CN103365087A - Photosensitive resin composition for formation of insulating film, insulating film, a method for forming insulating film - Google Patents
Photosensitive resin composition for formation of insulating film, insulating film, a method for forming insulating film Download PDFInfo
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- CN103365087A CN103365087A CN2013100971025A CN201310097102A CN103365087A CN 103365087 A CN103365087 A CN 103365087A CN 2013100971025 A CN2013100971025 A CN 2013100971025A CN 201310097102 A CN201310097102 A CN 201310097102A CN 103365087 A CN103365087 A CN 103365087A
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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
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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
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
- G03F7/09—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
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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
- G03F7/20—Exposure; Apparatus therefor
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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
- G03F7/20—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
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
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- Spectroscopy & Molecular Physics (AREA)
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- Materials For Photolithography (AREA)
Abstract
The invention provides an insulating film which has excellent insulation performance and reagent resistance, and a photosensitive resin composition for the formation of the insulating film, which has wide exposure margin during formation of patterns of the insulating film. In addition, the invention provides an insulating film that is formed by using the photosensitive resin composition and a method for forming the insulating film by using the photosensitive resin composition. According to the photosensitive resin composition, a compound with a specific structure is cooperated in (A) an alkali soluble resin, (B) a photo-polymerizable monomer and (C) a photo-polymerization initiator, and a resin that includes a specific amount of structural units from an unsaturated compound containing an epoxy group is taken as the (A) alkali soluble resin.
Description
Technical field
The present invention relates to dielectric film forms with photosensitive polymer combination, forms the dielectric film that forms with photosensitive polymer combination and use this dielectric film to form the formation method of the dielectric film of using photosensitive polymer combination by this dielectric film.
Background technology
, in the electronic units such as liquid crystal display cells, integrated circuit component, solid-state photographic element, to insulate between the distribution that is configured to stratiform in order making in the past, and to form dielectric film etc. at wiring closet.This dielectric film is formed by various materials such as inoranic membrane, organic films, and in the situation of organic film, it mostly uses hot curing resin composition or photosensitive polymer combination and forms.
As the photosensitive polymer combination that is used to form such dielectric film, known have the polymerizable compound that comprises alkali soluble resin, have ethylenic unsaturated bond and a photosensitive polymer combination of light trigger, wherein, described alkali soluble resin be the monomer that comprises unsaturated double-bond, the monomer that comprises carboxylic acid and unsaturated double-bond, with the multipolymer that comprises the monomer of allylic ad hoc structure, its molecular weight distribution (Mw/Mn) is 1.0～3.5 (with reference to patent documentations 1).
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2012-012602 communique
Summary of the invention
Invent problem to be solved
Yet, there are the following problems for the photosensitive polymer combination of record in the patent documentation 1: namely allow to form the good dielectric film of insulativity, exposure nargin (margin) the selection degree of freedom narrow and processing conditions in the time of also can making the pattern that forms dielectric film is low.In addition, dielectric film is in its manufacturing procedure or comprise and can be exposed to such as various test solutions such as anticorrosive additive stripping liquid controllings in the manufacturing procedure of electronic unit of dielectric film, thereby requires reagent resistance excellent.Yet the photoresist elements of record may not be abundant to the permanance of the test solutions such as anticorrosive additive stripping liquid controlling in the patent documentation 1.
The present invention finishes in view of above-mentioned problem, and its purpose is, dielectric film and the wide dielectric film formation photosensitive polymer combination of the exposure nargin when forming the pattern of dielectric film that can form insulativity and reagent resistance excellence are provided.In addition, the present invention also aims to, the use dielectric film that above-mentioned dielectric film formation forms with photosensitive polymer combination is provided and uses above-mentioned dielectric film to form the formation method of the dielectric film of using photosensitive polymer combination.
For the method for dealing with problems
The inventor etc. conduct in-depth research repeatedly in order to solve above-mentioned problem.Found that: at the compound that comprises (A) alkali soluble resin, (B) photopolymerization monomer and (C) cooperate ad hoc structure in the photosensitive polymer combination of Photoepolymerizationinitiater initiater, and with the resin of the structural unit of the unsaturated compound of the next self-contained epoxy radicals that comprises specified quantitative as (A) alkali soluble resin, thereby can solve above-mentioned problem, so that finish the present invention.Specifically, the invention provides following scheme.
The first scheme of the present invention is a kind of dielectric film formation photosensitive polymer combination, it contains (A) alkali soluble resin, (B) photopolymerization monomer, (C) Photoepolymerizationinitiater initiater and (D) compound shown in the following formula (1)
Above-mentioned (A) alkali soluble resin is the multipolymer of structural unit that comprises the unsaturated compound of self-contained epoxy radicals,
The ratio of the structural unit of unsaturated compound in above-mentioned (A) alkali soluble resin, above-mentioned next self-contained epoxy radicals is 20～60 quality %.
(in the formula, R
1And R
2Represent independently respectively hydrogen atom or organic group.Wherein, R
1And R
2In at least one party represent organic group.R
1And R
2Can be bonded to each other and form ring texture, also can comprise heteroatomic key.R
3Expression singly-bound or organic group.R
4And R
5Represent independently respectively hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether group, silicyl, silanol base, nitro, nitroso-, sulfino (sulfino), sulfo group (sulfo), sulphonic acid ester (sulfonate) base, phosphino-(phosphino), phosphinyl (phosphinyl), phosphono (phosphono), phosphonate ester (phosphonate) base or organic group.R
6, R
7, R
8And R
9Represent independently respectively hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether group, silicyl, silanol base, nitro, nitroso-, sulfino, sulfo group, sulfonate group, phosphino-, phosphinyl, phosphono, phosphonate group, amino, ammonium (ammonio) or organic group.Wherein, R
6And R
7It is not hydroxyl.R
6, R
7, R
8And R
9Can make combination more than 2 wherein and form ring texture, also can comprise heteroatomic key.R
10Expression hydrogen atom or organic group.)
Alternative plan of the present invention is to use the described dielectric film of the first scheme to form the dielectric film that forms with photosensitive polymer combination.
The formation method that third party's case of the present invention is a kind of dielectric film, it comprises following operation:
Painting process is applied to the described dielectric film formation of the first scheme on the substrate with photosensitive polymer combination, forms photo-sensitive resin;
Exposure process, the pattern of dielectric film according to the rules exposes to above-mentioned photo-sensitive resin; And
Developing procedure develops the photo-sensitive resin after the above-mentioned exposure, forms the pattern of dielectric film.
The invention effect
According to the present invention, can provide dielectric film and the wide dielectric film formation photosensitive polymer combination of the exposure nargin when forming the pattern of dielectric film that can form insulativity and reagent resistance excellence.In addition, according to the present invention, the use dielectric film that above-mentioned dielectric film formation forms with photosensitive polymer combination can be provided and use above-mentioned dielectric film to form the formation method of the dielectric film of using photosensitive polymer combination.
Embodiment
" dielectric film forms and uses photosensitive polymer combination "
Dielectric film formation photosensitive polymer combination of the present invention (below, be also referred to as " photosensitive polymer combination ".) contain at least (A) alkali soluble resin (below, be also referred to as " (A) composition ".), (B) photopolymerization monomer (below, be also referred to as " (B) composition ".), (C) Photoepolymerizationinitiater initiater (below, be also referred to as " (C) composition ".) and (D) compound shown in the above-mentioned formula (1) (below, be also referred to as " (D) composition ".)。Below, describe with each contained composition of photosensitive polymer combination for dielectric film formation of the present invention.
＜(A) alkali soluble resin 〉
Alkali soluble resin refers to: utilizing resin concentration is the resin solution (solvent: propylene glycol monomethyl ether) form the resin molding of thickness 1 μ m at substrate of 20 quality %, be that dipping dissolved the resin of the above thickness of 0.01 μ m in the time of 1 minute in the KOH aqueous solution of 0.05 quality % with it in concentration.
As (A) alkali soluble resin, use the multipolymer of the structural unit of the unsaturated compound that comprises to come self-contained epoxy radicals.(A) ratio of the structural unit of unsaturated compound in the alkali soluble resin, that come self-contained epoxy radicals is 20～60 quality %, is preferably 20～40 quality %.By using (A) alkali soluble resin that comprises the structural unit of the unsaturated compound that comes self-contained epoxy radicals with such ratio, thereby formed easily the dielectric film of insulativity excellence by photosensitive polymer combination.
As (A) as long as the resin that composition is used contains the structural unit of unsaturated compound of the next self-contained epoxy radicals of ormal weight then to be not particularly limited, can be from the alkali soluble resin that in the past various photosensitive polymer combinations, used suitable choice for use.As the resin that is suitable as (A) composition, from the viewpoint of the dielectric film of easy acquisition reagent resistance excellence, can list and comprise at least the resin that makes the multipolymer (A1) that (a1) unsaturated carboxylic acid and the unsaturated polymerizable compound that (a2) contains epoxy radicals form.
As (a1) unsaturated carboxylic acid, can list the monocarboxylic acids such as (methyl) acrylic acid, crotonic acid; The dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; The acid anhydrides of these dicarboxylic acid; Etc..In the middle of these, from the alkali dissolubility of the resin of copolyreaction, gained, the viewpoints such as easiness of acquisition, preferred (methyl) acrylic acid and maleic anhydride.These (a1) unsaturated carboxylic acids can be used alone or in combination of two or more kinds.
The unsaturated compound that contains epoxy radicals as (a2), can list the unsaturated compound that (a2-I) has the unsaturated compound of ester ring type epoxy radicals and (a2-II) do not have the ester ring type epoxy radicals, the unsaturated compound that preferred (a2-I) has the ester ring type epoxy radicals.
(a2-I) have in the unsaturated compound of ester ring type epoxy radicals, the ester ring type base that consists of the ester ring type epoxy radicals can be that monocycle also can be many rings.Ester ring type base as monocycle can list cyclopentyl, cyclohexyl etc.In addition, as the ester ring type base of many rings, can list norborny, isobornyl, three ring nonyls, three ring decyls, Fourth Ring dodecyl etc.The unsaturated compound that these (a2-I) contain the ester ring type epoxy radicals can be used alone or in combination of two or more kinds.
Specifically, the unsaturated compound as (a2-I) contains the ester ring type epoxy radicals can list for example compound shown in the following formula (a2-1)～(a2-16).In the middle of these, in order to obtain the development of appropriateness, the compound shown in the preferred following formula (a2-1)～(a2-6), the more preferably compound shown in the following formula (a2-1)～(a2-4).
In the above-mentioned formula, R
11Expression hydrogen atom or methyl, R
12The divalent sturated aliphatic hydrocarbon base of expression carbon number 1～6, R
13The divalent alkyl of expression carbon number 1～10, n represents 0～10 integer.As R
12, the alkylidene of preferred straight chain shape or a chain, for example methylene, ethylidene, propylidene, tetramethylene, ethyl ethylidene, pentamethylene, hexa-methylene.As R
13, preference such as methylene, ethylidene, propylidene, tetramethylene, ethyl ethylidene, pentamethylene, hexa-methylene, phenylene, cyclohexylidene ,-CH
2-Ph-CH
2-(Ph represents phenylene).
The unsaturated compound that contains epoxy radicals that does not have the ester ring type base as (a2-II), can list (methyl) glycidyl acrylate, (methyl) acrylic acid 2-methyl ethylene oxidic ester, (methyl) acrylic acid 3,4-epoxy radicals butyl ester, (methyl) acrylic acid 6, (methyl) acrylic acid epoxy base alkyl esters such as 7-epoxy radicals heptyl ester; α-ethylacrylate ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, α-ethylacrylate 6, the alpha-alkyl acrylic acid epoxy base alkyl esters such as 7-epoxy radicals heptyl ester; Etc..In the middle of these, the viewpoints such as intensity of the resin after copolyreaction, curing, preferred (methyl) glycidyl acrylate, (methyl) acrylic acid 2-methyl ethylene oxidic ester and (methyl) acrylic acid 6,7-epoxy radicals heptyl ester.The unsaturated compound that contains epoxy radicals that these (a2-II) do not have the ester ring type base can be used alone or in combination of two or more kinds.
Multipolymer (A1) can be to make the unsaturated compound that contains the ester ring type base that (a3) do not have an epoxy radicals with above-mentioned (a1) unsaturated carboxylic acid and (a2) contain the multipolymer that the unsaturated compound of epoxy radicals is polymerized.
Contain the unsaturated compound of ester ring type base as (a3), just be not particularly limited so long as have the unsaturated compound of ester ring type base.The ester ring type base can be that monocycle also can be many rings.Ester ring type base as monocycle can list cyclopentyl, cyclohexyl etc.In addition, as the ester ring type base of many rings, can list adamantyl, norborny, isobornyl, three ring nonyls, three ring decyls, Fourth Ring dodecyl etc.The unsaturated compound that these (a3) contain the ester ring type base can be used alone or in combination of two or more kinds.
Specifically, the unsaturated compound as (a3) contains the ester ring type base can list for example compound shown in the following formula (a3-1)～(a3-7).In the middle of these, from the viewpoint of the good photosensitive polymer combination of easy acquisition development, the compound shown in the preferred following formula (a3-3)～(a3-8), the more preferably compound shown in following formula (a3-3), (a3-4).
In the above-mentioned formula, R
21Expression hydrogen atom or methyl, R
22The divalent sturated aliphatic hydrocarbon base of expression singly-bound or carbon number 1～6, R
23The alkyl of expression hydrogen atom or carbon number 1～5.As R
22, the alkylidene of preferred singly-bound, straight chain shape or a chain, for example methylene, ethylidene, propylidene, tetramethylene, ethyl ethylidene, pentamethylene, hexa-methylene.As R
23, preference such as methyl, ethyl.
Multipolymer (A1) also can be the multipolymer that also copolymerization has above-mentioned other compounds in addition.As other such compounds, can list (methyl) esters of acrylic acid, (methyl) acrylic amide, allyl compound, vinyl ethers, vinyl ester, phenylethylene etc.These compounds can be used alone or in combination of two or more kinds.
As (methyl) esters of acrylic acid, can list (methyl) alkyl acrylate of the straight chain shape such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) acrylic acid uncle monooctyl ester or a chain; (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, can list (methyl) acrylamide, N-alkyl (methyl) acrylamide, N-aryl (methyl) acrylamide, N, N-dialkyl group (methyl) acrylamide, N, N-aryl (methyl) acrylamide, N-methyl-N-phenyl (methyl) acrylamide, N-hydroxyethyl-N-methyl (methyl) acrylamide etc.
As allyl compound, can list the allyl ester classes such as allyl acetate, allyl hexanoate, allyl octanoate, lauric acid allyl ester, palmitic acid allyl ester, stearic acid allyl ester, benzoic acid allyl ester, acetoacetic acid allyl ester, lactic acid allyl ester; The allyl ethoxy-ethanol; Etc..
As vinyl ethers, can list hexyl vinyl ether, octyl group vinyl ether, decave, ethylhexyl vinyl ether, methoxy ethyl vinyl ether, ethoxyethyl group vinyl ether, chloroethyl vinyl ether, 1-methyl-2, the alkyl vinyl ethers such as 2-dimethyl propyl vinyl ether, 2-ethyl-butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethyl aminoethyl vinyl ether, diethylamino ethyl vinyl ether, butyl amino-ethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; Vinyl phenyl ether, vinyltoluene base ether, vinyl chloride phenyl ether, vinyl-2, the ethenyl aromatic yl ethers such as 4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthryl ether; Etc..
As vinyl ester, can list vinyl butyrate, isobutyric acid vinyl acetate, vinyl trimethylace tonitric ester, vinyl diethacetic acid ester, valeric acid vinyl acetate, vinyl caproate, vinyl chloroacetate, dichloroacetic acid vinyl acetate, vinyl methoxyacetic acid ester, vinyl butoxy acetic acid ester, vinyl benzene yl acetate, vinyl acetoacetic ester, lactic acid vinyl acetate, vinyl-beta-phenyl butyric ester, vinyl benzoate, vinyl salicylate, chlorobenzoic acid vinyl acetate, tetrachloro-benzoic acid vinyl acetate, naphthoic acid vinyl acetate etc.
As phenylethylene, can list styrene; The ring-alkylated styrenes such as methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, diethylbenzene ethene, cumene ethene, butylstyrene, hexyl benzene ethene, cyclohexyl benzene ethene, decyl styrene, benzyl styrene, 1-chloro-4-methyl-benzene, trifluoromethyl styrene, ethoxyl methyl styrene, acetoxy-methyl styrene; The alkoxystyrene such as methoxy styrene, 4-methoxyl-3-methyl styrene, dimethoxy styrene; The halogenated styrenes such as chlorostyrene, dichlorostyrene, trichloro-benzenes ethene, tetrachlorobenzene ethene, pentachlorobenzene ethene, bromstyrol, Dowspray 9, iodobenzene ethene, fluorobenzene ethene, trifluorostyrene, 2-bromo-4-trifluoromethyl styrene, 4-fluoro-3-trifluoromethyl styrene; Etc..
Be preferably 1～25 quality %, 8～16 quality % more preferably from structural unit shared ratio in multipolymer (A1) of above-mentioned (a1) unsaturated carboxylic acid.In addition, the structural unit shared ratio in multipolymer (A1) that contains the unsaturated compound of ester ring type base from above-mentioned (a3) is preferably 1～30 quality %, 5～20 quality % more preferably.
The matter average molecular weight of multipolymer (A1) (Mw: the styrene that utilizes gel permeation chromatography (GPC) convert and measured value.Synonym all in this instructions.) be preferably 2000～200000, more preferably 5000～30000.By making the matter average molecular weight in above-mentioned scope, thereby exist the film of obtaining easily photosensitive polymer combination to form the tendency of the balance of the development after ability, the exposure.
Multipolymer (A1) can be made by known radical polymerization.That is, make each compound and known radical polymerization initiator be dissolved in polymer solvent after, add thermal agitation, thereby can make this multipolymer (A1).
In addition, as (A) alkali soluble resin, can be fit to use comprise the structural unit that has at least from above-mentioned (a1) unsaturated carboxylic acid, contain from above-mentioned (a2) epoxy radicals unsaturated compound structural unit and have can with the resin of the multipolymer (A2) of the structural unit at the position of (B) described later photopolymerization monomer polymerization.Comprise in the situation of multipolymer (A2) at alkali soluble resin (A), can improve photosensitive polymer combination to adaptation, the breakdown strength of photosensitive polymer combination after curing of substrate.
Multipolymer (A2) yet copolymerization have in the multipolymer (A1) as other compounds put down in writing, the multipolymer of (methyl) esters of acrylic acid, (methyl) acrylic amide, allyl compound, vinyl ethers, vinyl ester, phenylethylene etc.
Have can preferably have with the structural unit at the position of (B) photopolymerization monomer polymerization ethylenically unsaturated group as can with the structural unit at the position of (B) photopolymerization monomer polymerization.Have from the structural unit of above-mentioned (a1) unsaturated carboxylic acid and contain the part and (a1) unsaturated carboxylic acid reaction of the epoxy radicals in the multipolymer of structural unit of unsaturated compound of epoxy radicals from above-mentioned (a2) by making, thereby can prepare multipolymer (A2).
The matter average molecular weight of multipolymer (A2) is preferably 2000～50000, more preferably 5000～30000.By making the matter average molecular weight in above-mentioned scope, exist the film of obtaining easily photosensitive polymer combination to form the tendency of the balance of the development after ability, the exposure.
(A) content of alkali soluble resin is preferably 30～90 quality %, 45～75 quality % more preferably with respect to the solid constituent of photosensitive polymer combination.By making this content in above-mentioned scope, there is the tendency of the balance that obtains easily development.
＜(B) photopolymerization monomer 〉
Form with contained (B) photopolymerization monomer in the photosensitive polymer combination as dielectric film of the present invention, can preferably use the monomer with ethylenically unsaturated group.As this monomer with ethylenically unsaturated group, monofunctional monomer and polyfunctional monomer are arranged.
As monofunctional monomer, can list (methyl) acrylamide, methylol (methyl) acrylamide, methoxy (methyl) acrylamide, ethoxyl methyl (methyl) acrylamide, propoxyl group methyl (methyl) acrylamide, butoxy methoxy (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxymethyl (methyl) acrylamide, (methyl) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, the 2-acrylamide-2-methyl propane sulfonic, N-tert-butyl acrylamide sulfonic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (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) acryloxy-2-hydroxypropyl phthalic ester, single (methyl) acrylic acid glyceride, (methyl) tetrahydrofurfuryl acrylate, dimethylamino (methyl) acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid 2,2, the 2-trifluoro ethyl ester, (methyl) acrylic acid 2,2,3,3-tetrafluoro propyl ester, half (methyl) acrylate of phthalic acid derivatives etc.These monofunctional monomers can be used alone or in combination of two or more kinds.
On the other hand; as polyfunctional monomer; can list ethylene glycol bisthioglycolate (methyl) acrylate; diethylene glycol two (methyl) acrylate; TEG two (methyl) acrylate; propylene glycol two (methyl) acrylate; many propylene glycol two (methyl) acrylate; butylene glycol two (methyl) acrylate; neopentyl glycol two (methyl) acrylate; 1; 6-hexanediol two (methyl) acrylate; trimethylolpropane tris (methyl) acrylate; glycerine two (methyl) acrylate; pentaerythritol triacrylate; tetramethylol methane tetraacrylate; dipentaerythritol five acrylate; dipentaerythritol acrylate; pentaerythrite two (methyl) acrylate; pentaerythrite three (methyl) acrylate; pentaerythrite four (methyl) acrylate; dipentaerythritol five (methyl) acrylate; dipentaerythritol six (methyl) acrylate; 2; two (4-(methyl) the acryloxy diethoxy phenyl) propane of 2-; 2; two (4-(methyl) the acryloxy polyethoxy phenyl) propane of 2-; 2-hydroxyl-3-(methyl) acryloxy propyl group (methyl) acrylate; ethylene glycol bisthioglycolate glycidyl ether two (methyl) acrylate; diethylene glycol diglycidyl ether two (methyl) acrylate; phthalic acid diglycidyl ester two (methyl) acrylate; glycerol tri-acrylate; glycerine poly epihydric alcohol base ether gathers (methyl) acrylate; carbamate (methyl) acrylate (namely; toluene diisocyanate); the reactant of trimethyl hexamethylene diisocyanate and hexamethylene diisocyanate etc. and 2-hydroxyethyl (methyl) acrylate; di-2-ethylhexylphosphine oxide (methyl) acrylamide; (methyl) acrylamide methylene ether; the polyfunctional monomers such as condensation product of polyvalent alcohol and N-methylol (methyl) acrylamide; 1; 3; 5-triacryl six hydrogen-1; 3,5-triazine (triacrylformal) etc.These polyfunctional monomers can be used alone or in combination of two or more kinds.
These have in the monomer of ethylenically unsaturated group, form with photosensitive polymer combination the adaptation of substrate, the viewpoint of the intensity of photosensitive polymer combination after curing from improving dielectric film, the polyfunctional monomer that preferred 3 officials can be above, more preferably 6 officials can above polyfunctional monomer.
(B) content of composition forms solid constituent with photosensitive polymer combination with respect to dielectric film and is preferably 5～60 quality %, 10～50 quality % more preferably.By making this content in above-mentioned scope, there is the tendency of the balance that obtains easily light sensitivity, development, sharpness.
＜(C) Photoepolymerizationinitiater initiater 〉
Form with contained (C) Photoepolymerizationinitiater initiater of photosensitive polymer combination as dielectric film of the present invention, be not particularly limited, can use in the past known Photoepolymerizationinitiater initiater.
As Photoepolymerizationinitiater initiater; specifically; can list the 1-hydroxycyclohexylphenylketone; 2-hydroxy-2-methyl-1-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-dimethoxy-1; 2-diphenylethane-1-ketone; two (4-dimethylaminophenyl) ketone; 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholino propane-1-ketone; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethyl ketone-1-(O-acetyl oxime); (9-ethyl-6-nitro-9H-carbazole-3-yl) [4-(2-methoxyl-1-methyl ethoxy)-2-aminomethyl phenyl] ketone O-acetyl oxime; 1-[4-(thiophenyl)]-1; 2-octadione-2-(O-benzoyl oximes); 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; 4-benzoyl-4 '-methyl dimethoxy base thioether; the 4-dimethylaminobenzoic acid; 4-dimethylaminobenzoic acid methyl esters; EDMAB; 4-dimethylaminobenzoic acid butyl ester; 4-dimethylamino-2-ethylhexyl benzoic acid; 4-dimethylamino-2-isoamyl benzene formic acid; benzyl-'beta '-methoxy ethyl acetal; the benzil dimethyl ketal; 1-phenyl-1; 2-propanedione-2-(O-ethoxy carbonyl) oxime; o-benzoyl yl benzoic acid methyl esters; 2; the 4-diethyl thioxanthone; CTX; 2; 4-dimethyl thioxanthones; 1-chloro-4-propoxyl group thioxanthones; thioxanthene; 2-diuril ton; 2; 4-diethyl thioxanthene; 2-methyl thioxanthene; 2-isopropyl thioxanthene; the 2-EAQ; the prestox anthraquinone; 1; 2-benzo anthraquinone; 2; 3-diphenyl anthraquinone; azoisobutyronitrile; benzoyl peroxide; cumene peroxide; 2-mercaptobenzimidazole; the 2-mercaptobenzoxazole; 2-mercaptobenzothiazole; 2-(Chloro-O-Phenyl)-4; 5-two (m-methoxyphenyl)-imidazole radicals dipolymer; benzophenone; the 2-chlorobenzophenone; p; p '-two (dimethylamino) benzophenone; 4; 4 '-two (diethylamino) benzophenone; 4; 4 '-dichloro benzophenone; 3; 3-dimethyl-4-methoxy benzophenone; benzil; benzoin; benzoin methyl ether; the benzoin ethylether; the benzoin isopropyl ether; the benzoin n-butyl ether; the benzoin isobutyl ether; the benzoin butyl ether; acetophenone; 2; the 2-diethoxy acetophenone; to dimethyl acetophenone; to the dimethylamino propiophenone; dichloroacetophenone; trichloroacetophenone; p-tert.-butyl acetophenone; to the dimethylamino benzoylformaldoxime; to tert-butyl group trichloroacetophenone; to tert-butyl group dichloroacetophenone; α; α,α-dichloro-4-phenoxy acetophenone; thioxanthones; 2-methyl thioxanthones; ITX; Dibenzosuberone; amyl group-4-dimethylaminobenzoic acid ester; the 9-phenylacridine; 1; 7-pair-(9-acridinyl) heptane; 1; 5-pair-(9-acridinyl) pentane; 1; 3-pair-(9-acridinyl) propane; to the methoxyl triazine; 2; 4; 6-three (trichloromethyl) s-triazine; 2-methyl-4; two (trichloromethyl) s-triazine of 6-; 2-[2-(5-methylfuran-2-yl) vinyl]-4; two (trichloromethyl) s-triazine of 6-; 2-[2-(furans-2-yl) vinyl]-4; two (trichloromethyl) s-triazine of 6-; 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4; two (trichloromethyl) s-triazine of 6-; 2-[2-(3; the 4-Dimethoxyphenyl) vinyl]-4; two (trichloromethyl) s-triazine of 6-; 2-(4-methoxyphenyl)-4; two (trichloromethyl) s-triazine of 6-; 2-(4-ethoxybenzene vinyl)-4; two (trichloromethyl) s-triazine of 6-; 2-(4-n-butoxy phenyl)-4; two (trichloromethyl) s-triazine of 6-; 2; 4-pair-trichloromethyl-6-(3-bromo-4-methoxyl) phenyl s-triazine; 2; 4-pair-trichloromethyl-6-(2-bromo-4-methoxyl) phenyl s-triazine; 2; 4-pair-trichloromethyl-6-(3-bromo-4-methoxyl) styryl phenyl s-triazine; 2,4-pair-trichloromethyl-6-(2-bromo-4-methoxyl) styryl phenyl s-triazine etc.These Photoepolymerizationinitiater initiaters can be used alone or in combination of two or more kinds.
In the middle of these, aspect light sensitivity, particularly preferably use the Photoepolymerizationinitiater initiater of oxime system.As more preferred example in the Photoepolymerizationinitiater initiater of oxime system; can list 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethyl ketone-1-(O-acetyl oxime), (9-ethyl-6-nitro-9H-carbazole-3-yl) [4-(2-methoxyl-1-methyl ethoxy)-2-aminomethyl phenyl] ketone O-acetyl oxime and 1-[4-(thiophenyl)]-1,2-octadione-2-(O-benzoyl oximes).
(C) content of composition forms solid constituent with photosensitive polymer combination with respect to dielectric film and is preferably 0.5～30 quality %, 1～20 quality % more preferably.Content by making (C) composition is in above-mentioned scope, thereby can obtain to form the photosensitive polymer combination of the dielectric film of reagent resistance excellence.
In addition, in this (C) composition, can combined light cause auxiliary agent.As light-initiated auxiliary agent, can list triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, benzoic acid 2-dimethylamino ethyl ester, N, the N-dimethyl-p-toluidine, 4,4 '-two (dimethylamino) benzophenone, 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene, 2-mercaptobenzothiazole, the 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-5-methoxybenzothiazole, the 3-mercaptopropionic acid, the 3-mercapto-propionate, pentaerythrite four mercaptoacetates, the mercaptan compounds such as 3-mercaptopropionic acid ester etc.These light-initiated auxiliary agents can be used alone or in combination of two or more kinds.
＜(D) compound shown in the formula (1) 〉
Dielectric film of the present invention forms and contains the compound shown in the following formula (1) with photosensitive polymer combination.By making photosensitive polymer combination contain this compound, can widen the exposure nargin of photosensitive polymer combination.In addition, the compound shown in the formula (1) brings harmful effect for easily the light sensitivity of photosensitive polymer combination, the dielectric film intensity of gained.
In the above-mentioned formula (1), R
1And R
2Represent independently respectively hydrogen atom or organic group, R
1And R
2In at least one party represent organic group.
As R
1And R
2In organic group, can list alkyl, thiazolinyl, naphthenic base, cycloalkenyl group, aryl, aralkyl etc.For this organic group, can in this organic group, comprise the key except alkyl, the substituting group of heteroatoms etc.In addition, this organic group can be in straight chain shape, chain, the ring-type any one.This organic group is generally 1 valency, when the situation that forms ring texture etc., can also be the above organic group of divalent.
R
1And R
2Can be bonded to each other and form ring texture, also can further comprise heteroatomic key.As ring texture, can list Heterocyclylalkyl, heteroaryl etc., also can be condensed ring.
As R
1And R
2Organic group in the key except alkyl, only otherwise damaging effect of the present invention then is not particularly limited, can list heteroatomic keys such as comprising oxygen atom, nitrogen-atoms, silicon atom.As object lesson, can list ehter bond, thioether bond, carbonyl key, thion key, ester bond, amido link, amino-formate bond, imido key (N=C (R)-,-C (=NR)-: R represents hydrogen atom or organic group), carbonic acid ester bond, sulphonyl key, sulfenyl key, azo bond etc.
From stable on heating viewpoint, as R
1And R
2Organic group in the key except alkyl, preferred ehter bond, thioether bond, carbonyl key, thion key, ester bond, amido link, amino-formate bond, imido key (N=C (R)-,-C (=NR)-: R represents hydrogen atom or 1 valency organic group), carbonic acid ester bond, sulphonyl key, sulfenyl key.
As R
1And R
2Organic group in the substituting group except alkyl; only otherwise damaging effect of the present invention then is not particularly limited, can list halogen atom; hydroxyl; sulfydryl; thioether group; cyano group; isocyano group; cyanate ester based; isocyanate group; thiocyanate groups; isothiocyanate group; silicyl; the silanol base; alkoxy; alkoxy carbonyl; carbamyl; thiocarbamoyl; nitro; nitroso-; carboxyl; carboxylic acid ester groups; acyl group; acyloxy; sulfino; sulfo group; sulfonate group; phosphino-; phosphinyl; phosphono; phosphonate group; oxyimino; alkylether radicals; the thiazolinyl ether; the alkyl sulfide ether; the thiazolinyl thioether group; the aryl ether; the aryl thioethers base; amino (NH
2,-NHR ,-NRR ': R and R ' represent respectively alkyl independently) etc.The contained hydrogen atom of above-mentioned substituting group can be replaced by alkyl.In addition, the contained alkyl of above-mentioned substituting group can be in straight chain shape, a chain and the ring-type any one.
As R
1And R
2Organic group in the substituting group except alkyl, preferred halogen atom; hydroxyl; sulfydryl; thioether group; cyano group; isocyano group; cyanate ester based; isocyanate group; thiocyanate groups; isothiocyanate group; silicyl; the silanol base; alkoxy; alkoxy carbonyl; carbamyl; thiocarbamoyl; nitro; nitroso-; carboxyl; carboxylic acid ester groups; acyl group; acyloxy; sulfino; sulfo group; sulfonate group; phosphino-; phosphinyl; phosphono; phosphonate group; oxyimino; alkylether radicals; the thiazolinyl ether; the alkyl sulfide ether; the thiazolinyl thioether group; the aryl ether; the aryl thioethers base.
In above-mentioned, as R
1And R
2, preferred at least one party is the alkyl of carbon number 1～12 or the aryl of carbon number 1～12, perhaps is bonded to each other and forms Heterocyclylalkyl or the heteroaryl of carbon number 2～20.As Heterocyclylalkyl, can list piperidyl, morpholinyl etc., as heteroaryl, can list imidazole radicals, pyrazolyl etc.
In the above-mentioned formula (1), R
3Expression singly-bound or organic group.
As R
3In organic group, can list the group of from alkyl, thiazolinyl, naphthenic base, cycloalkenyl group, aryl, aralkyl etc., having removed behind 1 hydrogen atom.For this organic group, can in this organic group, comprise substituting group.As substituting group, can list R
1And R
2In illustrative group.In addition, this organic group can be in straight chain shape, the chain any one.
In above-mentioned, as R
3, preferred singly-bound or from the aryl of the alkyl of carbon number 1～12 or carbon number 1～12, removed 1 hydrogen atom after group.
In the above-mentioned formula (1), R
4And R
5Represent independently respectively hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether group, silicyl, silanol base, nitro, nitroso-, sulfino, sulfo group, sulfonate group, phosphino-, phosphinyl, phosphono, phosphonate group or organic group.
As R
4And R
5In organic group, can list R
1And R
2In illustrative group.For this organic group, with R
1And R
2Situation same, can in this organic group, comprise the key except alkyl, the substituting group of heteroatoms etc.In addition, this organic group can be in straight chain shape, chain, the ring-type any one.
In above-mentioned, as R
4And R
5, preferred is hydrogen atom respectively independently; the alkyl of carbon number 1～10; the naphthenic base of carbon number 4～13; the cycloalkenyl group of carbon number 4～13; the aryloxy alkyl of carbon number 7～16; the aralkyl of carbon number 7～20; alkyl with carbon number 2～11 of cyano group; alkyl with carbon number 1～10 of hydroxyl; the alkoxy of carbon number 1～10; the amide group of carbon number 2～11; the alkylthio group of carbon number 1～10; the acyl group of carbon number 1～10; ester group (the COOR of carbon number 2～11;-OCOR:R represents alkyl); the aryl of carbon number 6～20; given the aryl of the carbon number 6～20 after electronics group and/or electrophilic group replace; given the benzyl after electronics group and/or electrophilic group replace; cyano group; methyl mercapto.More preferably R
4And R
5Both are hydrogen atom, or R
4Be methyl, R
5Be hydrogen atom.
In the above-mentioned formula (1), R
6, R
7, R
8And R
9Represent independently respectively hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether group, silicyl, silanol base, nitro, nitroso-, sulfino, sulfo group, sulfonate group, phosphino-, phosphinyl, phosphono, phosphonate group, amino, ammonium or organic group.
As R
6, R
7, R
8And R
9In organic group, can list R
1And R
2In illustrative group.For this organic group, with R
1And R
2Situation same, can in this organic group, comprise the key except alkyl, the substituting group of heteroatoms etc.In addition, this organic group can be in straight chain shape, chain, the ring-type any one.
In addition, in the above-mentioned formula (1), R
6And R
7It is not hydroxyl.
R
6, R
7, R
8And R
9Can make combination more than 2 wherein and form ring texture, also can comprise heteroatomic key.As ring texture, can list Heterocyclylalkyl, heteroaryl etc., also can be condensed ring.For example, R
6, R
7, R
8And R
9Can make combination more than 2 wherein and have R
6, R
7, R
8And R
9The atom of the phenyl ring of institute's combination, thus the condensed ring such as naphthalene, anthracene, phenanthrene, indenes formed.
In above-mentioned, as R
6, R
7, R
8And R
9, preferred is hydrogen atom respectively independently; the alkyl of carbon number 1～10; the naphthenic base of carbon number 4～13; the cycloalkenyl group of carbon number 4～13; the aryloxy alkyl of carbon number 7～16; the aralkyl of carbon number 7～20; alkyl with carbon number 2～11 of cyano group; alkyl with carbon number 1～10 of hydroxyl; the alkoxy of carbon number 1～10; the amide group of carbon number 2～11; the alkylthio group of carbon number 1～10; the acyl group of carbon number 1～10; the ester group of carbon number 2～11; the aryl of carbon number 6～20; given the aryl of the carbon number 6～20 after electronics group and/or electrophilic group replace; given the benzyl after electronics group and/or electrophilic group replace; cyano group; methyl mercapto; nitro.
In addition, from making the viewpoint of absorbing wavelength long wavelengthization, R
6, R
7, R
8And R
9Preferred following situation: make wherein more than 2 in conjunction with and total R
6, R
7, R
8And R
9The atom of the phenyl ring of institute's combination is total, thereby forms the condensed ring such as naphthalene, anthracene, phenanthrene, indenes.
More preferably R
6, R
7, R
8And R
9All be hydrogen atom, perhaps R
6, R
7, R
8And R
9In any be that 3 of nitros, residue are for hydrogen atom.
In the above-mentioned formula (1), R
10Expression hydrogen atom or organic group.
As R
10In organic group, can list R
1And R
2In illustrative group.For this organic group, with R
1And R
2Situation same, can in this organic group, comprise the key except alkyl, the substituting group of heteroatoms etc.In addition, this organic group can be in straight chain shape, chain, the ring-type any one.
Compound shown in the above-mentioned formula (1) is owing to the contraposition at phenyl ring has-OR
10Base, thereby to the favorable solubility of solvent.
In above-mentioned, as R
10, be preferably the alkyl of hydrogen atom or carbon number 1～12, more preferably methyl.
As particularly preferred concrete example in the compound shown in the above-mentioned formula (1), can list the compound shown in the following formula.
The synthetic method of the compound shown in the above-mentioned formula (1) is not particularly limited, and can synthesize according to the method for putting down in writing among the embodiment described later.
Dielectric film form with in the photosensitive polymer combination, (D) composition is that the content of the compound shown in the above-mentioned formula (1) needs only and then is not particularly limited in the scope of not damaging purpose of the present invention.(D) use amount of composition preferably makes the content of (C) composition be the amount of 2.5/7.5～9.5/0.5, more preferably 3/7～9/1 amount with respect to the molar ratio of the content of (D) composition ((C) component content/(D) component content).By using (D) composition with such amount, the wide photosensitive polymer combination of nargin thereby easy preparation exposes.
＜(E) colorant 〉
Dielectric film of the present invention forms can further comprise (E) colorant with photosensitive polymer combination.
Form with contained (E) colorant of photosensitive polymer combination as dielectric film of the present invention, be not particularly limited, preferably use for example color index (C.I.; The distribution of The Society of Dyers and Colourists company) be classified as the compound of pigment (Pigment) in, specifically, the preferred compound that uses with following color index (C.I.) numbering.
As the example of the yellow uitramarine that can be fit to use, can list C.I. pigment yellow 1 (below, be " C.I. pigment yellow " too, record numbering only.), 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 of the orange pigment that can be fit to use, can list C.I. pigment orange 1 (below, be " C.I. pigment orange " too, record numbering only.), 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 of the violet pigment that can be fit to use, can list the C.I. pigment violet 1 (below, be " C.I. pigment violet " too, record numbering only.), 19,23,29,30,32,36,37,38,39,40 and 50.
As the example of the red pigment that can be fit to use, can list C.I. paratonere 1 (below, be " C.I. paratonere " too, record numbering only.) 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 of the blue pigment that can be fit to use, can list the C.I. pigment blue 1 (below, be " C.I. alizarol saphirol " too, record numbering only.), 2,15,15:3,15:4,15:6,16,22,60,64 and 66.
Example as the pigment of the form and aspect beyond that can be fit to use, above-mentioned can list the viridine greens such as C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 37; C.I. browns such as pigment brown 23, C.I. pigment brown 25, C.I. pigment brown 26, C.I. pigment brown 28; C.I. the black pigment such as pigment black 1, C.I. pigment black 7.
In addition, in the situation that makes colorant as opacifier, as opacifier, preferably use black pigment.As black pigment, can list that carbon black, perylene is black, titanium black, organism, the inorganicss such as metal oxide, double oxide, metal sulfide, metal sulfate or metal carbonate of copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver etc. all can various pigment.In the middle of these, the preferred carbon black with high light-proofness that uses.
As carbon black, can use channel black, furnace black, thermals, the known carbon black such as dim, preferably use the channel black of light-proofness excellence.In addition, can also use the carbon black of coated with resin.
In addition, in order to adjust the tone of carbon black, can suitably add above-mentioned organic pigment as auxiliary pigment.
For above-mentioned colorant is disperseed equably, can also use spreading agent in photosensitive polymer combination.As such spreading agent, preferably use the macromolecule dispersing agent of polyethyleneimine system, urethane resin system, acrylic resin.Particularly, using in the situation of carbon black as colorant, preferably use the spreading agent of acrylic resin as spreading agent.
In addition, inorganic pigment and organic pigment can distinguish separately use or and with more than 2 kinds, and the situation of usefulness under, total amount 100 mass parts with respect to inorganic pigment and organic pigment, preferably use organic pigment with the scope of 10～80 mass parts, more preferably use organic pigment with the scope of 20～40 mass parts.
The use amount of the colorant in the photosensitive polymer combination can suitably be selected in the scope of not damaging purpose of the present invention, typically, with respect to total amount 100 mass parts of the solid constituent of photosensitive polymer combination, be preferably 5～70 mass parts, 25～60 mass parts more preferably.
Colorant preferably adds in the photosensitive polymer combination after the use spreading agent is made the dispersion liquid that disperses to form with suitable concentration.
＜(F) light absorber 〉
Dielectric film of the present invention form with photosensitive polymer combination can also comprise as required (F) light absorber (below, be also referred to as " (F) composition ".)。As (F) light absorber, be not particularly limited, can use the light absorber that can absorb exposure light, particularly preferably absorb the light absorber of light of the wavelength region may of 200～450nm.Can list such as naphthalene compound, two naphthalene compounds, anthracene compound, phenanthroline compounds, dyestuff etc.
Specifically, can list alpha-Naphthol, betanaphthol, alpha-Naphthol methyl ether, alpha-Naphthol ethylether, 1,2-dihydroxy naphthlene, 1,3-dihydroxy naphthlene, 1,4-dihydroxy naphthlene, 1,5-dihydroxy naphthlene, 1,6-dihydroxy naphthlene, 1,7-dihydroxy naphthlene, 1,8-dihydroxy naphthlene, 2,3-dihydroxy naphthlene, 2,6-dihydroxy naphthlene, 2,7-dihydroxy naphthlene, anthracene, 9, naphthalene derivatives or the anthracene or derivatives thereofs such as 10-dihydroxy-anthracene; The dyestuffs such as azo based dye, benzophenone based dye, amino ketones based dye, quinoline based dye, anthraquinone based dye, diphenyl cyanoacrylate based dye, triazine based dye, p-aminobenzoic acid based dye; Etc..In the middle of these, preferably use naphthalene derivatives, particularly preferably have the naphthalene derivatives of hydroxyl.These light absorbers can be used alone or in combination of two or more kinds.
(F) content of composition with respect to (A) composition and (B) total amount 100 mass parts of composition be preferably 0.01～10 mass parts, more preferably 0.05～7 mass parts, 0.1～5 mass parts more preferably.
＜(S) organic solvent 〉
In order to improve coating, adjusting viscosity, dielectric film of the present invention form with photosensitive polymer combination preferably comprise (S) organic solvent (below, be also referred to as " (S) composition ".)。
As organic solvent, specifically, can list the glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl n-propyl ether, the glycol monomethyl n-butyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol list n-propyl ether, diethylene glycol list n-butyl ether, the triethylene glycol monomethyl ether, triethylene glycol list ethylether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether, DPGME, dihydroxypropane single-ethyl ether, the single n-propyl ether of dipropylene glycol, the single n-butyl ether of dipropylene glycol, the tripropylene glycol monomethyl ether, (gathering) the alkylene glycol monoalkyl ethers classes such as tripropylene glycol list ethylether; (gathering) the alkylene glycol monoalkyl ethers acetate esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, TC acetic acid esters, propylene glycol monomethyl ether (PGMEA), propylene glycol list ethylether acetic acid esters; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; The ketones such as MEK, cyclohexanone, 2-HEPTANONE, 3-heptanone; The lactic acid alkyl ester classes such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester; 2-hydroxy-2-methyl ethyl propionate, the 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl butane acid methyl esters, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butyl propionic ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, other ester classes such as 2-Oxobutyric acid ethyl ester; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; The amide-types such as 1-METHYLPYRROLIDONE, DMF, DMA; Etc..In the middle of these, be preferably alkylene glycol monoalkyl ethers class, alkylene glycol monoalkyl ethers acetate esters, above-mentioned other ethers, lactic acid alkyl ester class, above-mentioned other ester classes, more preferably alkylene glycol monoalkyl ethers acetate esters, above-mentioned other ethers, above-mentioned other ester classes.These solvents can be used alone or in combination of two or more kinds.
(S) content of composition is not particularly limited, and can suitably set according to coated film thickness with the concentration that can be applied to substrate etc.The viscosity of photosensitive polymer combination is preferably 5～500cp, more preferably 10～50cp, 20～30cp more preferably.In addition, solid component concentration is preferably 5～100 quality %, 20～50 quality % more preferably.
＜other compositions 〉
Can contain as required the adjuvants such as surfactant, adaptation improving agent, hot polymerization inhibitor, defoamer in the photosensitive polymer combination of the present invention.Any adjuvant all can use in the past known adjuvant.As surfactant, can list the compound of negative ion system, kation system, nonionic system etc., as the adaptation improving agent, can list in the past known silicone couplet, as hot polymerization inhibitor, quinhydrones, Hydroquinone monoethylether etc. can be listed, as defoamer, silicone-based, fluorine based compound etc. can be listed.
The preparation method of＜photosensitive polymer combination 〉
Photosensitive polymer combination of the present invention can be with the preparation of following method: above-mentioned each composition is mixed (dispersion, mixing) with stirring machines such as three-roll mill, bowl mill, sand mills, filter with filtrators such as 5 μ m membrane filters as required and prepare.
" dielectric film "
Dielectric film of the present invention is except using above-mentioned dielectric film to form with the photosensitive polymer combination, and the dielectric film in the past that forms with using photosensitive polymer combination is identical.Below only the formation method of dielectric film is described.
Be not particularly limited with the method that photosensitive polymer combination forms dielectric film with above-mentioned dielectric film formation, can from the method that in the past adopted, suitably select.Formation method as the dielectric film that is fit to can list the method that comprises following operation: painting process, above-mentioned dielectric film formation is applied on the substrate with photosensitive polymer combination, and form photo-sensitive resin; Exposure process, the pattern of dielectric film according to the rules exposes to photo-sensitive resin; Developing procedure develops the photo-sensitive resin after the exposure, forms the pattern of dielectric film.
At first, in the painting process, use roll coater, reverse coating machine (reverse coater), rod to be coated with contact transfer printing type apparatus for coating or the non-contact type apparatus for coating such as spinner (rotary apparatus for coating), curtain formula curtain coater (curtain flow coater) such as machine, will form the substrate coating photosensitive polymer combination of the present invention of dielectric film, and as required by dry desolventizing, form photo-sensitive resin.
Next, the substrate that the surface is formed with photo-sensitive resin supplies to exposure process.In the exposure process, across the mask of minus, to photo-sensitive resin irradiation ultraviolet radiation, excimer laser isoreactivity energy-ray, the pattern of dielectric film according to the rules carries out the part exposure to photo-sensitive resin.Exposure can use high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp, carbon arc lamp etc. to send ultraviolet light source.Exposure is according to the composition of photosensitive polymer combination and difference, and preference is such as 10～600mJ/cm
2About.
Above-mentioned photosensitive polymer combination is because exposure nargin is wide, thereby forming exposure section as protuberance, unexposed during as the pattern of recess, even improve exposure, unexposed section also is difficult to be not dissolved in alkali.Therefore, by using above-mentioned photosensitive polymer combination, easily exposure section is formed the pattern of excellent in shape as protuberance, unexposed the pattern as recess.In unexposed the pattern of holes as hole section, in the situation that improves exposure, be difficult for forming especially the hole of required form, but by using above-mentioned photosensitive polymer combination, form easily the pattern of holes in the hole with required form.
In the developing procedure, develop by make the photo-sensitive resin after the exposure with developer solution, thereby form the dielectric film of predetermined pattern.Developing method is not particularly limited, and can use infusion process, gunite etc.As the object lesson of developer solution, can list the developer solution of the organic systems such as monoethanolamine, diethanolamine, triethanolamine; The aqueous solution of NaOH, potassium hydroxide, sodium carbonate, ammoniacal liquor, quaternary ammonium salt etc.Photosensitive polymer combination of the present invention demonstrates the development of appropriateness, thereby can carry out appropriate development.
And, as required, cure after the pattern enforcement to the dielectric film after developing, be heating and curing.After the temperature of curing be preferably 150～250 ℃.
Embodiment
Below, further describe the present invention by embodiment, but the present invention is not subjected to the restriction of these embodiment.
＜embodiment 1～9, comparative example 1～4 〉
Each composition shown in the following table 1 is mixed, and the amount take solid component content as 24 quality % is dissolved in solvent, the preparation photosensitive polymer combination.In addition, as solvent, use PGMEA.
[table 1]
((A) composition)
Be alkali soluble resin as (A) composition, use acryl resin or phenolphthalein base (Cardo) resin of record in the following table 2.The value of record is that each structural unit is with respect to the content (quality %) of the quality of acryl resin in the table 2.In addition, phenolphthalein base resin uses synthetic by the following method resin.
[table 2]
The repetitive of record is as described below in the table 2.
(synthetic method of phenolphthalein base resin)
At first, in the 500ml four-hole boiling flask, add bisphenol fluorene type epoxy resin (epoxide equivalent 235) 235g, tetramethyl ammonium chloride 110mg, 2,6-two-tert-butyl-4-methyl-Phenol 100mg and acrylic acid 72.0g, to wherein being blown into air, heating for dissolving was carried out at 90～100 ℃ in the limit with 25ml/ minute speed on the limit.Then, be slowly to heat up under the state of gonorrhoea at solution, be heated to 120 ℃, it is dissolved fully.At this moment, the solution transparent thickness that becomes gradually continues to stir under this state.During this period, measure acid number, continue to add thermal agitation until the not enough 1.0mgKOH/g of acid number.Acid number arrives target needs 12 hours.Then, be cooled to room temperature, obtain the bisphenol fluorene type acrylic acid epoxy ester shown in the following formula of water white transparency and solid shape.
Next, after adding 3-methoxyl butylacetic acid ester 600g and dissolving in the above-mentioned bisphenol fluorene type epoxy acrylate 307.0g of such acquisition, mix benzophenone tetracarboxylic dianhydride 80.5g and tetraethylammonium bromide 1g, slowly heat up, make it 110～115 ℃ of lower reactions 4 hours.After confirming the anhydride group disappearance, mix 1,2,3,6-tetrabydrophthalic anhydride 38.0g, under 90 ℃, make its reaction 6 hours, obtain phenolphthalein base resin.Utilize IR spectrum to confirm the disappearance of acid anhydrides.
((B) composition)
Be photopolymerization monomer as (B) composition, use following material.
DPHA: dipentaerythritol acrylate
((C) composition)
Be Photoepolymerizationinitiater initiater as (C) composition, use following material.
OXE01:1-[4-(thiophenyl)]-1,2-octadione-2-(O-benzoyl oximes) (BASF AG's system " IRGACURE OXE01 ")
OXE02:1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethyl ketone-1-(O-acetyl oxime) (BASF AG's system " IRGACURE OXE02 ")
NCI-831:ADEKA company system " NCI-831 "
((D) composition)
In embodiment and the comparative example, be the compound shown in the formula (1) as (D) composition, use following MCIMA.Synthetic method for MCIMA is described below.
(synthetic method of MCIMA)
3-(4-methoxyphenyl) acryloyl chloride 5.90g (30mmol) is dissolved in the dry ether of 50ml, adds triethylamine 4.59ml (equivalent proportion 1.1), imidazoles 2.25ml (equivalent proportion 1.1), at room temperature stirred 1 hour.Water 50ml, saturated NaHCO
3Behind aqueous solution 50ml and the 1N salt acid elution, carry out drying with magnesium sulphate, under reduced pressure concentrated.With hexane-ethyl acetate as developing solvent, silica gel as prop carrier, utilize column chromatography to make with extra care, obtain MCIMA (3.41g, 15mmol).The yield of acryloyl chloride benchmark is 50%.
The dielectric film that forms for the photosensitive polymer combination that uses embodiment 1～9 and comparative example 1～4 in accordance with the following methods, carries out the mensuration of relative dielectric constant and the evaluation of reagent resistance.In addition, for the photosensitive polymer combination of embodiment 1～9 and comparative example 1～4, in accordance with the following methods, measure exposure nargin.
(relative dielectric constant assay method)
After utilizing spinner (MIKASASPINNER IH-360S, MIKASA Co., Ltd. system) with the rotating speed about 200～1000rpm the photosensitive polymer combination for preparing in the various embodiments described above and the comparative example to be spun onto the low resistance substrate of Shin-Etsu Chemial Co., Ltd's system, making films descended dry 5 minutes at 80 ℃, formed the photo-sensitive resin of thickness 1 μ m.Next, utilize exposure device (EXM-1066, ORC Mfg. Co., Ltd.'s system), with exposure 50mJ/cm
2, photo-sensitive resin is exposed.After under 230 ℃ of conditions of 20 minutes the photo-sensitive resin after the exposure being implemented, cure, form dielectric film.Utilize relative dielectric constant determinator (SSM495, Japanese SSM Co., Ltd. system) to measure the relative dielectric constant of formed dielectric film.The relative dielectric constant that record is measured in the table 3.
(exposure nargin assay method)
After utilizing spinner (MIKASASPINNER IH-360S, MIKASA Co., Ltd. system) with the rotating speed about 200～1000rpm the photosensitive polymer combination for preparing in the various embodiments described above and the comparative example to be spun onto the substrate of Shin-Etsu Chemial Co., Ltd's system, making films descended dry 2 minutes at 100 ℃, formed the photo-sensitive resin of thickness 2～4 μ m.Next, utilize exposure device (MPA-600FA, Canon Co., Ltd's system), with exposure 50mJ/cm
2, the mask across the pattern of holes of bore 5 μ m is used exposes to photo-sensitive resin.In addition, in order to determine exposure nargin, make exposure from 50mJ/cm
2With 10mJ/cm
2For unit increases and decreases, the mask across the pattern of holes of bore 5 μ m is used exposes to photo-sensitive resin.Next, use developing apparatus (TR-6132U, Tokyo Applied Chemistry Industrial Co., Ltd.'s system), under 23 ℃, developed for 100 seconds with the oar formula.After under 230 ℃, 20 minutes the condition pattern after developing being implemented, cure, form dielectric film.Can offer the difference of the minimum exposure amount in hole of bore 5 μ m and maximum exposure amount as exposure nargin.The exposure nargin that record is measured in the table 3.
(reagent resistance evaluation method)
After utilizing spinner (MIKASASPINNER IH-360S, MIKASA Co., Ltd. system) with the rotating speed about 200～1000rpm the photosensitive polymer combination for preparing in the various embodiments described above and the comparative example to be spun onto the substrate of Shin-Etsu Chemial Co., Ltd's system, making films descended dry 2 minutes at 100 ℃, formed the photo-sensitive resin of thickness 3 μ m.Next, utilize exposure device (EXM-1066, ORC Mfg. Co., Ltd.'s system), with exposure 50mJ/cm
2, photo-sensitive resin is exposed.After under 230 ℃, 20 minutes the condition photo-sensitive resin after the exposure being implemented, cure, form dielectric film.
Under 60 ℃ formed dielectric film was being flooded 3 minutes in anticorrosive additive stripping liquid controlling (ST-106, Tokyo Applied Chemistry Industrial Co., Ltd.'s system), utilizing the variation of the thickness of dipping front and back to estimate reagent resistance.Be " zero " with 120% average evaluation of the thickness before the not enough dipping of the thickness behind the dipping.In addition, be " * " with the thickness behind the dipping for the average evaluation more than 120% that floods front thickness.The evaluation result of record reagent resistance in the table 3.
[table 3]
According to embodiment 1～9 as can be known, comprising (A) alkali soluble resin, (B) photopolymerization monomer and (C) cooperate the compound shown in (D) above-mentioned formula (1) in the photosensitive polymer combination of Photoepolymerizationinitiater initiater, and with the content of the structural unit of the unsaturated compound of the next self-contained epoxy radicals in the resin be the resin of 20～60 quality % as (A) composition, obtain thus forming the reagent resistance excellence, and relative dielectric constant is low, the wide dielectric film of the dielectric film of insulativity excellence and exposure nargin forms uses photosensitive polymer combination.
According to comparative example 1 as can be known, in photosensitive polymer combination, content as the structural unit of the unsaturated compound of the next self-contained epoxy radicals in the resin of (A) composition is in the situation of 60 quality %, and the relative dielectric constant of formed dielectric film uprises, insulativity reduces.
According to comparative example 2 as can be known, do not contain at photosensitive polymer combination in the situation of the compound shown in (D) above-mentioned formula (1), the exposure nargin of photosensitive polymer combination significantly reduces.
According to comparative example 3 and 4 as can be known, in photosensitive polymer combination, content as the structural unit of the unsaturated compound of the next self-contained epoxy radicals in the resin of (A) composition is lower than in the situation of 20 quality %, and the reagent resistance of formed dielectric film reduces.In addition, also as can be known, in the case, according to the structure of resin, the insulativity of formed film reduces, and perhaps the exposure nargin stenosis of photosensitive polymer combination is narrow.
Claims (4)
1. a dielectric film forms and uses photosensitive polymer combination, and it contains (A) alkali soluble resin, (B) photopolymerization monomer, (C) Photoepolymerizationinitiater initiater and (D) compound shown in the following formula (1),
Described (A) alkali soluble resin is the multipolymer of structural unit that comprises the unsaturated compound of self-contained epoxy radicals,
The ratio of the structural unit of unsaturated compound in described (A) alkali soluble resin, described next self-contained epoxy radicals is 20～60 quality %,
In the formula, R
1And R
2Represent independently respectively hydrogen atom or organic group; Wherein, R
1And R
2In at least one party represent organic group; R
1And R
2Can be bonded to each other and form ring texture, also can comprise heteroatomic key; R
3Expression singly-bound or organic group; R
4And R
5Represent independently respectively hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether group, silicyl, silanol base, nitro, nitroso-, sulfino, sulfo group, sulfonate group, phosphino-, phosphinyl, phosphono, phosphonate group or organic group; R
6, R
7, R
8And R
9Represent independently respectively hydrogen atom, halogen atom, hydroxyl, sulfydryl, thioether group, silicyl, silanol base, nitro, nitroso-, sulfino, sulfo group, sulfonate group, phosphino-, phosphinyl, phosphono, phosphonate group, amino, ammonium or organic group; Wherein, R
6And R
7It is not hydroxyl; R
6, R
7, R
8And R
9Can make combination more than 2 wherein and form ring texture, also can comprise heteroatomic key; R
10Expression hydrogen atom or organic group.
2. dielectric film according to claim 1 forms and uses photosensitive polymer combination, and wherein, the content of described (C) composition is 2.5/7.5～9.5/0.5 with respect to the molar ratio of the content of described (D) composition.
3. dielectric film, it is that right to use requires 1 or 2 described dielectric films to form to form with photosensitive polymer combination.
4. the formation method of a dielectric film, it comprises following operation:
Painting process is applied to claim 1 or 2 described dielectric films formation on the substrate with photosensitive polymer combination, forms photo-sensitive resin;
Exposure process, the pattern of dielectric film according to the rules exposes to described photo-sensitive resin; And
Developing procedure develops the photo-sensitive resin after the described exposure, forms the pattern of dielectric film.
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| CN109946926A (en) * | 2017-12-21 | 2019-06-28 | 东友精细化工有限公司 | Photosensitive polymer combination and the insulating pattern formed by it |
| CN110045578A (en) * | 2018-01-16 | 2019-07-23 | 东友精细化工有限公司 | Negative light-sensitive resin combination, photocuring film and image display device |
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| KR20240013372A (en) | 2022-07-22 | 2024-01-30 | 주식회사 이엔에프테크놀로지 | Novel polymer and photosensitive resin composition comprising the same |
| KR20240025223A (en) | 2022-08-18 | 2024-02-27 | 주식회사 이엔에프테크놀로지 | Novel polymer and photosensitive resin composition comprising the same |
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| KR102007537B1 (en) | 2019-08-05 |
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