CN104380199A - Photosensitive composition - Google Patents

Photosensitive composition Download PDF

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Publication number
CN104380199A
CN104380199A CN201380031157.4A CN201380031157A CN104380199A CN 104380199 A CN104380199 A CN 104380199A CN 201380031157 A CN201380031157 A CN 201380031157A CN 104380199 A CN104380199 A CN 104380199A
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Prior art keywords
methyl
acid
compound
photosensitive
acrylate
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Inventor
长坂一辉
石黑智仁
羽手村建太郎
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Adeka Corp
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Asahi Denka Kogyo KK
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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
    • G03F7/075—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5465—Silicon-containing compounds containing nitrogen containing at least one C=N bond
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Provided are: a photosensitive composition which is capable of forming a desired pattern; and a colored photosensitive composition which provides a colored pattern that has improved adhesion to a base. A photosensitive composition which contains a silane coupling agent that is formed of a blocked isocyanate silane obtained by reacting an isocyanate compound represented by general formula (I) and a blocking agent. A colored photosensitive composition which is obtained by adding a coloring agent to the photosensitive composition. A black matrix which is obtained by curing the colored photosensitive composition on a base. A color filter which is provided with the black matrix.

Description

Photosensitive composite
Technical field
The present invention relates to the photosensitive composite containing the silane coupling agent comprising blocked isocyanate silane, in this photosensitive composite, with the addition of the coloring photosensitive combination of colorant and employ the black matrix" of this coloring photosensitive combination, specifically, relate to and the coloring photosensitive combination of the excellent adhesion of base material and the black matrix" employing it.
Background technology
Photosensitive polymer combination is the resin combination of photo-curable, representatively forms, and can list the resin combination containing the compound and Photoepolymerizationinitiater initiater with ethylenic unsaturated bond.This photosensitive polymer combination carries out polymerizing curable by irradiation ultraviolet radiation or electron ray, therefore can be used for photo-curable ink, photosensitive printing version, printed circuit board (PCB), various photoresists etc.
Especially, employ the photosensitive composition of carbon black as pigment owing to improving display comparison degree, color developing effect, the black matrix" therefore arranged as the boundary member between R, G, B dyed layer of color filter is useful.
About such coloring photosensitive combination, there are the following problems: via exposure, development, Post RDBMS and the black pattern (black matrix") that obtains is insufficient with the adaptation of transparency carrier, be recycled and reused for formed black pattern stripping process process in, sometimes before formed colored pattern a part is stripped simultaneously, pattern comes off or exposure curing portion can not exist on the transparent substrate.
Patent Document 1 discloses a kind of colored pixels pattern formation photosensitive color material, it contains: possess compound, especially silane coupling agent that the functional group that can carry out chemical bonding with transparency carrier and the functional group that can have with the composition in photosensitive color material carry out both functional groups of being polymerized.
In addition, the silane coupling agent comprising the blocked isocyanate silane with ad hoc structure is disclosed in patent documentation 2 ~ 4.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2004-191724 publication
Patent documentation 2: Japanese Unexamined Patent Publication 08-291186 publication
Patent documentation 3: Japanese Unexamined Patent Publication 10-067787 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2009-144255 publication
Summary of the invention
the problem that invention will solve
But the invention that above-mentioned patent documentation 1 is recorded is defined in and uses dry film to be formed based on the pattern of dry process development, in addition, the leeway of improvement is still had for the adaptation of itself and base material.In addition, do not record in citing document 2 ~ 4 or enlighten out the silane coupling agent recorded in respective document is used for photosensitive polymer combination.
Therefore, the object of the invention is to, the photosensitive composite that can form desired pattern and the coloring photosensitive combination that colored pattern is improved the adaptation of base material are provided.
for the scheme of dealing with problems
The present inventor etc. are repeated further investigation to solve above-mentioned problem, found that, photosensitive composite containing the silane coupling agent comprising specific blocked isocyanate silane can realize above-mentioned purpose, find in addition, the coloring photosensitive combination that with the addition of colorant in above-mentioned photosensitive composite is suitable for black matrix", thus achieves the present invention.
That is, the feature of photosensitive composite of the present invention is, it contains: the silane coupling agent comprising the blocked isocyanate silane making the isocyanate compound shown in following general formula (I) and end-capping reagent react and obtain.
(in formula, R 1represent the alkyl of carbon number 1 ~ 8, n is the number of 1 ~ 10, and a is the number of 1 ~ 3, and b is the number of 0 ~ 2, a+b=3.)
In addition, the feature of coloring photosensitive combination of the present invention is, in above-mentioned photosensitive composite, with the addition of colorant.
Photosensitive composite of the present invention and coloring photosensitive combination preferably contain: polymerizable compound and the Photoepolymerizationinitiater initiater with ethylenic unsaturated bond.
In addition, coloring photosensitive combination of the present invention is preferably containing black pigment.
In addition, photosensitive composite of the present invention and coloring photosensitive combination are preferably alkali-developable.
In addition, photosensitive composite of the present invention and the preferred aforementioned end-capping reagent of coloring photosensitive combination are oxime compound.
The feature of black matrix" of the present invention is, above-mentioned coloring photosensitive combination solidifies and forms by it on base material.
The feature of color filter of the present invention is, possesses above-mentioned black matrix".
the effect of invention
According to the present invention, the photosensitive composite that can form desired pattern can be provided, can provide in addition and make the coloring photosensitive combination that colored pattern improves the adaptation of base material and the black matrix" employing it.The solidfied material of coloring photosensitive combination of the present invention is suitable for display device color filter and display panels and organic EL display panel.
Embodiment
Below, about photosensitive composite of the present invention and coloring photosensitive combination, based on being preferred embodiment described.
The feature of photosensitive composite of the present invention is, it contains: make the blocked isocyanate silane that the isocyanate compound shown in above-mentioned general formula (I) and end-capping reagent react and obtain.As other composition, it is applicable for having the polymerizable compound of ethylenic unsaturated bond, Photoepolymerizationinitiater initiater etc., but is not limited to these.
In addition, coloring photosensitive combination of the present invention adds colorant and forms in photosensitive composite of the present invention.As colorant, preferably containing black pigments such as carbon blacks.By containing black pigment, be useful as the photosensitive composite for the formation of black matrix".And then, in order to not develop with causing burden to environment, be preferably alkali-developable.
As the R in above-mentioned general formula (I) 1the alkyl of shown carbon number 1 ~ 8, can list methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, isobutyl, amyl group, isopentyl, tertiary pentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, different heptyl, tertiary heptyl, 1-octyl group, iso-octyl, tertiary octyl group etc.
In above-mentioned general formula (I), R 1the viewpoint obtaining easness from raw material for methyl, ethyl or propyl group is preferred.
In addition, n is 2 ~ 4 is preferred from the viewpoint of boiling point.Boiling point is preferably higher than prebake temperature, rear stoving temperature.
In addition, a is 3, b be 0 is preferred from the viewpoint of adaptation.
As in order to obtain the end-capping reagent that spendable blocked isocyanate silane in the present invention uses, the end-capping reagent in the past used can be used.Include, for example out the carboxylic acid esters such as dimethyl malenate, diethyl malonate; Malonic acid, diacetone, acetoacetate (methyl acetoacetate, ethyl acetoacetate etc.) isoreactivity methylene compound; The oxime compounds such as formyl amidoxime, acetyl amidoxime, acetyl oxime, diacetyl monoxime, diphenyl-ketoxime, cyclohexanone-oxime, methyl ethyl ketoxime (MEK oxime), methyl isobutyl ketoxime (MIBK oxime), DMKO, diethyl ketoxime; Monohydroxy alcohol or their isomeride such as methyl alcohol, ethanol, propyl alcohol, butanols, 2-Ethylhexyl Alcohol, enanthol, hexanol, octanol, isononyl alcohol, stearyl alcohol, benzylalcohol; The diol, derivatives such as Propylene Glycol (methyl glycol), ethohexadiol, ethyl diethylene glycol (ethyl diglycol), ethyl triethylene glycol, butyl glycol, butyl diglycol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether; Phenols or their isomeride such as phenol, cresols, xylenol, ethyl-phenol, propylphenol, butylphenol, octyl phenol, nonyl phenol, nitrophenol, chlorophenol: the hydroxyl such as methyl lactate, amyl lactate ester; The amines such as dibutylamine, diisopropylamine, two tert-butylamines, two-2 ethyl hexylamine, dicyclohexyl amine, benzylamine, diphenylamine, aniline, carbazole; The group with imine moiety such as ethyleneimine, poly-ethyleneimine; The hydramine such as monomethyl-ethanolamine, diethyl ethanolamine, triethyl monoethanolamine; Alpha-pyrrolidone, β-butyrolactam, azetidinone, butyrolactam, δ-lactams such as valerolactam, epsilon-caprolactams; The thio-alcohols such as butanethiol, hexyl mercaptans, lauryl mercaptan; The imidazoles such as imidazoles, 2-ethyl imidazol(e); The sour amide-types such as antifebrin, acrylamide, acetic acid acid amides, dimer acid amide; The sour acid imides such as succinimide, maleimide, phthalimide; The carbamide compounds such as urea, thiocarbamide, ethylidene-urea; Benzotriazole; The pyrazoleses etc. such as 3,5-dimethyl pyrazole, they can be used alone one, or combinationally use two or more.
Among above-mentioned end-capping reagent, dissociation temperature be 100 ~ 200 DEG C from stable existence during prebake after cure time the viewpoint that reacts be preferred, wherein, be preferably oxime compound.
In order to the end capping reaction obtaining above-mentioned blocked isocyanate silane can be undertaken by known reaction method.The addition of end-capping reagent is generally 1 ~ 2 equivalent relative to free isocyanate group, is preferably 1.05 ~ 1.5 equivalents.The temperature of reaction of end capping reaction is generally 50 ~ 150 DEG C, is preferably 60 ~ 120 DEG C.Reaction time preferably carries out with 1 ~ 7 hours.In addition, catalyzer, solvent (aromatic series hydrocarbon system, ester system, ether system, ketone system and their two or more mixed solvent etc.) can also be added.
In photosensitive composite of the present invention, the content of above-mentioned silane coupling agent converts with solid constituent and is preferably 0.1 ~ 30 quality %, is particularly preferably 0.5 ~ 10 quality % in photosensitive composite of the present invention.When the content of above-mentioned silane coupling agent is less than 0.1 quality %, adaptation becomes insufficient sometimes, and when being greater than 30 quality %, silane coupling agent is separated out sometimes in photosensitive composite.
The polymerizable compound with ethylenic unsaturated bond can be used in photosensitive composite of the present invention.As this, there is the polymerizable compound of ethylenic unsaturated bond, be not particularly limited, the polymerizable compound in the past used in photosensitive composite can be used, include, for example out the unsaturated fatty hydrocarbons such as ethene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethene, (methyl) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, HIMIC acid, crotonic acid, iso-crotonic acid, vinylacetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, mono succinate [2-(methyl) acryloyloxyethyl ester], phthalic acid list [2-(methyl) acryloyloxyethyl ester], two ends of ω-carboxy-polycaprolactone list (methyl) acrylate etc. have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl, the unsaturated polyprotonic acid such as (methyl) Hydroxyethyl Acrylate maleic acid hydroxy methacrylate, (methyl) hydroxypropyl acrylate maleic acid hydroxy propyl ester, bicyclopentadiene maleate or multifunctional (methyl) acrylate with 1 carboxyl and more than 2 (methyl) acryloyl groups, (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) glycidyl acrylate, following compound N o.A1 ~ No.A4, (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) stearyl acrylate ester, (methyl) lauryl acrylate, (methyl) methoxyethyl acrylate, (methyl) acrylate methyl esters, (methyl) dimethylaminoethyl acrylate, (methyl) acrylic-amino propyl ester, (methyl) acrylate propyl ester, (methyl) ethoxyethyl acrylate, (methyl) acrylic acid gathers (ethoxy) ethyl ester, (methyl) acrylate, butoxy ethoxy ethyl ester, (methyl) EHA, (methyl) acrylate, (methyl) acrylic acid tetrahydrofuran ester, (methyl) vinyl acrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, BDO two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate, tristane dihydroxymethyl two (methyl) acrylate, three [(methyl) acryloyl ethyl] isocyanuric acid ester, the ester of the unsaturated monoacid such as polyester (methyl) acrylate oligomer and polyvalent alcohol or polyhydric phenol, the slaine of the unsaturated polyprotonic acids such as (methyl) zinc acrylate resin, (methyl) Magnesium Acrylate Prepared, maleic anhydride, itaconic anhydride, citraconic anhydride, methyl tetrahydrophthalic anhydride, tetrabydrophthalic anhydride, trialkyl tetrabydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl) acid anhydrides of the unsaturated polyprotonic acid such as-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyl tetrabydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, methyl HIMIC acid anhydrides, the acid amides of the unsaturated monoacid such as (methyl) acrylamide, di-2-ethylhexylphosphine oxide (methyl) acrylamide, Diethylenetriamine three (methyl) acrylamide, xylylene two (methyl) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (methyl) acrylamides and polyamines, the unsaturated aldehydes such as acryl aldehyde, (methyl) vinyl cyanide, α-chloro-acrylonitrile, the partially unsaturated nitrile such as dicyan, allyl cyanide, the unsaturated aromatics such as styrene, 4-methyl styrene, 4-ethyl styrene, 4-methoxy styrene, 4-Vinyl phenol, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinyl benzoic acid, vinylphenol, vinyl sulfonic acid, 4-vinylbenzenesulfonic acid, vinyl benzyl methyl ether, vinylbenzyl glycidyl ether, the beta-unsaturated ketones such as methyl vinyl ketone, the unsaturated amine compounds such as vinyl amine, allyl amine, NVP, vinylpiperidine, the vinyl alcohol such as allyl alcohol, crotonyl alcohol, the vinyl ether such as methoxy ethylene, ethyl vinyl ether, n-butyl vinyl ether, IVE, allyl glycidyl ether, the unsaturated acid imides such as maleimide, N-phenylmaleimide, N-N-cyclohexylmaleimide, the indenes classes such as indenes, 1-methyl indenes, the aliphatic conjugated diene classes such as 1,3-butadiene, isoprene, chlorbutadiene, polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, polysiloxane etc. have the polymeric monomer class of list (methyl) acryloyl group at the end of polymer molecular chain, the vinyl monomer of vinyl chloride, vinylidene chloride, divinyl succinate ester, diallyl phthalate, TAP, isocyanic acid triallyl, vinyl sulfide, vinyl imidazole, Yi Xi oxazolin, vinylcarbazole, vinyl pyrrolidone, vinylpyridine, hydroxyl and the vinyl urethane compound of polyisocyanate compounds, the vinyl monomer of hydroxyl and the vinyloxirane of polyepoxides.
In addition, as the above-mentioned polymerizable compound with ethylenic unsaturated bond, the multipolymer of acrylate can also be used; Phenol novolac epoxy resins and/or cresol novolac epoxy, have multi-functional epoxy's base polyphenylene methane type epoxy resin, acrylic acid epoxy ester resin, make unsaturated monoacid act on the epoxy compounds such as the epoxy compound shown in following general formula (II) and the resin making multi-anhydride act on it further and obtain.Among these, preferably, make unsaturated monoacid act on the epoxy compounds such as the epoxy compound shown in following general formula (II), make multi-anhydride act on it further and the resin obtained.In addition, the unsaturated group of these compounds preferably containing 0.2 ~ 1.0 equivalent.
(in formula, X 1the ester ring type alkyl that the alkylidene (alkylidene) that expression Direct Bonding, methylene, carbon number are 1 ~ 4, carbon number are 3 ~ 20, O, S, SO 2, SS, SO, CO, OCO or following formula (i), (ii) or the substituting group shown in (iii), above-mentioned alkylidene is optionally replaced by halogen atom, R 2, R 3, R 4and R 5represent the alkoxy of the alkyl of hydrogen atom, carbon number 1 ~ 5, carbon number 1 ~ 8, the alkenyl of carbon number 2 ~ 5 or halogen atom independently of one another, abovementioned alkyl, alkoxy and alkenyl are optionally replaced by halogen atom, m is the integer of 0 ~ 10, when m is not 0, the optical isomer of existence can be any isomeride.)
(in formula, Z 1the naphthenic base of carbon number 3 ~ 10 representing hydrogen atom, the phenyl optionally replaced by the alkoxy of the alkyl of carbon number 1 ~ 10 or carbon number 1 ~ 10 or optionally replaced by the alkoxy of the alkyl of carbon number 1 ~ 10 or carbon number 1 ~ 10, Y 1represent the alkyl of carbon number 1 ~ 10, the alkoxy of carbon number 1 ~ 10, the alkenyl of carbon number 2 ~ 10 or halogen atom, abovementioned alkyl, alkoxy and alkenyl are optionally replaced by halogen atom, and b is the integer of 0 ~ 5.)
(in formula, Y 2and Z 2represent the alkyl of the carbon number 1 ~ 10 optionally replaced by halogen atom independently of one another, the aryl of the carbon number 6 ~ 20 optionally replaced by halogen atom, the aryloxy group of the carbon number 6 ~ 20 optionally replaced by halogen atom, the artyl sulfo of the carbon number 6 ~ 20 optionally replaced by halogen atom, the aromatic yl alkenyl of the carbon number 6 ~ 20 optionally replaced by halogen atom, the aralkyl of the carbon number 7 ~ 20 optionally replaced by halogen atom, the heterocyclic radical of the carbon number 2 ~ 20 optionally replaced by halogen atom, or halogen atom, alkylene moiety in abovementioned alkyl and aralkyl is optionally by unsaturated link,-O-or-S-interrupts, Z 2optionally adjacent Z 2form ring each other, p represents the integer of 0 ~ 4, and q represents the integer of 0 ~ 8, and r represents the integer of 0 ~ 4, and s represents the integer of 0 ~ 4, and the sum of r and s is the integer of 2 ~ 4.)
As the above-mentioned unsaturated monoacid that will act on above-mentioned epoxy compound, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate maleic acid hydroxy methacrylate, Hydroxyethyl Acrylate maleic acid hydroxy methacrylate, hydroxy propyl methacrylate maleic acid hydroxy propyl ester, hydroxypropyl acrylate maleic acid hydroxy propyl ester, bicyclopentadiene maleate etc. can be listed.
In addition, the above-mentioned multi-anhydride played a role again after playing a role as making above-mentioned unsaturated monoacid, biphenyl tetracarboxylic dianhydride can be listed, tetrabydrophthalic anhydride, succinic anhydride, bibenzene tetracarboxylic dianhydride (biphthalic anhydride), maleic anhydride, trimellitic anhydride, pyromellitic dianhydride, 2, 2 '-3, 3 '-benzophenone tetracarboxylic anhydride, ethylene glycol bisthioglycolate trimellitic anhydride (anhydrotrimellitate), glycerine three trimellitic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, carbic anhydride, methyl norbornene dioic anhydride, trialkyl tetrabydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2, 5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trialkyl tetrabydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, methyl HIMIC acid anhydrides etc.
The reaction mol ratio of above-mentioned epoxy compound, above-mentioned unsaturated monoacid and above-mentioned multi-anhydride is preferably as follows setting.
Namely, have in the epoxy adduct of the structure of 0.1 ~ 1.0 above-mentioned unsaturated monacid carboxyl relative to 1 epoxy radicals addition of above-mentioned epoxy compound having, preferably, relative to 1 hydroxyl of this epoxy adduct, the acid anhydride structure of above-mentioned multi-anhydride reaches the ratio of 0.1 ~ 1.0.
The reaction of above-mentioned epoxy compound, above-mentioned unsaturated monoacid and above-mentioned multi-anhydride can conventionally be carried out.
As the above-mentioned polymerizable compound with ethylenic unsaturated bond, the polymkeric substance shown in following general formula (III) also can be used.
(in formula, X 11represent hydrogen atom or methyl, Y 11represent the bonding radical of divalence, R 11represent the aralkyl of the alkyl of carbon number 1 ~ 20, the aryl of carbon number 6 ~ 20 or carbon number 7 ~ 20, this alkyl, aryl and aralkyl are optionally replaced by halogen atom, hydroxyl or nitro, methylene in this alkyl and aralkyl optionally interrupt by the bonding radical of-O-,-S-,-CO-,-COO-,-OCO-or-NH-or their combination, R 12, R 13and R 14be hydrogen atom or carbon atom independently of one another, 0.1≤t≤0.65,0.3≤m≤0.8,0≤n≤0.2, t+m+n=1.)
As the Y in above-mentioned general formula (III) 11shown divalent linker radical, can list the structure shown in following formula (1).
(in formula, X 11expression-CR 20r 21-,-NR 20-, the heterocyclic radical of the chain alkyl of carbon number 1 ~ 35 of divalence, the ester ring type alkyl of the carbon number 3 ~ 35 of divalence, the aromatic hydrocarbyl of the carbon number 6 ~ 35 of divalence or the carbon number 2 ~ 35 of divalence and then represent groups multiple for these moiety combinations, R 20and R 21represent the aralkyl of hydrogen atom, the alkyl of carbon number 1 ~ 8, the aryl of carbon number 6 ~ 20 or carbon number 7 ~ 20, Z 11and Z 12represent Direct Bonding ,-O-,-S-,-SO independently of one another 2-,-SO-,-NR 10-,-PR 10-, R 10represent the aralkyl of hydrogen atom, the alkyl of carbon number 1 ~ 8, the aryl of carbon number 6 ~ 20 or carbon number 7 ~ 20, this alkyl, aryl and aralkyl are optionally replaced by halogen atom, hydroxyl or nitro, the methylene in this alkyl and aralkyl optionally interrupt by the bonding radical of-O-,-S-,-CO-,-COO-,-OCO-or-NH-or their combination.Wherein, the group shown in above-mentioned general formula (1) is in the scope of carbon number 1 ~ 35.)
Among the above-mentioned polymerizable compound with ethylenic unsaturated bond, when employing the compound with acid number, alkali-developable can be given to photosensitive composite of the present invention.Use above-mentioned when having the compound of acid number, preferably, its consumption reaches above-mentioned 50 ~ 99 quality % with the polymerizable compound entirety of ethylenic unsaturated bond.
In addition, the above-mentioned compound with acid number uses after also can reacting with simple function or multi-functional epoxy compound further and adjusting acid number.By adjusting the above-mentioned acid number with the compound of acid number, the alkali-developable of photoresist can be improved.The above-mentioned acid number with the solid constituent of the compound (namely there is the polymerizable compound of the ethylenic unsaturated bond giving alkali-developable) of acid number be preferably 5 ~ 120mgKOH/g scope, preferably with the consumption of the way selection simple function or multi-functional epoxy compound that meet above-mentioned acid number.
As above-mentioned monofunctional epoxy compound, glycidyl methacrylate can be listed, methyl glycidyl ether, ethyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, tertiary butyl glycidyl ether, amyl group glycidol ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidol ether, decyl glycidyl ether, undecyl glycidol ether, lauryl diglycidyl ether, tridecyl glycidol ether, myristyl glycidol ether, pentadecyl glycidol ether, cetyl glycidyl ether, 2-hexyl glycidyl ether, allyl glycidyl ether, propargyl glycidol ether, to methoxy ethyl glycidol ether, phenyl glycidyl ether, to methoxyl glycidol ether, p-butylphenol glycidol ether, cresyl glycidol ether, 2-methacresol base glycidol ether, 4-nonyl phenyl glycidyl glycerin ether, benzyl glycidyl ether, to cumyl phenyl glycidol ether, trityl glycidol ether, 2,3-epoxypropyl methacrylate, epoxidised soybean oil, epoxidised linseed oil, glycidyl butyrate, vinyl cyclohexane list oxide, 1,2-epoxy radicals-4-vinyl cyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide, above-claimed cpd No.A2, No.A3 etc.
As above-mentioned multi-functional epoxy compound, when using more than one compounds being selected from the group be made up of biphenol type epoxy compound and diglycidyl ethers, can the better photosensitive composition of acquired character, so preferably.
As above-mentioned biphenol type epoxy compound, the epoxy compound shown in above-mentioned general formula (II) can be used, in addition, such as, can also use the biphenol type epoxy compounds such as hydrogenated bisphenol type epoxy compound.
In addition, as above-mentioned diglycidyl ethers, ethylene glycol diglycidylether can be used, propylene glycol diglycidylether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 8-ethohexadiol diglycidyl ether, 1, 10-decanediol diglycidyl ether, 2, 2-dimethyl-1, ammediol diglycidyl ether, diethylene glycol diglycidyl glycerin ether, Triethylene Glycol Diglycidyl Ether, TEG diglycidyl ether, six ethylene glycol diglycidylethers, 1, 4-cyclohexanedimethanodiglycidyl diglycidyl ether, 1, 1, 1-tri-(glycidoxypropyl methyl) propane, 1, 1, 1-tri-(glycidoxypropyl methyl) ethane, 1, 1, 1-tri-(glycidoxypropyl methyl) methane, 1, 1, 1, 1-tetra-(glycidoxypropyl methyl) methane etc.
In addition, the novolak type epoxy compounds such as phenol novolak-type epoxy compound, biphenyl novolak type epoxy compounds, cresol novolak type epoxy compound, bisphenol A novolac type epoxy compound, dicyclopentadiene novolac type epoxy compound can also be used; The cycloaliphatic epoxy such as 3,4-epoxy radicals-6-methylcyclohexylmethyl-3,4-epoxy radicals-6-methylcyclohexanecarboxylic acid ester, 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate, 1-epoxy radicals ethyl-3,4-epoxy-cyclohexane; The ethylene oxidic ester classes such as o-phthalic acid diglycidyl ester, tetrahydrophthalic acid 2-glycidyl ester, dimer acid glycidyl ester; The glycidyl amines such as four glycidyl group diaminodiphenyl-methane, triglycidyl group para-aminophenol, N, N-diglycidylaniline; The hetero ring type epoxy compounds such as 1,3-diglycidyl-5,5-dimethyl hydantoin, triglycidyl group isocyanuric acid ester; The dioxide compound such as dicyclopentadiene; Naphthalene type epoxy compound; Triphenylmethane type epoxy compound; Dicyclopentadiene type epoxy compound etc.
In addition, photosensitive composite of the present invention can containing not having ethylenic unsaturated bond, giving the compound of alkali-developable, as such compound, as long as the compound of alkaline soluble aqueous solution because having acid number, just be not particularly limited, representatively property compound, can list alkali-soluble novolac resin (hreinafter referred to as " novolac resin ").Novolac resin is by the polycondensation and obtaining in the presence of acid catalyst of phenols and aldehydes.
As above-mentioned phenols, such as phenol can be used, orthoresol, metacresol, paracresol, o-ethyl phenol, m-ethylphenol, paraethyl phenol, adjacent butylphenol, between butylphenol, p-butylphenol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 3, 4-xylenol, 3, 5-xylenol, 2, 3, 5-pseudocuminol, p-phenyl phenol, p-dihydroxy-benzene, catechol, resorcinol, 2-methylresorcinol, pyrogallol, alpha-Naphthol, bisphenol-A, dihydroxy-benzoic acid ester, gallate etc., among these phenols, be preferably phenol, orthoresol, metacresol, paracresol, 2, 5-xylenol, 3, 5-xylenol, 2, 3, 5-pseudocuminol, resorcinol, 2-methylresorcinol and bisphenol-A.These phenols can be used alone or mix two or more use.
As above-mentioned aldehydes, such as can use formaldehyde, PARA FORMALDEHYDE PRILLS(91,95), acetaldehyde, propionic aldehyde, benzaldehyde, phenylacetaldehyde, α-benzenpropanal, β-phenylpropionaldehyde, salicylaldhyde, m-hydroxybenzaldehyde, parahydroxyben-zaldehyde, o-chlorobenzaldehyde, m chlorobenzaldehyde, 4-chloro-benzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, paranitrobenzaldehyde, o-tolualdehyde, a tolyl aldehyde, p-tolyl aldehyde, p-ethylbenzaldehyde, align butyl benzaldehyde etc., among these compounds, be preferably formaldehyde, acetaldehyde and benzaldehyde.These aldehydes can be used alone or mix two or more use.Aldehydes is to use relative to the ratio that phenols 1 mole is preferably 0.7 ~ 3 mole, be particularly preferably 0.7 ~ 2 mole.
As above-mentioned acid catalyst, such as, can use the mineral acids such as hydrochloric acid, nitric acid, sulfuric acid; Or the organic acids such as formic acid, oxalic acid, acetic acid.The consumption of these acid catalysts is preferably 1 × 10 relative to phenols 1 mole -4~ 5 × 10 -1mole.In condensation reaction, water usually can be used as reaction medium, but the phenols used in condensation reaction can not be dissolved in the aqueous solution of aldehydes and when initial reaction stage starts to form heterogeneous system, hydrophilic solvent also can be used as reaction medium.As these hydrophilic solvents, include, for example out the alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols; Or the ring-type such as tetrahydrofuran, dioxane ethers.The consumption of these reaction mediums is 20 ~ 1000 mass parts relative to reaction raw materials 100 mass parts usually.The temperature of reaction of condensation reaction suitably can adjust according to the reactivity of reaction raw materials, is generally 10 ~ 200 DEG C, is preferably 70 ~ 150 DEG C.After condensation reaction terminates, in order to remove system internal memory unreacting material, acid catalyst and reaction medium, by making internal temperature rise to 130 ~ 230 DEG C, volatile ingredient is removed under reduced pressure distillation, and the novolac resin curtain coating then by melting reclaims on stainless steel band etc.
In addition, after condensation reaction terminates, by solubilizing reaction potpourri in aforementioned hydrophilic solvent, and be added in the precipitation agents such as water, normal hexane, normal heptane, novolac resin separated out, precipitate is separated and carries out heat drying, thus also can reclaim.
As except above-mentioned novolac resin, not there is ethylenic unsaturated bond and the example of the compound of alkali-developable can be given, polycarboxylated styrene or derivatives thereof, styrene-maleic anhydride copolymer, polyvinyl hydroxybenzoate etc. can be listed.
Photoepolymerizationinitiater initiater can be used in photosensitive composite of the present invention.As this Photoepolymerizationinitiater initiater, existing known compound can be used, include, for example out benzophenone, phenylbiphenylyl ketone, 1-hydroxyl-1-2-benzoyl-cyclohexane, benzoin, benzyl dimethyl ketal, 1-benzyl-1-dimethylamino-1-(4 '-morpholino benzoyl) propane, 2-morpholinyl-2-(4 '-methyl mercapto) benzoyl propane, thioxanthone, 1-chloro-4-propoxyl group thioxanthone, isopropyl thioxanthone, diethyl thioxanthone, EAQ, 4-benzoyl-4 '-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxyl-2-benzoyl propane, 2-hydroxyl-2-(4 '-isopropyl) benzoyl propane, 4-butylbenzoyl methenyl choloride, 4-phenoxybenzoyl methylene chloride, methyl benzoylformate, two (9 '-acridinyl) heptane of 1,7-, two (the 2 '-morpholino isobutyryl) carbazole of 9-normal-butyl-3,6-, two (trichloromethyl) s-triazine of 2-methyl-4,6-, two (trichloromethyl) s-triazine of 2-phenyl-4,6-, two (trichloromethyl) s-triazine of 2-naphthyl-4,6-, two (2-chlorphenyl)-4,5,4 ', 5 '-tetraphenyl-1-2 '-bis-imidazoles of 2,2-, 4,4-azobis isobutyronitrile, triphenylphosphine, camphorquinone, benzoyl peroxides etc., as commercially available product, can list N-1414, N-1717, N-1919, PZ-408, NCI-831, NCI-930 (ADEKA Corporation system), IRGACURE369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (BASF AG's system) etc.
In photosensitive composite of the present invention, the content of above-mentioned Photoepolymerizationinitiater initiater is preferably 0.1 ~ 30 quality %, is particularly preferably 0.5 ~ 10 quality % in photosensitive composite of the present invention.When the content of above-mentioned Photoepolymerizationinitiater initiater is less than 0.1 quality %, based on exposure be solidified with time become insufficient, when being greater than 30 quality %, initiating agent is separated out sometimes in photosensitive composite.
Photosensitive composite of the present invention can add colorant further and make coloring photosensitive combination.As this colorant, inorganic look material, organic look material can be listed.These look materials can be used alone a kind, also can combinationally use two or more.
As above-mentioned inorganic look material and organic look material, such as, can use nitroso compound, nitro compound, azo-compound, bis-azo compound, xanthene compound, quinoline compound, anthraquinone compounds, coumarin compound, phthalocyanine compound, isoindolinone compounds, isoindoline compounds, quinacridone compound, anthanthrone compound, pyrene ketonic compound, perylene compound, diketopyrrolo-pyrrole compound, thioindigo compound, dioxazine compound, triphenylmethane compounds, quinoline promise phthalein ketonic compound, naphthalene tetracarboxylic acid; The metal complex compounds of azo dyes, cyanine (cyanine) dyestuff; Mordant pigment; Utilize oven process, channel process, carbon black that hot method obtains or acetylene black, Ketjen black or the carbon black such as dim; Above-mentioned carbon black epoxy resin is carried out the product adjusting, cover, above-mentioned carbon black is carried out dispersion treatment with resin in advance in a solvent and adsorbs the product of the resin of 20 ~ 200mg/g, above-mentioned carbon black is carried out the product of acidity or basic surface process, mean grain size is more than 8nm and DBP oil absorption is the product of below 90ml/100g, by CO, CO in the volatile ingredient at 950 DEG C 2the total oxygen demand calculated is relative to the surface area 100m of carbon black 2for the product of more than 9mg; The micro-coil of graphite, Graphon, activated charcoal, carbon fiber, carbon nano-tube, carbon, carbon nano rod, carbon aerogels, fullerene; Nigrosine, pigment black 7, titanium are black; Inorganic pigment or the organic pigment such as hydrophobic resin, chrome oxide green, milori blue, cobalt green, cobalt blue, manganese system, ferrocyanide, phosphate ultramarine, Prussian blue, ultramarine, cerulean blue (cerulean blue), viridian (viridian), emerald green (emerald green), lead sulfate, yellow lead, zinc yellow, colcother (iron oxide red (III)), cadmium red, synthesis iron oxide black, amber.
As above-mentioned inorganic look material and organic look material, also can use commercially available pigment, include, for example out paratonere 1,2,3,9,10,14,17,22,23,31,38,41,48,49,88,90,97,112,119,122,123,144,149,166,168,169,170,171,177,179,180,184,185,192,200,202,209,215,216,217,220,223,224,226,227,228,240,254; Pigment orange 13,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,65,71; Pigment yellow 1,3,12,13,14,16,17,20,24,55,60,73,81,83,86,93,95,97,98,100,109,110,113,114,117,120,125,126,127,129,137,138,139,147,148,150,151,152,153,154,166,168,175,180,185; Pigment Green 7,10,36; Pigment blue 15,15:1,15:2,15:3,15:4,15:5,15:6,22,24,56,60,61,62,64; Pigment violet 1,19,23,27,29,30,32,37,40,50 etc.
As above-mentioned inorganic look material and organic look material, also known dyestuff can be used.As known dyestuff, include, for example out the dyestuffs etc. such as azo dyes, anthraquinone dye, bipseudoindoxyl dye, triarylmethane dye, xanthene dye, alizarin dyes, acridine dye, stilbene dye, thiazole dye, naphthol dye, quinoline dye, nitro dye, indamines dyestuff, piperazine (oxazin) dyestuff, phthalocyanine dye, cyanine dye.
In coloring photosensitive combination of the present invention, the content of above-mentioned colorant is preferably 0 ~ 350 mass parts relative to above-mentioned polymerizable compound 100 mass parts with ethylenic unsaturated bond, is more preferably 0 ~ 250 mass parts.During more than 350 mass parts, employ the solidfied material of coloring photosensitive combination of the present invention, the light transmission of display device color filter can reduce, the brightness of display device reduces, therefore it is not preferred.
Solvent can be added further in photosensitive composite of the present invention and coloring photosensitive combination.As this solvent, solubilized as required can be listed usually or disperse the ketone such as solvent, such as MEK, methyl amyl ketone, metacetone, acetone, methyl isopropyl Ketone, methyl isobutyl ketone, cyclohexanone, 2-HEPTANONE of above-mentioned each composition (blocked isocyanate silane of the present invention etc.); The ether series solvent such as ether, dioxane, tetrahydrofuran, 1,2-dimethoxy-ethane, 1,2-diethoxyethane, dimethyl ether; The ester series solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, Texanol; The cellosolve such as glycol monoethyl ether, ethylene glycol monoethyl ether series solvent; Methyl alcohol, ethanol, isopropyl alcohol or n-propanol, isobutyl alcohol or the alcohol such as normal butyl alcohol, amylalcohol series solvent; The ether-ether series solvents such as ethylene glycol monomethyl acetate, ethylene glycol list ethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxy ethyl propionate; The BTX series solvents such as benzene,toluene,xylene; The aliphatic hydrocarbon series solvents such as hexane, heptane, octane, cyclohexane; The terpene system hydrocarbon ils such as turpentine oil (Turpentine oils), D-citrene, firpene; The paraffin series solvents such as mineral oil, SWASOL#310 (COSMO MATSUYAMA OILCO., LTD), SOLVESSO#100 (Exxon company); The halogenated aliphatic hydrocarbon system solvents such as phenixin, chloroform, triclene, methylene chloride, 1,2-ethylene dichloride; The halogenated aromatic hydrocarbon system solvents such as chlorobenzene; Carbitol series solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulphide, N, dinethylformamide, N, N-dimethyl acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), water etc., these solvents can be used alone a kind, also can combinationally use two or more.Among these, ketone, ether-ether series solvent etc., especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone etc. in photosensitive composite containing there is the polymerizable compound of ethylenic unsaturated bond, this compatibility with the compound of ethylenic unsaturated bond and Photoepolymerizationinitiater initiater is good, so preferably.
In photosensitive composite of the present invention, the mode that the consumption of above-mentioned solvent preferably reaches 5 ~ 30 quality % with the concentration of the composition except solvent (solid constituent) uses.When being less than 5 quality %, be sometimes difficult to the wavelength light increasing thickness, expectation cannot be absorbed fully, during more than 30 quality %, sometimes cause the keeping quality reduction of composition or viscosity to rise and operability reduction by the precipitation of photosensitive composite composition, thus not preferred.
Mineral compound can be contained further in photosensitive composite of the present invention.As this mineral compound, include, for example out the metal oxides such as nickel oxide, iron oxide, yttrium oxide, titanium dioxide, zinc paste, magnesium oxide, calcium oxide, kali, silicon dioxide, aluminium oxide; Layered clay mineral, milori blue, calcium carbonate, magnesium carbonate, cobalt system, manganese system, glass powder, mica, talcum, porcelain earth, ferrocyanide, various metal sulfate, sulfide, selenide, alumina silicate, calcium silicate, aluminium hydroxide, platinum, gold, silver, copper etc., among these, be preferably titanium dioxide, silicon dioxide, layered clay mineral, silver etc.In photosensitive composite of the present invention, the content of mineral compound is preferably 0.1 ~ 50 mass parts relative to above-mentioned polymerizable compound 100 mass parts with ethylenic unsaturated bond, is more preferably 0.5 ~ 20 mass parts.These mineral compounds can be used alone a kind, also can combinationally use two or more.
By making to contain mineral compound in photosensitive composite of the present invention, photosensitive paste composition can be used as.This photosensitive paste composition can be used for forming the calcined material patterns such as the partition pattern of plasma display device, dielectric pattern, electrode pattern and black matrix pattern.
These mineral compounds are such as also suitable as filling agent, anti-reflection agent, conductive agent, stabilizing agent, fire retardant, physical strength improving agent, special wavelength absorbing agent, refuse black agent etc.
In coloring photosensitive combination of the present invention, when using pigment isochrome material, mineral compound, spreading agent can be added.As this spreading agent, as long as the spreading agent of the dispersion of look material, mineral compound, stabilization can be made, the BYK series etc. that commercially available spreading agent, such as BYK company can be used to manufacture, is applicable to using the macromolecule dispersing agent be made up of the polyester with basic functionality, polyethers, polyurethane; As basic functionality, there is nitrogen-atoms and the functional group with nitrogen-atoms be amine and/or its level Four salt, amine value is the spreading agent of 1 ~ 100mgKOH/g.
In addition, photosensitive composite of the present invention can add as required to thermal polymerization inhibitors such as anisole, p-dihydroxy-benzene, catechol, tert-butyl catechol, phenothiazine; Plastifier; Adhesion promoters; Filling agent; Defoamer; Levelling agent; Surface conditioner; Antioxidant; Ultraviolet light absorber; Dispersing aid; Anticoalescent; Catalyzer; Effect promoter; Crosslinking chemical; The additive that tackifier etc. are usual.
In photosensitive composite of the present invention, the content of any composition (wherein not comprising solvent) outside blocked isocyanate silane, the polymerizable compound with ethylenic unsaturated bond and Photoepolymerizationinitiater initiater suitably can be selected according to its application target, be not particularly limited, preferably, relative to above-mentioned content 100 mass parts with the polymerizable compound of ethylenic unsaturated bond to add up to below 50 mass parts.
In addition, by using other organic polymer together with the above-mentioned polymerizable compound with ethylenic unsaturated bond, the characteristic of the solidfied material be made up of photosensitive composite of the present invention can also be improved.As above-mentioned organic polymer, include, for example out polystyrene, polymethylmethacrylate, Eudragit NE30D, poly-(methyl) acrylic acid, styrene-(methyl) acrylic copolymer, (methyl) acryl acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl base co-polymer, Corvic, ABS resin, nylon 6, nylon66 fiber, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose esters, polyacrylamide, saturated polyester, phenolic resin, phenoxy resin, polyamide-imide resin, polyamic acid resin, epoxy resin etc., among these, be preferably polystyrene, (methyl) acryl acid-methyl methacrylate copolymer, epoxy resin.
When using other organic polymer, its consumption is preferably 10 ~ 500 mass parts relative to above-mentioned polymerizable compound 100 mass parts with ethylenic unsaturated bond.
The monomer, chain-transferring agent, sensitizer, surfactant, melamine etc. with unsaturated link can also be combinationally used in photosensitive composite of the present invention.
As the above-mentioned monomer with unsaturated link, 2-Hydroxy ethyl acrylate can be listed, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl, Isooctyl acrylate monomer, acrylic acid ester in the different ninth of the ten Heavenly Stems, stearyl acrylate ester, methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate resin, 1, 6-hexanediyl ester, trimethylolpropane triacrylate, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, butyl methacrylate, Tert-butyl Methacrylate, cyclohexyl methacrylate, trimethylol-propane trimethacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, bisphenol A diglycidyl ether (methyl) acrylate, Bisphenol F diglycidyl ether (methyl) acrylate, bisphenol Z diglycidyl ether (methyl) acrylate, tripropylene glycol two (methyl) acrylate etc.
As above-mentioned chain-transferring agent, sensitizer, usually sulfur atom-containing compound can be used.Include, for example out thioglycolic acid, thiomalic acid, thiosalicylic acid, 2 mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercapto radical propionyl group) glycocoll, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl) carbamyl] propionic acid, 3-[N-(2-mercaptoethyl) is amino] propionic acid, N-(3-mercapto radical propionyl group) alanine, 2-mercapto ethane sulfonic acid, 3-mercaptopropanesulfonic acid, 4-sulfydryl butane sulfonic acid, dodecyl (4-methyl mercapto) phenylate, 2 mercapto ethanol, 3-sulfydryl-1,2-PD, 1-sulfydryl-2-propyl alcohol, 3-sulfydryl-2-butanols, mercapto-phenol, 2-MEA, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-sulfydryl-3-pyridol, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris (3-mercaptopropionic acid ester), the sulfhydryl compounds such as pentaerythrite four (3-mercaptopropionic acid ester), this sulfhydryl compound is carried out being oxidized and the di-sulphide compounds obtained, iodoacetic acid, iodopropionic acid, ethylene iodohydrin, 2-iodoethane sulfonic acid, the iodate alkylates such as 3-iodopropane sulfonic acid, trimethylolpropane tris (3-mercaptoisobutanoic acid esters), butylene glycol two (3-mercaptoisobutanoic acid esters), hexanedithiol, decanedithiol, Isosorbide-5-Nitrae-dimethyl sulfydryl benzene, the two thiopropionate of butylene glycol, the two mercaptoacetate of butylene glycol, ethylene glycol bis mercaptoacetate, trimethylolpropane tris mercaptoacetate, the two thiopropionate of butylene glycol, trimethylolpropane tris thiopropionate, trimethylolpropane tris mercaptoacetate, pentaerythrite tetrathio propionic ester, pentaerythrite four mercaptoacetate, trihydroxyethyl three thiopropionate, following compound N o.C1, the aliphatics multi-functional thiol compounds such as tri-thiol propionic acid three (2-hydroxyethyl) isocyanuric acid ester, the Karenz MT BD1 that Showa Denko K. K manufactures, PE1, NR1 etc.
As above-mentioned surfactant, the fluorine surfactant such as perfluoralkyl phosphate, perfluoroalkyl carboxylate can be used; The negative ion system surfactants such as higher aliphatic acid-alkali salt, alkyl sulfonate, alkyl sulfate; The kation system surfactants such as higher amines halogen acid salt, quaternary ammonium salt; The non-ionic surfactants such as polyethylene glycol alkyl ether, cithrol, sorbitan fatty acid ester, glycerine monofatty ester; Amphoteric surfactant; The surfactants such as silicone based surfactants, they also can combinationally use.
As above-mentioned melamine compound, the active methylol (CH in the nitrogen compounds such as (gathering) melamine methylol, (gathering) methylol glycoluril, (gathering) methylol benzoguanamine, (gathering) methylolurea can be listed 2oH yl) all or part of (at least two) carried out alkyl etherified compound., as the alkyl forming alkyl ether, methyl, ethyl or butyl can be listed herein, can be mutually the same, also can be different.In addition, not carrying out alkyl etherified methylol can carry out from condensation in a part, also can condensation between two molecules, and its result defines oligomer composition.Specifically, HMMM, six butoxymethyl melamines, tetramethoxymethylglycoluril, four butoxymethyl glycolurils etc. can be used.Among these, be preferably HMMM, six butoxymethyl melamines etc. and carried out alkyl etherified melamine.
Photosensitive composite of the present invention can be useful in the support substrate such as soda-lime glass, quartz glass, semiconductor substrate, metal, paper, plastics by the known approaches of spin coater, roll coater, bar coater, die coater, curtain painting machine, various printing, impregnating.In addition, also can temporarily implement then be transferred in other support substrate in the support substrate such as film, its usability methods is not limit.
In addition, the light source of the active light used when solidifying as making photosensitive composite of the present invention, can use the light source of the light that can send wavelength 300 ~ 450nm, such as, can use ultra high pressure mercury, mercury vapour arc, carbon arc, xenon arc etc.
And then, by using laser to exposure light source, do not use mask and the laser directly forming image by the data message of computing machine etc. is directly drawn method and not only can be boosted productivity, also resolving power, positional precision etc. can be improved, therefore be useful, as its laser, be applicable to using wavelength to be the light of 340 ~ 430nm, argon laser, He-Ne Lasers, YAG laser and semiconductor laser etc. can be used to send the laser of the light of visible ray ~ region of ultra-red.When using these laser, can add can absorb visible ~ region of ultra-red enhanced sensitivity pigment.
Photosensitive composite of the present invention (or its solidfied material) can be used for photo-curable coating or varnish, Photocurable adhesive agent, printed base plate, or colour television set, PC monitor, portable information terminal, color filter in the display panels of the colour such as digital camera display, the color filter of ccd image sensor, touch panel, the electrode material of plasma display, powdery paints, printer's ink, forme, bonding agent, gear division composition, light appearance resin, gel coat, the photoresist of electronics engineering, platedresist, etching resist, aqueous and desciccator diaphragm, welding resistance resist, dielectric film, for the manufacture of various display purposes color filter or at plasma display, the resist of structure is formed in the manufacturing process of electroluminescence display device and LCD, for sealing electrically and the composition of electronic unit, welding resistance resist, magnetic recording material, milli machine parts, guided wave road, photoswitch, plating mask, etching mask, color test system, glass fiber cable is coated, serigraphy template, for utilizing stereolithography to manufacture the material of three-dimensional body, holographic recording material, image recording material, fine circuits, decoloring material, for the decoloring material of image recording material, employ the decoloring material of the image recording material of microcapsules, use in printed circuit board photo anti-corrosion agent material, the photo anti-corrosion agent material of UV and visible laser through image system, the progressively stacked dielectric layer of tellite forms the various uses such as photo anti-corrosion agent material or diaphragm of middle use, and its purposes is not particularly limited.
Coloring photosensitive combination of the present invention uses to form black matrix".This black matrix" is useful especially for the device used for image display display device color filters such as display panels.
In addition, in display device color filter of the present invention, except solidfied material of the present invention, red, green, blue, orange, purple and black optical parameter can also be had.
Above-mentioned black matrix" preferably utilizes following operation to be formed: (1) forms the operation of the film of coloring photosensitive combination of the present invention (especially painted alkali-developable photosensitive composition) on substrate; (2) this film is irradiated to the operation of active light across the mask with predetermined pattern shape; (3) the overlay film developer solution (especially alkaline developer) after exposure is carried out the operation of developing; (4) operation of this overlay film after thermal development is added.In addition, coloring photosensitive combination of the present invention is also useful as the ink-jetting style of Nonvisualization operation, the coloured composition of transfer modes.
The manufacture of the color filter used in display panels etc. the application of the invention or coloured composition in addition can repeat the operation of above-mentioned (1) ~ (4), and pattern more than combination dichromatism makes.
Embodiment
Below, list embodiment etc. and illustrate in greater detail the present invention, the present invention is not limited to these embodiments.
The synthesis of [Production Example 1] blocked isocyanate silane No.1
In four neck flasks, drop into methyl ethyl ketoxime 500 mass parts and propylene glycol-1-monomethyl ether-2-acetate (PGMEA) 100 mass parts in a nitrogen atmosphere, make methyl ethyl ketoxime be dissolved in PGMEA.Then, internal temperature is remained less than 40 DEG C, spend 1 hour while stirring and add 3-isocyanato-triethoxy propyl silane 200 mass parts, thereafter, stir 1 hour with the internal temperature of 40 DEG C.Confirm that the peak of isocyanate group disappears with IR, obtain blocked isocyanate silane No.1.
The synthesis of [Production Example 2] blocked isocyanate silane No.2
Drop into 3,5-dimethyl pyrazole 500 mass parts and propylene glycol-1-monomethyl ether-2-acetate (PGMEA) 100 mass parts in a nitrogen atmosphere, make methyl ethyl ketoxime be dissolved in PGMEA.Then, internal temperature is remained less than 40 DEG C, spend 1 hour while stirring and add 3-isocyanato-triethoxy propyl silane 200 mass parts, thereafter, stir 1 hour with the internal temperature of 40 DEG C.Confirm that the peak of isocyanate group disappears with IR, obtain the blocked isocyanate silane No.2 of PGMEA solution form.
The preparation of [Production Example 3] alkali-developable photosensitive resin No.1
Drop into 1, two (the 4-(2 of 1-, 3-glycidoxy) phenyl) indenes 30.0g, acrylic acid 7.52g, 2,6-BHT 0.080g, tetrabutylammonium chloride 0.183g and PGMEA11.0g, with 90 DEG C of stirrings 1 hour, with 105 DEG C of stirrings 1 hour and with 120 DEG C of stirrings 17 hours.Be cooled to room temperature, add succinic anhydride 8.11g, tetrabutylammonium chloride 0.427g and PGMEA11.1g, stir 5 hours with 100 DEG C.And then, add 1, two (the 4-(2 of 1-, 3-glycidoxy) phenyl) indenes 12.0g, 2,6-BHT 0.080g and PGMEA0.600g, after 90 DEG C of stirrings 90 minutes, stirring 5 hours with 120 DEG C, adds PGMEA24.0g, obtain the alkali-developable photosensitive resin No.1 (Mw=4900, Mn=2250, acid number (solid constituent) is 47mgKOH/g) of PGMEA solution form.
The preparation of [Production Example 4] alkali-developable photosensitive resin No.2
Drop into bisphenol fluorene type epoxy resin (epoxide equivalent is 231) 184g, acrylic acid 58g, BHT 0.26g, tetra-n-butyl ammonium bromide 0.11g and PGMEA23g, stir 16 hours with 120 DEG C.Reactant liquor is cooled to room temperature, adds PGMEA35g, bibenzene tetracarboxylic dianhydride 59g and tetra-n-butyl ammonium bromide 0.24g, stir 4 hours with 120 DEG C.And then, add tetrabydrophthalic anhydride 20g, with 120 DEG C stir 4 hours, to stir with 100 DEG C 3 hours, to stir with 80 DEG C 4 hours, to stir with 60 DEG C 6 hours, stir after 11 hours with 40 DEG C, add PGMEA90g, obtain the alkali-developable photosensitive resin No.2 (Mw=5000, Mn=2100, acid number (solid constituent) are 92.7mgKOH/g) of PGMEA solution form.
The preparation of [Production Example 5] alkali-developable photosensitive resin No.3
Drop into 1, two (4 '-glycidoxy phenyl)-1-of 1-(1 "-xenyl)-1-cyclohexyl-methane 43g, acrylic acid 11g, 2; 6-BHT 0.05g, tetrabutylammonium acetate ammonium 0.11g and PGMEA23g, stir 16 hours with 120 DEG C.Be cooled to room temperature, add PGMEA35g and biphenyl tetracarboxylic dianhydride 9.4g, stir 8 hours with 120 DEG C.And then add tetrabydrophthalic anhydride 6.0g, with 120 DEG C stir 4 hours, to stir with 100 DEG C 3 hours, to stir with 80 DEG C 4 hours, to stir with 60 DEG C 6 hours, stir after 11 hours with 40 DEG C, add PGMEA29g, obtain object alkali-developable photosensitive resin No.3 (Mw=4000, Mn=2100, acid number (solid constituent) are for 86mgKOH/g) with the form of PGMEA solution.
[embodiment 1-1 ~ 1-8 and comparative example 1-1 ~ 1-2] coloring photosensitive combination No.1 ~ No.7, photosensitive composite No.8 and compare the preparation of coloring photosensitive combination No.1 ~ No.2
Compounding according to following table 1 and table 2, obtains coloring photosensitive combination No.1 ~ No.7 (corresponding respectively to embodiment 1-1 ~ embodiment 1-7), photosensitive composite No.8 (corresponding to embodiment 1-8) and compares coloring photosensitive combination No.1 ~ No.2 (corresponding respectively to comparative example 1-1, comparative example 1-2).In addition, numeral mass parts.
[table 1]
[table 2]
A-1 blocked isocyanate silane No.1
A-2 blocked isocyanate silane No.2
A '-13-isocyanates propyl-triethoxysilicane
A '-23-glycidoxypropyl group triethoxysilane
B-1 alkali-developable photosensitive resin No.1
B-2 alkali-developable photosensitive resin No.2
B-3 alkali-developable photosensitive resin No.3
B-4SPC-1000 (acrylic resin; Showa Denko K. K's system)
C-1IRGACURE 907 (Photoepolymerizationinitiater initiater; BASF AG's system)
C-2NCI-831 (Photoepolymerizationinitiater initiater; ADEKA Inc.)
C-3N-1919 (Photoepolymerizationinitiater initiater; ADEKA Inc.)
C-4NCI-930 (Photoepolymerizationinitiater initiater; ADEKA Inc.)
D-1Kayarad R-684 (Tricyclodecane Dimethanol diacrylate; Nippon Kayaku K. K's system)
D-2ARONIX M-405 (polyfunctional acrylic ester; Toagosei Co., Ltd's system)
D-3ARONIX M-402 (polyfunctional acrylic ester; Toagosei Co., Ltd's system)
E carbon black (MA100; Mitsubishi chemical Co., Ltd's system)
F-1 cyclohexanone
F-2PGMEA
The photo-thermal curing of [embodiment 2] photosensitive composite
By 1.0 mass parts of blocked isocyanate silane No.2, NK OLIGO EA-1020 (bisphenol A-type acrylic acid epoxy ester; Chemical industry Co., Ltd. of Xin Zhong village system) 58.8 mass parts, ARONIX M-313 (polyfunctional acrylic ester; Toagosei Co., Ltd's system) 39.2 mass parts, NCI-9301.0 mass parts triple-roller mill carry out mixing, then carries out stirring deaeration with planetary mixer.The alkali-free glass of 50mm × 25mm × thickness 4.0mm is coated with divider (dispenser), the glass that laminating size is identical.The high-pressure sodium lamp (750W) that have passed 400nm short wavelength's cutoff filter is utilized to irradiate 3000mJ/cm 2405nm light, with 120 DEG C solidification 1 hour.
[comparative example 2] compares the photo-thermal curing of photosensitive composite
Except not using blocked isocyanate silane No.2, operate similarly to Example 2, make to compare photosensitive composite solidification.
[evaluation Example 1-1 ~ 1-8 and comparative evaluation example 1-1 ~ 1-2]
The comparison coloring photosensitive combination No.1 ~ No.2 obtained in the photosensitive composite No.8 obtained in the coloring photosensitive combination No.1 ~ No.7, the embodiment 1-8 that obtain in embodiment 1-1 ~ 1-7 and comparative example 1-1 ~ 1-2 is coated with on the glass substrate under the condition of 410rpm × 7 second, utilizes hot plate to make its drying (90 DEG C, 90 seconds).Ultrahigh pressure mercury lamp is utilized to expose (150mJ/cm to gained film 2).Use the aqueous sodium carbonate of 2.5 quality % as developer solution, utilize spin developer to develop after 45 seconds, fully wash, after curing 30 minutes with 230 DEG C, pattern is fixed.About after cure after film, carry out following evaluation.Show the result in table 1 and table 2.
(tack test)
For after cure after film, the gridiron pattern adhesive tape method (cross cutting method) based on JIS K5600-5-6 is utilized to put cut channel under, gained test film is put into pressure cooker testing machine, under 120 DEG C/100%RH/, two atmospheric conditions, carries out the process of 2 hours.Peel off with adhesive tape, count the stripping number in 100 gridiron patterns, thus test as tack.
[evaluation Example 2 and comparative evaluation example 2]
About the test film obtained in embodiment 2 and comparative example 2, use universal testing machine HG-200 (Shimadzu science Co., Ltd. system), measure bonding strength.Show the result in table 3.
[table 3]
According to above result, containing the excellent adhesion of coloring photosensitive combination of the present invention of silane coupling agent comprising blocked isocyanate silane.Therefore, coloring photosensitive combination of the present invention is useful for black matrix".

Claims (11)

1. a photosensitive composite, is characterized in that, it contains: the silane coupling agent comprising the blocked isocyanate silane making the isocyanate compound shown in following general formula (I) and end-capping reagent react and obtain,
In formula (I), R represents the alkyl of carbon number 1 ~ 8, and n is the number of 1 ~ 10, and a is the number of 1 ~ 3, and b is the number of 0 ~ 2, a+b=3.
2. photosensitive composite according to claim 1, it contains: polymerizable compound and the Photoepolymerizationinitiater initiater with ethylenic unsaturated bond.
3. photosensitive composite according to claim 1, it is alkali-developable.
4. photosensitive composite according to claim 1, wherein, described end-capping reagent is oxime compound.
5. a coloring photosensitive combination, is characterized in that, in photosensitive composite according to claim 1, with the addition of colorant further.
6. coloring photosensitive combination according to claim 5, it contains: polymerizable compound and the Photoepolymerizationinitiater initiater with ethylenic unsaturated bond.
7. coloring photosensitive combination according to claim 5, it contains black pigment.
8. coloring photosensitive combination according to claim 5, it is alkali-developable.
9. coloring photosensitive combination according to claim 5, wherein, described end-capping reagent is oxime compound.
10. a black matrix", is characterized in that, coloring photosensitive combination according to claim 5 solidifies and forms by it on base material.
11. 1 kinds of color filters, is characterized in that, it possesses black matrix" according to claim 10.
CN201380031157.4A 2012-06-12 2013-05-23 Photosensitive composition Pending CN104380199A (en)

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