CN108535958A

CN108535958A - Photosensitive composite, cured film, colored filter, interlayer dielectric and application type polarizer

Info

Publication number: CN108535958A
Application number: CN201810156959.2A
Authority: CN
Inventors: 中原铁舟; 堀田佑策; 藤马佐知子; 横手友纪
Original assignee: JNC Corp
Current assignee: JNC Corp
Priority date: 2017-03-02
Filing date: 2018-02-24
Publication date: 2018-09-14
Also published as: TW201833188A; JP2018146963A; KR20180101198A

Abstract

The present invention relates to a kind of photosensitive composite, cured film, colored filter, interlayer dielectric and application type polarizers.The photosensitive composite includes that polyesteramide is sour (A), epoxide (B), include the compound (C) with polymeric double bond of the compound with carbamate skeleton, Photoepolymerizationinitiater initiater (D), and additive (E), the polyesteramide sour (A) is by making X moles of tetracarboxylic dianhydride, Y moles of diamines and Z moles of multi-hydroxy compound are reacted with the ratio that the relationship of following formula (1) and formula (2) is set up and are obtained, wherein, relative to sour (A) 100 parts by weight of the polyesteramide, the total amount of the epoxide (B) is the parts by weight of 20 parts by weight~200, the total amount of the compound (C) with polymeric double bond is the parts by weight of 20 parts by weight~300.0.2≤Z/Y≤8.0···············(1)0.2≤(Y+Z)/X≤5.0···(2).

Description

Photosensitive composite, cured film, colored filter, interlayer dielectric and application type are inclined Tabula rasa

Technical field

It is formed by firmly for the photosensitive composite of various elements, by the photosensitive composite the present invention relates to a kind of Change film and colored filter, insulating film and application type polarizer using the cured film.

Background technology

In the manufacturing step of the elements such as display element, it will usually implement chemical treatments to the surface of element or high temperature adds Heat treatment.Therefore, the surface deterioration of element, damage, rotten in order to prevent, is equipped with protective film mostly.To institute's group in display element Protective film requirement heat resistance, chemical-resistant, the adhesion, the transparency and flatness etc. to substrate entered.

Protective film is broadly divided into thermosetting composition and photo-hardening composition according to its method for curing.Including heat is hard It is widely used due to the protective film of the property changed composition volatile ingredient when method for curing is easy, heat resistance is high and film forming is few. On the other hand, the formation for not considering the pattern using alkaline development in most cases, is not only microfabrication, it is also difficult to be formed and be carved Line (scribeline), it is sometimes desirable to carry out the cleaning step of generated clast when screen segmentation.

Including the protective film of photo-hardening composition can initially consider the formation of the pattern using alkaline-based developer, because This, needless to say, the requirement to the microfabrication in various elements improves for the formation of groove, therefore horizontal with some tens of pm The material of analyticity is also more.For example, as shown in Patent Document 1, microfabrication can both be carried out by having developed, also have heat resistance, The material of residual film ratio after high sensitivity and high development.

On the other hand, recently based on the needs to flexible displays or foldable (foldable) equipment, occur considering The necessity of the bending resistance of element especially requires the protective film comprising photo-hardening composition maintaining previous analyticity etc. Bending resistance is assigned in the state of characteristic.In addition, in the case where protective film is applied to the optical system in element, it is also desirable to high The transparency.

For these requirements characteristic, each characteristic such as analyticity, the transparency, sensitivity and heat resistance of the patent document 1 is good It is good, on the other hand, the shortcomings that having when forming a film in flexible printed base plate etc., crackle will produce if being bent.In addition, In patent document 2, for identical protective film purposes, it can parse and have high bending characteristic, but the level of analyticity is Secondary grade, the required light exposure for hardening is also more, and does not consider the transparency.

[existing technical literature]

[patent document]

[patent document 1] Japanese Patent Laid-Open 2016-103010

[patent document 2] Japanese Patent Laid-Open 2010-250059

Invention content

[problem to be solved by the invention]

The issue of the present invention is to provide residual film ratios after a kind of heat resistance, sensitivity, analyticity, the development, transparency, resistant to bending Property is excellent, especially the excellent cured film of analyticity, bending resistance and the element with the cured film.

[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, use following composition And formed the heat resistance of cured film, sensitivity, analyticity, residual film ratio, the transparency, bending resistance are excellent after development, especially parse Property, bending resistance are excellent, so as to complete the present invention：The composition is a kind of photosensitive composite, and it includes polyesteramides Sour (A), epoxide (B), the compound (C) with polymeric double bond, Photoepolymerizationinitiater initiater (D), additive (E), wherein It include the compound with carbamate skeleton (- NH-C (=O)-O-) in the compound (c) with polymeric double bond.

[1] a kind of photosensitive composite it includes polyesteramide sour (A), epoxide (B), has polymeric double bond Compound (C), Photoepolymerizationinitiater initiater (D) and additive (E),

The polyesteramide sour (A) is by making X moles of tetracarboxylic dianhydride, Y moles of diamines and Z moles of polynary hydroxyl Based compound is reacted with the ratio that the relationship of following formula (1) and formula (2) is set up and is obtained；

The compound (C) with polymeric double bond includes the compound with carbamate skeleton；

Relative to sour (A) 100 parts by weight of polyesteramide, the total amount of epoxide (B) is the weight of 20 parts by weight~200 Part, the total amount of the compound (C) with polymeric double bond is the parts by weight of 20 parts by weight~300.

0.2≤Z/Y≤8.0……………(1)

0.2≤(Y+Z)/X≤5.0…(2)

[2] according to the photosensitive composite described in [1], wherein the full dose of the compound (C) with polymeric double bond In, the ratio of the compound with carbamate skeleton is 50 weight % or more.

[3] according to the photosensitive composite described in [1] or [2], wherein the compound with carbamate skeleton It is the compound for including more than two polymeric double bonds in each molecule.

[4] photosensitive composite according to any one of [1]~[3], wherein described have carbamate skeleton Compound molecular weight less than 10,000.

[5] photosensitive composite according to any one of [1]~[4], wherein the raw material of polyesteramide acid (A) Ingredient also includes monohydroxy compound.

[6] according to the photosensitive composite described in any one of [1]~[5], wherein the tetracarboxylic dianhydride is selected from 3, 3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydrides, 2,2- [bis- (3,4- dicarboxyl benzene Base)] in hexafluoropropane dianhydride, 1,2,3,4- butane tetracarboxylic acid dianhydrides and ethylene glycol bis- (dehydrations trimellitate) at least one Kind,

The diamines be in 3,3 '-diamino diphenyl sulfones and bis- [4- (3- amino-benzene oxygens) phenyl] sulfones at least One kind,

The multi-hydroxy compound be selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1, Bis- (4- hydroxy-cyclohexyls) propane of 5- pentanediols, 1,6- hexylene glycols, 1,7- heptandiols, 1,8- ethohexadiols, 2,2-, 4,4 '-dihydroxies Base dicyclohexyl, isocyanuric acid three (2- hydroxyethyls) ester, 2- hydroxy-benzyl alcohols, 4- hydroxy-benzyl alcohols, 2- (4- hydroxy phenyls) ethyl alcohol, Glycerine list (methyl) acrylate, trimethylolpropane list (methyl) acrylate, pentaerythrite list (methyl) acrylate, season Penta tetrol two (methyl) acrylate, dipentaerythritol list (methyl) acrylate, dipentaerythritol two (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, D-sorbite list (methyl) acrylic acid Ester, D-sorbite two (methyl) acrylate, D-sorbite three (methyl) acrylate, D-sorbite four (methyl) acrylic acid Ester, 4,4 '-isopropylidenes bis- (2- phenoxetols), (methyl) acrylic acid modified object of ethylene glycol diglycidylether, the third two (methyl) acrylic acid modified object of alcohol diglycidyl ether, (methyl) acrylic acid modified object of tripropyleneglycol diglycidyl ether, (methyl) acrylic acid modified object of glycerin diglycidyl ether, (methyl) acrylic acid modified object, the ring of bisphenol A diglycidyl ether (methyl) acrylic acid modified object of Ethylene Oxide modified bisphenol A diglycidyl ether and in each molecule comprising more than two At least one of (methyl) acrylic acid modified object of the compound of epoxy group.

[7] according to the photosensitive composite described in [5], wherein the monohydroxy compound is selected from isopropanol, benzylalcohol, third 2-ethoxyethanol, 3- ethyl -3- hydroxymethyl oxetanes, furfuryl alcohol, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid Hydroxybutyl, (methyl) acrylic acid -2- hydroxyl -3- phenoxy-propyls, (methyl) acrylic acid -4- hydroxylphenyl esters, to hydroxyl (first Base) acrylic acid aniline, 1,4-CHDM list (methyl) acrylate, (methyl) acrylic acid -3- (2- hydroxy phenyls) ester, Glycerine two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, two (methyl) acrylate of pentaerythrite five and (methyl) acrylic acid of compound comprising an epoxy group changes in each molecule At least one of property object.

[8] photosensitive composite according to any one of [1]~[7], wherein the weight of polyesteramide acid (A) Average molecular weight is 1,000~200,000.

[9] photosensitive composite according to any one of [1]~[8], wherein the epoxide (B) is each Include 2~35 epoxy groups in molecule, weight average molecular weight is less than 5,000；

The Photoepolymerizationinitiater initiater (D) is selected from alpha-amido benzene alkyl ketone system Photoepolymerizationinitiater initiater, acylphosphine oxide system light At least one of polymerization initiator, oxime ester system Photoepolymerizationinitiater initiater；

Additive (E) includes to be selected from least one of coupling agent and surfactant.

[10] a kind of cured film is obtained by the photosensitive composite according to any one of [1]~[9].

[11] a kind of colored filter has according to the cured film described in [10] as transparent protective film.

[12] a kind of interlayer dielectric has according to the cured film described in [10] as transparent protective film.

[13] a kind of application type polarizer has according to the cured film described in [10] as basilar memebrane.

[The effect of invention]

The residual film ratio after the heat resistance, sensitivity of the cured film that is formed, development, transparent using the photosensitive composite of the present invention Property and analyticity and bending resistance are excellent.It is various that the cured film can be applied to colored filter or protective film, insulating film etc. Purposes.

Specific implementation mode

1. photosensitive composite

The photosensitive composite of the present invention is comprising polyesteramide sour (A), epoxide (B), has polymeric double bond Compound (C), Photoepolymerizationinitiater initiater (D) and additive (E) composition, the polyesteramide sour (A) is by making tetracarboxylic acid Acid dianhydride, diamines, multi-hydroxy compound are reacted as required material composition and are obtained.In turn, have polymerism double The compound (C) of key includes the compound with carbamate skeleton.Relative to sour (A) 100 parts by weight of the polyesteramide, The total amount of the epoxide (B) is the parts by weight of 20 parts by weight~200, the compound (C) with polymeric double bond Total amount is the parts by weight of 20 parts by weight~300.

Furthermore photosensitive composite of the invention can also further contain described in the range of obtaining the effect of the present invention Other compositions in addition.

1-1. polyesteramides are sour (A)

Polyesteramide acid (A) be by make tetracarboxylic dianhydride, diamines and multi-hydroxy compound be used as required raw material at Divide and is reacted and obtained.Specifically, polyesteramide sour (A) is by the tetracarboxylic dianhydride that makes X moles, Y moles of diamines And Z moles of multi-hydroxy compound is reacted with the ratio that the relationship of formula (1) and formula (2) is set up and is obtained.

0.2≤Z/Y≤8.0……………(1)

0.2≤(Y+Z)/X≤5.0…(2)

In addition, polyesteramide acid (A) has the Component units represented by formula (3) and the Component units represented by formula (4).Formula (3) and in formula (4), R¹To remove residue made of two-CO-O-CO-, R from tetracarboxylic dianhydride²For from diamines remove two- NH₂Made of residue, R³To remove residue made of two-OH from multi-hydroxy compound.

Solvent is at least needed in the synthesis of polyesteramide sour (A).It can make the solvent directly residual and be made and consider The liquid of operability etc. or gelatinous composition, and in addition the solvent can also be removed and consolidating in view of carrying property etc. is made The composition of body shape.

In addition, also can include optionally that styrene-maleic anhydride copolymer is used as original in the synthesis of polyesteramide acid (A) Material, in addition, also can be in the range of not undermining the purpose of the present invention, including other compounds other than described.As other originals The example of material can enumerate siliceous monoamine.

1-1-1. tetracarboxylic dianhydride

In the present invention, as to obtain the material of polyesteramide sour (A), tetracarboxylic dianhydride is used.About tetrabasic carboxylic acid The concrete example of dianhydride can enumerate 3 used in embodiment, and 3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydrides are (hereinafter sometimes referred to simply as ODPA), 1,2,3,4- butane tetracarboxylic acid dianhydrides (hereinafter sometimes referred to simply as BT-100), styrene-maleic anhydride copolymer are (following Sometimes SMA-1000P is referred to as with trade name).

As tetracarboxylic dianhydride, in addition to the compound, can also enumerate：3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acids two Acid anhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydrides, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-diphenyl Sulfone tetracarboxylic dianhydride, 2,2 ', 3,3 '-diphenyl sulfone tetracarboxylic dianhydrides, 2,3,3 ', 4 '-diphenyl sulfone tetracarboxylic dianhydrides, 2,2 ', 3,3 '-diphenyl ether tetracarboxylic dianhydrides, 2,3,3 ', 4 '-diphenyl ether tetracarboxylic dianhydrides, 2,2- [bis- (3,4- dicarboxyphenyis)] Bis- (dehydration the trimellitate) (trade names of hexafluoropropane dianhydride, ethylene glycol：TMEG-100, the new limited public affairs of Japan Chemical share Department), cyclobutane tetracarboxylic dianhydride, methyl cyclobutane tetracarboxylic dianhydride, pentamethylene tetracarboxylic dianhydride, cyclopentanetetracarboxylic's dianhydride, And ethane tetracarboxylic dianhydride.At least one of the tetracarboxylic dianhydride can be used.

In these tetracarboxylic dianhydrides, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acids of good transparency are preferably assigned to cured film Dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydrides, 2,2- [bis- (3,4- dicarboxyphenyis)] hexafluoropropane dianhydride, 1,2,3, 4- butane tetracarboxylics acid dianhydride and TMEG-100, more preferable 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydrides, 3,3 ', 4,4 '-hexichol Base sulfone tetracarboxylic dianhydride and 1,2,3,4- butane tetracarboxylic acid dianhydrides.

1-1-2. diamines

In the present invention, as to obtain the material of polyesteramide sour (A), diamines is used.About the concrete example of diamines, 3 used in embodiment, 3 '-diamino diphenyl sulfones (hereinafter sometimes referred to simply as DDS) can be enumerated.

As diamines, in addition to the compound, can also enumerate：4,4 '-diamino diphenyl sulfones, 3,4 '-diamino two Phenylsulfone, bis- [4- (4- amino-benzene oxygens) phenyl] sulfones, bis- [4- (3- amino-benzene oxygens) phenyl] sulfones, bis- [3- (4- aminobenzene oxygen Base) phenyl] sulfone, [4- (4- amino-benzene oxygens) phenyl] [3- (4- amino-benzene oxygens) phenyl] sulfone, [4- (3- amino-benzene oxygens) benzene Base] [3- (4- amino-benzene oxygens) phenyl] sulfone and 2, bis- [4- (4- amino-benzene oxygens) phenyl] hexafluoropropane of 2-.It can be used described At least one of diamines.

In these diamines, preferably 3,3 '-diamino diphenyl sulfones of good transparency and bis- [4- (3- are assigned to cured film Amino-benzene oxygen) phenyl] sulfone, more preferable 3,3 '-diamino diphenyl sulfones.

1-1-3. multi-hydroxy compounds

The present invention is used as to obtain the material of polyesteramide sour (A) using multi-hydroxy compound.About polynary hydroxyl The concrete example of based compound can enumerate the 1,4-butanediol used in embodiment, triethylene glycol, diethylene glycol, 4,4 '-sub- isopropyls (methyl) acrylic acid modified object (epoxy-ester (EpoxyEster) of base bis- (2- phenoxetols), propylene glycol diglycidylether 70PA；Trade name；Chemistry limited liability company of common prosperity society).

As multi-hydroxy compound, in addition to the compound, can also enumerate：Ethylene glycol, tetraethylene glycol, weight average Molecular weight is 1,000 polyethylene glycol below, propylene glycol, dipropylene glycol, tripropylene glycol, four propylene glycol, weight average molecular weight Be 1,000 polypropylene glycol below, 1,2- butanediols, 1,3-BDO, 1,2- pentanediols, 1,5-PD, 2,4- pentanediols, 1,2,5- penta triol, 1,2- hexylene glycols, 1,6- hexylene glycols, 2,5- hexylene glycols, 1,2,6- hexanetriols, 1,2- heptandiols, 1,7- heptan Glycol, 1,2,7- heptan triol, 1,2- ethohexadiols, 1,8- ethohexadiols, 3,6- ethohexadiols, 1,2,8- pungent triols, 1,2- nonanediols, 1, 9- nonanediols, 1,2,9- nonyl triols, 1,2- decanediols, 1,10- decanediols, 1,2,10- last of the ten Heavenly stems triols, 1,2- dodecanediols, 1, 12- dodecanediols, glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol, isocyanuric acid three (2- hydroxyethyls) ester, Bisphenol-A (2,2- bis- (4- hydroxy phenyls) propane), bisphenol S (bis- (4- hydroxy phenyls) sulfones), Bisphenol F (bis- (4- hydroxy phenyls) first Alkane), bis- (4- hydroxy-cyclohexyls) propane of 2,2-, 4,4 '-dihydroxyl dicyclohexyls, 2- hydroxy-benzyl alcohols, 4- hydroxy-benzyl alcohols, 2- (4- Hydroxy phenyl) ethyl alcohol, diethanol amine, triethanolamine, allylin, trimethyolol propane monoallyl ether, Ji Wusi Alcohol mono allyl ether, pentaerythritol diallyl ether, dipentaerythritol mono allyl ether, dipentaerythritol diallyl ether, two Pentaerythritol triallyl ether, dipentaerythritol tetraallyl ether, D-sorbite mono allyl ether, D-sorbite diallyl Ether, D-sorbite triallyl ether, D-sorbite tetraallyl ether, glycerine 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, two seasons penta 4 Alcohol four (methyl) acrylate, D-sorbite list (methyl) acrylate, D-sorbite two (methyl) acrylate, D-sorbite Three (methyl) acrylate, D-sorbite four (methyl) acrylate, ethylene glycol diglycidylether (methyl) acrylic acid change (methyl) acrylic acid of property object, (methyl) acrylic acid modified object of tripropyleneglycol diglycidyl ether, glycerin diglycidyl ether Modifier, (methyl) acrylic acid modified object of bisphenol A diglycidyl ether, epoxy pronane modification bisphenol A diglycidyl ether (methyl) the acrylic acid modified object, epoxy pronane modification bisphenol S two of (methyl) acrylic acid modified object, bisphenol-S diglycidyl ether (methyl) acrylic acid modified object of glycidol ether, (methyl) acrylic acid modified object, the propylene oxide of Bisphenol F diglycidyl ether (methyl) acrylic acid modified object of modified bisphenol F diglycidyl ethers, (methyl) propylene of union II cresols diglycidyl ether (methyl) third of acid modifier, (methyl) acrylic acid modified object of xenol diglycidyl ether, fluorenes diphenol diglycidyl ether Olefin(e) acid modifier, (methyl) acrylic acid modified object of hexamethylene-Isosorbide-5-Nitrae-dimethanol diglycidyl ether, hydrogenated bisphenol A two shrink (methyl) acrylic acid modified object of glycerin ether, (methyl) acrylic acid modified object of tricyclodecane Dimethanol diglycidyl ether and (methyl) acrylic acid modified object of other compounds comprising more than two epoxy groups in each molecule.

In these polyols, preferably to the ethylene glycol of the favorable solubility of reaction dissolvent, diethylene glycol, three second two Alcohol, propylene glycol, 1,4-butanediol, 1,5-PD, 1,6- hexylene glycols, 1,7- heptandiols, 1,8- ethohexadiols, isocyanuric acid three Bis- (4- hydroxy-cyclohexyls) propane of (2- hydroxyethyls) ester, 2,2-, 4,4 '-dihydroxyl dicyclohexyls, 2- hydroxy-benzyl alcohols, 4- hydroxyls (the first of benzylalcohol, 2- (4- hydroxy phenyls) ethyl alcohol, 4,4 '-isopropylidenes bis- (2- phenoxetols), 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) acrylic acid modified object of glycerin ether, (methyl) acrylic acid modified object, the epoxy pronane modification of bisphenol-S diglycidyl ether (methyl) acrylic acid modified object of bisphenol-S diglycidyl ether, (methyl) acrylic acid modified object of Bisphenol F diglycidyl ether, And (methyl) acrylic acid modified object of epoxy pronane modification Bisphenol F diglycidyl ether.In turn, especially more preferable diethylene glycol, Oneself two ferment, 2- hydroxy-benzyl alcohols, 4- hydroxy-benzyl alcohols, 4,4 '-isopropylidenes of triethylene glycol, 1,4-butanediol, 1,5-PD, 1,6- Bis- (2- phenoxetols), 2- (4- hydroxy phenyls) 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 (methyl) acrylic acid modified object of object and epoxy pronane modification bisphenol A diglycidyl ether.

1-1-4. monohydroxy compound

In the present invention, as to obtain the material of polyesteramide sour (A), monohydroxy compound can be used.

As the concrete example of monohydroxy compound, the benzylalcohol used in embodiment can be enumerated.In the conjunction of polyesteramide sour (A) Cheng Zhong, it is believed that：Without using monohydroxy compound in the range of the formula (2), the superfluous condition for using X relative to Y+Z Under, than more excessively being generated in molecule of the end with anhydride group (- CO-O-CO-) in molecule of the end with amino or hydroxyl. On the other hand, in the case where being reacted with the composition of such monomer, if addition monohydroxy compound, with molecular end Anhydride group is reacted, and can be esterified to end.It is obtained by adding monohydroxy compound and it is made to be reacted Polyesteramide acid (A) can improve the compatibility with epoxide and epoxy curing agent, the storage stability of photosensitive composite It improves, and the coating of photosensitive composite can be improved.

As the concrete example of monohydroxy compound, can enumerate isopropanol, benzylalcohol, dihydroxypropane single-ether, propylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol monoethyl ether, diethylene glycol monoethyl ether, diethyl two Alcohol monomethyl ether, terpinol (terpineol), 3- ethyl -3- hydroxymethyl oxetanes, dimethyl benzyl carbinol (dimethylbenzylcarbinol), furfuryl alcohol, allyl alcohol, (methyl) Hydroxyethyl Acrylate, (methyl) dihydroxypropyl Propyl ester, (methyl) hydroxy butyl acrylate, (methyl) acrylic acid -2- hydroxyl -3- phenoxy-propyls, (methyl) acrylic acid -4- hydroxyls Base phenyl ester, to hydroxyl (methyl) acrylic acid aniline, 1,4-CHDM list (methyl) acrylate, (methyl) acrylic acid- 3- (2- hydroxy phenyls) ester, glycerine two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, phenyl glycidyl ether (methyl) acrylic acid modified object, (methyl) acrylic acid modified object of tert-butyl-phenyl glycidol ether and other changes for including an epoxy group in each molecule Close (methyl) acrylic acid modified object of object.

In these monohydroxy compounds, preferred compound is benzylalcohol, dihydroxypropane single-ether, 3- ethyl -3- hydroxymethyls Oxetanes, (methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, (first Base) acrylic acid -2- hydroxyl -3- phenoxy-propyls, (methyl) acrylic acid -4- hydroxylphenyl esters, to hydroxyl (methyl) acrylic acid aniline, 1,4-CHDM list (methyl) acrylate and (methyl) acrylic acid -3- (2- hydroxy phenyls) ester.If in view of that will make The compatibility when polyesteramide that is synthesized with monohydroxy compound sour (A) is mixed with epoxide (B) and epoxy curing agent, Or photosensitive composite then in monohydroxy compound, more preferably uses benzylalcohol, (methyl) acrylic acid to the coating of substrate It is hydroxy methacrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, (methyl) acrylic acid -4- hydroxylphenyl esters, right Hydroxyl (methyl) acrylic acid aniline and 1,4-CHDM list (methyl) acrylate.

Relative to 100 parts by weight of total amount of tetracarboxylic dianhydride, diamines and multi-hydroxy compound, preferably contain 0 weight Part~300 parts by weight monohydroxy compound and reacted.The parts by weight of more preferably 5 parts by weight~200.

1-1-5. styrene-maleic anhydride copolymer

Sour (A) about the polyesteramide used in the present invention, tool can be also added in the raw material, and there are three the above acid The compound of anhydride group and synthesize.The transparency of cured film improves as a result, therefore preferably.As tool, there are three the above anhydride groups The example of compound can enumerate styrene-maleic anhydride copolymer.About constitute styrene-maleic anhydride copolymer it is each at The ratio divided, the molar ratio of phenylethylene/maleic anhydride is preferably 0.5~4.

As the concrete example of styrene-maleic anhydride copolymer, can enumerate：SMA3000P、SMA2000P、SMA1000P (it is trade name；River crude oil limited liability company).In these concrete examples, the particularly preferably heat resistance of cured film and alkaline-resisting The good SMA1000P of property.

Preferably contain 0 weight relative to 100 parts by weight of total amount of tetracarboxylic dianhydride, diamines and multi-hydroxy compound Measure the styrene-maleic anhydride copolymer of the parts by weight of part~500.The parts by weight of more preferably 10 parts by weight~300.

The siliceous monoamines of 1-1-6.

In the present invention, as to obtain the material of polyesteramide sour (A), siliceous monoamine can be used.If using containing The photosensitive composite of following polyesteramide sour (A), then the acid resistance improvement of cured film：The polyesteramide sour (A) is to pass through It adds siliceous monoamine and so that it is reacted and obtained.

As the concrete example of the siliceous monoamine used in the present invention, can enumerate：3- TSL 8330s, 3- Aminopropyltriethoxywerene werene, 3- aminopropylmethyldimethoxysilanes, 3-amino propyl methyl diethoxy silane, 4- Aminobutyl trimethoxy silane, 4- ammobutyltriethoxysilanes, 4- aminobutyls methyldiethoxysilane, to amino Phenyltrimethoxysila,e, p-aminophenyl triethoxysilane, p-aminophenyl methyl dimethoxysilane, p-aminophenyl Methyldiethoxysilane, m-aminophenyl base trimethoxy silane and m-aminophenyl ylmethyl diethoxy silane.This can be used At least one of a little siliceous monoamines.

In these concrete examples, the good 3-aminopropyltriethoxysilane of acid resistance of more preferably cured film and to ammonia Base phenyltrimethoxysila,e, for acid resistance, the viewpoint of compatibility, particularly preferably 3- aminopropyls triethoxysilicane Alkane.

100 parts by weight of total amount preferably relative to tetracarboxylic dianhydride, diamines and multi-hydroxy compound contain 0 weight Part~300 parts by weight siliceous monoamine, the parts by weight of more preferably 5 parts by weight~200.

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

As the concrete example of the solvent used in the synthetic reaction to obtain polyesteramide sour (A), can enumerate：Diethyl Glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetic acid esters, ethylene glycol list second Ether acetic acid ester, propylene glycol methyl ether acetate, 3- methoxy methyl propionates, 3- ethoxyl ethyl propionates, ethyl lactate, hexamethylene Ketone.In these concrete examples, preferably propylene glycol methyl ether acetate, 3- methoxy methyl propionates or diethylene glycol Methylethyl Ether.

The synthetic method of 1-1-8. polyesteramide acid

The synthetic method of polyesteramide sour (A) used in the present invention is the tetrabasic carboxylic acid for making X moles in the solvent Dianhydride, Y moles of diamines, Z moles of multi-hydroxy compound and monohydroxy compound reaction.At this point, X, Y and Z are preferably set For the ratio that the relationship of following formula (1) and formula (2) is set up between these X, Y and Z.If the range, then polyesteramide is sour (A) dissolubility in a solvent is high, and the coating of composition improves.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)

If using 100 weight relative to 100 parts by weight of total amount of tetracarboxylic dianhydride, diamines and multi-hydroxy compound Part or more reaction dissolvent, then react and successfully carry out, thus preferably.Reaction with reacted at 40 DEG C~200 DEG C 0.2 hour~ It is advisable within 20 hours.

Order of addition of the raw material into reaction system is not particularly limited.That is, any means below can be used：By tetracarboxylic acid Acid dianhydride, diamines and multi-hydroxy compound are added simultaneously to the method in reaction dissolvent；Make diamines and multi-hydroxy compound After being dissolved in reaction dissolvent, the method for adding tetracarboxylic dianhydride；Keep tetracarboxylic dianhydride and multi-hydroxy compound anti-in advance Ying Hou, the method that diamines is added in its reaction product；Or after so that tetracarboxylic dianhydride is reacted in advance with diamines, in its reaction production The method etc. of multi-hydroxy compound is added in object.Monohydroxy compound can be added in the random time point of reaction.

In the case where making the siliceous monoamine reaction, in reacting for tetracarboxylic dianhydride and diamines and multi-hydroxy compound Afterwards, after reaction solution being cooled to 40 DEG C or less, siliceous monoamine is added, is reacted 0.1 hour~6 hours at 10 DEG C~40 DEG C and is Preferably.In addition, monohydroxy compound can be added in the random time point of reaction.

The polyesteramide sour (A) synthesized as described above includes Component units represented by formula (3), represented by formula (4) Component units represented by Component units and formula (5), and its end is by from as the tetracarboxylic dianhydride of raw material, diamines, polynary Other than the anhydride group of hydroxy compounds or monohydroxy compound, amino, the organic group of hydroxyl or monovalence or these compounds Additive constitute.By the way that comprising such composition, hardenability becomes good.

In formula (3), formula (4) and formula (5), R¹To remove residue made of two-CO-O-CO-, R from tetracarboxylic dianhydride²For Two-NH are removed from diamines₂Made of residue, R³To remove residue made of two-OH, R from multi-hydroxy compound⁴For certainly Monohydroxy compound removes residue made of-an OH.R in formula¹、R²、R³And R⁴It can be independently a structure, can also wrap Containing more than two structures.

The weight average molecular weight of the polyesteramide that is obtained sour (A) is preferably 1,000~200,000, more preferably 3, 000~50,000.If being in the range, flatness and heat resistance are good.

Weight average molecular weight in this specification is to pass through gel permeation chromatography (GelPermeationChromatography, GPC) method (tubing string temperature：35 DEG C, flow velocity：Polyphenyl second calculated by 1ml/min) The value of alkene conversion.Polystyrene that molecular weight is 645~132,900 (such as Agilent Technologies can be used in the polystyrene of standard (AgilentTechnologies) polystyrene calibration set group (calibrationkit) PL2010- of limited liability company 0102), PLgelMIXED-D (Agilent Technologies Co., Ltd.) can be used in tubing string, and tetrahydrofuran can be used as mobile phase (Tetrahydrofuran, THF) is measured.The weight average molecular weight of commercially available product in this specification is that catalogue publishes value.

1-2. epoxides (B)

By the addition epoxide (B) in the photosensitive composite of the present invention, the heat resistance, resistance to of cured film can be improved Solvent borne.

As the example of epoxide (B), can enumerate：3,4- 7-oxa-bicyclo[4.1.0 carboxylic acids -3 ', 4 '-epoxycyclohexyl first Ester is (for example, trade name：Sai Luo West Germany (Celloxide) 2021P, Daicel (Daicel) limited liability company), 1- methyl -4- (2- methyl oxiranyl) -7- oxabicyclos [4.1.0] heptane is (for example, trade name：Sai Luo West Germany (Celloxide) 3000, Daicel (Daicel) limited liability company), 2- [4- (2,3- glycidoxy) phenyl] -2- [4- [1,1- bis- [4- (2,3- rings Oxygen propoxyl group) phenyl] ethyl] phenyl] propane and 1, bis- [4- [1- [4- (2, the 3- glycidoxy) phenyl] -1- [4- [1- of 3- [4- (2,3- glycidoxy) phenyl] -1- Methylethyls] phenyl] ethyl] phenoxy group] -2- propyl alcohol mixture (for example, quotient The name of an article：Tyke not (TECHMORE) VG3101L, general woods Tyke (Printec) limited liability company), 2- [4- (2,3- epoxies third Oxygroup) phenyl] -2- [4- [1,1- bis- [4- ([2,3- glycidoxy] phenyl)] ethyls] phenyl] propane, 1,1,1- tri- (4- hydroxyls Base phenyl) ethane triglycidyl ether is (for example, trade name：JER1032H60, limited liability company of Mitsubishi Chemical), 1,3- it is bis- (oxiranyl methyl) -5- (2- acrylic) -1,3,5-triazines -2,4, bis- (the hydroxyl first of 6 (1H, 3H, 5H)-triketones, 2,2- Base)-n-butyl alcohol 1,2- epoxy groups -4- (2- oxiranyls) hexamethylene addition product (for example, trade name：EHPE3150, contest Fine jade (Daicel) limited liability company).

The epoxide (B) used in the present invention can be the polymer containing epoxy group.The polymer containing epoxy group Can be by making (methyl) glycidyl acrylate separately as the free-radical polymerised compound with epoxy group, or make (methyl) glycidyl acrylate and without epoxy group free-radical polymerised compound reaction and obtain.By using containing The transparency of the polymer of epoxy group, the cured film obtained by photosensitive composite is got higher, and can inhibit smelly in ultraviolet light (UV) The transparency in oxygen processing step or ultraviolet exposure step reduces, thus preferably.In the case of the copolymer, with regard to flatness, For heat resistance, the viewpoint of solvent resistance, preferably in all monomers for constituting the polymer containing epoxy group, contain 50 weights Measure (methyl) glycidyl acrylate of the weight of %~99 %.

As the preference of the free-radical polymerised compound without epoxy group, can enumerate：Two (first of ethylene glycol Base) acrylate, diethylene glycol two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,3-BDO two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, N- phenyl Maleimide, N- N-cyclohexylmaleimides, indenes.These examples with (methyl) glycidyl acrylate due to by reacting And the compatibility change with polyesteramide sour (A) of the epoxide obtained is good and preferred.

1-3.Compound (C) with polymeric double bond

The present invention uses the compound (C) with polymeric double bond as obtaining the material of photosensitive polymer combination Material.Compound (C) with polymeric double bond includes the compound with polymeric double bond with carbamate skeleton.Tool There is the compound (C) of polymeric double bond that can also be used in mixed way the compound with polymeric double bond with carbamate skeleton And the compound with polymeric double bond without carbamate skeleton.

In the present invention, relative to sour (A) 100 parts by weight of polyesteramide, having for the parts by weight of 20 parts by weight~300 is used The compound (C) of polymeric double bond.If the compound (C) with polymeric double bond is the parts by weight of 50 parts by weight~300, develop Residual film ratio becomes good afterwards, thus preferably.

Compounds (UM) with polymeric double bond of the 1-3-1. with carbamate skeleton

The compound with polymeric double bond with carbamate skeleton used in the present invention is (sometimes simple below Referred to as UM) as long as good with the compatibility of the other compositions for the photosensitive composite for forming the present invention, then it is not particularly limited.

The quantity of the polymeric double bond base of UM used in the present invention is preferably two or more.Pass through polymeric double bond base Quantity be two or more, it can be expected that the raising of the sensitivity under low light exposure.The quantity of polymeric double bond be more preferably three with On.

The molecular weight of UM used in the present invention is preferably 10,000 or less.If 10,000 hereinafter, then when with do not have There are the compound (hereinafter sometimes referred to simply as NM) with polymeric double bond of carbamate skeleton and used time, it can be expected that analyticity Raising.The molecular weight of UM is more preferably 5,000 or less.

About the specific example of UM, can enumerate：Isophorone diisocyanate and pentaerythritol triacrylate it is anti- Answer object (UA-306I, trade name；Chemistry limited liability company of common prosperity society), hexamethylene diisocyanate and phenyl glycidyl Reactant (AH-600, the trade name of ether acrylate；Chemistry limited liability company of common prosperity society), hexamethylene diisocyanate with Reactant (UA-510H, the trade name of Dipentaerythritol Pentaacrylate；Chemistry limited liability company of common prosperity society), U-15HA (quotient The name of an article；Chemistry limited liability company of the villages Xin Zhong), as the reactant of hexamethylene diamine and isocyanuric acid poly- isocyanuric acid with The reactant etc. of dipentaerythritol tetraacrylate.

1-3-2. does not have the compound (NM) with polymeric double bond of carbamate skeleton

NM used in the present invention is not particularly limited, and has more than two polymerisms preferably in each molecule The compound of double bond.

It is contained in photosensitive composite as the present invention, double with more than two polymerisms in each molecule The compound of key can be enumerated：Ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, epichlorohydrin are modified second Glycol two (methyl) acrylate, epichlorohydrin are modified diethylene glycol two (methyl) acrylate, epichlorohydrin is modified triethylene glycol two (methyl) acrylate, epichlorohydrin are modified tetraethylene glycol two (methyl) acrylate, epichlorohydrin modified poly (ethylene glycol) two (methyl) Acrylate, propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) propylene Acid esters, four propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, epichlorohydrin are modified two (first of propylene glycol Base) acrylate, epichlorohydrin be modified dipropylene glycol two (methyl) acrylate, epichlorohydrin be modified tripropylene glycol two (methyl) propylene Acid esters, epichlorohydrin are modified four propylene glycol two (methyl) acrylate, epichlorohydrin is modified polypropylene glycol two (methyl) acrylate, three Hydroxymethyl-propane three (methyl) acrylate, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, propylene oxide Modified trimethylolpropane tris (methyl) acrylate, epichlorohydrin are modified trimethylolpropane tris (methyl) acrylate, two-three Hydroxymethyl-propane four (methyl) acrylate, glycerine (methyl) acrylate, glycerine two (methyl) acrylate, three (first of glycerine Base) acrylate, epichlorohydrin modified glycerol three (methyl) acrylate, 1,6- hexylene glycols two (methyl) acrylate, epichlorohydrin Modified 1,6- hexylene glycols, two (methyl) acrylate, methoxylation cyclohexyl two (methyl) acrylate, two (first of neopentyl glycol Base) acrylate, 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, caprolactone modification 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, two glycerine four (methyl) acrylate, the oxide-modified acrylate of two glycerol epoxies, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, stearic acid modified pentaerythrite two (methyl) acrylate, two Pentaerythrite five (methyl) acrylate, alkyl-modified dipentaerythritol five (methyl) acrylate, alkyl-modified two season penta 4 Alcohol four (methyl) acrylate, alkyl-modified dipentaerythritol three (methyl) acrylate, dipentaerythritol six (methyl) propylene Acid esters, caprolactone modification dipentaerythritol six (methyl) acrylate, modified by polyacid (methyl) acrylate oligomers, allyl Change cyclohexyl two (methyl) acrylate, bis- [(methyl) acryloxy neopentyl glycol] adipate esters, bisphenol-A two (methyl) third It is olefin(e) acid ester, ethylene-oxide-modified bisphenol-A two (methyl) acrylate, Bisphenol F two (methyl) acrylate, ethylene-oxide-modified double Phenol F bis- (methyl) acrylate, bisphenol S two (methyl) acrylate, ethylene-oxide-modified bisphenol S two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,3-BDO (methyl) acrylate, bicyclopentyl diacrylate, polyester two Acrylate, polyester triacrylate, polyester tetra acrylate, five acrylate of polyester, polyester hexaacrylate, ethylene oxide Modified phosphate two (methyl) acrylate, ethylene-oxide-modified tricresyl phosphate (methyl) acrylate, ethylene-oxide-modified di(2-ethylhexyl)phosphate (methyl) acrylate, ethylene-oxide-modified tricresyl phosphate (methyl) acrylate, epichlorohydrin are modified phthalic acid two (methyl) Acrylate, tetrabromobisphenol A two (methyl) acrylate, triglycerin two (methyl) acrylate, neopentyl glycol are modified three hydroxyl first Base propane two (methyl) acrylate, the ethylene-oxide-modified diacrylate of isocyanuric acid, isocyanuric acid ethylene-oxide-modified three Acrylate, caprolactone modification three [(methyl) acryloyl-oxyethyl] isocyanuric acid ester, phenol novolak-type epoxy chemical combination (methyl) acrylic acid modified object of object and (methyl) acrylic acid modified object of cresol novolak type epoxy compound etc..

The compound with more than two polymeric double bonds can be used alone the compound in each molecule, also may be used It is used in mixed way two or more.

For the heat resistance of cured film, the viewpoint of chemical-resistant, there are more than two polymerizations in each molecule In the compound of property double bond, it is preferable to use ethylene-oxide-modified bisphenol-A two (methyl) acrylate, trimethylolpropane tris third Olefin(e) acid ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol Six acrylate, modified by polyacid (methyl) acrylate oligomers, the ethylene-oxide-modified diacrylate of isocyanuric acid, isocyanide urea Sour ethylene-oxide-modified triacrylate or these mixture.

As ethylene-oxide-modified bisphenol-A two (methyl) acrylate, trimethylolpropane trimethacrylate, pentaerythrite It is triacrylate, pentaerythritol tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate, polynary Modified (methyl) acrylate oligomers of acid, the ethylene-oxide-modified diacrylate of isocyanuric acid, isocyanuric acid are ethylene-oxide-modified Triacrylate or these mixture, can be used following commercially available products.

The concrete example of ethylene-oxide-modified bisphenol-A two (methyl) acrylate is model gram force (Fancryl) FA-324A (quotient The name of an article；Hitachi be melted into limited liability company), Aronix (Aronix) M-208 (trade names；East Asia synthesizes the limited public affairs of share Department).

The concrete example of trimethylolpropane trimethacrylate is Aronix (Aronix) M-309 (trade names；East Asia synthesizes Limited liability company), Lay spy acrylate (LightAcrylate) TMP-A (trade names；The limited public affairs of common prosperity society chemistry share Department).The concrete example of the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate is Aronix (Aronix) M-306 (the 65 weight % of weight %~70), M-305 (the 55 weight % of weight %~63) and M-450 (less than 10 weight %) are ( For trade name；East Asia synthesizes limited liability company, and the containing ratio in bracket is the pentaerythritol triacrylate in mixture The catalogue of containing ratio publishes value).The mixture of Dipentaerythritol Pentaacrylate and dipentaerythritol hexaacrylate it is specific Example is Aronix (Aronix) M-403 (the 50 weight % of weight %~60), M-400 (the 40 weight % of weight %~50), M-402 (the 30 weight % of weight %~40), M-404 (the 30 weight % of weight %~40), M-406 (the 25 weight % of weight %~35) and M- 405 (the 10 weight % of weight %~20) (are trade name；East Asia synthesizes limited liability company, and the containing ratio in bracket is mixing The catalogue of the containing ratio of Dipentaerythritol Pentaacrylate in object publishes value).Modified by polyacid (methyl) acrylate oligomers Concrete example be Aronix (Aronix) M-510 and Aronix (Aronix) M-520 (be trade name；East Asia synthesizes stock Part Co., Ltd).The concrete example of the ethylene-oxide-modified diacrylate of isocyanuric acid is Aronix (Aronix) M-215 (quotient The name of an article；East Asia synthesizes limited liability company).The ethylene-oxide-modified diacrylate of isocyanuric acid and isocyanuric acid ethylene oxide change Property triacrylate mixture concrete example be Aronix (Aronix) M-315 (the 3 weight % of weight %~13) (commodity Name；East Asia synthesizes limited liability company, and the containing ratio in bracket is ethylene-oxide-modified two propylene of isocyanuric acid in mixture The catalogue of the containing ratio of acid esters publishes value).The concrete example of the acrylic acid modified object of phenol novolak-type epoxy compound is TEA-100 (trade names；KSM limited liability companies).The acrylic acid modified object of cresol novolak type epoxy compound it is specific Example is CNEA-100 (trade names；KSM limited liability companies).

1-4. Photoepolymerizationinitiater initiaters (D)

As long as the present invention photosensitive composite contained in Photoepolymerizationinitiater initiater can make containing polyesteramide acid (A), The composition of epoxide (B), the compound (C) with polymeric double bond, Photoepolymerizationinitiater initiater (D) and additive (E) Polymerization starts, then is not particularly limited.

The Photoepolymerizationinitiater initiater contained in photosensitive composite as the present invention, can enumerate：Benzophenone, Michaelis Ketone, 4,4 '-bis- (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4- diethyl sulfides Miscellaneous anthrone, 2- ethyl hydrazine, acetophenone, 2- hydroxy-2-methyls propiophenone, 2- hydroxy-2-methyls -4 '-cumene acetone, 1- Hydroxycyclohexylphenylketone, isopropyl benzoin ether, isobutyl group benzoin ether, 2,2- diethoxy acetophenones, 2,2- dimethoxies Base -2- phenyl acetophenones, camphorquinone, benzanthrone, 2- methyl-1s-[4- (methyl mercapto) phenyl] -2- (4- morpholinyls) -1- acetone (for example, trade name：Gorgeous good solid (IRGACURE) 907, Japanese BASF (BASFJapan) limited liability company), 2- (dimethyl Amino) -1- [4- (4- morpholinoes) phenyl] -2- (phenyl methyl) -1- butanone is (for example, trade name：Gorgeous good solid (IRGACURE) 369, Japanese BASF (BASFJapan) limited liability company), ethyl 4-dimethylaminobenzoate, 4- dimethylamino benzene Isoamyl formate, 4,4 '-two (t-butylperoxycarbonyl) benzophenone, 3,4,4 '-three (t-butylperoxycarbonyl) hexichol Ketone, 1,2- acetyl caproyls, 1- [4- (thiophenyl) phenyl]-, 2- (O- benzoyl oximes) is (for example, trade name：It is gorgeous good solid (IRGACURE) OXE01, Japanese BASF (BASFJapan) limited liability company), ethyl ketone, 1- [9- ethyls -6- (2- methylbenzenes Formoxyl) -9H- carbazole -3- bases] -, 1- (O- acetyl group oxime) is (for example, trade name：Gorgeous good solid (IRGACURE) OXE02, Japan BASF (BASFJapan) limited liability company), gorgeous good solid (IRGACURE) OXE03 (trade names；Japanese BASF (BASFJapan) limited liability company), 1,2- propanedione, 1- [4- [4- (2- hydroxyl-oxethyls) phenyl sulphur] phenyl] -2- (O- Acetyl group oxime) (for example, trade name：Hereby (AdekaarcLuz) NCI-930, Ai Dike (ADEKA) share is limited for Ai Dike arcs Shandong Company), Ai Dike arcs Shandong hereby (AdekaarcLuz) NCI-831 (trade names；Ai Dike (ADEKA) limited liability company), Ai Di Ke Aoputuoma (AdekaOptomer) N-1919 (trade names；Ai Dike (ADEKA) limited liability company), 2,4,6- trimethyls Benzoyl diphenyl phosphine oxide, bis- (the trichloromethyl)-s-triazine of 2- (4 '-methoxyl-styrene) -4,6-, 2- (3 ', 4 ' - Dimethoxy-styryl) bis- (the trichloromethyl)-s-triazine of -4,6-, 2- (2 ', 4 '-dimethoxy-styryl) -4,6- be bis- (trichloromethyl)-s-triazine, bis- (the trichloromethyl)-s-triazine of 2- (2 '-methoxyl-styrene) -4,6-, 2- (4 '-amoxys Styryl) bis- (the trichloromethyl)-s-triazine of -4,6-, 4- [p- N, N- bis- (ethoxy carbonyl methyl)] (three chloromethanes of -2,6- bis- Base)-s-triazine, bis- (trichloromethyl) -5- (2 '-the chlorphenyl)-s-triazine of 1,3-, bis- (trichloromethyl) -5- (4 '-methoxies of 1,3- Base phenyl)-s-triazine, 2- is (to dimethylaminostyryl) benzoxazoles, 2- (to dimethylaminostyryl) benzo Thiazole, 2-mercaptobenzothiazole, 3,3 '-carbonyls bis- (7- diethyl amino coumarins), 2- (Chloro-O-Phenyl) -4,4 ', 5,5 '-four 1,2 '-bisglyoxaline of phenyl -, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (4- carboethoxyphenyls) -1,2 '-join miaow Azoles, 2,2 '-bis- (2,4- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxalines, 2,2 '-bis- (2,4- dibromo phenyls) - 4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxalines, 2,2 '-bis- (2,4,6- trichlorophenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-connection Imidazoles, 3- (2- methyl -2- dimethylaminos propiono) carbazole, bis- (2- methyl -2- morpholinoes the propiono) -9- positive 12 of 3,6- Alkyl carbazole, 1- hydroxycyclohexylphenylketones and bis- (η⁵- 2,4- cyclopentadiene -1- bases)-bis- (2,6- bis- fluoro- 3- (1H- pyrroles - 1- yls)-phenyl) titanium etc..

Photoepolymerizationinitiater initiater can be used alone, and can also be used in mixed way two or more.In Photoepolymerizationinitiater initiater, when just exposing For the viewpoint of the sensitivity of film and the transparency of cured film, preferably alpha-amido benzene alkyl ketone system, acylphosphine oxide system, oxime ester It is Photoepolymerizationinitiater initiater.Furthermore it in the present specification, will be to being formed on substrate using spin coating, printing and other methods The film that the film of photosensitive composite carries out predrying (prebake conditions) and obtains is known as " film ".The film is by thereafter Exposure-development-cleaning-drying and other steps after, form cured film by formally calcining (rear baking).In the present specification, It will be referred to as " film " from the film in the predrying to dry step, and for example, by " film when exposure ", " development The statements such as film afterwards " come indicate be which stage of film formation step film.

For the viewpoint of the sensitivity of film and the transparency of cured film, in Photoepolymerizationinitiater initiater, more preferably 1,2- Acetyl caproyl, 1- [4- (thiophenyl) phenyl]-, 2- (O- benzoyl oximes) or 1,2- propanedione, 1- [4- [4- (2- '-hydroxyethoxies Base) phenyl sulphur] phenyl] -2- (O- acetyl group oxime) relative to the total weight of Photoepolymerizationinitiater initiater is 20 weight % or more.Separately Outside, if 50 weight % or more, then further preferably.Photoepolymerizationinitiater initiater also can only include 1,2- acetyl caproyls, 1- [4- (benzene sulphur Base) phenyl] -, 2- (O- benzoyl oximes) or 1,2- propanedione, 1- [4- [4- (2- hydroxyl-oxethyls) phenyl sulphur] phenyl] -2- (O- acetyl group oxime).

1-5. polyesteramides sour (A), epoxide (B), the compound (C) with polymeric double bond, photopolymerization cause The ratio of agent (D)

In the photosensitive composite of the present invention, relative to sour (A) 100 parts by weight of polyesteramide, epoxide (B) Ratio is the parts by weight of 20 parts by weight~200.If the ratio of epoxide (B) is in the range, heat resistance, flatness Balance is good.If epoxide (B) is the range of the parts by weight of 20 parts by weight~150, further preferably.

In the photosensitive composite of the present invention, relative to sour (A) 100 parts by weight of polyesteramide, there is polymeric double bond The ratio of compound (C) be the parts by weight of 20 parts by weight~300.If the ratio of the compound (C) with polymeric double bond is in The range, then the balance of residual film ratio is good after heat resistance, flatness, chemical-resistant, development.If with polymeric double bond Compound (C) is in the range of the parts by weight of 50 parts by weight~300, then further preferably.

1-6. additives (E)

In the photosensitive composite of the present invention, various additives can be added to improve coating homogeneity, cementability, transparent Property, analyticity, flatness and chemical-resistant.Additive can mainly be enumerated：Anionic system, cationic system, nonionic system, fluorine The levelling agent surfactant of system or silicon systems, the coupling agents such as silane coupling agent, hindered phenolic, amine system of being obstructed, phosphorus system, sulphur system Close the antioxidants such as object, molecular weight regulator, epoxy curing agent.

1-6-1. surfactant

Surfactant can be added to improve coating homogeneity in the photosensitive composite of the present invention.About surfactant Concrete example, can enumerate：Pohle not Lip river (Polyflow) No.75, Pohle not Lip river (Polyflow) No.90, Pohle not Lip river (Polyflow) No.95 (is trade name；Chemistry limited liability company of 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 Sipabike (Disperbyk) -180, Di Sipabike (Disperbyk) -181, Di Sipabike (Disperbyk) -182, Bi Ke (BYK) -300, Bi Ke (BYK) -306, Bi Ke (BYK) -310, Bi Ke (BYK) -320, Bi Ke (BYK) -330, Bi Ke (BYK) - 342, Bi Ke (BYK) -346, Bi Ke (BYK) -361N, Bi Ke (BYK)-UV3500, Bi Ke (BYK)-UV3570 (are commodity Name；Chemical (BYKChemieJapan) limited liability company of Japanese Bi Ke), KP-341, KP-368, KF-96-50CS, KF-50- 100CS (is trade name；Shin-Estu Chemical Co., Ltd), Sha Fulong (Surflon) S611 (trade names；AGC is beautiful clearly Chemical (AGCSeimiChemical) limited liability company), Fu Jite (Ftergent) 222F, Fu Jite (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) 650A, FTX-218 (be commodity Name；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；DIC (DIC) limited liability company), enlightening Height village (TEGOTwin) 4000, Di Gaotun (TEGOTwin) 4100, Di Gaofuluo (TEGOFlow) 370, the Riders Di Gaoge (TEGOGlide) 440, the Riders Di Gaoge (TEGOGlide) 450, the high ladd of enlightening (TEGORad) 2200N (are trade name；Day This win create Degussa (Evonik-DegussaJapan) limited liability company), fluoroalkyl benzene sulfonate, fl muoroalkyl's salt, fluorine Alkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl glycine betaine, fluoroalkyl sulfonate, two glycerine, four (fluoroalkyl polyoxyethylene Ether), fluoroalkyl leptodactyline, fluoroalkyl sulfamate, ethylene nonyl phenyl ether, NONIN HS 240, Polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene Cetyl ether, polyoxyethylene laurate, polyoxyethylene oleate, Myrj 45, is gathered at polyoxyethylene stearyl base ether Ethylene oxide lauryl amine, sorbitol anhydride laurate, sorbitol anhydride palmitate, sorbitan tristearate, sorbitol anhydride oil Acid esters, sorbitan carboxylic esters, polyoxyethylene sorbitol acid anhydride laurate, polyoxyethylene sorbitol acid anhydride palmitate, polyoxy Ethylene sorbitan tristearate, polyoxyethylene sorbitol acid anhydride oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate and alkane Base diphenyl ether disulfonate.Preferably using selected from least one of these surfactants.

In these surfactants, if selected from Bi Ke (BYK) -306, Bi Ke (BYK) -342, Bi Ke (BYK) -346, KP-341, KP-368, Sha Fulong (Surflon) S611, Fu Jite (Ftergent) 710FL, Fu Jite (Ftergent) 710FM, Fu Jite (Ftergent) 710FS, Fu Jite (Ftergent) 601AD, Fu Jite (Ftergent) 650A, Mei Jiafa (Megafac) F-477, Mei Jiafa (Megafac) F-556, Mei Jiafa (Megafac) F-559, Mei Jiafa (Megafac) RS- 72-K, Mei Jiafa (Megafac) DS-21, Di Gaotun (TEGOTwin) 4000, fluoroalkyl benzene sulfonate, fl muoroalkyl's salt, fluorine At least one of alkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyl leptodactyline and fluoroalkyl sulfamate, Then the coating homogeneity of photosensitive composite is got higher, therefore preferably.

The present invention photosensitive composite in surfactant content relative to photosensitive composite full dose and it is preferred that For 0.01 weight of weight %~10 %.

1-6-2. coupling agent

For making the viewpoint that the adhesion for being formed by cured film and substrate further increases, photonasty group of the invention Closing object can also further contain coupling agent.

As such coupling agent, such as the coupling agent of silane system, aluminium system or titanate esters system can be used.Specifically, can arrange It lifts：3- glycidoxypropyls dimethylethoxysilane, 3- glycidoxypropyls diethoxy silane, 3- contractings Water glycerine oxygroup propyl trimethoxy silicane is (for example, trade name：Sa Laaisi (Sila-Ace) S510, prompt grace intelligence (JNC) share Co., Ltd), 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane is (for example, trade name：Sa Laaisi (Sila-Ace) S530, prompt grace intelligence (JNC) limited liability company), 3-mercaptopropyi trimethoxy silane is (for example, trade name：Sa Laaisi (Sila-Ace) S810, prompt grace intelligence (JNC) limited liability company), 3- glycidyls-oxygroup propyl trimethoxy silicane is total to Polymers is (for example, trade name：Special Olso (CoatOSi1) MP200 is examined, figure new high-tech material is stepped (MomentivePerformanceMaterials) Co., Ltd) etc. silane system coupling agent, acetyl alkoxy diisopropanol The titanate esters system coupling agent such as the aluminium such as aluminium system's coupling agent and bis- (dioctyl phosphito ester) titanate esters of tetra isopropyl.

In these coupling agents, 3- glycidoxypropyltrimewasxysilanes and its copolymer make the effect that adhesion improves Fruit is big, therefore preferably.

The content of coupling agent is 0.01 weight % or more relative to photosensitive composite full dose and 10 weight % are below Situation can improve the adhesion for being formed by cured film and substrate, therefore preferably.

1-6-3. antioxidant

For improving the transparency, preventing the viewpoint of the xanthochromia of cured film exposure in the event of high temperatures, sense of the invention Photosensitiveness composition can also further contain antioxidant.

It is anti-oxidant that hindered phenolic, amine system of being obstructed, phosphorus system, chalcogenide compound etc. can be added in the photosensitive composite of the present invention Agent.Wherein, for the viewpoint of weatherability, preferably hindered phenolic.As concrete example, can enumerate：Easy fine jade Jia Nuosi (Irganox) 1010, Yi Lu Jia Nuosi (Irganox) 1010FF, Yi Lu Jia Nuosi (Irganox) 1035, Yi Lu Jia Nuosi (Irganox) 1035FF, Yi Lu Jia Nuosi (Irganox) 1076, Yi Lu Jia Nuosi (Irganox) 1076FD, Yi Lu Jia Nuosi (Irganox) 1076DWJ, Yi Lu Jia Nuosi (Irganox) 1098, Yi Lu Jia Nuosi (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) 245DWJ, Yi Lu Jia Nuosi (Irganox) 259, Yi Lu Jia Nuosi (Irganox) 3114, Yi Lu Jia Nuosi (Irganox) 565, Yi Lu Jia Nuosi (Irganox) 565DD, Yi Lu Jia Nuosi (Irganox) 295 (are trade name；Japan BASF (BASFJapan) limited liability company), Ai Di Coase tower wave (ADKSTAB) AO-20, Ai Di Coase tower wave (ADKSTAB) AO-30, Ai Di Coase tower wave (ADKSTAB) AO-50, Ai Di Coase tower wave (ADKSTAB) AO-60, Ai Di Coase Tower wave (ADKSTAB) AO-80 (is trade name；Ai Dike (ADEKA) limited liability company).Wherein, more preferably Yi Lujia Northey (Irganox) 1010, Ai Di Coase tower wave (ADKSTAB) AO-60.

Relative to photosensitive composite full dose, the antioxidant of the parts by weight of 0.1 parts by weight of addition~10 and use.

1-6-4. molecular weight regulators

Molecular weight regulator can be added in the photosensitive composite of the present invention, with inhibition, molecular weight is got higher due to polymerization, and Show excellent analyticity.As molecular weight regulator, can enumerate：Thio-alcohol, xanthan acids, quinones, hydroquinones, phenols, youngster Tea phenols, 2,4- diphenyl -4-methyl-1-pentene etc..

As the concrete example of molecular weight regulator, can enumerate：1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, 1,2- benzoquinones, 1, 4- benzoquinones, methyl -1,4-benzoquinone, anthraquinone, quinhydrones, methylnaphthohydroquinone, tert-butyl hydroquinone, 2,5- di-t-butyls quinhydrones, 2,5-, bis--uncles Amylhydroquinone, Isosorbide-5-Nitrae-dihydroxy naphthlene, 3,6- dihydroxy benzos norbornane, 4- metoxyphenols, 2,2 ', 6,6 '-four-tertiary fourths 4,4 '-dihydroxybiphenyl of base -, 3- (3,5- di-t-butyl -4- hydroxy phenyls) propionic acid stearate, 2,2 '-di-2-ethylhexylphosphine oxide (6- Tertiary butyl -4- ethyl -phenols), 2,4,6- tri- (3 ', 5 ' -4 '-hydroxybenzyl of di-t-butyl -) mesitylene, pentaerythrite four [3- (3,5- di-t-butyl -4- hydroxy phenyls) propionic ester], 4- tert-butyl catechols, n-hexyl mercaptan, n octylmercaptan, Positive dodecylmercaptan, tertiary dodecylmercaptan, thioglycolic acid, dimethyl sulfide xanthate, curing diisopropyl xanthic acid Ester, 2,6- di-t-butyls paracresol, 4,4 '-butylidenebis (6- tert-butyl-m-cresols), 4,4 '-thiobis (first between 6- tertiary butyls Phenol), 2,4- diphenyl -4-methyl-1-pentene and phenthazine.

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 analyticity preferably.

In molecular weight regulator, if the 2-hydroxy-1,4-naphthoquinone with phenolic hydroxyl group, then for the viewpoint of analyticity More preferably.In addition, for the viewpoint of analyticity, molecular weight regulator is preferably more than with the content of Photoepolymerizationinitiater initiater (D) 5.0 times of content and the mode less than 30 times contain molecular weight regulator, more preferably with the content of Photoepolymerizationinitiater initiater (D) Contain molecular weight regulator more than 5.1 times of the content of molecular weight regulator and for 20 times of modes below.Further preferably By 5.2 times of content of the content of Photoepolymerizationinitiater initiater (D) more than molecular weight regulator and for 10 times it is below in a manner of contain point Son amount regulator.

1-6-5. epoxy curing agent

The photosensitive composite of the present invention can also contain epoxy curing agent so that flatness, chemical-resistant improve.As Epoxy curing agent, there are acid anhydrides system curing agent, amine system curing agent, phenol system curing agent, imidazoles system curing agent, catalyst type hardening Thermonasties acid producing agent such as agent and sulfonium salt, benzothiazolium salt, ammonium salt, phosphonium salts etc., it is avoided that coloring and the cured film of cured film Heat resistance viewpoint for, preferred anhydrides system curing agent or imidazoles system curing agent.

As the concrete example of acid anhydrides system curing agent, can enumerate：Aliphatic dicarboxylic acid acid anhydride, such as maleic anhydride, tetrahydrochysene neighbour's benzene Dicarboxylic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydro trimellitic anhydride etc., aromatic polyvalent carboxylic Acid anhydrides, such as phthalic anhydride, trimellitic anhydride etc..In these acid anhydrides system curing agents, it can particularly preferably make cured film Heat resistance improves and will not damage deliquescent trimellitic anhydride and hexahydro trimellitic acid of the photosensitive composite relative to solvent Acid anhydride.

As the concrete example of imidazoles system curing agent, can enumerate：2- undecyl imidazoles, 2- heptadecyl imidazoles, 2- phenyl Imidazoles, 2- phenyl -4-methylimidazole, 2,3- dihydro -1H- pyrrolo-es [1,2-a] benzimidazole, 1- cyano ethyl -2- hendecanes Base imidazoles trimellitic acid salt.In these imidazoles system curing agents, can particularly preferably make cured film hardenability improve and will not Damage deliquescent 2- undecyl imidazole of the photosensitive composite relative to solvent.

Epoxy curing agent is relative to 100 parts by weight of epoxide (B), ring relative to the ratio of epoxide (B) Oxygen curing agent is the parts by weight of 0.1 parts by weight~60.For example, the addition in the case of being acid anhydrides system curing agent about epoxy curing agent Amount, more specifically, preferably with for epoxy group, acid anhydride or carboxyl in epoxy curing agent become 0.1 times The mode of equivalent~1.5 times equivalent is added.At this point, acid anhydride is calculated with divalent.If with acid anhydride or carboxyl Mode as 0.15 times of equivalent~0.8 times equivalent is added, then chemical-resistant further increases, therefore further excellent Choosing.

1-6-6. ultra-violet absorber

For the viewpoint of degradation inhibiting ability for further increasing pattern-like hyaline membrane, photosensitive composite of the invention It also may include ultra-violet absorber.

The concrete example of ultra-violet absorber 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 (BASFJapan) share Department).

Relative to photosensitive composite full dose, the ultra-violet absorber of the parts by weight of 0.01 parts by weight of addition~10 and use.

The anti-flocculating agents of 1-6-7.

For so that solid constituent is merged with solvent, preventing the viewpoint of cohesion, photosensitive composite of the invention may be used also Including 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 (BYKChemieJapan) limited liability companies 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 photosensitive composite full dose, the anti-flocculating agent of the parts by weight of 0.01 parts by weight of addition~10 and use.

1-6-8. thermal cross-linking agent

Just further increase heat resistance, chemical-resistant, film inner evenness, pliability, flexibility, the viewpoint of elasticity and Speech, photosensitive composite of the invention also may include 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 it is chemical (share)).

Relative to photosensitive composite full dose, the thermal cross-linking agent of the parts by weight of 0.1 parts by weight of addition~10 and use.

1-6-9. photoacid generator

For improving the viewpoint of resolution, photosensitive composite of the invention also may include photoacid generator.As light 1,2- quinone di-azido compounds can be used in acid producing agent.

The concrete example of 1,2- quinone di-azido compound is：2,3,4- trihydroxybenzophenone -1,2- naphthoquinones, two nitrine -4- sulphurs Acid esters, 2,3,4- trihydroxybenzophenone -1,2- naphthoquinones, two nitrine -5- sulphonic acid esters, 2,4,6- trihydroxybenzophenone -1,2- naphthalenes Two nitrine -4- sulphonic acid esters of quinone, 2,4,6- trihydroxybenzophenone -1,2- naphthoquinones, two nitrine -5- sulphonic acid esters；

2,2 ', 4,4 '-tetrahydroxybenzophenone -1,2- naphthoquinones, two nitrine -4- sulphonic acid esters, 2,2 ', 4,4 '-tetrahydroxy hexichol Two nitrine -5- sulphonic acid esters of ketone -1,2- naphthoquinones, 2,3,3 ', 4- tetrahydroxybenzophenones -1,2- naphthoquinones, two nitrine -4- sulphonic acid esters, Two nitrine -5- sulphonic acid esters of 2,3,3 ', 4- tetrahydroxybenzophenone -1,2- naphthoquinones, 2,3,4,4 '-tetrahydroxybenzophenones -1,2- Two nitrine -4- sulphonic acid esters of naphthoquinones, 2,3,4,4 '-tetrahydroxybenzophenone -1,2- naphthoquinones, two nitrine -5- sulphonic acid esters；

Bis- two nitrine -4- sulphonic acid esters of (2,4- dihydroxy phenyl) methane -1,2- naphthoquinones, bis- (2,4- dihydroxy phenyl) first Two nitrine -5- sulphonic acid esters of alkane -1,2- naphthoquinones；

Two nitrine -4- sulphonic acid esters of bis- (p-hydroxybenzene) methane -1,2- naphthoquinones, bis- (p-hydroxybenzene) methane -1,2- naphthalenes Two nitrine -5- sulphonic acid esters of quinone；

Three (p-hydroxybenzene) methane -1,2- naphthoquinones, two nitrine -4- sulphonic acid esters, three (p-hydroxybenzene) methane -1,2- naphthalenes Two nitrine -5- sulphonic acid esters of quinone, 1,1,1- tri- (p-hydroxybenzene) ethane -1,2- naphthoquinones, two nitrine -4- sulphonic acid esters, 1,1,1- tri- Two nitrine -5- sulphonic acid esters of (p-hydroxybenzene) ethane -1,2- naphthoquinones；

Bis- two nitrine -4- sulphonic acid esters of (2,3,4- trihydroxy phenyl) methane -1,2- naphthoquinones, bis- (2,3,4- trihydroxy phenyl) The bis- two nitrine -4- sulphurs of (2,3,4- trihydroxy phenyl) propane -1,2- naphthoquinones of two nitrine -5- sulphonic acid esters of methane -1,2- naphthoquinones, 2,2- The bis- two nitrine -5- sulphonic acid esters of (2,3,4- trihydroxy phenyl) propane -1,2- naphthoquinones of acid esters, 2,2-；

1,1,3- tri- (2,5- dimethyl -4- hydroxy phenyls) -3- phenyl-propanes -1,2- naphthoquinones, two nitrine -4- sulphonic acid esters, 1, 1,3- tri- (2,5- dimethyl -4- hydroxy phenyls) -3- phenyl-propanes -1,2- naphthoquinones, two nitrine -5- sulphonic acid esters；

4,4 '-[1- [4- [1- [4- hydroxy phenyls] -1- Methylethyls] phenyl] ethylidene] bis-phenol -1,2- naphthoquinones two are folded Nitrogen -4- sulphonic acid esters, 4,4 '-[1- [4- [1- [4- hydroxy phenyls] -1- Methylethyls] phenyl] ethylidene] bis-phenol -1,2- naphthoquinones two Nitrine -5- sulphonic acid esters；

It is bis- two nitrine -4- sulphonic acid esters of (2,5- dimethyl -4- hydroxy phenyls) -2- hydroxy phenyl methane -1,2- naphthoquinones, double Two nitrine -5- sulphonic acid esters of (2,5- dimethyl -4- hydroxy phenyls) -2- hydroxy phenyl methane -1,2- naphthoquinones；

3,3,3 ', 3 '-tetramethyl -1,1 '-spirobindene -5,6,7,5 ', 6 ', 7 '-hexanol -1,2- naphthoquinones, two nitrine -4- sulphurs Acid esters, 3,3,3 ', 3 '-tetramethyl -1,1 '-spirobindene -5,6,7,5 ', 6 ', 7 '-hexanol -1,2- naphthoquinones, two nitrine -5- sulfonic acid Ester；

2,2,4- trimethyl -7,2 ', 4 '-trihydroxy flavane (flavane) -1,2- naphthoquinones, two nitrine -4- sulphonic acid esters and 2, 2,4- trimethyl -7,2 ', 4 '-trihydroxy flavane -1,2- naphthoquinones, two nitrine -5- sulphonic acid esters.

Relative to photosensitive composite full dose, the photoacid generator of the parts by weight of 0.01 parts by weight of addition~10 and use.

Other additives of 1-6-10.

It is (hereinafter sometimes referred to " free-radical polymerized that the photosensitive composite of the present invention can also further contain following polymer Polymer "), the polymer is to make free-radical polymerised compound (P1) represented by following formula (6), have alkoxy silane The free-radical polymerised compound (P2) of base and at least one free-radical polymerised with epoxy group, carboxyl, hydroxy phenyl Compound (P3) carries out free-radical polymerized form.

In formula (6), R⁵For hydrogen or methyl, R⁶~R⁹For the alkyl of carbon number 1~5, R¹⁰For the alkyl of carbon number 1~10, m is 1~ 10 integer, the integer that n is 1~150.

1-6-10-1. free-radical polymerised compound (P1)

Free-radical polymerised compound (P1) represented by formula (6) plays a role as surfactant, thus pass through by (P1) it is used in raw material, and free-radical polymerized polymer is made to play a role as surfactant, even if in addition not adding surface Activating agent can also make flatness, be improved to the adhesion of basal substrate, coating.By adding free-radical polymerised compound (P1), free-radical polymerized polymer becomes to be easy to come to the surface in film surface.

In the present invention, in the free-radical polymerised compound (P1) represented by formula (6), preferably R⁵For hydrogen or methyl, R⁶ ~R⁹For methyl, R¹⁰The compound for the integer that integer that alkyl, m for carbon number 1~10 are 1~5, n are 1~150.More preferably R⁵For methyl, R⁶~R⁹For methyl, R¹⁰For the compound of butyl, m 3, the n integer for being 1~150, in addition, being preferably that n is in turn The compound for the integer that the compound of 30~70 integer, particularly preferably n are 50~70.Radical polymerization represented by formula (6) The weight average molecular weight of conjunction property compound (P1) is preferably 500~8000.

Free-radical polymerised compound (P1) can be manufactured by well known method.In addition, it is possible to use commercially available product.Such as It (is trade name that FM-0711, FM-0721, FM-0725, which can be enumerated,；Prompt grace intelligence (JNC) limited liability company) etc..

1-6-10-2. has the free-radical polymerised compound (P2) of alkoxysilane group

In the present invention, the free-radical polymerised compound (P2) with alkoxysilane group is used as to obtain it is described from By the raw material of base copolymerized polymer.Preferred free-radical polymerised compound (P2) is selected from by 3- (methyl) acryloxy third Base trimethoxy silane, 3- (methyl) acryloxypropyls triethoxysilane, 3- (methyl) acryloxypropyl Dimethoxysilane, 3- (methyl) acryloxypropyls diethoxy silane, vinyltrimethoxysilane, vinyl Triethoxysilane, one or more of the group that styryltrimethoxysilane is formed.These are free-radical polymerised In compound, 3- (methyl) acryloyloxypropyltrimethoxysilane, 3- (methyl) acryloxypropyl triethoxysilicane The flatness of alkane is good and preferred.By using (P2), the raisings such as the transparency, chemical-resistant.It is imitated in addition, being coupled using silane Fruit is improved with the adhesion of base material.

1-6-10-3. has the free-radical polymerised compound of at least one (P3) of epoxy group, carboxyl, hydroxy phenyl

In the present invention, by the free-radical polymerised compound of at least one (P3) with epoxy group, carboxyl, hydroxy phenyl As obtaining the raw material of the free-radical polymerized polymer.Preferred free-radical polymerised compound (P3) be selected from by (methyl) glycidyl acrylate, 4- hydroxybutyls (methyl) acrylate glycidol ether, (methyl) acrylic acid, 4- hydroxyls One or more of the group that phenyl vinyl ketone is formed.(P3) it functions, contributes to resistance to as the crosslinking agent of polymer The raising of hot, chemical-resistant etc..

1-6-10-4. the manufacturing method of free-radical polymerized polymer

Free-radical polymerized polymer is by free-radical polymerised compound (P1) represented by formula (6), has alcoxyl The free-radical polymerised compound (P2) of base silane base and the free radical of at least one with epoxy group, carboxyl, hydroxy phenyl Polymerizable compound (P3) is carried out free-radical polymerized and is obtained.There is no particular restriction for the manufacturing method of free-radical polymerized polymer, The free-radical polymerised compound class can be heated in the presence of radical initiators and be manufactured free-radical polymerized poly- Close object.As radical initiator, organic peroxide, azo-compound etc. can be used.Free-radical polymerized reaction temperature is simultaneously It is not particularly limited, usually 50 DEG C~150 DEG C of range.Reaction time is also not particularly limited, usually 1 hour~48 hours Range.In addition, under the arbitrary pressure of pressurization, decompression or atmospheric pressure, the reaction can be carried out.

Solvent used in the free radicals copolymerization reaction preferably makes the solvent that generated polymer dissolves.It is described The concrete example of solvent is ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methoxy menthyl acetate, first Ethoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3- oxygroups methyl propionate, 3- hydroxyls Base ethyl propionate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxypropanoates, 3- ethoxy-propionic acid second Ester, 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid propyl ester, 2- methoxy methyl propionates, 2- methoxypropionates, 2- methoxy propyls Propyl propionate, 2- ethoxypropanoates, 2- ethoxyl ethyl propionates, 2- hydroxy-2-methyls methyl propionate, 2- hydroxy-2-methyls Ethyl propionate, 2- methoxyl groups -2 Methylpropionic acid methyl esters, 2- ethyoxyls -2 Methylpropionic acid ethyl ester, methyl pyruvate, pyruvic acid second Ester, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid methyl esters, 2-Oxobutyric acid ethyl ester, 4- hydroxyls- 4-methyl-2 pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol list Methyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether Acetic acid esters, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether.Solvent can be these concrete examples One kind or these concrete examples two or more mixtures.

About the free-radical polymerized polymer used in the present invention, can make solvent used in polymerization directly residual and The free-radical polymerized polymer solution in view of operability etc. is made, the solvent can also be removed and be made in view of carrying property Deng solid-like free-radical polymerized polymer.

If free-radical polymerized polymer passes through the weight average molecular weight that is found out as the gpc analysis of standard using polystyrene It is 1,000~50,000 range, then film forming is good and preferred.In turn, if weight average molecular weight is 2,500~20,000 Range, then the flatness of cured film is good and more preferable.In turn, if the model that weight average molecular weight is 2,500~15,000 It encloses, then the flatness of cured film, chemical-resistant are good and particularly preferred.

Relative to photosensitive composite full dose, other additives of the parts by weight of 0.1 parts by weight of addition~20 and use.

1-7. solvent

Solvent can be also added in the photosensitive composite of the present invention.It is arbitrarily added in the photosensitive composite of the present invention Solvent preferably can dissolve polyesteramide sour (A), epoxide (B), the compound (C) with polymeric double bond, photopolymerization The solvent of initiator (D), additive (E) etc..The concrete example of the solvent is ethyl acetate, butyl acetate, propyl acetate, propionic acid Butyl ester, ethyl lactate, methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethoxy acetate, second Ethoxyacetic acid ethyl ester, acetic acid -3- methoxybutyls, 3- oxygroups methyl propionate, 3- hydroxypropionates, 3- methoxypropionic acid first Ester, 3- methoxypropionates, 3- ethoxypropanoates, 3- ethoxyl ethyl propionates, 2 hydroxy propanoic acid methyl esters, 2- hydroxyls third Propyl propionate, 2- methoxy methyl propionates, 2- methoxypropionates, 2- methoxy propyls propyl propionate, 2- ethoxypropanoates, 2- Ethoxyl ethyl propionate, 2- hydroxy-2-methyls methyl propionate, 2- hydroxy-2-methyls ethyl propionate, 2- methoxyl group -2- methyl-props Sour methyl esters, 2- ethyoxyls -2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, Ethyl acetoacetate, 2-Oxobutyric acid methyl esters, 2-Oxobutyric acid ethyl ester, 4- hydroxy-4-methyl-2-pentanones, 1,4-butanediol, third Glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, ethylene glycol list Butyl ether acetic acid esters, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether, Diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether, butyl carbitol acetate, diethylene glycol dimethyl ether, diethyl Glycol diethyl ether and diethylene glycol methyl ethyl ether.Solvent can be these concrete examples one kind or these concrete examples two Kind or more mixture.

The preservation of 1-8. photosensitive composites

If the photosensitive composite of the present invention preserves in the range of -30 DEG C~25 DEG C, the ageing stability of composition Become good.It, will not be more preferable with precipitate if storage temperature is -20 DEG C~10 DEG C.

2. the cured film of photosensitive composite

The photosensitive composite of the present invention can obtain in the following manner：By polyesteramide sour (A), epoxide (B), the compound with polymeric double bond (C), Photoepolymerizationinitiater initiater (D) and additive (E) are mixed, and further regarding needs It wants and selectivity adds solvent, by these compounds equably mixed dissolution.As additive (E), can be regarded according to target property Selection is needed to use coupling agent, surfactant and other additives.

If the photosensitive composite prepared as described above (and in the case of solvent-free solid state, is dissolved in molten After in agent) it is coated on matrix surface, solvent is removed for example, by heating etc., then can form film.In matrix surface Spin-coating method, rolling method, infusion process, flexographic printing process, spray-on process and slot coated method etc. can be used by being coated with photosensitive composite Conventionally known method.Then, (preliminary drying is heated to the film using heating plate (hotplate) or baking oven (oven) etc. It is roasting).Heating condition is different because of the type of each ingredient and allotment ratio, usually 70 DEG C~150 DEG C, if baking oven is then 5 minutes ~15 minutes, if heating plate is then 1 minute~5 minutes.

Thereafter, ultraviolet light is irradiated to film across the mask of desired pattern form.Ultraviolet irradiation amount is with i radiation meters It is suitably 5mJ/cm²~1000mJ/cm².The photosensitive composite irradiated through ultraviolet light passes through the compound with polymeric double bond Be polymerized as three-dimensional cross-linked body, it is insoluble in alkaline-based developer.

Then, film is impregnated in alkaline development bys spraying development, spray development, covering liquid development, immersion development etc. In liquid, removing is partly dissolved by unwanted.The concrete example of alkaline-based developer is the nothings such as sodium carbonate, sodium hydroxide, potassium hydroxide The aqueous solution of the organic bases such as the aqueous solution and tetramethyl ammonium hydroxide of machine bases, tetraethyl ammonium hydroxide.In addition, also may be used Methanol, ethyl alcohol and surfactant of appropriate amount etc. is added in the alkaline-based developer and is used.

Finally, in order to keep film fully hardened, cured film can be obtained by heat treatment, the heat treatment be 180 DEG C~250 DEG C, preferably at 200 DEG C~250 DEG C, then carried out if baking oven 30 minutes~90 minutes, if heating plate then into Row 5 minutes~30 minutes.

Cured film obtained by as described above when heated, and then 1) the partially dehydrated ring of polyamic acid of polyesteramide sour (A) Change and forms imide bond and 2) carboxylic acid of polyesteramide sour (A) and the polymer reaction containing epoxy group and molecular weight, because This is very tough, and the transparency, heat resistance, chemical-resistant, flatness, adhesion, light resistance and resistant sputtering are excellent.Cause This, cured film of the invention is effective if the protective film as colored filter, and colored filter can be used to manufacture liquid crystal Display element or solid-state imager.Other than the protective film of colored filter, if cured film of the invention is used as being formed In transparent insulating film of the thin film transistor (TFT) (ThinFilmTransistor, TFT) between transparent electrode or it is formed in transparent electricity Transparent insulating film between pole and alignment films is then also effective.In turn, cured film of the invention is used as light emitting diode The protective film of (LightEmittingDiode, LED) illuminator or the basilar memebrane of application type polarizer are also effective.

[embodiment]

Then, added a concrete explanation to the present invention by synthesis example, embodiment and comparative example, but the present invention not by Any restriction of these embodiments.First, synthesis includes tetracarboxylic dianhydride, diamines, monohydroxy compound, polynary hydroxyl as shown below The polyesteramide acid solution (1~synthesis example of synthesis example 7) of the reaction products such as based compound.

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 (methyl3-methoxypropionate, hereinafter referred to as " MMP "), 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydrides (3, 3 ', 4,4 '-diphenylethertetracarboxylicdianhydride, hereinafter referred to as " ODPA "), 1,4-butanediol, Benzylalcohol carries 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 sulfones is put into following weight (diaminodiphenylsulfone, hereinafter referred to as " DDS "), MMP, after stirring in 2 hours is carried out at 20 DEG C~30 DEG C, Stirring in 1 hour (synthesis second stage) is carried out at 125 DEG C.

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 polymer (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 (propyleneglycolmonomethyletheracetate, PGMEA), 1,2,3,4- butane tetracarboxylic acid dianhydrides (1,2,3,4-butanetetracarboxylicdianhydride) (BT-100), SMA1000P (trade names；Styrene horse Come acid anhydride copolymer, river crude oil limited liability company), 1,4-butanediol, benzylalcohol, carried out under drying nitrogen stream, at 125 DEG C Stirring in 2 hours (synthesis first stage).

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 polymer (A2) is 10,000.

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

According to the method for synthesis example 2, with temperature, time and the ratio (unit described in table 1-1：G) make each ingredient anti- It answers, obtains sour (A7) the respective solution of sour (the A3)~polyesteramide of polyesteramide.

Furthermore about the title in table 1-1, epoxy-ester (EpoxyEster) 70PA indicates propylene glycol diglycidylether Acrylic acid modified object (trade name；Chemistry limited liability company of common prosperity society), Bis-A-2EOH indicates 4, the 4 '-bis- (2- of isopropylidene Phenoxetol).

Table 1-1

Then, it synthesizes as follows comprising (methyl) glycidyl acrylate, the radical polymerization without epoxy group The polymer (8~synthesis example of synthesis example 11) containing epoxy group of the reaction product of conjunction property compound.

The synthesis of polymer (B2) solution of [synthesis example 8] containing epoxy group

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 glycidyl methacrylate of the free-radical polymerised compound with epoxy group (glycidylmethacrylate), bis- (the 2- methyl-props of 2,2 '-azos for and then with following weight being loaded as polymerization initiator Acid) dimethyl ester (V-601, trade name；With Wako Pure Chemical Industries limited liability company), under drying nitrogen stream, 2 are carried out at 110 DEG C Hour stirring.

PGMEA 31.50g

Glycidyl methacrylate 13.50g

V-601 1.35g

Solution is cooled to room temperature, 30 weight % solution of the polymer (B2) containing epoxy group are obtained.To one of solution Divide and be sampled, gpc analysis (polystyrene standard) is utilized to measure weight average molecular weight.As a result, what is obtained contains epoxy The weight average molecular weight of the polymer (B2) of base is 3,900.

The synthesis of polymer (B3) solution of [synthesis example 9] containing epoxy group

In the four-hole boiling flask with blender, the dehydration and purification that carried out of polymer solvent is loaded as with following weight MMP, as the glycidyl methacrylate of the free-radical polymerised compound with epoxy group, as without epoxy group Free-radical polymerised compound dimethacrylate (NK esters (NKEster) 2G, trade name；The villages Xin Zhong Learn), and then 2 that polymerization initiator is loaded as with following weight, 2 '-azos bis- (2 Methylpropionic acid) dimethyl ester (V-601, quotient The name of an article；With Wako Pure Chemical Industries limited liability company), it carries out stirring for 2 hours under drying nitrogen stream, at 110 DEG C.

Solution is cooled to room temperature, 30 weight % solution of the polymer (B3) containing epoxy group are obtained.To one of solution Divide and be sampled, gpc analysis (polystyrene standard) is utilized to measure weight average molecular weight.As a result, what is obtained contains epoxy The weight average molecular weight of the polymer (B3) of base is 4,000.

[10~synthesis example of synthesis example 11] polymer (B4) solution containing epoxy group~polymer (B5) containing epoxy group is molten The synthesis of liquid

According to the method for synthesis example 9, with temperature, time and the ratio (unit described in table 1-2：G) make each ingredient anti- It answers, obtains the polymer (B4) containing epoxy group~polymer (B5) containing epoxy group.

Furthermore about the title in table 1-2, GMA indicates that glycidyl methacrylate, 2G indicate diethylene glycol diformazan Base acrylate (NK esters (NKEster) 2G, trade name；The villages Xin Zhong chemistry), NPM indicates N-phenylmaleimide, CHMI tables Show that N- N-cyclohexylmaleimides, V-601 indicate bis- (2 Methylpropionic acid) dimethyl esters of 2,2 '-azos.

Table 1-2

[embodiment 1]

Nitrogen displacement is carried out to the detachable flask of the 500ml with stirring wing and is loaded as polyester in this flask Polyesteramide acid (A1) solution 100.0g obtained in amic acid (A), synthesis example 1, the Tyke as epoxide (B) Not (TECHMORE) VG3101L (B1) (trade name；General woods Tyke (Printec) limited liability company) 12.0g, as with poly- UA-510H (the trade names of UM in the compound (C) of conjunction property double bond；Chemistry limited liability company of common prosperity society) 18.00g, as The Ai Dike arcs Shandong of Photoepolymerizationinitiater initiater (D) hereby (AdekaarcLuz) NCI-9303.0g, the Sa Laaisi as additive (E) (Sila-Ace) S510 (trade names；Prompt grace intelligence (JNC) limited liability company) 1.5g, the dehydration and purification that carried out as solvent MMP39.2g, diethylene glycol methyl ethyl ether 109.2g and PGMEA54.6g, carry out stirring for 3 hours at room temperature, make it uniformly It dissolves on ground.

Then, Mei Jiafa (Megafac) F-556 (trade names of input as additive (E)；DIC (DIC) share has Limit company) 0.2g, it carries out stirring for 1 hour at room temperature, is filtered using molecular filter (0.2 μm) and prepares photosensitive composition Object.

[production method of evaluation substrate]

10 seconds are lasted with 400rpm the photosensitive composite is spun on glass substrate, in 100 DEG C of heating plate Carry out 2 minutes prebake conditions.Then, in air, using proximity printing machine TME-150PRC (trade names；Open up Pu Kang (Topcon) limited liability company), 350nm light below is ended through wavelength cut-off filter, and take out g rays (436nm), h rays (405nm), i rays (365nm), and be exposed.Light exposure is to utilize accumulative quantometer UIT-102 (quotient The name of an article；Oxtail (USHIO) Electric Co., Ltd), optical receiver UVD-365PD (trade names；Oxtail (USHIO) motor stock Part Co., Ltd) it is measured and is set as 50mJ/cm².Using 2.38 weight % tetramethyl ammonium hydroxide aqueous solutions, after exposure Film carried out at 25 DEG C 60 seconds development after, using pure water to film carry out 20 seconds cleaning after, using 100 DEG C of heating plates into Row drying in 2 minutes.And then toasted after being carried out 30 minutes with 230 DEG C in an oven, acquisition film thickness is 4.0 μm with cured film Glass substrate.

About the cured film of acquisition as described above, for sensitivity, bending resistance, parsing as shown in table 2-1~table 2-3 Property and the transparency and evaluate characteristic.

[evaluation method of sensitivity]

Measure before development film thickness after film thickness and development using P-16, and calculate residual film ratio after development (film thickness after development × Film thickness before 100/ development).By 50mJ/cm²Under development after residual film ratio be 70% or more situation be set as zero, by residual film after development The case where rate is less than 70% is set as ×.In the case where evaluation result is zero, 50mJ/cm is recorded²Under development after residual film ratio Numerical value, evaluation result be × in the case of, with 50mJ/cm²Under development after residual film ratio numerical value not up to 70% meaning remember It is ＜ 70% to carry.

Herein, refer to after referring to cleaning-drying before development after prebake conditions after development.

In addition, in the evaluation of sensitivity, in 50mJ/cm²Under development after in the case that residual film ratio is not shown 70% or more, Stop hereafter recorded evaluation, and "-" is recorded as with unenforced meaning.

[making of bending resistance evaluation substrate]

Except the substrate for being coated with photosensitive composite is set as polyimide film (kapton (Kapton) 200H, trade name；East Beautiful Du Pont (TorayDupont) limited liability company) other than, carry out substrate system according to [production method of evaluation substrate] Make, obtains the polyimide film substrate with cured film.

[bending resistance evaluation method]

The polyimide film substrate with cured film obtained is cut out into 8cm × 4cm, the substrate cut out is rolled over It folds, and then places the counterweight of 100g on the film surface of upside, after standing 60 seconds, micro- sem observation is carried out to flexure plane.It will not produce The case where raw crackle, is set as "○", and "×" will be set as the case where producing crackle.

[making of analyticity evaluation substrate]

The mask with hole and line pattern across 50 μm wide is exposed in air, in addition to this, according to [evaluation is used The production method of substrate] substrate manufacture is carried out, obtain the substrate with pattern-like cured film.

[evaluation method of analyticity]

Measure the film thickness and 50 μm of wide line patterns of the exposure portion of the glass substrate with pattern-like cured film obtained Depth, utilize following calculating formulas calculate analyticity.It is fine using scale surface roughness in the measurement of film thickness and depth Shape measuring apparatus P-16 (trade names；Ke Lei (KLATENCOR) limited liability company, hereinafter referred to as " P-16 ").It will parsing Property for 95% or more situation be set as "○", by analyticity less than 95% the case where is set as "×".

Analyticity=(film thickness of depth/exposure portion of 50 μm of wide line patterns) × 100

[transparent evaluation method]

In the glass substrate with cured film obtained, UV, visible light near infrared spectrometer (trade name is utilized： V-670, light splitting limited liability company of Japan) wavelength of only cured film is measured as the transmissivity under the light of 400nm.By transmissivity It is set as zero for 95% or more situation, by less than 95% the case where is set as ×.

[2~embodiment of embodiment 12]

According to the method for embodiment 1, with the ratio (unit described in table 2-1~table 2-3：G) by each ingredient mixed dissolution And obtain photosensitive composite.

Title in table 2-1~table 2-3 indicates following raw material.

[epoxy resin]

B1：Tyke not (TECHMORE) VG3101L (trade names；General woods Tyke (Printec) limited liability company)

[polyfunctional monomer (UM) with carbamate skeleton]

U1：UA-510H (trade names；Chemistry limited liability company of common prosperity society)

U2：U-15HA (trade names；Chemical industry limited liability company of the villages Xin Zhong)

[polyfunctional monomer (NM) for not having carbamate skeleton]

M1：Aronix (Aronix) M-402 (trade names；East Asia synthesizes limited liability company)

M2：Aronix (Aronix) M-520 (trade names；East Asia synthesizes limited liability company)

M3：Aronix (Aronix) M-450 (trade names；East Asia synthesizes limited liability company)

M4：Lay spy acrylate (LightAcrylate) TMP-A (trade names；Chemistry limited liability company of common prosperity society)

M5：Aronix (Aronix) M-208 (trade names；East Asia synthesizes limited liability company)

[Photoepolymerizationinitiater initiater]

Ai Dike arcs Shandong hereby (AdekaarcLuz) NCI-930 (trade names；Ai Dike (ADEKA) limited liability company, letter Referred to as " NCI-930 ")

[epoxy curing agent]

TMA：Trimellitic anhydride

[additive]

Sa Laaisi (Sila-Ace) S510 (trade names；Prompt grace intelligence (JNC) limited liability company, referred to as " S510 ")

Ai Di Coase tower wave (ADKSTAB) AO-60 (trade names；Ai Dike (ADEKA) limited liability company, referred to as “AO-60”)

Mei Jiafa (Megafac) F-556 (trade names；DIC (DIC) limited liability company, referred to as " F-556 ")

Table 2-1

Table 2-2

Table 2-3

[1~comparative example of comparative example 7]

According to the method for embodiment 1, with the ratio (unit of table 3：G) each ingredient mixed dissolution is obtained into photosensitive composition Object.

Table 3

According to result shown in table 2-1~table 2-3：The cured film for having used UM of 1~embodiment of embodiment 17 Bending resistance is excellent, and balance is achieved at all aspects of analyticity, sensitivity and the transparency.

On the other hand, although the cured film transparency, the analyticity that only used NM of 1~comparative example of comparative example 5 of table 3 are excellent It is different, but bending resistance is poor.About comparative example 6 and comparative example 7,50mJ/cm²Under development after residual film ratio numerical value not up to 70%, For the result of sensitivity difference.As described above, only by UM be used as must can meet all characteristics in the case of ingredient.

[industrial availability]

The bending resistance, analyticity, sensitivity of the cured film that obtains and as optics by the photosensitive composite of the present invention Characteristic necessary to material the transparency it is excellent, for the aspect, can be used as colored filter, LED light-emitting component and The protective film of the various optical materials of light receiving element etc. etc. and be formed between TFT and transparent electrode and transparent electrode with Transparent insulating film between alignment films is especially expected to be applied to institute in flexible displays, foldable device of required bendability etc. In the element used.

Claims

1. a kind of photosensitive composite, it includes polyesteramide sour (A), epoxide (B), with the chemical combination of polymeric double bond Object (C), Photoepolymerizationinitiater initiater (D) and additive (E), the photosensitive composite are characterized in that：

The polyesteramide sour (A) is by making X moles of tetracarboxylic dianhydride, Y moles of diamines and Z moles of multi-hydroxy Object is closed to be reacted and obtained with the ratio that the relationship of following formula (1) and formula (2) is set up；

Relative to sour (A) 100 parts by weight of polyesteramide, the total amount of epoxide (B) is the parts by weight of 20 parts by weight~200, tool It is the parts by weight of 20 parts by weight~300 to have the total amount of the compound (C) of polymeric double bond；

0.2≤Z/Y≤8.0···············(1)

0.2≤(Y+Z)/X≤5.0···(2)。

2. photosensitive composite according to claim 1, it is characterised in that：The compound with polymeric double bond (C) in full dose, the ratio of the compound with carbamate skeleton is 50 weight % or more.

3. photosensitive composite according to claim 1 or 2, it is characterised in that：It is described with carbamate skeleton Compound is to include the compound of more than two polymeric double bonds in each molecule.

4. photosensitive composite according to any one of claim 1 to 3, it is characterised in that：It is described that there is carbamic acid The molecular weight of the compound of ester skeleton is less than 10,000.

5. photosensitive composite according to any one of claim 1 to 4, it is characterised in that：The polyesteramide is sour (A) Material composition also include monohydroxy compound.

6. photosensitive composite according to any one of claim 1 to 5, it is characterised in that：The tetracarboxylic dianhydride is Selected from 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydrides, 2,2- [bis- (3,4- bis- Carboxyl phenyl)] in hexafluoropropane dianhydride, 1,2,3,4- butane tetracarboxylic acid dianhydrides and ethylene glycol bis- (dehydrations trimellitate) At least one,

The diamines is at least one in 3,3 '-diamino diphenyl sulfones and bis- [4- (3- amino-benzene oxygens) phenyl] sulfones Kind,

The multi-hydroxy compound is selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5- penta Bis- (4- hydroxy-cyclohexyls) propane of glycol, 1,6- hexylene glycols, 1,7- heptandiols, 1,8- ethohexadiols, 2,2-, 4,4 '-dihydroxy two Cyclohexyl, isocyanuric acid three (2- hydroxyethyls) ester, 2- hydroxy-benzyl alcohols, 4- hydroxy-benzyl alcohols, 2- (4- hydroxy phenyls) ethyl alcohol, glycerine Single (methyl) acrylate, trimethylolpropane list (methyl) acrylate, pentaerythrite list (methyl) acrylate, Ji Wusi Alcohol two (methyl) acrylate, dipentaerythritol list (methyl) acrylate, dipentaerythritol two (methyl) acrylate, two seasons Penta tetrol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, D-sorbite list (methyl) acrylate, mountain Pears sugar alcohol two (methyl) acrylate, D-sorbite three (methyl) acrylate, D-sorbite four (methyl) acrylate, 4, 4 '-isopropylidenes bis- (2- phenoxetols), (methyl) acrylic acid modified object of ethylene glycol diglycidylether, propylene glycol two contract (methyl) acrylic acid modified object of water glycerin ether, (methyl) acrylic acid modified object, the glycerine two of tripropyleneglycol diglycidyl ether (methyl) acrylic acid modified object of glycidol ether, (methyl) acrylic acid modified object, the propylene oxide of bisphenol A diglycidyl ether (methyl) acrylic acid modified object of modified bisphenol A diglycidyl ether and in each molecule include more than two epoxy groups At least one of (methyl) acrylic acid modified object of compound.

7. photosensitive composite according to claim 5, it is characterised in that：The monohydroxy compound is selected from isopropyl Alcohol, benzylalcohol, dihydroxypropane single-ether, 3- ethyl -3- hydroxymethyl oxetanes, furfuryl alcohol, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, (methyl) acrylic acid -2- hydroxyl -3- phenoxy-propyls, (methyl) acrylic acid -4- hydroxy benzenes Ester, to hydroxyl (methyl) acrylic acid aniline, 1,4-CHDM list (methyl) acrylate, (methyl) acrylic acid -3- (2- Hydroxy phenyl) ester, glycerine two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, three (first of pentaerythrite Base) acrylate, dipentaerythritol five (methyl) acrylate and the compound comprising an epoxy group in each molecule At least one of (methyl) acrylic acid modified object.

8. photosensitive composite according to any one of claim 1 to 7, it is characterised in that：The polyesteramide is sour (A) Weight average molecular weight be 1,000~200,000.

9. photosensitive composite according to any one of claim 1 to 8, it is characterised in that：The epoxide (B) Include 2~35 epoxy groups in each molecule, weight average molecular weight is less than 5,000；

The Photoepolymerizationinitiater initiater (D) is selected from alpha-amido benzene alkyl ketone system Photoepolymerizationinitiater initiater, the photopolymerization of acylphosphine oxide system At least one of initiator, oxime ester system Photoepolymerizationinitiater initiater；

10. a kind of cured film, it is characterised in that：It is by photosensitive composite according to any one of claim 1 to 9 And it obtains.

11. a kind of colored filter, it is characterised in that：With cured film according to claim 10 as transparency protected Film.

12. a kind of interlayer dielectric, it is characterised in that：With cured film according to claim 10 as transparency protected Film.

13. a kind of application type polarizer, it is characterised in that：With cured film according to claim 10 as basilar memebrane.