CN102395614B - Photosensitive polyester composition for use in forming thermally cured film - Google Patents

Photosensitive polyester composition for use in forming thermally cured film Download PDF

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CN102395614B
CN102395614B CN201080016297.0A CN201080016297A CN102395614B CN 102395614 B CN102395614 B CN 102395614B CN 201080016297 A CN201080016297 A CN 201080016297A CN 102395614 B CN102395614 B CN 102395614B
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cured film
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compound
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CN102395614A (en
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畑中真
安达勲
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/22—Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20

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

Heat cured film forms uses the photosensitivity polymer blend
Technical field
The present invention relates to heat cured film and form the cured film of using the photosensitivity polymer blend and being formed by said composition.More specifically, the heat cured 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 heat cured film forms with the photosensitivity polymer blend particularly preferably as the colour filter overcoating agent that has the liquid crystal aligning function concurrently in the liquid-crystal display.
Background technology
Generally speaking, in the 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 protecting, solvent resistance is high, also requires the performances such as the transparency, thermotolerance.
Such protective membrane is in 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 polymer planarization, namely 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 the optical transmission rate through colour filter, need high transparent as these planarization films of its protective membrane.
On the other hand, studied in recent years by in the liquid crystal cell of liquid-crystal display, importing the phase differential material and realized cost degradation, lightweight, such phase differential material normal operation 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 has orientation after friction treatment.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, technique is counted the greater advantages such as minimizing, therefore the such material of strong expectation.
Generally speaking, the outer covering layer of this colour filter uses the high acrylic resin of the transparency.From security, operability, prevent that pigment composition from the viewpoint of colour filter stripping, is widely used glycol series solvent and/or the ester series solvents such as ethyl lactate, n-Butyl lactate such as propylene glycol monomethyl ether, propylene glycol methyl ether acetate in such acrylic resin.Such acrylic resin is given thermotolerance, solvent resistance (patent documentation 1,2) by thermofixation, photocuring.Yet, although existing Thermocurable, light solidified acrylic resin demonstrate the suitable transparency, smooth voltinism, can not show sufficient orientation even such planarization film is carried out friction treatment.
On the other hand, liquid crystal aligning layer uses the material that comprises solvent-soluble polyimide and/or polyamic acid usually.Reported and to have given solvent resistance by making these materials complete imidization when the rear baking, shown sufficient orientation (patent documentation 3) by friction treatment.Yet, in the situation of the planarization film of these materials being made colour filter, have the problems such as smooth voltinism and transparent decrease.
In addition, in order to improve smooth voltinism, polyester-polyamide acid, polyester-polyimide copolymer (patent documentation 4) have been reported.Yet, although these polyester-polyamide acid, polyester-polyimide copolymer also similarly 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 occuring 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, also there is not up to now report to have the planarization film of photosensitivity, display orientation.
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 by alkaline-based developer, after forming, cured film shows high solvent resistance, liquid crystal aligning, high transparent and high smooth voltinism, and the material that when cured film forms, can in applicable to the glycol series solvent of the production line of the planarization film of colour filter and lactate series solvent, dissolve.
Be used for solving the method for problem
The present inventor conducts in-depth research in order to solve above-mentioned problem, and the result has finished the present invention.
That is, as the 1st viewpoint, relate to a kind of heat cured 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 that comprises structural unit shown in the following formula (1) and have the compound reaction that is selected from the functional group in glycidyl and the isocyanate group and the modified polyester that gets,
(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: 1,2-quinone di-azido compound,
Figure BDA0000097956120000031
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 heat cured film formation of the 1st viewpoint photosensitivity polymer blend, wherein, the polyester that comprises structural unit shown in the above-mentioned formula (1) be comprise tetracarboxylic dianhydride shown in the following formula (i) tetracarboxylic dianhydride's composition with the diol component reaction that comprises diol compound shown in the following formula (ii) polyester
Figure BDA0000097956120000041
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 heat cured film formation of the 1st viewpoint or the 2nd viewpoint photosensitivity polymer blend, in the above-mentioned formula (1), A represents to be selected from least a group in the group shown in following formula (A-1)～formula (A-8), B represents to be selected from least a group in the group shown in following formula (B-1)～formula (B-5)
As the 4th viewpoint, each the described heat cured film that relates to the 1st viewpoint～the 3rd viewpoint forms uses the photosensitivity polymer blend, and wherein, the modified polyester of described conduct (A) composition has take polystyrene conversion as 1,000～3,000 weight-average molecular weight.
As the 5th viewpoint, each the described heat cured film that relates to the 1st viewpoint～the 4th viewpoint forms uses the photosensitivity polymer blend, wherein, described (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 heat cured film that relates to the 1st viewpoint～the 5th viewpoint forms uses the photosensitivity polymer blend, wherein, based on described (A) composition 100 mass parts, contain respectively described (B) composition of 3～50 mass parts, described (C) composition of 3～50 mass parts, described (D) composition of 5～80 mass parts.
As the 7th viewpoint, each the described heat cured 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 heat cured film formation of the 6th viewpoint and use the photosensitivity polymer blend, wherein, based on described (A) composition 100 mass parts, contain the 7th viewpoint described (E) composition of 0.5～50 mass parts.
As the 9th viewpoint, each the described heat cured 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 heat cured 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
Heat cured 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 the liquid crystal orientation film of in the past independent formation and the outer covering layer of colour filter once can be formed as " liquid crystal aligning layer " that have both both characteristics, thereby can reduce to realize cost degradation etc. by simplification and the technique number of manufacturing process.
In addition, heat cured 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 composition on the step difference substrate.
Fig. 2 shows to contrast the synoptic diagram that shows by the prior art liquid crystal aligning layer (a) that obtains and the liquid crystal aligning layer (b) that has used heat cured film of the present invention to form with the photosensitivity polymer blend.
Embodiment
As mentioned above, in the cured film of the 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 up to now to use polyester as the scheme (with reference to Japanese kokai publication hei 5-158055 communique, TOHKEMY 2002-229039 communique) of the oriented material of liquid crystal display device, but these materials all do not have Thermocurable, the poor solvent resistance of formed film.
Therefore, feature of the present invention is to use the Thermocurable polyester to realize the raising of above-mentioned performance.Namely, 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, the heat cured film formation photosensitivity polymer blend of 2-quinone di-azido compound.In addition, the present invention is except containing (A) composition, (B) composition, (C) composition, (D) composition, can also contain bismaleimide compound as the heat cured film formation photosensitivity polymer blend of (E) composition.
Below, describe each composition in detail.
＜(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 isocyanate group modified polyester.Be preferably and make the polyester that is consisted of by structural unit shown in the following formula (1) and have the compound reaction that is selected from the functional group in glycidyl and the isocyanate group and the modified polyester that gets.
Figure BDA0000097956120000061
(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 the saturated hydrocarbyl of expression singly-bound, ehter bond, carbonyl, sulfonic group, carbonatoms 1～8 or the carbonatoms 1～8 that replaced by fluorine atom.Other R 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 more preferably represents the cyclic saturated hydrocarbon base of carbonatoms 4～6.Other A 1Any hydrogen atom contained in the base can be replaced by aliphatic group independently of one another, 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.Form in the situation of ring endocyclics such as norbornene, adamantyl of formation alkyl, the fused polycyclic alkyl that part or all is hydrogenated in these substituting groups combinations.
In addition, R 1The saturated hydrocarbyl of the saturated hydrocarbyl of preferred expression singly-bound, ehter bond, carbonyl, sulfonic group, carbonatoms 1～5 or the carbonatoms 1～5 that replaced by fluorine atom.
In addition, R 2The saturated hydrocarbyl of preferred expression carbonatoms 1～5 more preferably represents 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 particularly preferably the group that is selected from following formula (A-1) or the formula (A-2).
Figure BDA0000097956120000072
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).
Figure BDA0000097956120000081
Formula (1B1) and (1B2) in, B 1Expression ring-type saturated hydrocarbyl, B 2The expression phenylene.In addition, R 3The saturated hydrocarbyl of the saturated hydrocarbyl of expression singly-bound, ehter bond, carbonyl, sulfonic group, carbonatoms 1～8 or the carbonatoms 1～8 that replaced by fluorine atom, R 4, R 5The alkylidene group that represents independently of one another singly-bound or carbonatoms 1～5, R 6, R 7The alkylidene group that represents independently of one another carbonatoms 1～5.In addition, k represents 0 or 1.}
In the above-mentioned formula, B 1Preferred expression carbonatoms is 4～8 cyclic saturated hydrocarbon base, represents that more preferably carbonatoms is 4～6 cyclic saturated hydrocarbon base.In addition, B 1Any hydrogen atom 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.Form in the situation of ring endocyclics such as norbornene, adamantyl of formation alkyl, the fused polycyclic alkyl that part or all is hydrogenated in these substituting groups combinations.
R 3The saturated hydrocarbyl of the saturated hydrocarbyl of preferred expression singly-bound, ehter bond, carbonyl, sulfonic group, carbonatoms 1～5 or the carbonatoms 1～5 that replaced by 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 particularly preferably the group in the following formula (B-1) that is selected from～formula (B-4).
Figure BDA0000097956120000082
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 other structure except group shown in above-mentioned formula (1A1)～formula (1A3).At this moment, as long as form the structure of polyester, 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).
Figure BDA0000097956120000091
In formula (1A4) and formula (1A5), R 8, R 9, R 10The saturated hydrocarbyl of the carbonatoms 1～8 that represents independently of one another the saturated hydrocarbyl of singly-bound, ehter bond, carbonyl, sulfonic group, carbonatoms 1～8 or replaced by fluorine atom.H represents 0 or 1 in addition.}
In the above-mentioned formula, R 8, R 9, R 10The saturated hydrocarbyl of the saturated hydrocarbyl of preferred expression singly-bound, ehter bond, carbonyl, sulfonic group, carbonatoms 1～5 or the carbonatoms 1～5 that replaced by fluorine atom.
R 8The saturated hydrocarbyl of the carbonatoms 1～5 that is particularly preferably the saturated hydrocarbyl of singly-bound, ehter bond, carbonyl, sulfonic group, carbonatoms 1～5 or is replaced by fluorine atom.
In addition, R 9The saturated hydrocarbyl of the carbonatoms 1～5 that is preferably the saturated hydrocarbyl of ehter bond, carbonatoms 1～5 or is replaced by fluorine atom.
And, R 10The saturated hydrocarbyl of the carbonatoms 1～5 that is preferably the saturated hydrocarbyl of ehter bond, carbonyl, sulfonic group, carbonatoms 1～5 or is replaced by fluorine atom.
The preferred object lesson of above-mentioned formula (1A4)～formula (1A5) is shown in following formula (a1)～formula (a7).
Figure BDA0000097956120000092
In particular polymers, preferably comprise the A of structural unit shown in the above-mentioned formula (1) more than at least 60 % by mole for being selected from least a structural unit in the group shown in above-mentioned formula (1A1)～formula (1A3).
As the modified polyester of (A) composition, as described below, can react to obtain by making particular polymers and having the compound that is selected from the functional group in glycidyl and the isocyanate group.
Weight-average molecular weight as the modified polyester of (A) composition is preferably 1,000～30 with polystyrene conversion, and 000, more preferably 1,500～10,000.In 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 heat cured film of the present invention, if surpass above-mentioned scope, then smooth voltinism reduces sometimes.
The manufacture method of＜particular polymers 〉
In the present invention, tetracarboxylic dianhydride's composition that particular polymers can be by comprising tetracarboxylic dianhydride shown in the following formula (i) (below be also referred to as sour composition) and diol compound shown in the following formula (ii) (below be also referred to as diol component) reaction obtains.
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, diol compound can use separately or also can use more than 2 kinds independently of one another shown in tetracarboxylic dianhydride shown in the above-mentioned formula (i), the above-mentioned formula (ii).
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).
Figure BDA0000097956120000102
{ in the formula (i2), W represents to be selected from least a structure in the group shown in the middle above-mentioned formula (1A4) that defines of above-mentioned formula (1) and the formula (1A5), R 8, R 9, R 10Identical with above-mentioned definition implication with h.}
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-mentioned formula (i) more than at least 60 % by mole in the preferred acid composition.
In above-mentioned particular polymers, preferred tetracarboxylic dianhydride's total amount (total amount of sour composition) with the proportioning of the total amount (total amount of diol component) of diol compound, namely＜total mole number of diol compound/＜total mole number of tetracarboxylic dianhydride's compound be 0.95～1.5.With common polycondensation similarly, this mol ratio is more near 1, the polymerization degree of the particular polymers of generation is larger, molecular weight is larger.
The end of above-mentioned particular polymers changes according to the proportioning of sour composition and diol component.For example, in the situation that makes sour composition excessive response, the terminal acid anhydrides that forms easily.
In addition, carry out in the situation of polymerization 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 the compound reaction with glycidyl under because gelation occurs for the hydroxyl and the anhydride reaction that generate, so need to 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 ℃ arbitrarily temperature.Can be that 100～140 ℃, reaction times are to obtain particular polymers under 2～48 hours the condition in temperature of reaction for example.
In addition, can select 50～200 ℃, be preferably 80～170 ℃ arbitrarily temperature with the temperature of reaction in 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, so long as the solvent of hydroxyl, amino etc. and the functional group of anhydride reaction does not get final product, be not particularly limited.For example can enumerate, N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, NVP, the N-methyl caprolactam, methyl-sulphoxide, tetramethyl-urea, dimethyl sulfone, the hexamethyl sulfoxide, meta-cresol, gamma-butyrolactone, pimelinketone, cyclopentanone, methylethylketone, methyl iso-butyl ketone (MIBK), 2-heptanone, methylcellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ether acetate, propylene glycol propyl ether acetic ester, the 3-methoxy methyl propionate, the 2-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 2-methoxy propyl acetoacetic ester, the 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 by 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 salt, the tetraphenylphosphonichloride chloride 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
Figure BDA0000097956120000121
Tetraphenylphosphonibromide bromide
Figure BDA0000097956120000122
Benzyl triphenyl phosphonium chloride
Figure BDA0000097956120000123
Benzyl triphenyl bromination
Figure BDA0000097956120000124
The ethyl triphenyl chlorination
Figure BDA0000097956120000125
The ethyl triphenyl bromination
Figure BDA0000097956120000126
In season
Figure BDA0000097956120000127
Salt.
＜(A) manufacturing of composition 〉
The compound that is selected from the functional group in glycidyl and the isocyanate group that has that can add by the carboxyl with respect to particular polymers 10～90 % by mole as the polyester of (A) composition makes it react 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, propylene glycol list ethyl ether, propylene glycol single-butyl ether, propylene glycol 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, n-butyl alcohol, 2-butanols, the trimethyl carbinol, hexalin etc.These solvents can use separately or be used in combination more than 2 kinds.
As with the concrete example of the compound with glycidyl of the carboxyl addition of particular polymers, can enumerate glycidyl methacrylate, glycidyl acrylate, the methyl glycidyl ether, ethyl glycidyl ether, allyl glycidyl ether, 4-tert-butyl-phenyl glycidyl ether, the glycidyl phenyl ether, glycidyl-2-methyl phenyl ether, the glycidyl propyl ether, the glycidyl isopropyl ether, the glycidyl butyl ether, the 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 isocyanate group of the carboxyl addition of particular polymers, can enumerate methyl isocyanate, ethyl isocyanate, the propyl group isocyanic ester, isopropyl isocyanate, n-butyl isocyanate, the 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, the benzyl isocyanate ester, methacrylic acid 2-isocyanate group ethyl ester, 2-anisole based isocyanate, 3-anisole based isocyanate, 4-anisole based isocyanate, the amyl group isocyanic ester, hexyl isocyanic ester etc.
The carboxyl of particular polymers with and the temperature of reaction with the compound that is selected from the functional group in glycidyl and the isocyanate group of its reaction can select 50～160 ℃, be preferably 80～140 ℃ arbitrarily temperature.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 be directly used in modulation heat cured film formation of the present invention photosensitivity polymer blend.In addition, can make polyester precipitate and separate and recovery in the poor solvents such as water, methyl alcohol, ethanol, ether, hexane, then use.
＜(B) composition 〉
The epoxy compounds with 2 above epoxy group(ing) as (B) of the present invention composition, for example can enumerate, three (2, the 3-epoxypropyl) isocyanuric acid ester, 1, the 4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxy ethyl) hexanaphthene, T 55, the 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, the 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 product.Below enumerate its concrete example (trade(brand)name), but be not limited to this: YH-434, YH434L (Dongdu changes into (strain) system) etc. have amino Resins, epoxy; 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 Resins, epoxy 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, the bisphenol A type epoxy resins such as エ ピ コ one ト 1010, エ ピ コ one ト 828 (oiling シ エ Le エ Port キ シ (strain) (existing ジ ヤ パ Application エ Port キ シ レ ジ Application (strain)) system); The bisphenol f type epoxy resins such as エ ピ コ one ト 807 (oiling シ エ Le エ Port キ シ (strain) (existing ジ ヤ パ Application エ Port キ シ レ ジ Application (strain)) system); 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), the phenol phenolic resin type Resins, epoxy such as EPPN201, EPPN202 (Japanese chemical drug (strain) system); EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (Japanese chemical drug (strain) system), the cresol novolac resin type Resins, epoxy such as エ ピ コ one ト 180S75 (oiling シ エ Le エ Port キ シ (strain) (existing ジ ヤ パ Application エ Port キ シ レ ジ Application (strain)) system); 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 (large 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, the alicyclic epoxy resins such as ED-5662 (セ ラ ニ one ズ コ one テ イ Application グ (strain) system); The aliphatics polyglycidyl ethers such as 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 (Na ガ セ ケ system テ Star Network ス (strain) system) etc.
In addition, as the compound with at least two epoxy group(ing), can use the polymkeric substance with epoxy group(ing).As such polymkeric substance, namely can use so long as have the polymkeric substance of epoxy group(ing), be not particularly limited.
Above-mentioned polymkeric substance with epoxy group(ing) for example can be made by carrying out addition polymerization with the addition polymerization monomer with epoxy group(ing).As an example, can enumerate multipolymer, glycidyl methacrylate and the vinylbenzene of polyacrylic acid glycidyl ester, glycidyl methacrylate and β-dimethyl-aminoethylmethacrylate and the addition polymer such as multipolymer of 2-hydroxyethyl methacrylate, and/or the polycondensate such as epoxy-Novolak resin.
Perhaps, above-mentioned polymkeric substance with epoxy group(ing) can also react to make by the compound that makes macromolecular compound with hydroxyl and Epicholorohydrin, toluenesulphonic acids glycidyl ester etc. have epoxy group(ing).
As the weight-average molecular weight of such polymkeric substance, take polystyrene conversion for example as 300～200,000.
These epoxy compoundss with 2 above epoxy group(ing) can use separately or be used in combination more than 2 kinds.
Heat cured 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 particularly preferably 10～30 mass parts.In 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 heat cured film reduce sometimes, and on the other hand, in 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 by diamine compound and dicarboxylic acid dianhydride reaction.Particularly, be by 1 mole of the diamine compound shown in the following formula (iii) and 1.7～2 moles of dicarboxylic acid dianhydride shown in the following formula (iv), be preferably the amino carboxylic acid cpd that contains that 1.8～2 molar reactives get.
H 2N-P-NH 2 (iii)
Figure BDA0000097956120000151
{ in formula (iii) and the formula (iv), P and Q represent the divalent organic group independently of one another.}
Therefore, by making the dicarboxylic acid reaction shown in the diamine compound shown in the above-mentioned formula (iii) and the above-mentioned formula (iv), can obtain the compound shown in the following formula (2).
Figure BDA0000097956120000161
{ in the formula, P and Q are identical with definition implication in above-mentioned formula (iii) and the formula (iv).}
In the present invention, diamine compound and dicarboxylic acid dianhydride can only be used respectively a kind of, 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.
In the above-mentioned formula (iii), as the ring structure that P has, be preferably the alicyclic ring of phenyl ring, carbonatoms 4～8, the fused polycyclic hydrocarbon of carbonatoms 7～16.
Therefore, concrete example as the diamine compound with such ring structure, can enumerate following compound: Ursol D, mphenylenediamine, 2, the 4-diaminotoluene, 2, the 5-diaminotoluene, 2, the 6-diaminotoluene, 2,4-dimethyl-1, the 3-diaminobenzene, 2,5-dimethyl-1, the 4-diaminobenzene, 2,3,5,6-tetramethyl--1, the 4-diaminobenzene, 2, the 4-diaminophenol, 2, the 5-diaminophenol, 4, the 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, the 5-naphthylene diamine, 2, the 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-benzanilide, two (4-aminophenyl) ethane of 1,2-, 1, two (3-aminophenyl) ethane of 2-, 4,4 '-diamino tolane, two (4-aminophenyl) propane of 1,3-, two (3-aminophenyl) propane of 1,3-, 2, two (4-aminophenyl) propane of 2-, 2, two (3-aminophenyl) propane of 2-, two (3-amino-4-aminomethyl phenyl) propane of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 2, two (3-aminophenyl) HFC-236fa of 2-, 2, two (3-amino-4-aminomethyl phenyl) HFC-236fa of 2-, two (4-amino-benzene oxygen) propane of 1,3-, Isosorbide-5-Nitrae-two (4-amino-benzene oxygen) butane, 1, two (4-amino-benzene oxygen) pentanes of 5-, 1, two (4-amino-benzene oxygen) hexanes of 6-, two (4-amino-benzene oxygen) heptane of 1,7-, two (4-amino-benzene oxygen) octanes of 1,8-, 1, two (4-amino-benzene oxygen) nonanes of 9-, 1, two (4-amino-benzene oxygen) decane of 10-, two (4-amino-benzene oxygen) undecanes of 1,11-, two (4-amino-benzene oxygen) dodecanes of 1,12-, 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 of 4-, 1, two (4-aminophenyl) benzene of 3-, Isosorbide-5-Nitrae-two (4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, 1, two (4-aminobenzyl) benzene of 4-, 1, 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, Isosorbide-5-Nitrae-phenylene two [(4-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two [(3-aminophenyl) ketone], 1,3-phenylene two [(4-aminophenyl) ketone], 1,3-phenylene two [(3-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two (PABA ester), Isosorbide-5-Nitrae-phenylene two (3-Aminobenzoate), 1,3-phenylene two (PABA ester), 1,3-phenylene two (3-Aminobenzoate), N, N '-(Isosorbide-5-Nitrae-phenylene) two (4-aminobenzamides), N, N '-(1, the 3-phenylene) two (4-aminobenzamide), N, N '-(Isosorbide-5-Nitrae-phenylene) two (3-ABs), N, N '-(1, the 3-phenylene) two (3-AB), two (4-aminophenyl) terephthalamide, two (3-aminophenyl) terephthalamide, two (4-aminophenyl) isophthaloyl amine, two (3-aminophenyl) isophthaloyl amine, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, 4,4 '-two (4-amino-benzene oxygen) sulfobenzide, 2, the 6-diamino-pyridine, 2,4-diamino-pyridine, 2,4-diaminostilbene, 3, the 5-triazine, 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, two (the 4-aminophenyls)-1 of 2,5-, 3,4-
Figure BDA0000097956120000171
Diazole, Isosorbide-5-Nitrae-diamino-cyclohexane, 1,3-diamino-cyclohexane, two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane etc.
In addition, in the above-mentioned formula (iv), as the ring structure that Q has, 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 the 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 ℃ arbitrarily temperature.
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, N,N-dimethylacetamide, METHYLPYRROLIDONE, NVP, the N-methyl caprolactam, methylimidazole, methyl-sulphoxide, tetramethyl-urea, dimethyl sulfone, the hexamethyl sulfoxide, meta-cresol, gamma-butyrolactone, pimelinketone, cyclopentanone, methylethylketone, methyl iso-butyl ketone (MIBK), 2-heptanone, propylene glycol methyl ether acetate, propylene glycol propyl ether acetic ester, the 3-methoxy methyl propionate, the 2-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 2-methoxy propyl acetoacetic ester, the 3-ethoxyl ethyl propionate, the 2-ethoxyl ethyl propionate, methylcellosolve acetate, ethyl cellosolve acetate, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, propylene glycol monomethyl ether, the propylene glycol propyl ether, hexalin, ethyl acetate, butylacetate, ethyl lactate, n-Butyl lactate etc.
These solvents can be used alone, but also also mix together, but from the solvability aspect, preferred propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N,N-dimethylacetamide, METHYLPYRROLIDONE, 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 by polyreaction is not separated out, be blended in the above-mentioned solvent and use.
The content of (C) composition in the polyester composite for forming thermoset films of the present invention is preferably 3～50 mass parts based on polyester 100 mass parts as (A) composition, more preferably 5～40 mass parts.In the too small situation of this ratio, the orientation of the cured film that is formed by polyester composite for forming thermoset films of the present invention reduces sometimes, and on the other hand, in excessive situation, loss of transmission and/or smooth voltinism reduces sometimes.
＜(D) composition 〉
As 1 of (D) composition, the 2-quinone di-azido compound, it is the compound with hydroxyl or amino any one or hydroxyl and amino both, can use in these hydroxyls or the amino (in the situation with hydroxyl and amino both, being their total amount) preferred 10～100 % by mole, particularly preferably 20～95 % by mole by the sulfonic acid esterification of 1,2-quinone diazido or amidated compound.
As above-mentioned compound with hydroxyl, 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, 4,4-isopropylidene xenol, 2, two (4-hydroxy phenyl) propane of 2-, 1, the 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, the 4-dihydroxy benaophenonel, 2,3, the 4-trihydroxybenzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, 2,2 ', 3,4,4 '-pentahydroxybenzophenone, the phenolic compound such as two (the 2-hydroxy-5-methyl base benzyl) methyl of 2,5-, ethanol, the 2-propyl alcohol, the 4-butanols, hexalin, ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, 2-methyl cellosolve, butoxy ethanol, the 2-methoxypropanol, 2-butoxy propyl alcohol, ethyl lactate, the aliphatics alcohols such as n-Butyl lactate.
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, the 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, p-aminophenol, the 4-aminoresorcinol, 2, the 3-diaminophenol, 2, the 4-diaminophenol, 4,4 '-diamino-4 "-the 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 of 2-, the aminophenols such as two (4-amino-3-carboxyl-5-hydroxy phenyl) HFC-236fa of 2,2-, the 2-monoethanolamine, the 3-aminopropanol, the alkanol amines such as 4-Trans-4-Amino Cyclohexanol.
These 1, the 2-quinone di-azido compound can use separately or be used in combination more than 2 kinds.
Heat cured 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 particularly preferably 10～50 mass parts.In the too small situation of this ratio, sometimes diminish to the dissolution rate of developing solution is poor, be difficult to form by developing pattern.In addition, if greater than 100 mass parts, then owing to can not decompose fully 1,2-quinone di-azido compound by the exposure in the short period of time, therefore sometimes sensitivity 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.
Figure BDA0000097956120000201
(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 the 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-diethyl-5, the 5-dimethyl)-4,4-phenylbenzene-methane bismaleimides, N, N '-4,4-ditan bismaleimides, 3,3-sulfobenzide bismaleimides, 4,4-sulfobenzide bismaleimides, N, N '-to the benzophenone 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 '-(3,3-diethyl)-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, two (4-(4-maleimide phenoxyl) phenyl) propane of 2,2-, two (3-chloro-4-(4-maleimide phenoxyl) phenyl) propane of 2,2-, 2, two (3-bromo-4-(4-maleimide phenoxyl) phenyl) propane of 2-, 2, two (3-ethyl-4-(4-maleimide phenoxyl) phenyl) propane of 2-, two (3-propyl group-4-(4-maleimide phenoxyl) phenyl) propane of 2,2-, two (3-sec.-propyl-4-(4-maleimide phenoxyl) phenyl) propane of 2,2-, 2, two (3-butyl-4-(4-maleimide phenoxyl) phenyl) propane of 2-, 2, two (3-methoxyl group-4-(4-maleimide phenoxyl) phenyl) propane of 2-, two (4-(4-maleimide phenoxyl) phenyl) ethane of 1,1-, two (3-methyl-4-(4-maleimide phenoxyl) phenyl) ethane of 1,1-, 1, two (3-chloro-4-(4-maleimide phenoxyl) phenyl) ethane of 1-, 1, two (3-bromo-4-(4-maleimide phenoxyl) phenyl) ethane of 1-, two (4-(4-maleimide phenoxyl) phenyl) pentanes of 3,3-, 1,1,1,3,3,3-hexafluoro-2, two (4-(4-maleimide phenoxyl) phenyl) propane of 2-, 1,1,1,3,3,3-hexafluoro-2, two (3,5-dimethyl-4-(4-maleimide phenoxyl) phenyl) propane of 2-, 1,1,1,3,3,3-hexafluoro-2, two (3,5-, two bromo-4-(4-maleimide phenoxyl) phenyl) propane of 2-, 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 particularly limited in above-claimed cpd.
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-diethyl-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.
Heat cured film of the present invention forms the content with (E) composition in the photosensitivity polymer blend, be preferably 0.5～50 mass parts with respect to polyester 100 mass parts as (A) composition, more preferably 1～30 mass parts is particularly preferably 2～20 mass parts.In the too small situation of this ratio, the smooth voltinism that is formed the cured film that forms with the photosensitivity polymer blend by heat cured film of the present invention reduces sometimes, in excessive situation, and the loss of transmission and/or film cracking of cured film sometimes.
＜solvent 〉
Heat cured film of the present invention forms and often uses under the solution state in being dissolved in solvent with the photosensitivity polymer blend.The solvent that uses this moment is for the composition of dissolving (A) composition～(D) and the solvent of (E) composition and/or other additive of aftermentioned as required, get final product so long as have the solvent of such dissolving power, its kind and structure etc. are not particularly limited.
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 ethyl acetate, butylacetate etc. in addition.
These solvents can use separately or be used in combination more than two kinds.
＜other additive 〉
In addition, only otherwise destroy effect of the present invention, heat cured film of the present invention forms can contain the dissolution accelerators such as the adhesive aids such as tensio-active agent, rheology control agent, silane coupling agent, pigment, dyestuff, preserving stabilizer, defoamer, polyphenol and/or polycarboxylic acid etc. as required with the photosensitivity polymer blend.
＜heat cured film forms uses the photosensitivity polymer blend 〉
Heat cured film of the present invention form with the photosensitivity polymer blend be the epoxy compounds with 2 above epoxy group(ing) that comprises polyester as (A) composition, conduct (B) composition, conduct (C) composition the carboxylic acid cpd that contains amino, conduct (D) composition 1, the 2-quinone di-azido compound, also can contain as required the bismaleimide compound of conduct (E) composition and more than one the composition in other additive.And these compositions often are dissolved in and make solution in the solvent and use usually.
Wherein, heat cured film of the present invention forms with the preferred example of photosensitivity polymer blend as follows.
[1]: based on (A) composition 100 mass parts, the heat cured 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, contain (B) composition of 3～50 mass parts, (C) composition of 3～50 mass parts, (D) composition of 5～80 mass parts, the heat cured film formation photosensitivity polymer blend of solvent.
[3]: based on (A) composition 100 mass parts, the heat cured 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, contain (B) composition of 3～50 mass parts, (C) composition of 3～50 mass parts, (D) composition of 5～80 mass parts, (E) composition of 0.5～50 mass parts, the heat cured film formation photosensitivity polymer blend of solvent.
Mixing ratio when below detailed description heat cured film formation of the present invention is used as solution with the photosensitivity polymer blend, modulator approach etc.
Form the ratio of using the solids component in the photosensitivity polymer blend for heat cured film of the present invention, so long as each homogeneous chemical composition be dissolved in solvent and get final product, be not particularly limited, can be 1～80 quality %, preferred 5～60 quality %, more preferably 10～50 quality %.Here, solids component refers to form with the part after the desolventizing whole compositions of photosensitivity polymer blend from heat cured film.
The modulator approach that heat cured film of the present invention is formed with the photosensitivity polymer blend is not particularly limited, 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 be blended in this solution with the regulation ratio, make the method for homogeneous solution, the method for perhaps further adding as required other additive and mixing in the suitable stage of this modulator approach.
When modulation heat cured film of the present invention forms with the photosensitivity polymer blend, can directly use by 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 making homogeneous solution with above-mentioned (B) composition, (C) composition, (D) composition, (E) of similarly adding, can further add solvent in order to adjust concentration.At this moment, the solvent that uses in the generative process of polyester can be identical for the solvent of adjusting concentration when forming with the photosensitivity polymer blend with the modulation heat cured film, also can be different.
And the heat cured film that modulates forms solution with the photosensitivity polymer blend, and preferably to use the aperture be to re-use after the filtrations such as strainer about 0.2 μ m.
＜film, cured film and liquid crystal aligning layer
By spin coating, flow coat, roller coat, slot coated, slot coated is follow-up with spin coating, ink-jet application, the modes such as printing are coated on substrate with heat cured film formation of the present invention with the photosensitivity polymer blend, and (for example silicon/silicon dioxide coats substrate, silicon nitride board, be coated with for example aluminium of metal, molybdenum, the substrate of chromium etc., glass substrate, quartz base plate, ito substrate etc.), film (tri acetyl cellulose membrane for example, polyester film, the resin moldings such as vinylformic acid mesentery) etc. on, then can form and film by carry out predrying (prebake conditions) with hot plate or baking oven etc.Then, carry out heat treated by 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, the thickness that is formed the coating that forms with the photosensitivity polymer blend by heat cured film for example is 0.1～30 μ m, can consider that step difference, optical property, the electrical properties of employed substrate suitably selected.
As rear baking, generally adopt following method: under the Heating temperature of from the scope of 140～250 ℃ of temperature, selecting, processed 5～30 minutes in the situation of use hot plate, processed 30～90 minutes in the situation of use baking oven.
Under aforesaid condition, by being formed with the photosensitivity polymer blend, heat cured film of the present invention solidifies, and the abundant planarization of step difference of substrate can be made, and the cured film with high transparent can be formed.
Carry out friction treatment by the cured film to such formation, 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 by carrying out ultrasonic cleaning with pure water etc.
Then liquid crystal aligning layer coating phase differential material forming like this makes the phase differential material be light-cured into and is mesomorphic state, has optically anisotropic layer thereby can form.
As the phase differential material, can use such as the liquid crystal monomer with polymerizable group or contain composition of this liquid crystal monomer etc.
In addition, be in 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 mentioned above the liquid crystal aligning layer that forms are bonding in the relative mode of liquid crystal aligning layer across spacer, then between these substrates, inject liquid crystal, thus make liquid crystal aligning liquid crystal display device.
Therefore, heat cured 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 heat cured 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, and particularly preferably conduct forms the material of the outer cover material material of 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 as described below.
＜polyester raw material 〉
BPDA: bibenzene tetracarboxylic dianhydride
HBPDA:3,3 '-4,4 '-dicyclohexyl tetracarboxylic acid dianhydride
HBPA: Hydrogenated Bisphenol A
THPA:1,2,5,6-Tetra Hydro Phthalic Anhydride
BTEAC: benzyltriethylammoinium chloride
TPPB: tetraphenylphosphonibromide bromide
GMA: glycidyl methacrylate
GME: glycidyl methyl ether
DTBC: di-tertiary butyl methyl phenol
＜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:1,2,4-benzenetricarboxylic anhydride
DDS:4,4 '-diamino diphenyl sulfone
PDA: Ursol D
＜acrylic copolymer raw material 〉
MAA: methacrylic acid
MMA: methyl methacrylate
HEMA: 2-hydroxyethyl methacrylate
The CHMI:N-N-cyclohexylmaleimide
AIBN: Diisopropyl azodicarboxylate
＜epoxy compounds 〉
CEL: ダ イ セ Le chemical industry (strain) セ ロ processed 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-diethyl-5,5-dimethyl)-4,4-phenylbenzene-methane bismaleimides
＜1,2-quinone di-azido compound 〉
QD1: by 1 mole of 1,3,3-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: by 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 the resulting polyester of following synthesis example, polyimide precursor and acrylic copolymer are measured under the following conditions: use Japanese light splitting (strain) GPC device processed (Shodex (registered trademark) chromatographic column KF803L and KF804L), the eluting solvent tetrahydrofuran (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 (hereinafter referred to as Mn) and weight-average molecular weight (hereinafter referred to as Mw) are with the polystyrene conversion value representation.
＜synthesis 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 that 1,500, Mw is 3,430.
＜synthesis example 2 〉
Add GMA 18.42g, DTBC 0.057g, PGME 42.99g among solution (P1) 252.00g of the particular polymers that in synthesis 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 that 1,260, Mw is 6,880.
＜synthesis example 3 〉
In solution (P1) 252.00g of the particular polymers that synthesis example 1 obtains, 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 Isosorbide-5-Nitrae 50, and Mw is 5,340.
＜synthesis 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 high performance liquid chromatography to confirm not have remaining THPA.
＜synthesis 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 high performance liquid chromatography to confirm not have remaining THPA.
＜synthesis 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 that 1,100, 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 that 1,580, Mw is 7,540.
＜synthesis 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 that 5,800, Mw is 12,500.
＜synthesis 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 temperature 60 C～100 ℃, 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 that 3,800, Mw is 6,700.
＜embodiment 1～5 and comparative example 1～5 〉
According to each composition of the composition shown in the table 1 modulation embodiment 1～5 and comparative example 1～5, smooth voltinism, solvent resistance, orientation, thermotolerance, pattern formative and the transmissivity of the cured film that obtained by said composition are estimated.
Table 1
Figure BDA0000097956120000281
※ 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 composition of embodiment 1～embodiment 5 and comparative example 1～comparative example 5 is coated on the step difference substrate (glass system) of height 0.5 μ m, live width 10 μ m, wire spacing 50 μ m, then under 110 ℃ of temperature, carry out prebake conditions 120 seconds at hot plate, formed filming of thickness 2.8 μ m.Thickness uses the F20 processed of FILMETRICS society to measure.By baking after 230 ℃ of lower heating of temperature were carried out in 30 minutes that this is filmed, formed the cured film of thickness 2.5 μ m.
Measure on the step difference plate line film and the interval on the film thickness difference of filming (with reference to Fig. 1), use the formula of smooth rate (DOP)=100 * (height of the film thickness difference that 1-{ films (μ m)/step difference substrate (0.5 μ m) }) to obtain smooth rate.
[evaluation of pattern formative]
Use the rotary coating machine that each composition of embodiment 1～embodiment 5 and comparative example 1～comparative example 5 is coated on the glass substrate, then under 110 ℃ of temperature, carried out prebake conditions 120 seconds at hot plate, formed filming of thickness 2.8 μ m.Thickness uses the F20 processed of FILMETRICS society to measure.Across the Xian ﹠amp with 10 μ m; The mask of intermittent pattern, UV irradiation equipment PLA-600FA processed films with 100mJ/cm to this by キ ヤ ノ Application (strain) 2The light intensity of irradiation 365nm is 5.5mW/cm 2Ultraviolet ray.Then, developed in 60 seconds by dipping in Tetramethylammonium hydroxide (hereinafter referred to as the TMAH) aqueous solution of 0.2 quality %, then carry out flowing water washing 20 seconds with ultrapure water.Line with the observation by light microscope gained; Intermittent pattern, with obtain meeting mask design pattern be designated as zero, with pattern not by exploring, being designated as of dissolving when developing *.
[evaluation of solvent resistance]
Use the rotary coating machine that each composition 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 F20 processed of FILMETRICS society to measure.With this baking 30 minutes of filming under 230 ℃ of temperature after hot plate carries out, formed the cured film of thickness 2.5 μ m.
This cured film was flooded 60 seconds in PGMEA or NMP, then descended dry 60 seconds 100 ℃ of temperature respectively, measure thickness.Be designated as zero with thickness is unconverted behind PGMEA or the NMP dipping, with being designated as of observing behind the dipping that thickness reduces *.
[evaluation of optical transmittance (transparency)]
Use the rotary coating machine that each composition of embodiment 1～embodiment 5 and comparative example 1～comparative example 5 is coated on the quartz base plate, then under 100 ℃ of temperature, carried out prebake conditions 120 seconds at hot plate, formed filming of thickness 2.8 μ m.Thickness uses the F20 processed of FILMETRICS society to measure.Dipping developed in 60 seconds in the TMAH aqueous solution of 0.2 quality % by this is filmed, and then carried out flowing water washing 20 seconds with ultrapure water.Then, by キ ヤ ノ Application (strain) UV irradiation equipment PLA-600FA processed with 500mJ/cm 2The light intensity of irradiation 365nm is 5.5mW/cm 2Ultraviolet ray.With this baking 30 minutes of filming under 230 ℃ of temperature after hot plate carries out, formed cured film.
Use ultraviolet-visible pectrophotometer (the SHIMADSU UV-2550 processed of (strain) Shimadzu Seisakusho Ltd. model) to measure the transmissivity of this cured film when wavelength 400nm.
[evaluation of orientation]
Use the rotary coating machine that each composition 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 F20 processed of FILMETRICS society to measure.With this baking 30 minutes of filming under 230 ℃ of temperature after hot plate carries out, 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.Substrate after the friction treatment is used 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, then carries out 100 ℃ of lower 40 seconds, 55 ℃ lower prebake conditions of 30 seconds at hot plate, has formed filming of thickness 1.1 μ m.This substrate is exposed with 2,000mJ under nitrogen atmosphere.With the substrate clamping made between deflector plate, the Visual Confirmation orientation.Be designated as zero with what substrate tilted the 45 optical transmission noticeable changes when not tilting when spending, with indeclinable being designated as *.
[stable on heating evaluation]
Use the rotary coating machine that each composition 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, then baking 30 minutes after hot plate carries out under 230 ℃ of temperature, formed cured film, thickness uses the F20 processed of FILMETRICS society to measure.Then, again with cured film under 230 ℃ of temperature hot plate baking 60 minutes, again measure thickness, calculate the velocity of variation of the thickness that begins after the rear baking.In addition, be considered to have stable on heating cured film, need to have at least the Thickness Variation rate to be lower than ± 5% performance.
[result of evaluation]
That carries out that above evaluation obtains the results are shown in following table 2.
Table 2
Figure BDA0000097956120000311
In embodiment 1～embodiment 5, can form pattern, smooth 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 section also is dissolved in the developing solution, can not form pattern.
In comparative example 2, exposure section 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, smooth rate is low, can not form pattern.
On the other hand, in comparative example 5, the result is that although can form pattern, smooth rate, thermotolerance, solvent resistance and transmissivity are good, poor orientation.
As mentioned above, obtained following result: heat cured film formation of the present invention can be used the glycol series solvents such as propylene glycol methyl ether acetate when cured film forms with the photosensitivity polymer blend.In addition, can form pattern by 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 heat cured 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 (8)

1. a heat cured 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 that comprises structural unit shown in the following formula (1) and have the compound reaction that is selected from the functional group in glycidyl and the isocyanate group and the modified polyester that gets,
(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: 1,2-quinone di-azido compound,
Figure FDA00003245078400011
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,
Based on described (A) composition 100 mass parts, contain respectively described (B) composition of 3～50 mass parts, described (C) composition of 3～50 mass parts, described (D) composition of 5～80 mass parts.
2. heat cured film according to claim 1 forms and uses the photosensitivity polymer blend, wherein, the polyester that comprises structural unit shown in the above-mentioned formula (1) be comprise tetracarboxylic dianhydride shown in the following formula (i) tetracarboxylic dianhydride's composition with the diol component reaction that comprises diol compound shown in the following formula (ii) polyester
Figure FDA00003245078400012
Formula (i) and (ii) in, A and B are identical with definition implication in the above-mentioned formula (1).
3. heat cured film according to claim 1 and 2 forms and uses the photosensitivity polymer blend, in the above-mentioned formula (1), A represents to be selected from least a group in the group shown in following formula (A-1)～formula (A-8), B represents to be selected from least a group in the group shown in following formula (B-1)～formula (B-5)
Figure FDA00003245078400021
4. heat cured film according to claim 1 forms and uses the photosensitivity polymer blend, and wherein, the modified polyester of described conduct (A) composition has take polystyrene conversion as 1,000～30 000 weight-average molecular weight.
5. heat cured film according to claim 1 forms and uses the photosensitivity polymer blend, and wherein, described (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. heat cured film according to claim 1 forms and uses the photosensitivity polymer blend, wherein, also contain bismaleimide compound as (E) composition, based on described (A) composition 100 mass parts, contain (E) composition of 0.5～50 mass parts.
7. each the described heat cured film by claim 1～6 forms the cured film that forms with the photosensitivity polymer blend.
8. each described heat cured film of right to use requirement 1～6 forms the liquid crystal aligning layer that obtains with the photosensitivity polymer blend.
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JP5626536B2 (en) 2014-11-19
JPWO2010119868A1 (en) 2012-10-22
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KR101660827B1 (en) 2016-09-28
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