CN109423192A - Thermosetting composition, cured film and colored filter - Google Patents

Abstract

The present invention relates to a kind of thermosetting composition, cured film and colored filter, the thermosetting composition includes the polymer (B) and curing agent (C) of polyesteramide sour (A), cyclic ether compound.The polyesteramide sour (A) is derived from the reaction product for raw material of the ratio comprising X moles of tetracarboxylic dianhydride, Y moles of diamines and Z moles of multi-hydroxy compound set up with the relationship of following formula (1) and formula (2), and the polymer (B) of cyclic ether compound is the polymer with the compound (b1) of oxetanylmethoxy.Barrier excellent cured film can be formed by thermosetting composition of the invention, and the reliability of the electronic component with the cured film improves.0.2≦Z/Y≦8.0·······(1)0.2≦(Y+Z)/X≦5.0···(2).

Description

Thermosetting composition, cured film and colored filter

Technical field

The present invention relates in a kind of insulating materials that can be used for being formed in electronic component, semiconductor device passivating film, Buffer film, interlayer dielectric, planarization film, the interlayer dielectric in liquid crystal display element, colored filter (color Filter) with the thermosetting composition of protective film etc., the hyaline membrane formed by the thermosetting composition and with described The electronic component of film.

Background technique

In the manufacturing step of the elements such as liquid crystal display element, variousization of organic solvent, acid, aqueous slkali etc. are carried out sometimes Product processing, or when wiring electrode is formed a film by sputtering (sputtering), surface is locally heated at high temperature. Therefore, sometimes for the deterioration on the surface for preventing various elements, damage, rotten purpose and surface protection film is set.To these Protective film requires each characteristic for the various processing that can be resistant in manufacturing step as described above.Specifically, it is desirable that heat resistance, The chemical-resistants such as solvent resistance acid resistance alkali resistance, water resistance, the adhesion to basal substrates such as glass, the transparency, Scratch resistance, flatness, light resistance etc..The requirement characteristic of the reliability required by with to display element improves, to display During heat resistance required by members improves, it is good comprising polyesteramide acid and epoxide to advocate heat resistance Thermosetting composition (patent document 1).In turn, in recent years to the liquid crystal display element through High precision, slimming Required flatness improves, and advocates heat resistance well and the good thermosetting composition (patent document 2) of flatness.

It is (following to the characteristic of the dissolution of the reduction substrate composition except heat resistance, flatness recently in addition to the characteristic It is also referred to as barrier) requirement reinforce.In this context, especially in the field of colored filter, have for wide colour gamut Reply, in each colored filter manufacturer, it is seen that the pigment or take off in order to prevent that good using color and easy dissolution is decomposed Color and the tendency for making the processing bottom line of photo-hardening etc..As a result, for do not cope with these tendency existing protective film and Speech inhibits the dissolution of substrate with being unable to fully, and generates and be mixed into dissolved element when forming panel, makes the display quality of display The problem of reducing, as a result reducing yield.

For this requirement, as to specific countermeasure required by protective film, it is desirable that be to be prevented when forming alignment films Capture (trap) comes from colored filter in the calcination process in step after being orientated the solvent circulation of coating solution, forming protective film Gas componant etc..

The Protective coatings excellent as these, except thermosetting resin composition illustrated above (patent document 1 and specially Sharp document 2) other than, there are also thermosetting polymer composition (patent documents 3).On the other hand, patent document 1 and patent document Although 3 composition presence is good to the patience of various processing, flatness is insufficient, and optionally different and barrier low Problem.Although in addition, the composition of patent document 2 there is also to various processing patience and flatness it is good, it is barrier low The problem of.

[existing technical literature]

[patent document]

[patent document 1] Japanese Patent Laid-Open 2005-105264

[patent document 2] Japanese Patent Laid-Open 2008-156546

[patent document 3] Japanese Patent Laid-Open 2006-282995

Summary of the invention

[problem to be solved by the invention]

The issue of the present invention is to provide a kind of offers to prevent the dissolution of substrate composition and the excellent cured film of flatness Thermosetting composition and the cured film formed by the thermosetting composition, and then provide a kind of with the cured film Electronic component.

[technical means to solve problem]

The inventors of the present invention people has carried out making great efforts research in order to solve the problem, as a result, it has been found that, utilize following cured film It may achieve the purpose, so as to complete the present invention, the cured film is made comprising as tetracarboxylic dianhydride, diamines and polynary hydroxyl The composition hardening of the polyesteramide acid, the polymer of cyclic ether compound and curing agent of the reaction product of based compound and It obtains.

The present invention includes composition below.

[1] a kind of thermosetting composition, it includes polyesteramides sour (A), the polymer (B) of cyclic ether compound and hard Agent (C),

It includes X moles that the polyesteramide sour (A), which is derived from the ratio that the relationship of following formula (1) and formula (2) is set up, The reaction product of the raw material of tetracarboxylic dianhydride, Y moles of diamines and Z moles of multi-hydroxy compound,

0.2≦Z/Y≦8.0·······(1)

0.2≦(Y+Z)/X≦5.0···(2)

The polymer (B) of the cyclic ether compound be selected from oxetanylmethoxy compound (b1) homopolymer, The mutual copolymer of compound (b1) with oxetanylmethoxy and the compound (b1) with oxetanylmethoxy with there is oxa- At least one of the copolymer of the compound (b2) of cyclopropyl.

[2] according to the thermosetting composition of [1] Xiang Suoshu, wherein polyesteramide acid (A) includes following formula (3) institute Structural unit represented by the structural unit and following formula (4) of expression.

In formula (3) and formula (4), R¹It is to remove residue made of two-CO-O-CO-, R from tetracarboxylic dianhydride²It is from diamines Remove two-NH₂Made of residue, R³It is to remove residue made of two-OH from multi-hydroxy compound.

[3] according to [1] item or the thermosetting composition of [2] Xiang Suoshu, wherein the chemical combination with oxetanylmethoxy Object (b1) is selected from acrylic acid (3- Ethyloxetane -3- base) methyl esters, methacrylic acid (3- Ethyloxetane -3- At least one of base) methyl esters.

[4] according to [1] item or the thermosetting composition of [2] Xiang Suoshu, wherein the chemical combination with oxiranyl Object (b2) is selected from glycidyl acrylate, glycidyl methacrylate, methacrylic acid methyl ethylene oxidic ester, 4- At least one of hydroxybutyl acrylate glycidol ether.

[5] the thermosetting composition according to any one of [1]~[4], wherein sour (A) relative to polyesteramide 100 parts by weight, the content of the polymer (B) of the cyclic ether compound are 20 parts by weight~400 parts by weight.

[6] a kind of cured film is that the thermosetting composition according to any one of [1]~[5] is made to harden and obtain ?.

[7] a kind of colored filter has according to the cured film of [6] Xiang Suoshu as transparent protective film.

[The effect of invention]

The thermosetting composition of the preferred embodiment of the present invention is to prevent the dissolution of substrate composition and flatness is excellent Material can make display quality in the protective films of color filters as color liquid crystal display device and in the case where use It improves.Especially act effectively as the colored filter manufactured using decoration method, pigment dispersion method, electrodeposition process and print process Protective film.Moreover, it is also possible to as various optical materials protective film and transparent insulating film and use.

Specific embodiment

1. thermosetting composition of the invention

Thermosetting composition of the invention be containing polyesteramide sour (A), cyclic ether compound polymer (B), with And the composition of curing agent (C), the polyesteramide sour (A) are derived from comprising tetracarboxylic dianhydride, diamines and multi-hydroxy chemical combination The reaction product of the raw material of object, and the polymer (B) of cyclic ether compound is selected from the compound (b1) with oxetanylmethoxy Homopolymer, the mutual copolymer of compound (b1) with oxetanylmethoxy and the compound (b1) with oxetanylmethoxy With at least one of the copolymer of the compound (b2) with oxiranyl.

1-1. polyesteramide is sour (A)

Polyesteramide acid is derived from the reaction product of the raw material comprising tetracarboxylic dianhydride, diamines and multi-hydroxy compound. More specifically, it includes X moles that the polyesteramide acid, which is derived from the ratio that the relationship of following formula (1) and formula (2) is set up, The reaction product of the raw material of tetracarboxylic dianhydride, Y moles of diamines and Z moles of multi-hydroxy compound.

0.2≦Z/Y≦8.0·······(1)

0.2≦(Y+Z)/X≦5.0···(2)

Polyesteramide acid (A) preferably has structure list represented by structural unit represented by following formula (3) and formula (4) Member.

In formula (3) and formula (4), R¹It is to remove residue, preferably carbon number made of two-CO-O-CO- from tetracarboxylic dianhydride 2~30 organic group.R²It is to remove two-NH from diamines₂Made of residue, the preferably organic group of carbon number 2~30.R³It is certainly Multi-hydroxy compound removes residue, the preferably organic group of carbon number 2~20 made of two-OH.

The synthesis of polyesteramide acid (A) at least needs solvent, and the solvent can be made directly to remain and be made in view of operation Property etc. liquid or gelatinous thermosetting composition, or the solvent can also be removed and be made in view of carry property etc. Solid-like composition.Moreover, the synthesis of polyesteramide acid (A) optionally also may include selected from monohydroxy compound and benzene second The compound of one or more of alkene-copolymer-maleic anhydride particularly preferably includes monohydroxy compound as raw material.And And the synthesis of polyesteramide sour (A) can also be in the range of not undermining the purpose of the present invention, optionally comprising its other than described His compound is as raw material.

1-1-1. tetracarboxylic dianhydride

In the present invention, as the material to obtain polyesteramide sour (A), tetracarboxylic dianhydride is used.Preferred tetracarboxylic acid The concrete example of acid dianhydride are as follows: 3,3',4,4' benzophenone tetracarboxylic dianhydride, 2,2', 3,3'- benzophenone tetracarboxylic dianhydride, 2, 3,3', 4'- benzophenone tetracarboxylic dianhydride, 3,3', 4,4'- diphenyl sulfone tetracarboxylic dianhydride, 2,2', 3,3'- diphenyl sulfone four Carboxylic acid dianhydride, 2,3,3', 4'- diphenyl sulfone tetracarboxylic dianhydride, 3,3', 4,4'- diphenyl ether tetracarboxylic dianhydride, 2,2', 3,3'- Diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'- diphenyl ether tetracarboxylic dianhydride, 2,2- [bis- (3,4- dicarboxyphenyis)] hexafluoro Bis- (dehydration the trimellitate) (trade names of propane dianhydride, 1,2,3,4- butane tetracarboxylic acid dianhydride, ethylene glycol；TMEG-100, new day This physics and chemistry limited liability company), cyclobutane tetracarboxylic dianhydride, methyl cyclobutane tetracarboxylic dianhydride, pentamethylene tetracarboxylic dianhydride, ring Hexane tetracarboxylic dianhydride, ethane tetracarboxylic dianhydride and butane tetracarboxylic acid dianhydride.One or more of these can be used.

In these tetracarboxylic dianhydrides, more preferable 3,3', 4, the 4'- diphenyl sulfone tetracarboxylic dianhydrides for assigning good transparency, 3,3', 4,4'- diphenyl ether tetracarboxylic dianhydride, 2,2- [bis- (3,4- dicarboxyphenyis)] hexafluoropropane dianhydride, 1,2,3,4- fourth Alkane tetracarboxylic dianhydride and ethylene glycol are bis- (dehydration trimellitate), and then preferably 3,3', 4,4'- diphenyl sulfone tetracarboxylic dianhydrides, 3,3', 4,4'- diphenyl ether tetracarboxylic dianhydride and 1,2,3,4- butane tetracarboxylic acid dianhydride.

1-1-2. diamines

In the present invention, as the material to obtain polyesteramide sour (A), diamines is used.Preferably diamines is specific Example are as follows: 4,4'- diamino diphenyl sulfone, 3,3'- diamino diphenyl sulfone, 3,4'- diamino diphenyl sulfone, bis- [4- (4- amino Phenoxy group) phenyl] sulfone, bis- [4- (3- amino-benzene oxygen) phenyl] sulfones, bis- [3- (4- amino-benzene oxygen) phenyl] sulfones, [4- (4- ammonia Phenoxyl) phenyl] [3- (4- amino-benzene oxygen) phenyl] sulfone, [4- (3- amino-benzene oxygen) phenyl] [3- (4- aminobenzene oxygen Base) phenyl] sulfone and bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 2,2-.One or more of these can be used.

In these diamines, 3, the 3'- diamino diphenyl sulfone and bis- [4- (3- aminobenzenes of good transparency are more preferably assigned Oxygroup) phenyl] sulfone, and then preferably 3,3'- diamino diphenyl sulfone.

1-1-3. multi-hydroxy compound

In the present invention, as the material to obtain polyesteramide sour (A), multi-hydroxy compound is used.

The concrete example of preferred multi-hydroxy compound can be enumerated: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, Weight average molecular weight is that 1,000 polyethylene glycol below, propylene glycol, dipropylene glycol, tripropylene glycol, four propylene glycol, weight are flat Average molecular weight is 1,000 polypropylene glycols below, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 1,2- pentanediol, 1, 5- pentanediol, 2,4-PD, penta triol of 1,2,5-, 1,2- hexylene glycol, 1,6-HD, 2,5-HD, 1,2,6- oneself three Alcohol, 1,2- heptandiol, 1,7- heptandiol, 1,2,7- triol in heptan, 1,2- ethohexadiol, 1,8- ethohexadiol, 3,6- ethohexadiol, 1,2,8- Pungent triol, 1,2- nonanediol, 1,9- nonanediol, 1,2,9- nonyl triol, Decane-1,2-diol, 1,10- decanediol, the 1,2,10- last of the ten Heavenly stems three Alcohol, 1,2- dodecanediol, 1,12- dodecanediol, glycerol, trimethylolpropane, pentaerythrite, dipentaerythritol, isocyanide It is urea acid three (2- hydroxyethyl) ester, bisphenol-A (bis- (4- hydroxy phenyl) propane of 2,2-), bisphenol S (bis- (4- hydroxy phenyl) sulfones), double Phenol F (bis- (4- hydroxy phenyl) methane), 4,4, isopropylidene bis (2- phenoxetol), bis- (the 4- hydroxy-cyclohexyls) third of 2,2- Alkane, 4,4'- dihydroxyl dicyclohexyl, 2- hydroxy-benzyl alcohol, 4- hydroxy-benzyl alcohol, 2- (4- hydroxy phenyl) ethyl alcohol, diethanol amine, three second Hydramine,

Allylin, trimethyolol propane monoallyl ether, pentaerythritol monoallyl ether, pentaerythrite diene Propyl ether, dipentaerythritol mono allyl ether, dipentaerythritol diallyl ether, dipentaerythritol triallyl ether, two seasons penta Tetrol tetraallyl ether, D-sorbite mono allyl ether, D-sorbite diallyl ether, D-sorbite triallyl ether, sorb Sugar alcohol tetraallyl ether, glycerol list (methyl) acrylate, trimethylolpropane list (methyl) acrylate, pentaerythrite list (methyl) acrylate, pentaerythrite two (methyl) acrylate, dipentaerythritol list (methyl) acrylate, dipentaerythritol Two (methyl) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, sorbose Alcohol list (methyl) acrylate, D-sorbite two (methyl) acrylate, D-sorbite three (methyl) acrylate, D-sorbite Four (methyl) acrylate, (methyl) acrylic acid modified object of ethylene glycol diglycidylether, propylene glycol diglycidylether (methyl) the acrylic acid modified object, glycerin diglycidyl ether of (methyl) acrylic acid modified object, tripropyleneglycol diglycidyl ether (methyl) acrylic acid modified object, bisphenol A diglycidyl ether (methyl) acrylic acid modified object, epoxy pronane modification bisphenol-A (methyl) the acrylic acid modified object, epoxy third of (methyl) acrylic acid modified object of diglycidyl ether, bisphenol-S diglycidyl ether (methyl) acrylic acid modified object of alkane modified bisphenol S diglycidyl ether, (methyl) acrylic acid of Bisphenol F diglycidyl ether change Property object, (methyl) acrylic acid modified object of epoxy pronane modification Bisphenol F diglycidyl ether, union II cresols diglycidyl ether (methyl) acrylic acid modified object, xenol diglycidyl ether (methyl) acrylic acid modified object, fluorenes diphenol 2-glycidyl (methyl) acrylic acid modified object of ether, (methyl) acrylic acid modified object of hexamethylene -1,4- dimethanol diglycidyl ether, hydrogenation (methyl) propylene of (methyl) acrylic acid modified object of bisphenol A diglycidyl ether, tricyclodecane Dimethanol diglycidyl ether (methyl) acrylic acid modified object of other compounds in acid modifier and each molecule comprising more than two epoxy groups.

In these multi-hydroxy compounds, preferably to the ethylene glycol of the favorable solubility of reaction dissolvent, diethylene glycol, three second Glycol, propylene glycol, 1,4- butanediol, 1,5- pentanediol, 1,6-HD, 1,7- heptandiol, 1,8- ethohexadiol, isocyanuric acid three Bis- (4- hydroxy-cyclohexyl) propane of (2- hydroxyethyl) ester, 2,2-, 4,4'- dihydroxyl dicyclohexyl, 2- hydroxy-benzyl alcohol, 4- hydroxyl (the first of benzylalcohol, 2- (4- hydroxy phenyl) ethyl alcohol, 4,4, isopropylidene bis (2- phenoxetol), ethylene glycol diglycidylether Base) acrylic acid modified object, (methyl) acrylic acid modified object of propylene glycol diglycidylether, glycerin diglycidyl ether (first Base) acrylic acid modified object, (methyl) acrylic acid modified object of bisphenol A diglycidyl ether, epoxy pronane modification bisphenol-A two shrink (methyl) the acrylic acid modified object, epoxy pronane modification of (methyl) acrylic acid modified object of glycerin ether, bisphenol-S diglycidyl ether (methyl) acrylic acid modified object of bisphenol-S diglycidyl ether, Bisphenol F diglycidyl ether (methyl) acrylic acid modified object, And (methyl) acrylic acid modified object of epoxy pronane modification Bisphenol F diglycidyl ether.In turn, especially more preferable diethylene glycol, Triethylene glycol, 1,4- butanediol, 1,5- pentanediol, 1,6-HD, 2- hydroxy-benzyl alcohol, 4- hydroxy-benzyl alcohol, 4,4'- isopropylidene Bis- (2- phenoxetols), 2- (4- hydroxy phenyl) ethyl alcohol, (methyl) acrylic acid modified object of ethylene glycol diglycidylether, third (methyl) acrylic acid modified object, (methyl) of tripropyleneglycol diglycidyl ether of Hexanediol diglycidyl ether are acrylic acid modified Object, (methyl) acrylic acid modified object of glycerin diglycidyl ether, (methyl) of bisphenol A diglycidyl ether are acrylic acid modified The acrylic acid modified object of (methyl) of object and epoxy pronane modification bisphenol A diglycidyl ether.

Change as the acrylic modified object of ethylene glycol diglycidylether, the acrylic acid of propylene glycol diglycidylether Property object, the acrylic acid modified object of tripropyleneglycol diglycidyl ether, glycerin diglycidyl ether acrylic acid modified object, bisphenol-A The acrylic modified object of diglycidyl ether, the acrylic acid modified object of bisphenol A diglycidyl ether, epoxy pronane modification are double The acrylic modified object of phenol A diglycidyl ether and epoxy pronane modification bisphenol A diglycidyl ether it is acrylic acid modified Following commercially available products can be used in object.

The concrete example of the acrylic modified object of ethylene glycol diglycidylether is epoxy-ester 40EM (trade name: common prosperity Chemistry limited liability company, society).The concrete example of the acrylic acid modified object of propylene glycol diglycidylether is epoxy-ester 70PA (commodity Name: chemistry limited liability company, common prosperity society).The concrete example of the acrylic acid modified object of tripropyleneglycol diglycidyl ether is epoxy-ester 200PA (trade name: chemistry limited liability company, common prosperity society).The concrete example of the acrylic acid modified object of glycerin diglycidyl ether is Epoxy-ester 80MFA (trade name: chemistry limited liability company, common prosperity society).Bisphenol A diglycidyl ether it is acrylic modified The concrete example of object is epoxy-ester 3000MK (trade name: chemistry limited liability company, common prosperity society).The third of bisphenol A diglycidyl ether The concrete example of olefin(e) acid modifier is epoxy-ester 3000A (trade name: chemistry limited liability company, common prosperity society).Epoxy pronane modification is double The concrete example of the acrylic modified object of phenol A diglycidyl ether is epoxy-ester 3002M (N) (trade name: common prosperity society chemistry stock Part Co., Ltd).The concrete example of the acrylic acid modified object of epoxy pronane modification bisphenol A diglycidyl ether is epoxy-ester 3002A (N) (trade name: chemistry limited liability company, common prosperity society).

1-1-4. monohydroxy compound

In the present invention, as the material to obtain polyesteramide sour (A), monohydroxy compound can be used.By making It is improved with the storage stability of monohydroxy compound, thermosetting composition.The concrete example of preferred monohydroxy compound are as follows: first Alcohol, ethyl alcohol, 1- propyl alcohol, isopropanol, allyl alcohol, benzylalcohol, dihydroxypropane single-ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, two Propylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, dragon Brain (borneol), maltol (maltol), linalool (linalool), terpinol (terpineol), dimethyl benzyl carbinol (dimethyl benzyl carbinol) and 3- ethyl -3- hydroxymethyl oxetane.One of these can be used More than.

In these monohydroxy compounds, more preferable isopropanol, allyl alcohol, benzylalcohol, dihydroxypropane single-ether or 3- ethyl -3- Hydroxymethyl oxetane.If considering that these monohydroxy compounds will be used and the polyesteramide that is formed sour (A) and cyclic ether Compatibility or thermosetting composition in the case where polymer (B) and curing agent (C) mixing of compound is in colorized optical filtering The coating of on piece, then it is preferable to use benzylalcohols in turn for monohydroxy compound.

Relative to 100 parts by weight of total amount of tetracarboxylic dianhydride, diamines and multi-hydroxy compound, preferably contain 0 weight It measures part~300 parts by weight monohydroxy compound and is reacted.More preferably 5 parts by weight~200 parts by weight.

1-1-5. styrene-maleic anhydride copolymer

Moreover, the acid of polyesteramide used in the present invention (A) can also add tool in the raw material, there are three the above acid The compound of anhydride group and synthesize.Add the transparent of the polyesteramide sour (A) that tool is synthesized there are three the compound of the above anhydride group Property raising expected, therefore preferably.The example of the compound for the above anhydride group that there are three tools is total for phenylethylene-maleic anhydride Polymers.About the ratio for each ingredient for constituting styrene-maleic anhydride copolymer, the molar ratio of phenylethylene/maleic anhydride is 0.5 ~4, preferably 1~3.The molar ratio of phenylethylene/maleic anhydride is more preferably 1 or 2, and then preferably 1.

The concrete example of styrene-maleic anhydride copolymer is that SMA3000P, SMA2000P and SMA1000P (are commodity Name；River crude oil limited liability company).Particularly preferred heat resistance and the good SMA1000P of alkali resistance in these.

Relative to 100 parts by weight of total amount of tetracarboxylic dianhydride, diamines and multi-hydroxy compound, styrene-maleic acid Anhydride copolymer preferably contains 0 parts by weight~500 parts by weight.More preferably 10 parts by weight~300 parts by weight.

1-1-6. has the amino silane compounds of an amino

It can also optionally include institute in the range of not undermining the purpose of the present invention in the synthesis of polyesteramide sour (A) For other raw materials other than stating as raw material, the example of other such raw materials is the amino silane compounds with an amino.Tool The amino silane compounds of one amino are to import to react with the anhydride group of the end of polyesteramide sour (A) in end Silylation.If cured film obtained can be improved using the thermosetting composition of the invention containing polyesteramide sour (A) Acid resistance, the polyesteramide sour (A) is that by adding there are the amino silane compounds of an amino react obtaining ?.In turn, in the case where being reacted with the composition of the monomer, it can also add monohydroxy compound and there is an ammonia The amino silane compounds of base this both and reacted.

Preferably there is the concrete example of the amino silane compounds of an amino are as follows: 3- aminopropan used in the present invention Base trimethoxy silane, 3-aminopropyltriethoxysilane, 3- aminopropylmethyldimethoxysilane, 3- aminopropyl first Base diethoxy silane, 4- aminobutyl trimethoxy silane, 4- ammobutyltriethoxysilane, 4- aminobutyl methyl two Ethoxysilane, p-aminophenyl trimethoxy silane, p-aminophenyl triethoxysilane, p-aminophenyl methyl dimethoxy oxygen Base silane, p-aminophenyl methyldiethoxysilane, m-aminophenyl base trimethoxy silane and m-aminophenyl ylmethyl diethyl Oxysilane.One or more of these can be used.

Acid resistance of more preferable cured film becomes good 3-aminopropyltriethoxysilane and p-aminophenyl in these Trimethoxy silane, for acid resistance, the viewpoint of compatibility, and then preferred 3-aminopropyltriethoxysilane.

Relative to 100 parts by weight of total amount of tetracarboxylic dianhydride, diamines and multi-hydroxy compound, there is an amino Amino silane compounds preferably contain 0 parts by weight~300 parts by weight.More preferably 5 parts by weight~200 parts by weight.

Solvent used in the synthetic reaction of 1-1-7. polyesteramide sour (A)

Solvent (hereinafter sometimes referred to " reaction dissolvent ") used in synthetic reaction to obtain polyesteramide sour (A) Concrete example be diethylene glycol dimethyl ether, diethylene glycol Methyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetic acid Ester, ethylene glycol monoethylether acetate, propylene glycol methyl ether acetate, 3- methoxy methyl propionate, 3- ethoxyl ethyl propionate, cream Acetoacetic ester, cyclohexanone, n-methyl-2-pyrrolidone and DMAC N,N' dimethyl acetamide.Preferred propylene glycol monomethyl ether acetic acid in these Ester, 3- methoxy methyl propionate and diethylene glycol Methyl ether.

The synthetic method of 1-1-8. polyesteramide sour (A)

Polyesteramide used in the present invention acid (A) preferably by make in the solvent X moles of tetracarboxylic dianhydride, Y moles of diamines and multi-hydroxy compound Z molar reactive and synthesize, X, Y and Z are determined as following formula (1) between these at this time And the ratio that the relationship of formula (2) is set up.If the range, then the dissolubility of polyesteramide sour (A) in a solvent is high, therefore group The coating for closing object is improved, and as a result can get the excellent cured film of flatness.

0.2≦Z/Y≦8.0·······(1)

0.2≦(Y+Z)/X≦5.0···(2)

Formula (1) is preferably 0.7≤Z/Y≤7.0, more preferably 1.0≤Z/Y≤5.0.Moreover, formula (2) be preferably 0.5≤ (Y+Z)/X≤4.0, more preferably 0.6≤(Y+Z)/X≤2.0.

It is believed that polyesteramide sour (A) used in the present invention is the mistake relative to (Y+Z) under the cited reaction conditions It remains using under conditions of X, there is anhydride group (- CO- in end than more excessively generating in molecule of the end with amino or hydroxyl O-CO- molecule).In the case where being reacted with the composition of such monomer, in order to be reacted with the anhydride group of molecular end and End is esterified, the monohydroxy compound can be optionally added.It is reacted by adding monohydroxy compound And the polyesteramide sour (A) obtained can improve the compatibility with the polymer of cyclic ether compound (B) and curing agent (C), and can Improve the coating of the thermosetting composition of the invention comprising these compounds.

If using 100 parts by weight relative to the adding up to 100 parts by weight of tetracarboxylic dianhydride, diamines and multi-hydroxy compound Above reaction dissolvent is then reacted and is successfully carried out, therefore preferably.Reaction at 40 DEG C~200 DEG C to react 0.2 hour~20 Hour is advisable.

Order of addition of the reaction raw materials in reaction system is not particularly limited.That is, any side below can also be used Method: the method into reaction dissolvent is added in tetracarboxylic dianhydride, diamines and multi-hydroxy compound simultaneously；Make diamines and polynary hydroxyl After based compound is dissolved in reaction dissolvent, the method for adding tetracarboxylic dianhydride；Make tetracarboxylic dianhydride and multi-hydroxy chemical combination After object reacts in advance, the method for diamines is added in its reaction product；Or after reacting tetracarboxylic dianhydride and diamines in advance, The method etc. of multi-hydroxy compound is added in its reaction product.

In the case where making the amino silane compounds reaction with an amino, in tetracarboxylic dianhydride and two After reaction, after the solution after reaction is cooled to 40 DEG C or less, addition has an ammonia for amine and multi-hydroxy compound The amino silane compounds of base, reacting 0.1 hour~6 hours at 10 DEG C~40 DEG C is advisable.Moreover, can reaction it is any when Between point addition monohydroxy compound.

The polyesteramide sour (A) synthesized as described above includes represented by structural unit represented by formula (3) and formula (4) Structural unit, and its end is from as the tetracarboxylic dianhydride of raw material, the anhydride group of diamines or multi-hydroxy compound, amino Or the additive other than hydroxyl or these compounds constitutes its end.By the inclusion of such composition, hardenability becomes good.

The weight average molecular weight of polyesteramide obtained sour (A) is preferably 1,000~200,000, more preferably 2, 000~50,000.If being in these ranges, flatness and heat resistance become good.

Weight average molecular weight in this specification is to utilize gel permeation chromatography (Gel Permeation Chromatography, GPC) method (tubing string temperature: 35 DEG C, flow velocity: 1ml/min) and find out polystyrene conversion value.Mark The polystyrene that quasi- polystyrene is 645~132900 using molecular weight is (for example, Agilent Technologies (Agilent Technologies) polystyrene calibration set group (calibration kit) PL2010-0102 of limited liability company), tubing string (PLgel MIXED)-D (Agilent Technologies (Agilent Technologies) limited liability company) is mixed using PL gel, Tetrahydrofuran (Tetrahydrofuran, THF) can be used to be measured as mobile phase.Furthermore it is commercially available in this specification The weight average molecular weight of product is catalogue (catalogue) record value.

The polymer (B) of 1-2. cyclic ether compound

The polymer (B) of cyclic ether compound used in the present invention is selected from the compound (b1) with oxetanylmethoxy Homopolymer, the mutual copolymer of compound (b1) with oxetanylmethoxy and the compound (b1) with oxetanylmethoxy With at least one of the copolymer of the compound (b2) with oxiranyl.The polymer (B) of cyclic ether compound can be It is a kind of, it is possible to use two or more.

The case where being copolymerized the compound with oxetanylmethoxy (b1) with the compound (b2) with oxiranyl Under, if with oxetanylmethoxy compound (b1) ratio in the polymer (B) of cyclic ether compound for 50 weight %~ 90 weight %, then for barrier viewpoint preferably.If the ratio of the compound (b1) with oxetanylmethoxy is 70 weights Measure the weight % of %~90, then it is barrier to further increase.

It as the concrete example of the compound (b1) with oxetanylmethoxy, can enumerate: acrylic acid (3- ethyl oxa- ring fourth Alkane -3- base) methyl esters (for example, trade name: OXE-10, Osaka Organic Chemical Industry limited liability company), methacrylic acid (3- second Base oxetanes -3- base) methyl esters (for example, trade name: OXE-30, Osaka Organic Chemical Industry limited liability company).

As the concrete example of the compound (b2) with oxiranyl, can enumerate: glycidyl acrylate, methyl-prop Olefin(e) acid ethylene oxidic ester, methacrylic acid methyl ethylene oxidic ester, 4- hydroxybutyl acrylate glycidol ether.

Ratio of the polymer (B) of 1-3. cyclic ether compound relative to polyesteramide sour (A)

Relative to sour (A) 100 parts by weight of polyesteramide in thermosetting composition of the invention, cyclic ether compound The ratio of the total amount of polymer (B) is 20 parts by weight~400 parts by weight.If the total amount of the polymer (B) of cyclic ether compound Ratio is the range, then barrier, flatness, the balance of heat resistance are good.

1-4. curing agent (C)

In thermosetting composition of the invention, in order to improve flatness, chemical-resistant, it is possible to use curing agent (C). As curing agent (C), there are acid anhydrides system curing agent, polymer carboxylic-containing acid, amine system curing agent, phenol system curing agent, imidazoles systems Curing agent, pyrazoles system curing agent, triazole system curing agent, catalyst type curing agent and sulfonium salt, benzothiazolium salt, ammonium salt, phosphonium salt Etc. thermonasties acid producing agent etc., it is avoided that preferred anhydrides system is hard for the viewpoint of the heat resistance of the coloring and cured film of cured film Agent or imidazoles system curing agent.

The concrete example of acid anhydrides system curing agent are as follows: maleic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic acid The aliphatic dicarboxylic acids acid anhydrides such as acid anhydride, methylhexahydrophthalic anhydride, hexahydro trimellitic anhydride；Phthalic anhydride, trimellitic acid The aromatic polycarboxylic acids acid anhydride such as acid anhydride；And styrene-maleic anhydride copolymer.In these acid anhydrides system curing agents, preferred heat resistance With the good trimellitic anhydride of deliquescent balance and hexahydro trimellitic anhydride to solvent.

It as the concrete example of the polymer carboxylic-containing acid, can enumerate: A Lufeng (ARUFON) UC-3000, A Lufeng (ARUFON) UC-3090 (is trade name；East Asia synthesize limited liability company), Ma Pulufu (Marproof) MA-0215Z, Ma Pulufu (Marproof) MA-0217Z and Ma Pulufu (Marproof) MA-0221Z (is trade name；Day, oily share had Limit company).In these polymer carboxylic-containing acid, the balance of preferably heat resistance and dissolubility and flatness to solvent is good A Lufeng (ARUFON) UC-3000.

The concrete example of imidazoles system curing agent are as follows: 2- undecyl imidazole, 2- heptadecyl imidazole, 2- phenylimidazole, 2- phenyl -4-methylimidazole, 2,3- dihydro -1H- pyrrolo- [1,2-a] benzimidazole, 1- cyano ethyl -2- undecyl imidazole Trimellitic acid salt, 1 benzyl 2 methyl imidazole and 1- benzyl -2- phenylimidazole.In these imidazoles system curing agents, preferably harden Property with to the good 2- undecyl imidazole of the deliquescent balance of solvent, 2- phenyl -4-methylimidazole and 1- benzyl -2- phenyl Imidazoles.

The concrete example of phenol system curing agent can be enumerated: α, α, α '-three (4- hydroxy phenyl) -1- ethyl -4- cumene, 1,1, Bis- (the 4- hydroxy-3-methyl phenyl) fluorenes of 1- tri- (4- hydroxy phenyl) ethane, 9,9-, bis- [2- (4- the hydroxy phenyl) -2- third of 1,3- Base] benzene, 4,4'- (3,3,5- trimethyl -1,1- hexamethylene diyl) bis- (phenol) and 1,1,2,2- tetra- (4- hydroxy phenyl) second Alkane.Balance good α, α, α '-three (4- hydroxy phenyl) -1- second of preferred heat resistance and compatibility in these phenol system curing agents Base -4- cumene, (4- hydroxy phenyl) ethane of 1,1,1- tri- and bis- (the 4- hydroxy-3-methyl phenyl) fluorenes of 9,9-.

Using curing agent (C), relative to 100 parts by weight of polymer (B) of cyclic ether compound, curing agent (C) ratio is 0.1 parts by weight~60 parts by weight.Additive amount in the case where being acid anhydrides system curing agent about curing agent (C), more Specifically, preferably with for oxetanylmethoxy and oxiranyl, acid anhydride or carboxyl in curing agent at Mode for 0.1 times of equivalent~1.5 times equivalent is added.At this point, acid anhydride is calculated with divalent.If to become 0.15 The mode of times equivalent~0.8 times equivalent adds acid anhydride or carboxyl, then chemical-resistant further increases, therefore more preferably.

1-5. other compositions

In thermosetting composition of the invention, various additives can be added to improve flatness, scratch resistance, coating The films physical property such as uniformity, cementability.Additive can mainly be enumerated: the epoxidation other than the compound (b2) with oxiranyl Object is closed, the compound with polymeric double bond, solvent, the levelling of anionic system, cationic system, nonionic system, fluorine system or silicon systems Agent surfactant, the adhesions elevator such as silane coupling agent, hindered phenolic, amine system of being obstructed, phosphorus system, chalcogenide compound etc. are anti- Oxidant.

1-5-1. epoxide

The epoxy other than the compound (b2) with oxiranyl can also be used in thermosetting composition of the invention Compound.The arbitrarily used epoxide of institute is to have two or more in each molecule in thermosetting composition of the invention Epoxy group compound.Epoxide can be one kind, it is possible to use two or more.

The example of the epoxide are as follows: bisphenol A type epoxy compound, bisphenol F type epoxy compound, glycidol ether Type ring oxygen compound, glycidyl ester type epoxy compound, biphenol type epoxy compound, phenol novolak-type epoxy chemical combination Object, cresol novolak type epoxy compound, bisphenol A novolac type ring oxygen compound, aliphatic polyglycidyl etherificate are closed Object, ring type aliphatic epoxy compound, the monomer with epoxy group and other monomers copolymer and there is siloxanes key knot The epoxide of position.

The concrete example of the commercially available product of bisphenol A type epoxy compound is jER 828, jER 1004, jER 1009 (are commodity Name；Limited liability company, Mitsubishi Chemical)；The concrete example of the commercially available product of bisphenol F type epoxy compound is jER 806, jER 4005P It (is trade name；Limited liability company, Mitsubishi Chemical)；The concrete example of the commercially available product of diglycidyl ether type epoxy compound is spy Gram not (TECHMORE) VG3101L (trade name；Pu Lintaike (Printec) limited liability company), EHPE3150 (trade name； Daicel (Daicel) limited liability company), EPPN-501H, EPPN-502H (are trade name；The Japanese limited public affairs of chemical drug share Department) and jER 1032H60 (trade name；Limited liability company, Mitsubishi Chemical)；The commercially available product of glycidyl ester type epoxy compound Concrete example be that pellet receives Cauer (Denacol) EX-721 (trade name；The long rapids chemical conversion limited public affairs of (Nagase chemteX) share Department) and 1,2- cyclohexane dicarboxylic acid 2-glycidyl ester (trade name；Tokyo chemical conversion industry limited liability company manufacture)；Bis-phenol The concrete example of the commercially available product of type ring oxygen compound is jER YX4000, jER YX4000H, jER YL6121H (are trade name； Limited liability company, Mitsubishi Chemical) and NC-3000, NC-3000-L, NC-3000-H, NC-3100 (be trade name；Japanization Medicine limited liability company)；The concrete example of the commercially available product of phenol novolak-type epoxy compound is EPPN-201 (trade name；Day This chemical drug limited liability company) and jER 152, jER 154 (be trade name；Limited liability company, Mitsubishi Chemical) etc.；Cresols The concrete example of the commercially available product of novolak type epoxy compounds is EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 It (is trade name；NIPPON PHARMACEUTICAL CO., LTD) etc.；The concrete example of the commercially available product of bisphenol A novolac type ring oxygen compound It (is trade name for jER 157S65, jER 157S70；Limited liability company, Mitsubishi Chemical)；Ring type aliphatic epoxy compound Commercially available product concrete example be Sai Luo West Germany (Celloxide) 2021P, Sai Luo West Germany (Celloxide) 3000 (be commodity Name；Daicel (Daicel) limited liability company)；The concrete example of the commercially available product of epoxide with siloxanes key knot position For bis- [2- (3,4- epoxycyclohexyl) ethyl] tetramethyl disiloxane (trade names of 1,3-；Prompt Leicester limited liability company (Gelest Incorporated)), TSL9906 (trade name；Japan figure new high-tech material (Momentive Performance advanced in years Materials Japan) Co., Ltd), examine special Olso (COATOSIL) MP200 (trade name；Japanese Mai Tugao green wood Expect (Momentive Performance Materials Japan) Co., Ltd), empty Po Sailang (Conpoceran) SQ506 (trade name；Waste river chemistry limited liability company), ES-1023 (trade name；Shin-Estu Chemical Co., Ltd).

Furthermore Te Kemo (TECHMORE) VG3101L (trade name；Pu Lintaike (Printec) limited liability company) be 2- [4- (2,3- glycidoxy) phenyl] -2- [4- [bis- [4- (2,3- glycidoxy) phenyl] ethyls of 1,1-] phenyl] third Alkane and bis- [4- [1- [4- (2,3- glycidoxy) phenyl] -1- [4- [1- [4- (2,3- glycidoxy) the phenyl] -1- of 1,3- Methylethyl] phenyl] ethyl] phenoxy group] -2- propyl alcohol mixture；EHPE3150 (trade name；Daicel (Daicel) share Co., Ltd) be bis- (the hydroxymethyl)-n-butyl alcohols of 2,2- 1,2- epoxy group -4- (2- Oxyranyle (oxiranyl)) hexamethylene Alkane addition product；Sai Luo West Germany (Celloxide) 2021P (trade name；Daicel (Daicel) limited liability company) it is 3', 4'- Epoxycyclohexyl-methyl -3,4- epoxycyclohexane carboxylate；3000 (trade name of Sai Luo West Germany (Celloxide)；Daicel (Daicel) limited liability company) it is 1- methyl -4- (2- methyl oxirane base) -7- oxabicyclo [4.1.0] heptane；Examine spy Olso (COATOSIL) MP200 (trade name；Japan figure new high-tech material (Momentive Performance Materials advanced in years Japan) Co., Ltd) be 3- glycidoxypropyltrimewasxysilane polymer.

The epoxide can be used alone the compound, can also be used in mixed way two or more.

1-5-2. has the epoxide other than the compound (b2) of oxiranyl relative to polyesteramide sour (A) Ratio

It is described that there is oxa- ring relative to sour (A) 100 parts by weight of polyesteramide in thermosetting composition of the invention The ratio of the total amount of epoxide other than the compound (b2) of propyl is 0 parts by weight~100 parts by weight.If having oxa- ring The ratio of the total amount of epoxide other than the compound (b2) of propyl is the range, then flatness, heat resistance, chemically-resistant Moral character, adhesion, barrier balance are good.In the case where more paying attention to barrier, the compound with oxiranyl (b2) total amount of the epoxide other than is preferably 0 parts by weight~50 parts by weight range.

1-5-3. has the compound of polymeric double bond

In thermosetting composition of the invention, it is possible to use the compound with polymeric double bond.Heat of the invention As long as the compound used in curable adhensive compositions with polymeric double bond has more than two poly- in each molecule Conjunction property double bond, then be not particularly limited.

Has the tool of the compound there are two polymeric double bond in the compound with polymeric double bond in each molecule Body example are as follows: ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylic acid Ester, tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, epichlorohydrin are modified ethylene glycol two (methyl) Modified diethylene glycol two (methyl) acrylate of acrylate, epichlorohydrin, modified triethylene glycol two (methyl) acrylic acid of epichlorohydrin Modified tetraethylene glycol two (methyl) acrylate of ester, epichlorohydrin, epichlorohydrin modified poly (ethylene glycol) two (methyl) acrylate, the third two Alcohol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, four propylene glycol Two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, epichlorohydrin modified propylene glycol two (methyl) acrylate, table Chloropharin is modified the modified tripropylene glycol two (methyl) acrylate of dipropylene glycol two (methyl) acrylate, epichlorohydrin, epichlorohydrin changes Property four propylene glycol two (methyl) acrylate, epichlorohydrin modified polypropylene glycol two (methyl) acrylate, glycerine acrylate The modified 1,6- of methacrylate, glycerine two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, epichlorohydrin Hexylene glycol two (methyl) acrylate, methoxylation cyclohexyl two (methyl) acrylate, neopentyl glycol two (methyl) acrylic acid Ester, hydroxyl trimethylace tonitric neopentyl glycol two (methyl) acrylate, caprolactone modification hydroxyl trimethylace tonitric neopentyl glycol two (methyl) acrylate, stearic acid modified pentaerythrite two (methyl) acrylate, allylation cyclohexyl two (methyl) propylene It is acid esters, bis- [(methyl) acryloxy neopentyl glycol] adipate esters, bisphenol-A two (methyl) acrylate, ethylene-oxide-modified Bisphenol-A two (methyl) acrylate, Bisphenol F two (methyl) acrylate, ethylene-oxide-modified Bisphenol F two (methyl) acrylic acid Ester, bisphenol S two (methyl) acrylate, ethylene-oxide-modified bisphenol S two (methyl) acrylate, 1,4- butanediol two (methyl) Acrylate, 1,3 butylene glycol two (methyl) acrylate, diacrylate bicyclopentyl ester, ethylene-oxide-modified di(2-ethylhexyl)phosphate (first Base) acrylate, the ethylene-oxide-modified di(2-ethylhexyl)phosphate of caprolactone (methyl) acrylate, the modified phthalic acid two of epichlorohydrin (methyl) acrylate, tetrabromobisphenol A two (methyl) acrylate, three glycerine two (methyl) acrylate, neopentyl glycol change Property (methyl) acrylate of trimethylolpropane two and the ethylene-oxide-modified diacrylate of isocyanuric acid.

Has the compound there are three the above polymeric double bond in the compound with polymeric double bond in each molecule Concrete example are as follows: trimethylolpropane tris (methyl) acrylate, ethylene-oxide-modified trimethylolpropane tris (methyl) propylene Acid esters, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, epichlorohydrin are modified trimethylolpropane tris (methyl) Acrylate, glycerine three (methyl) acrylate, epichlorohydrin modified glycerine three (methyl) acrylate, pentaerythrite three (methyl) acrylate, alkyl-modified dipentaerythritol three (methyl) acrylate, ethylene-oxide-modified tricresyl phosphate (methyl) third The ethylene-oxide-modified tricresyl phosphate of olefin(e) acid ester, caprolactone (methyl) acrylate, [(methyl) acryloxy of caprolactone modification three Ethyl] isocyanuric acid ester, two-trimethylolpropane four (methyl) acrylate, two glycerol four (methyl) acrylate, Ji Wusi (methyl) acrylate of alcohol four and alkyl-modified dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) third Olefin(e) acid ester, alkyl-modified dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, caprolactone change Property dipentaerythritol six (methyl) acrylate and carboxylic multifunctional (methyl) acrylate.

The compound with polymeric double bond can be used alone the compound, can also be used in mixed way two or more.

In the 100 weight % of compound with polymeric double bond, for the viewpoint of scratch resistance, preferably wrap Has the compound there are three the above polymeric double bond in each molecule containing 50 weight % or more.

In the compound with polymeric double bond, for the viewpoint of flatness and scratch resistance, preferably make With the ethylene-oxide-modified diacrylate of isocyanuric acid, the ethylene-oxide-modified triacrylate of isocyanuric acid, trimethylolpropane Triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, Dipentaerythritol Pentaacrylate, two seasons penta Six acrylate of tetrol and carboxylic multifunctional (methyl) acrylate.

The commercially available product as following can be used in the compound with polymeric double bond.Isocyanuric acid ethylene oxide changes Property diacrylate concrete example be Aronix (Aronix) M-215 (trade name；East Asia synthesizes limited liability company)；Isocyanide The concrete example of the mixture of the urea ethylene-oxide-modified diacrylate of acid and the ethylene-oxide-modified triacrylate of isocyanuric acid is Aronix (Aronix) M-313 (the 30 weight % of weight %~40) and (3 weight %~13 Aronix (Aronix) M-315 Weight % is slightly denoted as " M-315 " below) it (is trade name；East Asia synthesizes limited liability company, and the containing ratio in bracket is mixed Close the catalogue record value of the containing ratio of the ethylene-oxide-modified diacrylate of isocyanuric acid in object)；Trimethylolpropane tris third The concrete example of olefin(e) acid ester is Aronix (Aronix) M-309 (trade name；East Asia synthesizes limited liability company)；Pentaerythrite three The concrete example of the mixture of acrylate and pentaerythritol tetraacrylate is Aronix (Aronix) M-306 (65 weight % ~70 weight %), Aronix (Aronix) M-305 (the 55 weight % of weight %~63), Aronix (Aronix) M-303 (the 30 weight % of weight %~60), Aronix (Aronix) M-452 (the 25 weight % of weight %~40) and Aronix (Aronix) M-450 (less than 10 weight %) (is trade name；East Asia synthesizes limited liability company, and the containing ratio in bracket is The catalogue record value of the containing ratio of pentaerythritol triacrylate in mixture)；Dipentaerythritol Pentaacrylate and two seasons The concrete example of the mixture of penta tetrol, six acrylate be Aronix (Aronix) M-403 (the 50 weight % of weight %~60), Aronix (Aronix) M-400 (the 40 weight % of weight %~50), (30 weight %~40 Aronix (Aronix) M-402 Weight % is slightly denoted as " M-402 " below), Aronix (Aronix) M-404 (the 30 weight % of weight %~40), Aronix (Aronix) M-406 (the 25 weight % of weight %~35) and Aronix (Aronix) M-405 (the 10 weight % of weight %~20) It (is trade name；East Asia synthesizes limited liability company, and the containing ratio in bracket is five acrylic acid of dipentaerythritol in mixture The catalogue record value of the containing ratio of ester)；The concrete example of carboxylic multifunctional (methyl) acrylate is Aronix (Aronix) M-510 and Aronix (Aronix) M-520 (being slightly denoted as " M-520 " below) (is trade name；East Asia synthesizes stock Part Co., Ltd).

1-5-4. has ratio of the compound of polymeric double bond relative to polyesteramide sour (A)

Relative to sour (A) 100 parts by weight of polyesteramide in thermosetting composition of the invention, there is polymeric double bond Compound total amount ratio be 0 parts by weight~100 parts by weight.If the ratio of the total amount of the compound with polymeric double bond For the range, then flatness, heat resistance, scratch resistance and barrier balance are good.In the case where more paying attention to barrier, The total amount of compound with polymeric double bond is preferably 0 parts by weight~50 parts by weight range.

1-5-5. solvent (D)

In thermosetting composition of the invention, it is possible to use solvent (D).Institute in thermosetting composition of the invention The solvent (D) arbitrarily added preferably can be with dissolved polyester amic acid (A), the polymer (B) of cyclic ether compound, curing agent (C) Deng solvent.The concrete example of the solvent (D) are as follows: methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, isobutanol, The tert-butyl alcohol, acetone, 2- butanone, ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, hydroxy methyl acetate, Hydroxyl ethyl acetate, Butyl Glycolate, methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethyoxyl Methyl acetate, ethoxy ethyl acetate, 3- oxygroup methyl propionate, 3- hydroxypropionate, 3- methoxy methyl propionate, 3- methoxy Base ethyl propionate, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid propyl ester, 2- Methoxy methyl propionate, 2- methoxypropionate, 2- methoxy propyl propyl propionate, 2- ethoxypropanoate, 2- ethoxy-c Acetoacetic ester, 2- hydroxy-2-methyl methyl propionate, 2- hydroxy-2-methyl ethyl propionate, 2- methoxyl group -2 Methylpropionic acid methyl esters, 2- Ethyoxyl -2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, acetoacetate Ethyl ester, 2-Oxobutyric acid methyl esters, 2-Oxobutyric acid ethyl ester, 4- hydroxy-4-methyl-2-pentanone, ethylene glycol, diethylene glycol, three second Glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4- butanediol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol Dan Yi Propyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol list Propyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetic acid esters, diethyl 2-ethoxyethanol, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether, butyl carbitol acetate, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Methyl ether, tetrahydrofuran, acetonitrile, dioxanes, toluene, dimethylbenzene, γ-fourth Lactone or DMAC N,N' dimethyl acetamide and cyclohexanone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, weight average point Son amount is for 1,000 polyethylene glycol below, propylene glycol, dipropylene glycol, tripropylene glycol, four propylene glycol, weight average molecular weight 1,000 polypropylene glycols below.Solvent can be one kind of these solvents, can also be the two or more mixtures of these solvents.

Relative to thermosetting total composition, the content of solvent (D) is preferably 65 weight of weight %~95 %.More preferably For 70 weight of weight %~90 %.

1-5-6. surfactant

In thermosetting composition of the invention, surfactant can also be added to improve coating homogeneity.Surface is living The concrete example of property agent are as follows: Pohle not Lip river (Polyflow) No.75, Pohle not Lip river (Polyflow) No.90, Pohle not Lip river (Polyflow) No.95 (is trade name above；Chemistry limited liability company, common prosperity society), Di Sipabike (Disperbyk)- 161, Di Sipabike (Disperbyk) -162, Di Sipabike (Disperbyk) -163, Di Sipabike (Disperbyk) -164, Di Sipabike (Disperbyk) -166, Di Sipabike (Disperbyk) -170, Di Sipabi Gram (Disperbyk) -180, Di Sipabike (Disperbyk) -181, Di Sipabike (Disperbyk) -182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (more than It is trade name；Chemical (the BYK Chemie Japan) limited liability company of Japanese Bi Ke), KP-341, KP-368, KF-96- 50CS, KF-50-100CS (are trade name above；Shin-Estu Chemical Co., Ltd), Sha Fulong (Surflon) S611 (trade name；AGC beautifies clearly (AGC Seimi Chemical) limited liability company), Fu Jite (Ftergent) 222F, good fortune Ji Te (Ftergent) 208G, Fu Jite (Ftergent) 251, Fu Jite (Ftergent) 710FL, Fu Jite (Ftergent) 710FM, Fu Jite (Ftergent) 710FS, Fu Jite (Ftergent) 601AD, Fu Jite (Ftergent) 602A, Fu Jite (Ftergent) 650A, FTX-218 (are trade name above；Ni Aosi (Neos) limited liability company), Mei Jiafa (Megafac) F-410, Mei Jiafa (Megafac) F-430, Mei Jiafa (Megafac) F-444, Mei Jiafa (Megafac) F- 472SF, Mei Jiafa (Megafac) F-475, Mei Jiafa (Megafac) F-477, Mei Jiafa (Megafac) F-552, Mei Jiafa (Megafac) F-553, Mei Jiafa (Megafac) F-554, Mei Jiafa (Megafac) F-555, Mei Jiafa (Megafac) F- 556, Mei Jiafa (Megafac) F-558, Mei Jiafa (Megafac) F-559, Mei Jiafa (Megafac) R-94, Mei Jiafa (Megafac) RS-75, Mei Jiafa (Megafac) RS-72-K, Mei Jiafa (Megafac) RS-76-NS, Mei Jiafa (Megafac) DS-21 (is trade name above；DIC (DIC) limited liability company), Digao village (TEGO Twin) 4000, Digao village (TEGO Twin) 4100, Digao not Lip river (TEGO Flow) 370, Digao Ge Laide (TEGO Glide) 440, Digao Ge Laide (TEGO Glide) 450, Digao ladd (TEGO Rad) 2200N (are trade name above；Japan wins wound (Evonik Japan) Limited liability company), fluoroalkyl benzene sulfonate, fl muoroalkyl's salt, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluothane Base glycine betaine, fluoroalkyl sulfonate, two glycerol four (fluoroalkyl polyoxyethylene ether), fluoroalkyl leptodactyline, fluoroalkyl amino Sulfonate, ethylene nonyl phenyl ether, NONIN HS 240, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, Polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl base ether, polyoxyethylene stearyl base ether, polyoxy second Alkene laurate, polyoxyethylene oleate, Myrj 45, polyoxyethylene laural base amine, sorbitol anhydride laurate, Sorbitol anhydride palmitate, sorbitan tristearate, sorbitan oleate, sorbitan carboxylic esters, polyoxyethylene mountain Pears alcohol acid anhydride laurate, polyoxyethylene sorbitol acid anhydride palmitate, polyoxyethylene sorbitol acid anhydride stearate, polyoxyethylene Alcohol acid anhydride oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate and alkyl diphenyl base ether disulfonate.Preferably using being selected from At least one of these compounds.

In these surfactants, if selected from BYK306, BYK342, BYK346, KP-341, KP-368, Sha Fulong (Surflon) S611, Fu Jite (Ftergent) 710FL, Fu Jite (Ftergent) 710FM, Fu Jite (Ftergent) 710FS, Fu Jite (Ftergent) 650A, Mei Jiafa (Megafac) F-477, Mei Jiafa (Megafac) F-556, Mei Jiafa (Megafac) RS-72-K, Mei Jiafa (Megafac) DS-21, Digao collect (TEGO Twin) 4000, fluoroalkyl benzene sulfonate, fluorine Alkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyl leptodactyline and fluoroalkyl sulfamate At least one of, then the coating homogeneity of thermosetting composition is got higher, therefore preferably.

Relative to thermosetting total composition, the content of the surfactant in thermosetting composition of the invention is excellent It is selected as 0.01 weight of weight %~10 %.

1-5-7. adhesion elevator

For the viewpoint for further increasing the adhesion for being formed by cured film and substrate, thermosetting of the invention Composition can also also contain adhesion elevator.Silane system, aluminium system or metatitanic acid can be used in the example of such adhesion elevator The coupling agent of ester system.Specifically are as follows: 3- glycidoxypropyl dimethylethoxysilane, 3- glycidoxypropyl Methyldiethoxysilane, 3- glycidoxypropyltrimewasxysilane are (for example, Sa Laaisi (Sila-Ace) S510； Trade name；Prompt grace intelligence (JNC) limited liability company), 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane (for example, Sa draw Ai Si (Sila-Ace) S530；Trade name；Prompt grace intelligence (JNC) limited liability company), 3-mercaptopropyi trimethoxy silane (example Such as, Sa Laaisi (Sila-Ace) S810；Trade name；Prompt grace intelligence (JNC) limited liability company), 3- glycidoxypropyl The copolymer of trimethoxy silane is (for example, trade name；Examine special Olso (COATOSIL) MP200, Japan's figure new high-tech material advanced in years (Momentive Performance Materials Japan) Co., Ltd) etc. silane series coupling agents, acetyl alkoxy The titanate esters system coupling agent such as the aluminium system coupling agents such as aluminum-diisopropoxide and bis- (dioctyl phosphito ester) titanate esters of tetra isopropyl.

In these adhesion elevators, the effect of the promotion adhesion of 3- glycidoxypropyltrimewasxysilane Greatly, therefore preferably.

Relative to thermosetting total composition, the content of adhesion elevator is preferably 0.01 weight % or more and 10 weights Measure % or less.

1-5-8. antioxidant

It is of the invention for the viewpoint of the xanthochromia in the case where improving the transparency, preventing cured film exposure at high temperature Thermosetting composition can also also contain antioxidant.

It is anti-that hindered phenolic, amine system of being obstructed, phosphorus system, chalcogenide compound etc. can also be added in thermosetting composition of the invention Oxidant.Wherein, for sunproof viewpoint, preferred hindered phenolic.Concrete example are as follows: Yi Lu Jia Nuosi (Irganox) 1010, Easy fine jade Jia Nuosi (Irganox) FF, Yi Lu Jia Nuosi (Irganox) 1035, Yi Lu Jia Nuosi (Irganox) 1035FF, Yi Lu Good Northey (Irganox) 1076, Yi Lu Jia Nuosi (Irganox) 1076FD, Yi Lu Jia Nuosi (Irganox) 1098, Yi Lujia Northey (Irganox) 1135, Yi Lu Jia Nuosi (Irganox) 1330, Yi Lu Jia Nuosi (Irganox) 1726, Yi Lu Jia Nuosi (Irganox) 1425WL, Yi Lu Jia Nuosi (Irganox) 1520L, Yi Lu Jia Nuosi (Irganox) 245, Yi Lu Jia Nuosi (Irganox) 245FF, Yi Lu Jia Nuosi (Irganox) 259, Yi Lu Jia Nuosi (Irganox) 3114, Yi Lu Jia Nuosi (Irganox) 565, Yi Lu Jia Nuosi (Irganox) 565DD (is trade name；Japanese BASF (BASF Japan) share has Limit company), Ai Di Coase tower wave (ADK STAB) AO-20, Ai Di Coase tower wave (ADK STAB) AO-30, Ai Di Coase tower wave (ADK STAB) AO-50, Ai Di Coase tower wave (ADK STAB) AO-60, Ai Di Coase tower wave (ADK STAB) AO-80 (is Trade name；Ai Dike (ADEKA) limited liability company).Wherein, more preferably easy fine jade Jia Nuosi (Irganox) 1010, Ai Di Coase Tower wave (ADK STAB) AO-60.

Relative to thermosetting total composition, adds 0.1 parts by weight~5 parts by weight antioxidant and use.

1-5-9. molecular weight regulator

Thermosetting composition of the invention can also also contain molecular weight regulator, to inhibit molecule quantitative change due to polymerization Height, and show excellent storage stability.It as molecular weight regulator, can enumerate: thio-alcohol, xanthan acids, quinones, hydroquinones And 2,4- diphenyl -4-methyl-1-pentene etc..

As the concrete example of molecular weight regulator, can enumerate: 1,4-naphthoquinone, 1,2- benzoquinones, Isosorbide-5-Nitrae-benzoquinones, methyl-are to benzene Quinone, anthraquinone, quinhydrones, methylnaphthohydroquinone, tert-butyl hydroquinone, 2,5- di-t-butyl quinhydrones, bis--amyl hydroquinone of 2,5-, 1,4- dihydroxy Base naphthalene, 3,6- dihydroxy benzo norbornane, 4- metoxyphenol, 2,2', tetra--tert-butyl of 6,6'- -4,4' dihydroxy diphenyl, 3- (3,5- di-t-butyl -4- hydroxy phenyl) propionic acid stearyl ester, 2,2' methylene bis (6- tert-butyl -4- ethyl -phenol), 2, 4,6- tri- (3', 5'- di-t-butyl -4'- hydroxybenzyl) mesitylene, [3- (the 3,5- di-t-butyl -4- hydroxyl of pentaerythrite four Base phenyl) propionic ester], 4- tert-butyl catechol, n-hexyl mercaptan, n octylmercaptan, n-dodecyl mercaptan, tertiary dodecane Base mercaptan, thioglycolic acid (thioglycolic acid), dimethyl yellow ortho acid thioether, diisopropyl xanthic acid disulfide, 2, 6- di-t-butyl-paracresol, 4,4' butylidene biss (6- tert-butyl-metacresol), 4,4'- thiobis (6- tert-butyl-first Phenol), 2,4- diphenyl -4-methyl-1-pentene, phenthazine, 2 hydroxy 1,4 naphthoquinone (lawsone) etc..

Molecular weight regulator can be used alone, and also can be used in combination two or more.In molecular weight regulator, if naphthoquinones system Molecular weight regulator, then for showing the aspect of excellent storage stability preferably.

In molecular weight regulator, if the 2-hydroxy-1,4-naphthoquinone with phenolic hydroxyl group, then with regard to the viewpoint of storage stability For more preferably.

1-5-10. ultraviolet absorbing agent

From further increase be formed by hyaline membrane degradation inhibiting ability from the viewpoint of, thermosetting group of the invention Ultraviolet absorbing agent can also be contained by closing object.

The concrete example of ultraviolet absorbing agent is refined (TINUVIN) P of Supreme Being slave, refined (TINUVIN) 120 of Supreme Being slave, Supreme Being slave are refined (TINUVIN) 144, refined (TINUVIN) 213 of Supreme Being slave, refined (TINUVIN) 234 of Supreme Being slave, refined (TINUVIN) 326 of Supreme Being slave, Supreme Being slave are refined (TINUVIN) 571, Supreme Being slave refined (TINUVIN) 765 (is trade name；The limited public affairs of Japanese BASF (BASF Japan) share Department).

Relative to thermosetting total composition, adds 0.01 parts by weight~10 parts by weight ultraviolet absorbing agent and make With.

The anti-flocculating agent of 1-5-11.

From merging the polyesteramide with polymeric double bond sour (A) or epoxide (B) with solvent, prevent from agglomerating From the viewpoint of, thermosetting composition of the invention can also contain anti-flocculating agent.

The concrete example of anti-flocculating agent is Di Sipabike (Disperbyk) -145, Di Sipabike (Disperbyk) - 161, Di Sipabike (Disperbyk) -162, Di Sipabike (Disperbyk) -163, Di Sipabike (Disperbyk) -164, Di Sipabike (Disperbyk) -182, Di Sipabike (Disperbyk) -184, Di Sipabi Gram (Disperbyk) -185, Di Sipabike (Disperbyk) -2163, Di Sipabike (Disperbyk) -2164, Bi Ke (BYK) -220S, Di Sipabike (Disperbyk) -191, Di Sipabike (Disperbyk) -199, Di Sipabike (Disperbyk) -2015 (be trade name；Chemical (the BYK Chemie Japan) limited liability company of Japanese Bi Ke), FTX- 218, Fu Jite (Ftergent) 710FM, Fu Jite (Ftergent) 710FS (is trade name；Ni Aosi (Neos) share has Limit company), Fu Luolun (Flowlen) G-600, Fu Luolun (Flowlen) G-700 (be trade name；Common prosperity society chemistry share has Limit company).

Relative to thermosetting total composition, adds the anti-flocculating agent of 0.01 parts by weight~10 parts by weight and use.

1-5-12. thermal cross-linking agent

It is examined from heat resistance, chemical-resistant, film inner evenness, flexibility, flexibility, the viewpoint of elasticity is further increased Consider, thermosetting composition of the invention can also contain thermal cross-linking agent.

The concrete example of thermal cross-linking agent be Ni Kalake (Nikalac) MW-30HM, Ni Kalake (Nikalac) MW-100LM, Ni Kalake (Nikalac) MX-270, Ni Kalake (Nikalac) MX-280, Ni Kalake (Nikalac) MX-290, Buddhist nun's card Clarke (Nikalac) MW-390, Ni Kalake (Nikalac) MW-750LM (is trade name；Three and the chemical limited public affairs of share Department).

Relative to thermosetting total composition, adds 0.1 parts by weight~10 parts by weight thermal cross-linking agent and use.

The preservation of 1-6. thermosetting composition

If thermosetting composition of the invention saves in the range of -30 DEG C~25 DEG C, composition through Shi Wending Property become it is good and preferred.If storage temperature is -20 DEG C~10 DEG C, precipitate is also not present and more preferable.

2. the cured film obtained by thermosetting composition

Thermosetting composition of the invention can obtain in the following way: optionally select addition polyesteramide Sour (A), the polymer (B) of cyclic ether compound, curing agent (C), solvent (D) and the compound with oxiranyl (b2) epoxide other than, the compound with polymeric double bond, surfactant, adhesion elevator, antioxidant And other additives, by these compounds equably mixed dissolution.

If the thermosetting composition prepared as described above (in the case where solvent-free solid state, is dissolved in After in solvent) it is coated on matrix surface, solvent is removed for example, by heating etc., then can form film.To matrix It is existing known that the coating of the thermosetting composition on surface can use spin-coating method, rolling method, infusion process and slot coated method etc. Method formed film.Secondly, the film is temporarily calcined using heating plate or baking oven etc..Temporary calcination condition view it is each at Point type and allotment ratio and difference is 5 minutes~15 minutes if using baking oven usually at 70 DEG C~150 DEG C, if making It is then 1 minute~5 minutes with heating plate.Thereafter, it is formally calcined to harden film.Formal calcination condition view it is each at Point type and allotment ratio and difference, usually at 180 DEG C~250 DEG C, preferably 200 DEG C~250 DEG C, if using baking oven It is 30 minutes~90 minutes, is 5 minutes~30 minutes if using heating plate, can be hardened and being heated Film.

The cured film obtained as described above when heated, 1) partially dehydrated be cyclized of the polyamic acid of polyesteramide acid and shape At imide bond, 2) carboxylic acid of polyesteramide acid is reacted with epoxide and molecular weight and 3) epoxide harden And molecular weight, therefore it is very tough, and the transparency, heat resistance, chemical-resistant, flatness, adhesion are excellent.Moreover, For identical reason, it is also contemplated that light resistance, resistant sputtering, scratch resistance, coating are excellent.Therefore, hardening of the invention If film as colored filter protective film and use, effectively, the colored filter can be used to manufacture liquid crystal Show element or solid-state imager.Moreover, other than the protective film of colored filter, if cured film of the invention is as shape At the transparent insulating film between thin film transistor (TFT) (Thin Film Transistor, TFT) and transparent electrode or it is formed in transparent Transparent insulating film between electrode and alignment films and use, then effectively.In turn, even if cured film of the invention is as light emitting diode The protective film of (Light Emitting Diode, LED) illuminator and use, also effectively.

[embodiment]

Secondly, being added a concrete explanation by synthesis example, Examples and Comparative Examples to the present invention, but the present invention is not by this Any restriction of a little embodiments.

The abbreviation of compound used in synthesis example, Examples and Comparative Examples indicates following raw material.

[tetracarboxylic anhydride]

ODPA:3,3', 4,4'- diphenyl ether tetracarboxylic dianhydride

BT-100:1,2,3,4- butane tetracarboxylic acid dianhydride

[diamines]

DDS:3,3'- diamino diphenyl sulfone

[multi-hydroxy compound]

Bis-A-2EOH:4,4'- isopropylidene is bis- (2- phenoxetol)

70PA: epoxy-ester 70PA (trade name；Chemistry limited liability company, common prosperity society)

[styrene-maleic anhydride copolymer]

SMA1000P (trade name: river crude oil limited liability company)

[cyclic ether compound]

OXE-30: methacrylic acid (3- Ethyloxetane -3- base) methyl esters

OXE-10: acrylic acid (3- Ethyloxetane -3- base) methyl esters

GMA: glycidyl methacrylate

E6: Tyke not (Techmore) VG3101L (trade name；General Lin Taike (Printec) limited liability company)

[free-radical polymerised compound other than cyclic ether compound]

MMA: methyl methacrylate

NPM:N- phenylmaleimide

[thermal polymerization]

V-601: dimethyl 2,2'- azo is bis- (2 Methylpropionic acid ester)

[curing agent (C)]

TMA: trimellitic anhydride

UC-3000: A Lufeng (ARUFON) UC-3000 (trade name: East Asia synthesizes limited liability company)

[additive]

S510: Sa Laaisi (Sila-Ace) S510 (trade name；Prompt grace intelligence (JNC) limited liability company)；Coupling agent

AO-60: Ai Di Coase tower wave (ADK STAB) AO-60 (trade name；Ai Dike (ADEKA) limited liability company)； Antioxidant

F-556: Mei Jiafa (Megafac) F-556 (trade name；DIC (DIC) limited liability company)；Surfactant

[solvent]

MMP:3- methoxy methyl propionate

PGMEA: propylene glycol methyl ether acetate

Firstly, synthesizing tetracarboxylic dianhydride, diamines, monohydroxy compound, multi-hydroxy compound etc. as shown below The polyesteramide acid solution (1~synthesis example of synthesis example 7) of reaction product.

The synthesis of [synthesis example 1] polyesteramide acid (A1) solution

In the four-hole boiling flask with blender, the 3- methoxypropionic acid first for having carried out dehydration and purification is packed into following weight Ester (methyl 3-methoxy propionate, be slightly denoted as " MMP " below), 3,3', 4,4'- diphenyl ether tetracarboxylic dianhydrides (3,3', 4,4'-diphenylether tetracarboxylic dianhydride, be slightly denoted as " ODPA " below), Isosorbide-5-Nitrae-fourth Glycol, benzylalcohol carry out stirring in 2 hours (synthesis first stage) under drying nitrogen stream, at 125 DEG C.

Thereafter, reaction solution is cooled to 25 DEG C, 3,3'- diamino diphenyl sulfone (diamino is put into following weight Diphenyl sulfone is slightly denoted as " DDS " below), MMP, carried out at 20 DEG C~30 DEG C 2 hours stirring after, at 125 DEG C Carry out stirring in 1 hour (synthesis second stage).

DDS 3.26g

MMP 21.00g

[Z/Y=3.0, (Y+Z)/X=0.8]

Solution is cooled to room temperature, 30 weight % solution of the polyesteramide sour (A1) of pale yellow transparent are obtained.To solution A part be sampled, utilize gpc analysis (polystyrene standard) measure weight average molecular weight.As a result, obtained The weight average molecular weight of polyesteramide acid (A1) is 4,200.

The synthesis of [synthesis example 2] polyesteramide acid (A2) solution

In the four-hole boiling flask with blender, the propylene glycol list first for having carried out dehydration and purification is sequentially packed into following weight Ether acetic acid ester (propylene glycol monomethyl ether acetate, PGMEA), 1,2,3,4- butane tetracarboxylic acid Dianhydride (BT-100), SMA1000P (trade name；Styrene-Maleic Anhydride Copolymer, river crude oil limited liability company), 1,4-butanediol, benzylalcohol carry out stirring in 2 hours (synthesis first stage) under drying nitrogen stream, at 125 DEG C.

Thereafter, reaction solution is cooled to 25 DEG C, DDS, PGMEA is put into following weight, it is small that 2 are carried out at 20 DEG C~30 DEG C When stirring after, stirring (synthesize second stage) in 1 hour is carried out at 125 DEG C.

DDS 1.20g

PGMEA 16.51g

[Z/Y=2.7, (Y+Z)/X=0.9]

Solution is cooled to room temperature, 30 weight % solution of the polyesteramide sour (A2) of pale yellow transparent are obtained.To solution A part be sampled, utilize gpc analysis (polystyrene standard) measure weight average molecular weight.As a result, obtained The weight average molecular weight of polyesteramide acid (A2) is 10,000.

The synthesis of sour (A7) solution of [3~synthesis example of synthesis example 7] polyesteramide acid (A3)~polyesteramide

According to synthesis example 1 and the method for synthesis example 2, made with temperature, time and the ratio (unit: g) recorded in table 1-1 Each ingredient reaction obtains sour (A7) solution of sour (the A3)~polyesteramide of polyesteramide.

Table 1-1

The unit of the charge weight of each sample and solvent is gram (g)

Secondly, the solution (synthesis example 8) of the polymer (B) of synthesis of cyclic ether compound as shown below.

The synthesis of polymer (B1) solution of [synthesis example 8] cyclic ether compound

In the four-hole boiling flask with blender, the dehydration and purification that carried out of polymer solvent is loaded as with following weight PGMEA, as the OXE-30 of the compound (b1) with oxetanylmethoxy, and then polymerization initiator is loaded as with following weight V-601, carried out under drying nitrogen stream, at 110 DEG C 2 hours stir.

PGMEA 31.50g

OXE-30 13.50g

V-601 1.35g

Solution is cooled to room temperature, 30 weight % solution of the polymer (B1) of cyclic ether compound are obtained.To solution A part is sampled, and measures weight average molecular weight using gpc analysis (polystyrene standard).As a result, ring obtained The weight average molecular weight of the polymer (B1) of shape ether compound is 7,200.

The synthesis of polymer (B2) solution of [synthesis example 9] cyclic ether compound

In the four-hole boiling flask with blender, the dehydration and purification that carried out of polymer solvent is loaded as with following weight PGMEA, as the OXE-30 of the compound (b1) with oxetanylmethoxy, as the compound (b2) with oxiranyl GMA, and then it is loaded as with following weight the V-601 of polymerization initiator, stir within 2 hours under drying nitrogen stream, at 110 DEG C It mixes.

Solution is cooled to room temperature, 30 weight % solution of the polymer (B2) of cyclic ether compound are obtained.To solution A part is sampled, and measures weight average molecular weight using gpc analysis (polystyrene standard).As a result, ring obtained The weight average molecular weight of the polymer (B2) of shape ether compound is 7,300.

Polymer (B3)~cyclic ether compound polymer of [10~synthesis example of synthesis example 13] cyclic ether compound (B6) synthesis of solution

According to synthesis example 8 and the method for synthesis example 9, made with temperature, time and the ratio (unit: g) recorded in table 1-2 Each ingredient reaction, obtains polymer (B3)~cyclic ether compound polymer (B6) solution of cyclic ether compound.

Table 1-2

The unit of the charge weight of each sample and solvent is gram (g)

Cyclic ether compound (E1)~cyclic ether compound (E5) other than [compare synthesis example 1~compare synthesis example 5] (B) The synthesis of solution

According to synthesis example 8 and the method for synthesis example 9, made respectively with temperature, time and the ratio (unit: g) recorded in table 1-3 Ingredient reaction, obtains cyclic ether compound (E1)~cyclic ether compound (E5) solution other than (B).

Table 1-3

The unit of the charge weight of each sample and solvent is gram (g)

[embodiment 1]

Nitrogen displacement is carried out to the detachable flask of the 500ml with stirring wing, is packed into 100.0g in the flask The synthesis example 1 as polyesteramide sour (A) obtained in sour (A1) solution of polyesteramide, 100.0g cyclic ether compound Polymer (B1), 6.0g TMA, 3.3g as curing agent S510,0.3g as adhesion elevator conduct it is anti- The PGMEA of the MMP and 97.6g for having carried out dehydration and purification as solvent (D) of AO-60,41.7g of oxidant, at room temperature Stir within 3 hours, dissolves it equably.

Secondly, Mei Jiafa (Megafac) F-556 (trade name as surfactant of investment 0.2g；DIC (DIC) limited liability company), it carries out stirring for 1 hour at room temperature, is filtered and is prepared using molecular filter (0.2 μm of aperture) Thermosetting composition.

[barrier evaluation method]

When utilization UV, visible light near infrared spectrometer (trade name；V-670, light splitting limited liability company, Japan) it carries out When measurement, last 10 seconds for thermosetting composition with 300rpm and be spun near 560nm have absorption and have comprising R, on the colored filter substrate without cured film of the pixel of G, B, prebake conditions 2 minutes in 90 DEG C of heating plate.Then, it is drying To toast 30 minutes after 230 DEG C in case, the colorized optical filtering chip base with cured film that the average film thickness of protective film is 2.0 μm is obtained Plate.

Secondly, the 1- first of 0.5ml is added dropwise on the colored filter substrate with cured film for cut out 10 centimeter squares The glass (hereinafter referred to as cover glass) for cutting out 9 centimeter squares is statically placed in the colored filter with cured film by base -2-Pyrrolidone On mating plate substrate, heat within 5 minutes with 180 DEG C using heating plate.After heating, cover glass is removed, the 1- first of 5ml is utilized Cleaning solution is moved to the capacity of 10ml to clean cover glass and with the colored filter substrate of cured film by base -2-Pyrrolidone Bottle.Until addition 1-Methyl-2-Pyrrolidone is filled up to 10ml in the volumetric flask for being put into cleaning solution, by mixed solution Dissolution fluid as the colored filter substrate with cured film.Then, using the UV, visible light near infrared spectrometer, Using 1-Methyl-2-Pyrrolidone as reference sample, the transmissivity of dissolution fluid is measured.According to determining as a result, by 560nm's The situation that transmissivity is 90% or more is evaluated as zero, and by less than 90% the case where is evaluated as ×.

[evaluation method of flatness]

Fine shape measurement device (trade name is used in advance；P-17, Ke Lei (KLA TENCOR) limited liability company), with 300rpm lasts the nothing with the pixel comprising R, G, B for being spun on thermosetting composition in 10 seconds and determining surface scale On the colored filter substrate of cured film, prebake conditions 2 minutes in 90 DEG C of heating plate.Then, in an oven to dry after 230 DEG C It is 30 minutes roasting, obtain the colored filter substrate with cured film that the average film thickness of protective film is 2.0 μm.Thereafter, to being obtained The colored filter substrate with cured film obtained measures surface scale.

According to the colored filter substrate of no cured film and the surface scale of the colored filter substrate with cured film Maximum value (is slightly denoted as " maximum scale ") below, and flat rate is calculated using following calculating formulas.It is 75% by flat rate Above situation is evaluated as flatness zero, flat rate is less than 75% the case where be evaluated as flatness ×.Furthermore no cured film Colored filter substrate be using maximum scale be 1.5 μm of persons.

Flat rate=[(the maximum scale-of the colored filter substrate of no cured film has the colored filter of cured film The maximum scale of substrate)/(the maximum scale of the colored filter substrate of no cured film)] × 100%

[evaluation method of heat resistance]

Thermosetting composition is spun on glass substrate secondly, lasting 10 seconds with 800rpm, in 90 DEG C of heating Prebake conditions 2 minutes on plate.Then, in an oven to toast 30 minutes after 230 DEG C, the band that the film thickness of protective film is 1.0 μm is obtained There is the glass substrate of cured film.Glass substrate obtained with cured film is carried out at 230 DEG C 1 hour after reheating, Film thickness before measurement heating and the film thickness after heating, calculate residual film ratio by following calculating formulas.The measurement of film thickness uses described micro- Thin shape measuring apparatus (trade name: P-17, Ke Lei (KLA TENCOR) limited liability company).It is by the residual film ratio after heating 95% or more situation is evaluated as zero, and residual film ratio after heating is less than 95% the case where is evaluated as ×.

[2~embodiment of embodiment 13]

It is with ratio (unit: g) documented in table 2-1~table 2-2 that the mixing of each ingredient is molten according to the method for embodiment 1 It solves and obtains thermosetting composition.

Table 2-1

The unit of charge weight is gram (g)

Table 2-2

The unit of charge weight is gram (g)

[1~comparative example of comparative example 6]

According to the method for embodiment 1, each ingredient mixed dissolution is obtained by thermosetting group with the ratio (unit: g) of table 3 Close object.

Table 3

The unit of charge weight is gram (g)

According to result shown in table 2-1~table 2-2: 1~embodiment of embodiment 13 has used cyclic ether compound Polymer (B) cured film it is barrier excellent, obtain balance about flatness and heat resistance.

Know the cured film of the cyclic ether compound (E) that only used other than (B) of 1~comparative example of comparative example 6 of table 3 Excellent heat resistance.On the other hand, about comparative example 1, the result is that it is barrier good, but flatness is poor.About comparative example 2~compare Example 3, the result is that flatness is also poor in addition to barrier.About 4~comparative example of comparative example 6, flatness is good, but barrier does not obtain Obtain good result.

As described above, only can satisfy in the case where the polymer (B) of cyclic ether compound is used as required ingredient All characteristics.

[industrial availability]

By barrier high, the flatness height for the cured film that thermosetting composition of the invention obtains, with regard to the aspect Speech may be used as the protective film of various optical materials such as colored filter, LED light-emitting component and light receiving element etc., and be formed Insulating film between TFT and transparent electrode and between transparent electrode and alignment films.

Claims (7)

1. a kind of thermosetting composition, it includes polyesteramides sour (A), the polymer (B) and curing agent of cyclic ether compound (C), the thermosetting composition is characterized in that,

It includes X moles of tetracarboxylic acid with the ratio that the relationship of following formula (1) and formula (2) is set up that the polyesteramide sour (A), which is derived from, The reaction product of the raw material of acid dianhydride, Y moles of diamines and Z moles of multi-hydroxy compound,

0.2≦Z/Y≦8.0·······(1)

0.2≦(Y+Z)/X≦5.0···(2)

The polymer (B) of the cyclic ether compound is the homopolymer for being selected from the compound (b1) with oxetanylmethoxy, has The mutual copolymer of compound (b1) of oxetanylmethoxy and compound (b1) with oxetanylmethoxy with there is oxa- cyclopropyl At least one of the copolymer of the compound (b2) of base.

2. thermosetting composition according to claim 1, which is characterized in that the polyesteramide sour (A) includes following Structural unit represented by structural unit represented by formula (3) and following formula (4):

In formula (3) and formula (4), R¹It is to remove residue made of two-CO-O-CO-, R from tetracarboxylic dianhydride²It is to be removed from diamines Two-NH₂Made of residue, R³It is to remove residue made of two-OH from multi-hydroxy compound.

3. thermosetting composition according to claim 1 or 2, which is characterized in that the change with oxetanylmethoxy Closing object (b1) is selected from acrylic acid (3- Ethyloxetane -3- base) methyl esters, methacrylic acid (3- Ethyloxetane - At least one of 3- yl) methyl esters.

4. thermosetting composition according to claim 1 or 2, which is characterized in that the change with oxiranyl Close object (b2) be selected from glycidyl acrylate, glycidyl methacrylate, methacrylic acid methyl ethylene oxidic ester, At least one of 4- hydroxybutyl acrylate glycidol ether.

5. thermosetting composition according to any one of claim 1 to 4, which is characterized in that relative to polyesteramide Sour (A) 100 parts by weight, the content of the polymer (B) of the cyclic ether compound are 20 parts by weight~400 parts by weight.

6. a kind of cured film, which is characterized in that it is to combine thermosetting according to any one of claim 1 to 5 Object is hardened and is obtained.

7. a kind of colored filter, which is characterized in that have cured film according to claim 6 as transparent protective film.