CN102395614A - Photosensitive polyester composition for use in forming thermally cured film - Google Patents

Abstract

Disclosed is a material which enables pattern formation in an alkaline developer, and shows high solvent resistance, liquid crystal orientation, heat resistance, high transparency, and high planarity after being formed into a cured film, and can be dissolved in a glycol solvent which can be applied to the production line of a planarized film of a color filter while being formed into a cured film. Specifically disclosed is a photosensitive polyester composition for use in forming thermally cured film, containing component (A), component (B), component (C), and component (D): component (A): a modified polyester obtained by reacting a compound having a functional group selected from a glycidyl group and an isocyanate group with a polyester containing a structural unit represented by formula (1); component (B): an epoxy compound having two or more epoxy groups; component (C): an amino group-containing carboxylic acid compound obtained by reacting a diamine compound with dicarboxylic acid dianhydride; and component (D): 1,2-quinone diazide compound. In formula (1), A and B each independently represent an organic group containing a cyclic structure.

Description

The thermofixation film forms uses the photosensitivity polymer blend

Technical field

The present invention relates to the thermofixation film forms with photosensitivity polymer blend and the cured film that formed by said composition.More specifically, the thermofixation film that the present invention relates to form the cured film that has high transparent, smooth voltinism and have liquid crystal aligning ability, high solvent resistance forms with photosensitivity polymer blend and cured film thereof, and relates to the application of this cured film.This thermofixation film forms with the photosensitivity polymer blend preferred especially as the colour filter overcoating agent that has the liquid crystal aligning function concurrently in the liquid-crystal display.

Background technology

Generally speaking, in optics such as liquid crystal display device, organic EL (electroluminescent) element, solid-state imager, be provided with protective membrane in order to prevent element surface in manufacturing process, to be exposed to solvent and/or heat.For this protective membrane, not only requirement is high with the tack of the substrate of being protected, solvent resistance is high, also requires performances such as the transparency, thermotolerance.

Such protective membrane is under the situation that the protective membrane as the colour filter that is used for color liquid crystal display arrangement, solid-state imager uses; General requirement has the colour filter that makes its basal substrate or the performance of black matrix resin planarization, promptly as the performance of planarization film.Particularly when making the color liquid crystal display device of STN mode or TFT mode, need very strictly to control the bonding precision between filter substrate and the subtend substrate, must make the cel-gap between substrate even.In addition, in order to keep optical transmission rate, need high transparent as these planarization films of its protective membrane through colour filter.

On the other hand, studied in recent years through in the liquid crystal cell of liquid-crystal display, importing the phase differential material and realized cost degradation, lightweight, such phase differential material generally use the coating of liquid crystalline monomer make its orientation, then make its photocuring and material.In order to make this phase differential material orientation, needing lower membrane is the material that after friction treatment, has orientation.Thereby form phase differential material (with reference to Fig. 2 (a)) after film forming goes out liquid crystal aligning layer on the outer covering layer of colour filter.If can form the film (with reference to Fig. 2 (b)) of the outer covering layer of holding a concurrent post this liquid crystal aligning layer and colour filter, then cost degradation can be obtained, technology is counted greater advantages such as minimizing, the such material of therefore strong expectation.

Generally speaking, the outer covering layer of this colour filter uses the high acrylic resin of the transparency.From security, operability, prevent the viewpoint of pigment composition, glycol series solvent and/or ester series solvents such as ethyl lactate, n-Butyl lactate such as the propylene glycol monomethyl ether that in such acrylic resin, is widely used, propylene glycol methyl ether acetate from the colour filter stripping.Such acrylic resin is given thermotolerance, solvent resistance (patent documentation 1,2) through thermofixation, photocuring.Yet,, can not show sufficient orientation even such planarization film is carried out friction treatment though existing Thermocurable, light solidified acrylic resin demonstrate the suitable transparency, smooth voltinism.

On the other hand, liquid crystal aligning layer uses the material that comprises solvent soluble polyimide and/or polyamic acid usually.Reported and can give solvent resistance, shown sufficient orientation (patent documentation 3) through friction treatment through making these materials complete imidization when afterwards toasting.Yet, under the situation of the planarization film of these materials being processed colour filter, have problems such as the smooth voltinism and the transparency reduce significantly.

In addition, in order to improve smooth voltinism, polyester-polyamide acid, polyester-polyimide copolymer (patent documentation 4) have been reported.Yet; Though these polyester-polyamide acid, polyester-polyimide copolymer also likewise dissolve in N-Methyl pyrrolidone, gamma-butyrolactone equal solvent with polyimide, polyamic acid; But the solvability to glycol series solvent, ester series solvent is low; Pigment composition, liquid crystal pollution composition taking place from the colour filter stripping, thereby is difficult to be applicable to the planarization film production line when the polyimide film production.

In addition, in order to improve the adhesion strength of the sealing material that uses with the base plate bonding of tft array side the time, preferably can use photo-mask process to remove the film of adhesive segment.

In addition, the planarization film that does not also have report to have photosensitivity, display orientation property up to now.

Patent documentation 1: TOHKEMY 2000-103937 communique

Patent documentation 2: TOHKEMY 2000-119472 communique

Patent documentation 3: TOHKEMY 2005-037920 communique

Patent documentation 4: TOHKEMY 2008-033244 communique

Summary of the invention

Problem to be solved by this invention

The present invention is based on the above-mentioned fact and proposes; Problem to be solved provides and can form pattern through alkaline-based developer; Form the back in cured film and show high solvent resistance, liquid crystal aligning property, high transparent and high smooth voltinism, and can be in when cured film forms applicable to the glycol series solvent of the production line of the planarization film of colour filter and lactate series solvent the dissolved material.

Be used to solve the method for problem

The present inventor furthers investigate in order to solve above-mentioned problem, and the result has accomplished the present invention.

That is, as the 1st viewpoint, relate to a kind of thermofixation film and form and use the photosensitivity polymer blend, it contains (A) composition, (B) composition, (C) composition and (D) composition,

(A) composition: make the polyester polyester that the warp that gets modified with having the compound reaction that is selected from the functional group in glycidyl and the NCO that comprises structural unit shown in the following formula (1),

(B) composition: have the epoxy compounds of 2 above epoxy group(ing),

(C) composition: the reaction of diamine compound and dicarboxylic acid dianhydride and contain amino carboxylic acid cpd,

(D) composition: 1, the 2-quinone di-azido compound,

In the formula, A is illustrated in the 4 valency organic groups that are combined with 4 connecting keys on ester ring type skeleton or the aliphatics skeleton, and B is illustrated in the divalent organic group that is combined with 2 connecting keys on ester ring type skeleton or the aliphatics skeleton.

As the 2nd viewpoint; Relate to the described thermofixation film formation of the 1st viewpoint and use the photosensitivity polymer blend; Wherein, The polyester that comprises structural unit shown in the above-mentioned formula (1) be tetracarboxylic dianhydride's composition of comprising tetracarboxylic dianhydride shown in the following formula (i) with comprise following formula (ii) shown in diol compound the diol component reaction and polyester

HO-B-OH (ii)

Formula (i) and (ii) in, A and B are identical with definition implication in the above-mentioned formula (1).

As the 3rd viewpoint; Relate to the described thermofixation film formation of the 1st viewpoint or the 2nd viewpoint and use the photosensitivity polymer blend; In the above-mentioned formula (1); A representes to be selected from least a group in the group shown in following formula (A-1)～formula (A-8), and B representes to be selected from least a group in the group shown in following formula (B-1)～formula (B-5)

As the 4th viewpoint, relate to the described thermofixation film of each of the 1st viewpoint～the 3rd viewpoint and form and use the photosensitivity polymer blend, wherein, it is 1,000～3,000 weight-average molecular weight that the polyester through modification of said conduct (A) composition has with polystyrene conversion.

As the 5th viewpoint; Each the described thermofixation film that relates to the 1st viewpoint～the 4th viewpoint forms uses the photosensitivity polymer blend; Wherein, said (C) composition is the carboxylic acid cpd that contains amino that 1 mole of diamine compound gets with dicarboxylic acid dianhydride 1.7～2 molar reactives.

As the 6th viewpoint; Each the described thermofixation film that relates to the 1st viewpoint～the 5th viewpoint forms uses the photosensitivity polymer blend; Wherein, Based on said (A) composition 100 mass parts, contain said (B) composition of 3～50 mass parts, said (C) composition of 3～50 mass parts, said (D) composition of 5～80 mass parts respectively.

As the 7th viewpoint, each the described thermofixation film that relates to the 1st viewpoint～the 5th viewpoint forms uses the photosensitivity polymer blend, wherein, also contains bismaleimide compound as (E) composition.

As the 8th viewpoint, relate to the described thermofixation film formation of the 6th viewpoint and use the photosensitivity polymer blend, wherein,, contain the 7th viewpoint described (E) composition of 0.5～50 mass parts based on said (A) composition 100 mass parts.

As the 9th viewpoint, each the described thermofixation film that relates to by the 1st viewpoint～the 8th viewpoint forms the cured film that forms with the photosensitivity polymer blend.

As the 10th viewpoint, relate to each the described thermofixation film that uses the 1st viewpoint～the 8th viewpoint and form the liquid crystal aligning layer that obtains with the photosensitivity polymer blend.

The effect of invention

Thermofixation film of the present invention forms can form the cured film that has photosensitivity and have high smooth voltinism, high transparent, high solvent resistance, high heat resistance and liquid crystal aligning ability with the photosensitivity polymer blend, therefore can be used as the formation material of liquid crystal orientation film, planarization film.Particularly can the independent liquid crystal orientation film that forms and the outer covering layer of colour filter in the past once be formed as " liquid crystal aligning layer " that have both both characteristics, realize cost degradation etc. thereby simplification that can be through manufacturing process and technology number reduce.

In addition, thermofixation film of the present invention forms and dissolves in glycol series solvent and lactate series solvent with the photosensitivity polymer blend, so can be suitable for mainly using the production line of the planarization film of these solvents.

Description of drawings

Fig. 1 is the synoptic diagram of the cured film that forms when being presented at coated heat curable polyester compsn on the step difference substrate.

Fig. 2 shows to form the synoptic diagram with liquid crystal aligning layer (b) the contrast demonstration of photosensitivity polymer blend with having used thermofixation film of the present invention through the liquid crystal aligning layer (a) that prior art obtains.

Embodiment

As stated, in the cured film of acrylic resin that up to the present proposes and polyimide resin system, also there is not fully to satisfy the cured film of all properties such as liquid crystal orientation film, the desired smooth voltinism of planarization film, the transparency, orientation.

In addition; Proposed to use the scheme (with reference to japanese kokai publication hei 5-158055 communique, TOHKEMY 2002-229039 communique) of polyester up to now as the oriented material of liquid crystal display device; But these materials all do not have Thermocurable, the poor solvent resistance of formed film.

Therefore, characteristic of the present invention is to use the Thermocurable polyester to realize the raising of above-mentioned performance.Promptly; The present invention is 1 of the carboxylic acid cpd that contains amino that contains the epoxy compounds with 2 above epoxy group(ing) as the polyester of (A) composition, conduct (B) composition, conduct (C) composition, conduct (D) composition, and the photosensitivity polymer blend is used in the thermofixation film formation of 2-quinone di-azido compound.In addition, the present invention is except containing (A) composition, (B) composition, (C) composition, (D) the composition, can also containing bismaleimide compound and use the photosensitivity polymer blend as the thermofixation film formation of (E) composition.

Below, specify each composition.

(A) composition

(A) polyester of composition be make the polyester that comprises structural unit shown in the following formula (1) (below be also referred to as particular polymers) with having the compound reaction that is selected from the functional group in glycidyl and the NCO the polyester through modification.Be preferably and make the polyester polyester that the warp that gets modified with having the compound reaction that is selected from the functional group in glycidyl and the NCO that constitutes by structural unit shown in the following formula (1).

(in the formula, A is illustrated in the 4 valency organic groups that are combined with 4 connecting keys on ester ring type skeleton or the aliphatics skeleton, and B is illustrated in the divalent organic group that is combined with 2 connecting keys on ester ring type skeleton or the aliphatics skeleton.)

Above-mentioned A is preferably the group shown in following formula (1A1), formula (1A2) or the formula (1A3).

Formula (1A1), (1A2) and (1A3) in, A ¹Expression ring-type saturated hydrocarbyl, R ¹The saturated hydrocarbyl of expression singly-bound, ehter bond, carbonyl, sulfonic group, carbonatoms 1～8 or by the saturated hydrocarbyl of the substituted carbonatoms 1～8 of fluorine atom.R in addition ²The saturated hydrocarbyl of expression carbonatoms 1～8.}

In the above-mentioned formula, A ¹The cyclic saturated hydrocarbon base of preferred expression carbonatoms 4～8 is more preferably represented the cyclic saturated hydrocarbon base of carbonatoms 4～6.A in addition ¹Contained any Wasserstoffatoms can be replaced by aliphatic group independently of one another in the base, and 2 substituting groups wherein can be bonded to each other and form 4～6 yuan of rings.

Here, be preferably the aliphatic group of carbonatoms 1～5, the more preferably aliphatic group of carbonatoms 1～3 as this substituent aliphatic group.Combine and form under the situation of ring at these substituting groups, the fused polycyclic alkyl that forms for example endocyclic such as norbornene, adamantyl alkyl, a part or all be hydrogenated.

In addition, R ¹The saturated hydrocarbyl of preferred expression singly-bound, ehter bond, carbonyl, sulfonic group, carbonatoms 1～5 or by the saturated hydrocarbyl of the substituted carbonatoms 1～5 of fluorine atom.

In addition, R ²The saturated hydrocarbyl of preferred expression carbonatoms 1～5 is more preferably represented the saturated hydrocarbyl of carbonatoms 1～3.

The preferred object lesson as the A of 4 valency organic groups in the above-mentioned formula (1) is shown in following formula (A-1)～formula (A-8).In the group shown in following formula (A-1)～formula (A-8), A is preferably the group that is selected from following formula (A-1) or the formula (A-2) especially.

In the above-mentioned formula (1), B is illustrated in the divalent organic group that is combined with 2 connecting keys on ester ring type skeleton or the aliphatics skeleton, is preferably the group shown in following formula (1B1) or the formula (1B2).

Formula (1B1) and (1B2) in, B ¹Expression ring-type saturated hydrocarbyl, B ²The expression phenylene.In addition, R ³The saturated hydrocarbyl of expression singly-bound, ehter bond, carbonyl, sulfonic group, carbonatoms 1～8 or by the saturated hydrocarbyl of the substituted carbonatoms 1～8 of fluorine atom, R ⁴, R ⁵The alkylidene group of representing singly-bound or carbonatoms 1～5 independently of one another, R ⁶, R ⁷The alkylidene group of representing carbonatoms 1～5 independently of one another.In addition, k representes 0 or 1.}

In the above-mentioned formula, B ¹Preferred expression carbonatoms is 4～8 cyclic saturated hydrocarbon base, representes that more preferably carbonatoms is 4～6 cyclic saturated hydrocarbon base.In addition, B ¹Any Wasserstoffatoms contained in the base can be replaced by aliphatic group independently of one another.

Here, be preferably the aliphatic group of carbonatoms 1～5, the more preferably aliphatic group of carbonatoms 1～3 as this substituent aliphatic group.Combine and form under the situation of ring at these substituting groups, the fused polycyclic alkyl that forms for example endocyclic such as norbornene, adamantyl alkyl, a part or all be hydrogenated.

R ³The saturated hydrocarbyl of preferred expression singly-bound, ehter bond, carbonyl, sulfonic group, carbonatoms 1～5 or by the saturated hydrocarbyl of the substituted carbonatoms 1～5 of fluorine atom.

In addition, R ⁴, R ⁵The alkylidene group of preferred expression singly-bound, carbonatoms 1～3.

In addition, R ⁶, R ⁷The alkylidene group of preferred expression carbonatoms 1～3.

The preferred object lesson as the B of divalent organic group in the above-mentioned formula (1) is shown in following formula (B-1)～formula (B-5).In the group shown in following formula (B-1)～formula (B-5), B is preferably the group in the following formula (B-1) that is selected from～formula (B-4) especially.

Particular polymers preferably is contained in shown in the above-mentioned formula (1) in the structural unit A for to be selected from least a structure in the group shown in above-mentioned formula (1A1)～formula (1A3), but can also comprise except other structure the group shown in above-mentioned formula (1A1)～formula (1A3).At this moment,, its structure is had no particular limits, be preferably and be selected from least a structure in the group shown in following formula (1A4) and the formula (1A5) as long as form the structure of polyester.

In formula (1A4) and formula (1A5), R ⁸, R ⁹, R ¹⁰Represent the saturated hydrocarbyl of singly-bound, ehter bond, carbonyl, sulfonic group, carbonatoms 1～8 independently of one another or by the saturated hydrocarbyl of the substituted carbonatoms 1～8 of fluorine atom.H representes 0 or 1 in addition.}

In the above-mentioned formula, R ⁸, R ⁹, R ¹⁰The saturated hydrocarbyl of preferred expression singly-bound, ehter bond, carbonyl, sulfonic group, carbonatoms 1～5 or by the saturated hydrocarbyl of the substituted carbonatoms 1～5 of fluorine atom.

R ⁸Be preferably the saturated hydrocarbyl of singly-bound, ehter bond, carbonyl, sulfonic group, carbonatoms 1～5 especially or by the saturated hydrocarbyl of the substituted carbonatoms 1～5 of fluorine atom.

In addition, R ⁹Be preferably the saturated hydrocarbyl of ehter bond, carbonatoms 1～5 or by the saturated hydrocarbyl of the substituted carbonatoms 1～5 of fluorine atom.

And, R ¹⁰Be preferably the saturated hydrocarbyl of ehter bond, carbonyl, sulfonic group, carbonatoms 1～5 or by the saturated hydrocarbyl of the substituted carbonatoms 1～5 of fluorine atom.

The preferred object lesson of above-mentioned formula (1A4)～formula (1A5) is shown in following formula (a1)～formula (a7).

In particular polymers, the A that preferably comprises structural unit shown in the above above-mentioned formula (1) of at least 60 moles of % is for being selected from least a structural unit in the group shown in above-mentioned formula (1A1)～formula (1A3).

The polyester through modifying as (A) composition is described below, can be through making particular polymers and having the compound that is selected from the functional group in glycidyl and the NCO and react and obtain.

The weight-average molecular weight through the polyester modified as (A) composition is preferably 1,000～30 with polystyrene conversion, and 000, more preferably 1,500～10,000.Under the situation of weight-average molecular weight less than above-mentioned scope of this polyester; Form the orientation of the cured film that forms with the photosensitivity polymer blend and the tendency that solvent resistance has reduction by thermofixation film of the present invention; If surpass above-mentioned scope, then smooth voltinism reduces sometimes.

< method of manufacture of particular polymers >

In the present invention, tetracarboxylic dianhydride's composition that particular polymers can be through comprising tetracarboxylic dianhydride shown in the following formula (i) (below be also referred to as sour composition) and following formula (ii) shown in diol compound (below be also referred to as diol component) reaction obtain.

HO-B-OH (ii)

Formula (i) and (ii) in, A and B are identical with definition implication in the above-mentioned formula (1).}

In addition, about above-mentioned A and B, preferred mode is identical with aforesaid way.

In the present invention, tetracarboxylic dianhydride, above-mentioned formula shown in the above-mentioned formula (i) (ii) shown in diol compound can use separately independently of one another or also can use more than 2 kinds.

In the manufacturing of above-mentioned particular polymers, as sour composition, not only can use tetracarboxylic dianhydride shown in the above-mentioned formula (i), can also merge the tetracarboxylic dianhydride that uses other (below be also referred to as other acid dianhydride).At this moment, for other acid dianhydride, only otherwise destroying effect of the present invention gets final product, have no particular limits.Be preferably tetracarboxylic dianhydride shown in the following formula (i2).

{ in the formula (i2), W representes to be selected from least a structure in the group shown in middle above-mentioned formula (1A4) that defines of above-mentioned formula (1) and the formula (1A5), R ⁸, R ⁹, R ¹⁰Identical with h with above-mentioned definition implication.}

In addition, the preferred concrete example of above-mentioned formula (1A4) and formula (1A5) is also with above-mentioned formula (a1)～formula (a7) expression.

In the present invention, comprise tetracarboxylic dianhydride shown in the above above-mentioned formula (i) of at least 60 moles of % in the preferred acid composition.

In above-mentioned particular polymers, the proportioning of preferred tetracarboxylic dianhydride's total amount (total amount of sour composition) and the total amount (total amount of diol component) of diol compound, promptly < total mole number of diol compound >/< total mole number of tetracarboxylic dianhydride's compound>is 0.95～1.5.With common polycondensation likewise, this mol ratio is more near 1, the polymerization degree of the particular polymers of generation is bigger, molecular weight is big more.

The end of above-mentioned particular polymers changes according to the proportioning of sour composition and diol component.For example, under the situation that makes sour composition excessive response, the terminal acid anhydrides that forms easily.

In addition, carry out under the polymeric situation the terminal hydroxyl that forms easily at excessive use diol component.In this case, can make the reaction of this terminal hydroxyl and carboxylic acid anhydride, thereby terminal hydroxyl is sealed with acid anhydrides.Example as such carboxylic acid anhydride; Can enumerate Tetra hydro Phthalic anhydride, 1; 2,4-benzenetricarboxylic anhydride, maleic anhydride, naphthalic anhydride, hydrogenation Tetra hydro Phthalic anhydride, methyl-5-norbornylene-2,3-dicarboxylic acid anhydride, itaconic anhydride, Tetra Hydro Phthalic Anhydride etc.

In follow-up addition reaction with the situation of compound reaction with glycidyl under because gelation takes place for the hydroxyl and the anhydride reaction that generate, so need make the end of particular polymers become hydroxyl or with acid anhydrides closed end hydroxyl.

In the manufacturing of particular polymers, the temperature of reaction of sour composition and diol component can be selected 50～200 ℃, be preferably 80～170 ℃ temperature arbitrarily.Can be that 100～140 ℃, reaction times are to obtain particular polymers under 2～48 hours the condition for example in temperature of reaction.

In addition, can select 50～200 ℃, be preferably 80～170 ℃ temperature arbitrarily with the temperature of reaction under the situation of acid anhydrides protection terminal hydroxyl.

(the following solvent that uses during with the polymerization particular polymers is called " polymer solvent ") carried out in the reaction of above-mentioned sour composition and above-mentioned diol component usually in solvent.As operable solvent this moment,, do not limit especially so long as the solvent of hydroxyl, amino etc. and the functional group of anhydride reaction get final product not.For example can enumerate; N; Dinethylformamide, DMAC N,N, N-Methyl pyrrolidone, N-vinyl pyrrolidone, N-methyl caprolactam, methyl-sulphoxide, tetramethyl-urea, MSM, hexamethyl sulfoxide, meta-cresol, gamma-butyrolactone, pimelinketone, ketopentamethylene, methylethylketone, MIBK, 2-heptanone, methylcellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ether acetate, Ucar 35 propyl ether acetic ester, 3-methoxypropionic acid methyl esters, 2-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 2-methoxy propyl acetoacetic ester, 3-ethoxyl ethyl propionate, 2-ethoxyl ethyl propionate etc.

These solvents can use separately also can mix use, but from security, to the suitability aspect of the production line of the overcoating agent of colour filter, more preferably propylene glycol methyl ether acetate.

In addition, even do not dissolve the solvent of particular polymers, also can in the scope that the particular polymers that generates through polyreaction is not separated out, be blended in the above-mentioned solvent and use.

Also can use catalyzer when in addition, above-mentioned sour composition (formula (i) and formula (i2)) is with above-mentioned diol component (formula (ii)) reaction.

The concrete example of the catalyzer that uses during as the polymerization of particular polymers can be enumerated quaternary ammonium salts such as benzyl trimethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl tripropyl ammonium chloride, benzyl tripropyl brometo de amonio, tetramethyl ammonium chloride, tetraethylammonium bromide, 4-propyl ammonium chloride, 4-propyl bromide, tetraphenylphosphonichloride chloride

tetraphenylphosphonibromide bromide

benzyl triphenyl phosphonium chloride

benzyl triphenyl bromination ethyl triphenyl chlorination

ethyl triphenyl bromination seasons such as

salt.

< (A) manufacturing of composition >

The compound that is selected from the functional group in glycidyl and the NCO that has that can add 10～90 moles of % as the polyester of (A) composition through the carboxyl with respect to particular polymers reacts it to obtain.At this moment, can directly use the polymeric solution of particular polymers.

In addition, if make the coexistence of pure series solvent, therefore the gelation in then can inhibited reaction is preferred.As the concrete example of so pure series solvent (below be also referred to as reaction solvent), can enumerate propylene glycol monomethyl ether, Ucar 35 list ethyl ether, Ucar 35 single-butyl ether, Ucar 35 propyl ether, diethylene glycol monomethyl ether, carbiphene, diglycol monotertiary butyl ether, methylcyclohexane, ethylene glycol butyl ether, ethyl lactate, n-Butyl lactate, methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, the trimethyl carbinol, hexalin etc.These solvents can use separately or combination use more than 2 kinds.

As with the concrete example of the compound with glycidyl of the carboxyl addition of particular polymers, can enumerate SY-Monomer G, glycidyl acrylate, methyl glycidyl ether, ethyl glycidyl ether, allyl glycidyl ether, 4-tert-butyl-phenyl glycidyl ether, glycidyl phenyl ether, glycidyl-2-methyl phenyl ether, glycidyl propyl ether, glycidyl isopropyl ether, glycidyl butyl ether, glycidyl tertbutyl ether, 2-xenyl glycidyl ether, glycidyl-4-p-methoxy-phenyl ether etc.

In addition; As with the concrete example of the compound with NCO of the carboxyl addition of particular polymers, can enumerate methyl isocyanate, ethyl isocyanate, propyl group isocyanic ester, isopropyl isocyanate, n-butyl isocyanate, isobutyl-isocyanic ester, tertiary butyl isocyanic ester, phenyl isocyanate, 2-toluyl isocyanic ester, 3-toluyl isocyanic ester, 4-toluyl isocyanic ester, 1-naphthyl isocyanic ester, cyclohexyl isocyanate, benzyl isocyanate ester, methylacrylic acid 2-NCO ethyl ester, 2-anisole based isocyanate, 3-anisole based isocyanate, 4-anisole based isocyanate, amyl group isocyanic ester, hexyl isocyanic ester etc.

The carboxyl of particular polymers with can select 50～160 ℃, be preferably 80～140 ℃ temperature arbitrarily with the temperature of reaction with the compound that is selected from the functional group in glycidyl and the NCO of its reaction.The polyester of (A) composition that uses in for example, can under temperature of reaction is 100～130 ℃, the condition in 2～48 hours reaction times, obtaining as the present invention.

The solution of the polyester that comprises conduct (A) composition that obtains like this can directly be used to modulate thermofixation film formation of the present invention and use the photosensitivity polymer blend.In addition, can make polyester precipitate and separate and recovery in poor solvents such as water, methyl alcohol, ethanol, ether, hexane, use then.

(B) composition

As the epoxy compounds with 2 above epoxy group(ing) of (B) of the present invention composition, for example can enumerate three (2; The 3-epoxypropyl) isocyanuric acid ester, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxy ethyl) hexanaphthene, T 55, glycol ether diglycidylether, 2; 6-diglycidyl phenyl glycidyl ether, 1,1,3-three is [to (2; The 3-glycidoxy) phenyl] propane, 1; 2-cyclohexane cyclohexanedimethanodibasic 2-glycidyl ester, 4,4 '-methylene-bis (N, N-diglycidylaniline), 3; 4-epoxy cyclohexane formic acid-3,4-epoxycyclohexyl methyl esters, trimethylolethane trimethacrylate glycidyl ether, bisphenol A diglycidyl ether and tetramethylolmethane polyglycidyl ether etc.

In addition, from obtaining easy aspect, can use the compound of commercially available article.Below enumerate its concrete example (trade(brand)name), but be not limited thereto: YH-434, YH434L (Dongdu changes into (strain) system) etc. has amino epoxy resin; エ Port リ one De GT-401, エ Port リ one De GT-403, エ Port リ one De GT-301, エ Port リ one De GT-302, セ ロ キ サ イ De 2021, セ ロ キ サ イ De 3000 (ダ イ セ Le chemical industry (strain) system) etc. have the epoxy resin of cyclohexene oxide structure; エ ピ コ one ト 1001, エ ピ コ one ト 1002, エ ピ コ one ト 1003, エ ピ コ one ト 1004, エ ピ コ one ト 1007, エ ピ コ one ト 1009, エ ピ コ one ト 1010, エ ピ コ one ト 828 bisphenol A type epoxy resins such as (oiling シ エ Le エ Port キ シ (strain) (existing ジ ヤ パ Application エ Port キ シ レ ジ Application (strain)) systems); エ ピ コ one ト 807 bisphenol f type epoxy resins such as (oiling シ エ Le エ Port キ シ (strain) (existing ジ ヤ パ Application エ Port キ シ レ ジ Application (strain)) systems); エ ピ コ one ト 152, エ ピ コ one ト 154 (oiling シ エ Le エ Port キ シ (strain) (existing ジ ヤ パ Application エ Port キ シ レ ジ Application (strain)) system), EPPN201, EPPN202 phenol phenolic resin type epoxy resin such as (Japanese chemical drug (strain) systems); EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (Japanese chemical drug (strain) system), エ ピ コ one ト 180S75 cresol novolac resin type epoxy resin such as (oiling シ エ Le エ Port キ シ (strain) (existing ジ ヤ パ Application エ Port キ シ レ ジ Application (strain)) systems); デ Na コ one Le EX-252 (Na ガ セ ケ system テ Star Network ス (strain) system); CY175, CY177, CY179, ア ラ Le ダ イ ト CY-182, ア ラ Le ダ イ ト CY-192, ア ラ Le ダ イ ト CY-184 (CIBA-GEIGY A.G system); エ ピ Network ロ Application 200, エ ピ Network ロ Application 400 (big Japanese イ Application キ chemical industry (strain) system); エ ピ コ one ト 871, エ ピ コ one ト 872 (oiling シ エ Le エ Port キ シ (strain) (existing ジ ヤ パ Application エ Port キ シ レ ジ Application (strain)) system), ED-5661, ED-5662 alicyclic epoxy resins such as (セ ラ ニ one ズ コ one テ イ Application グ (strain) systems); デ Na コ one Le EX-611, デ Na コ one Le EX-612, デ Na コ one Le EX-614, デ Na コ one Le EX-622, デ Na コ one Le EX-411, デ Na コ one Le EX-512, デ Na コ one Le EX-522, デ Na コ one Le EX-421, デ Na コ one Le EX-313, デ Na コ one Le EX-314, デ Na コ one Le EX-321 aliphatics polyglycidyl ethers such as (Na ガ セ ケ system テ Star Network ス (strain) systems) etc.

In addition, as compound, can use polymkeric substance with epoxy group(ing) with at least two epoxy group(ing).As such polymkeric substance, promptly can use not special restriction so long as have the polymkeric substance of epoxy group(ing).

Above-mentioned polymkeric substance with epoxy group(ing) for example can carry out addition polymerization through the addition polymerization property monomer that use has an epoxy group(ing) and make.As an example; Can enumerate multipolymer, SY-Monomer G and the vinylbenzene of ROHM glycidyl ester, SY-Monomer G and Jia Jibingxisuanyizhi and the addition polymer such as multipolymer of 2-hydroxyethyl methacrylate, and/or polycondensate such as epoxy-Novolak resin.

Perhaps, above-mentioned polymkeric substance with epoxy group(ing) can also react through the compound that makes macromolecular compound with hydroxyl and Epicholorohydrin, toluenesulphonic acids glycidyl ester etc. have epoxy group(ing) and make.

As the weight-average molecular weight of such polymkeric substance, for example be 300～200,000 with polystyrene conversion.

These epoxy compoundss with 2 above epoxy group(ing) can use separately or combination use more than 2 kinds.

Thermofixation film of the present invention forms the content with (B) composition in the photosensitivity polymer blend, is preferably 3～50 mass parts based on polyester 100 mass parts as (A) composition, and more preferably 5～40 mass parts are preferably 10～30 mass parts especially.Under the too small situation of this ratio, the solvent resistance, the thermotolerance that are formed the cured film that forms with the photosensitivity polymer blend by the thermofixation film reduce sometimes, and on the other hand, under excessive situation, solvent resistance reduces and/or storage stability reduces sometimes.

(C) composition

(C) composition is the carboxylic acid cpd that contains amino that gets through diamine compound and dicarboxylic acid dianhydride reaction.Particularly, be through 1 mole of the diamine compound of following formula shown in (iii) and following formula 1.7～2 moles of dicarboxylic acid dianhydride shown in (iv), be preferably the amino carboxylic acid cpd that contains that 1.8～2 molar reactives get.

H ₂N-P-NH ₂?(iii)

Formula (iii) with formula (iv) in, P and Q represent the divalent organic group independently of one another.}

Therefore, through making the dicarboxylicacid reaction shown in (iv) of the diamine compound of above-mentioned formula shown in (iii) and above-mentioned formula, can obtain the compound shown in the following formula (2).

{ in the formula, P and Q and above-mentioned formula are (iii) identical with the definition implication of formula in (iv).}

In the present invention, diamine compound and dicarboxylic acid dianhydride can only be used a kind of respectively, also can use multiple.Therefore, the amino carboxylic acid cpd that contains as (C) of the present invention composition not only can use a kind of of the compound shown in the above-mentioned formula (2), and can use multiple.

Above-mentioned P and Q are especially preferred independently of one another for having the divalent organic group of ring structure.Here, as ring structure, can enumerate phenyl ring, alicyclic ring, fused polycyclic hydrocarbon.

Above-mentioned formula (iii) in, as the ring structure that P had, be preferably the alicyclic ring of phenyl ring, carbonatoms 4～8, the fused polycyclic hydrocarbon of carbonatoms 7～16.

Therefore, as the concrete example of diamine compound, can enumerate following compound: Ursol D, mphenylenediamine, 2,4 di amino toluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,4-dimethyl--1,3-diaminobenzene, 2 with such ring structure; 5-dimethyl--1,4-diaminobenzene, 2,3,5,6-tetramethyl--1,4-diaminobenzene, 2,4-diaminophenol, 2; 5-diaminophenol, 4,6-diamino resorcin, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, N, N-diallyl-2,4-diamino-aniline, N, N-diallyl-2; 5-diamino-aniline, 4-aminobenzyl amine, 3-aminobenzyl amine, 2-(4-aminophenyl) ethylamine, 2-(3-aminophenyl) ethylamine, 1,5-naphthylene diamine, 2,7-naphthylene diamine, 4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-dimethyl--4; 4 '-benzidine, 3,3 '-dimethyl--4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxyl-4,4 '-benzidine, 3; 3 '-dicarboxyl-4,4 '-benzidine, 3,3 '-two fluoro-4,4 '-benzidine, 2,2 '-trifluoromethyl-4,4 '-benzidine, 3,3 '-trifluoromethyl-4; 4 '-benzidine, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl ether 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4; 4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diamino-diphenyl amine, 3,3 '-diamino-diphenyl amine, 3,4 '-diamino-diphenyl amine, N-methyl (4,4 '-diamino-diphenyl) amine, N-methyl (3,3 '-diamino-diphenyl) amine, N-methyl (3; 4 '-diamino-diphenyl) amine, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 4,4 '-diamino-N-N-benzoylaniline, 1, two (4-aminophenyl) ethane, 1 of 2-, two (3-aminophenyl) ethane, 4 of 2-; 4 '-diamino-tolane, 1, two (4-aminophenyl) propane, 1 of 3-, two (3-aminophenyl) propane, 2 of 3-, two (4-aminophenyl) propane, 2 of 2-, two (3-aminophenyl) propane, 2 of 2-, two (3-amino-4-aminomethyl phenyl) propane, 2 of 2-, two (4-aminophenyl) HFC-236fas, 2 of 2-; Two (3-aminophenyl) HFC-236fas, 2 of 2-, two (3-amino-4-aminomethyl phenyl) HFC-236fas, 1 of 2-, two (4-amino-benzene oxygen) propane, 1 of 3-, two (4-amino-benzene oxygen) butane, 1 of 4-, two (4-amino-benzene oxygen) pentanes, 1 of 5-, two (4-amino-benzene oxygen) hexanes, 1 of 6-, two (4-amino-benzene oxygen) heptane, 1 of 7-; Two (4-amino-benzene oxygen) octanes, 1 of 8-, two (4-amino-benzene oxygen) nonanes, 1 of 9-, two (4-amino-benzene oxygen) decane, 1 of 10-, two (4-amino-benzene oxygen) undecanes, 1 of 11-, two (4-amino-benzene oxygen) dodecyls of 12-, two (4-aminophenyl) malonic ester, two (4-aminophenyl) succinate, two (4-aminophenyl) glutarate, two (4-aminophenyl) adipic acid ester, two (4-aminophenyl) pimelate, two (4-aminophenyl) suberate, two (4-aminophenyl) azelate, two (4-aminophenyl) sebate, 1, two (4-aminophenyl) benzene, 1 of 4-, two (4-aminophenyl) benzene, 1 of 3-; Two (4-amino-benzene oxygen) benzene, 1 of 4-, two (4-amino-benzene oxygen) benzene, 1 of 3-, two (4-aminobenzyl) benzene, 1 of 4-, two (4-aminobenzyl) benzene of 3-, two (4-aminophenyl) terephthalate, two (3-aminophenyl) terephthalate, two (4-aminophenyl) isophthalic acid ester, two (3-aminophenyl) isophthalic acid ester, 1,4-phenylene two [(4-aminophenyl) ketone], 1,4-phenylene two [(3-aminophenyl) ketone], 1,3-phenylene two [(4-aminophenyl) ketone], 1; 3-phenylene two [(3-aminophenyl) ketone], 1,4-phenylene two (4-Aminobenzoate), 1,4-phenylene two (3-Aminobenzoate), 1,3-phenylene two (4-Aminobenzoate), 1,3-phenylene two (3-Aminobenzoate), N, N '-(1, the 4-phenylene) two (4-aminobenzamides), N; N '-(1, the 3-phenylene) two (4-aminobenzamides), N, N '-(1, the 4-phenylene) two (3-aminobenzamides), N, N '-(1, the 3-phenylene) two (3-aminobenzamides), two (4-aminophenyl) terephthalamide, two (3-aminophenyl) terephthalamide, two (4-aminophenyl) isophthaloyl amine, two (3-aminophenyl) isophthaloyl amine, 2, two [4-(4-amino-benzene oxygen) phenyl] propane, 2 of 2-; Two [4-(4-amino-benzene oxygen) phenyl] HFC-236fas, 4 of 2-, 4 '-two (4-amino-benzene oxygen) sulfobenzide, 2,6-diamino-pyridine, 2,4-diamino-pyridine, 2,4-diamino-1,3,5-triazines, 2; 6-diamino-dibenzofuran, 2,7-diamino-dibenzofuran, 3,6-diamino-dibenzofuran, 2,6-diamino-carbazole, 2,7-diamino-carbazole, 3,6-diamino-carbazole, 2,4-diamino--6-sec.-propyl-1; 3,5-triazine, 2, two (the 4-aminophenyls)-1,3 of 5-, 4-

diazole, 1,4-DACH, 1,3-DACH, two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane etc.

In addition, above-mentioned formula (iv) in, as the ring structure that Q had, be preferably the alicyclic ring of phenyl ring, carbonatoms 4～8, the fused polycyclic hydrocarbon of carbonatoms 7～16.As preferred Q, be the alicyclic ring of phenyl ring, carbonatoms 4～8, the fused polycyclic hydrocarbon of carbonatoms 7～16.

Concrete example as dicarboxylic acid dianhydride with such ring structure; Can enumerate Tetra hydro Phthalic anhydride, 1; 2,4-benzenetricarboxylic anhydride, maleic anhydride, naphthalic anhydride, hydrogenation Tetra hydro Phthalic anhydride, methyl-5-norbornylene-2,3-dicarboxylic acid anhydride, itaconic anhydride, Tetra Hydro Phthalic Anhydride etc.

In the manufacturing of the compound of above-mentioned conduct (C) composition, the temperature of reaction of diamine compound and dicarboxylic acid dianhydride can be selected 5～80 ℃, be preferably 10～50 ℃ temperature arbitrarily.

Above-mentioned reaction is carried out in solvent usually.As operable solvent this moment, do not get final product so long as do not contain the solvent of hydroxyl, amino etc. and the functional group of anhydride reaction, have no particular limits.For example can enumerate; N; Dinethylformamide, DMAC N,N, N-N-methyl-2-2-pyrrolidone N-, N-vinyl pyrrolidone, N-methyl caprolactam, methylimidazole, methyl-sulphoxide, tetramethyl-urea, MSM, hexamethyl sulfoxide, meta-cresol, gamma-butyrolactone, pimelinketone, ketopentamethylene, methylethylketone, MIBK, 2-heptanone, propylene glycol methyl ether acetate, Ucar 35 propyl ether acetic ester, 3-methoxypropionic acid methyl esters, 2-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 2-methoxy propyl acetoacetic ester, 3-ethoxyl ethyl propionate, 2-ethoxyl ethyl propionate, methylcellosolve acetate, ethyl cellosolve acetate, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, propylene glycol monomethyl ether, Ucar 35 propyl ether, hexalin, ETHYLE ACETATE, butylacetate, ethyl lactate, n-Butyl lactate etc.

These solvents can use separately, also can mix use, but from the solvability aspect, preferred propylene glycol monomethyl ether, propylene glycol methyl ether acetate, DMAC N,N, N-N-methyl-2-2-pyrrolidone N-, methylimidazole.

In addition, even do not dissolve the solvent that contains amino carboxylic acid cpd, also can in the scope that this compound that generates through polyreaction is not separated out, be blended in the above-mentioned solvent and use.

Thermofixation film of the present invention forms the content with (C) composition in the polymer blend, is preferably 3～50 mass parts based on polyester 100 mass parts as (A) composition, more preferably 5～40 mass parts.Under the too small situation of this ratio, the orientation that forms the cured film that forms with polymer blend by thermofixation film of the present invention reduces sometimes, and on the other hand, under excessive situation, loss of transmission sometimes and/or smooth voltinism reduces.

(D) composition

As 1 of (D) composition; The 2-quinone di-azido compound; It is compound with hydroxyl or amino any one or hydroxyl and amino both; Can use preferred 10～100 moles of % in these hydroxyls or the amino (under the situation with hydroxyl and amino both is their total amount), preferred especially 20～95 moles of % by 1, sulfonic acid esterification of 2-quinone diazido-or amidated compound.

As above-mentioned compound, can enumerate for example phenol, ortho-cresol, meta-cresol, p-cresol, quinhydrones, Resorcinol, catechol, methyl gallate, Progallin A, 1,3,3-three (4-hydroxy phenyl) butane, 4 with hydroxyl; 4-isopropylidene xenol, 2, two (4-hydroxy phenyl) propane, 1 of 2-, 1-bis(4-hydroxyphenyl) cyclohexane, 4,4 '-dihydroxy phenyl sulfone, 4; 4-hexafluoro isopropylidene xenol, 4,4 ', 4 "-trihydroxy-phenyl ethane, 1,1; 1-trihydroxy-phenyl ethane, 4,4 '-[1-[4-[1-(4-hydroxy phenyl)-1-methylethyl] phenyl] ethylidene] bis-phenol, 2,4 dihydroxyl benzophenone, 2,3; 4-trihydroxybenzophenone, 2,2 ', 4; 4 '-tetrahydroxybenzophenone, 2,3,4; 4 '-tetrahydroxybenzophenone, 2,2 ', 3; 4,4 '-pentahydroxybenzophenone, 2, aliphatics alcohols such as phenolic compound, ethanol, 2-propyl alcohol, 4-butanols, hexalin, terepthaloyl moietie, Ucar 35, glycol ether, dipropylene glycol, 2-methyl cellosolve, butoxy ethanol, 2-methoxypropanol, 2-butoxy propyl alcohol, ethyl lactate, n-Butyl lactate such as two (the 2-hydroxy-5-methyl base benzyl) methyl of 5-.

In addition; As the above-mentioned compound that contains amino; For example can enumerate; Aniline, Ortho Toluidine, meta-aminotoluene, para-totuidine, 4-ADP methylmethane, 4-phenylaniline, O-Phenylene Diamine, mphenylenediamine, Ursol D, 4,4 '-tetramethyl triaminotriphenyl methane NH2,4, phenyl amines, aminocyclohexanes such as 4 '-diamino-diphenyl ether.

In addition; As above-mentioned hydroxyl and both compounds of amino of containing; For example can enumerate; Ortho-Aminophenol, Metha Amino Phenon, PARA AMINOPHENOL, 4-aminoresorcinol, 2,3-diaminophenol, 2,4-diaminophenol, 4; 4 '-diamino--4 "-hydroxyl triphenyl methane, 4-amino-4 '; 4 "-dihydroxyl triphenyl methane, two (4-amino-3-carboxyl-5-hydroxy phenyl) ether, two (4-amino-3-carboxyl-5-hydroxy phenyl) methane, 2, two (4-amino-3-carboxyl-5-hydroxy phenyl) propane, 2 of 2-, aminophenols such as two (4-amino-3-carboxyl-5-hydroxy phenyl) HFC-236fas of 2-, 2-monoethanolamine, alkanol amines such as 3-aminopropanol, 4-Trans-4-Amino Cyclohexanol.

These 1, the 2-quinone di-azido compound can use separately or more than 2 kinds combination use.

Thermofixation film of the present invention forms the content with (D) composition in the photosensitivity polymer blend, is preferably 5～80 mass parts with respect to (A) composition 100 mass parts, and more preferably 8～60 mass parts are preferably 10～50 mass parts especially.Under the too small situation of this ratio, the dissolution rate difference to developing solution diminishes sometimes, is difficult to form through developing pattern.In addition, if greater than 100 mass parts, then owing to can not decompose 1 fully through the exposure in the short period of time, the 2-quinone di-azido compound, therefore sensitivity sometimes reduces and/or (D) composition absorb light and the transparency of cured film is reduced.

(E) composition

In the present invention, as (E) composition, can contain the bismaleimide compound shown in the following formula (3).

Bismaleimide compound as (E) composition can improve smooth voltinism.

(in the formula, M ₁Expression is selected from aliphatic group, comprises the aliphatic group of ring type structure and the organic group of aromatic group, or the organic group that is combined by a plurality of organic groups that are selected from these organic groups.And, M ₁Can comprise keys such as ester bond, ehter bond, amido linkage, amino-formate bond.)

As such bismaleimide compound, for example can enumerate N, N '-3,3-ditan bismaleimides, N; N '-(3,3-diethylammonium-5,5-dimethyl-)-4,4-phenylbenzene-methane bismaleimides, N, N '-4; 4-ditan bismaleimides, 3,3-sulfobenzide bismaleimides, 4,4-sulfobenzide bismaleimides, N, N '-to UVNUL MS-40 bismaleimides, N, N '-diphenylethane bismaleimides, N; N '-diphenyl ether bismaleimides, N, N '-(methylene radical two-two tetrahydrochysene phenyl) bismaleimides, N, N '-(3-ethyl)-4,4-ditan bismaleimides, N, N '-(3; The 3-dimethyl-)-4,4-ditan bismaleimides, N, N '-(3, the 3-diethylammonium)-4,4-ditan bismaleimides, N; N '-(3, the 3-dichloro)-4,4-ditan bismaleimides, N, N '-isophorone bismaleimides, N, N '-tolidine bismaleimides, N; N '-diphenyl propane bismaleimides, N, N '-naphthalene bismaleimides, N, a N '-penylene bismaleimides, N, N '-5-methoxyl group-1,3-penylene bismaleimides, 2; Two (4-(4-maleimide phenoxyl) phenyl) propane, 2 of 2-, two (3-chloro-4-(4-maleimide phenoxyl) phenyl) propane, 2 of 2-, two (3-bromo-4-(4-maleimide phenoxyl) phenyl) propane, 2 of 2-, two (3-ethyl-4-(4-maleimide phenoxyl) phenyl) propane, 2 of 2-; Two (3-propyl group-4-(4-maleimide phenoxyl) phenyl) propane, 2 of 2-, two (3-sec.-propyl-4-(4-maleimide phenoxyl) phenyl) propane, 2 of 2-, two (3-butyl-4-(4-maleimide phenoxyl) phenyl) propane, 2 of 2-, two (3-methoxyl group-4-(4-maleimide phenoxyl) phenyl) propane, 1 of 2-; Two (4-(4-maleimide phenoxyl) phenyl) ethane, 1 of 1-, two (3-methyl-4-(4-maleimide phenoxyl) phenyl) ethane, 1 of 1-, two (3-chloro-4-(4-maleimide phenoxyl) phenyl) ethane, 1 of 1-, two (3-bromo-4-(4-maleimide phenoxyl) phenyl) ethane, 3 of 1-; Two (4-(4-maleimide phenoxyl) phenyl) pentanes, 1,1 of 3-, 1,3; 3,3-hexafluoro-2, two (4-(4-maleimide phenoxyl) phenyl) propane, 1,1 of 2-; 1,3,3,3-hexafluoro-2; Two (3,5-dimethyl--4-(4-maleimide phenoxyl) phenyl) propane, 1,1 of 2-, 1; 3,3,3-hexafluoro-2,2-two (3; 5-two bromo-4-(4-maleimide phenoxyl) phenyl) propane, N, N '-ethylenebis maleimide, N, N '-hexa-methylene bismaleimides, N, N '-ten dimethylene bismaleimides, N; N '-m-xylene bismaleimides, N, N '-p-Xylol bismaleimides, N, N '-1,3-Dimethylenecyclohexacompound bismaleimides, N; N '-2,4-toluene bismaleimides, N, N '-2,6-toluene bismaleimides etc.These bismaleimide compounds are not limited to above-claimed cpd especially.

These compounds can use separately or composition merging use more than 2 kinds.

In these bismaleimidess, preferred 2, two (4-(4-maleimide phenoxyl) phenyl) propane of 2-, N; N '-4; 4-ditan bismaleimides, N, N '-(3,3-diethylammonium-5; The 5-dimethyl-)-4,4-phenylbenzene-aromatic series bismaleimidess such as methane bismaleimides.

In addition, in these aromatic series bismaleimidess, in order to obtain higher smooth voltinism, preferred molecular weight is the aromatic series bismaleimides below 1,000.

Thermofixation film of the present invention forms the content with (E) composition in the photosensitivity polymer blend, is preferably 0.5～50 mass parts with respect to polyester 100 mass parts as (A) composition, and more preferably 1～30 mass parts is preferably 2～20 mass parts especially.Under the too small situation of this ratio, the smooth voltinism that is formed the cured film that forms with the photosensitivity polymer blend by thermofixation film of the present invention reduces sometimes, under excessive situation, and the loss of transmission and/or film cracking of cured film sometimes.

< solvent >

Thermofixation film of the present invention forms with the photosensitivity polymer blend and often uses under the solution state in being dissolved in solvent.The solvent that uses this moment be used for the composition of dissolving (A) composition～(D) and (E) composition as required and/or after state the solvent of other additive, get final product so long as have the solvent of such dissolving power, its kind and structure etc. are not limited especially.

As such solvent, can be set forth in the solvent (polymer solvent) that uses in the polymerization of particular polymers, above-mentioned reaction solvent, can enumerate ETHYLE ACETATE, butylacetate etc. in addition.

These solvents can use separately or combination use more than two kinds.

< other additive >

In addition; Only otherwise destroy effect of the present invention, thermofixation film of the present invention forms can contain dissolution accelerators such as adhesive aids such as tensio-active agent, rheology control agent, silane coupling agent, pigment, dyestuff, preserving stabilizer, skimmer, polyphenol and/or polycarboxylic acid etc. as required with the photosensitivity polymer blend.

< the thermofixation film forms and uses the photosensitivity polymer blend >

Thermofixation film of the present invention form with the photosensitivity polymer blend be the epoxy compounds that comprises polyester as (A) composition, conduct (B) composition, conduct (C) composition with 2 above epoxy group(ing) the carboxylic acid cpd that contains amino, conduct (D) composition 1, the 2-quinone di-azido compound, also can contain bismaleimide compound of conduct (E) composition and more than one the compsn in other additive as required.And these compositions often are dissolved in and process solution in the solvent and use usually.

Wherein, thermofixation film of the present invention forms following with the preferred example of photosensitivity polymer blend.

[1]: based on (A) composition 100 mass parts, the thermofixation film of (D) composition that contains (C) composition, 5～80 mass parts of (B) composition, 3～50 mass parts of 3～50 mass parts forms uses the photosensitivity polymer blend.

[2]: based on (A) composition 100 mass parts, the thermofixation film that contains (D) composition, the solvent of (C) composition, 5～80 mass parts of (B) composition, 3～50 mass parts of 3～50 mass parts forms uses the photosensitivity polymer blend.

[3]: based on (A) composition 100 mass parts, the thermofixation film of (E) composition that contains (D) composition, 0.5～50 mass parts of (C) composition, 5～80 mass parts of (B) composition, 3～50 mass parts of 3～50 mass parts forms uses the photosensitivity polymer blend.

[4]: based on (A) composition 100 mass parts, the thermofixation film that contains (E) composition, the solvent of (D) composition, 0.5～50 mass parts of (C) composition, 5～80 mass parts of (B) composition, 3～50 mass parts of 3～50 mass parts forms uses the photosensitivity polymer blend.

Cooperation ratio when below detailed description thermofixation film formation of the present invention is used as solution with the photosensitivity polymer blend, modulator approach etc.

Form ratio for thermofixation film of the present invention with the solids component in the photosensitivity polymer blend; Get final product so long as each composition is dissolved in solvent equably, not special restriction can be 1～80 quality %; Preferred 5～60 quality %, more preferably 10～50 quality %.Here, solids component is meant from the thermofixation film and forms with the part of removing whole compositions of photosensitivity polymer blend after desolvating.

Thermofixation film of the present invention is formed with the not special restriction of the modulator approach of photosensitivity polymer blend; As its modulator approach; For example can enumerate, (A) composition is dissolved in the solvent, with (B) composition, (C) composition, (D) composition and (E) composition with the regulation mixed in this solution; Process the method for homogeneous solution, perhaps further add other additive and method of mixing as required in the suitable stage of this modulator approach.

When modulation thermofixation film of the present invention forms with the photosensitivity polymer blend, can directly use through in solvent, carrying out the solution of the polyester that polyreaction gets.In this case, when in the solution of this (A) composition, becoming to grade when processing homogeneous solution, can further add solvent in order to adjust concentration with above-mentioned (B) composition, (C) composition, (D) composition, (E) of likewise adding.At this moment, the solvent that uses in the generative process of polyester is used to adjust the solvent of concentration when forming with the photosensitivity polymer blend with modulation thermofixation film can be identical, also can difference.

And it is to re-use after the filtrations such as strainer about 0.2 μ m that the thermofixation film formation that modulates uses the solution of photosensitivity polymer blend preferably to use the aperture.

< film, cured film and liquid crystal aligning layer >

Be coated on substrate (for example silicon/silicon dioxide coating substrate, silicon nitride substrate, be coated with the metal for example substrate, glass substrate, quartz base plate, ito substrate etc. of aluminium, molybdenum, chromium etc.), the film (for example resin moldings such as tri acetyl cellulose membrane, polyester film, vinylformic acid mesentery) etc. through follow-up thermofixation film of the present invention the formation with the photosensitivity polymer blend of spin coating, flow coat, roller coat, slot coated, slot coated, can form and film through carry out predrying (prebake conditions) with hot plate or baking oven etc. then with modes such as spin coating, ink-jet application, printings.Then, carry out heat treated through this is filmed and form tunicle.

As the condition of this heat treated, for example, can adopt Heating temperature and the heat-up time from 70～160 ℃ of temperature, the scope of 0.3～60 minute time, suitably selected.Are preferably Heating temperature and heat-up time 80～140 ℃, 0.5～10 minute.

In addition, form by the thermofixation film that to use the thickness of the coating that the photosensitivity polymer blend forms for example be 0.1～30 μ m, can consider that step difference, optical property, the electrical properties of employed substrate comes suitably selection.

As the back baking, generally adopt following method: under the Heating temperature of from the scope of 140～250 ℃ of temperature, selecting, handled 5～30 minutes under the situation of use hot plate, handled 30～90 minutes under the situation of use baking oven.

Under aforesaid condition, through being formed with the photosensitivity polymer blend, thermofixation film of the present invention solidifies, and the abundant planarization of step difference of substrate can be made, and cured film can be formed with high transparent.

Cured film through to such formation is carried out friction treatment, and it is played a role as the liquid crystal material oriented layer, that is, play a role as the layer that makes the compound orientation with liquid crystal liquid crystal property.

As the condition of friction treatment, generally adopt speed of rotation 300～1000rpm, speed of feed 3～200mm/ second, the such condition of the amount of being pressed into 0.1～1mm.

Then, remove by fricative residue through using pure water etc. to carry out ultrasonic cleaning.

Coating phase differential material makes phase differential material photocuring become mesomorphic state then on the liquid crystal aligning layer that forms like this, has optically anisotropic layer thereby can form.

As the phase differential material, can use the liquid crystal monomer that for example has polymerizable group or contain compsn of this liquid crystal monomer etc.

In addition, be under the situation of film at the base material that forms liquid crystal aligning layer, be useful as optical anisotropic film.

In addition, can 2 plate bases that have as stated the liquid crystal aligning layer that forms are bonding with the relative mode of liquid crystal aligning layer across spacer, between these substrates, inject liquid crystal then, thus process liquid crystal aligning liquid crystal display device.

Therefore, thermofixation film of the present invention forms and can be suitable for various optical anisotropic films, liquid crystal display device with the photosensitivity polymer blend.

In addition; Because thermofixation film of the present invention forms the smooth voltinism that has necessary at least level with the photosensitivity polymer blend; Therefore the material as cured film such as the protective membrane in the various indicating meters such as formation thin film transistor (TFT) type liquid crystal display device, organic EL, planarization film, insulating films also is useful, the preferred especially material as the outer cover material material that forms colour filter, the interlayer dielectric of TFT type liquid crystal cell, the insulating film of organic EL etc.

Embodiment

Below enumerate embodiment and illustrate in greater detail the present invention, but the invention is not restricted to these embodiment.

[dummy suffix notation that uses among the embodiment]

The implication of the dummy suffix notation that uses in following examples is described below.

< polyester raw material >

BPDA: bibenzene tetracarboxylic dianhydride

HBPDA:3,3 '-4,4 '-dicyclohexyl tetracarboxylic acid dianhydride

HBPA: Hydrogenated Bisphenol A 99

THPA:1,2,5, the 6-Tetra Hydro Phthalic Anhydride

BTEAC: benzyltriethylammoinium chloride

TPPB: tetraphenylphosphonibromide bromide

GMA: SY-Monomer G

GME: glycidyl methyl ether

DTBC: DBMP

< polyimide precursor and the carboxylic acid cpd raw material that contains amino >

CBDA: hexanaphthene tetracarboxylic acid dianhydride

DA-4P:1, two (4-aminophenyl) benzene of 3-

DA-1M:4,4 '-two (4-amino-benzene oxygen) sulfobenzide

TA:1,2, the 4-benzenetricarboxylic anhydride

DDS:4,4 '-diamino diphenyl sulfone

PDA: Ursol D

< acrylic copolymer raw material >

MAA: methylacrylic acid

MMA: TEB 3K

HEMA: 2-hydroxyethyl methacrylate

CHMI:N-cyclohexyl maleimide

AIBN: Diisopropyl azodicarboxylate

< epoxy compounds >

CEL: ダ イ セ Le chemical industry (strain) system セ ロ キ サ イ De p-2021 (goods name) (compound name: 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxy cyclohexane manthanoate)

<bismaleimide compound >

BMI1:N, N '-(3,3-diethylammonium-5,5-dimethyl-)-4,4-phenylbenzene-methane bismaleimides

< 1, the 2-quinone di-azido compound >

QD1: through 1,3,1 mole of 3-three (4-hydroxy phenyl) butane and 1, the condensation reaction that 2-naphthoquinones-2-diazido--5-SULPHURYL CHLORIDE is 2 moles and synthetic compound.

QD2: through α, α, 1 mole of α '-three (4-hydroxy phenyl)-1-ethyl-4-isopropyl benzene be with 1, the condensation reaction that 2-naphthoquinones-2-diazido--5-SULPHURYL CHLORIDE is 2 moles and synthetic compound.

< solvent >

PGMEA: propylene glycol methyl ether acetate

PGME: propylene glycol monomethyl ether

DMAc:N, the N-N,N-DIMETHYLACETAMIDE

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

Number-average molecular weight and weight-average molecular weight according to following synthetic routine resulting polyester, polyimide precursor and acrylic copolymer are measured under following condition: use Japanese beam split (strain) system GPC device (Shodex (registered trademark) chromatographic column KF803L and KF804L), the eluting solvent THF is carried out wash-out with (40 ℃ of column temperatures) in flow 1ml/ minute chromatographic column of flowing through.In addition, following number-average molecular weight (below be called Mn) and weight-average molecular weight (below be called Mw) are with the polystyrene conversion value representation.

< synthetic example 1 >

HBPDA 40.0g, BPDA 8.23g, HBPA 49.3g, THPA 5.96g, BTEAC 0.18g, TPPB 0.33g are made its reaction 17 hours in PGMEA 241.96g, thereby obtained the solution (solid component concentration: 30.0 quality %) (P1) of particular polymers under 120 ℃.The Mn of the particular polymers of gained is 1,500, and Mw is 3,430.

< synthetic example 2 >

Add GMA 18.42g, DTBC 0.057g, PGME 42.99g among solution (P1) 252.00g of the particular polymers that in synthetic example 1, obtains; Under 110 ℃, make its reaction 9 hours, thereby obtained polyester liquid (solid component concentration: 30.0 quality %) (P2).The Mn of the polyester of gained is 1,260, and Mw is 6,880.

< synthetic example 3 >

In solution (P1) 252.00g of the particular polymers that synthetic example 1 is obtained, add GME 11.16g, PGME 26.05g, under 110 ℃, make its reaction 9 hours, thereby obtained polyester liquid (solid component concentration: 30.0 quality %) (P3).The Mn of the polyester of gained is 1,450, and Mw is 5,340.

< synthetic example 4 >

DA-1M 15.14g, THPA 10.64g are made its reaction 24 hours in PGME 60.15g, thereby obtained to contain amino carboxylic acid cpd solution (solid component concentration 30.0 quality %) (A1) under 23 ℃.The amino carboxylic acid cpd that contains for gained uses performance liquid chromatography to confirm not have remaining THPA.

< synthetic example 5 >

DA-4P 10.23g, THPA 10.64g are made its reaction 24 hours in PGME 48.71g, thereby obtained to contain amino carboxylic acid cpd solution (solid component concentration 30.0 quality %) (A2) under 23 ℃.The amino carboxylic acid cpd that contains for gained uses performance liquid chromatography to confirm not have remaining THPA.

< synthetic example 6 >

BPDA 40.0g, HBPA 35.3g, THPA 3.31g, BTEAC 0.77g are made its reaction 19 hours in PGMEA 175.7g, thereby obtained the solution (solid component concentration: 30.0 quality %) of particular polymers under 120 ℃.The Mn of the particular polymers of gained is 1,100, and Mw is 2,580.In the solution 252.00g of this particular polymers, add GMA 18.42g, DTBC 0.057g, PGME 42.99g, under 110 ℃, make its reaction 9 hours, thereby obtained polyester liquid (solid component concentration: 30.0 quality %) (P4).The Mn of the polyester of gained is 1,580, and Mw is 7,540.

< synthetic example 7 >

CBDA 17.7g, pDA10.2g are made its reaction 24 hours in NMP 66.4g, thereby obtained polyimide precursor solution (solid component concentration: 30.0 quality %) (P5) under 23 ℃.The Mn of the polyimide precursor of gained is 5,800, and Mw is 12,500.

< synthetic example 8 >

Use MAA 10.9g, CHMI 35.3g, HEMA 25.5g, MMA 28.3g as monomer component; Use AIBN 5g as radical polymerization initiator; Make them in solvent PGMEA 150g, under 60 ℃～100 ℃ of temperature, carry out polyreaction, thereby obtained acrylic copolymer solution (solid component concentration: 40.0 quality %) (P6).The Mn of the solution of the acrylic copolymer of gained is 3,800, and Mw is 6,700.

< embodiment 1～5 and comparative example 1～5 >

According to each compsn of the composition shown in the table 1 modulation embodiment 1～5 and comparative example 1～5, smooth voltinism, solvent resistance, orientation, thermotolerance, the pattern of the cured film that obtained by said composition become second nature and transsmissivity is estimated.

Table 1

※ P1: particular polymers solution P2～P4: polyester liquid P5: polyimide precursor solution

P6: acrylic copolymer solution

[evaluation of smooth voltinism]

Use the rotary coating machine that each compsn of embodiment 1～embodiment 5 and comparative example 1～comparative example 5 is coated on the step difference substrate (glass) of height 0.5 μ m, live width 10 μ m, wire spacing 50 μ m; Under 110 ℃ of temperature, on hot plate, carry out prebake conditions 120 seconds then, formed filming of thickness 2.8 μ m.Thickness uses the system F20 of FILMETRICS society to measure.Carry out the back baking through this is filmed in 30 minutes in 230 ℃ of following heating of temperature, formed the cured film of thickness 2.5 μ m.

Measure on the step difference plate line film with at interval on the film thickness difference of filming (with reference to Fig. 1), use the formula of planarization rate (DOP)=100 * (height of the film thickness difference that 1-{ films (μ m)/step difference substrate (0.5 μ m) }) to obtain the planarization rate.

[evaluation that pattern becomes second nature]

Use the rotary coating machine that each compsn of embodiment 1～embodiment 5 and comparative example 1～comparative example 5 is coated on the glass substrate, under 110 ℃ of temperature, on hot plate, carried out prebake conditions 120 seconds then, formed filming of thickness 2.8 μ m.Thickness uses the system F20 of FILMETRICS society to measure.Across the mask of the line & intermittent pattern with 10 μ m, PLA-600FA films with 100mJ/cm to this through キ ヤ ノ Application (strain) system UV irradiation equipment ²The light intensity of irradiation 365nm is 5.5mW/cm ²Ultraviolet ray.Then, developed in 60 seconds, carry out flowing water washing 20 seconds with ultrapure water then through dipping in the TMAH of 0.2 quality % (below the be called TMAH) aqueous solution.With the line intermittent pattern of observation by light microscope gained, with the pattern that obtains meeting mask design be designated as zero, with pattern not by exploring, when developing dissolved be designated as *.

[evaluation of solvent resistance]

Use the rotary coating machine that each compsn of embodiment 1～embodiment 5 and comparative example 1～comparative example 5 is coated on the silicon chip, then under 100 ℃ of temperature on hot plate prebake conditions 120 seconds, formed filming of thickness 2.8 μ m.Thickness uses the system F20 of FILMETRICS society to measure.This is filmed under 230 ℃ of temperature, on hot plate, carry out back baking 30 minutes, formed the cured film of thickness 2.5 μ m.

This cured film was flooded 60 seconds in PGMEA or NMP, descended dry 60 seconds 100 ℃ of temperature respectively then, measure thickness.Be designated as zero with thickness is unconverted in PGMEA or NMP dipping back, with being designated as of observing behind the dipping that thickness reduces *.

[evaluation of optical transmittance (transparency)]

Use the rotary coating machine that each compsn of embodiment 1～embodiment 5 and comparative example 1～comparative example 5 is coated on the quartz base plate, under 100 ℃ of temperature, on hot plate, carried out prebake conditions 120 seconds then, formed filming of thickness 2.8 μ m.Thickness uses the system F20 of FILMETRICS society to measure.Dipping developed in 60 seconds in the TMAH aqueous solution of 0.2 quality % through this is filmed, and carried out flowing water washing 20 seconds with ultrapure water then.Then, make UV irradiation equipment PLA-600FA with 500mJ/cm through キ ヤ ノ Application (strain) ²The light intensity of irradiation 365nm is 5.5mW/cm ²Ultraviolet ray.This is filmed under 230 ℃ of temperature, on hot plate, carry out back baking 30 minutes, formed cured film.

Use ultraviolet-visible pectrophotometer (the system SHIMADSU UV-2550 of (strain) Shimadzu Seisakusho Ltd. model) to measure the transsmissivity of this cured film when wavelength 400nm.

[evaluation of orientation]

Use the rotary coating machine that each compsn of embodiment 1～embodiment 5 and comparative example 1～comparative example 5 is coated on the ito substrate, then under 100 ℃ of temperature on hot plate prebake conditions 120 seconds, formed filming of thickness 2.8 μ m.Thickness uses the system F20 of FILMETRICS society to measure.This is filmed under 230 ℃ of temperature, on hot plate, carry out back baking 30 minutes, formed cured film.

This cured film is carried out friction treatment under the condition of speed of rotation 300rpm, speed of feed 10mm/ second, the amount of being pressed into 0.45mm.With the substrate after the friction treatment with pure water ultrasonic cleaning 5 minutes.The phase differential material that uses the rotary coating machine will comprise liquid crystal monomer is coated on this substrate, on hot plate, carries out 100 ℃ of following 40 seconds, 55 ℃ following prebake conditions of 30 seconds then, has formed filming of thickness 1.1 μ m.With this substrate under nitrogen atmosphere with 2,000mJ exposure.The substrate of making is clamped between deflector plate the Visual Confirmation orientation.Be designated as zero with what substrate tilted the 45 optical transmission property noticeable changes when not tilting when spending, with indeclinable being designated as *.

[stable on heating evaluation]

Use the rotary coating machine that each compsn of embodiment 1～embodiment 5 and comparative example 1～comparative example 5 is coated on the quartz base plate; Then under 100 ℃ of temperature on hot plate prebake conditions 120 seconds; Under 230 ℃ of temperature, on hot plate, carry out back baking 30 minutes then; Formed cured film, thickness uses the system F20 of FILMETRICS society to measure.Then, with cured film baking 60 minutes on hot plate under 230 ℃ of temperature, measure thickness once more again, calculate the velocity of variation of the thickness that begins after the baking of back.In addition, be considered to have stable on heating cured film, need have the Thickness Variation rate at least to be lower than ± 5% performance.

[result of evaluation]

Carry out the result that above evaluation obtains and be shown in following table 2.

Table 2

In embodiment 1～embodiment 5, can form pattern, planarization rate, thermotolerance be high, PGMEA, NMP are also all observed patience.In addition, all demonstrate good orientation, also realized high-transmission rate (transparency) behind the high bake.

In comparative example 1, unexposed also is dissolved in the developing solution, can not forms pattern.

In comparative example 2, exposure portion does not dissolve in developing solution, can not form pattern.

In comparative example 3, thermotolerance is low, can not form pattern.

In comparative example 4, the planarization rate is low, can not form pattern.

On the other hand, in comparative example 5, the result is that though can form pattern, planarization rate, thermotolerance, solvent resistance and transsmissivity are good, poor orientation.

As stated, obtained following result: thermofixation film formation of the present invention can be used glycol series solvents such as propylene glycol methyl ether acetate when cured film forms with the photosensitivity polymer blend.In addition, can form pattern through alkaline-based developer, and arbitrary performance of the transmitance of gained cured film excellence, solvent resistance, thermotolerance, smooth voltinism and orientation is all good.

The industry utilizability

It is very useful as the liquid crystal aligning layer of optical anisotropic film, liquid crystal display device that thermofixation film of the present invention forms with the photosensitivity polymer blend; In addition, material, the particularly material as the interlayer dielectric that forms TFT type liquid crystal cell, the protective membrane of colour filter, the insulating film of organic EL etc. as cured film such as the protective membrane in the various indicating meters such as formation thin film transistor (TFT) type liquid crystal display device, organic EL, planarization film, insulating films also is fit to.

Claims (10)

1. a thermofixation film forms and use the photosensitivity polymer blend, and it contains (A) composition, (B) composition, (C) composition and (D) composition,

(A) composition: make the polyester polyester that the warp that gets modified with having the compound reaction that is selected from the functional group in glycidyl and the NCO that comprises structural unit shown in the following formula (1),

(B) composition: have the epoxy compounds of 2 above epoxy group(ing),

(C) composition: the reaction of diamine compound and dicarboxylic acid dianhydride and contain amino carboxylic acid cpd,

(D) composition: 1, the 2-quinone di-azido compound,

In the formula, A is illustrated in the 4 valency organic groups that are combined with 4 connecting keys on ester ring type skeleton or the aliphatics skeleton, and B is illustrated in the divalent organic group that is combined with 2 connecting keys on ester ring type skeleton or the aliphatics skeleton.

2. thermofixation film according to claim 1 forms uses the photosensitivity polymer blend; Wherein, The polyester that comprises structural unit shown in the above-mentioned formula (1) be tetracarboxylic dianhydride's composition of comprising tetracarboxylic dianhydride shown in the following formula (i) with comprise following formula (ii) shown in diol compound the diol component reaction and polyester

HO-B-OH (ii)

Formula (i) and (ii) in, A and B are identical with definition implication in the above-mentioned formula (1).

3. thermofixation film according to claim 1 and 2 forms uses the photosensitivity polymer blend; In the above-mentioned formula (1); A representes to be selected from least a group in the group shown in following formula (A-1)～formula (A-8), and B representes to be selected from least a group in the group shown in following formula (B-1)～formula (B-5)

4. form according to the described thermofixation film of each of claim 1～3 and use the photosensitivity polymer blend, wherein, it is 1,000～30,000 weight-average molecular weight that the polyester through modification of said conduct (A) composition has with polystyrene conversion.

5. use the photosensitivity polymer blend according to each described thermofixation film formation of claim 1～4, wherein, said (C) composition is the carboxylic acid cpd that contains amino that 1 mole of diamine compound gets with dicarboxylic acid dianhydride 1.7～2 molar reactives.

6. use the photosensitivity polymer blend according to each described thermofixation film formation of claim 1～5; Wherein, Based on said (A) composition 100 mass parts, contain said (B) composition of 3～50 mass parts, said (C) composition of 3～50 mass parts, said (D) composition of 5～80 mass parts respectively.

7. use the photosensitivity polymer blend according to each described thermofixation film formation of claim 1～5, wherein, also contain bismaleimide compound as (E) composition.

8. thermofixation film according to claim 6 forms and uses the photosensitivity polymer blend, wherein, based on said (A) composition 100 mass parts, contains claim 7 described (E) composition of 0.5～50 mass parts.

9. each the described thermofixation film by claim 1～8 forms the cured film that forms with the photosensitivity polymer blend.

10. use each described thermofixation film of claim 1～8 to form the liquid crystal aligning layer that obtains with the photosensitivity polymer blend.

Images