CN106959576A - Photosensitive composite and its application - Google Patents

Photosensitive composite and its application Download PDF

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Publication number
CN106959576A
CN106959576A CN201610842654.8A CN201610842654A CN106959576A CN 106959576 A CN106959576 A CN 106959576A CN 201610842654 A CN201610842654 A CN 201610842654A CN 106959576 A CN106959576 A CN 106959576A
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China
Prior art keywords
methyl
radical polymerization
free radical
acrylate
photosensitive composite
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CN201610842654.8A
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Chinese (zh)
Inventor
尾崎刚史
近藤学
奈良和美
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JNC Corp
JNC Petrochemical Corp
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JNC Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H01L27/1462—Coatings
    • H01L27/14621—Colour filter arrangements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies

Abstract

The present invention provides a kind of photosensitive composite and its application.The present invention relates to a kind of photosensitive composite, it contains alkali-soluble polymer (A), epoxide (B), the compound (C) with polymerism double bond, Photoepolymerizationinitiater initiater (D), molecular weight regulator (E) and solvent (F).If using the photosensitive composite of the present invention, the excellent cured film of heat resistance, particularly planarization characteristics and analyticity can be formed.

Description

Photosensitive composite and its application
Technical field
The present invention relates to a kind of insulating materials in electronic component, the passivating film in semiconductor device, buffering film, layer Between dielectric film or interlayer dielectric or colored filter diaphragm in planarization film, or display element etc. formation in institute Photosensitive composite, the hyaline membrane using the photosensitive composite and the electronic component comprising the film used.
Background technology
In the manufacturing process of the elements such as display element, carry out sometimes at the various chemicals such as organic solvent, acid, aqueous slkali Reason, or when by sputtering (sputtering) and film forming wired electric pole, surface is locally heated by as high temperature.Therefore, have When for the deterioration on the surface that prevents various elements, damage, rotten and set surface protection film.For these diaphragms, it is desirable to Each characteristic for the various processing that can be resistant in manufacturing process as described above.Specifically, it is desirable to heat resistance, solvent resistance/ It is the chemical-resistants such as acid resistance/alkali resistance, water resistance, the adhesion to basal substrates such as glass, the transparency, scratch resistance, flat Smooth property, light resistance etc..Moreover, promoting showing for the high performance-baseds such as high visual angle, high-speed response, the High precision of display element Under shape, in the case of the use as protective films of color filters, the material that reliability and planarization characteristics are improved is expected Material.Further, since the variation of display element etc., it is necessary to the guarantor of pattern form in addition to these desired characteristics in the past The demand of cuticula is also in increase.
In the formation of these diaphragms with pattern form, photosensitive composite is used.Make photosensitive composition Thing forms film on substrate, and Jie is exposed every the photomask with defined pattern, developed using alkaline-based developer And removal is partly dissolved by unwanted, then form the cured film with pattern form by being toasted after progress.
In recent years, for the pattern formed in diaphragm, the requirement enhancing of further miniaturization, and expect to meet this It is required that photosensitive composite.
As the example that photosensitive composite is used in the diaphragm of colored filter, patent document 1 there are and special Sharp document 2.The human desiress such as the present inventor form diaphragm using photosensitive composite described in these, though as a result meet flat Smoothization characteristic, but expect for the formation of fine pattern to be improved.Moreover, with regard to the photosensitive composite of patent document 3 For, though fine pattern can be formed, expect to be changed for the heat resistance required by diaphragm, planarization characteristics It is good, so as to seek fully to meet the photosensitive composite of various characteristics.
Moreover, for photosensitive composite, it is desirable to which the coating of the basal substrate to forming cured film is excellent.
[prior art literature]
[patent document]
[patent document 1] Japanese Patent Laid-Open 2014-074787 publications
[patent document 2] Japanese Patent Laid-Open 2009-286904 publications
[patent document 3] Japanese Patent Laid-Open 2015-143813 publications
The content of the invention
[the problem of invention is to be solved]
The problem of the present invention is to provide a kind of to form heat resistance, planarization characteristics and particularly analyticity is excellent The photosensitive composite of cured film.There is provided in addition and cured film and include the cured film as formed by the photosensitive composite Electronic component.
[technological means for solving problem]
The present inventor et al. has carried out various researchs to solve described problem point, as a result finds by as follows photosensitive Property composition, can form fine pattern shape, so as to complete the present invention：The photosensitive composite contains alkali-soluble polymerization Thing (A), epoxide (B), the compound (C) with polymerism double bond, Photoepolymerizationinitiater initiater (D), molecular weight regulator (E) and solvent (F), the alkali-soluble polymer (A) be make containing the free radical polymerization monomer (a1) with carboxyl and The free-radical polymerised list of other free radical polymerization monomers (a2) (these monomers are without epoxy radicals and oxetanylmethoxy) The mixture of body polymerize and obtained.
The present invention includes following composition.
[1] a kind of photosensitive composite, it contains alkali-soluble polymer (A), epoxide (B), with polymerism Compound (C), Photoepolymerizationinitiater initiater (D), molecular weight regulator (E) and the solvent (F) of double bond, wherein,
The weight of Photoepolymerizationinitiater initiater (D) is more than 5.0 times of the weight of molecular weight regulator (E) and for less than 20 times.
[2] photosensitive composite according to [1], wherein, molecular weight regulator (E) is to be selected from mercaptan (mercaptan) in class, xanthic acid (xanthogen) class, quinone (quinone) class, 2,4- diphenyl -4-methyl-1-pentene More than one.
[3] photosensitive composite according to [1], wherein, molecular weight regulator (E) is naphthoquinones (naphthoquinone) class.
[4] photosensitive composite according to [1], wherein, molecular weight regulator (E) is HNQ.
[5] photosensitive composite according to any one of [1]~[4], wherein, alkali-soluble polymer (A) is to make Contain free radical polymerization monomer (a1) and the free-radical polymerised list of other free radical polymerization monomers (a2) with carboxyl The mixture of body polymerize and obtained, free radical polymerization monomer (a1) and other free radical polymerization monomers (a2) with carboxyl Do not have epoxy radicals or oxetanylmethoxy (oxetanyl)；
Epoxide (B) is to be selected from diglycidyl ether type epoxy compound (Ba), ester ring type aliphatic epoxy compound (Bb) and at least one in the polymer containing epoxy radicals (Bc),
Polymer (Bc) containing epoxy radicals be make containing with epoxy radicals free radical polymerization monomer (b1) and other The mixture of the free radical polymerization monomer of free radical polymerization monomer (b2) polymerize and obtained, and
Free radical polymerization monomer (b1) and other free radical polymerization monomers (b2) with epoxy radicals do not have carboxylic Base；
Compound (C) with polymerism double bond is to be selected from Dipentaerythritol Pentaacrylate, the propylene of dipentaerythritol six The ethylene-oxide-modified triacrylate of acid esters, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, isocyanuric acid, neighbour Phthalic acid monohydroxy ethyl propylene acid esters, succinate modified pentaerythritol triacrylate, orthophthalic modified Ji Wusi Alcohol triacrylate, succinate modified Dipentaerythritol Pentaacrylate, the acrylic acid of orthophthalic modified dipentaerythritol five At least one in ester and modified by polyacid acrylate oligomers；Moreover,
Photoepolymerizationinitiater initiater (D) be selected from alpha-amido benzene alkyl ketone (α-aminoalkylphenone) be photopolymerization trigger Agent, acylphosphine oxide (acylphosphine oxide) are Photoepolymerizationinitiater initiater and oxime ester (oxime ester) is photopolymerization One or more of initiator.
[6] photosensitive composite according to [5], wherein, alkali-soluble polymer (A) is made relative to carboxyl Free radical polymerization monomer (a1) and other free radical polymerization monomers (a2) gross weight and contain the weight of 10 weight %~60 Measure % free radical polymerization monomer (a1) with carboxyl and the weight % of 40 weight %~90 other free-radical polymerised lists The copolymer that the mixture of the free radical polymerization monomer of body (a2) polymerize and obtained；
Diglycidyl ether type epoxy compound (Ba) be selected from 1,3- it is double [4- [1- [4- (2,3- glycidoxy) phenyl]- 1- [4- [1- [4- (2,3- glycidoxy) phenyl] -1- Methylethyls] phenyl] ethyl] phenoxy group] -2- propyl alcohol and 2- [4- (2,3- glycidoxy) phenyl] -2- [4- [1,1- double [4- ([2,3- glycidoxy] phenyl)] ethyls] phenyl] in propane At least one,
Ester ring type aliphatic epoxy compound (Bb) is 1, the 2- epoxy radicals -4- (2- of double (the hydroxymethyl)-n-butyl alcohols of 2,2- Oxiranyl) hexamethylene (1,2-epoxy-4- (2-oxiranyl) cyclohexane) addition product；
Compound (C) with polymerism double bond is to be selected from Dipentaerythritol Pentaacrylate, the propylene of dipentaerythritol six At least one in acid esters, pentaerythritol triacrylate, tetramethylol methane tetraacrylate and modified by polyacid acrylate oligomers Kind；Moreover,
Photoepolymerizationinitiater initiater (D) is O- acyl group oxime compounds.
[7] photosensitive composite according to [6], wherein, the free radical polymerization monomer (a1) with carboxyl is choosing At least one from acrylic acid and methacrylic acid；
Photoepolymerizationinitiater initiater (D) be selected from 1,2- octadione- 1- [4- (thiophenyl) phenyl] -2- (O- benzoyl oximes), Ethyl ketone, 1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -, 1- (O- acetyl group oxime) and 1,2- propanedione - At least one in 1- [4- [4- (2- hydroxyl-oxethyls) thiophenyl] phenyl] -2- (O- acetyl group oxime).
[8] photosensitive composite according to [7], wherein, other free radical polymerization monomers (a2) are included selected from tool There are (methyl) acrylate, (methyl) acrylate with bicyclopentyl, (methyl) with dicyclopentenyl of aromatic rings At least one in acrylate and N- substituted maleimide amine.
[9] photosensitive composite according to [8], wherein, other free radical polymerization monomers (a2) are to be selected from (first Base) benzyl acrylate, (methyl) acrylic acid bicyclopentyl ester, (methyl) acrylic acid dicyclopentenyl epoxide ethyl ester, N- phenyl horses At least one come in acid imide and N- N-cyclohexylmaleimides.
[10] photosensitive composite according to [9], wherein, other free radical polymerization monomers (a2) are relative to it The gross weight of his free radical polymerization monomer (a2) and containing more than 50 weight % be selected from (methyl) benzyl acrylate, (first Base) acrylic acid bicyclopentyl ester, (methyl) acrylic acid dicyclopentenyl epoxide ethyl ester, N-phenylmaleimide and N- cyclohexyl At least one in maleimide.
[11] a kind of cured film, it is as being obtained according to the photosensitive composite any one of [1]~[10].
[12] a kind of colored filter, it uses the cured film described in basis [11] as diaphragm.
[13] a kind of display element, it uses the colored filter according to [12].
[14] a kind of solid-state imager, it uses the colored filter according to [12].
[15] a kind of display element, it uses the cured film described in basis [11] as formation in thin film transistor (TFT) (Thin Film Transistor, TFT) transparent insulating film between transparency electrode.
[16] a kind of display element, it uses the cured film described in basis [11] as formation in transparency electrode and alignment films Between transparent insulating film.
[17] a kind of touch-screen, it uses the cured film described in basis [11] as formation in interelectrode transparent insulation Film.
[18] a kind of light emitting diode (Light Emitting Diode, LED) illuminator, it uses according to [11] Cured film be used as diaphragm.
[The effect of invention]
Can be provided by the present invention can form the photosensitive composite of the fine pattern shape transparent body.
Embodiment
In this manual, so-called " flatness " is used as the sentence of performance is expressed as follows, i.e. as by photosensitive Property cured film itself formed by composition character, uniform film thickness and as flat surface configuration.Moreover, so-called " flat Change characteristic " it is to be used as the sentence of performance is expressed as follows, i.e. formed in cured film in the form of diaphragm in colorized optical filtering In the case of on the such irregular substrate of tool of piece, fill the bumps of substrate and form flat surface.
In this manual, so-called " fine pattern " is to represent 10 μm~50 μm of line and space pattern and 10 μm~50 μm Sectional hole patterns.Moreover, so-called " the pattern-like transparent body " is expressed as irregular membranaceous, perforate the membranaceous, overshooting shape of tool, wire Etc. shape, and thickness be less than 10 μm and wavelength 400nm light transmitance be more than 80% hardening thing (cured film). Wherein, using the present invention photosensitive composite formed by cured film not with " pattern-like " be necessary condition, may be used also To obtain the cured film for meeting the characteristic as not so-called " integral membrane " of formation pattern.Description more than, this The cured film of invention and without prejudice to as " overall membranaceous " hardening thing use.
In this manual, one or two sometimes for expression acrylic acid and methacrylic acid, such as " (methyl) propylene Acid " is stated in this wise.Moreover, similarly sometimes for represent acrylate and methacrylate one or two, As " (methyl) acrylate " is stated in this wise.
In this manual, so-called " alkenyl " is straight chain with double bond or the alkenyl of branched chain, can specifically be enumerated Vinyl, 1- acrylic, 2- acrylic, 1- methyl ethylenes, 1- cyclobutenyls, 2- cyclobutenyls, 3- cyclobutenyls, 2- methyl -2- third Alkenyl, 1- pentenyls, 2- pentenyls, 4- pentenyls, 3- methyl-2-butenes base, 1- hexenyls, 2- hexenyls, 1- heptenyls, 2- Heptenyl, 1- octenyls, 2- octenyls, 1,3- octadienyls, 2- nonenyls, 1,3- nonadienes base and 2- decene bases.It is so-called " alkynyl " be with three keys straight chain or branched chain alkynyl, can specifically enumerate acetenyl, 1- propinyls, 2-propynyl, 1- butynyls, 2- butynyls, 3- butynyls, 1- pentynyls, valerylene base, 4- pentynyls, 1- octynyls, 6- methyl isophthalic acids-heptyne Base and 2- decynyls.
<1. the photosensitive composite of the present invention>
The first embodiment of the present invention is related to a kind of photosensitive composite, and it contains alkali-soluble polymer (A), epoxy Compound (B), the compound (C) with polymerism double bond, Photoepolymerizationinitiater initiater (D), molecular weight regulator (E) and solvent (F)。
Contain alkali-soluble polymer (A), epoxide (B), the compound with polymerism double bond in the present invention (C), in the photosensitive composite of Photoepolymerizationinitiater initiater (D), molecular weight regulator (E) and solvent (F), alkali-soluble polymer (A), epoxide (B), the compound (C) with polymerism double bond, Photoepolymerizationinitiater initiater (D) and molecular weight regulator (E) Weight ratio preferably with respect to the parts by weight of alkali-soluble polymer (A) 100 for, epoxide (B) be 10 parts by weight~150 Parts by weight, the compound (C) with polymerism double bond are that the parts by weight of 40 parts by weight~400, Photoepolymerizationinitiater initiater (D) are 2 weight Part~60 parts by weight and molecular weight regulator (E) be the parts by weight of 0.1 parts by weight~12.Also, it is preferred that with solid component concentration into For the weight % of 10 weight %~50 mode and in the photosensitive composite of the present invention coordinating solvents (F).
The photosensitive composite of the present invention is not limited to by the following description, can be solvable by using specific alkali Property polymer and the raising for realizing analyticity.
<1-1. alkali-solubles polymer (A)>
As described above, the alkali-soluble polymer (A) used in the present invention is made containing the radical polymerization with carboxyl Conjunction property monomer (a1) (hereinafter sometimes referred to " composition (a1) ") and radical polymerization that can be with free radical polymerization monomer (a1) copolymerization The radical polymerization of other free radical polymerization monomers (a2) (hereinafter sometimes referred to " composition (a2) ") beyond conjunction property monomer (a1) The copolymer that the mixture of conjunction property monomer polymerize and obtained.Herein, with carboxyl free radical polymerization monomer (a1) and its with Other outer free radical polymerization monomers (a2) do not have epoxy radicals and oxetanylmethoxy.Alkali-soluble polymer (A) can be with It is that one kind can also be two or more.
In the photosensitive composite of the present invention during polymerization of contained alkali-soluble polymer (A), preferably use relative It is 10 weights for free radical polymerization monomer (a1) and the gross weight of other free radical polymerization monomers (a2) with carboxyl Measure the weight % of %~60 free radical polymerization monomer (a1) with carboxyl.If the scope, then photonasty of the invention The analyticity of composition is improved, and easily forms fine pattern.If the scope of the monomer is the weight % of 15 weight %~40, Then when the photosensitive composite using the present invention manufactures the pattern-like transparent body, sensitivity height (obtains institute's phase with low exposure The pattern-like transparent body of prestige), therefore further preferably.
The method that alkali-soluble polymer (A) is added into the photosensitive composite of the present invention can be direct using poly- Close reacted solution or the solution is concentrated and solid constituent is taken out, and only add solid constituent.
<1-1-1. has the free radical polymerization monomer (a1) of carboxyl>
The free radical polymerization monomer (a1) with carboxyl of one of raw material as alkali-soluble polymer (A) is if full Foot and the condition without epoxy radicals and oxetanylmethoxy, then be not particularly limited.Free radical polymerization monomer with carboxyl (a1) concrete example is (methyl) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, lemon health Acid, mesaconic acid, ω-carboxy-polycaprolactone list (methyl) acrylate, mono succinate [2- (methyl) acryloyl-oxyethyl] ester, Maleic acid list [2- (methyl) acryloyl-oxyethyl] ester, cyclohexene -3,4- dicarboxylic acids list [2- (methyl) acryloxy second Base] ester.
Preferred (methyl) acrylic acid, mono succinate [2- (methyl) acryloyl-oxyethyl] ester in these monomers, particularly If using (methyl) acrylic acid, the analyticity of photosensitive composite is improved, and obtains the high hardening thing of the transparency, therefore is entered One step is preferred.
There is the free radical polymerization monomer (a1) of carboxyl can be used alone the compound for these, can also be used in mixed way It is two or more.
<Other free radical polymerization monomers (a2) of 1-1-2.>
Other alternative free radical polymerization monomers (a2) of the raw material of alkali-soluble polymer (A) are not if having Have carboxyl, epoxy radicals and an oxetanylmethoxy, and can be with free radical polymerization monomer (a1) copolymerization with carboxyl radical polymerization Conjunction property monomer, then be not particularly limited.The example of such a free radical polymerization monomer is (methyl) acrylate, N- substitutions Malaysia Acid imide, macromonomer, styrene, methyl styrene, to acetoxy-styrene, vinyltoluene, 1-chloro-4-methyl-benzene, Indenes, (methyl) acrylamide, 4- hydroxyphenylmethyls acrylamide and N- acryloyl morpholines.(methyl) acrylate it is specific Example is (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobomyl acrylate Ester, (methyl) acrylic acid bicyclopentyl ester, (methyl) acrylic acid dicyclopentenyl base ester, (methyl) acrylic acid dicyclopentenyl epoxide Ethyl ester, (methyl) phenyl acrylate, (methyl) benzyl acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, (methyl) Between 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, glycerine list (methyl) acrylate, (methyl) acrylic acid Phenoxy benzyl ester, (methyl) acrylic acid tetrahydro furfuryl ester and methacrylic acid 4- hydroxylphenyl esters.N- substituted maleimide amine Concrete example is N-phenylmaleimide and N- N-cyclohexylmaleimides.The concrete example of macromonomer is that polystyrene divides greatly Sub- monomer and polymethyl methacrylate macromonomer.
In these monomers, the pattern-like manufactured using the photosensitive composite containing alkali-soluble polymer (A) is transparent The heat resistance of body is high, therefore preferably, the alkali-soluble polymer (A) is by selected from (methyl) acrylic acid bicyclopentyl ester, (first Base) acrylic acid dicyclopentenyl epoxide ethyl ester, (methyl) benzyl acrylate, N-phenylmaleimide and N- cyclohexyl horses At least one copolymerization come in acid imide is formed.Selected from (methyl) the acrylic acid bicyclopentyl ester, the ring of (methyl) acrylic acid two In pentenyl epoxide ethyl ester, (methyl) benzyl acrylate, N-phenylmaleimide and N- N-cyclohexylmaleimides extremely Few one kind is more preferably for the gross weight of other free radical polymerization monomers (a2), and the gross weight of its (these monomers) contains Have more than 50 weight %.
These other free radical polymerization monomers (a2) can be used alone the compound, can also be used in mixed way two kinds with On.
<1-2. epoxides (B)>
The epoxide (B) of the present invention is the compound in the molecule with epoxy radicals, as long as with such a structure Feature, then be not particularly limited.Epoxide can be used alone, and can also be used in mixed way two or more.
If the content of contained epoxide (B) is relative to 100 weight in the photosensitive composite of the present invention It is the parts by weight of 10 parts by weight~150 for part alkali-soluble polymer (A), then the planarization of photosensitive composite of the invention is special Property it is good and preferred, if 20 parts by weight~100 parts by weight, the then pattern manufactured using the photosensitive composite of the present invention The transparency of the shape transparent body is well and more preferably.
The example of epoxide (B) is bisphenol A type epoxy compound, bisphenol F type epoxy compound, diglycidyl ether type Epoxide (Ba), phenol novolak-type epoxy compound, cresol novolak type epoxy compound, bisphenol-A phenolic are clear Paint shaped epoxide, naphthalene type epoxide, aliphatic polyglycidyl ether, ester ring type aliphatic epoxy compound (Bb), And the polymer (Bc) containing epoxy radicals.Herein, so-called " polymer (Bc) containing epoxy radicals " is made containing with epoxy radicals Free radical polymerization monomer (b1) and other free radical polymerization monomers (b2) free radical polymerization monomer mixture gather The copolymer for closing and obtaining.
In these compounds, preferably diglycidyl ether type epoxy compound (Ba), bisphenol A novolac type epoxy compound Thing, ester ring type aliphatic epoxy compound (Bb) and the polymer (Bc) containing epoxy radicals, more preferably diglycidyl ether type epoxy Compound (Ba), ester ring type aliphatic epoxy compound (Bb) and the polymer (Bc) containing epoxy radicals.Use photosensitive composition The transparency of thing and the pattern-like transparent body that manufactures is high, and the photosensitive composite has used these epoxides.
<1-2-1. diglycidyl ether type epoxies compound (Ba)>
The preferred concrete example of diglycidyl ether type epoxy compound (Ba) is double [4- [1- [4- (2, the 3- epoxies third of 1,3- Epoxide) phenyl] -1- [4- [1- [4- (2,3- glycidoxy) phenyl] -1- Methylethyls] phenyl] ethyl] phenoxy group] -2- third Alcohol and 2- [4- (2,3- glycidoxy) phenyl] -2- [4- [1,1- double [4- ([2,3- glycidoxy] phenyl)] ethyls] benzene Base] propane.
<1-2-2. ester ring types aliphatic epoxy compound (Bb)>
The preferred concrete example of ester ring type aliphatic epoxy compound (Bb) is the 1 of double (the hydroxymethyl)-n-butyl alcohols of 2,2-, 2- epoxy radicals -4- (2- oxiranyls) hexamethylene addition product.
Commercially available product as described below can be used in these epoxides (B).The concrete example of bisphenol A type epoxy compound is JER 828, jER 1004 and jER 1009 (are trade name；Limited company of Mitsubishi Chemical).Bisphenol F type epoxy chemical combination The concrete example of thing is that jER 806 and jER 4005P (are trade name；Limited company of Mitsubishi Chemical).Diglycidyl ether type The concrete example of epoxide (Ba) is Tai Kumoya (Tecmoa) VG3101L (trade names；Pu Linteke (Printec) share Co., Ltd), EPPN-501H, EPPN-502H (be trade name；NIPPON PHARMACEUTICAL CO., LTD) and jER 1032H60 (trade name；Limited company of Mitsubishi Chemical).The concrete example of phenol novolak-type epoxy compound is EPPN-201 (commodity Name；NIPPON PHARMACEUTICAL CO., LTD), jER 152 and jER 154 (be trade name；Limited company of Mitsubishi Chemical).Make It is EOCN-102S, EOCN-103S, EOCN-104S and EOCN-1020 for the concrete example of cresol novolak type epoxy compound (it is trade name；NIPPON PHARMACEUTICAL CO., LTD).The concrete example of bisphenol A novolac type epoxide is jER 157S65 and iER 157S70 (are trade name；Limited company of Mitsubishi Chemical).The example of naphthalene type epoxide is HP4700 and HP4710 (are trade name；DIC (DIC) limited company).Ester ring type aliphatic epoxy compound (Bb) Concrete example be that Sai Luo West Germany (Celloxide) 2021P and Sai Luo West Germany (Celloxide) EHPE-3150 (is trade name； Daicel (Daicel) limited company).Furthermore, it is used as diglycidyl ether type epoxy compound (Ba) Tai Kumoya (Tecmoa) VG3101L is 2- [4- (2,3- glycidoxy) phenyl] -2- [4- [1,1- double [4- ([2,3- glycidoxy] Phenyl)] ethyl] phenyl] double [4- [1- [4- (2,3- glycidoxy) phenyl] -1- [4- [1- [4- (2, the 3- rings of propane and 1,3- Oxygen propoxyl group) phenyl] -1- Methylethyls] phenyl] ethyl] phenoxy group] -2- propyl alcohol mixture.It is used as ester ring type aliphatic ring The EHPE-3150 of oxygen compound (Bb) is 1, the 2- epoxy radicals -4- (2- oxiranyls) of double (the hydroxymethyl)-n-butyl alcohols of 2,2- Hexamethylene addition product.
<1-2-3. contains the polymer (Bc) of epoxy radicals>
As described above, the polymer (Bc) containing epoxy radicals used in the present invention be make containing with epoxy radicals from By base polymerizable monomer (b1) and can be with free radical polymerization monomer (b1) copolymerization with epoxy radicals other radical polymerizations Property monomer (b2) free radical polymerization monomer mixture polymerization and obtain copolymer.
In the polymerization of the polymer (Bc) containing epoxy radicals, preferably use relative to the radical polymerization with epoxy radicals Property monomer (b1) and other free radical polymerization monomers (b2) gross weight for there is ring for the weight % of 20 weight %~95 The free radical polymerization monomer (b1) of epoxide.If such a scope, then manufactured using the photosensitive composite of the present invention The pattern dimension of the pattern-like transparent body becomes close to mask size, and chemical-resistant is uprised.If the scope of the monomer For the weight % of 50 weight %~80, then the heat resistance of the pattern-like transparent body manufactured using the photosensitive composite of the present invention is become Obtain well, therefore more preferably.
The method that polymer (Bc) containing epoxy radicals is added into the photosensitive composite of the present invention can be direct Using the solution after polymerisation or the solution is concentrated and take out solid constituent, and only add solid constituent.
<1-2-3-1. has the free radical polymerization monomer (b1) of epoxy radicals>
It is used as the free radical polymerization monomer (b1) with epoxy radicals of the raw material of the polymer (Bc) containing epoxy radicals There is at least one epoxy radicals, then be not particularly limited.The example of free radical polymerization monomer (b1) with epoxy radicals is (methyl) glycidyl acrylate and (methyl) acrylic acid methylglycidyl esters.Use the polymer (Bc) containing epoxy radicals Photosensitive composite can form small pattern, and the chemically-resistant of the pattern-like transparent body manufactured using the photosensitive composite Moral character is high, therefore preferably, the polymer (Bc) containing epoxy radicals is to make in these free radical polymerization monomers extremely Few one kind polymerize and obtained.
Particularly if using by least one in glycidyl acrylate and GMA The polymer (Bc) containing epoxy radicals of copolymerization is planted as the free radical polymerization monomer (b1) with epoxy radicals, then it is heat-resisting Property is uprised, therefore more preferably.
Free radical polymerization monomer (b1) with epoxy radicals can be used alone, and can also be used in mixed way two or more.
<Other free radical polymerization monomers (b2) of 1-2-3-2.>
With other free radical polymerization monomers (b2) of free radical polymerization monomer (b1) copolymerization with epoxy radicals as long as It is not have carboxyl, epoxy radicals and oxetanylmethoxy, and can be with free radical polymerization monomer (b1) copolymerization with epoxy radicals Free radical polymerization monomer, then be not particularly limited.The example of such a free radical polymerization monomer can be set forth in described with tool Have free radical polymerization monomer (a1) copolymerization of carboxyl other free radical polymerization monomers (a2) explanation in it is illustrated from By base polymerizable monomer.
In these monomers, the transparency of the pattern-like transparent body manufactured using photosensitive composite is high, and heat resistance is high, Therefore preferably, the photosensitive composite use will selected from (methyl) benzyl acrylate, (methyl) acrylic acid bicyclopentyl ester, In (methyl) acrylic acid dicyclopentenyl epoxide ethyl ester, N-phenylmaleimide and N- N-cyclohexylmaleimides at least A kind of copolymerization and the polymer (Bc) containing epoxy radicals obtained.
Other free radical polymerization monomers (b2) can be used alone the compound, can also be used in mixed way two or more.
<1-3. has the compound (C) of polymerism double bond>
The contained compound (C) with polymerism double bond in the photosensitive composite of the present invention is as long as with polymerism Double bond, then be not particularly limited.
The example of the contained compound (C) with polymerism double bond is ethylene glycol in the photosensitive composite of the present invention 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 ethylene glycol two (methyl) acrylate, table chlorine Alcohol is modified diethylene glycol two (methyl) acrylate, epichlorohydrin and is modified triethylene glycol two (methyl) acrylate, epichlorohydrin modification Tetraethylene glycol two (methyl) acrylate, epichlorohydrin modified poly (ethylene glycol) two (methyl) acrylate, propane diols two (methyl) third Olefin(e) acid ester, DPG two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, four propane diols two (methyl) propylene Acid esters, polypropylene glycol two (methyl) acrylate, epichlorohydrin are modified propane diols two (methyl) acrylate, epichlorohydrin and are modified dipropyl Glycol two (methyl) acrylate, epichlorohydrin are modified tripropylene glycol two (methyl) acrylate, epichlorohydrin and are modified four propane diols two (methyl) acrylate, epichlorohydrin are modified polypropylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylic acid Ester, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) Acrylate, epichlorohydrin are modified trimethylolpropane tris (methyl) acrylate, two-trimethylolpropane four (methyl) acrylic acid Ester, glyceryl acrylate methacrylate, glycerine two (methyl) acrylate, glycerine three (methyl) acrylate, epichlorohydrin Modified glycerol three (methyl) acrylate, 1,6- hexylene glycols two (methyl) acrylate, epichlorohydrin are modified the (first of 1,6- hexylene glycols two Base) acrylate, methoxylation cyclohexyl two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, hydroxyl spy penta It is sour neopentyl glycol two (methyl) acrylate, caprolactone modification 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, two sweet Oily four (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, stearic acid change Property pentaerythrite two (methyl) acrylate, dipentaerythritol five (methyl) acrylate, (first of alkyl-modified dipentaerythritol five Base) acrylate, alkyl-modified dipentaerythritol four (methyl) acrylate, alkyl-modified dipentaerythritol three (methyl) propylene Acid esters, dipentaerythritol six (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate, allylation Cyclohexyl two (methyl) acrylate, double [(methyl) acryloxy neopentyl glycol] adipate esters, bisphenol-A two (methyl) propylene Acid esters, ethylene-oxide-modified bisphenol-A two (methyl) acrylate, Bisphenol F two (methyl) acrylate, ethylene-oxide-modified bis-phenol F bis- (methyl) acrylate, bisphenol S two (methyl) acrylate, ethylene-oxide-modified bisphenol S two (methyl) acrylate, 1, 4- butanediols two (methyl) acrylate, 1,3-BDO (methyl) acrylate, bicyclopentyl diacrylate, oxirane Modified phosphate two (methyl) acrylate, ethylene-oxide-modified tricresyl phosphate (methyl) acrylate, ethylene-oxide-modified di(2-ethylhexyl)phosphate (methyl) acrylate, epichlorohydrin are modified phthalic acid two (methyl) acrylate, tetrabromobisphenol A two (methyl) acrylic acid Ester, triglycerin two (methyl) acrylate, neopentyl glycol are modified trimethylolpropane two (methyl) acrylate, isocyanuric acid ring The ethylene-oxide-modified triacrylate of oxidative ethane modified diacrylate, isocyanuric acid, [(methyl) acryloyl of caprolactone modification three Epoxide ethyl] isocyanuric acid ester, (methyl) acrylic isocyanuric acid ester, ω-carboxy-polycaprolactone list (methyl) acrylic acid Ester, phthalic acid monohydroxy ethyl propylene acid esters, succinate modified pentaerythritol triacrylate, orthophthalic modified season Penta tetrol triacrylate, succinate modified Dipentaerythritol Pentaacrylate, orthophthalic modified dipentaerythritol 5 third Olefin(e) acid ester, modified by polyacid acrylate oligomers, hydroquinones (methyl) acrylate, phenyl glycidyl ether acrylate/ Hexamethylene diisocyanate/carbamate prepolymer, phenyl glycidyl ether acrylate/toluene di-isocyanate(TDI)/ammonia Carbamate prepolymer, pentaerythritol triacrylate/hexamethylene diisocyanate/carbamate prepolymer, Ji Wusi Alcohol triacrylate/toluene di-isocyanate(TDI)/carbamate prepolymer, pentaerythritol triacrylate/isophorone two are different Cyanate/carbamate prepolymer, Dipentaerythritol Pentaacrylate/hexamethylene diisocyanate/carbamate are pre- Polymers, without xanthochromia type oligocarbamates acrylate, the urethane acrylate oligomer containing carboxylic acid, phenol novolac The acrylic acid modified thing of type epoxy resin and the acrylic acid modified thing of cresol novolak type epoxy resin.
Compound (C) with polymerism double bond can be used alone the compound, can also be used in mixed way two or more.
Trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, two seasons penta 4 The acrylate of alcohol five, dipentaerythritol acrylate, the ethylene-oxide-modified diacrylate of isocyanuric acid, isocyanuric acid epoxy Oxide-modified triacrylate or the mixture of these compounds, ω-carboxy-polycaprolactone list (methyl) acrylate, adjacent benzene Diformate mono hydroxyethylmethacry,ate, modified by polyacid acrylate oligomers, the propylene of phenol novolak type epoxy resin Commercially available product as described below can be used in the acrylic acid modified thing of acid modifier and cresol novolak type epoxy resin.Three hydroxyl first The concrete example of base propane triacrylate is Aronix (Aronix) M-309 (trade names；East Asia synthesizes limited company), A-TMPT (trade names；Chemistry limited company of Xin Zhong villages).Pentaerythritol triacrylate and tetramethylol methane tetraacrylate The concrete example of mixture be Aronix (Aronix) M-306 (65 weight %~70 weight %), Aronix (Aronix) M-305 (55 weight %~63 weight %), Aronix (Aronix) M-303 (30 weight %~60 weight %), Aronix (Aronix) M-452 (25 weight %~40 weight %) and Aronix (Aronix) M-450 (less than 10 weight %) (are Trade name；East Asia synthesizes limited company, and the containing ratio in bracket is containing for the pentaerythritol triacrylate in mixture Have the catalogue record value of rate), A-TMM-3L (55 weight %), A-TMM-3LA (57 weight %), A-TMMT (be trade name；Newly Containing ratio in chemical limited company of middle village, bracket is the mesh of the containing ratio of the pentaerythritol triacrylate in mixture Record record value).The concrete example of the mixture of Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate is Ya Luoni This (Aronix) M-403 (50 weight %~60 weight %), Aronix (Aronix) M-400 (weights of 40 weight %~50 Measure %), Aronix (Aronix) M-402 (30 weight %~40 weight %), Aronix (Aronix) M-404 (30 weights Measure the weight % of %~40), Aronix (Aronix) M-406 (25 weight %~35 weight %) and Aronix (Aronix) M-405 (10 weight %~20 weight %) (is trade name；The containing ratio that East Asia is synthesized in limited company, bracket is mixed The catalogue record value of the containing ratio of Dipentaerythritol Pentaacrylate in compound)；Dipentaerythritol acrylate it is specific Example is A-DPH (trade names；Limited company of Xin Zhong villages).The concrete example of the ethylene-oxide-modified diacrylate of isocyanuric acid is Aronix (Aronix) M-215 (trade names；East Asia synthesizes limited company).Ethylene-oxide-modified three propylene of isocyanuric acid The concrete example of acid esters is A-9300 (trade names；Chemistry limited company of Xin Zhong villages).The ethylene-oxide-modified dipropyl of isocyanuric acid The concrete example of the mixture of olefin(e) acid ester and the ethylene-oxide-modified triacrylate of isocyanuric acid is Aronix (Aronix) M-313 (30 weight %~40 weight %) and Aronix (Aronix) M-315 (3 weight %~13 weight %) (are trade name；East Containing ratio in Asia synthesis limited company, bracket is the ethylene-oxide-modified diacrylate of isocyanuric acid in mixture The catalogue record value of containing ratio).The concrete example of ω-carboxy-polycaprolactone mono acrylic ester is Aronix (Aronix) M-5300 (trade name；East Asia synthesizes limited company).The concrete example of phthalic acid monohydroxy ethyl propylene acid esters is Aronix (Aronix) M-5400 (trade names；East Asia synthesizes limited company).The concrete example of modified by polyacid acrylate oligomers is M-510 (trade names；East Asia synthesizes limited company) and M-520 (trade names；East Asia synthesizes limited company).Phenol The concrete example of the acrylic acid modified thing of phenolic resin varnish type epoxy resin is TEA-100 (trade names；KSM limited companies).First The concrete example of the acrylic acid modified thing of phenol phenolic resin varnish type epoxy resin is CNEA-100 (trade names；KSM limited companies).
<1-4. Photoepolymerizationinitiater initiaters (D)>
Contained Photoepolymerizationinitiater initiater (D) in the photosensitive composite of the present invention is if can trigger poly- containing alkali-soluble The composition of compound (A), epoxide (B), the compound (C) with polymerism double bond and molecular weight regulator (E) it is poly- Close, be then not particularly limited.
As Photoepolymerizationinitiater initiater contained in the photosensitive composite of the present invention, it can enumerate：Benzophenone, Michaelis Ketone, 4,4 '-bis- (diethylamino) benzophenone, xanthone, thioxanthones, isopropyl xanthone, 2,4- diethyl thioxanthenes Ketone, 2- EAQs, acetophenone, 2- hydroxy-2-methyls propiophenone, 2- hydroxy-2-methyls -4 '-cumene acetone, 1- hydroxyls Cyclohexyl-phenyl ketone, isopropyl benzoin ether, isobutyl group benzoin ether, 2,2- diethoxy acetophenones, 2,2- dimethoxys -2- Phenyl acetophenone, camphorquinone, benzanthrone, 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholino propane -1- ketone are (such as gorgeous Good solid (IRGACURE) 907；Trade name；Japanese BASF (BASF Japan) limited company), 2- benzyl -2- dimethyl Amino -1- (4- morphlinophenyls)-butanone -1 (such as gorgeous good solid (IRGACURE) 369；Trade name；Japanese BASF (BASF Japan) limited company), EDMAB, 4- dimethylaminobenzoic acids isopentyl ester, 4,4 '-two (t-butylperoxycarbonyl) benzophenone, 3,4,4 '-three (t-butylperoxycarbonyl) benzophenone, 1,2- octadione- 1- [4- (thiophenyl) phenyl] -2- (O- benzoyl oximes) (such as gorgeous good solid (IRGACURE) OXE-01；Trade name；Japanese Bath Husband (BASF Japan) limited company), ethyl ketone, 1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -, 1- (O- acetyl group oxime) (such as gorgeous good solid (IRGACURE) OXE-02；Trade name；Japanese BASF (BASF Japan) share has Limit company), OXE-03 (trade names；Japanese BASF (BASF Japan) limited company), 1- (O- acetyl group oxime), 1,2- Propanedione -1- [4- [4- (2- hydroxyl-oxethyls) thiophenyl] phenyl] -2- (O- acetyl group oxime), 2,4,6- trimethylbenzoyls Diphenyl phosphine oxide, 2- (4 '-methoxyl-styrene) -4,6- double (trichloromethyl)-s-triazine, 2- (3 ', 4 '-dimethoxys Styryl) -4,6- pairs of (trichloromethyl)-s-triazine, double (three chloromethanes of 2- (2 ', 4 '-dimethoxy-styryl) -4,6- Base)-s-triazine, 2- (2 '-methoxyl-styrene) -4,6- double (trichloromethyl)-s-triazine, 2- (4 '-amyl phenyl ether ethene Base) -4,6- couples of (trichloromethyl)-s-triazine, 4- [p- N, N- bis- (ethoxy carbonyl methyl)] -2,6- bis- (trichloromethyl)-equal Double (trichloromethyl) -5- (2 '-chlorphenyl)-s-triazine of triazine, 1,3-, double (trichloromethyl) -5- (4 '-methoxybenzenes of 1,3- Base)-s-triazine, 2- (to dimethylaminostyryl) benzoxazoles, 2- (to dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3 '-carbonyl double (7- diethyl amino coumarins), 2- (Chloro-O-Phenyl) -4,4 ', 5,5 '-tetraphenyl - 1,2 '-bisglyoxaline, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (4- carboethoxyphenyls) -1,2 '-bisglyoxaline, 2, 2 '-bis- (2,4- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 2,2 '-bis- (2,4- dibromo phenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 2,2 '-bis- (2,4,6- trichlorophenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, Double (2- methyl -2- morpholinoes the propiono) -9- of 3- (2- methyl -2- dimethylaminos propiono) carbazole (carbazole), 3,6- Dodecyl carbazole, 1- hydroxycyclohexylphenylketones, double (η5- 2,4- cyclopentadiene -1- bases)-bis- (2,6- bis- fluoro- 3- (1H- Pyrroles -1- bases)-phenyl) titanium, N-1919, NCI-831 and NCI-930 (be trade name；Ai Dike (ADEKA) share is limited Company) etc..
Photoepolymerizationinitiater initiater can be used alone, and can also be used in mixed way two or more.In Photoepolymerizationinitiater initiater, if α- Aminoalkylphenones system, acylphosphine oxide system, oxime ester system Photoepolymerizationinitiater initiater, then sensitivity from film, the pattern-like transparent body From the viewpoint of the transparency and it is preferred that.
In Photoepolymerizationinitiater initiater, if oxime ester system's Photoepolymerizationinitiater initiater is 20 weights relative to the gross weight of Photoepolymerizationinitiater initiater Measure from the viewpoint of more than %, then sensitivity from film, the transparency of the pattern-like transparent body and more preferably.Moreover, if 50 More than weight %, then further preferably.Photoepolymerizationinitiater initiater also can only include oxime ester system Photoepolymerizationinitiater initiater.
<1-5. molecular weight regulator (E)>
Uprise to suppress the molecular weight because of polymerization and show excellent analyticity, in photosensitive composite of the invention Use molecular weight regulator.As molecular weight regulator, it can enumerate：Thio-alcohol, xanthan acids, quinones and 2,4- diphenyl -4- Methyl-1-pentene etc..As the molecular weight regulator of quinones, naphthoquinones class can be enumerated.
As the concrete example of molecular weight regulator, it can enumerate：HNQ, benzoquinones, 1,4-naphthoquinone, Isosorbide-5-Nitrae-two Hydroxyl naphthoquinone, 2,5- di-t-butyls quinhydrones, quinhydrones, methylnaphthohydroquinone, tertiary butylated hydroquinone, first quinone (methoquinone), to benzene Quinone, methyl -1,4-benzoquinone, tert-butyl-p-benzo-quinone, anthraquinone, n-hexyl mercaptan, n octylmercaptan, positive dodecylmercaptan, tertiary dodecyl Mercaptan, thioglycolic acid, dimethyl yellow ortho acid thioether, diisopropyl xanthic acid thioether, 2,4- diphenyl -4-methyl-1-pentene Deng.
Molecular weight regulator can be used alone, and can also be applied in combination two or more.In molecular weight regulator, if naphthalene The molecular weight regulator of quinones, then from from the aspect of showing excellent analyticity and it is preferred that.
In the molecular weight regulator of naphthoquinones class, if the HNQ with phenolic hydroxyl group, then self-analytic data From the viewpoint of and more preferably.Moreover, from the viewpoint of self-analytic data, be preferably more than with the weight of Photoepolymerizationinitiater initiater and divided Son measures 5.0 times of the weight of regulator and contains molecular weight regulator for less than 20 times of mode, more preferably with photopolymerization The weight of initiator is more than 5.0 times of the weight of molecular weight regulator and contains molecular weight regulator for less than 15 times of mode. Even more preferably with the weight of Photoepolymerizationinitiater initiater more than 5.0 times of the weight of molecular weight regulator and for less than 10 times Mode contain molecular weight regulator.
<1-6. solvents (F)>
Solvent (F) preferably boiling point used in the present invention is at least one of 100 DEG C~200 DEG C of compound or contained There is the mixed solvent of more than 20 weight % compounds.Boiling point is water, acetic acid fourth for the example of 100 DEG C~200 DEG C of compound Ester, butyl propionate, ethyl lactate, ethoxyacetic acid methyl esters, ethoxyacetic acid ethyl ester, ethoxyacetic acid butyl ester, methoxy menthyl acetate, first Ethoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, acetic acid 3- methoxybutyls, 3- Epoxide methyl propionate, 3- epoxides ethyl propionate, 3- methoxy methyl propionates (hereinafter sometimes referred to simply as " MMP "), 3- methoxy propyls Acetoacetic ester, 3- ethoxypropanoates, 3- ethoxyl ethyl propionates, 2- epoxides methyl propionate, 2- epoxides ethyl propionate, 2- epoxides Propyl propionate, 2- methoxy methyl propionates, 2- methoxypropionates, 2- methoxy propyls propyl propionate, 2- ethoxypropanoates, 2- ethoxyl ethyl propionates, 2- epoxides -2 Methylpropionic acid methyl esters, 2- epoxides -2 Methylpropionic acid ethyl ester, 2- methoxyl group -2- methyl Methyl propionate, 2- ethyoxyls -2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, acetoacetate first Ester, ethyl acetoacetate, 2-Oxobutyric acid methyl esters, 2-Oxobutyric acid ethyl ester, dioxanes, ethylene glycol, diethylene glycol, three second two Alcohol, propane diols, DPG, tripropylene glycol, BDO, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propane diols list first Ether, propylene glycol methyl ether acetate (hereinafter sometimes referred to simply as " PGMEA "), 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 monomethyl ether acetic acid esters, Diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether, butyl carbitol acetate, diethyl Glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether (hereinafter sometimes referred to simply as " EDM "), toluene, diformazan Benzene, gamma-butyrolacton and DMA.
In these solvents, if using selected from propylene glycol monomethyl ether, PGMEA, propylene glycol monoethyl ether acetate, 3- methoxyl groups Methyl propionate, 3- ethoxyl ethyl propionates, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, diethylene glycol At least one in dimethyl ether, diethylene glycol methyl ethyl ether and ethyl lactate, then be coated with homogeneity and uprise, therefore more preferably. If using selected from PGMEA, 3- methoxy methyl propionate, 3- ethoxyl ethyl propionates, diethylene glycol methyl ethyl ether and lactic acid At least one in ethyl ester, then the coating homogeneity of photosensitive composite uprise, the security to human body is uprised, therefore further More preferably.
Solvent (F) can be made in the polymerisation of the polymer (Bc) by alkali-soluble polymer (A) or containing epoxy radicals Solvent is made solution and is directly used in photosensitive composite, can also add in addition to solvent contained in the solution Enter dilution solvent (solid component concentration adjustment solvent).Moreover, on the polymer, after it will only concentrate polymerisation Solution and in the case that the solid constituent that is taken out is used in photosensitive composite, system of the solvent (F) in photosensitive composite When standby its whole amount is together added with composition (A)~(E).
<1-7. additives>
Improved from the characteristic for the photosensitive composite for making the present invention such as resolution, coating homogeneity, developability, cementability Viewpoint considers that photosensitive composite of the invention can also contain additive.The example of additive is acrylic acid series, styrene The macromolecule dispersing agents such as system, polyethyleneimine amine system and carbamate system；Anion system, cation system, nonionic system and fluorine system Deng surfactant；Silicon polymer system coating elevator；The adhesion elevator such as silane series coupling agent and aluminium system coupling agent；1, The light acid producing agent such as 2- quinone di-azido compounds；The ultra-violet absorbers such as alkoxy benzophenone class；Sodium Polyacrylate etc. is anti-condensation Poly- agent；The thermal cross-linking agents such as cyclic ether compound, melamine compound and double azido compound beyond epoxide (B)； Carboxyl compound, carboxylic acid anhydrides beyond alkali-soluble polymer (A), the compound containing phenolic hydroxyl group, amine compound, imidazoles system The epoxy curing agents such as compound, catalyst-based compound；And it is the antioxidants such as phenol to be obstructed.
If the total amount of whole additives is relative to alkali-soluble polymer (A), epoxide (B), with poly- It is 10 for total 100 parts by weight of the conjunction property compound (C) of double bond, Photoepolymerizationinitiater initiater (D) and molecular weight regulator (E) Below parts by weight, then improve can with not undermining the purpose of the present invention characteristic of photosensitive composite, therefore preferably.
From from the viewpoint of improving to the wetability of basal substrate, levelability or coating, photosensitive composition of the invention Macromolecule dispersing agent, surfactant, coating elevator can also be contained.
Macromolecule dispersing agent, surfactant, the concrete example of coating elevator can enumerate Pohle not Lip river (Polyflow) No.45, Pohle not Lip river (Polyflow) KL-245, Pohle not Lip river (Polyflow) No.75, Pohle not Lip river (Polyflow) Not Lip river (Polyflow) No.95 (is trade name above for No.90, Pohle；Chemical industry limited company of common prosperity society), Di Si Pa Bike (Disperbyk) 161, Di Sipabike (Disperbyk) 162, Di Sipabike (Disperbyk) 163, Di Sipa Bi Ke (Disperbyk) 164, Di Sipabike (Disperbyk) 166, Di Sipabike (Disperbyk) 170, Di Sipabi Gram (Disperbyk) 180, Di Sipabike (Disperbyk) 181, Di Sipabike (Disperbyk) 182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346 (are trade name above；Japanese Bi Ke chemistry (BYK Chemie Japan) limited company), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (trade name is above；Shin-Estu Chemical Co., Ltd), Sha Fulong (Surflon) SC-101, Sha Fulong (Surflon) KH-40, Sha Fulong (Surflon) S-611 (is trade name above；AGC beautifies clearly (AGC Seimi Chemical) limited 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) 602A, Fu Jite (Ftergent) 650A, DFX-18, FTX-218 (is trade name above；Ni Aosi (Neos) limited company), Ai Futuo (EFTOP) EF-351, Ai Futuo (EFTOP) EF-352, Ai Futuo (EFTOP) EF-601, Ai Futuo (EFTOP) EF-801, Ai Futuo (EFTOP) EF-802 (with On be trade name；Mitsubishi Materials (Mitsubishi Material) limited company), Mei Jiafa (Megafac) F-171, Mei Jiafa (Megafac) F-177, 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- 477th, 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- 559th, Mei Jiafa (Megafac) R-08, Mei Jiafa (Megafac) R-30, Mei Jiafa (Megafac) R-94, Mei Jiafa (Megafac) RS-75, Mei Jiafa (Megafac) RS-72-K, Mei Jiafa (Megafac) RS-76-NS, Mei Jiafa (Megafac) DS-21 (is trade name above；DIC (DIC) limited company), Tai Gaotun (TEGO Twin) 4000, Tai Gaotun (TEGO Twin) 4100, Tai Gaofuluo (TEGO Flow) 370, the suitable moral (TEGO Glide) 420 of platform height leather, the suitable moral of platform height leather (TEGO Glide) 440, the suitable moral (TEGO Glide) 450 of platform height leather, the high rad of platform (TEGO Rad) 2200N, the high rad of platform (TEGORad) 2250N (is trade name above；Japan wins the wound limited public affairs of Degussa (Evonik-Degussa Japan) share Department), fluoroalkyl benzene sulfonate, fl muoroalkyl's salt, fluoroalkyl APEO, fluoroalkyl ammonium iodide, fluoroalkyl glycine betaine, fluorine Alkylsulfonate, two glycerine four (fluoroalkyl APEO), fluoroalkyl leptodactyline, fluoroalkyl sulfamate, polyoxy Ethene nonylplenyl ether, NONIN HS 240, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oil Alkene ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl base ether, polyoxyethylene stearyl base ether, polyoxyethylene laurate, Polyoxyethylene oleate, Myrj 45, polyoxyethylene laural base amine, sorbitan laurate, D-sorbite Acid anhydride palmitate, sorbitan stearate, sorbitol anhydride oleate, sorbitan fatty acid ester, polyoxyethylene mountain Pears sugar alcohol acid anhydride laurate, polyoxyethylene sorbitol acid anhydride palmitate, polyoxyethylene sorbitol acid anhydride stearate, polyoxy second Alkene sorbitol anhydride oleate, polyoxyethylene naphthyl ether, alkylbenzenesulfonate or alkyl diphenyl base ether disulfonate.
From from the viewpoint of being improved the adhesion for making the pattern-like transparent body and substrate, photosensitive composition of the invention can be with Contain adhesion elevator.
The coupling agents such as silane series coupling agent, aluminium system coupling agent, titanate esters system coupling agent can be used in adhesion elevator.Silane The concrete example for being coupling agent is 3- glycidoxypropyls dimethylethoxysilane, 3- glycidoxypropyls two Ethoxysilane, 3- glycidoxypropyltrimewasxysilanes and 3- glycidoxypropyltrimewasxysilanes (3- Glycidoxy propyl trimethoxy silane) copolymer (such as trade name：Can Te Ouxier (CoatOSil) MP200, figure new high-tech material (Momentive Performance Materials) limited company advanced in years).Aluminium system coupling agent Concrete example is acetyl alkoxy aluminum-diisopropoxide.The concrete example of titanate esters system coupling agent is the double (dioctyl phosphitos of tetra isopropyl Ester) titanate esters.
From from the viewpoint of improving analyticity, photosensitive composition of the invention can also contain light acid producing agent.Light acid production 1,2- quinone di-azido compounds can be used in raw agent.
The concrete example of 1,2- quinone di-azido compound is the nitrine -4- sulphurs of 2,3,4- trihydroxybenzophenone -1,2- naphthoquinones two Acid esters, 2, the nitrine -5- sulphonic acid esters of 3,4- trihydroxybenzophenone -1,2- naphthoquinones two, 2,4,6- trihydroxybenzophenone -1,2- naphthalenes Nitrine -4- the sulphonic acid esters of quinone two, the nitrine -5- sulphonic acid esters of 2,4,6- trihydroxybenzophenone -1,2- naphthoquinones two；2,2 ', 4,4 '-four hydroxyls Base BP-1, the nitrine -4- sulphonic acid esters of 2- naphthoquinones two, 2,2 ', 4, the nitrine -5- of 4 '-tetrahydroxybenzophenone -1,2- naphthoquinones two Sulphonic acid ester, 2,3, the nitrine -4- sulphonic acid esters of 3 ', 4- tetrahydroxybenzophenones -1,2- naphthoquinones two, 2,3,3 ', 4- tetrahydroxy hexichol first Nitrine -5- the sulphonic acid esters of ketone -1,2- naphthoquinones two, 2,3,4, the nitrine -4- sulphonic acid esters of 4 '-tetrahydroxybenzophenone -1,2- naphthoquinones two, 2, 3,4, the nitrine -5- sulphonic acid esters of 4 '-tetrahydroxybenzophenone -1,2- naphthoquinones two；Double (2,4- dihydroxy phenyl) methane -1,2- naphthoquinones Two nitrine -4- sulphonic acid esters, double nitrine -5- sulphonic acid esters of (2,4- dihydroxy phenyl) methane -1,2- naphthoquinones two, double (p-hydroxybenzenes) Nitrine -4- the sulphonic acid esters of methane -1,2- naphthoquinones two, the nitrine -5- sulphonic acid esters of double (p-hydroxybenzene) methane -1,2- naphthoquinones two；Three is (right Hydroxy phenyl) two nitrine -4- sulphonic acid esters of methane -1,2- naphthoquinones, the nitrine -5- sulphurs of three (p-hydroxybenzene) methane -1,2- naphthoquinones two Acid esters, 1, the nitrine -4- sulphonic acid esters of 1,1- tri- (p-hydroxybenzene) ethane -1,2- naphthoquinones two, 1,1,1- tri- (p-hydroxybenzene) second Nitrine -5- the sulphonic acid esters of alkane -1,2- naphthoquinones two；Double nitrine -4- sulphonic acid esters of (2,3,4- trihydroxy phenyl) methane -1,2- naphthoquinones two, Double (2,3, the 4- trihydroxy phenyl) third of double nitrine -5- sulphonic acid esters of (2,3,4- trihydroxy phenyl) methane -1,2- naphthoquinones two, 2,2- Double nitrine -5- the sulfonic acid of (2,3,4- trihydroxy phenyl) propane -1,2- naphthoquinones two of the nitrine -4- sulphonic acid esters of alkane -1,2- naphthoquinones two, 2,2- Ester；Nitrine -4- the sulphonic acid esters of 1,1,3- tri- (2,5- dimethyl -4- hydroxy phenyls) -3- phenyl-propanes -1,2- naphthoquinones two, 1,1,3- Nitrine -5- the sulphonic acid esters of three (2,5- dimethyl -4- hydroxy phenyls) -3- phenyl-propanes -1,2- naphthoquinones two, 4,4 '-[1- [4- [1- [4- hydroxy phenyls] -1- Methylethyls] phenyl] ethylidene] two nitrine -4- sulphonic acid esters of bis-phenol -1,2- naphthoquinones, 4,4 '-[1- [4- [1- [4- hydroxy phenyls] -1- Methylethyls] phenyl] ethylidene] two nitrine -5- sulphonic acid esters of bis-phenol -1,2- naphthoquinones；Double (2,5- bis- Methyl -4- hydroxy phenyls) two nitrine -4- sulphonic acid esters of -2- hydroxy phenyl methane -1,2- naphthoquinones, double (2,5- dimethyl -4- hydroxyls Phenyl) two nitrine -5- sulphonic acid esters of -2- hydroxy phenyl methane -1,2- naphthoquinones, 3,3,3 ', 3 '-tetramethyl -1,1 '-spirobindene -5, 6,7, the nitrine -4- sulphonic acid esters of 5 ', 6 ', 7 '-hexanol -1,2- naphthoquinones two, 3,3,3 ', 3 '-tetramethyl -1,1 '-spirobindene -5,6,7, Nitrine -5- the sulphonic acid esters of 5 ', 6 ', 7 '-hexanol -1,2- naphthoquinones two；2,2,4- trimethyl -7,2 ', 4 '-trihydroxy flavane -1,2- naphthalene Nitrine -4- the sulphonic acid esters of quinone two and 2,2,4- trimethyl -7, the nitrine -5- sulphonic acid esters of 2 ', 4 '-trihydroxy flavane -1,2- naphthoquinones two.
From from the viewpoint of the further degradation inhibiting ability for improving formed pattern-like hyaline membrane, of the invention is photosensitive Property composition can also contain ultra-violet absorber.
The concrete example of ultra-violet absorber is that refined (TINUVIN) P of Supreme Being slave, refined (TINUVIN) 120 of Supreme Being slave, Supreme Being slave are refined (TINUVIN) 144, refined (TINUVIN) 213 of Supreme Being slave, refined (TINUVIN) 234 of Supreme Being slave, refined (TINUVIN) 326 of Supreme Being slave, Supreme Being slave are refined (TINUVIN) 571, Supreme Being slave refined (TINUVIN) 765 (is trade name, the limited public affairs of Japanese BASF (BASF Japan) share Department).
From not making solid constituent be merged with solvent, prevent cohesion from the viewpoint of, photosensitive composite of the invention may be used also To contain anti-flocculating agent.
The concrete example of anti-flocculating agent be Di Sipabike (DISPERBYK) -145, Di Sipabike (DISPERBYK) - 161st, 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, BYK- 220S, Di Sipabike (DISPERBYK) -191, Di Sipabike (DISPERBYK) -199, Di Sipabike (DISPERBYK) -2015 (being chemical (the BYK Chemie Japan) limited company of trade name, Japan Bi Ke), FTX- 218th, (be trade name, Ni Aosi (Neos) share has Fu Jite (Ftergent) 710FM, Fu Jite (Ftergent) 710FS Limit company), Fu Luolun (Flowlen) G-600, Fu Luolun (Flowlen) G-700 (be trade name, common prosperity society chemical industry stock Part Co., Ltd).
Examined from further heat resistance, chemical-resistant, film inner evenness, flexibility, flexibility, the viewpoint of elasticity of improving Consider, photosensitive composite of the invention can also contain thermal cross-linking agent.
The concrete example of thermal cross-linking agent be Ni Kalake (Nikalac) MW-30HM, Ni Kalake (Nikalac) MW-100LM, Ni Kalake (Nikalac) MW-270, Ni Kalake (Nikalac) MW-280, Ni Kalake (Nikalac) MW-290, Buddhist nun's card Clarke (Nikalac) MW-390, Ni Kalake (Nikalac) MW-750LM (is trade name, three and the chemical limited public affairs of share Department).
From from the viewpoint of further raising planarization characteristics, chemical-resistant, photosensitive composite of the invention may be used also To contain epoxy curing agent.
The concrete example of epoxy curing agent is maleic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methyl six Hydrogen phthalic anhydride, hexahydro trimellitic anhydride, phthalic anhydride, trimellitic anhydride etc., 2- undecyl imidazoles, 2- Heptadecyl imidazole, 2- phenylimidazoles, 2- phenyl -4-methylimidazole, 2,3- dihydro -1H- pyrrolo-es [1,2-a] benzimidazole, 1- cyanoethyl -2- undecyl imidazoles end trimellitate.
From the viewpoint of picking up by oneself high transparency, preventing cured film exposure xanthochromia in the event of high temperatures, sense of the invention Photosensitiveness composition can also contain antioxidant.
It is the antioxidants such as phenol as being obstructed, can also be further using such as there is the tert-butyl group at the OH of phenol ortho position Compound with substituents such as alkyl, and the compound being bonded via the divalent organic base of contraposition in contraposition Known compound as dimer~tetramer.The example of commercially available product is Ai Di Coase tower ripple (Adekastab) AO-60 (trade name；Ai Dike (ADEKA) limited company).
<The manufacture method of 1-8. alkali-solubles polymer (A) or polymer (Bc) containing epoxy radicals>
The polymerization of alkali-soluble polymer (A) or polymer (Bc) containing epoxy radicals is not particularly limited, preferably Radical polymerization in the solution using solvent.Polymerization temperature by used polymerization initiator if fully trigger freedom The temperature of base, then be not particularly limited, typically 50 DEG C~150 DEG C of scope.Polymerization time is also not particularly limited, and typically 1 Hour~scope of 24 hours.Moreover, the polymerization can be carried out under any pressure of pressurization, decompression or atmospheric pressure.
<Used in the polymerisation of 1-8-1. alkali-solubles polymer (A) or polymer (Bc) containing epoxy radicals Solvent>
Solvent used in the polymerisation of alkali-soluble polymer (A) is preferably to have carboxyl used in dissolving Free radical polymerization monomer (a1), other free radical polymerization monomers (a2) and the alkali-soluble polymer (A) that is generated it is molten Agent.Solvent used in the polymerisation of polymer (Bc) containing epoxy radicals is preferably to have epoxy radicals used in dissolving Free radical polymerization monomer (b1), other free radical polymerization monomers (b2) and the polymer containing epoxy radicals generated (Bc) solvent.Hereinafter, the solvent used in polymerisation is referred to as " polymer solvent " sometimes.
The tool of solvent used in the polymerisation of alkali-soluble polymer (A) or polymer (Bc) containing epoxy radicals Style be methanol, ethanol, 1- propyl alcohol, 2- propyl alcohol, acetone, 2- butanone, ethyl acetate, propyl acetate, 3- methoxyacetic acids butyl ester, Tetrahydrofuran, acetonitrile, dioxanes, toluene, dimethylbenzene, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, PGMEA, diethylene glycol diformazan Ether, diethylene glycol methyl ethyl ether, 3- methoxy methyl propionates, 3- ethoxyl ethyl propionates, cyclopentanone, cyclohexanone, N- methyl- 2-Pyrrolidone and DMF.Polymer solvent can be used alone, and can also be used in mixed way two or more.
In these solvents, preferably propylene glycol monomethyl ether, PGMEA, 3- methoxy methyl propionate and diethylene glycol Methylethyl Ether.
<Used in the polymerisation of 1-8-2. alkali-solubles polymer (A) or polymer (Bc) containing epoxy radicals Polymerization initiator>
Known polymerization can be used to draw in the polymerization of alkali-soluble polymer (A) or polymer (Bc) containing epoxy radicals Send out agent.Polymerization initiator used in polymerization on the alkali-soluble polymer (A) used in the present invention and contain ring Polymerization initiator used in the polymerization of the polymer (Bc) of epoxide, uses compound, the azo that free radical is produced from Yin Re At least oneization suitably selected in the peroxide series initiators such as the azo such as bis-isobutyronitrile series initiators and benzoyl peroxide Compound.In the Raolical polymerizable, in order to adjust generated alkali-soluble polymer (A) and containing epoxy radicals The molecular weight of polymer (Bc), can also add the chain-transferring agents such as appropriate thioglycolic acid.
<The weight average molecular weight of 1-8-3. alkali-solubles polymer (A) or polymer (Bc) containing epoxy radicals>
The weight average molecular weight of the alkali-soluble polymer (A) of gained or the polymer (Bc) containing epoxy radicals is preferably 1,000~100,000, more preferably 2,000~30,000.If the thickness homogeneity after these scopes, coating is entered One step becomes good.
Weight average molecular weight in this specification is by gel permeation chromatography (Gel Permeation Chromatography, GPC) method (tubing string temperature：35 DEG C, flow velocity：Being converted with polystyrene basis calculated by 1mL/min) Value.The polystyrene of standard is using polystyrene (such as Agilent (Agilent) S- that molecular weight is 645~132,900 M2-10 polystyrene calibrations are set with (calibration kit) PL2010-0102 (trade names；Agilent Technologies (Agilent Technologies) limited company)), tubing string is to use PLgel MIXED-D (trade names；Agilent Technologies (Agilent Technologies) limited company), tetrahydrofuran (Tetrahydrofuran, THF) can be used to come as mobile phase It is measured.Furthermore, the weight average molecular weight of the commercially available product in this specification is catalogue record value.
<2. the pattern-like transparent body manufactured using the photosensitive composite of the present invention>
The pattern-like that the 2nd embodiment of the present invention is related to a kind of photosensitive composite using the present invention and manufactured is transparent Body.The photosensitive composite of the present invention is coated on the substrates such as glass, solvent is removed for example, by heating etc., then can shape Into film.The example of substrate is the transparent glass substrates such as blank glass, blue or green glass sheet and the blue or green glass sheet of silica dioxide coating, is gathered Carbonic ester, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamidoimide and polyimides etc. Synthetic resin sheet, film or substrate, the metal substrate such as aluminium sheet, copper coin, nickel plate and stainless steel plate, other ceramic wafers, and tool There is the semiconductor substrate of photo-electric conversion element.Optionally these substrates can be carried out the chemical treatments such as silane coupler, etc. Gas ions processing, ion plating, sputtering, gas-phase reaction method and vacuum evaporation etc. are pre-processed.Using spin-coating method, rolling method and leaching The existing known method such as stain method and photosensitive polymer combination is coated on substrate.Secondly, heating plate (hot is utilized ) or baking oven (oven) etc. is heated (prebake conditions) to the film plate.Heating condition is regarded because of the species of each composition and allotment ratio Example and it is different, generally at 70 DEG C~150 DEG C, if baking oven is used be 5 minutes~15 minutes, if heating plate is used be 1 Minute~5 minutes.
Then, it is situated between every the mask with desired pattern to film irradiation ultraviolet radiation.Ultraviolet irradiation amount is with i radiation meters It is suitably 5mJ/cm2~1000mJ/cm2.The photosensitive composite irradiated through ultraviolet passes through the compound with polymerism double bond (C) be polymerized as three dimensional stress crosslinked, becomes insoluble relative to alkaline-based developer.
Secondly, using spray development, spray development, covering liquid development, immersion development etc., film is dipped in alkaline-based developer In, it is partly dissolved removing by unwanted.The concrete example of alkaline-based developer is sodium carbonate, sodium acid carbonate, NaOH, hydroxide The aqueous solution of the inorganic base of potassium etc., and the organic bases such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide the aqueous solution.And And, methanol, ethanol and surfactant of appropriate amount etc. can also be added in the alkaline-based developer and used.Finally, it is Make the film fully hardened and the calcining of 10 minutes~120 minutes is carried out at 150 DEG C~250 DEG C, then can obtain desired figure The pattern-like transparent body of case.
[embodiment]
Secondly, the present invention is added a concrete explanation by synthesis example, embodiment and comparative example, but the present invention not by These embodiments are any to be limited.
The synthesis of [synthesis example 1] alkali-soluble polymer solution (A-1)
In the four-hole boiling flask with mixer, load 3- methoxy methyl propionates (hereinafter referred to as with following compositions " MMP "), the methacrylic acid as composition (a1), the benzyl methacrylate as composition (a2) and N- cyclohexyl Malaysia Acid imide, as polymerization initiator double (isobutyric acid) dimethyl esters of 2,2- azos (hereinafter referred to as " V-601 ".V-601 is commodity Name；With Wako Pure Chemical Industries limited company), carry out heating for 3 hours at 110 DEG C.
The solution reacted after terminating is cooled to room temperature, 25.0 weight % solution of alkali-soluble polymer (A-1) are obtained. The weight average molecular weight obtained using gpc analysis is 3,100.
Furthermore, so-called herein " 25.0 weight % solution of alkali-soluble polymer (A-1) " are represented as described above The compound of loading is considered as the concentration converted by the weight of solid constituent and the weight of solvent reacted and obtained completely 25.0 weight %.
The synthesis of [synthesis example 2] alkali-soluble polymer solution (A-2)
In the four-hole boiling flask with mixer, load 3- methoxy methyl propionates (hereinafter referred to as with following compositions " MMP "), the methacrylic acid as composition (a1), methacrylic acid dicyclopentenyl ester and N- cyclohexyl as composition (a2) Maleimide, as polymerization initiator double (isobutyric acid) dimethyl esters of 2,2- azos (hereinafter referred to as " V-601 ".V-601 is Trade name；With Wako Pure Chemical Industries limited company), carry out heating for 3 hours at 110 DEG C.
The solution reacted after terminating is cooled to room temperature, 25.0 weight % solution of alkali-soluble polymer (A-2) are obtained. The weight average molecular weight obtained using gpc analysis is 3,300.
[embodiment 1]
Detachable flask to the 500ml with agitator carries out nitrogen displacement, and 157.3g is mixed in the flask and is closed Into in example 1 gained alkali-soluble polymer solution (A-1), 47.2g as the compound (C) with polymerism double bond M- 520th, 4.72g makees as OXE-01,27.5g of Photoepolymerizationinitiater initiater (D) as VG3101L, 0.79g of epoxide (B) For molecular weight regulator (E) HNQ, be respectively 55.8g, 105.2g being taken off as retarder thinner The diethylene glycol methyl ethyl ether (hereinafter referred to as " EDM ") and MMP of water purifying, and 3hr stirrings are carried out at room temperature, make its equal Dissolve on one ground.Secondly, 0.10g Mei Jiafa (Megafac) F-556 (trade names are put into；DIC (DIC) limited company), Carry out stirring for 1 hour at room temperature, filtered with molecular filter (0.2 μm) and prepare coating fluid.Furthermore, alkali-soluble polymer Solution (A-1) contains reaction dissolvent.The solvent (F) of the present embodiment turns into the total of the reaction dissolvent and the retarder thinner.Should Regulation is also applied in following embodiment and comparative example.
[making of analyticity evaluation substrate]
The photosensitive composite was spun on glass substrate with 10 seconds with 800rpm, 2 are carried out in 80 DEG C of heating plate Minute prebake conditions.Secondly, in atmosphere, across the mask of the sectional hole patterns with 20 μm, proximity exposure machine TME- is used 150PRC (trade names；Open up Pu Kang (Topcon) limited company), it is exposed with 100 μm of exposing clearance.Light exposure is Utilize accumulative quantometer UIT-102 (trade names；Oxtail (USHIO) limited company), optical receiver UVD-365PD (commodity Name；Oxtail (USHIO) limited company) it is measured and is set to 30mJ/cm2.By the film after exposure in 0.04 weight % Potassium hydroxide aqueous solution in carry out after the covering liquid development of 60 seconds, with pure water to applying after Membrane cleaning 20 seconds, utilize 100 DEG C of heating Plate carries out drying in 2 minutes.Toasted after further being carried out 30 minutes with 230 DEG C in an oven, obtain the hardening that thickness is 1.5 μm Film.
On the cured film of acquisition as described above, characteristic is evaluated for analyticity.
[evaluation method of analyticity]
The glass substrate with the pattern-like transparent body of gained is observed with 1,000 times of light microscope, confirmed The analyticity of 20 μm of sectional hole patterns.Using the situation of parsing as "○", there will be residue and situation about can not parse is as "×".
[evaluation method of residual film ratio]
The thickness after prebake conditions and the thickness after development are determined, residual film ratio is calculated with following calculating formulas.After development The value of residual film ratio is evaluated as "○" for more than 80% situation, and the situation less than 80% is evaluated as into "×".
Residual film ratio=(thickness after thickness/prebake conditions after development) × 100
[evaluation method of resistance to heating rate]
After the reheating that the glass substrate with cured film of gained is carried out at 230 DEG C to 90 minutes, determine before heating Thickness and heating after thickness, calculate residual film ratio with following calculating formulas.By the feelings that the residual film ratio after heating is more than 95% Condition is evaluated as "○", and the situation by the residual film ratio after heating less than 95% is evaluated as "×".
Residual film ratio=(thickness before thickness/heating after heating) × 100
[making of planarization characteristics evaluation substrate]
Secondly, resin black photosensitive composite being spun on using maximum about 0.8 μm of jump for 10 seconds is lasted with 800rpm On the pigment self-dispersible color filter sheet base plate of colour moment battle array, 2 minutes prebake conditions are carried out in 80 DEG C of heating plate.Secondly, using connecing Nearly formula exposure machine TME-150PRC (trade names；Open up Pu Kang (Topcon) limited company) it is exposed.Light exposure is to utilize Accumulative quantometer UIT-102 (trade names；Oxtail (USHIO) limited company), optical receiver UVD-365PD (trade names；Ox Tail (USHIO) limited company) it is measured and is set to 30mJ/cm2.Using 0.04 weight % potassium hydroxide aqueous solutions, with 25 DEG C are carried out to the film after exposure after the covering liquids development of 1 minute, with pure water to applying after Membrane cleaning 20 seconds, utilize 100 DEG C plus Hot plate carries out drying in 2 minutes.Further in an oven to be toasted after being carried out 30 minutes at 230 DEG C, it is 1.5 μm to obtain with thickness Cured film colored filter substrate.
On the cured film of acquisition as described above, evaluated for planarization characteristics.
[evaluation methods of planarization characteristics]
Device (trade name is determined using jump surface roughness fine shape；P-16, KLA-Tencor (KLA TENCOR) stock Part Co., Ltd) determine obtained by the colored filter substrate with cured film cured film surface jump.Black will be included The maximum of jump between R, G, B pixel of matrix (is slightly designated as " maximum jump ") situation less than 0.16 μm and is evaluated as below "○", "×" is evaluated as by more than 0.16 μm of situation.
[2~embodiment of embodiment 7]
According to the method for embodiment 1, with ratio (unit described in table 1：G) each composition mixed dissolution is felt Photosensitiveness composition.
[table 1]
Table 1
Unit is gram (g)
Implement the evaluation of 2~embodiment of embodiment 7.Evaluation result is shown in table 2.
[table 2]
Table 2
[1~comparative example of comparative example 4]
According to the method for embodiment 1, with ratio (unit described in table 3：G) each composition mixed dissolution is felt Photosensitiveness composition.
[table 3]
Table 3
Unit is gram (g)
Implement the evaluation of 1~comparative example of comparative example 4.Evaluation result is shown in table 4.
[table 4]
Table 4
It can be seen from the result shown in table：1~embodiment of embodiment 7 analyticity, development after residual film ratio, heat resistance, All aspects of planarization characteristics obtain balance and excellent.Film formed in comparative example 1 is completely dissolved in development, therefore Residual film ratio, heat resistance, the evaluation of planarization characteristics after analyticity, development can not be carried out.This is thought, due to 2- hydroxyl-Isosorbide-5-Nitraes- The addition of naphthoquinones exceedes appropriate weight, so the carry out of polymerisation during exposure is insufficient, film can be formed by not generating Polymer.Understand the cured film of 2~comparative example of comparative example 4 analyticity or development after residual film ratio, planarization characteristics it is poor.
[industrial applicability]
Analyticity, the transparency, heat resistance and the planarization spy of the cured film obtained by the photosensitive composite of the present invention Property etc. is excellent as the characteristic of optical material, since then from the aspect of, can be connect as colored filter, LED light-emitting component and light Receive the diaphragm of the various optical materials of element etc. etc. and formed between TFT and transparency electrode and transparency electrode and orientation Transparent insulating film, formation between film are utilized in interelectrode transparent insulating film.

Claims (18)

1. a kind of photosensitive composite, it contains alkali-soluble polymer (A), epoxide (B), with polymerism double bond Compound (C), Photoepolymerizationinitiater initiater (D), molecular weight regulator (E) and solvent (F), it is characterised in that：
The weight of Photoepolymerizationinitiater initiater (D) is more than 5.0 times of the weight of molecular weight regulator (E) and for less than 20 times.
2. photosensitive composite according to claim 1, it is characterised in that：Molecular weight regulator (E) be selected from thio-alcohol, One or more of xanthan acids, quinones, 2,4- diphenyl -4-methyl-1-pentene.
3. photosensitive composite according to claim 1, it is characterised in that：Molecular weight regulator (E) is naphthoquinones class.
4. photosensitive composite according to claim 1, it is characterised in that：Molecular weight regulator (E) is 2- hydroxyl-Isosorbide-5-Nitraes- Naphthoquinones.
5. photosensitive composite according to any one of claim 1 to 4, it is characterised in that：Alkali-soluble polymer (A) It is to make the radical polymerization containing free radical polymerization monomer (a1) and other free radical polymerization monomers (a2) with carboxyl Property monomer mixture polymerization and obtain, free radical polymerization monomer (a1) and other free radical polymerization monomers with carboxyl (a2) do not have epoxy radicals or oxetanylmethoxy；
Epoxide (B) be selected from diglycidyl ether type epoxy compound (Ba), ester ring type aliphatic epoxy compound (Bb), And at least one in the polymer (Bc) containing epoxy radicals,
Polymer (Bc) containing epoxy radicals is made containing free radical polymerization monomer (b1) and other freedom with epoxy radicals The mixture of the free radical polymerization monomer of base polymerizable monomer (b2) polymerize and obtained,
Free radical polymerization monomer (b1) and other free radical polymerization monomers (b2) with epoxy radicals do not have carboxyl；
Compound (C) with polymerism double bond be selected from Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, The ethylene-oxide-modified triacrylate of pentaerythritol triacrylate, tetramethylol methane tetraacrylate, isocyanuric acid, O-phthalic Sour monohydroxy ethyl propylene acid esters, succinate modified pentaerythritol triacrylate, orthophthalic modified pentaerythrite 3 third Olefin(e) acid ester, succinate modified Dipentaerythritol Pentaacrylate, orthophthalic modified Dipentaerythritol Pentaacrylate and many At least one in first acid modified acroleic acid oligomer；Moreover,
Photoepolymerizationinitiater initiater (D) is triggered selected from alpha-amido benzene alkyl ketone system Photoepolymerizationinitiater initiater, the photopolymerization of acylphosphine oxide system One or more of agent and oxime ester system Photoepolymerizationinitiater initiater.
6. photosensitive composite according to claim 5, it is characterised in that：Alkali-soluble polymer (A) be make relative to The gross weight of free radical polymerization monomer (a1) and other free radical polymerization monomers (a2) with carboxyl and containing 10 weights Measure the weight % of %~60 free radical polymerization monomer (a1) with carboxyl and the weight % of 40 weight %~90 other freedom The copolymer that the mixture of the free radical polymerization monomer of base polymerizable monomer (a2) polymerize and obtained；
Diglycidyl ether type epoxy compound (Ba) is selected from double [4- [1- [4- (2,3- glycidoxy) the phenyl] -1- of 1,3- [4- [1- [4- (2,3- glycidoxy) phenyl] -1- Methylethyls] phenyl] ethyl] phenoxy group] -2- propyl alcohol and 2- [4- (2, 3- glycidoxies) phenyl] -2- [4- [1,1- double [4- ([2,3- glycidoxy] phenyl)] ethyls] phenyl] and in propane extremely Few one kind,
Ester ring type aliphatic epoxy compound (Bb) is 1,2- epoxy radicals -4- (the 2- oxa-s of double (the hydroxymethyl)-n-butyl alcohols of 2,2- Cyclopropyl) hexamethylene addition product；
Compound (C) with polymerism double bond be selected from Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, At least one in pentaerythritol triacrylate, tetramethylol methane tetraacrylate and modified by polyacid acrylate oligomers；And And,
Photoepolymerizationinitiater initiater (D) is O- acyl group oxime compounds.
7. photosensitive composite according to claim 6, it is characterised in that：Free radical polymerization monomer with carboxyl (a1) it is at least one in acrylic acid and methacrylic acid；
Photoepolymerizationinitiater initiater (D) is to be selected from 1,2- octadione- 1- [4- (thiophenyl) phenyl] -2- (O- benzoyl oximes), ethyl ketone, 1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -, 1- (O- acetyl group oxime) and 1,2- propanedione -1- [4- [4- (2- hydroxyl-oxethyls) thiophenyl] phenyl] at least one in -2- (O- acetyl group oxime).
8. photosensitive composite according to claim 7, it is characterised in that：Other free radical polymerization monomers (a2) are included Selected from (methyl) acrylate with aromatic rings, (methyl) acrylate with bicyclopentyl, with dicyclopentenyl At least one in (methyl) acrylate and N- substituted maleimide amine.
9. photosensitive composite according to claim 8, it is characterised in that：Other free radical polymerization monomers (a2) are choosings From (methyl) benzyl acrylate, (methyl) acrylic acid bicyclopentyl ester, (methyl) acrylic acid dicyclopentenyl epoxide ethyl ester, N- benzene At least one in base maleimide and N- N-cyclohexylmaleimides.
10. photosensitive composite according to claim 9, it is characterised in that：Other free radical polymerization monomers (a2) are Relative to the gross weight of other free radical polymerization monomers (a2) (methyl) acrylic acid benzyl is selected from containing more than 50 weight % Base ester, (methyl) acrylic acid bicyclopentyl ester, (methyl) acrylic acid dicyclopentenyl epoxide ethyl ester, N-phenylmaleimide and At least one in N- N-cyclohexylmaleimides.
11. a kind of cured film, it is characterised in that：It is by photosensitive composition according to any one of claim 1 to 10 Thing and obtain.
12. a kind of colored filter, it is characterised in that：Diaphragm is used as using cured film according to claim 11.
13. a kind of display element, it is characterised in that：Use colored filter according to claim 12.
14. a kind of solid-state imager, it is characterised in that：Use colored filter according to claim 12.
15. a kind of display element, it is characterised in that：It is brilliant in film using cured film according to claim 11 as being formed Transparent insulating film between body pipe and transparency electrode.
16. a kind of display element, it is characterised in that：Using cured film according to claim 11 as formation in transparent electricity Transparent insulating film between pole and alignment films.
17. a kind of touch-screen, it is characterised in that：Using cured film according to claim 11 as formation interelectrode Transparent insulating film.
18. a kind of LED illuminant heart, it is characterised in that：Protection is used as using cured film according to claim 11 Film.
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