CN103365087B - Insulating film forms the forming method with photosensitive polymer combination, insulating film and insulating film - Google Patents

Insulating film forms the forming method with photosensitive polymer combination, insulating film and insulating film Download PDF

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Publication number
CN103365087B
CN103365087B CN201310097102.5A CN201310097102A CN103365087B CN 103365087 B CN103365087 B CN 103365087B CN 201310097102 A CN201310097102 A CN 201310097102A CN 103365087 B CN103365087 B CN 103365087B
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insulating film
methyl
photosensitive polymer
polymer combination
carbon number
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CN103365087A (en
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大内康秀
染谷和也
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Tokyo Ohka Kogyo Co Ltd
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Tokyo Ohka Kogyo Co Ltd
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Priority claimed from JP2012174451A external-priority patent/JP6022847B2/en
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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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
    • G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
    • G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor

Abstract

The present invention, which provides, is capable of forming insulating properties and the excellent insulating film of reagent resistance and the wide insulating film formation photosensitive polymer combination of exposure margin when forming the pattern of insulating film.In addition, the present invention also provides the forming methods of insulating film and the insulating film for using above-mentioned insulating film formation photosensitive polymer combination for using above-mentioned insulating film formation photosensitive polymer combination and being formed.Photosensitive polymer combination of the invention, in (A) alkali soluble resin, (B) photopolymerization monomer and (C) Photoepolymerizationinitiater initiater cooperate specific structure compound, and use comprising specific quantity self-contained epoxy group unsaturated compound structural unit resin as (A) alkali soluble resin.

Description

Insulating film forms the formation for using photosensitive polymer combination, insulating film and insulating film Method
Technical field
The present invention relates to insulating film formation photosensitive polymer combination, pass through the insulating film formation photoresist group Close the insulating film and the forming method that the insulating film with photosensitive polymer combination is formed using the insulating film that object is formed.
Background technique
In the past, in the electronic components such as liquid crystal display element, integrated circuit component, solid state photo element, in order to make to configure It insulate between the wiring of layered, and forms insulating film etc. in wiring closet.The insulating film is by a variety of materials such as inoranic membrane, organic films It is formed, in the case where organic film, uses hot curing resin composition or photosensitive polymer combination mostly and formed.
As the photosensitive polymer combination for being used to form such insulating film, it is known to include alkali soluble resin, tool There are the polymerizable compound of ethylenic unsaturated bond and the photosensitive polymer combination of photoinitiator, wherein the alkali-soluble tree Rouge is the monomer comprising unsaturated double-bond, the monomer comprising carboxylic acid and unsaturated double-bond and the specific structure comprising allyl The copolymer of monomer, molecular weight distribution (Mw/Mn) were 1.0~3.5 (referring to patent document 1).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2012-012602 bulletin
Summary of the invention
Problem to be solved by the invention
However, there are the following problems for the photosensitive polymer combination recorded in patent document 1: even if being capable of forming insulating properties Good insulating film, the exposure margin (margin) when also can make to form the pattern of insulating film is narrow and selection of processing conditions from It is low by spending.In addition, insulating film can be exposed to for example in its manufacturing procedure or the manufacturing procedure of the electronic component comprising insulating film In the various test solutions such as anticorrosive additive stripping liquid controlling, thus require reagent resistance excellent.However, the photonasty tree recorded in patent document 1 Rouge elements may not be abundant to the durability of the test solutions such as anticorrosive additive stripping liquid controlling.
The present invention is completed in view of the above subject, is capable of forming insulating properties and reagent resistance it is intended that providing Excellent insulating film and the wide insulating film formation photosensitive resin composition of exposure margin when forming the pattern of insulating film Object.In addition, the present invention also aims to provide using above-mentioned insulating film formation photosensitive polymer combination and formed Insulating film and the forming method that the insulating film with photosensitive polymer combination is formed using above-mentioned insulating film.
The method for solving problem
Further investigation has been repeated in the inventors of the present invention in order to solve the above problems.As a result, it has been found that: can comprising (A) alkali Cooperate specific structure in the photosensitive polymer combination of soluble resin, (B) photopolymerization monomer and (C) Photoepolymerizationinitiater initiater Compound, and use comprising specific quantity come self-contained epoxy group unsaturated compound structural unit resin as (A) alkali soluble resin, so as to solve the above subject, so that complete the present invention.Specifically, the present invention is provided with lower section Case.
First scheme of the invention is a kind of insulating film formation photosensitive polymer combination, contains (A) alkali-soluble Resin, (B) photopolymerization monomer, (C) Photoepolymerizationinitiater initiater and (D) following formula (1) compound represented,
Above-mentioned (A) alkali soluble resin is the copolymerization comprising the structural unit for carrying out the unsaturated compound of self-contained epoxy group Object,
The structural unit of the unsaturated compound of next self-contained epoxy group in above-mentioned (A) alkali soluble resin, above-mentioned Ratio is 20~60 mass %.
(in formula, R1And R2Separately indicate hydrogen atom or organic group.Wherein, R1And R2In at least one party indicate Organic group.R1And R2It can be bonded to each other and form cyclic structure, also may include heteroatomic key.R3It indicates singly-bound or has Machine group.R4And R5Separately indicate hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether group, silicyl, silanol group, nitre Base, nitroso, sulfino (sulfino), sulfo group (sulfo), sulphonic acid ester (sulfonate) base, phosphino- (phosphino), oxygen Phosphino- (phosphinyl), phosphono (phosphono), phosphonate ester (phosphonate) base or organic group.R6、R7、R8And R9Separately indicate hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether group, silicyl, silanol group, nitro, nitroso, Sulfino, sulfo group, sulfonate group, phosphino-, phosphinyl, phosphono, phosphonate group, amino, ammonium (ammonio) or organic group Group.Wherein, R6And R7It is not hydroxyl.R6、R7、R8And R9Can make 2 therein or more in conjunction with and form cyclic structure, can also be with Include heteroatomic key.R10Indicate hydrogen atom or organic group.)
Alternative plan of the invention is shape using insulating film formation photosensitive polymer combination described in first scheme At insulating film.
Third program of the invention is a kind of forming method of insulating film comprising following process:
Insulating film formation described in first scheme is applied on substrate, shape by painting process with photosensitive polymer combination At photo-sensitive resin；
Exposure process is exposed above-mentioned photo-sensitive resin according to the pattern of the insulating film of regulation；And
Developing procedure, the photo-sensitive resin development after making above-mentioned exposure, forms the pattern of insulating film.
Invention effect
It is capable of forming insulating properties and the excellent insulating film of reagent resistance according to the present invention it is possible to provide and insulate being formed Photosensitive polymer combination is used in the wide insulating film formation of exposure margin when the pattern of film.In addition, in accordance with the invention it is possible to providing It the insulating film that is formed using above-mentioned insulating film formation photosensitive polymer combination and is formed using above-mentioned insulating film With the forming method of the insulating film of photosensitive polymer combination.
Specific embodiment
" insulating film, which is formed, uses photosensitive polymer combination "
Insulating film of the present invention is formed with photosensitive polymer combination (hereinafter also referred to as " photosensitive resin composition Object ".) at least containing (A) alkali soluble resin (hereinafter also referred to as " (A) ingredient ".), (B) photopolymerization monomer (hereinafter, also referred to as For " (B) ingredient ".), (C) Photoepolymerizationinitiater initiater is (hereinafter also referred to as " (C) ingredient ".) and (D) above-mentioned formula (1) shown in Compound is (hereinafter also referred to as " (D) ingredient ".).Hereinafter, for insulating film formation photosensitive resin composition of the present invention Each ingredient contained by object is illustrated.
<(A) alkali soluble resin>
Alkali soluble resin refers to: the resin solution (solvent: propylene glycol monomethyl ether for being 20 mass % using resin concentration Acetic acid esters) 1 μm of film thickness of resin film is formed on substrate, it is impregnated 1 point in the KOH aqueous solution that concentration is 0.05 mass % Zhong Shi, the resin of 0.01 μm of dissolution or more film thickness.
As (A) alkali soluble resin, the structural unit of unsaturated compound comprising carrying out self-contained epoxy group is used Copolymer.(A) in alkali soluble resin, come self-contained epoxy group unsaturated compound structural unit ratio be 20~ 60 mass %, preferably 20~40 mass %.It include to carry out the unsaturationization of self-contained epoxy group by using with such ratio (A) alkali soluble resin of the structural unit of object is closed, to be easy to form excellent exhausted of insulating properties by photosensitive polymer combination Velum.
As (A) as long as the knot for the unsaturated compound that carrys out self-contained epoxy group of the resin containing specified amount that ingredient uses Structure unit is not particularly limited, and can fit from the alkali soluble resin used in various photosensitive polymer combinations in the past When selection uses.As the resin for being suitable as (A) ingredient, go out from the viewpoint for being easy to get the excellent insulating film of reagent resistance Hair can be enumerated comprising being total to (a1) unsaturated carboxylic acid containing what the unsaturated compound of epoxy group was polymerized with (a2) The resin of polymers (A1).
As (a1) unsaturated carboxylic acid, the monocarboxylic acids such as (methyl) acrylic acid, crotonic acid can be enumerated；Maleic acid, rich horse The dicarboxylic acids such as acid, citraconic acid, mesaconic acid, itaconic acid；The acid anhydrides of these dicarboxylic acids；Etc..In these, from copolyreaction, The alkali-solubility of resulting resin, acquisition the viewpoints such as easiness set out, preferably (methyl) acrylic acid and maleic anhydride.These (a1) unsaturated carboxylic acid can be used alone or in combination of two or more kinds.
Unsaturated compound as (a2) containing epoxy group can enumerate the insatiable hunger that (a2-I) has ester ring oxygroup Do not have the unsaturated compound of ester ring oxygroup with compound and (a2-II), preferably (a2-I) has ester ring oxygroup Unsaturated compound.
(a2-I) in the unsaturated compound with ester ring oxygroup, the ester ring type base for constituting ester ring oxygroup can be with It is polycyclic to be that monocycle is also possible to.As the ester ring type base of monocycle, cyclopenta, cyclohexyl etc. can be enumerated.In addition, as polycyclic Ester ring type base can enumerate norborny, isobornyl, three cyclononyls, tricyclodecyl, tetracyclododecyl group etc..These (a2- I the unsaturated compound) containing ester ring oxygroup can be used alone or in combination of two or more kinds.
Specifically, the unsaturated compound as (a2-I) containing ester ring oxygroup can enumerate such as following formula (a2-1)~(a2-16) compound represented.In these, in order to obtain appropriate developability, preferably following formula (a2-1)~ (a2-6) compound represented, more preferable following formula (a2-1)~(a2-4) compound represented.
In above-mentioned formula, R11Indicate hydrogen atom or methyl, R12Indicate the divalent sturated aliphatic hydrocarbon base of carbon number 1~6, R13It indicates The divalent alkyl of carbon number 1~10, n indicate 0~10 integer.As R12, the preferably alkylidene of straight-chain or branched, such as Asia Methyl, ethylidene, propylidene, tetramethylene, ethylethylene residue, pentamethylene, hexa-methylene.As R13, preferred such as methylene Base, ethylidene, propylidene, tetramethylene, ethylethylene residue, pentamethylene, hexa-methylene, phenylene, cyclohexylidene ,-CH2- Ph-CH2(Ph indicates phenylene).
Do not have the unsaturated compound containing epoxy group of ester ring type base as (a2-II), (methyl) third can be enumerated Olefin(e) acid ethylene oxidic ester, (methyl) acrylic acid 2- methylglycidyl esters, (methyl) acrylic acid 3,4- epoxy group butyl ester, (methyl) Acrylic acid 6,7- epoxy group heptyl ester etc. (methyl) acrylic acid epoxy base alkyl esters；α-ethylacrylate ethylene oxidic ester, α-are just Propylacrylate ethylene oxidic ester, α-n-butyl acryloyloxy ethyl acid glycidyl ester, α-ethylacrylate 6, the α-such as 7- epoxy group heptyl ester Alkyl acrylic epoxy alkyl esters；Etc..In these, from viewpoints such as the intensity of the resin after copolyreaction, solidification It sets out, preferably (methyl) glycidyl acrylate, (methyl) acrylic acid 2- methylglycidyl esters and (methyl) acrylic acid 6,7- epoxy group heptyl esters.The unsaturated compound containing epoxy group that these (a2-II) do not have ester ring type base can individually make With or combine two or more use.
Copolymer (A1) can be make (a3) do not have epoxy group unsaturated compound containing ester ring type base with it is above-mentioned (a1) copolymer that unsaturated carboxylic acid and (a2) are polymerized together containing the unsaturated compound of epoxy group.
Unsaturated compound as (a3) containing ester ring type base, as long as the unsaturated compound with ester ring type base It is not particularly limited.Ester ring type base can be monocycle be also possible to it is polycyclic.As the ester ring type base of monocycle, ring penta can be enumerated Base, cyclohexyl etc..In addition, adamantyl, norborny, isobornyl, tricyclic nonyl can be enumerated as polycyclic ester ring type base Base, tricyclodecyl, tetracyclododecyl group etc..These (a3) can be used alone containing the unsaturated compound of ester ring type base or group Close two or more use.
Specifically, the unsaturated compound as (a3) containing ester ring type base can enumerate such as following formula (a3-1) ~(a3-7) compound represented.In these, go out from the viewpoint for being easy to get the good photosensitive polymer combination of developability It sends out, preferably following formula (a3-3)~(a3-8) compound represented, chemical combination shown in more preferable following formula (a3-3), (a3-4) Object.
In above-mentioned formula, R21Indicate hydrogen atom or methyl, R22Indicate the divalent sturated aliphatic hydrocarbon base of singly-bound or carbon number 1~6, R23Indicate the alkyl of hydrogen atom or carbon number 1~5.As R22, the preferably alkylidene of singly-bound, straight-chain or branched, such as methylene Base, ethylidene, propylidene, tetramethylene, ethylethylene residue, pentamethylene, hexa-methylene.As R23, preferably such as methyl, second Base.
Copolymer (A1) is also possible to the copolymer that also copolymerization has other compounds other than the above.As it is such other Compound can enumerate (methyl) esters of acrylic acid, (methyl) acrylic amide, allyl compound, vinyl ethers, ethylene Base ester class, phenylethylene etc..These compounds can be used alone or in combination of two or more kinds.
As (methyl) esters of acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) can be enumerated (methyl) acrylic acid of the straight-chains such as propyl acrylate, (methyl) amyl acrylate, the tertiary monooctyl ester of (methyl) acrylic acid or branched Arrcostab；(methyl) acrylic acid chloroethene ester, (methyl) acrylic acid 2,2- dimethyl hydroxypropyl acrylate, (methyl) acrylic acid 2- hydroxyl ethyl ester, Trimethylolpropane list (methyl) acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid chaff ester；Etc..
As (methyl) acrylic amide, (methyl) acrylamide, N- alkyl (methyl) acrylamide, N- virtue can be enumerated Base (methyl) acrylamide, N, N- dialkyl group (methyl) acrylamide, N, N- aryl (methyl) acrylamide, N- methyl-N- benzene Base (methyl) acrylamide, N- ethoxy-N- methyl (methyl) acrylamide etc..
As allyl compound, allyl acetate, allyl hexanoate, allyl octanoate, lauric acid allyl can be enumerated The allyl esters such as ester, palm allyl propionate, stearic allyl propionate, allyl benzoate, acetoacetic acid allyl ester, allyl lactate Class；Allyl ethoxy-ethanol；Etc..
As vinyl ethers, hexylvinyl ether, octyl vinyl ether, decave, ethyl hexyl can be enumerated Base vinyl ethers, methoxy-ethylvinyl ether, ethoxy ethyl vinyl ether, chloroethyl vinyl ether, 1- methyl -2,2- bis- Methyl-propyl vinyl ethers, 2- ethylbutyl vinyl ether, hydroxyethyl vinylethers, diethylene glycol vinyl ethers, dimethylamino Base ethyl vinyl ether, diethylamino ethyl vinyl ether, Butylaminoethyl vinyl ethers, benzyl vinyl ether, tetrahydro The alkyl vinyl ethers such as furfuryl group vinyl ethers；Vinyl phenyl ether, vinyltoluene base ether, vinyl chloride phenyl ether, vinyl- The ethenyl aromatic yls ethers such as 2,4- dichlorophenyl ethers, vinyl naphthyl ether, vinyl anthryl ether；Etc..
As vinyl ester, vinyl butyrate, vinyl isobutyrate ester, vinyl trimethyl acetic acid esters, second can be enumerated Alkenyl diethacetic acid ester, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate ester, vinyl methoxy Yl acetate, vinyl butoxy acetic acid ester, vinyl benzene yl acetate, vinylacetyl acetic acid esters, lactate, ethylene Base-beta-phenyl butyrate, vinyl benzoate, vinyl salicylate, chlorobenzoic acid vinyl acetate, tetrachloro-benzoic acid vinyl acetate, naphthalene Vinyl formate etc..
As phenylethylene, styrene can be enumerated；Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl Styrene, diethyl, isopropyl styrene, butylstyrene, hexyl styrene, cyclohexylstyrenes, decyl benzene second Alkene, benzylstyrene, 1-chloro-4-methyl-benzene, trifluoromethyl styrene, ethoxyl methyl styrene, acetoxymethylstyrene Equal ring-alkylated styrenes；The alkoxystyrenes such as methoxy styrene, 4- methoxyl group -3- methyl styrene, dimethoxy styrene； Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachloro styrene, pentachloro- styrene, bromstyrol, Dowspray 9, iodobenzene The halogeno-benzenes such as the bromo- 4- trifluoromethyl styrene of ethylene, fluorobenzene ethene, trifluorostyrene, 2-, the fluoro- 3- trifluoromethyl styrene of 4- Ethylene；Etc..
Structural unit from above-mentioned (a1) unsaturated carboxylic acid ratio shared in copolymer (A1) is preferably 1~25 matter Measure %, more preferably 8~16 mass %.In addition, coming from the structure list of the above-mentioned unsaturated compound of (a3) containing ester ring type base Member ratio shared in copolymer (A1) is preferably 1~30 mass %, more preferably 5~20 mass %.
The matter average molecular weight of copolymer (A1) (Mw: measures obtained by the styrene conversion using gel permeation chromatography (GPC) Value.It is all synonymous in this specification.) it is preferably 2000~200000, more preferably 5000~30000.By making matter average molecular weight In above range, to there is the balance of the developability after the film Forming ability for being easy to obtain photosensitive polymer combination, exposure Tendency.
Copolymer (A1) can be manufactured by well known radical polymerization.That is, making each compound and well known After radical polymerization initiator is dissolved in polymer solvent, heating stirring is carried out, so as to manufacture the copolymer (A1).
In addition, can be suitble to as (A) alkali soluble resin using comprising at least having from above-mentioned (a1) unsaturated carboxylic Acid structural unit, from the above-mentioned unsaturated compound of (a2) containing epoxy group structural unit and have can with it is rear The resin of the copolymer (A2) of the structural unit at the position for (B) the photopolymerization monomer polymerization stated.It is wrapped at alkali soluble resin (A) In the case where containing copolymer (A2), adaptation of the photosensitive polymer combination to substrate, photosensitive polymer combination can be improved Breakdown strength after hardening.
Copolymer (A2), which is also possible to also copolymerization, has copolymer (A1) is middle to record, (methyl) third as other compounds The copolymerization of olefin(e) acid esters, (methyl) acrylic amide, allyl compound, vinyl ethers, vinyl ester, phenylethylene etc. Object.
Structural unit with the position that can polymerize with (B) photopolymerization monomer preferably has ethylenically unsaturated group work Structural unit for the position that can polymerize with (B) photopolymerization monomer.By making to have from above-mentioned (a1) unsaturated carboxylic acid Structural unit and from the above-mentioned unsaturated compound of (a2) containing epoxy group structural unit copolymer in epoxy group A part reacted with (a1) unsaturated carboxylic acid, so as to prepare copolymer (A2).
The matter average molecular weight of copolymer (A2) is preferably 2000~50000, more preferably 5000~30000.By making matter Average molecular weight exists in above range and is easy to obtain the developability after the film Forming ability of photosensitive polymer combination, exposure The tendency of balance.
(A) content of alkali soluble resin is preferably 30~90 matter relative to the solid component of photosensitive polymer combination Measure %, more preferably 45~75 mass %.By making the content in above range, there is inclining for the balance for being easy to obtain developability To.
<(B) photopolymerization monomer>
As (B) optical polymerism list contained in insulating film formation photosensitive polymer combination of the present invention It is preferable to use the monomers with ethylenically unsaturated group for body.As the monomer with ethylenically unsaturated group, there is single official It can monomer and polyfunctional monomer.
As monofunctional monomer, (methyl) acrylamide, methylol (methyl) acrylamide, methoxy can be enumerated (methyl) acrylamide, ethoxyl methyl (methyl) acrylamide, propoxy methyl (methyl) acrylamide, butoxymethoxy Methyl (methyl) acrylamide, N- methylol (methyl) acrylamide, N- hydroxymethyl (methyl) acrylamide, (methyl) propylene Acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2- acrylamide- 2- methyl propane sulfonic acid, tert-butyl acrylamide sulfonate, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propylene Acid butyl ester, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- hydroxyl ethyl ester, (methyl) Acrylic acid 2- hydroxypropyl acrylate, (methyl) acrylic acid 2- hydroxy butyl ester, (methyl) acrylic acid 2- phenoxy group -2- hydroxypropyl acrylate, 2- (methyl) third Alkene acyloxy -2- hydroxypropylphthalate, single (methyl) glycerol acrylate, (methyl) tetrahydrofurfuryl acrylate, diformazan Base amino (methyl) acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid 2,2,2- trifluoro ethyl ester, (methyl) 2,2,3,3- tetrafluoro propyl ester of acrylic acid, half (methyl) acrylate of phthalic acid derivatives etc..These monofunctional monomers can To be used alone or in combination of two or more kinds.
On the other hand, as polyfunctional monomer, ethylene glycol two (methyl) acrylate, two (first of diethylene glycol can be enumerated Base) acrylate, tetraethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, more propylene glycol two (methyl) Acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6- hexylene glycol two (methyl) third Olefin(e) acid ester, trimethylolpropane tris (methyl) acrylate, glycerol two (methyl) acrylate, pentaerythritol triacrylate, Pentaerythritol tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate, pentaerythrite two (methyl) Acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) Bis- (4- (methyl) the acryloxy diethoxy phenyl) third of acrylate, dipentaerythritol six (methyl) acrylate, 2,2- Bis- (4- (methyl) acryloxypolyethoxyphenyl) propane of alkane, 2,2-, 2- hydroxyl -3- (methyl) acryloxypropyl (methyl) acrylate, ethylene glycol diglycidyl base ether two (methyl) acrylate, diethylene glycol diglycidyl glyceryl ether two (methyl) acrylate, phthalic acid 2-glycidyl base ester two (methyl) acrylate, glycerol tri-acrylate, glycerol are poly- Poly- (methyl) acrylate of glycidyl ether, carbamate (methyl) acrylate (that is, toluene di-isocyanate(TDI)), front three The reactant with 2- ethoxy (methyl) acrylate such as base hexamethylene diisocyanate and hexamethylene diisocyanate, Asia Bis- (methyl) acrylamides of methyl, (methyl) acrylamide methylene ether, polyalcohol and N- methylol (methyl) acrylamide The polyfunctional monomers such as condensation product, 1,3,5- triacryl hexahydros -1,3,5-triazines (triacrylformal) etc..These more officials Energy monomer can be used alone or in combination of two or more kinds.
In these monomers with ethylenically unsaturated group, from insulating film formation photosensitive polymer combination is improved to base From the perspective of the adaptation of plate, the intensity of photosensitive polymer combination after hardening, multifunctional lists more than preferably 3 functions Polyfunctional monomer more than body, more preferable 6 function.
(B) content of ingredient is preferably 5~60 relative to the solid component of insulating film formation photosensitive polymer combination Quality %, more preferably 10~50 mass %.By making the content in above range, exist be easy to obtain sensitivity, developability, The tendency of the balance of clarity.
<(C) Photoepolymerizationinitiater initiater>
As (C) Photoepolymerizationinitiater initiater contained by insulating film formation photosensitive polymer combination of the present invention, It is not particularly limited, known Photoepolymerizationinitiater initiater can be used.
As Photoepolymerizationinitiater initiater, specifically, 1- hydroxycyclohexylphenylketone, 2- hydroxy-2-methyl -1- can be enumerated Phenyl-propane -1- ketone, 1- (4- (2- hydroxyl-oxethyl) phenyl) -2- hydroxy-2-methyl -1- propane -1- ketone, 1- (4- isopropyl Phenyl) -2- hydroxy-2-methyl propane -1- ketone, 1- (4- dodecylphenyl) -2- hydroxy-2-methyl propane -1- ketone, 2,2- bis- Methoxyl group-1,2- diphenylethane-1- ketone, bis- (4- dimethylaminophenyl) ketone, 2- methyl-1-(4- (methyl mercapto) phenyl)- 2- morpholino propane -1- ketone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butane -1- ketone, 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] ethyl ketone -1- (O- acetyl oxime), (9- ethyl -6- nitro -9H- carbazole -3- base) [4- (2- methoxyl group -1- methyl ethoxy) -2- aminomethyl phenyl] ketone O- acetyl oxime, 1- [4- (thiophenyl)] -1,2- octadione- 2- (O- benzoyl oximes), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4- benzoyl -4 '-methyl dimethoxy base sulphur Ether, 4- dimethylaminobenzoic acid, 4- dimethylaminobenzoic acid methyl esters, ethyl 4-dimethylaminobenzoate, 4- dimethyl Butyl aminobenzoate, 4- dimethylamino -2- ethylhexyl Benzoic acid, 4- dimethylamino -2- isoamyl benzene formic acid, benzyl Base-'beta '-methoxy ethyl acetal, benzil dimethyl ketal, 1- phenyl -1,2- propanedione -2- (O- ethoxy carbonyl) oxime, Chloro- the third oxygen of 4- of o-benzoyl yl benzoic acid methyl esters, 2,4- diethyl thioxanthone, 2-chlorothioxanthone, 2,4- dimethyl thioxanthone, 1- Base thioxanthones, thioxanthene, 2- diuril ton, 2,4- diethyl thioxanthene, 2- methyl thioxanthene, 2- isopropylthioxanthones, 2- ethyl hydrazine, eight first Base anthraquinone, 1,2- benzo anthraquinone, 2,3- diphenyl anthraquinone, azodiisobutyronitrile, benzoyl peroxide, cumene peroxide, 2- mercapto Base benzimidazole, 2- mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (Chloro-O-Phenyl) -4,5- bis- (m-methoxyphenyl)-miaow Oxazolyl dimer, benzophenone, 2- chlorobenzophenone, p, bis- (dimethylamino) benzophenone of p '-, 4,4 '-bis- (diethyl aminos Base) benzophenone, 4,4 '-dichloro benzophenones, 3,3- dimethyl -4- methoxy benzophenone, benzil, benzoin, benzene are even Relation by marriage methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl Ether, acetophenone, 2,2- diethoxy acetophenone, to dimethyl acetophenone, to dimethylamino propiophenone, dichloroacetophenone, three Chloro-acetophenone, p-tert.-butyl acetophenone, to dimethylamino benzoylformaldoxime, to tert-butyl trichloroacetophenone, to tert-butyl dichloro-benzenes Ethyl ketone, α, α,α-dichloro-4-phenoxy acetophenone, thioxanthones, 2- methyl thioxanthones, 2-isopropylthioxanthone, Dibenzosuberone, Amyl -4- dimethyl aminobenzoate, 9- phenylacridine, 1,7- be bis--and (9- acridinyl) heptane, 1,5- be bis--(9- acridinyl) Pentane, 1,3- be bis--(9- acridinyl) propane, to methoxyl group triazine, 2,4,6- tri- (trichloromethyl) s-triazine, 2- methyl -4,6- Bis- (trichloromethyl) s-triazine, 2- [2- (5- methylfuran -2- base) vinyl] bis- (trichloromethyl) s-triazine of -4,6-, 2- [2- (furans -2- base) vinyl] bis- (trichloromethyl) s-triazine of -4,6-, 2- [2- (4- diethylamino -2- aminomethyl phenyl) ethylene Base] bis- (trichloromethyl) s-triazine of -4,6-, 2- [2- (3,4- Dimethoxyphenyl) vinyl] -4,6- bis- (trichloromethyls) be equal Triazine, bis- (trichloromethyl) s-triazine of 2- (4- methoxyphenyl) -4,6-, 2- (4- ethoxystyrene base) bis- (trichlorines of -4,6- Methyl) s-triazine, bis- (trichloromethyl) s-triazine of 2- (4- n-butoxyphenyl) -4,6-, 2,4- be bis--trichloromethyl -6- (3- Bromo- 4- methoxyl group) phenyl s-triazine, 2,4- be bis--trichloromethyl -6- (the bromo- 4- methoxyl group of 2-) phenyl s-triazine, 2,4- bis--three Chloromethyl -6- (the bromo- 4- methoxyl group of 3-) styryl phenyl s-triazine, 2,4- be bis--trichloromethyl -6- (the bromo- 4- methoxyl group of 2-) Styryl phenyl s-triazine etc..These Photoepolymerizationinitiater initiaters can be used alone or in combination of two or more kinds.
In these, the Photoepolymerizationinitiater initiater of oxime system is particularly preferably used in terms of sensitivity.Light as oxime system is poly- More preferred example in initiator is closed, 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] second can be enumerated Ketone -1- (O- acetyl oxime), (9- ethyl -6- nitro -9H- carbazole -3- base) [4- (2- methoxyl group -1- methyl ethoxy) -2- methyl Phenyl] ketone O- acetyl oxime and 1- [4- (thiophenyl)] -1,2- octadione- 2- (O- benzoyl oximes).
(C) content of ingredient relative to the solid component of insulating film formation photosensitive polymer combination be preferably 0.5~ 30 mass %, more preferably 1~20 mass %.By making the content of (C) ingredient in above range, it is hereby achieved that being capable of shape At the photosensitive polymer combination of the excellent insulating film of reagent resistance.
In addition, light-initiated auxiliary agent can be combined in (C) ingredient.As light-initiated auxiliary agent, can enumerate triethanolamine, Methyl diethanolamine, triisopropanolamine, 4- dimethylaminobenzoic acid methyl esters, ethyl 4-dimethylaminobenzoate, 4- diformazan Base aminobenzoic isoamyl valerate, 4- dimethylaminobenzoic acid 2- ethylhexyl, benzoic acid 2- dimethylamino ethyl ester, N, N- bis- Methyl para-totuidine, 4,4 '-bis- (dimethylamino) benzophenone, 9,10- dimethoxy anthracene, 2- ethyl -9,10- dimethoxy Anthracene, 9,10- diethoxy anthracene, 2- ethyl -9,10- diethoxy anthracene, 2-mercaptobenzothiazole, 2- mercaptobenzoxazole, 2- mercapto Base benzimidazole, 2- sulfydryl -5- methoxybenzothiazole, 3- mercaptopropionic acid, 3- mercapto-propionate, four sulfydryl second of pentaerythrite Mercaptan compounds such as acid esters, 3-thiopropionate etc..These light-initiated auxiliary agents can be used alone or in combination of two or more kinds.
<(D) formula (1) compound represented>
Insulating film formation photosensitive polymer combination of the present invention contains following formula (1) compound represented.It is logical Crossing makes photosensitive polymer combination contain the compound, can widen the exposure margin of photosensitive polymer combination.In addition, formula (1) compound represented is easy to carry out adverse effect to the sensitivity of photosensitive polymer combination, resulting insulating film intensity band.
In above-mentioned formula (1), R1And R2Separately indicate hydrogen atom or organic group, R1And R2In at least one party's table Show organic group.
As R1And R2In organic group, alkyl, alkenyl, naphthenic base, cycloalkenyl, aryl, aralkyl etc. can be enumerated. It can include the key in addition to alkyl, substituent group of hetero atom etc. in the organic group for the organic group.Separately Outside, which can be any one of straight-chain, branched, ring-type.The organic group is usually 1 valence, is forming ring Whens the case where shape structure etc., the organic group of divalent or more can also be.
R1And R2It can be bonded to each other and form cyclic structure, heteroatomic key can also be further included.It is tied as ring-type Structure can enumerate Heterocyclylalkyl, heteroaryl etc., be also possible to condensed ring.
As R1And R2Organic group in the key other than alkyl, do not have as long as not damaging effect of the invention It is particularly limited to, can enumerate comprising the heteroatomic key such as oxygen atom, nitrogen-atoms, silicon atom.As specific example, ether can be enumerated Key, thioether bond, carbonyl key, thion key, ester bond, amido bond, urethane bond, imido key (- N=C (- R)-,-C (=NR)-: R Indicate hydrogen atom or organic group), carbonic acid ester bond, sulphonyl key, sulfenyl key, azo bond etc..
From the viewpoint of heat resistance, as R1And R2Organic group in the key other than alkyl, preferably ehter bond, (- N=C (- R)-,-C (=NR)-: R are indicated for thioether bond, carbonyl key, thion key, ester bond, amido bond, urethane bond, imido key Hydrogen atom or 1 valence organic group), carbonic acid ester bond, sulphonyl key, sulfenyl key.
As R1And R2Organic group in the substituent group other than alkyl, as long as not damaging effect of the invention It is not particularly limited, halogen atom, hydroxyl, sulfydryl, thioether group, cyano, isocyano group, cyanic acid ester group, isocyanates can be enumerated Base, thiocyanate groups, isothiocyanate group, silicyl, silanol group, alkoxy, alkoxy carbonyl, carbamyl, thio ammonia Formoxyl, nitro, nitroso, carboxyl, carboxylate, acyl group, acyloxy, sulfino, sulfo group, sulfonate group, phosphino-, phosphine oxide Base, phosphono, phosphonate group, oxyimino, alkylether radicals, alkenyl ether, alkyl sulfide ether, alkenyl thioether group, aryl ether Base, aryl thioethers base, amino (- NH2,-NHR ,-NRR ': R and R ' separately indicate alkyl) etc..Contained by above-mentioned substituent group Hydrogen atom can be replaced by alkyl.In addition, alkyl contained by above-mentioned substituent group can be straight-chain, branched and ring-type Any one of.
As R1And R2Organic group in the substituent group other than alkyl, preferably halogen atom, hydroxyl, sulfydryl, sulphur Ether, cyano, isocyano group, cyanic acid ester group, isocyanate group, thiocyanate groups, isothiocyanate group, silicyl, silanol group, Alkoxy, alkoxy carbonyl, carbamyl, thiocarbamoyl, nitro, nitroso, carboxyl, carboxylate, acyl group, acyl-oxygen Base, sulfino, sulfo group, sulfonate group, phosphino-, phosphinyl, phosphono, phosphonate group, oxyimino, alkylether radicals, alkenyl Ether, alkyl sulfide ether, alkenyl thioether group, aryl ether, aryl thioethers base.
Among the above, as R1And R2, a preferably at least side be carbon number 1~12 alkyl or carbon number 1~12 aryl, or It is bonded to each other and is formed the Heterocyclylalkyl or heteroaryl of carbon number 2~20.As Heterocyclylalkyl, piperidyl, morpholinyl can be enumerated Deng imidazole radicals, pyrazolyl etc. can be enumerated as heteroaryl.
In above-mentioned formula (1), R3Indicate singly-bound or organic group.
As R3In organic group, can enumerate from alkyl, alkenyl, naphthenic base, cycloalkenyl, aryl, aralkyl etc. Group after eliminating 1 hydrogen atom.It can include substituent group in the organic group for the organic group.As Substituent group can enumerate R1And R2The group of middle illustration.In addition, the organic group can be any in straight-chain, branched Person.
Among the above, as R3, preferably singly-bound or 1 is eliminated from the aryl of the alkyl of carbon number 1~12 or carbon number 1~12 Group after a hydrogen atom.
In above-mentioned formula (1), R4And R5Separately indicate hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether group, first silicon Alkyl, silanol group, nitro, nitroso, sulfino, sulfo group, sulfonate group, phosphino-, phosphinyl, phosphono, phosphonate group have Machine group.
As R4And R5In organic group, R can be enumerated1And R2The group of middle illustration.For the organic group, With R1And R2The case where it is also possible to the key other than alkyl, substituent group in the organic group comprising hetero atom etc..Separately Outside, which can be any one of straight-chain, branched, ring-type.
Among the above, as R4And R5, preferably it is separately hydrogen atom, the ring of the alkyl of carbon number 1~10, carbon number 4~13 Alkyl, the cycloalkenyl of carbon number 4~13, the aryloxy alkyl of carbon number 7~16, the aralkyl of carbon number 7~20, the carbon number with cyano 2~11 alkyl, the alkyl of carbon number 1~10 with hydroxyl, the alkoxy of carbon number 1~10, the amide groups of carbon number 2~11, carbon The alkylthio group of number 1~10, the acyl group of carbon number 1~10, carbon number 2~11 ester group (- COOR ,-OCOR:R indicate alkyl), carbon number 6 ~20 aryl, is powered sub- property at the aryl for being powered the carbon number 6~20 after sub- property group and/or electron-withdrawing group replace Benzyl, cyano, methyl mercapto after group and/or the substitution of electron-withdrawing group.More preferable R4And R5The two is hydrogen atom or R4For Methyl, R5For hydrogen atom.
In above-mentioned formula (1), R6、R7、R8And R9Separately indicate hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether Base, silicyl, silanol group, nitro, nitroso, sulfino, sulfo group, sulfonate group, phosphino-, phosphinyl, phosphono, phosphonate ester Base, amino, ammonium or organic group.
As R6、R7、R8And R9In organic group, R can be enumerated1And R2The group of middle illustration.For the organic group For, with R1And R2The case where it is also possible to the key other than alkyl in the organic group comprising hetero atom etc., replace Base.In addition, the organic group can be any one of straight-chain, branched, ring-type.
In addition, in above-mentioned formula (1), R6And R7It is not hydroxyl.
R6、R7、R8And R9Can make 2 therein or more in conjunction with and form cyclic structure, also may include heteroatomic Key.As cyclic structure, Heterocyclylalkyl, heteroaryl etc. can be enumerated, or condensed ring.For example, R6、R7、R8And R9It can make 2 therein or more in conjunction with and shared R6、R7、R8And R9In conjunction with phenyl ring atom, so that it is thick to form naphthalene, anthracene, phenanthrene, indenes etc. Ring.
Among the above, as R6、R7、R8And R9, preferably separately for hydrogen atom, the alkyl of carbon number 1~10, carbon number 4~ 13 naphthenic base, the cycloalkenyl of carbon number 4~13, the aryloxy alkyl of carbon number 7~16, carbon number 7~20 aralkyl, there is cyano The alkyl of carbon number 2~11, the alkyl of carbon number 1~10 with hydroxyl, the alkoxy of carbon number 1~10, carbon number 2~11 amide Base, the alkylthio group of carbon number 1~10, the acyl group of carbon number 1~10, the ester group of carbon number 2~11, carbon number 6~20 aryl, be powered son Property group and/or electron-withdrawing group replace after carbon number 6~20 aryl, be powered sub- property group and/or electron-withdrawing base Benzyl, cyano, methyl mercapto, nitro after group's substitution.
In addition, from the viewpoint of making absorbing wavelength long wavelengthization, R6、R7、R8And R9It is preferred that following situations: making therein 2 A above combine and share R6、R7、R8And R9In conjunction with phenyl ring atom it is shared, to form the condensed ring such as naphthalene, anthracene, phenanthrene, indenes.
More preferable R6、R7、R8And R9All hydrogen atoms or R6、R7、R8And R9Any of for nitro, 3 remaining For hydrogen atom.
In above-mentioned formula (1), R10Indicate hydrogen atom or organic group.
As R10In organic group, R can be enumerated1And R2The group of middle illustration.For the organic group, with R1 And R2The case where it is also possible to the key other than alkyl, substituent group in the organic group comprising hetero atom etc..In addition, The organic group can be any one of straight-chain, branched, ring-type.
Above-mentioned formula (1) compound represented has-OR due to the contraposition in phenyl ring10Base, thus it is good to the dissolubility of solvent It is good.
Among the above, as R10, the preferably alkyl of hydrogen atom or carbon number 1~12, more preferably methyl.
As particularly preferred concrete example in above-mentioned formula (1) compound represented, chemical combination shown in following formula can be enumerated Object.
The synthetic method of above-mentioned formula (1) compound represented is not particularly limited, can be according to remembering in aftermentioned embodiment The method of load is synthesized.
Insulating film is formed in photosensitive polymer combination, (D) ingredient, that is, above-mentioned formula (1) compound represented content As long as being not particularly limited in the range for not damaging the purpose of the present invention.(D) usage amount of ingredient preferably makes containing for (C) ingredient The molar ratio ((C) component content/(D) component content) for measuring the content relative to (D) ingredient is 2.5/7.5~9.5/0.5's Amount, more preferably 3/7~9/1 amount.By using (D) ingredient with such amount, to be easy the wide sense of preparation exposure margin Photosensitive resin composition.
<(E) colorant>
Insulating film formation photosensitive polymer combination of the present invention can further include (E) colorant.
As (E) colorant contained by insulating film formation photosensitive polymer combination of the present invention, without spy It Xian Ding not be, it is preferable to use such as color index (C.I.；The Society of Dyers and Colourists company distribution) In be classified as the compound of pigment (Pigment), specifically, it is preferable to use being numbered with following color indexs (C.I.) Compound.
As the example that can be suitble to the yellow uitramarine used, C.I. pigment yellow 1 can be enumerated (hereinafter, being similarly " C.I. pigment yellow " only records number.),3,11,12,13,14,15,16,17,20,24,31,53,55,60,61,65,71, 73,74,81,83,86,93,95,97,98,99,100,101,104,106,108,109,110,113,114,116,117, 119、120、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、 166,167,168,175,180 and 185.
As the example that can be suitble to the orange pigment used, C.I. pigment orange 1 can be enumerated (hereinafter, being similarly " C.I. pigment orange " only records number.),5,13,14,16,17,24,34,36,38,40,43,46,49,51,55,59,61, 63,64,71 and 73.
As the example that can be suitble to the violet pigment used, C.I. pigment violet 1 can be enumerated (hereinafter, being similarly " C.I. pigment violet " only records number.), 19,23,29,30,32,36,37,38,39,40 and 50.
As the example that can be suitble to the red pigment used, C.I. paratonere 1 can be enumerated (hereinafter, being similarly " C.I. paratonere " only records number.)2,3,4,5,6,7,8,9,10,11,12,14,15,16,17,18,19,21,22,23, 30、31、32、37、38、40、41、42、48:1、48:2、48:3、48:4、49:1、49:2、50:1、52:1、53:1、57、57:1、 57:2、58:2、58:4、60:1、63:1、63:2、64:1、81:1、83、88、90:1、97、101、102、104、105、106、 108、112、113、114、122、123、144、146、149、150、151、155、166、168、170、171、172、174、175、 176、177、178、179、180、185、187、188、190、192、193、194、202、206、207、208、209、215、216、 217,220,223,224,226,227,228,240,242,243,245,254,255,264 and 265.
As the example that can be suitble to the blue pigment used, C.I. pigment blue 1 can be enumerated (hereinafter, being similarly " C.I. pigment blue " only records number.), 2,15,15:3,15:4,15:6,16,22,60,64 and 66.
As the example that can be suitble to pigment use, form and aspect other than the above, can enumerate C.I. pigment Green 7, C.I. the viridine greens such as pigment green 36, C.I. naphthol green 37；C.I. pigment brown 23, C.I. pigment brown 25, C.I. pigment brown 26, C.I. the browns such as pigment brown 28；C.I. the black pigments such as pigment black 1, C.I. pigment black 7.
In addition, in the case where making colorant as opacifier, as opacifier, it is preferable to use black pigment.As black Color pigment, can enumerate that carbon black, black, titanium is black, the metal oxide of copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver etc., reoxygenation The organic matters such as object, metal sulfide, metal sulfate or metal carbonate, inorganic matter can various pigment.It is excellent in these Choosing uses the carbon black with high light-proofness.
As carbon black, carbon black well known to channel black, furnace black, thermal crack black, lampblack etc. can be used, preferably make With the channel black that light-proofness is excellent.Furthermore it is also possible to use the carbon black of coated with resin.
In addition, above-mentioned organic pigment can be properly added as auxiliary pigment in order to adjust the tone of carbon black.
In order to be uniformly dispersed above-mentioned colorant in photosensitive polymer combination, dispersing agent can also be used.Make For such dispersing agent, it is preferable to use polyethyleneimine amine system, polyurethane resin system, acrylic resin macromolecule dispersing agent. In particular, in the case where using carbon black as colorant, it is preferable to use the dispersing agent of acrylic resin is as dispersing agent.
In addition, inorganic pigment and organic pigment can be used individually or be used in combination of two or more, in the case where being used in combination, Relative to 100 mass parts of total amount of inorganic pigment and organic pigment, organic pigment is preferably used with the range of 10~80 mass parts, Organic pigment is more preferably used with the range of 20~40 mass parts.
The usage amount of colorant in photosensitive polymer combination can be appropriate in the range for not damaging the purpose of the present invention Selection, typically, 100 mass parts of total amount of the solid component relative to photosensitive polymer combination, preferably 5~70 mass Part, more preferably 25~60 mass parts.
Colorant is preferably added to after being made using dispersing agent with dispersion liquid made of concentration appropriate dispersion photosensitive In property resin combination.
<(F) light absorber>
Insulating film formation photosensitive polymer combination of the present invention can also include (F) light absorber as needed (hereinafter also referred to as " (F) ingredient ".).It as (F) light absorber, is not particularly limited, can be used can absorb exposure light Light absorber, the particularly preferably light absorber of the light of the wavelength region of 200~450nm of absorption.Can enumerate such as naphthalene compound, Two naphthalene compounds, anthracene compound, phenanthroline compounds, dyestuff etc..
Specifically, alpha-Naphthol, betanaphthol, alpha-Naphthol methyl ether, alpha-Naphthol ethylether, 1,2- dihydroxy can be enumerated Naphthalene, 1,3- dihydroxy naphthlene, Isosorbide-5-Nitrae-dihydroxy naphthlene, 1,5- dihydroxy naphthlene, 1,6- dihydroxy naphthlene, 1,7- dihydroxy naphthlene, 1,8- dihydroxy Naphthalene derivatives or the anthracenes such as base naphthalene, 2,3- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, 2,7- dihydroxy naphthlene, anthracene, 9,10- dihydroxy-anthracene Or derivatives thereof；Azo based dye, benzophenone based dye, amino ketones based dye, quinoline based dye, anthraquinone based dye, hexichol The dyestuffs such as base cyanoacrylate based dye, triazine based dye, p-aminobenzoic acid based dye；Etc..In these, preferably make With naphthalene derivatives, particularly preferably there are the naphthalene derivatives of hydroxyl.These light absorbers, which can be used alone or combine two or more, to be made With.
(F) content of ingredient is preferably 0.01~10 mass relative to 100 mass parts of total amount of (A) ingredient and (B) ingredient Part, more preferably 0.05~7 mass parts, further preferably 0.1~5 mass parts.
<(S) organic solvent>
In order to improve coating, adjust viscosity, insulating film formation photosensitive polymer combination of the present invention is preferred Comprising (S) organic solvent (hereinafter also referred to as " (S) ingredient ".).
As organic solvent, specifically, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol list can be enumerated N-propyl ether, ethylene glycol list n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list n-propyl Ether, diethylene glycol list n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol Single ethylether, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether, dipropylene glycol monomethyl ether, dihydroxypropane single-ethyl ether, (poly-) such as dipropylene glycol list n-propyl ether, dipropylene glycol list n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol list ethylethers Alkylene glycol monoalkyl ethers class；Ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl Ether acetic acid ester, diethylene glycol monoethyl ether acetic acid esters, propylene glycol monomethyl ether (PGMEA), propylene glycol monoethyl second Acid esters etc. (poly-) alkylene glycol monoalkyl ethers acetate esters；Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethyl Other ethers such as glycol diethyl ether, tetrahydrofuran；The ketones such as methyl ethyl ketone, cyclohexanone, 2-HEPTANONE, 3- heptanone；2 hydroxy propanoic acid The lactic acid alkyl esters classes such as methyl esters, 2 hydroxy propanoic acid ethyl ester；2- hydroxy-2-methyl ethyl propionate, 3- methoxy methyl propionate, 3- first Oxygroup ethyl propionate, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2- Hydroxy-3-methyl butane acid methyl esters, 3- methoxybutyl acetic acid esters, 3- methyl -3- methoxybutyl acetic acid esters, 3- methyl -3- Methoxybutyl propionic ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid are just Pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, butyric acid N-butyl, pyruvic acid first Other esters such as ester, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid ethyl ester Class；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；N-Methyl pyrrolidone, n,N-Dimethylformamide, n,N-dimethylacetamide etc. Amides；Etc..In these, preferably alkylene glycol monoalkyl ethers class, alkylene glycol monoalkyl ethers acetate esters, on State other ethers, lactic acid alkyl ester class, other above-mentioned esters, more preferably alkylene glycol monoalkyl ethers acetate esters, above-mentioned Other ethers, other above-mentioned esters.These solvents can be used alone or in combination of two or more kinds.
(S) content of ingredient is not particularly limited, can be can be applied to the concentration of substrate etc. according to coated film thickness It is appropriately configured.The viscosity of photosensitive polymer combination is preferably 5~500cp, is more preferably 10~50cp, is further preferred For 20~30cp.In addition, solid component concentration is preferably 5~100 mass %, more preferably 20~50 mass %.
<other compositions>
It is can according to need in photosensitive polymer combination of the present invention containing surfactant, adaptation raising The additives such as agent, hot polymerization inhibitor, defoaming agent.Known additive can be used in any additive.As surface-active Agent can enumerate the compound of anionic system, cationic system, nonionic system etc., as adaptation enhancer, can enumerate previous Well known silicone couplet can enumerate quinhydrones, Hydroquinone monoethylether etc. as hot polymerization inhibitor, as defoaming agent, can enumerate silicon Ketone system, fluorine system compound etc..
<preparation method of photosensitive polymer combination>
Photosensitive polymer combination of the present invention can be prepared in the following manner: by above-mentioned each ingredient triple-roller mill The blenders such as machine, ball mill, sand mill are mixed (dispersion is kneaded), are carried out as needed with filters such as 5 μm of molecular filters It filters and prepares.
" insulating film "
Insulating film of the present invention and makes other than using above-mentioned insulating film formation photosensitive polymer combination The previous insulating film formed with photosensitive polymer combination is identical.Only the forming method of insulating film is illustrated below.
It is not particularly limited using the method that above-mentioned insulating film formation forms insulating film with photosensitive polymer combination, It can suitably be selected from the method used in the past.As the forming method of suitable insulating film, can enumerate including following work The method of sequence: above-mentioned insulating film formation is applied on substrate by painting process with photosensitive polymer combination, forms photonasty Resin layer；Exposure process is exposed photo-sensitive resin according to the pattern of the insulating film of regulation；Developing procedure makes to expose Photo-sensitive resin development afterwards, forms the pattern of insulating film.
Firstly, using roll coater, the contacts such as coating machine (reverse coater), bar coater is reversed to turn in painting process Print type apparatus for coating or rotator (rotary apparatus for coating), curtain curtain coater (curtain flow coater) etc. are non-contact Type apparatus for coating is coated with photosensitive polymer combination of the present invention on the substrate that will form insulating film, and according to need Photo-sensitive resin is formed by drying and removing solvent.
Next, the substrate that surface is formed with photo-sensitive resin is supplied to exposure process.In exposure process, across negative The mask of type irradiates ultraviolet light, excimer laser isoreactivity energy-ray to photo-sensitive resin, according to the insulating film of regulation Pattern carries out Partial exposure to photo-sensitive resin.High-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp, carbon arc lamp etc. can be used in exposure Issue the light source of ultraviolet light.Light exposure different, preferably such as 10~600mJ/cm according to the composition of photosensitive polymer combination2 Left and right.
Above-mentioned photosensitive polymer combination is forming exposure portion as protrusion, unexposed since exposure margin is wide When pattern of the portion as recess portion, even if improving light exposure, unexposed portion is also difficult to be not dissolved in alkali.Therefore, by using above-mentioned Photosensitive polymer combination, be easy exposure portion being formed as excellent in shape as protrusion, unexposed portion as the pattern of recess portion Pattern.In pattern of holes of the unexposed portion as hole portion, in the case where improving light exposure, especially it is not easy needed for being formed The hole of shape, but by using above-mentioned photosensitive polymer combination, the hole in the hole easy to form with required shape Pattern.
In developing procedure, by making the photo-sensitive resin after exposure develop with developer solution, to form predetermined pattern Insulating film.Developing method is not particularly limited, and infusion process, gunite etc. can be used.As the specific example of developer solution, can arrange Enumerate the developer solution of the organic systems such as monoethanolamine, diethanol amine, triethanolamine；Sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium hydroxide, The aqueous solution of quaternary ammonium salt etc..Photosensitive polymer combination of the present invention shows appropriate developability, it is thus possible to carry out Appropriate development.
Also, it bakes, is heating and curing after as needed, implementing to the pattern of the insulating film after development.It bakes afterwards Temperature is preferably 150~250 DEG C.
Embodiment
Hereinafter, present invention will be further described in detail through examples, but the present invention and it is not limited to the examples restriction.
<Examples 1 to 9, comparative example 1~4>
Each ingredient shown in following table 1 is mixed, solvent is dissolved in the amount that solid component content is 24 mass %, is prepared Photosensitive polymer combination.In addition, using PGMEA as solvent.
[table 1]
((A) ingredient)
As (A) ingredient, that is, alkali soluble resin, the acrylic resin or phenolphthalein base (Cardo) recorded in the following table 2 are used Resin.The value recorded in table 2 is content (quality %) of each structural unit relative to the quality of acrylic resin.In addition, phenolphthalein Base resin uses the resin synthesized by the following method.
[table 2]
The repetitive unit recorded in table 2 is as described below.
(synthetic method of phenolphthalein base resin)
Firstly, bisphenol fluorene type epoxy resin (epoxide equivalent 235) 235g, tetramethyl chlorine is added into 500ml four-hole boiling flask Change ammonium 110mg, 2,6-Di-tert-butyl-4-methylphenol 100mg and acrylic acid 72.0g, while with 25ml/ minutes speed to It is wherein blown into air, 90~100 DEG C of Bian are dissolved by heating.Then, it is slowly heated up in the state that solution is gonorrhoea, 120 DEG C are heated to, is made it completely dissolved.At this point, solution gradually becomes clear viscous, continue to stir in this case.In this phase Between, acid value is measured, continues heating stirring until acid value is less than 1.0mgKOH/g.Acid value reaches target and needs 12 hours.Then, cold But to room temperature, bisphenol fluorene type acrylic acid epoxy ester shown in colorless and transparent and solid-like following formula is obtained.
Next, 3- methoxyl group fourth is added into the above-mentioned bisphenol fluorene type epoxy acrylate 307.0g being achieved in that Yl acetate 600g and dissolve after, mix benzophenone tetracarboxylic dianhydride 80.5g and tetraethylammonium bromide 1g, slowly heat up, make It is reacted 4 hours at 110~115 DEG C.After confirming anhydride group and disappearing, 1,2,3,6- tetrabydrophthalic anhydrides are mixed 38.0g reacts it 6 hours, obtains phenolphthalein base resin.The disappearance of acid anhydrides is confirmed using IR spectrum.
((B) ingredient)
As (B) ingredient, that is, photopolymerization monomer, following substance is used.
DPHA: dipentaerythritol hexaacrylate
((C) ingredient)
As (C) ingredient, that is, Photoepolymerizationinitiater initiater, following substance is used.
OXE01:1- [4- (thiophenyl)] -1,2- octadione- 2- (O- benzoyl oximes) (BASF AG system " IRGACURE OXE01”)
OXE02:1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] ethyl ketone -1- (O- acetyl oxime) (BASF AG's system " IRGACURE OXE02 ")
NCI-831:ADEKA corporation " NCI-831 "
((D) ingredient)
In Examples and Comparative Examples, as (D) ingredient, that is, formula (1) compound represented, following MCIMA is used.For The synthetic method of MCIMA, is described below.
(synthetic method of MCIMA)
3- (4- methoxyphenyl) acryloyl chloride 5.90g (30mmol) is dissolved in the drying ether of 50ml, three second are added Amine 4.59ml (equivalent proportion 1.1), imidazoles 2.25ml (equivalent proportion 1.1), are stirred at room temperature 1 hour.With water 50ml, saturation NaHCO3After aqueous solution 50ml and 1N salt acid elution, it is dried, is concentrated under reduced pressure with magnesium sulfate.By hexane-acetic acid second Ester, as support carrier, is refined using column chromatography as developing solvent, silica gel, obtains MCIMA (3.41g, 15mmol).Third The yield of alkene acyl chlorides benchmark is 50%.
The insulating film formed for using the photosensitive polymer combination of Examples 1 to 9 and comparative example 1~4, according to Following methods carry out the measurement of relative dielectric constant and the evaluation of reagent resistance.In addition, for Examples 1 to 9 and comparative example 1~4 photosensitive polymer combination measures exposure margin in accordance with the following methods.
(relative dielectric constant measuring method)
Using rotator (MIKASASPINNER IH-360S, MIKASA Co. Ltd. system) with 200~1000rpm or so Revolving speed the photosensitive polymer combination prepared in the various embodiments described above and comparative example is spun onto SHIN-ETSU HANTOTAI's chemical industry strain After the low resistance substrate of formula commercial firm, keeps film 5 minutes dry at 80 DEG C, form 1 μm of film thickness of photo-sensitive resin.It connects down Come, using exposure device (EXM-1066, ORC Mfg. Co., Ltd.'s system), with light exposure 50mJ/cm2, to photo-sensitive resin It is exposed.It is baked after implementing under conditions of 230 DEG C 20 minutes to the photo-sensitive resin after exposure, forms insulating film.Benefit The opposite dielectric of insulating film is formed by with relative dielectric constant measurement device (SSM495, Japan's SSM Co. Ltd. system) measurement Constant.Measured relative dielectric constant is recorded in table 3.
(exposure margin measuring method)
Using rotator (MIKASASPINNER IH-360S, MIKASA Co. Ltd. system) with 200~1000rpm or so Revolving speed the photosensitive polymer combination prepared in the various embodiments described above and comparative example is spun onto SHIN-ETSU HANTOTAI's chemical industry strain After the substrate of formula commercial firm, keeps film 2 minutes dry at 100 DEG C, form 2~4 μm of film thickness of photo-sensitive resin.It connects down Come, using exposure device (MPA-600FA, Canon Co., Ltd's system), with light exposure 50mJ/cm2, across 5 μm of hole of bore The mask of pattern, is exposed photo-sensitive resin.In addition, making light exposure from 50mJ/cm to determine exposure margin2 With 10mJ/cm2It is increased and decreased for unit, across the mask of 5 μm of pattern of holes of bore, photo-sensitive resin is exposed Light.Next, using developing apparatus (TR-6132U, Tokyo Applied Chemistry Industrial Co., Ltd.'s system), with paddle development 100 at 23 DEG C Second.It is baked after implementing under conditions of 230 DEG C, 20 minutes to the pattern after development, forms insulating film.Bore will be opened up The minimum exposure amount in 5 μm of hole and the difference of maximum exposure amount are as exposure margin.Measured exposure margin is recorded in table 3.
(reagent resistance evaluation method)
Using rotator (MIKASASPINNER IH-360S, MIKASA Co. Ltd. system) with 200~1000rpm or so Revolving speed the photosensitive polymer combination prepared in the various embodiments described above and comparative example is spun onto SHIN-ETSU HANTOTAI's chemical industry strain After the substrate of formula commercial firm, keeps film 2 minutes dry at 100 DEG C, form 3 μm of film thickness of photo-sensitive resin.Next, sharp With exposure device (EXM-1066, ORC Mfg. Co., Ltd.'s system), with light exposure 50mJ/cm2, photo-sensitive resin is carried out Exposure.It is baked after implementing under conditions of 230 DEG C, 20 minutes to the photo-sensitive resin after exposure, forms insulating film.
Insulating film will be formed by 60 DEG C in anticorrosive additive stripping liquid controlling (ST-106, Tokyo Applied Chemistry Industrial Co., Ltd.'s system) Middle dipping 3 minutes evaluates reagent resistance using the variation of the film thickness of dipping front and back.Before the film thickness deficiency dipping after dipping Film thickness 120% the case where be evaluated as "○".In addition, by the film thickness after dipping be dipping before film thickness 120% or more feelings Condition is evaluated as "×".The evaluation result of reagent resistance is recorded in table 3.
[table 3]
According to Examples 1 to 9 it is found that including (A) alkali soluble resin, (B) photopolymerization monomer and (C) photopolymerization Formula (1) compound represented for cooperating (D) above-mentioned in the photosensitive polymer combination of initiator, and packet is come from using in resin The resin that the content of the structural unit of unsaturated compound containing epoxy group is 20~60 mass % is used as (A) ingredient, thus To being capable of forming reagent resistance is excellent and relative dielectric constant is low, insulating properties is excellent insulating film and wide exhausted of exposure margin Photosensitive polymer combination is used in velum formation.
According to comparative example 1 it is found that in photosensitive polymer combination, carry out self-contained ring as in the resin of (A) ingredient In the case that the content of the structural unit of the unsaturated compound of oxygroup is 60 mass %, it is formed by the opposite dielectric of insulating film Constant is got higher, insulating properties reduces.
According to comparative example 2 it is found that in feelings of the photosensitive polymer combination without (D) above-mentioned formula (1) compound represented Under condition, the exposure margin of photosensitive polymer combination is significantly reduced.
According to comparative example 3 and 4 it is found that in photosensitive polymer combination, as next self-contained in the resin of (A) ingredient In the case that the content of the structural unit of the unsaturated compound of epoxy group is lower than 20 mass %, it is formed by the resistance to examination of insulating film Agent reduces.In addition, also knowing, in the case, according to the structure of resin, the insulating properties for being formed by film is reduced, or sense The exposure margin stenosis of photosensitive resin composition is narrow.

Claims (4)

1. a kind of insulating film, which is formed, uses photosensitive polymer combination, contain (A) alkali soluble resin, (B) photopolymerization monomer, (C) Photoepolymerizationinitiater initiater and (D) following formula (1) compound represented,
(A) alkali soluble resin be comprising
8 mass of mass %~16 % of structural unit (a1) from unsaturated carboxylic acid,
Carry out the copolymer of 20 mass of mass %~60 % of structural unit (a2) of the unsaturated compound of self-contained epoxy group,
In formula, R1And R2It is bonded to each other and is formed the Heterocyclylalkyl or heteroaryl or R of carbon number 2~201And R2Independently earth's surface Show the aryl of hydrogen atom, the alkyl of carbon number 1~12 or carbon number 1~12, wherein R1And R2In at least one party be carbon number 1~12 The aryl of alkyl or carbon number 1~12；R3Indicate singly-bound；R4And R5Separately indicate hydrogen atom, the alkyl of carbon number 1~10, carbon The naphthenic base of number 4~13, the cycloalkenyl of carbon number 4~13, the aralkyl of carbon number 7~20, carbon number 1~10 alkoxy or carbon number 6 ~20 aryl；R6、R7、R8And R9Separately indicate hydrogen atom, halogen atom, hydroxyl or nitro；Wherein, R6And R7No For hydroxyl；R10Indicate the alkyl of hydrogen atom or carbon number 1~12.
2. insulating film according to claim 1, which is formed, uses photosensitive polymer combination, wherein the content of (C) ingredient The molar ratio of content relative to (D) ingredient is 2.5/7.5~9.5/0.5.
3. a kind of insulating film is formed using insulating film formation photosensitive polymer combination described in as claimed in claim 1 or 22 's.
4. a kind of forming method of insulating film comprising following process:
Insulating film formation of any of claims 1 or 2 is applied on substrate, shape by painting process with photosensitive polymer combination At photo-sensitive resin；
Exposure process is exposed the photo-sensitive resin according to the pattern of the insulating film of regulation；And
Developing procedure, the photo-sensitive resin development after making the exposure, forms the pattern of insulating film.
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