Classifications

• • 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

Definitions

• the present invention relates to a photosensitive composition containing a silane coupling agent comprising a blocked isocyanate silane, a colored photosensitive composition obtained by adding a colorant to the photosensitive composition, and a black matrix using the colored photosensitive composition.
• the present invention relates to a colored photosensitive composition having excellent adhesion to a substrate and a black matrix using the same.
• the photosensitive resin composition is a photocurable resin composition
• a typical composition includes a compound having an ethylenically unsaturated bond and a photopolymerization initiator. Since this photosensitive resin composition can be polymerized and cured by irradiation with ultraviolet rays or electron beams, it is used in photocurable inks, photosensitive printing plates, printed wiring plates, various photoresists, and the like.
• a colored photosensitive resin composition using carbon black as a pigment is useful as a black matrix provided at a boundary portion between the R, G, and B colored layers of a color filter in order to enhance display contrast and color forming effect.
• the black pattern (black matrix) obtained through exposure, development and post-cure and the adhesion of the transparent substrate are not sufficient, and a peeling process for forming a black pattern is performed.
• some of the previously formed colored patterns are peeled off at the same time, and there are problems that the pattern may be lost or the exposed and cured part may not remain on the transparent substrate.
• Patent Document 1 discloses a colored pixel containing a compound having both a functional group chemically bonded to a transparent substrate and a functional group of a component in the photosensitive coloring material and a polymerizable functional group, particularly a silane coupling agent.
• a photosensitive coloring material for pattern formation is disclosed.
• Patent Documents 2 to 4 disclose silane coupling agents composed of a blocked isocyanate silane having a specific structure.
• JP 2004-191724 A Japanese Patent Laid-Open No. 08-291186 Japanese Patent Application Laid-Open No. 10-067787 JP 2009-144255 A
• Patent Document 1 is limited to pattern formation by dry development using a dry film, and there is still room for improvement in adhesion to the substrate. Also, in the cited documents 2 to 4, there is no description or suggestion that the silane coupling agent described in each document is used for the photosensitive resin composition.
• an object of the present invention is to provide a photosensitive composition capable of forming a desired pattern, and a colored photosensitive composition having improved adhesion of a colored pattern to a substrate.
• a photosensitive composition containing a silane coupling agent composed of a predetermined blocked isocyanate silane can achieve the above-described object, Further, the present inventors have found that a colored photosensitive composition obtained by adding a colorant to the photosensitive composition is suitable for a black matrix, and have reached the present invention.
• the photosensitive composition of the present invention comprises a silane coupling agent comprising a blocked isocyanate silane obtained by reacting an isocyanate compound represented by the following general formula (I) with a blocking agent.
• a silane coupling agent comprising a blocked isocyanate silane obtained by reacting an isocyanate compound represented by the following general formula (I) with a blocking agent.
• R 1 represents an alkyl group having 1 to 8 carbon atoms
• n is a number from 1 to 10
• a is a number from 1 to 3
• b is a number from 0 to 2.
• a + b 3.
• the colored photosensitive composition of the present invention is characterized in that a colorant is added to the photosensitive composition.
• the photosensitive composition and the colored photosensitive composition of the present invention preferably contain a polymerizable compound having an ethylenically unsaturated bond and a photopolymerization initiator.
• the colored photosensitive composition of the present invention preferably contains a black pigment.
• the photosensitive composition and the colored photosensitive composition of the present invention are preferably alkali developable.
• the blocking agent is preferably an oxime compound.
• the black matrix of the present invention is characterized in that the colored photosensitive composition is cured on a substrate.
• the color filter of the present invention is characterized by comprising the above black matrix.
• the photosensitive composition which can form a desired pattern can be provided, the coloring photosensitive composition which improved the adhesiveness to the base material of a coloring pattern, and a black matrix using the same are provided. It becomes possible.
• the cured product of the colored photosensitive composition of the present invention is suitable for a color filter for a display device, a liquid crystal display panel, and an organic EL display panel.
• the photosensitive composition of the present invention comprises a blocked isocyanate silane obtained by reacting the isocyanate compound represented by the general formula (I) with a blocking agent.
• a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and the like are preferable, but not limited thereto.
• the colored photosensitive composition of the present invention is obtained by adding a colorant to the photosensitive composition of the present invention.
• the colorant preferably contains a black pigment such as carbon black. By containing a black pigment, it becomes useful as a photosensitive composition for forming a black matrix. Furthermore, since it can develop without burdening the environment, it is preferably alkaline developability.
• Examples of the alkyl group having 1 to 8 carbon atoms represented by R 1 in the general formula (I) include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl and pentyl.
• R 1 is preferably methyl, ethyl or propyl from the viewpoint of easy availability of raw materials.
• n is preferably 2 to 4 from the viewpoint of boiling point.
• the boiling point is preferably higher than the pre-bake temperature or the post-bake temperature.
• carboxylic acid esters such as dimethyl malonate and diethyl malonate: active methylene compounds such as malonic acid, acetylacetone, acetoacetate (methyl acetoacetate, ethyl acetoacetate, etc.); formamide oxime, acetamide oxime, acetoxime, Oxime compounds such as diacetyl monooxime, benzophenone oxime, cyclohexanone oxime, methyl ethyl ketoxime (MEK oxime), methyl isobutyl ketoxime (MIBK oxime), dimethyl ketoxime, diethyl ketoxime, etc .; methanol, ethanol, propanol, butanol, 2-ethylhexanol , Monohydric alcohols such as heptanol, hexanol
• Glycol derivatives phenols such as phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, octylphenol, nonylphenol, nitrophenol, chlorophenol or their isomers: hydroxyl-containing esters such as methyl lactate and amyl lactate; dibutylamine, Diisopropylamine, di-tert-butylamine, di-2-ethylhexylamine, dicyclohexyl Amine compounds such as silamine, benzylamine, diphenylamine, aniline and carbazole; imine compounds such as ethyleneimine and polyethyleneimine; alcohol amines such as monomethylethanolamine, diethylethanolamine and triethylethanolamine; ⁇ -pyrrolidone, ⁇ -butyrolactam, ⁇ -Lactams such as propiolactam, ⁇ -butyrolactam, ⁇ -valerolactam, ⁇
• blocking agents those having a dissociation temperature of 100 to 200 ° C. are preferable because they exist stably during pre-baking and react during post-baking, and among them, oxime compounds are preferable.
• the blocking reaction for obtaining the blocked isocyanate silane is performed by a known reaction method.
• the addition amount of the blocking agent is usually 1 to 2 equivalents, preferably 1.05 to 1.5 equivalents, relative to the free isocyanate group.
• the reaction temperature of the blocking reaction is usually 50 to 150 ° C., preferably 60 to 120 ° C.
• the reaction time is preferably about 1 to 7 hours.
• the content of the silane coupling agent in the photosensitive composition of the present invention is preferably 0.1 to 30% by mass, particularly 0.5 to 10% by mass in terms of solid content.
• the content of the silane coupling agent is less than 0.1% by mass, the adhesion may be insufficient.
• the silane coupling agent is precipitated in the photosensitive composition. There is.
• a polymerizable compound having an ethylenically unsaturated bond can be used.
• the polymerizable compound having an ethylenically unsaturated bond is not particularly limited, and those conventionally used in photosensitive compositions can be used.
• ethylene, propylene, butylene, isobutylene, vinyl chloride can be used.
• Unsaturated aliphatic hydrocarbons such as vinylidene chloride, vinylidene fluoride, tetrafluoroethylene; (meth) acrylic acid, ⁇ -chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, highmic acid, crotonic acid, Isocrotonic acid, vinyl acetic acid, allylic acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ⁇ - Carboxypolycaprolactone mono (meth) acrylate has carboxy group and hydroxyl group at both ends Mono (meth) acrylate of polymer; having hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene
• A4 methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (
• Examples of the polymerizable compound having an ethylenically unsaturated bond include acrylic ester copolymers, phenol and / or cresol novolac epoxy resins, polyphenylmethane type epoxy resins having polyfunctional epoxy groups, and epoxy acrylate resins.
• a resin obtained by allowing an unsaturated monobasic acid to act on an epoxy compound such as an epoxy compound represented by the following general formula (II), and further causing a polybasic acid anhydride to act thereon can also be used.
• a resin obtained by allowing an unsaturated monobasic acid to act on an epoxy compound such as an epoxy compound represented by the following general formula (II) and further causing a polybasic acid anhydride to act thereon is preferable. Further, these compounds preferably contain 0.2 to 1.0 equivalent of unsaturated groups.
• X 1 is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, O, S, SO 2 , SS, SO, CO, It represents a substituent represented by OCO or the following formula (i), (ii) or (iii), the alkylidene group may be substituted with a halogen atom, and R 2 , R 3 , R 4 and R 5 are Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom, and the above alkyl group, alkoxy group and The alkenyl group may be substituted with a halogen atom, m is an integer of 0 to 10, and the optical isomer present when m is not 0 may be any isomer.)
• Z 1 represents a hydrogen atom, a phenyl group optionally substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, or A cycloalkyl group having 3 to 10 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms, wherein Y 1 is an alkyl group having 1 to 10 carbon atoms, an alkoxy having 1 to 10 carbon atoms Group, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, wherein the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and b is an integer of 0 to 5.
• Y 2 and Z 2 are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or 6 to 20 carbon atoms which may be substituted with a halogen atom.
• An arylalkenyl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms that may be substituted with a halogen atom, or a complex having 2 to 20 carbon atoms that may be substituted with a halogen atom Represents a cyclic group or a halogen atom, and the alkylene part in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -
• Examples of the unsaturated monobasic acid that acts on the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl Acrylate / malate, dicyclopentadiene / malate and the like can be mentioned.
• the polybasic acid anhydride to be acted after the unsaturated monobasic acid is allowed to act is biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, Trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene -1,2-dicarboxylic an
• the reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows. That is, in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, the hydroxyl group 1 of the epoxy adduct is It is preferable that the ratio of the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0. Reaction of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride can be performed in accordance with a conventional method.
• polymerizable compound having an ethylenically unsaturated bond a polymer represented by the following general formula (III) can also be used.
• X 11 represents a hydrogen atom or a methyl group
• Y 11 represents a divalent linking group
• R 11 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms
• R 11 represents an alkyl group having 7 to 20 carbon atoms
• the alkyl group, aryl group and arylalkyl group may be substituted with a halogen atom, a hydroxyl group or a nitro group.
• the methylene group may be interrupted by a linking group of —O—, —S—, —CO—, —COO—, —OCO— or —NH—, or a combination thereof
• Examples of the divalent linking group represented by Y 11 in the general formula (III) include a structure represented by the following formula (1).
• X 11 is —CR 20 R 21 —, —NR 20 —, a divalent chain hydrocarbon group having 1 to 35 carbon atoms, or an alicyclic carbon atom having 3 to 35 carbon atoms.
• the amount used is preferably 50 to 99% by mass of the entire polymerizable compound having an ethylenically unsaturated bond.
• the compound having an acid value can be used after adjusting the acid value by further reacting with a monofunctional or polyfunctional epoxy compound.
• the alkali developability of the photosensitive resin can be improved by adjusting the acid value of the compound having an acid value.
• the compound having an acid value (that is, a polymerizable compound having an ethylenically unsaturated bond imparting alkali developability) preferably has a solid acid value in the range of 5 to 120 mgKOH / g, and is monofunctional or polyfunctional.
• the amount of the functional epoxy compound used is preferably selected so as to satisfy the acid value.
• Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecy
• the polyfunctional epoxy compound it is preferable to use one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers because a colored photosensitive resin composition with better characteristics can be obtained.
• the bisphenol-type epoxy compound an epoxy compound represented by the general formula (II) can be used, and for example, a bisphenol-type epoxy compound such as a hydrogenated bisphenol-type epoxy compound can also be used.
• glycidyl ethers examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-to (Glycidyloxymethyl) ethane, 1,1,1-tri (glycidy
• novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; heterocycl
• the photosensitive composition of the present invention may contain a compound that does not have an ethylenically unsaturated bond and imparts alkali developability.
• an alkaline aqueous solution can be obtained by having an acid value.
• a typical example is an alkali-soluble novolak resin (hereinafter simply referred to as “novolak resin”).
• the novolak resin is obtained by polycondensation of phenols and aldehydes in the presence of an acid catalyst.
• phenols examples include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2- Methyl resorcinol, pyrogallol, ⁇ -naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester, etc.
• phenols are used.
• phenol, o-cresol, m-cresol, p-cresol, 2,5-kis Renoru, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methyl resorcinol and bisphenol A are preferred.
• These phenols are used alone or in combination.
• aldehydes examples include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, ⁇ -phenylpropylaldehyde, ⁇ -phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o -Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p N-butylbenzaldehyde is
• the acid catalyst examples include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as formic acid, oxalic acid, and acetic acid.
• the amount of these acid catalysts used is preferably 1 ⁇ 10 ⁇ 4 to 5 ⁇ 10 ⁇ 1 mol per mol of phenol.
• water is usually used as a reaction medium.
• the reaction medium is hydrophilic.
• a solvent can also be used.
• hydrophilic solvents examples include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane.
• the amount of these reaction media used is usually 20 to 1000 parts by mass per 100 parts by mass of the reaction raw material.
• the reaction temperature of the condensation reaction can be appropriately adjusted according to the reactivity of the reaction raw materials, but is usually 10 to 200 ° C., preferably 70 to 150 ° C. After completion of the condensation reaction, in order to remove unreacted raw materials, acid catalyst and reaction medium present in the system, the internal temperature is generally increased to 130 to 230 ° C., and the volatile component is distilled off under reduced pressure.
• the melted novolac resin is collected on a steel belt or the like.
• the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitating agent such as water, n-hexane, or n-heptane to precipitate a novolak resin, and the precipitate is separated and dried by heating. It can also be recovered by doing so.
• Examples of compounds other than the novolak resin that do not have an ethylenically unsaturated bond and impart alkali developability include polyhydroxystyrene or a derivative thereof, a styrene-maleic anhydride copolymer, and polyvinylhydroxybenzoate. It is done.
• a photopolymerization initiator can be used.
• the photopolymerization initiator conventionally known compounds can be used.
• N-1414, N-1717, N-1919, and PZ. 408 (manufactured by (Corporation) ADEKA Corporation) NCI-831, NCI-930, IRGACURE369, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02 (BASF (Co.) Co., Ltd.).
• the content of the photopolymerization initiator is preferably 0.1 to 30% by mass, particularly preferably 0.5 to 10% by mass in the photosensitive composition of the present invention. If the content of the photopolymerization initiator is less than 0.1% by mass, curing by exposure may be insufficient, and if it is greater than 30% by mass, the initiator may be precipitated in the photosensitive composition. is there.
• a colored photosensitive composition can be obtained by further adding a colorant to the photosensitive composition of the present invention.
• a colorant include inorganic color materials and organic color materials. These color materials may be used alone or in combination of two or more.
• inorganic colorant and organic colorant examples include, for example, nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridones.
• Compound anthanthrone compound, perinone compound, perylene compound, diketopyrrolopyrrole compound, thioindigo compound, dioxazine compound, triphenylmethane compound, quinophthalone compound, naphthalenetetracarboxylic acid; azo dye, metal complex compound of cyanine dye; lake pigment; Carbon black obtained by the method, channel method, thermal method, or carbon black such as acetylene black, ketjen black or lamp black; Carbon black adjusted with epoxy resin and coated, carbon black previously treated with resin in a solvent, 20 to 200 mg / g of resin adsorbed, carbon black treated with acidic or alkaline surface, An average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, and a total oxygen amount calculated from CO and CO 2 in a volatile content at 950 ° C.
• pigments can also be used as the inorganic color material and the organic color material, for example, Pigment Red 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
• dyes can be used as the inorganic color material and organic color material.
• known dyes include, for example, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, Examples thereof include phthalocyanine dyes and cyanine dyes.
• the content of the colorant is preferably 0 to 350 parts by mass, more preferably 0 to 250 parts per 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. Part by mass.
• the amount exceeds 350 parts by mass, the light transmittance of the cured product using the colored photosensitive composition of the present invention and the color filter for display device is lowered, and the luminance of the display device is lowered.
• a solvent can be further added to the photosensitive composition and the colored photosensitive composition of the present invention.
• the solvent is usually a solvent that can dissolve or disperse the above-described components (the blocked isocyanate silane of the present invention) as necessary, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl Ketones such as isobutyl ketone, cyclohexanone, 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate Ester solvents such as ethyl acetate, isopropyl acetate, isopropyl acetate, n-butyl acetate,
• solvents may be used individually by 1 type, and may use 2 or more types together.
• ketones, ether ester solvents, etc., especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. are used when the photosensitive composition contains a polymerizable compound having an ethylenically unsaturated bond. This is preferable because the compatibility between the compound having an ethylenically unsaturated bond and the photopolymerization initiator is good.
• the solvent is preferably used so that the concentration (solid content) of the composition other than the solvent is 5 to 30% by mass. If the amount is less than 5% by mass, it is difficult to increase the film thickness and the desired wavelength light may not be sufficiently absorbed. If the amount exceeds 30% by mass, the composition is preserved by precipitation of the photosensitive composition component. This is not preferable because the properties may decrease or the viscosity may increase and handling may decrease.
• the photosensitive composition of the present invention can further contain an inorganic compound.
• the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper Among these, titanium oxide, silica, layered clay mineral, silver and the like are preferable.
• the content of the inorganic compound is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. ⁇ 20 parts by mass.
• These inorganic compounds may be used individually by 1 type, and may use 2 or more types together.
• an inorganic compound in the photosensitive composition of the present invention By containing an inorganic compound in the photosensitive composition of the present invention, it can be used as a photosensitive paste composition.
• the photosensitive paste composition is used to form a fired product pattern such as a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.
• These inorganic compounds are also suitably used as, for example, fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellent agents, and the like.
• a dispersant can be added.
• any colorant or inorganic compound can be used as long as it can disperse and stabilize, and commercially available dispersants such as BYK series manufactured by BYK Chemie can be used, and polyester having a basic functional group, Polymer dispersant made of polyether, polyurethane, having a nitrogen atom as a basic functional group, the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH / g Those are preferably used.
• the photosensitive composition of the present invention includes, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; a plasticizer; an adhesion promoter; a filler; Conventional additives such as a foaming agent, a leveling agent, a surface conditioner, an antioxidant, an ultraviolet absorber, a dispersion aid, a coagulation inhibitor, a catalyst, an effect accelerator, a cross-linking agent, and a thickener can be added.
• the content of optional components other than the blocked isocyanate silane, the polymerizable compound having an ethylenically unsaturated bond, and the photopolymerization initiator depends on the purpose of use. Although it selects suitably and it does not restrict
• cured material which consists of the photosensitive composition of this invention can also be improved by using another organic polymer with the polymeric compound which has the said ethylenically unsaturated bond.
• the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate.
• Copolymer ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Polyester, phenolic resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, and the like.
• polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are included.
• the amount used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond.
• a monomer having an unsaturated bond a chain transfer agent, a sensitizer, a surfactant, melamine and the like can be used in combination.
• Examples of the monomer having an unsaturated bond include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, acrylic acid Methoxyethyl, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, methacrylic acid Tertiary butyl, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pen Examples include erythritol tetraacrylate, pentaeryth
• a sulfur atom-containing compound is generally used.
• Alkyl compounds trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, the following compound no. C1, aliphatic polyfunctional thiol
• the surfactant examples include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.
• fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates
• anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates,
• Examples of the melamine compound include all or part of active methylol groups (CH 2 OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified.
• examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other.
• the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed.
• an oligomer component may be formed.
• hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used.
• alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.
• the photosensitive composition of the present invention is a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, semiconductor substrate, metal, paper, plastic. It can be applied on a supporting substrate such as. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base
• the light source of the active light used for curing the photosensitive composition of the present invention one that emits light having a wavelength of 300 to 450 nm can be used, for example, ultrahigh pressure mercury, mercury vapor arc, carbon An arc, a xenon arc, or the like can be used.
• the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy.
• the laser beam light having a wavelength of 340 to 430 nm is preferably used, but an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, etc. are visible to infrared region. Those that emit light are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.
• the photosensitive composition of the present invention (or a cured product thereof) is a photocurable paint or varnish, a photocurable adhesive, a printed circuit board, or a color display liquid crystal such as a color television, a PC monitor, a portable information terminal, or a digital camera.
• the colored photosensitive composition of the present invention is used for the purpose of forming a black matrix.
• the black matrix is particularly useful for color filters for display devices for image display devices such as liquid crystal display panels.
• the color filter for display devices of the present invention may have red, green, blue, orange, purple and black optical elements in addition to the cured product of the present invention.
• the black matrix includes (1) a step of forming a coating film of the colored photosensitive composition of the present invention (particularly a colored alkali-developable photosensitive composition) on a substrate, and (2) a predetermined pattern shape on the coating film. It is preferably formed by a step of irradiating active light through a mask having, (3) a step of developing a film after exposure with a developer (particularly an alkali developer), and (4) a step of heating the film after development.
• the colored photosensitive composition of the present invention is also useful as a coloring composition for an ink jet system or a transfer system without a development step.
• a color filter used for a liquid crystal display panel or the like is produced by repeating the steps (1) to (4) using a coloring composition of the present invention or other combination, and combining patterns of two or more colors. Can do.
• Photothermal curing of photosensitive composition Blocked isocyanate silane No. 2 1.0 part by mass of No. 2, 58.8 parts by mass of NK oligo EA-1020 (bisphenol A type epoxy acrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.), 39 of Aronix M-313 (polyfunctional acrylate; manufactured by Toagosei Co., Ltd.) 2 parts by mass and 1.0 part by mass of NCI-930 were kneaded with three rolls, and then stirred and degassed with a planetary mixer. It apply
• Comparative Example 2 Photothermal curing of comparative photosensitive composition Blocked isocyanate silane no.
• the comparative photosensitive composition was cured in the same manner as in Example 2 except that 2 was not used.
• the post-baked coating film was cut by a cross-cut tape method (cross-cut method) according to JIS K5600-5-6, and the obtained test piece was put into a pressure cooker tester at 120 ° C./100 The treatment was performed for 2 hours under the condition of% RH / 2 atm. The adhesion test was made by peeling the tape and counting the number of peels per 100 grids.
• Example 2 and Comparative Evaluation Example 2 The test pieces obtained in Example 2 and Comparative Example 2 were measured for adhesive strength using a universal testing machine HG-200 (manufactured by Shimadzu Science Co., Ltd.). The results are shown in Table 3.
• the colored photosensitive composition of the present invention containing a silane coupling agent composed of blocked isocyanate silane is excellent in adhesion. Therefore, the colored photosensitive composition of the present invention is useful for a black matrix.

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