solvent on the contrary, add the method for two amine components; Alternately add the method for tetracarboxylic dianhydride and two amine components etc., can adopt any method wherein.While using respectively multiple two amine components or tetracarboxylic dianhydride to react, can under the state be pre-mixed, make its reaction, also can make its respectively reaction successively, can also make to react respectively and lower molecular weight body hybrid reaction and obtain polymkeric substance.Polymerization temperature now can be selected the arbitrary temp of-20 ℃～150 ℃, is better the scope of-5 ℃～100 ℃.Reaction can be carried out under any concentration, if but concentration is too low, be difficult to obtain the polymkeric substance of high molecular, if excessive concentration, the viscosity of reaction solution is too high, is difficult to uniform stirring.Therefore, be preferably 1～50 quality %, more preferably 5～30 quality %.Initial reaction stage is carried out under high density, can append organic solvent afterwards.

In the polyreaction of polyimide precursor, the relatively good of the total mole number of two amine components and tetracarboxylic dianhydride's total mole number is 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 two amine components, or, by tetracarboxylic acid diester and two amine components are reacted under the inferior condition of existing of suitable condensing agent, alkali, can obtain poly amic acid ester.Perhaps, 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.

Particularly, for example can make tetracarboxylic acid diester diacid chloride and two amine components under the existence of alkali and organic solvent, and react 30 minutes～24 hours, preferably 1 hour～4 hours under-20 ℃～150 ℃, preferably 0 ℃～50 ℃, thus the synthesizing polyamides acid esters.

As alkali, can use pyridine, triethylamine, DMAP, because reacting balance ground carries out, so preferred pyridine.From the amount easily to remove, easily obtain the viewpoint consideration of high molecular body, the addition of alkali is better 2～4 times moles with respect to tetracarboxylic acid diester diacid chloride.

In addition, make tetracarboxylic acid diester and two amine components in the situation that polycondensation under the existence of condensing agent, as alkali, can use triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride, N, N '-carbonyl dimidazoles, dimethoxy-1,3,5-triazine methylmorpholine, O-(benzotriazole-1-yl)-N, N, N ', N '-tetramethylurea (TMU) Tetrafluoroboric acid ester, O-(benzotriazole-1-yl)-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-yl) 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 with respect to the diamines reacted or tetracarboxylic acid diester.

As solvent used in above-mentioned reaction, can use with above shown in synthesizing polyamides when acid solvent phase used with solvent, from the solvability of monomer and polymkeric substance, considering, is better METHYLPYRROLIDONE, gamma-butyrolactone, and they can one or more mix use.Concentration when synthetic, from being difficult for occurring the viewpoint consideration of separating out and easily obtain the high molecular body of polymkeric substance, the tetracarboxylic acid derivatives such as tetracarboxylic acid diester diacid chloride or tetracarboxylic acid diester and the total concn of two amine components 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 synthetic middle solvent used of poly amic acid ester is better to dewater as far as possible, is better in nitrogen atmosphere, to prevent sneaking into of ambient atmos.

Polyimide film of the present invention forms with the contained polyimide of coating fluid by above-mentioned polyimide precursor dehydration closed-loop is obtained.In this polyimide, it is 100% that the dehydration closed-loop rate of acid amides acidic group (imide rate) not necessarily needs, and can adjust arbitrarily according to purposes or purpose.

As the method that makes the polyimide precursor imidization, can exemplify the direct heating polyimide precursor solution hot-imide or in the solution of polyimide precursor, add the catalysis imidization of catalyzer.

Temperature while making the polyimide precursor hot-imide in solution is 100～400 ℃, is better 120～250 ℃, is better to carry out when the water that will generate by imidization reaction is got rid of to system.

The catalysis imidization of polyimide precursor is by polyimide precursor solution, adding basic catalyst and acid anhydrides, and at-20～250 ℃, is better under 0～180 ℃, to stir and carry out.The amount of basic catalyst to be mole to count 0.5～30 times of acid amides acidic group, and preferably 2～20 times, the amount of acid anhydrides is mole to count 1～50 times of acid amides acidic group, preferably 3～30 times.As basic catalyst, can exemplify pyridine, triethylamine, Trimethylamine 99, Tributylamine or trioctylamine etc., wherein pyridine have for make to react carry out for appropriate alkalescence, therefore preferably.As acid anhydrides, can exemplify diacetyl oxide, trimellitic acid 1,2-anhydride or pyromellitic dianhydride etc., wherein, while using diacetyl oxide, be easy to react the purifying after end, therefore preferably.Adopt the imide rate of catalysis imidization to control by adjusting catalytic amount and temperature of reaction, reaction times.

During from the polyimide precursor that reclaim to generate the reaction soln of polyimide precursor or polyimide or polyimide, be better reaction soln is put in solvent and to be made its precipitation.Solvent as for precipitation, can exemplify methyl alcohol, acetone, hexane, ethylene glycol butyl ether, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene, water etc.Put in solvent and the polymkeric substance of precipitation can, after filtered and recycled, carry out drying in normal temperature or heating under normal pressure or decompression.In addition, the polymkeric substance that makes to precipitate recovery if repeat is dissolved in the operation 2～10 times that organic solvent redeposition reclaim again, can reduce the impurity in polymkeric substance.As solvent now, can exemplify such as alcohols, ketone or hydrocarbon etc., if use the solvent more than 3 kinds that is selected from these solvents, purification efficiency further improves, therefore preferably.

Polyimide film of the present invention forms with contained polyimide precursor or the polyimide of coating fluid, in operability when considering that the polyimide film strength of gained, polyimide film form, the inhomogeneity situation of polyimide film, the weight-average molecular weight of utilizing GPC (gel permeation chromatography) method to measure is better 5000～1000000, is more preferably 10000～150000.

Polyimide film of the present invention forms with coating fluid can contain above-mentioned polyimide precursor or polyimide polymkeric substance in addition as component of polymer.As the polymkeric substance beyond polyimide precursor or polyimide, but 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 that is used to form liquid crystal orientation film etc. form the difunctional compound meaned with following formula [A] with further containing in coating fluid, thereby become the polyimide film formation coating fluid of the polyimide film that can obtain more freely having improved various characteristics; Described polymkeric substance be selected from polyimide precursor and by this polyimide precursor imidization and polyimide at least a, at least a tetracarboxylic acid composition and two amine components of described polyimide precursor by making to be selected from tetracarboxylic acid and derivative thereof carry out polyreaction and obtain, described difunctional compound be on two amino of diamine compound, introduce respectively Michaelis acid structure and the difunctional compound meaned with following formula [A].

If describe in detail, the difunctional compound meaned with following formula [A] has 2 Michaelis acid structures at two ends, namely derive from the structure of Michaelis acid, this Michaelis acid structure for example, by heating (more than 180～250 ℃), along with carbonic acid gas and leaving away of acetone and become ketenes (namely have divalent group > C=C=O carbonyl compound), the independent dimerization of ketenes, or the carboxyl had with polyimide precursor or polyimide, hydroxyl, amino, sulfydryl, aldehyde, ketone, unsaturated link(age) (carbon-to-carbon double bond for example, carbon-to-carbon triple bond, imines (the two keys of carbon-nitrogen), carbodiimide, the 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 meaned with following formula [A] for example, forms with under the state of coating fluid and with polyimide precursor or polyimide, does not react at the polyimide film that is not heated to high temperature (below 100 ℃), but, by heating, be introduced into polyimide precursor or polyimide via Michaelis acid structure.The difunctional compound meaned with following formula [A] is because have 2 Michaelis acid structures, so infer, form after heating polyimide by the difunctional compound meaned with following formula [A] crosslinked structure.

Thus, polyimide film of the present invention is formed with coating fluid and coats in the polyimide film that substrate burns till and obtain, in polyimide, introduce the Y structure that difunctional compound was had meaned with following formula [A], namely derived from the Y structure of conduct with the diamine compound of the raw material of the difunctional compound of formula [A] expression.

In the past; polyimide film is because its feature, namely higher physical strength, thermotolerance, solvent resistance are widely used as protecting materials, the insulating material in liquid crystal orientation film, electric-electronic applications; in order to improve desired characteristic, use the part of various two amine components as raw material, but sometimes can't freely use desired two amine components.For example, in liquid crystal orientation film, for raising of carrying out liquid crystal aligning and tilt angle etc., namely in order to improve desired characteristic, use the part of various two amine components as raw material, but the difference according to kind, combination and amount in order to obtain two amine components that desired characteristic used, the polymerisation reactivity variation of two amine components and tetracarboxylic acid composition, therefore want kind, combination and the amount of two amine components of characteristic to be restricted sometimes be used to obtaining.In addition, for various kinds and the combination of two amine components of wanting characteristic be used to obtaining, need to study respectively the polymeric reaction condition of two amine components and tetracarboxylic acid composition.In addition, in order to make the polyimide film formation coating fluid that can form uniform polyimide film, containing composition must be the solution state that is dissolved in solvent, but, according to the difference of kind, combination and the amount of two amine components of wanting characteristic be used to obtaining, exist polyimide film to form the problem by the solvability variation of the contained polyimide precursor of coating fluid or polyimide.

In the present invention, at polyimide film, form the stage with coating fluid, as different compounds, contain respectively polyimide precursor or polyimide and conduct are wanted the compound of characteristic be used to obtaining the difunctional compound with following formula [A] expression, polyimide film is being formed to the stage of heating (burning till) with coating fluid, will introduce polyimide precursor or polyimide as the difunctional compound with following formula [A] expression of the compound of wanting characteristic be used to obtaining.Therefore, polyimide film forms is wanted two amine components of characteristic to be raw material with the contained polyimide precursor of coating fluid or polyimide without take be used to obtaining, therefore can not produce the poor problem of the polymerisation reactivity of two amine components and tetracarboxylic acid composition, for the various kinds of two amine components of wanting characteristic be used to obtaining with combine problem, polyimide film the formation contained polyimide precursor of coating fluid or the poorly soluble problem of polyimide of the polymeric reaction condition that need to study respectively two amine components and tetracarboxylic acid composition.Thus, polyimide film of the present invention forms can use with coating fluid the diamine compound of wanting characteristic be used to obtaining, and need not consider the solvability of Necessity of Study, polyimide precursor or polyimide of polymerisation reactivity, the polymeric reaction condition of two amine components and tetracarboxylic acid composition, with existing polyimide film, form and compare with coating fluid, can more freely improve the various characteristics of gained polyimide film.

In addition, in difunctional compound with following formula [A] expression, on two amino of diamine compound, introduce respectively Michaelis acid structure, as this diamine compound, can use for obtain two amine components of the characteristic of wanting of carrying out research in the past, namely for the tetracarboxylic acid composition, carrying out two amine components that polyreaction is manufactured polyimide precursor or polyimide and wanted characteristic be used to obtaining.Therefore, can easily improve the various characteristics of gained polyimide film.

Also have, polyimide film of the present invention forms with the contained polyimide precursor of coating fluid or polyimide crosslinked under the effect of the difunctional compound meaned with following formula [A] by heating, therefore the polyimide film of gained has the patience to organic solvent, and becomes dura mater.

Polyimide film of the present invention forms and is not particularly limited by the manufacture method of coating fluid, as long as make polymkeric substance and difunctional compound be dissolved in solvent, described polymkeric substance be selected from polyimide precursor and by this polyimide precursor imidization and polyimide at least a, at least a tetracarboxylic acid composition and two amine components of described polyimide precursor by making to be selected from tetracarboxylic acid and derivative thereof carry out polyreaction and obtain, described difunctional compound be on two amino of diamine compound, introduce respectively Michaelis acid structure and the difunctional compound meaned with following formula [A].

Polyimide film of the present invention forms with the solvent of coating fluid as long as energy dissolve polymer and difunctional compound can exemplify for example DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, the N-methyl caprolactam, 2-Pyrrolidone, the N-ethyl-2-pyrrolidone, NVP, methyl-sulphoxide, tetramethyl-urea, pyridine, dimethyl sulfone, the 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 be selected from above-mentioned polyimide precursor and by this polyimide precursor imidization and polyimide at least a, at least a tetracarboxylic acid composition and two amine components of described polyimide precursor by making to be selected from tetracarboxylic acid and derivative thereof carry out polyreaction and obtain, described difunctional compound be on two amino of diamine compound, introduce respectively Michaelis acid structure and the difunctional compound meaned with following formula [A].These solvents can be used alone, but also also mix together.

From the viewpoint that forms uniform polyimide film by coating, consider, the content of the organic solvent in polyimide film formation use coating fluid of the present invention is 70～97 quality % preferably.This content can be according to the thickness of the polyimide films such as Object LC alignment films and appropriate change.

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

Polyimide film of the present invention forms with the content of the difunctional compound meaned with following formula [A] in coating fluid with respect to total amount 100 mass parts of polyimide precursor and polyimide 1～200 mass parts preferably, in order to carry out crosslinking reaction to embody desired film solidified nature and the orientation of liquid crystal is descended, more preferably 1～100 mass parts, particularly preferably 1～50 mass parts.

Polyimide film of the present invention forms with in coating fluid, in the scope of not damaging effect of the present invention, can contain the homogeneity of the thickness that is improved the polyimide film while being coated with polyimide film formation of the present invention with coating fluid and organic solvent (also referred to as Weak solvent) or the compound of surface smoothness.Can also use the compound of the adaptation that improves polyimide film and substrate etc.

Concrete example as the Weak solvent of the homogeneity that improves thickness and surface smoothness, can exemplify for example Virahol, the methoxymethyl amylalcohol, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monobutyl ether, ethyl carbitol, the ethyl carbitol acetic ester, ethylene glycol, ethylene glycol acetate, the glycol monomethyl isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, the propylene glycol monoacetate, propylene glycol monomethyl ether, the glycol tertiary butyl ether, dipropylene glycol monomethyl ether, Diethylene Glycol, the Diethylene Glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol monoacetate list ether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxyl group butylacetic acid ester, the tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, the 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, the acetic acid dihydroxypropane single-ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, the 3-methoxy methyl propionate, 3-ethoxy-propionic acid methylethyl ester, 3-methoxy propyl acetoacetic ester, the 3-ethoxy-propionic acid, the 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, the 1-methoxy-2-propanol, 1-oxyethyl group-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, the propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic ester, the mono-ether of propylene glycol-1--2-acetic ester, dipropylene glycol, 2-(2-oxyethyl group propoxy-) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, the organic solvent with low surface tension of n-butyl lactate or isoamyl lactate etc. etc.These Weak solvents can one or more mix use.While using Weak solvent as above, be better that polyimide film forms 1～50 quality % by the organic solvent total amount comprised in coating fluid, be more preferably 5～30 quality %.

As the homogeneity that improves thickness and the compound of surface smoothness, can exemplify fluorine class tensio-active agent, siloxane type surfactants, nonionic class tensio-active agent etc., specifically can exemplify for example エ Off トップ EF301, EF303, EF352 (the (トーケ of illuminating product Co., Ltd. system プロダ Network Star 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 forms total amount 100 mass parts with the component of polymer comprised in coating fluid with respect to polyimide film, is better 0.01～2 mass parts, is more preferably 0.01～1 mass parts.

Concrete example as the compound of the adaptation that improves polyimide film and substrate, can exemplify the 3-TSL 8330, APTES, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, 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)-APTESs of N-, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, the 1-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2-dibromoneopentyl glycol diglycidylether, 1,3,5,6-four glycidyl group-2, the 4-hexylene glycol, N, N, N ', N ' ,-four glycidyl group-m-xylene diamine, two (N, N-diglycidyl amino methyl) hexanaphthene or the N of 1-, N, N ', N ' ,-four glycidyl group-4, 4 '-diaminodiphenyl-methanes etc. contain the compound of functional silanes or contain the compound of epoxy group(ing).

While using the compound of these and substrate driving fit, forming by component of polymer total amount 100 mass parts that contain in coating fluid with respect to polyimide film of the present invention, is better 0.1～30 mass parts, is more preferably 1～20 mass parts.If less than 0.1 mass parts, can't expect the effect that adaptation improves, if more than 30 mass parts, the orientation variation of liquid crystal sometimes.

In addition, as long as in the scope of not damaging effect of the present invention, polyimide film of the present invention forms with dielectric medium and the conducting material that in coating fluid, can add be used to electrical characteristic such as the specific inductivity that changes polyimide film and electroconductibility.

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

This polyimide film of the present invention forms the liquid crystal aligning agent that can be used to form liquid crystal orientation film with coating fluid.Liquid crystal orientation film refers to be used to making the film of liquid crystal along the direction orientation of regulation.

By polyimide film formation of the present invention is coated to substrate with coating fluid, burn till, can form polyimide film.In addition, use polyimide film of the present invention to form while using coating fluid as liquid crystal aligning agent, it 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., thereby form liquid crystal orientation film.

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

Coating process on substrate is not particularly limited with coating fluid in polyimide film formation, the method that industrial common employing is coated with by silk screen printing, offset printing, flexographic printing, ink-jet etc.As other coating process, dip coating, rolling method, slot coated, spin-coating method etc. are arranged, can use these methods according to purpose.

Polyimide film is formed and coats on substrate with coating fluid, after making as required the part or all of drying of solvent, burn till.During this burnt till, the Michaelis acid structure of the difunctional compound meaned with following formula [A] as long as be heated to can become ketenes etc. and temperature that the carboxyl that had with polyimide precursor or polyimide etc. react.Such as heating installations such as utilizing hot-plate, recirculation furnace, infrared heating heating furnace, heat under 180～250 ℃, make the solvent evaporation, and Michaelis acid structure is reacted with polyimide precursor or polyimide, thereby can in polyimide precursor or polyimide, introduce the difunctional compound meaned with following formula [A], form polyimide film of the present invention.The polyimide film obtained as mentioned above passes through the difunctional compound meaned with following formula [A] and crosslinked structure because have polyimide, so become dura mater, anti-excellent in machinability.

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

Liquid crystal display device of the present invention is after by aforesaid method, obtaining the substrate with liquid crystal orientation film, manufactures by known method the liquid crystal display device that liquid crystal cells forms.If exemplify an example, it is the liquid crystal display device that possesses liquid crystal cells, this liquid crystal cells comprises: in opposite directions two substrates of configuration, be arranged at liquid crystal layer between substrate, be arranged at the above-mentioned liquid crystal orientation film between substrate and liquid crystal layer, this liquid crystal orientation film is formed with the liquid crystal aligning agent that coating fluid forms and is formed by polyimide film of the present invention.As this liquid crystal display device of the present invention, can exemplify the various liquid crystal display device such as twisted-nematic (TN:Twisted Nematic) mode, vertical orientated (VA:Vertical Alignment) mode, horizontal alignment (IPS:In-Plane Switching) mode.

As liquid crystal display device of the present invention substrate used, so long as the high substrate of the transparency gets final product, be not particularly limited, normally on substrate, be formed with the substrate be used to the transparency electrode that drives liquid crystal.As concrete example, can exemplify the substrate identical with the substrate put down in writing in above-mentioned polyimide film.

In addition, liquid crystal orientation film is by burning till and form after coating liquid crystal aligning agent of the present invention on this substrate, and details as mentioned above.

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

If exemplify an example of liquid crystal cells manufacture method, can exemplify following method: a pair of substrate of preparing to be formed with liquid crystal orientation film, on the liquid crystal orientation film of a substrate, scatter uniformly-spaced thing of pearl, make the liquid crystal aligning face become interior rear flank another baseplate-laminating, the method for liquid crystal sealing is injected in decompression; Or after on being scattered with the liquid crystal aligning face of spacer, dripping liquid crystal, the method that baseplate-laminating is sealed etc.The thickness of spacer now is 1～30 μ m preferably, more preferably 2～10 μ m.

The liquid crystal display device of making as mentioned above is to use the liquid crystal aligning agent contain the difunctional compound with following formula [A] expression that can introduce desired characteristic and at least one party in polyimide precursor and polyimide and the liquid crystal display device of making, so various characteristics can improve.

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 embodiment.

[difunctional compound meaned with following formula [A] synthetic]

With the compound 5 that following formula [4] means, 5'-'s (Isosorbide-5-Nitrae-phenylene two (azane two bases)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) is synthetic

[changing 22]

In the 300mL four-hole boiling flask, add 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

With the compound 5 that following formula [6] means, 5'-'s (1,3-phenylene two (azane two bases)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) is synthetic

[changing 23]

In the 300mL four-hole boiling flask, add 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

With the compound 5 that following formula [8] means, 5'-'s (pyridine-2,6-bis-bases two (azane two bases)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) is synthetic

[changing 24]

In the 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

With the compound 5 that following formula [10] means, 5'-'s (4,4'-methylene-bis (4,1-phenylene) two (azane two bases)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) is synthetic

[changing 25]

In the 300mL four-hole boiling flask, add 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

With the compound 5 that following formula [12] means, 5'-'s (two (4,1-phenylene) two (azane two bases) of 4,4'-oxygen base) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) is synthetic

[changing 26]

In the 200mL four-hole boiling flask, add 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

With the compound 5 that following formula [14] means, 5'-'s (two (4,1-phenylene) two (azane two bases) of 4,4'-azane, two bases) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) is synthetic

[changing 27]

In the 200mL four-hole boiling flask, add 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

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

[changing 28]

In the 500mL four-hole boiling flask, add 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

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

[changing 29]

In the 300mL four-hole boiling flask, add 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

With the compound 1 that following formula [20] means, two (4-((2,2-dimethyl-4,6-dioxo-1, the 3-diox-5-subunit) methylamino) styroyl) ureas of 3-synthetic

[changing 30]

In the 200mL four-hole boiling flask, add 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

With the compound 5 that following formula [22] means, 5'-(6,7,9,10,17,18,20,21-octahydro dibenzo [b, k] [1,4,7,10,13,16] six oxa-ring octadecynes-2,13-bis-bases) two (azane two bases) two (methane-1-base-1-subunits) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthetic

[changing 31]

In the 200mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

With the compound 5-((3-((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methylamino) benzylamino) methylene radical)-2 that following formula [24] means, 2-dimethyl-1,3-diox-4,6-diketone synthetic

[changing 32]

In the 300mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

With the compound 5 that following formula [26] means, 5'-'s (4,4'-(propane-1,3-bis-bases) two (piperidines-4,1-bis-bases)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) is synthetic

[changing 33]

In the 200mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

With the compound 5 that following formula [28] means, 5'-'s (propane-1,3-bis-bases two (azane two bases)) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) is synthetic

[changing 34]

In the 500mL four-hole boiling flask, add 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

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

[changing 35]

In the 500mL four-hole boiling flask, add Michaelis acid [1] (44.6g, 309mmol) and trimethyl orthoformate [2] (200g), carry out 1 hour reflux.Then add 1,3-diamino methylcyclohexane (cis/trans mixture) [29] (20.0g, 141mmol), then carry out 2 hours reflux.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

With the compound 3 that following formula [32] means, 5-two ((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methylamino) is benzoic synthetic

[changing 36]

In the 200mL four-hole boiling flask, add 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

With the compound 3 that following formula [34] means, two ((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methylamino)-N-(pyridin-3-yl methyl) benzamide of 5-synthetic

[changing 37]

In the 200mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

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

[changing 38]

In the 200mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

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

[changing 39]

In the 200mL four-hole boiling flask, add 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

With the compound 5 that following formula [40] means, 5'-'s (4-(dodecyloxy)-1,3-phenylene) two (azane two bases) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) is synthetic

[changing 40]

In the 300mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

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

[changing 41]

In the 100mL four-hole boiling flask, add 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

Compound 5 with following formula [44] expression, 5'-(4-(4-(trans-4-heptyl cyclohexyl) phenoxy group)-1,3-phenylene) two (2,2-dimethyl-1 of two (azane two bases) two (methane-1-base-1-subunit), 3-diox-4,6-diketone) synthetic

[changing 42]

In the 100mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

Compound 5 with following formula [46] expression, 5'-(4-(trans-4-(two (the hexanaphthene)-4-yls of trans-4'-amyl group) phenoxy group)-1, the 3-phenylene) two (azane two bases) two (methane-1-base-1-subunits) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthetic

[changing 43]

In the 300mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

Compound 5 with following formula [48] expression, 5'-(5-((trans-4-(two (the hexanaphthene)-4-yls of trans-4'-amyl group) phenoxy group) methyl)-1, the 3-phenylene) two (azane two bases) two (methane-1-base-1-subunits) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthetic

[changing 44]

In the 500mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

With the compound 3 that following formula [50] means, two (trans-the hexanaphthene)-4-base esters of two ((2,2-dimethyl-4,6-dioxo-1, the 3-diox-5-subunit) methylamino) phenylformic acid-4'-amyl groups of 5-synthetic

[changing 45]

In the 500mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

The compound N meaned with following formula [52]-(two ((2,2-dimethyl-4,6-dioxo-1, the 3-diox-5-subunit) methylamino) phenyl of 2,4-)-4-(trans-4-amyl group cyclohexyl) benzamide synthetic

[changing 46]

In the 300mL four-hole boiling flask, add 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

The compound N meaned with following formula [54]-(two ((2,2-dimethyl-4,6-dioxo-1, the 3-diox-5-subunit) methylamino) phenyl of 2,4-)-4-(trans-4-heptyl cyclohexyl) benzamide synthetic

[changing 47]

In the 300mL four-hole boiling flask, add 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 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).

With the compound 5 that following formula [56] means, 5'-(4-((3S, 8S, 9S, 10R, 13R, 14S, 17R)-10,13-dimethyl-17-((R)-5-methyl oneself-2-yl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-, ten tetrahydrochysenes-1H-encircles penta [a] phenanthrene-3-base oxygen base)-1, the 3-phenylene) two (azane two bases) two (methane-1-base-1-subunit) two (2,2-dimethyl-1,3-diox-4,6-diketone) is synthetic

[changing 48]

In the 100mL four-hole boiling flask, add 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.Reaction is cooled to room temperature by reaction soln after finishing, and filters the solid of separating out, and with the hexane washing, then makes solid drying, obtains 9.9g compound [56] (yield 99%).

With compound 3-(4-(oxygen base in the last of the ten Heavenly stems) phenyl) vinylformic acid (E)-2 that following formula [58] means, two ((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methylamino) the styroyl esters of 4-synthetic

[changing 49]

In the 200mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

With compound 3-(4-(oxygen base in the last of the ten Heavenly stems) phenyl) vinylformic acid (E)-3 that following formula [60] means, two ((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methylamino) the benzyl esters of 5-synthetic

[changing 50]

In the 200mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

With 5 of following formula [62] expression, 5'-(((6,7,9,10,17,18,20,21-octahydro dibenzo [b, k] [1,4,7,10,13,16] six oxa-ring octadecynes-2,14-bis-bases) two (azane two bases)) two (methyl subunits)) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthetic

[changing 51]

In the 200mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

With 5 of following formula [64] expression, 5'-'s ((Isosorbide-5-Nitrae, 10,13-, tetra-oxa-s-7,16-diazacyclo octadecane-7,16-bis-bases) two (methyl subunits)) two (2,2-dimethyl-1,3-diox-4,6-diketone) is synthetic

[changing 52]

In the 500mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, obtain 43.2g compound [64] (yield 100%).

With 5 of following formula [66] expression, 5'-(((((two (ethane-2 of oxygen base, 1-bis-bases)) two (oxygen bases)) two (4, the 1-phenylene)) two (azane two bases)) two (methyl subunits)) two (2,2-dimethyl-1,3-diox-4,6-diketone) synthetic

[changing 53]

In the 500mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

With following formula [68] mean 3, two (((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methyl) amino) phenylformic acid-2-(methacryloxy) ethyl esters of 5-synthetic

[changing 54]

In the 500mL four-hole boiling flask, add 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 finishes, after the 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).

With 3-(4'-butoxy-[1,1'-the phenylbenzene]-4-yl) vinylformic acid (E)-2 that following formula [70] means, two (((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methyl) amino) the styroyl esters of 4-synthetic

[changing 55]

In the 100mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

With 3-(4-cyclohexyl phenyl) vinylformic acid (E)-2 that following formula [72] means, two (((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methyl) amino) the styroyl esters of 4-synthetic

[changing 56]

In the 200mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

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

[changing 57]

In the 200mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

With 3-(4-(the trans-4-amyl group cyclohexyl) phenyl) vinylformic acid (E)-2 that following formula [76] means, two (((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methyl) amino) the styroyl esters of 4-synthetic

[changing 58]

In the 300mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

With 3-(4-(the trans-4-heptyl cyclohexyl) phenyl) vinylformic acid (E)-2 that following formula [78] means, two (((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methyl) amino) the styroyl esters of 4-synthetic

[changing 59]

In the 100mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

With 3-(4-(the trans-4-amyl group cyclohexyl) phenyl) vinylformic acid (E)-3 that following formula [80] means, two (((2,2-dimethyl-4,6-dioxo-1,3-diox-5-subunit) methyl) amino) the benzyl esters of 5-synthetic

[changing 60]

In the 300mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

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

[changing 61]

In the 200mL four-hole boiling flask, add 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 finishes, except desolventizing, carry out drying with vaporizer, 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).

[preparation of the synthetic and solution of polyamic acid or polyimide]

Hereinafter abbreviation 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)

The 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) is normal temperature gel permeation chromatography (GPC) device (GPC-101) that uses clear and electrician (Shodex) Co., Ltd. system, the post (KD-803 of Showa Denko K. K's system, KD-805), following mensuration.

Column temperature: 50 ℃

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

Flow velocity: 1.0ml/ minute

Calibration curve is made and to be used standard test specimen: (East ソー society of eastern Cao company) TSK standard polyethylene oxide processed (molecular weight approximately 900000,150000,100000,30000) and polymkeric substance laboratory company (Port リマーラボラトリー society) polyoxyethylene glycol processed (molecular weight approximately 12000,4000,1000).

(mensuration of imide rate)

In the present embodiment, the following mensuration of imide rate of polyimide.

The polyimide powder of about 20mg is added to the NMR stopple coupon, add the deuterate methyl-sulphoxide (DMSO-d of about 0.53ml ₆, the 0.05%TMS melange), by ultrasonic wave, make its dissolving fully.This solution is measured to the proton N MR of 500MHz with the NMR determinator.The imide rate is as described below tries to achieve: the proton that will come from the structure do not changed before and after imidization is decided to be the standard proton, utilize near the accumulated value of the proton peak of the NH base that comes from amido acid occurred the accumulated value of this proton peak and 10.0ppm, try to achieve by following formula.In following formula, x is the accumulated value of proton peak that comes from the NH base of amido acid, and y is the accumulated value of standard proton peak, and α is with respect to the number ratio of the standard proton of 1 NH matrix of amido acid during for polyamic acid (the imide rate is 0%).

Imide rate (%)=(1-α x/y) * 100

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

After in the 100mL four-hole boiling flask, adding DDM7.93g (40mmol), NMP (20g) and it being dissolved, be cooled to approximately 10 ℃, add NMP (67g) pulp solution of CBDA7.46g (38mmol), return to room temperature, reaction is 6 hours under nitrogen atmosphere, and the concentration that obtains polyamic acid (PAA-1) is the solution of 15 quality %.

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

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

After in the 200mL four-hole boiling flask, adding p-PDA8.65g (80mmol), NMP (49g) and it being dissolved, be cooled to approximately 10 ℃, add NMP (80g) pulp solution of CBDA14.1g (72mmol), return to room temperature, reaction is 6 hours under nitrogen atmosphere, and the concentration that obtains polyamic acid (PAA-2) is the solution of 15 quality %.

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

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

After in the 200mL four-hole boiling flask, adding p-PDA8.05g (74mmol), PCH7AB2.13g (5.6mmol), NMP (118g) and it being dissolved, be cooled to approximately 10 ℃, add NMP (100g) pulp solution of CBDA14.1g (72mmol), return to room temperature, reaction is 6 hours under nitrogen atmosphere, and the concentration that obtains polyamic acid (PAA-3) is the solution of 10 quality %.

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

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

In the 300mL four-hole boiling flask by BODA (16.9g, 68mmol), p-PDA (6.8g, 63mmol), PCH7AB (10.3g, 27mmol) in NMP (100g), mix, in reaction under 40 ℃, after 3 hours, add CBDA (4.1g, 21mmol) and NMP (52g), reaction is 3 hours under 40 ℃, obtains polyamic acid solution.After interpolation NMP is diluted to it 6 quality % in this polyamic acid solution (130g), add diacetyl oxide (16g), pyridine (12g) as imidization catalyst, reaction is 3 hours under 80 ℃.This reaction soln is put in methyl alcohol (1.6L) to the throw out that filtering separation obtains.By this throw out methanol wash, at 100 ℃ of lower drying under reduced pressure, obtain 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 with respect to repeating unit.

At the polyimide powder obtained as mentioned above (SPI-1), add NMP (98g), BCS (90g) in (12.0g), stir and made its dissolving in 40 hours under 80 ℃, make soluble polyimide (SPI-1) solution.

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

In the polyamic acid made as mentioned above (PAA-1) solution (10.0g), add the compound of record in the following table 1 made in the above-mentioned synthesis example as the compound meaned with following formula [A], make them with respect to the solids component (being polyamic acid (PAA-1)) of polyamic acid (PAA-1) solution, reach 10mol% respectively, under room temperature (25 ℃), stir, until become homogeneous solution, the polyimide film of making embodiment 1～9 forms with coating fluid (the functional polymer film forms and uses coating fluid).

[table 1]

In the polyamic acid made as mentioned above (PAA-1) solution (10.0g), add the compound of record in the following table 2 made in the above-mentioned synthesis example as the compound meaned with following formula [A], make them with respect to the solids component (being polyamic acid (PAA-1)) of polyamic acid (PAA-1) solution, reach respectively the ratio of record in following table 2, at room temperature stir, until become homogeneous solution, the polyimide film of making embodiment 10～34 forms uses coating fluid.

[table 2]

In the polyamic acid made as mentioned above (PAA-2) solution (10.0g), add the compound of record in the following table 3 made in the above-mentioned synthesis example as the compound meaned with following formula [A], make them with respect to the solids component (being polyamic acid (PAA-2)) of polyamic acid (PAA-2) solution, reach 10mol% respectively, at room temperature stir, until become homogeneous solution, the polyimide film of making embodiment 35～45 forms uses coating fluid.

[table 3]

In the polyamic acid made as mentioned above (PAA-3) solution (40.0g), add the compound of record in the following table 4 made in the above-mentioned synthesis example as the compound meaned with following formula [A], make them with respect to the solids component (being polyamic acid (PAA-3)) of polyamic acid (PAA-3) solution, reach respectively the quality % of record in table 4, at room temperature stir, until become homogeneous solution, the polyimide film of making embodiment 46～59 forms uses coating fluid.

[table 4]

In the polyamic acid made as mentioned above (PAA-2) solution (70.0g), add the compound of record in the following table 5 made in the above-mentioned synthesis example as the compound meaned with following formula [A], make them with respect to the solids component (being polyamic acid (PAA-2)) of polyamic acid (PAA-2) solution, reach respectively the ratio of record in following table 5, at room temperature stir, until become homogeneous solution, the polyimide film of making embodiment 60～62 forms uses coating fluid.

[table 5]

In the soluble polyimide made as mentioned above (SPI-1) solution (10.0g), add the compound of record in the following table 6 made in the above-mentioned synthesis example as the compound meaned with following formula [A], make them with respect to the solids component (being solubility polyimide (SPI-1)) of soluble polyimide (SPI-1) solution, reach respectively the ratio of record in following table 6, at room temperature stir, until become homogeneous solution, the polyimide film of making embodiment 63～76 forms uses coating fluid.

[table 6]

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

The polyimide film of above-described embodiment 63～72 is formed and to be spun on silicon wafer (2500rpm/30 second) with coating fluid, on the hot-plate of 230 ℃, carry out 30 minutes burn till, form film [a1].With the little slope institute system Surfcorder ET4000M of Co., Ltd., measure the thickness of film [a1] of gained.Then, the silicon wafer that will be formed with film [a1] is arranged at spin coater again, drip NMP, until the whole surface of silicon wafer all is capped, after standing 60 seconds, by NMP Rotary drying (1500rpm/30 second), on the hot-plate of 100 ℃, carry 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 a comparative example 1, for the soluble polyimide made as mentioned above (SPI-1) solution, the soluble polyimide solution that namely do not contain the compound meaned with following formula [A] also carries out same operation, calculates residual film ratio.The results are shown in table 7.

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

Consequently, confirm that the polyimide film that is added with the compound meaned with following formula [A] by use forms with coating fluid (aligning agent for liquid crystal), can improve the solvent resistance of film (polyimide film).Therefore infer, soluble polyimide is crosslinked under the effect of the compound meaned with following formula [A].Also confirm, by suitably selecting the difunctional compound with following formula [A] expression added, can more freely control the solvability of filming.

Similarly with the polyimide film formation of embodiment 1～62 and embodiment 73～76, form and film with coating fluid, carry out stripping test, consequently, with the example that does not add the compound meaned with following formula [A], compare, their residual film ratio is higher, confirmation is used coating fluid by the polyimide film formation that use is added with the compound meaned with following formula [A], can improve the solvent resistance of polyimide film.

[table 7]

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

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

Polyimide film is formed with coating fluid (liquid crystal aligning agent) and is spun on glass substrate or with the glass substrate of ito transparent electrode, after dry 70 seconds on the hot-plate of 80 ℃, formation thickness 100nm's films under the firing condition of regulation.

Then, process for the liquid crystal aligning that adopts friction, use the friction gear of roller diameter 120mm, this coated surface is rubbed under the friction condition of regulation with Artificial Fibers cloth, obtain the substrate with liquid crystal orientation film.For the liquid crystal aligning that adopts light, process, make straight line polarization UV light (UV wavelength 313nm, exposure intensity 8.0mW/cm ^-2) exposure between 0mJ～1000mJ, change, with respect to 40 ° of the normal slopes of plate, this coated surface is irradiated.Straight line 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 two and carried out as mentioned above the substrate with liquid crystal orientation film that liquid crystal aligning is processed, after on the liquid crystal aligning face of, scattering the spacer of 6 μ m therein, printing and sealing agent from the upper side, by another piece baseplate-laminating, make the liquid crystal aligning face toward each other, frictional direction (the antiparallel type liquid crystal cells that is parallel to each other, embodiment 87～116) or quadrature (twisted nematic liquid crystals unit, embodiment 155～179, embodiment 296～315, embodiment 316～321), perhaps for the substrate irradiated through UV, in the mode that the polarization direction of light with irradiating is parallel, fitting, (vertical alignment mode is with antiparallel type liquid crystal cells, embodiment 180～182, 183～294), make sealant cures, make dummy cell.For antiparallel type liquid crystal cells, by the decompression injection method, inject liquid crystal MLC-2003 (Merck & Co., Inc.'s system) in this dummy cell, for the twisted nematic liquid crystals unit, by the decompression injection method, inject the liquid crystal MLC-2003 (Merck & Co., Inc.'s system) that is added with the chirality agent in this dummy cell, for vertical alignment mode antiparallel type liquid crystal cells, by the decompression injection method, inject liquid crystal MLC-6608 (Merck & Co., Inc.'s system) in this dummy cell, by the inlet sealing, obtain each liquid crystal cells.

[evaluation of liquid crystal cells]

The method of the mensuration of the physical property of each liquid crystal cells made and the evaluation of characteristic is as described below.The liquid crystal orientation film that each makes in measuring, estimating and substrate, firing condition and the friction condition of liquid crystal cells illustrate in the lump.

The polyimide film prepared in each embodiment shown in use table 8 is formed and clamps with polaroid with the liquid crystal cells that coating fluid makes, from rear portion, irradiating under state backlight and make the liquid crystal cells rotation, whether be orientated according to the variation of light and shade and the liquid crystal that detects by an unaided eye that has or not of flow orientation.Now, according to following standard, estimate.For the liquid crystal cells preparation as described below made for the liquid crystal aligning evaluation: use glass substrate as substrate, polyimide film is formed to the firing condition of filming with coating fluid and be made as and on the hot-plate of 230 ℃, burnt till 30 minutes being heated to, friction condition is made as to roller rotating speed 300rpm, roller gait of march 50mm/sec, the amount of being pressed into 0.15mm.In addition, preparation do not add using compound that following formula [A] means and linking agent coating fluid (comparative example 2) and be added with the coating fluid (comparative example 3 or comparative example 4) as the following linking agent of common commercially available linking agent, comparative effectiveness in the lump.The results are shown in table 8.

Judgement criteria

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

Zero: although liquid crystal is orientated, observe some flow orientation

*: although liquid crystal is orientated, observe much flow orientation

[changing 64]

Consequently, when confirmation is used commercially available linking agent as shown in comparative example 3 and comparative example 4, the easy affected tendency of orientation that liquid crystal is arranged usually, and use the polyimide film that is added with the compound meaned with formula [A] of the present invention to form while using coating fluid, the orientation of liquid crystal can be do not affected, according to circumstances also orientation can be improved.

[table 8]

With the polyimide film prepared in each embodiment shown in confocal laser microscopic examination use table 9-1～table 9-2, form the surface of the liquid crystal orientation film made with coating fluid, estimate according to following standard.Use with the glass substrate of ito transparent electrode as substrate, polyimide film is formed to the firing condition of filming with coating fluid to be made as and on the hot-plate of 230 ℃, to burn till 30 minutes being heated to, friction condition is made as to roller rotating speed 1000rpm, roller gait of march 50mm/sec, the amount of being pressed into 0.5mm, thereby makes.In addition, the coating fluid (comparative example 5 and comparative example 6) of the compound meaned with following formula [A], comparative effectiveness are not in the lump added in preparation.The results are shown in table 9-1～table 9-2.

Zero: do not observe grinding and friction scar.

△: observe grinding and friction scar.

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

Consequently, confirm to compare with comparative example 6 with the comparative example 5 that does not add the compound meaned with following formula [A], use the polyimide film that is added with the compound meaned with following formula [A] of the present invention to form while using coating fluid, can improve anti-machinability with any polymkeric substance.

[table 9-1]

[table 9-2]

For the polyimide film prepared in each embodiment shown in use table 10, form the liquid crystal cells made with coating fluid, after 5 minutes, carry out the mensuration of tilt angle in heating under 105 ℃.Tilt angle adopts the Muller matrix method to measure with " the Axo Scan " of Axo Metrix company.The liquid crystal cells preparation as described below made for the tilt angle be used to measuring the twisted nematic liquid crystals unit: use glass substrate with ito transparent electrode as substrate, polyimide film is formed to the firing condition of filming with coating fluid and be made as and on the hot-plate of 230 ℃, burnt till 30 minutes being heated to, friction condition is made as to roller rotating speed 1000rpm, roller gait of march 50mm/sec, the amount of being pressed into 0.3mm.In addition, the coating fluid (comparative example 7) of the compound meaned with following formula [A], comparative effectiveness are not in the lump added in preparation.The results are shown in table 10.

Consequently, confirm can at random obtain desired tilt angle by suitably selecting kind and the addition of the compound meaned with following formula [A].

[table 10]

For the polyimide film prepared in each embodiment shown in use table 11, form the liquid crystal cells made with coating fluid, after 1 hour, carry out the mensuration of tilt angle in heating under 120 ℃.Tilt angle adopts the Muller matrix method to measure with " the Axo Scan " of Axo Metrix company.The liquid crystal cells made as the tilt angle for be used to measuring antiparallel type liquid crystal cells, use with the glass substrate of ito transparent electrode as substrate, polyimide is formed to the firing condition of filming with coating fluid to be made as in being heated to the heated air circulation type stove of 200 ℃ and to burn 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 meaned with following formula [A], comparative effectiveness are not in the lump added in preparation.The results are shown in table 11.

Consequently, confirm to compare with the comparative example 8 that does not add the compound meaned with following formula [A], use the polyimide film that is added with the compound meaned with following formula [A] to form while using coating fluid, can increase significantly tilt angle.Therefore, by adding the compound meaned with following formula [A], even not at matrix polymer, be the side chain composition that during polyimide film formed the polyimide precursor contained with coating fluid or polyimide, introducing erected liquid crystal, also can make liquid crystal vertical-tropism.

[table 11]

Use is shown to the polyimide film prepared in each embodiment shown in 12-1～12-4 formation clamps with polaroid with the liquid crystal cells that coating fluid makes, from rear portion, irradiating under state backlight liquid crystal cells is rotated, whether according to the variation of light and shade and the liquid crystal that detects by an unaided eye that has or not of flow orientation, be orientated, 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 is orientated.Now, according to following standard, estimate.For the liquid crystal cells preparation as described below made for the liquid crystal aligning evaluation: use glass substrate as substrate, polyimide film is formed to the firing condition of filming with coating fluid and be made as in being heated to the heated air circulation type stove of 200 ℃ and burnt till 30 minutes, the glass substrate that the band of gained is filmed carries out being prepared after above-mentioned smooth orientation process.

Judgement criteria

Well: can confirm the orientation of liquid crystal, and without flow orientation

Bad: as although liquid crystal is orientated, to observe much flow orientation

In addition, for the polyimide film prepared in each embodiment shown in use table 12-1～12-4, form the liquid crystal cells made with coating fluid, after 1 hour, carry out the mensuration of tilt angle in heating under 120 ℃.Tilt angle adopts the Muller matrix method to measure with " the Axo Scan " of Axo Metrix company.

Consequently, confirmation forms with coating fluid (aligning agent for liquid crystal), even also can obtain good vertical orientated property in the situation that carried out the light orientation process by the polyimide film that use is added with the compound with following formula [A] expression with photoreactivity side chain.Also confirmation in addition, by polyimide film of the present invention being formed to the ultraviolet ray of irradiating polarization with coating fluid (aligning agent for liquid crystal), it has the ability that liquid crystal is orientated with the state that omits low dip with respect to vertical direction.Can also confirm, by controlling addition and irradiation dose, can finely tune tilt angle.Hence one can see that, and polyimide film of the present invention forms can be for the liquid crystal orientation film of the used for liquid crystal display element of vertical orientation mode with coating fluid (aligning agent for liquid crystal), and also can be as the liquid crystal orientation film used in optical alignment method.

[table 12-1]

[table 12-2]

[table 12-3]

[table 12-4]

For the polyimide film prepared in each embodiment shown in use table 13, form the liquid crystal cells made with coating fluid, carry out the voltage retention of original state and measure.The mensuration of voltage retention is the voltage 60 μ s that apply 4V at the temperature of 90 ℃, and the voltage after mensuration 16.67ms, calculate voltage and can remain to which kind of degree, as voltage retention.Mensuration use Japan (East Yang テ of scientific & technical corporation Network ニカ society of voltage retention) the VHR-1 voltage retention determinator of system.For the liquid crystal cells the made preparation as described below be used to measuring voltage retention (VHR): use glass substrate with ito transparent electrode as substrate, polyimide film is formed to the firing condition of filming with coating fluid and be made as and on the hot-plate of 230 ℃, burnt till 30 minutes being heated to, friction condition is made as to roller rotating speed 1000rpm, roller gait of march 50mm/sec, the amount of being pressed into 0.3mm.In addition, the coating fluid (comparative example 9) of the compound meaned with following formula [A], comparative effectiveness are not in the lump added in preparation.The results are shown in table 13.

Consequently, confirm to form and to use coating fluid by the polyimide film that use is added with the compound meaned with following formula [A], can obtain and compare more good voltage retention characteristic when not adding.

[table 13]

For the polyimide film prepared in each embodiment shown in use table 14, form the twisted nematic liquid crystals unit made with coating fluid, interval with 0.1V at the temperature of 23 ℃ applies the voltage from 0V to 1.0V, measure the flickering level under each voltage, make calibration curve.After ground connection 5 minutes, apply voltage of alternating current 3.0V, volts DS 5.0V, measure the flickering level after 1 hour, estimate RDC (flicker reference entry) by contrasting ready-made calibration curve.The liquid crystal cells the made preparation as described below in order to accumulate electric charge (RDC) for estimation: use glass substrate with ito transparent electrode as substrate, polyimide film is formed to the firing condition of filming with coating fluid and be made as and on the hot-plate of 230 ℃, burnt till 30 minutes being heated to, friction condition is made as to roller rotating speed 1000rpm, roller gait of march 50mm/sec, the amount of being pressed into 0.3mm.In addition, the coating fluid (comparative example 10) of the compound meaned with following formula [A], comparative effectiveness are not in the lump added in preparation.The results are shown in table 14.

Consequently, confirmation is used coating fluid by the polyimide film formation that use is added with the compound meaned with following formula [A], can obtain the liquid crystal cells that RDC is little.

[table 14]

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

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

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

In above-mentioned polyamic acid (PAA-1) solution (10.0g), add as the compound shown in the table 15 made in the synthesis example of modifying with compound, make them with respect to the solids component (being polyamic acid (PAA-1)) of polyamic acid (PAA-1) solution, reach respectively the ratio of record in following table 15, at room temperature stir, until become homogeneous solution, make polyimide film formation coating fluid.

Then, for using respectively these polymeric films to form the twisted nematic liquid crystals unit made from coating fluid (liquid crystal aligning agent), measure the ion density of original state (23 ℃), and the ion density of carrying out after keeping 30 hours (aging) under 60 ℃ is measured.During ion density is measured, measure the ion density when liquid crystal cells is applied to the choppy sea of voltage ± 10V, frequency 0.01Hz.Measuring temperature carries out under 80 ℃.Determinator is all used Japan scientific & technical corporation system 6245 type liquid crystal evaluation of physical property devices in each is measured.The results are shown in table 15.

In addition, except polyimide film being formed to the firing condition of filming with coating fluid, be made as being heated on the hot-plate of 200 ℃ to burn till 30 minutes, carry out the operation same with above-mentioned twisted nematic liquid crystals unit (embodiment 155～179), make the twisted nematic liquid crystals unit.In addition, for not adding to modify, also carry out same operation, comparative result in the lump with the coating fluid of compound.

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

[table 15]

In the polyamic acid made as mentioned above (PAA-1) solution (10.0g), add the compound as record in the following table 16 made in the above-mentioned synthesis example of modifying with compound, make them with respect to the solids component (being polyamic acid (PAA-1)) of polyamic acid (PAA-1) solution, reach respectively the ratio of record in following table 16, at room temperature stir, until become homogeneous solution, the polyimide film of making embodiment 330～342 forms uses coating fluid.

[table 16]

In the polyamic acid made as mentioned above (PAA-3) solution (40.0g), add the compound as record in the following table 17 made in the above-mentioned synthesis example of modifying with compound, make them with respect to the solids component (being polyamic acid (PAA-3)) of polyamic acid (PAA-3) solution, reach respectively the quality % of record in table 17, at room temperature stir, until become homogeneous solution, the polyimide film of making embodiment 343～344 forms uses coating fluid.

[table 17]

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

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

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

Polyimide film is formed and to be spun on glass substrate with coating fluid (liquid crystal aligning agent), after dry 70 seconds on the hot-plate of 80 ℃, burnt till 30 minutes in being heated to the heated air circulation type stove of 200 ℃, formation thickness 100nm films.

Then, make straight line polarization UV light (UV wavelength 313nm, exposure intensity 8.0mW/cm ^-2) exposure between 0mJ～1000mJ, change, with respect to 40 ° of the normal slopes of plate, this coated surface is irradiated.Straight line 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 two and carried out as mentioned above the substrate with liquid crystal orientation film that liquid crystal aligning is processed, after on the liquid crystal aligning face of, scattering the spacer of 6 μ m therein, printing and sealing agent from the upper side, by another piece baseplate-laminating, make the liquid crystal aligning face toward each other, the polarization direction of light of irradiating is parallel, make sealant cures, make dummy cell.Adopt the decompression injection method, inject liquid crystal MLC-6608 (Merck & Co., Inc.'s system) in this dummy cell, by the inlet sealing, obtain each vertical alignment mode antiparallel type liquid crystal cells.

Whether then, the above-mentioned liquid crystal cells made is clamped with polaroid, from rear portion, irradiating under state backlight and make the liquid crystal cells rotation, be orientated according to the variation of light and shade and the liquid crystal that detects by an unaided eye that has or not 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 is orientated.Now, according to following standard, estimate.The results are shown in table 18-1～18-4.

Judgement criteria

Bad: as although liquid crystal is orientated, to observe much flow orientation

In addition, for the above-mentioned liquid crystal cells made, after 1 hour, carry out the mensuration of tilt angle in heating under 120 ℃.Tilt angle adopts the Muller matrix method to measure with " the Axo Scan " of Axo Metrix company.The results are shown in table 18-1～table 18-4.

Consequently, as show as shown in 18-1～18-4, confirmation is added with the modification with photoreactivity side chain and forms with coating fluid (aligning agent for liquid crystal), even also can obtain good vertical orientated property in the situation that carried out the light orientation process with the polyimide film of compound by use.Also confirmation in addition, by polyimide film of the present invention being formed to the ultraviolet ray of irradiating polarization with coating fluid (aligning agent for liquid crystal), it has the ability that liquid crystal is orientated with the state that omits low dip with respect to vertical direction.Can also confirm, by controlling addition and irradiation dose, can finely tune tilt angle.Hence one can see that, and polyimide film of the present invention forms can be for the liquid crystal orientation film of the used for liquid crystal display element of vertical orientation mode with coating fluid (aligning agent for liquid crystal), and also can be as the liquid crystal orientation film used in optical alignment method.

[table 18-1]

[table 18-2]

[table 18-3]

[table 18-4]

In the polyamic acid made as mentioned above (PAA-1) solution (10.0g), add the compound as record in the following table 19 made in the above-mentioned synthesis example of modifying with compound, make them with respect to the solids component (being polyamic acid (PAA-1)) of polyamic acid (PAA-1) solution, reach respectively the ratio of record in following table 19, at room temperature stir, until become homogeneous solution, the polyimide film of making embodiment 448～471 forms uses coating fluid.

[table 19]

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

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

Then, make straight line polarization UV light (UV wavelength 313nm, exposure intensity 8.0mW/cm ^-2) exposure between 0mJ～1000mJ, change, with respect to substrate from directly over this coated surface is irradiated.Straight line 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 two and carried out as mentioned above the substrate with liquid crystal orientation film that liquid crystal aligning is processed, after on the liquid crystal aligning face of, scattering the spacer of 6 μ m therein, printing and sealing agent from the upper side, by another piece baseplate-laminating, make the liquid crystal aligning face toward each other, the polarization direction of light of irradiating is parallel, make sealant cures, make dummy cell.Adopt the decompression injection method, inject liquid crystal MLC-2041 (Merck & Co., Inc.'s system) in this dummy cell, by the inlet sealing, obtain horizontal alignment pattern antiparallel type liquid crystal cells.

Then, the above-mentioned horizontal alignment pattern made is clamped with polaroid with antiparallel type liquid crystal cells, from rear portion, irradiating under state backlight and make the liquid crystal cells rotation, whether be orientated according to the variation of light and shade and the liquid crystal that detects by an unaided eye that has or not of flow orientation.Now, according to following standard, estimate.The results are shown in table 20.

Judgement criteria

Zero: although liquid crystal is orientated, observe some flow orientation

△: although liquid crystal is orientated, observe much flow orientation

*: liquid crystal is fully non-oriented

Consequently, confirm not carry out light-struck liquid crystal cells and do not demonstrate orientation fully, and carried out in light-struck liquid crystal cells in each liquid crystal cells, liquid crystal is orientated by addition and the rayed amount of compound according to modifying.In addition, even, in the situation that the isotropy of under 130 ℃, each liquid crystal cells that confirms orientation being carried out 30 minutes is processed, also unconfirmedly to orientation, have significant change.That is, confirm by kind and the addition of suitably selecting additive, easily manufacture level orientation unit.

[table 20]

Claims

1. polyimide film forms and uses coating fluid, it is characterized in that, contain polymkeric substance and difunctional compound, described polymkeric substance be selected from polyimide precursor and by this polyimide precursor imidization and polyimide at least a, at least a tetracarboxylic acid composition and two amine components of described polyimide precursor by making to be selected from tetracarboxylic acid and derivative thereof carry out polyreaction and obtain, described difunctional compound be on two amino of diamine compound, introduce respectively Michaelis acid structure and the difunctional compound meaned with following formula [A];

[changing 1]

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

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

3. polyimide film, is characterized in that, polyimide film claimed in claim 1 is formed with coating fluid and coats substrate and burn till and obtain.

4. polyimide film, it is characterized in that, by polymkeric substance under the effect of difunctional compound crosslinked and polyimide form, described polymkeric substance be selected from polyimide precursor and by this polyimide precursor imidization and polyimide at least a, at least a tetracarboxylic acid composition and two amine components of described polyimide precursor by making to be selected from tetracarboxylic acid and derivative thereof carry out polyreaction and obtain, described difunctional compound be on two amino of diamine compound, introduce respectively Michaelis acid structure and the difunctional compound meaned with following formula [A];

[changing 2]

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

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