WO2011105443A1 - Negative photosensitive resin composition, interlayer insulating film and method of formation of same - Google Patents

Negative photosensitive resin composition, interlayer insulating film and method of formation of same Download PDF

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Publication number
WO2011105443A1
WO2011105443A1 PCT/JP2011/054019 JP2011054019W WO2011105443A1 WO 2011105443 A1 WO2011105443 A1 WO 2011105443A1 JP 2011054019 W JP2011054019 W JP 2011054019W WO 2011105443 A1 WO2011105443 A1 WO 2011105443A1
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WIPO (PCT)
Prior art keywords
group
carbon atoms
resin composition
photosensitive resin
negative photosensitive
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PCT/JP2011/054019
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French (fr)
Japanese (ja)
Inventor
雄大 福山
克之 増田
知広 平田
雄二 小林
克彦 安
智 二宮
Original Assignee
日立化成工業株式会社
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Application filed by 日立化成工業株式会社 filed Critical 日立化成工業株式会社
Priority to CN2011800109403A priority Critical patent/CN102782579A/en
Priority to JP2011509751A priority patent/JP5333581B2/en
Priority to KR1020127024435A priority patent/KR20120132509A/en
Publication of WO2011105443A1 publication Critical patent/WO2011105443A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F277/00—Macromolecular compounds obtained by polymerising monomers on to polymers of carbocyclic or heterocyclic monomers as defined respectively in group C08F32/00 or in group C08F34/00
    • 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
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G03F7/405—Treatment with inorganic or organometallic reagents after imagewise removal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

Definitions

  • the present invention relates to a negative photosensitive resin composition, an interlayer insulating film, and a method for forming the same.
  • TFT Thin film transistor
  • magnetic head elements integrated circuit elements
  • solid-state image pickup tube elements solid-state image pickup tube elements
  • other electronic components are generally provided with interlayer insulation to insulate the wiring arranged in layers.
  • a film is provided (see Patent Document 1).
  • a negative photosensitive resin composition is widely used since the number of steps for obtaining a required pattern shape is small and a material having sufficient flatness is preferable (see Patent Document 2). ).
  • JP 2000-10089 A Japanese Patent No. 3650985
  • the TFT type liquid crystal display element is manufactured through a process of forming a transparent electrode film on an interlayer insulating film and further forming a liquid crystal alignment film thereon. At this time, since the interlayer insulating film is exposed to high temperature conditions in the process of forming the transparent electrode film, sufficient resistance to this is required.
  • the present invention has been made in view of the above circumstances, and forms an interlayer insulating film having sufficiently excellent properties such as resolution, transparency, heat resistance, heat discoloration resistance, and solvent resistance even when the film thickness is increased.
  • An object of the present invention is to provide a negative photosensitive resin composition.
  • an object of this invention is to provide the interlayer insulation film formed from the negative photosensitive resin composition which concerns, and its formation method.
  • the present invention is a negative type containing (A) a cyclic olefin resin containing a repeating unit represented by the following general formula (1), (B) a polyfunctional acrylic monomer, and (C) a photopolymerization initiator.
  • a photosensitive resin composition is provided.
  • R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a cyclohexane having 5 to 15 carbon atoms.
  • the negative photosensitive resin composition having the above-described configuration can form an interlayer insulating film having sufficiently excellent properties such as resolution, transparency, heat resistance, heat discoloration resistance, and solvent resistance even when the film thickness is increased.
  • a cyclic olefin resin is represented by the general formula (1) preferably contains a structural unit R 1, R 2, R 3 and R 4 are hydrogen atoms.
  • the cyclic olefin resin (A) is a structural unit represented by the above general formula (1), and any one of R 1 , R 2 , R 3 and R 4 is an alkylcarbonyloxy group having 2 to 20 carbon atoms. It is preferable to contain.
  • the present invention relates to a negative photosensitive resin composition used in a method for forming an interlayer insulating film having a step of irradiating an ultraviolet ray having a wavelength of 400 nm or less onto at least a part of a film formed from the negative photosensitive resin composition.
  • I will provide a.
  • the negative photosensitive resin composition of the present invention preferably further contains (D) an alkali-soluble resin.
  • the present invention provides an interlayer insulating film formed from the above negative photosensitive resin composition.
  • the present invention includes a step of irradiating at least a part of a film formed from the negative photosensitive resin composition, a step of developing the film after the light irradiation, and the film after development. And a step of forming an interlayer insulating film by baking.
  • a negative photosensitive resin composition capable of forming an interlayer insulating film having excellent properties such as resolution, transparency, heat resistance, heat discoloration resistance and solvent resistance even when the film thickness is increased. It becomes possible to provide.
  • the negative photosensitive resin composition according to this embodiment contains (A) a cyclic olefin resin, (B) a polyfunctional acrylic monomer, and (C) a photopolymerization initiator.
  • A a cyclic olefin resin
  • B a polyfunctional acrylic monomer
  • C a photopolymerization initiator
  • Cyclic olefin resin- (A) Cyclic olefin resin which concerns on this embodiment is a polymer which has a repeating unit represented by following General formula (1).
  • R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 5 to 15 carbon atoms, a carbon atom
  • R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, or The substituent is selected from an alkoxy group having 6 to 20 carbon atoms and an alkylcarbonyloxy group having 2 to 20 carbon atoms.
  • hydrolyzable silyl group examples include trimethoxysilyl and methyldimethoxysilyl.
  • alkylcarbonyloxy group having 2 to 20 carbon atoms include methyl ester, t-butyl ester, 2-ethylhexyl ester, benzyl ester, cyclopentyl ester, cyclohexyl ester and allyl ester.
  • methyl ester and benzyl ester are particularly preferably used from the viewpoint of heat resistance.
  • the cyclic olefin resin (A) used in this embodiment is represented by the above general formula (1), and R 1 , R 2 , R 3, and R 4 are each a structural unit represented by the formula (1 ), Preferably 1 mol% or more, more preferably 10 mol% or more, based on the total amount of structural units. When this ratio is 1 mol% or more, the heat resistance of the obtained negative photosensitive resin composition tends to be improved.
  • the proportion is preferably 60 mol% or less, and more preferably 50 mol% or less. When the said ratio is 60 mol% or less, it exists in the tendency for the solubility to the solvent for negative photosensitive resin composition preparation to improve.
  • the (A) cyclic olefin resin used in the present embodiment is represented by the above general formula (1), and any one of R 1 , R 2 , R 3 and R 4 is an alkylcarbonyloxy group having 2 to 20 carbon atoms. It is preferable that 1 mol% or more is included on the basis of the whole quantity of the structural unit of Formula (1) in a cyclic olefin, and it is more preferable that 10 mol% or more is included. When this ratio is 1 mol% or more, there exists a tendency for the effect that the solubility to the solvent for negative photosensitive resin composition preparation improves. The proportion is preferably 60 mol% or less, and more preferably 50 mol% or less. When the said ratio is 60 mol% or less, it exists in the tendency for the effect that the heat resistance of the negative photosensitive resin composition obtained improves.
  • the (A) cyclic olefin resin can be produced by addition copolymerization of a monomer represented by the following general formula (2) in a solvent in the presence of a metal catalyst.
  • a solvent used for manufacture of cyclic olefin resin for example, aliphatic hydrocarbons such as pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, Examples include halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene, nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile, and ethers such as diethyl ether, dioxane and tetrahydrofuran. These solvents may be used alone or in combination of two or more.
  • the catalyst (E) used for the polymerization of the cyclic olefin resin includes at least cyclopentadienyl as one transition metal selected from Group 8 element, Group 9 element and Group 10 element of the periodic table.
  • a complex in which a system ligand is coordinated is preferred. Specific examples include iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), and platinum (Pt).
  • preferred elements from the viewpoint of increasing the polymerization activity of the catalyst are cobalt, nickel, palladium, and platinum, and it is particularly preferable to use palladium.
  • co-catalyst (F) used for the polymerization of the cyclic olefin resin one that promotes dissociation of the ligand of the complex forming the catalyst (E) is preferable.
  • the ionic compound which combined the non-coordinating anion and cation illustrated below is mentioned.
  • Non-coordinating anions include, for example, tetra (phenyl) borate, tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluoro) Phenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate and tridecahydride -7,8-dicarbaound decaborate.
  • Examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal.
  • the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and trisubstituted phenylcarbonium cation.
  • the tri-substituted phenyl carbonium cation include tri (methylphenyl) carbonium cation and tri (dimethylphenyl) carbonium cation.
  • ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation and tri (n-butyl) ammonium cation, N, N-diethylanilinium cation and N N, N-dialkylanilinium cations such as N, N-2,4,6-pentamethylanilinium cation, and dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation.
  • trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation and tri (n-butyl) ammonium cation, N, N-diethylanilinium cation
  • phosphonium cation examples include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation and tri (dimethylphenyl) phosphonium cation.
  • Examples of the ionic compound include trityl tetra (pentafluorophenyl) borate, triphenylcarbonium tetra (fluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl) borate, and 1,1′-dimethyl. Ferrocenium tetra (pentafluorophenyl) borate.
  • the ratio between the catalyst (E) and the cocatalyst (F) varies depending on various conditions and is not uniquely determined, but is usually 1 / 0.1 in terms of E / F (molar ratio). Is preferably 1 / 10,000, more preferably 1 / 0.5 to 1/5000, and still more preferably 1/1 to 1/2000.
  • the polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) of the (A) cyclic olefin resin in the present embodiment is preferably 2 ⁇ 10 3 to 2 ⁇ 10 5 , and preferably 2 ⁇ 10 4 to 1.8 ⁇ 10 5. More preferred.
  • Mw is less than 2 ⁇ 10 3 , the resulting film tends to have reduced heat resistance and surface hardness.
  • Mw exceeds 2 ⁇ 10 5 , developability and solubility in a solvent for preparing a photosensitive resin composition tend to be lowered.
  • a bifunctional or higher polyfunctional (meth) acrylate is used. Specifically, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, penta Erythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane tetra
  • the polyfunctional acrylic monomer can be easily obtained as a commercial product.
  • Pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate and pentaerythritol dimethacrylate are particularly preferred.
  • Photopolymerization initiator examples include a photosensitive radical polymerization initiator.
  • the photosensitive radical polymerization initiator include ⁇ -diketones such as benzyl and diacetyl, acyloins such as benzoin, acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, thioxanthone, 2,4 Benzophenones such as diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone, acetophenone, p-dimethylaminoacetophenone, ⁇ , ⁇ '-dimethoxyacetoxybenzophenone, 2,2'-d
  • photosensitive radical polymerization initiators examples include IRGACURE-184, 369, 500, 651, 907, 1700, 819, 124, 1000, 2959, 149, 1800, 1850, OXE-01, Darocur-1173, 1116, 2959, 1664, 4043 (above, manufactured by Ciba Specialty Chemicals), KAYACURE-DETX, MBP, DMBI, EPA, Same OA (manufactured by Nippon Kayaku Co., Ltd.), LUCIRINTPO (manufactured by BASF Co. LTD), VICURE-10, same as 55 (manufactured by STAFFFER Co. LTD), TRIGONALP1 (manufactured by AKZO Co.
  • ⁇ , ⁇ '-dimethoxyacetoxybenzophenone, 2-methyl (4- (methylthio) phenyl) is considered because of its solubility in the photosensitive resin composition preparation liquid and transparency after exposure.
  • 2-Morpholin-1-propanone and 2-methyl (4- (methylthio) phenyl) -2-morpholino-1-propanone are particularly preferred.
  • the alkali-soluble resin according to the present embodiment is a linear organic high molecular polymer, and has at least one molecule (preferably, a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group that promotes alkali solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Among these, more preferably, it is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.
  • a known radical polymerization method For the production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical polymerization initiator, and type of solvent when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and experimental conditions It is also possible to determine.
  • a polymer having a carboxylic acid in the side chain is preferable.
  • JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836 and JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, carboxyl in side chain Examples include acidic cellulose derivatives having an acid and polymer having an acid anhydride added to a polymer having a hydroxyl group, and a polymer having a (meth) acryloyl group in the side chain is also preferred.
  • benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable.
  • those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful.
  • the polymer can be used by mixing in an arbitrary amount.
  • 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macro described in JP-A-7-140654
  • Monomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer and 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Can be mentioned.
  • a specific structural unit of the alkali-soluble resin is particularly preferably a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith.
  • examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds.
  • the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
  • alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Mention may be made of (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate and cyclohexyl acrylate.
  • R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 7 represents an alkyl group having 1 to 8 carbon atoms or 6 carbon atoms. Represents -12 aralkyl groups. Can be mentioned.
  • the negative photosensitive resin composition is prepared by mixing the components of (A) cyclic olefin resin, (B) polyfunctional acrylic monomer, and (C) photopolymerization initiator.
  • the negative photosensitive resin composition is preferably used in the form of a solution after being dissolved in an appropriate solvent.
  • (A) a cyclic olefin resin, (B) a polyfunctional acrylic monomer, (C) a photopolymerization initiator, and, if necessary, other compounding agents are mixed at a predetermined ratio to obtain a negative type solution.
  • a photosensitive resin composition can be prepared.
  • the polyfunctional acrylic monomer is preferably 10 to 150 parts by weight, more preferably 40 to 40 parts by weight with respect to 10 parts by weight of the (A) cyclic olefin resin. It is contained at a ratio of 120 parts by weight.
  • B When the polyfunctional acrylic monomer is less than 10 parts by weight, sufficient photosensitivity tends not to be obtained. On the other hand, when it exceeds 150 parts by weight, the breaking strength tends to decrease.
  • the (C) photopolymerization initiator is preferably contained in an amount of 1 to 40 parts by weight, more preferably 3 to 35 parts by weight.
  • C When the photopolymerization initiator is less than 1 part by weight, heat resistance, surface hardness and chemical resistance tend not to be obtained. On the other hand, when it exceeds 40 weight part, it exists in the tendency for transparency to fall.
  • (A) a cyclic olefin resin, (B) a polyfunctional acrylic monomer, and (C) a photopolymerization initiator are dissolved. Those that do not react with each component are used.
  • alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate
  • Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether and diethylene glycol diethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether
  • Propylene glycol monoalkyl ethers such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol alkyl ether
  • propylene glycol alkyl ether acetates propylene glycol alkyl ether acetates and aromatic hydrocarbons are preferably used because of their solubility, reactivity with each component, and ease of formation of a coating film. .
  • a high boiling point solvent can be used in combination with the above solvent.
  • the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl.
  • the negative photosensitive resin composition of the present embodiment may contain other components in addition to the above as necessary, as long as the object of the present invention is not impaired.
  • the negative photosensitive resin composition prepared as described above can be used after being filtered using a Millipore filter having a pore diameter of about 0.2 to 0.5 ⁇ m.
  • the method for forming an interlayer insulating film includes at least the following steps. (1) a step of forming a film of the negative photosensitive resin composition on a substrate, (2) a step of irradiating at least a part of the film with light (hereinafter sometimes referred to as “exposure”); 3) a step of developing the film after exposure, and (4) a step of baking the film after development (hereinafter sometimes referred to as “baking”) to form an interlayer insulating film.
  • light in the present embodiment means light including ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, ⁇ rays, synchrotron light, proton beams, and the like.
  • the negative photosensitive resin composition is preferably formed as a liquid composition, a film is formed on the substrate surface, the solvent is removed by pre-baking, and the negative photosensitive resin composition A film is formed.
  • the film forming method of the composition solution is not particularly limited, but a method by coating is preferable.
  • a coating method an appropriate method such as a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, and an ink jet method can be employed.
  • the pre-baking conditions vary depending on the types of constituent components of the negative photosensitive resin composition and the usage ratio, but can be, for example, 60 to 130 ° C. for 30 seconds to 15 minutes.
  • the film thickness of the film to be formed is preferably 5 to 20 ⁇ m after pre-baking.
  • Process- (2) In the step, at least a part of the formed film is exposed.
  • the exposure is usually performed through a photomask having a pattern of a predetermined shape.
  • Examples of light used for exposure include ultraviolet rays such as i-rays (wavelength 365 nm), far ultraviolet rays such as KrF excimer laser and ArF excimer laser, X-rays such as synchrotron light, and charged particle beams such as electron beams. Can be mentioned. Of these lights, ultraviolet rays are preferred, ultraviolet rays having a wavelength of 400 nm or less are more preferred, and ultraviolet rays containing i-rays are even more preferred.
  • the exposure amount is preferably about 50 to 10,000 J / m 2 .
  • step (3) the film after exposure is developed to remove unexposed portions, thereby forming a pattern having a predetermined shape.
  • Developers used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene and 1,5-diazabicyclo [
  • An aqueous solution of an alkaline compound such as 4,3,0] -5-nonene is preferred.
  • An appropriate amount of a water-soluble organic solvent such as methanol and ethanol and a surfactant can be added to the aqueous solution of the alkaline compound.
  • the negative photosensitive resin composition does not contain insoluble components such as fillers and pigments
  • various organic solvents that dissolve the constituent components can also be used as the developer.
  • an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, a shower method, or the like can be employed.
  • the development time varies depending on the composition of the negative photosensitive resin composition, but can be, for example, 30 to 300 seconds.
  • the negative photosensitive resin composition conventionally used for forming an interlayer insulating film has a development time of more than 20 seconds from the optimum condition, a defect such as peeling occurs in the formed pattern.
  • a good pattern can be formed even if the excess time from the optimum development time is 30 seconds or more, and the product yield is increased. improves.
  • the film after development is post-exposed as necessary, and then baked by a heating device such as a hot plate and an oven to cure the film and form an interlayer insulating film.
  • a heating device such as a hot plate and an oven to cure the film and form an interlayer insulating film.
  • the light used for the post-exposure include ultraviolet rays such as i-rays (wavelength 365 nm), far ultraviolet rays such as KrF excimer laser and ArF excimer laser, X-rays such as synchrotron light, and charged particle beams such as electron beams. Can be mentioned.
  • ultraviolet rays are preferred, ultraviolet rays having a wavelength of 400 nm or less are more preferred, and ultraviolet rays containing i-rays are even more preferred.
  • the exposure amount for post-exposure is preferably 50 to 10,000 J / m 2 .
  • the baking conditions vary depending on the types and proportions of the constituent components of the negative photosensitive resin composition, the desired pattern shape, and the heating device used. In the case of a hot plate, for example, 150 to 240 ° C. In the case of an oven, for example, the temperature is 150 to 240 ° C. for 30 to 90 minutes. Moreover, the step baking method etc. which heat-process twice or more can also be employ
  • the desired interlayer insulating film can be formed on the substrate.
  • the obtained interlayer insulating film is excellent in various properties such as resolution, transparency, heat resistance, heat discoloration resistance and solvent resistance even when it is thickened.
  • various liquid crystals including TFT-type liquid crystal display elements It can be used very suitably for electronic components such as display elements, magnetic head elements, integrated circuit elements, and solid-state imaging elements.
  • an interlayer insulating film having excellent characteristics can be easily formed with a high product yield.
  • Example 1 Preparation of negative photosensitive resin composition- (B) 10 g of Aronix M-305 (trade name, manufactured by Toagosei Co., Ltd.) as a polyfunctional acrylic monomer is dissolved in 36.4 g of toluene, and R 1 , R 2 and R 4 are hydrogenated in the resulting solution.
  • Aronix M-305 trade name, manufactured by Toagosei Co., Ltd.
  • a monomer in which R 3 is a methyl ester group and a monomer in which R 1 , R 2 , R 3 and R 4 are hydrogen atoms were copolymerized at a 1: 1 (molar ratio)
  • A 1 g of cyclic olefin resin and
  • C 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals, trade name: IRGACURE- as photopolymerization initiator) 907) 0.6 g is added, and filtered through a membrane filter having a pore size of 0.5 ⁇ m, and the negative photosensitive resin composition (S-1) in a solution state in which the total solid content concentration is 30% by mass Adjust Made.
  • the negative photosensitive resin composition (S-1) was applied on a glass substrate using a desktop coater, and then pre-baked in an explosion-proof dryer at 80 ° C. for 10 minutes to form a coating film.
  • the coating film was exposed to ultraviolet rays having a wavelength of 365 nm so that the integrated exposure amount was 100 mJ / cm 2 through a photomask having a pattern of a predetermined shape.
  • a 2.38 mass% tetramethylammonium hydroxide aqueous solution is used for dipping development at 25 ° C. for 5 minutes, and then washed with pure water for 1 minute to remove unnecessary portions and obtain a patterned thin film. It was.
  • the obtained patterned thin film was baked in an oven at 200 ° C. for 30 minutes and cured to obtain an interlayer insulating film having a predetermined pattern shape and a film thickness of 50 ⁇ m.
  • the transmittance at a wavelength of 400 nm was measured and evaluated using a double beam spectrophotometer U-2900 (trade name, manufactured by Hitachi, Ltd.). When this transmittance exceeds 90%, it can be said that the transparency is good (A).
  • Example 2 In Example 1, in the same manner as in Example 1 except that 10 g of Aronix M-402 (trade name, manufactured by Toagosei Co., Ltd.) was used instead of 10 g of Aronix M-305.
  • a photosensitive resin composition (S-2) was prepared to obtain an interlayer insulating film having a predetermined pattern shape and a film thickness of 40 ⁇ m. The evaluation results are shown in Table 1.
  • both the interlayer insulating films of Examples 1 and 2 were excellent in resolution, transparency, heat resistance, heat discoloration resistance and solvent resistance even when the film thickness was increased.

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Abstract

Disclosed is a negative photosensitive resin composition comprised of (A) an annual olefin resin containing repeating units represented by a general formula (1) (where R1, R2, R3 and R4 each represent an independent substituent group chosen from: a hydrogen atom, an alkyl group having 1-15 carbon atoms, an alkenyl group with 2-20 carbon atoms, a cycloalkyl group with 5-15 carbon atoms, an aryl group with 6-20 carbon atoms or an alkoxy group with 1-20 carbon atoms; or a hydrolysable silyl group, an alkoxycarbonyl group with 2-20 carbon atoms, a trialkylsiloxy carbonyl group with 4-20 carbon atoms, an alkyl carbonyl oxy group with 2-20 carbon atoms, an alkenyl carbonyl oxy group with 3-20 carbon atoms and an oxetanyl group; attached directly or via and jointly with an oxygen atom, a nitrogen atom or a sulphur atom), (B) a polyfunctional acrylic monomer and (C) a photoinitiator.

Description

ネガ型感光性樹脂組成物、層間絶縁膜及びその形成方法Negative photosensitive resin composition, interlayer insulating film and method for forming the same
　本発明は、ネガ型感光性樹脂組成物、層間絶縁膜及びその形成方法に関する。 The present invention relates to a negative photosensitive resin composition, an interlayer insulating film, and a method for forming the same.
　薄膜トランジスタ（以下、「ＴＦＴ」と記す）型液晶表示素子、磁気ヘッド素子、集積回路素子及び固体撮像管素子等の電子部品には、一般に層状に配置される配線の間を絶縁するために層間絶縁膜が設けられている（特許文献１参照）。その材料としては、必要とするパターン形状を得るための工程数が少なく、しかも十分な平坦性を有するものが好ましいことから、ネガ型感光性樹脂組成物が幅広く使用されている（特許文献２参照）。 Thin film transistor (hereinafter referred to as “TFT”) type liquid crystal display elements, magnetic head elements, integrated circuit elements, solid-state image pickup tube elements, and other electronic components are generally provided with interlayer insulation to insulate the wiring arranged in layers. A film is provided (see Patent Document 1). As the material, a negative photosensitive resin composition is widely used since the number of steps for obtaining a required pattern shape is small and a material having sufficient flatness is preferable (see Patent Document 2). ).
特開２０００－１００８９号公報JP 2000-10089 A 特許第３６５０９８５号公報Japanese Patent No. 3650985
　上記電子部品のうち、ＴＦＴ型液晶表示素子は、層間絶縁膜の上に透明電極膜を形成し、更にその上に液晶配向膜を形成する工程を経て製造される。このとき、当該層間絶縁膜は、透明電極膜の形成工程において高温条件に曝されるため、これに対する十分な耐性が必要となる。 Among the above electronic components, the TFT type liquid crystal display element is manufactured through a process of forming a transparent electrode film on an interlayer insulating film and further forming a liquid crystal alignment film thereon. At this time, since the interlayer insulating film is exposed to high temperature conditions in the process of forming the transparent electrode film, sufficient resistance to this is required.
　また近年、ＴＦＴ型液晶表示素子においては、大画面化、高輝度化、高精細化、及び高速応答化等、多様な技術動向下にあり、それに伴って液晶表示素子の構造も複雑化している。そのため、用いられる層間絶縁膜に関しては、低誘電率、高光透過率（＞８０％、λ＝４００ｎｍ）等の面で、従来にも増して高性能が要求されていると共に、液晶表示素子の構造上、５０μｍ程度までの厚膜化が可能であること等特殊な要求も出てきている。 In recent years, TFT-type liquid crystal display elements are under various technological trends such as large screens, high brightness, high definition, and high speed response, and the structure of liquid crystal display elements has become complicated accordingly. . Therefore, the interlayer insulating film used is required to have higher performance than the conventional one in terms of low dielectric constant, high light transmittance (> 80%, λ = 400 nm), and the structure of the liquid crystal display element. In addition, there are special demands such as the possibility of increasing the film thickness to about 50 μm.
　しかし、従来の層間絶縁膜の形成に通常用いられているネガ型感光性樹脂組成物では、厚膜化と、高光透過率化及び高解像度とを同時に達成することが極めて困難であり、このような特性を併せもつ層間絶縁膜を形成しうるネガ型感光性樹脂組成物の開発が強く求められていた。 However, with the negative photosensitive resin composition normally used for forming the conventional interlayer insulating film, it is extremely difficult to achieve a thick film, a high light transmittance and a high resolution at the same time. Development of a negative photosensitive resin composition capable of forming an interlayer insulating film having excellent characteristics has been strongly demanded.
　本発明は、上記事情を鑑みてなされたものであり、厚膜化しても、解像度、透明性、耐熱性、耐熱変色性及び耐溶媒性等の諸特性が十分優れた層間絶縁膜を形成しうるネガ型感光性樹脂組成物を提供することを目的とする。また、本発明は、係るネガ型感光性樹脂組成物から形成された層間絶縁膜及びその形成方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and forms an interlayer insulating film having sufficiently excellent properties such as resolution, transparency, heat resistance, heat discoloration resistance, and solvent resistance even when the film thickness is increased. An object of the present invention is to provide a negative photosensitive resin composition. Moreover, an object of this invention is to provide the interlayer insulation film formed from the negative photosensitive resin composition which concerns, and its formation method.
　本発明は、下記一般式（１）で表される繰り返し単位を含む（Ａ）環状オレフィン樹脂と、（Ｂ）多官能性アクリルモノマーと、（Ｃ）光重合開始剤と、を含有するネガ型感光性樹脂組成物を提供する。式（１）中Ｒ１、Ｒ２、Ｒ３及びＲ４は、各々独立して水素原子、炭素数１～１５のアルキル基、炭素数２～２０のアルケニル基、炭素数５～１５のシクロアルキル基、炭素数６～２０のアリール基若しくは炭素数１～２０のアルコキシ基、又は、加水分解性シリル基、炭素数２～２０のアルコキシカルボニル基、炭素数４～２０のトリアルキルシロキシカルボニル基、炭素数２～２０のアルキルカルボニルオキシ基、炭素数３～２０のアルケニルカルボニルオキシ基及びオキセタニル基から選ばれる置換基を示し、直接、又は、酸素原子、窒素原子若しくは硫黄原子を介して互いに連結されていてもよい。 The present invention is a negative type containing (A) a cyclic olefin resin containing a repeating unit represented by the following general formula (1), (B) a polyfunctional acrylic monomer, and (C) a photopolymerization initiator. A photosensitive resin composition is provided. In formula (1), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a cyclohexane having 5 to 15 carbon atoms. An alkyl group, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, or a hydrolyzable silyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms, or a trialkylsiloxycarbonyl group having 4 to 20 carbon atoms. Represents a substituent selected from an alkylcarbonyloxy group having 2 to 20 carbon atoms, an alkenylcarbonyloxy group having 3 to 20 carbon atoms and an oxetanyl group, and is connected to each other directly or through an oxygen atom, a nitrogen atom or a sulfur atom May be.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　上記構成を備えるネガ型感光性樹脂組成物は、厚膜化しても、解像度、透明性、耐熱性、耐熱変色性及び耐溶媒性等の諸特性が十分優れた層間絶縁膜を形成しうる。 The negative photosensitive resin composition having the above-described configuration can form an interlayer insulating film having sufficiently excellent properties such as resolution, transparency, heat resistance, heat discoloration resistance, and solvent resistance even when the film thickness is increased.
　（Ａ）環状オレフィン樹脂は、上記一般式（１）で表され、Ｒ１、Ｒ２、Ｒ３及びＲ４が水素原子である構成単位を含むことが好ましい。 (A) a cyclic olefin resin is represented by the general formula (1) preferably contains a structural unit R 1, R 2, R 3 and R 4 are hydrogen atoms.
　また、（Ａ）環状オレフィン樹脂は、上記一般式（１）で表され、Ｒ１、Ｒ２、Ｒ３及びＲ４のいずれか一つが炭素数２～２０のアルキルカルボニルオキシ基である構成単位を含むことが好ましい。 The cyclic olefin resin (A) is a structural unit represented by the above general formula (1), and any one of R 1 , R 2 , R 3 and R 4 is an alkylcarbonyloxy group having 2 to 20 carbon atoms. It is preferable to contain.
　本発明は、当該ネガ型感光性樹脂組成物から形成された膜の少なくとも一部に波長４００ｎｍ以下の紫外線を照射する工程を有する層間絶縁膜の形成方法に用いられる、ネガ型感光性樹脂組成物を提供する。 The present invention relates to a negative photosensitive resin composition used in a method for forming an interlayer insulating film having a step of irradiating an ultraviolet ray having a wavelength of 400 nm or less onto at least a part of a film formed from the negative photosensitive resin composition. I will provide a.
　本発明のネガ型感光性樹脂組成物はまた、（Ｄ）アルカリ可溶性樹脂を更に含有することが好ましい。 The negative photosensitive resin composition of the present invention preferably further contains (D) an alkali-soluble resin.
　本発明は、上記ネガ型感光性樹脂組成物から形成された層間絶縁膜を提供する。 The present invention provides an interlayer insulating film formed from the above negative photosensitive resin composition.
　本発明は、上記ネガ型感光性樹脂組成物から形成された膜の少なくとも一部に光を照射する工程と、光が照射された後の上記膜を現像する工程と、現像後の上記膜を焼成し、層間絶縁膜を形成する工程と、を有する層間絶縁膜の形成方法を提供する。 The present invention includes a step of irradiating at least a part of a film formed from the negative photosensitive resin composition, a step of developing the film after the light irradiation, and the film after development. And a step of forming an interlayer insulating film by baking.
　本発明によれば、厚膜化しても、解像度、透明性、耐熱性、耐熱変色性及び耐溶媒性等の諸特性が十分優れた層間絶縁膜を形成しうるネガ型感光性樹脂組成物を提供することが可能となる。 According to the present invention, there is provided a negative photosensitive resin composition capable of forming an interlayer insulating film having excellent properties such as resolution, transparency, heat resistance, heat discoloration resistance and solvent resistance even when the film thickness is increased. It becomes possible to provide.
　以下、本発明の好適な実施形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail.
　本実施形態に係るネガ型感光性樹脂組成物は、（Ａ）環状オレフィン樹脂と、（Ｂ）多官能性アクリルモノマーと、（Ｃ）光重合開始剤と、を含有する。以下各成分について詳細に説明する。 The negative photosensitive resin composition according to this embodiment contains (A) a cyclic olefin resin, (B) a polyfunctional acrylic monomer, and (C) a photopolymerization initiator. Hereinafter, each component will be described in detail.
－（Ａ）環状オレフィン樹脂－
　本実施形態に係る（Ａ）環状オレフィン樹脂は、下記一般式（１）で表される繰り返し単位を有する重合体である。 -(A) Cyclic olefin resin-
(A) Cyclic olefin resin which concerns on this embodiment is a polymer which has a repeating unit represented by following General formula (1).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　上記Ｒ１、Ｒ２、Ｒ３及びＲ４は、各々独立して水素原子、炭素数１～１５のアルキル基、炭素数２～２０のアルケニル基、炭素数５～１５のシクロアルキル基、炭素数６～２０のアリール基若しくは炭素数１～２０のアルコキシ基、又は、加水分解性シリル基、炭素数２～２０のアルコキシカルボニル基、炭素数４～２０のトリアルキルシロキシカルボニル基、炭素数２～２０のアルキルカルボニルオキシ基、炭素数３～２０のアルケニルカルボニルオキシ基及びオキセタニル基から選ばれる置換基を示し、直接、又は、酸素原子、窒素原子若しくは硫黄原子を介して互いに連結されていてもよい。 R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 5 to 15 carbon atoms, a carbon atom An aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrolyzable silyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms, a trialkylsiloxycarbonyl group having 4 to 20 carbon atoms, or 2 carbon atoms Represents a substituent selected from an alkylcarbonyloxy group having 20 carbon atoms, an alkenylcarbonyloxy group having 3 to 20 carbon atoms, and an oxetanyl group, which may be connected directly or via an oxygen atom, a nitrogen atom, or a sulfur atom. Good.
　より好ましくは、Ｒ１、Ｒ２、Ｒ３、及びＲ４は各々独立して水素原子、１～１５のアルキル基、炭素数２～２０のアルケニル基、炭素数６～１５のアリール基、又は炭素数６～２０のアルコキシ基並びに炭素数２～２０のアルキルカルボニルオキシ基から選ばれる置換基である。このような構成とすることで、各種溶剤への溶解性が向上するといった効果が得られる。 More preferably, R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, or The substituent is selected from an alkoxy group having 6 to 20 carbon atoms and an alkylcarbonyloxy group having 2 to 20 carbon atoms. By setting it as such a structure, the effect that the solubility to various solvents improves is acquired.
　ここで、加水分解性シリル基としては、具体的には、トリメトキシシリル、メチルジメトキシシリルが挙げられる。 Here, specific examples of the hydrolyzable silyl group include trimethoxysilyl and methyldimethoxysilyl.
　炭素数２～２０のアルキルカルボニルオキシ基としては、具体的には、メチルエステル、ｔ－ブチルエステル、２－エチルヘキシルエステル、ベンジルエステル、シクロペンチルエステル、シクロヘキシルエステル及びアリルエステルを挙げることができる。これらのうち、耐熱性の点からメチルエステル及びベンジルエステル等が特に好ましく用いられる。 Specific examples of the alkylcarbonyloxy group having 2 to 20 carbon atoms include methyl ester, t-butyl ester, 2-ethylhexyl ester, benzyl ester, cyclopentyl ester, cyclohexyl ester and allyl ester. Of these, methyl ester and benzyl ester are particularly preferably used from the viewpoint of heat resistance.
　本実施形態で用いられる（Ａ）環状オレフィン樹脂は、上記一般式（１）で表され、Ｒ１、Ｒ２、Ｒ３及びＲ４が水素原子である構成単位を環状オレフィン中の式（１）の構成単位の全量を基準として１モル％以上含むことが好ましく、１０モル％以上含むことがより好ましい。この割合が１モル％以上である場合、得られるネガ型感光性樹脂組成物の耐熱性が向上する傾向にある。また、上記割合は、６０モル％以下であることが好ましく、５０モル％以下であることがより好ましい。上記割合が６０モル％以下である場合、ネガ型感光性樹脂組成物調製のための溶媒への可溶性が向上する傾向にある。 The cyclic olefin resin (A) used in this embodiment is represented by the above general formula (1), and R 1 , R 2 , R 3, and R 4 are each a structural unit represented by the formula (1 ), Preferably 1 mol% or more, more preferably 10 mol% or more, based on the total amount of structural units. When this ratio is 1 mol% or more, the heat resistance of the obtained negative photosensitive resin composition tends to be improved. The proportion is preferably 60 mol% or less, and more preferably 50 mol% or less. When the said ratio is 60 mol% or less, it exists in the tendency for the solubility to the solvent for negative photosensitive resin composition preparation to improve.
　本実施形態で用いられる（Ａ）環状オレフィン樹脂は、上記一般式（１）で表され、Ｒ１、Ｒ２、Ｒ３及びＲ４のいずれか一つが炭素数２～２０のアルキルカルボニルオキシ基である構成単位を環状オレフィン中の式（１）の構成単位の全量を基準として１モル％以上含むことが好ましく、１０モル％以上含むことがより好ましい。この割合が１モル％以上の場合、ネガ型感光性樹脂組成物調製のための溶媒への可溶性が向上するという効果が得られる傾向にある。上記割合は、６０モル％以下であることが好ましく、５０モル％以下であることがより好ましい。上記割合が６０モル％以下である場合、得られるネガ型感光性樹脂組成物の耐熱性が向上するという効果が得られる傾向にある。 The (A) cyclic olefin resin used in the present embodiment is represented by the above general formula (1), and any one of R 1 , R 2 , R 3 and R 4 is an alkylcarbonyloxy group having 2 to 20 carbon atoms. It is preferable that 1 mol% or more is included on the basis of the whole quantity of the structural unit of Formula (1) in a cyclic olefin, and it is more preferable that 10 mol% or more is included. When this ratio is 1 mol% or more, there exists a tendency for the effect that the solubility to the solvent for negative photosensitive resin composition preparation improves. The proportion is preferably 60 mol% or less, and more preferably 50 mol% or less. When the said ratio is 60 mol% or less, it exists in the tendency for the effect that the heat resistance of the negative photosensitive resin composition obtained improves.
　上記（Ａ）環状オレフィン樹脂は、下記一般式（２）で表されるモノマーを溶媒中で、金属触媒の存在下で付加共重合することによって製造することができる。 The (A) cyclic olefin resin can be produced by addition copolymerization of a monomer represented by the following general formula (2) in a solvent in the presence of a metal catalyst.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　（Ａ）環状オレフィン樹脂の製造に用いられる溶媒としては、例えば、ペンタン、ヘキサン及びヘプタン等の脂肪族炭化水素、シクロヘキサン等の脂環族炭化水素、ベンゼン、トルエン及びキシレン等の芳香族炭化水素、ジクロロメタン、クロロホルム及びクロロベンゼン等のハロゲン化炭化水素、ニトロメタン、ニトロベンゼン及びアセトニトリル等の含窒素系炭化水素、並びに、ジエチルエーテル、ジオキサン及びテトラヒドロフラン等のエーテル類が挙げられる。これらの溶媒は、１種を単独で、又は２種以上を混合して使用してもよい。 (A) As a solvent used for manufacture of cyclic olefin resin, for example, aliphatic hydrocarbons such as pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, Examples include halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene, nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile, and ethers such as diethyl ether, dioxane and tetrahydrofuran. These solvents may be used alone or in combination of two or more.
　（Ａ）環状オレフィン樹脂の重合に用いられる触媒（Ｅ）としては、周期律表第８族元素、第９族元素及び第１０族元素から選択される一つの遷移金属に、少なくともシクロペンタジエニル系配位子が配位した錯体が好ましい。具体例としては、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、ルテニウム（Ｒｕ）、ロジウム（Ｒｈ）、パラジウム（Ｐｄ）、及び白金（Ｐｔ）を挙げることができる。これらのうち、触媒の重合活性を高くする観点から好ましい元素は、コバルト、ニッケル、パラジウム、及び白金であり、パラジウムを用いることが特に好ましい。 (A) The catalyst (E) used for the polymerization of the cyclic olefin resin includes at least cyclopentadienyl as one transition metal selected from Group 8 element, Group 9 element and Group 10 element of the periodic table. A complex in which a system ligand is coordinated is preferred. Specific examples include iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd), and platinum (Pt). Among these, preferred elements from the viewpoint of increasing the polymerization activity of the catalyst are cobalt, nickel, palladium, and platinum, and it is particularly preferable to use palladium.
　（Ａ）環状オレフィン樹脂の重合に用いられる助触媒（Ｆ）としては、触媒（Ｅ）をなす錯体の配位子の解離を促進するものが好ましい。例えば以下に例示する非配位性アニオンとカチオンとを組み合わせたイオン性化合物が挙げられる。 (A) As the co-catalyst (F) used for the polymerization of the cyclic olefin resin, one that promotes dissociation of the ligand of the complex forming the catalyst (E) is preferable. For example, the ionic compound which combined the non-coordinating anion and cation illustrated below is mentioned.
　非配位性アニオンとしては、例えば、テトラ（フェニル）ボレート、テトラ（フルオロフェニル）ボレート、テトラキス（ジフルオロフェニル）ボレート、テトラキス（トリフルオロフェニル）ボレート、テトラキス（テトラフルオロフェニル）ボレート、テトラキス（ペンタフルオロフェニル）ボレート、テトラキス（テトラフルオロメチルフェニル）ボレート、テトラ（トリイル）ボレート、テトラ（キシリル）ボレート、（トリフェニル，ペンタフルオロフェニル）ボレート、［トリス（ペンタフルオロフェニル），フェニル］ボレート及びトリデカハイドライド－７，８－ジカルバウンデカボレートが挙げられる。 Non-coordinating anions include, for example, tetra (phenyl) borate, tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluoro) Phenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate and tridecahydride -7,8-dicarbaound decaborate.
　上記カチオンとしては、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン及び遷移金属を有するフェロセニウムカチオン等が挙げられる。 Examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal.
　カルボニウムカチオンの具体例としては、トリフェニルカルボニウムカチオン及びトリ置換フェニルカルボニウムカチオン等の三置換カルボニウムカチオンが挙げられる。トリ置換フェニルカルボニウムカチオンの具体例としては、トリ（メチルフェニル）カルボニウムカチオン及びトリ（ジメチルフェニル）カルボニウムカチオンが挙げられる。 Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and trisubstituted phenylcarbonium cation. Specific examples of the tri-substituted phenyl carbonium cation include tri (methylphenyl) carbonium cation and tri (dimethylphenyl) carbonium cation.
　アンモニウムカチオンの具体例としては、トリメチルアンモニウムカチオン、トリエチルアンモニウムカチオン、トリプロピルアンモニウムカチオン、トリブチルアンモニウムカチオン及びトリ（ｎ－ブチル）アンモニウムカチオン等のトリアルキルアンモニウムカチオン、Ｎ，Ｎ－ジエチルアニリニウムカチオン及びＮ，Ｎ－２，４，６－ペンタメチルアニリニウムカチオン等のＮ，Ｎ－ジアルキルアニリニウムカチオン、並びに、ジ（イソプロピル）アンモニウムカチオン及びジシクロヘキシルアンモニウムカチオン等のジアルキルアンモニウムカチオンが挙げられる。 Specific examples of ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation and tri (n-butyl) ammonium cation, N, N-diethylanilinium cation and N N, N-dialkylanilinium cations such as N, N-2,4,6-pentamethylanilinium cation, and dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation.
　ホスホニウムカチオンの具体例としては、トリフェニルホスホニウムカチオン、トリ（メチルフェニル）ホスホニウムカチオン及びトリ（ジメチルフェニル）ホスホニウムカチオン等のトリアリールホスホニウムカチオンが挙げられる。 Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation and tri (dimethylphenyl) phosphonium cation.
　上記イオン性化合物としては、例えば、トリチルテトラ（ペンタフルオロフェニル）ボレート、トリフェニルカルボニウムテトラ（フルオロフェニル）ボレート、Ｎ，Ｎ－ジメチルアニリニウムテトラ（ペンタフルオロフェニル）ボレート及び１，１’－ジメチルフェロセニウムテトラ（ペンタフルオロフェニル）ボレートである。 Examples of the ionic compound include trityl tetra (pentafluorophenyl) borate, triphenylcarbonium tetra (fluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl) borate, and 1,1′-dimethyl. Ferrocenium tetra (pentafluorophenyl) borate.
　本実施形態において、触媒（Ｅ）と助触媒（Ｆ）との割合は、各種の条件によって異なるため一義的には定められないが、通常はＥ／Ｆ（モル比）で１／０．１～１／１００００が好ましく、１／０．５～１／５０００がより好ましく、１／１～１／２０００が更により好ましい。 In the present embodiment, the ratio between the catalyst (E) and the cocatalyst (F) varies depending on various conditions and is not uniquely determined, but is usually 1 / 0.1 in terms of E / F (molar ratio). Is preferably 1 / 10,000, more preferably 1 / 0.5 to 1/5000, and still more preferably 1/1 to 1/2000.
　本実施形態おける（Ａ）環状オレフィン樹脂のポリスチレン換算重量平均分子量（以下、「Ｍｗ」という）は、２×１０３から２×１０５が好ましく、２×１０４から１．８×１０５がより好ましい。Ｍｗが２×１０３未満であると、得られる被膜は耐熱性及び表面硬度が低下する傾向にある。一方、Ｍｗが２×１０５を超えると、現像性、感光性樹脂組成物調製用溶媒への溶解性が低下する傾向にある。 The polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) of the (A) cyclic olefin resin in the present embodiment is preferably 2 × 10 3 to 2 × 10 5 , and preferably 2 × 10 4 to 1.8 × 10 5. More preferred. When the Mw is less than 2 × 10 3 , the resulting film tends to have reduced heat resistance and surface hardness. On the other hand, when Mw exceeds 2 × 10 5 , developability and solubility in a solvent for preparing a photosensitive resin composition tend to be lowered.
－（Ｂ）多官能性アクリルモノマー－
　本実施形態に係る（Ｂ）多官能性アクリルモノマーとしては、２官能以上の多官能（メタ）アクリレートが用いられる。具体的には、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールペンタメタクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールテトラメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールジメタクリレート、テトラメチロールプロパンテトラアクリレート、テトラメチロールプロパンテトラメタクリレート、テトラメチロールメタンテトラアクリレート、テトラメチロールメタンテトラメタクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、１，３，５－トリアクリロイルヘキサヒドロ－Ｓ－トリアジン、１，３，５－トリメタクリロイルヘキサヒドロ－Ｓ－トリアジン、トリス（ヒドロキシエチルアクリロイル）イソシアヌレート、トリス（ヒドロキシエチルメタクリロイル）イソシアヌレート、トリアクリロイルホルマール、トリメタクリロイルホルマール、１，６－ヘキサンジオールアクリレート、１，６－ヘキサンジオールメタクリレート、ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタクリレート、エタンジオールジアクリレート、エタンジオールジメタクリレート、２－ヒドロキシプロパンジオールジアクリレート、２－ヒドロキシプロパンジオールジメタクリレート、ジエチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、イソプロピレングリコールジアクリレート、イソプロピレングリコールジメタクリレート、トリエチレングリコールジアクリレート、トリエチレングリコールジメタクリレート、Ｎ，Ｎ’－ビス（アクリロイル）システイン、Ｎ，Ｎ’－ビス（メタクリロイル）システイン、チオジグリコールジアクリレート、チオジグリコールジメタクリレート、ビスフェノールＡジアクリレート、ビスフェノールＡジメタクリレート、ビスフェノールＦジアクリレート、ビスフェノールＦジメタクリレート、ビスフェノールＳジアクリレート、ビスフェノールＳジメタクリレート、ビスフェノキシエタノールフルオレンジアクリレート、ビスフェノキシエタノールフルオレンジメタクリレート、ジアリルエーテルビスフェノールＡ、ｏ－ジアリルビスフェノールＡ、マレイン酸ジアリル及びトリアリルトリメリテートが挙げられる。２官能以上の多官能（メタ）アクリレートを用いることで、機械的強度が増すといった効果が得られる。 -(B) Multifunctional acrylic monomer-
As the (B) polyfunctional acrylic monomer according to the present embodiment, a bifunctional or higher polyfunctional (meth) acrylate is used. Specifically, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, penta Erythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate 1,3,5-triacryloylhexahydro-S-triazine, 1,3,5-trimethacryloylhexahydro-S-triazine, tris (hydroxyethylacryloyl) isocyanurate, tris (hydroxyethylmethacryloyl) isocyanurate, Triacryloyl formal, trimethacryloyl formal, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethanediol diacrylate, ethanediol dimethacrylate, 2-hydroxypropane Diol diacrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol Dimethacrylate, isopropylene glycol diacrylate, isopropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N, N′-bis (acryloyl) cysteine, N, N′-bis (methacryloyl) cysteine, thio Diglycol diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full Orange methacrylate, diallyl ether bisphenol A, o- Allyl bisphenol A, include diallyl maleate, and triallyl trimellitate. By using a polyfunctional (meth) acrylate having two or more functions, an effect of increasing mechanical strength can be obtained.
　上記多官能性アクリルモノマーは、市販品として容易に入手が可能であり、例えば、ＫＹＡＲＡＤ　Ｔ－１４２０、同ＤＰＨＡ、同ＤＰＨＡ－２Ｃ、同Ｄ－３１０、同Ｄ－３３０、同ＤＰＣＡ－２０、同ＤＰＣＡ－３０、同ＤＰＣＡ－６０、同ＤＰＣＡ－１２０、同ＤＮ－００７５、同ＤＮ－２４７５、同Ｒ－５２６、同ＮＰＧＤＡ、同ＰＥＧ４００ＤＡ、同ＭＡＮＤＡ、同Ｒ－１６７、同ＨＸ－２２０、同ＨＸ６２０、同Ｒ－５５１、同Ｒ－７１２、同Ｒ－６０４、同Ｒ－６８４、同ＧＰＯ－３０３、同ＴＭＰＴＡ、同ＴＨＥ－３３０、同ＴＰＡ－３２０、同ＴＰＡ－３３０、同ＰＥＴ－３０、同ＲＰ－１０４０（以上、日本化薬（株）製）、アロニックスＭ－２１０、同Ｍ－２４０、同Ｍ－６２００、同Ｍ－３０５、同Ｍ－３０９、同Ｍ－４００、同Ｍ－４０２、同Ｍ－４０５、同Ｍ－４５０、同Ｍ－７１００、同Ｍ－８０３０、同Ｍ－８０６０、同Ｍ－１３１０、同Ｍ－１６００、同Ｍ－１９６０、同Ｍ－８１００、同Ｍ－８５３０、同Ｍ－８５６０、同Ｍ－９０５０（以上、東亞合成（株）製）、ビスコート２９５、同３００、同３６０、同ＧＰＴ、同３ＰＡ、同４００、同２６０、同３１２及び同３３５ＨＰ（以上、大阪有機化学工業（株）製）を挙げることができる。またこれら多官能性アクリルモノマーは、１種を単独で、又は２種以上を組み合わせて用いることができる。 The polyfunctional acrylic monomer can be easily obtained as a commercial product. For example, KYARAD T-1420, DPHA, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX620 R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040 (Nippon Kayaku Co., Ltd.), Aronix M-210, M-240, M-6200, M-305, M-309, -400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1600, M-1960, M -8100, M-8530, M-8560, M-8560, M-9050 (manufactured by Toagosei Co., Ltd.), Biscote 295, 300, 360, GPT, 3PA, 400, 260, 312 and 335HP (Osaka Organic Chemical Co., Ltd.). Moreover, these polyfunctional acrylic monomers can be used individually by 1 type or in combination of 2 or more types.
　これらの多官能性アクリルモノマーの中で、現像液への溶解性及び透明性から、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールペンタメタクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールテトラメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールジアクリレート及びペンタエリスリトールジメタクリレートが特に好ましい。 Among these polyfunctional acrylic monomers, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, due to solubility in developer and transparency Pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate and pentaerythritol dimethacrylate are particularly preferred.
－（Ｃ）光重合開始剤－
　本実施形態に係る（Ｃ）光重合開始剤としては、感光性ラジカル重合開始剤を挙げることができる。感光性ラジカル重合開始剤としては、例えば、ベンジル及びジアセチル等のα－ジケトン類、ベンゾイン等のアシロイン類、ベンゾインメチルエーテル、ベンゾインエチルエーテル及びベンゾインイソプロピルエーテル等のアシロインエーテル類、チオキサントン、２，４－ジエチルチオキサントン、チオキサントン－４－スルホン酸、ベンゾフェノン、４，４’－ビス（ジメチルアミノ）ベンゾフェノン及び４，４’－ビス（ジエチルアミノ）ベンゾフェノン等のベンゾフェノン類、アセトフェノン、ｐ－ジメチルアミノアセトフェノン、α，α’－ジメトキシアセトキシベンゾフェノン、２，２’－ジメトキシ－２－フェニルアセトフェノン、ｐ－メトキシアセトフェノン、２－メチル（４－（メチルチオ）フェニル）－２－モルフォリノ－１－プロパノン及び２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタン－１－オン等のアセトフェノン類、アントラキノン及び１，４－ナフトキノン等のキノン類、フェナシルクロライド、トリブロモメチルフェニルスルホン及びトリス（トリクロロメチル）－ｓ－トリアジン等のハロゲン化合物、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチル－ペンチルホスフィンオキサイド及びビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキサイド等のアシルホスフィンオキサイド、並びに、ジ－ｔ－ブチルパーオキサイド等の過酸化物等が挙げられる。感光性ラジカル重合開始剤を用いることで、ネガ型感光性樹脂組成物の光に対する感度が向上するといった効果が得られる。 -(C) Photopolymerization initiator-
Examples of the (C) photopolymerization initiator according to this embodiment include a photosensitive radical polymerization initiator. Examples of the photosensitive radical polymerization initiator include α-diketones such as benzyl and diacetyl, acyloins such as benzoin, acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, thioxanthone, 2,4 Benzophenones such as diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone, acetophenone, p-dimethylaminoacetophenone, α, α'-dimethoxyacetoxybenzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl (4- (methylthio) phenyl) -2-morpholino-1- Acetophenones such as propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, quinones such as anthraquinone and 1,4-naphthoquinone, phenacyl chloride, tribromomethyl Halogen compounds such as phenylsulfone and tris (trichloromethyl) -s-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide And acyl phosphine oxides such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and peroxides such as di-t-butyl peroxide. By using a photosensitive radical polymerization initiator, the effect that the sensitivity with respect to the light of a negative photosensitive resin composition improves is acquired.
　これら感光性ラジカル重合開始剤の市販品としては、例えば、ＩＲＧＡＣＵＲＥ－１８４、同３６９、同５００、同６５１、同９０７、同１７００、同８１９、同１２４、同１０００、同２９５９、同１４９、同１８００、同１８５０、同ＯＸＥ－０１、Ｄａｒｏｃｕｒ－１１７３、同１１１６、同２９５９、同１６６４、同４０４３（以上、チバ・スペシャルティ・ケミカルズ社製）、ＫＡＹＡＣＵＲＥ－ＤＥＴＸ、同ＭＢＰ、同ＤＭＢＩ、同ＥＰＡ、同ＯＡ（以上、日本化薬（株）製）、ＬＵＣＩＲＩＮＴＰＯ（ＢＡＳＦ　Ｃｏ．ＬＴＤ製）、ＶＩＣＵＲＥ－１０、同５５（以上、ＳＴＡＵＦＦＥＲ　Ｃｏ．ＬＴＤ製）、ＴＲＩＧＯＮＡＬＰ１（ＡＫＺＯ　Ｃｏ．ＬＴＤ製）、ＳＡＮＤＯＲＡＹ１０００（ＳＡＮＤＯＺ　Ｃｏ．ＬＴＤ製）、ＤＥＡＰ（ＡＰＪＯＨＮ　Ｃｏ．ＬＴＤ製）、ＱＵＡＮＴＡＣＵＲＥ－ＰＤＯ、同ＩＴＸ及び同ＥＰＤ（以上、ＷＡＲＤＢＬＥＫＩＮＳＯＰ　Ｃｏ．ＬＴＤ製）が挙げられる。また、これら感光性ラジカル重合開始剤と感光増感剤とを併用することによって酸素による失活の少ない、高感度のネガ型感光性樹脂組成物を得ることも可能である。 Examples of commercially available photosensitive radical polymerization initiators include IRGACURE-184, 369, 500, 651, 907, 1700, 819, 124, 1000, 2959, 149, 1800, 1850, OXE-01, Darocur-1173, 1116, 2959, 1664, 4043 (above, manufactured by Ciba Specialty Chemicals), KAYACURE-DETX, MBP, DMBI, EPA, Same OA (manufactured by Nippon Kayaku Co., Ltd.), LUCIRINTPO (manufactured by BASF Co. LTD), VICURE-10, same as 55 (manufactured by STAFFFER Co. LTD), TRIGONALP1 (manufactured by AKZO Co. LTD), SANDORAY1000 ( SANDOZ Co. LTD ), Manufactured by DEAP (APJOHN Co.LTD), QUANTACURE-PDO, the ITX and the EPD (manufactured by WARDBLEKINSOP Co.LTD) and the like. Moreover, it is also possible to obtain a highly sensitive negative photosensitive resin composition with little deactivation by oxygen by using these photosensitive radical polymerization initiators and a photosensitizer together.
　上記感光性ラジカル重合開始剤の中で、感光性樹脂組成物調製液への溶解性、露光後の透明性から、α，α’－ジメトキシアセトキシベンゾフェノン、２－メチル（４－（メチルチオ）フェニル）－２－モルフォリノ－１－プロパノン及び２－メチル（４－（メチルチオ）フェニル）－２－モルフォリノ－１－プロパノンが特に好ましい。 Among the above-mentioned photosensitive radical polymerization initiators, α, α'-dimethoxyacetoxybenzophenone, 2-methyl (4- (methylthio) phenyl) is considered because of its solubility in the photosensitive resin composition preparation liquid and transparency after exposure. -2-Morpholin-1-propanone and 2-methyl (4- (methylthio) phenyl) -2-morpholino-1-propanone are particularly preferred.
－（Ｄ）アルカリ可溶性樹脂－
　本実施形態に係るアルカリ可溶性樹脂としては、線状有機高分子重合体であって、分子（好ましくは、アクリル系共重合体、スチレン系共重合体を主鎖とする分子）中に少なくとも１つのアルカリ可溶性を促進する基（例えばカルボキシル基、リン酸基及びスルホン酸基等）を有するアルカリ可溶性樹脂の中から適宜選択することができる。このうち、更に好ましくは、有機溶媒に可溶で弱アルカリ水溶液によって現像可能なものである。 -(D) Alkali-soluble resin-
The alkali-soluble resin according to the present embodiment is a linear organic high molecular polymer, and has at least one molecule (preferably, a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group that promotes alkali solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Among these, more preferably, it is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.
　アルカリ可溶性樹脂の製造には、例えば、公知のラジカル重合法による方法を適用することができる。ラジカル重合法でアルカリ可溶性樹脂を製造する際の温度、圧力、ラジカル重合開始剤の種類及び量、並びに、溶媒の種類等の重合条件は、当業者において容易に設定可能であり、実験的に条件を定めるようにすることもできる。 For the production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical polymerization initiator, and type of solvent when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and experimental conditions It is also possible to determine.
　上記線状有機高分子重合体としては、側鎖にカルボン酸を有するポリマーが好ましい。例えば、特開昭５９－４４６１５号、特公昭５４－３４３２７号、特公昭５８－１２５７７号、特公昭５４－２５９５７号、特開昭５９－５３８３６号及び特開昭５９－７１０４８号の各公報に記載されているような、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体、側鎖にカルボン酸を有する酸性セルロース誘導体及び水酸基を有するポリマーに酸無水物を付加させた高分子重合体等が挙げられ、更に側鎖に（メタ）アクリロイル基を有する高分子重合体も好ましいものとして挙げられる。 As the linear organic polymer, a polymer having a carboxylic acid in the side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836 and JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, carboxyl in side chain Examples include acidic cellulose derivatives having an acid and polymer having an acid anhydride added to a polymer having a hydroxyl group, and a polymer having a (meth) acryloyl group in the side chain is also preferred.
　これらの中でも特に、ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体及びベンジル（メタ）アクリレート／（メタ）アクリル酸／他のモノマーからなる多元共重合体が好適である。このほか、メタクリル酸２－ヒドロキシエチルを共重合したもの等も有用なものとして挙げられる。該ポリマーは任意の量で混合して用いることができる。 Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable. In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.
　上記以外に、特開平７－１４０６５４号公報に記載の２－ヒドロキシプロピル（メタ）アクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシ－３－フェノキシプロピルアクリレート／ポリメチルメタクリレートマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／メチルメタクリレート／メタクリル酸共重合体及び２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体等が挙げられる。 In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macro described in JP-A-7-140654 Monomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer and 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Can be mentioned.
　（Ｄ）アルカリ可溶性樹脂の具体的な構成単位については、特に（メタ）アクリル酸と、これと共重合可能な他の単量体との共重合体が好適である。上記（メタ）アクリル酸と共重合可能な他の単量体としては、（メタ）アクリル酸アルキル、（メタ）アクリル酸アリール及びビニル化合物等が挙げられる。ここで、アルキル基及びアリール基の水素原子は、置換基で置換されていてもよい。 (D) A specific structural unit of the alkali-soluble resin is particularly preferably a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith. Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
　上記アルキル（メタ）アクリレート及びアリール（メタ）アクリレートの具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジルアクリレート、トリルアクリレート、ナフチルアクリレート及びシクロヘキシルアクリレートを挙げることができる。 Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Mention may be made of (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate and cyclohexyl acrylate.
　また、上記ビニル化合物としては、例えば、スチレン、α－メチルスチレン、ビニルトルエン、グリシジルメタクリレート、アクリロニトリル、ビニルアセテート、Ｎ－ビニルピロリドン、テトラヒドロフルフリルメタクリレート、ポリスチレンマクロモノマー、ポリメチルメタクリレートマクロモノマー、ＣＨ２＝ＣＲ５Ｒ６〔ここで、Ｒ５は水素原子又は炭素数１～５のアルキル基を示し、Ｒ６は炭素数６～１０の芳香族炭化水素環を示す。〕及びＣＨ２＝Ｃ（Ｒ５）（ＣＯＯＲ７）〔ここで、Ｒ５は水素原子又は炭素数１～５のアルキル基を示し、Ｒ７は炭素数１～８のアルキル基又は炭素数６～１２のアラルキル基を示す。〕を挙げることができる。これら共重合可能な他の単量体は、１種を単独で又は２種以上を組み合わせて用いることができる。 Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH 2. = CR 5 R 6 [wherein R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 6 represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. And CH 2 ═C (R 5 ) (COOR 7 ) [wherein R 5 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 7 represents an alkyl group having 1 to 8 carbon atoms or 6 carbon atoms. Represents -12 aralkyl groups. Can be mentioned. These other copolymerizable monomers can be used singly or in combination of two or more.
　好ましい共重合可能な他の単量体は、ＣＨ２＝ＣＲ５Ｒ６、ＣＨ２＝Ｃ（Ｒ５）（ＣＯＯＲ７）、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート及びスチレンから選択される少なくとも１種であり、特に好ましくは、ＣＨ２＝ＣＲ５Ｒ６及び／又はＣＨ２＝Ｃ（Ｒ５）（ＣＯＯＲ７）である。 Other preferred copolymerizable monomers are selected from CH 2 ═CR 5 R 6 , CH 2 ═C (R 5 ) (COOR 7 ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably, CH 2 = CR 5 R 6 and / or CH 2 = C (R 5 ) (COOR 7 ).
－ネガ型感光性樹脂組成物の調製－
　本実施形態に係るネガ型感光性樹脂組成物は、上記（Ａ）環状オレフィン樹脂、（Ｂ）多官能性アクリルモノマー及び（Ｃ）光重合開始剤の各成分を混合することによって調製される。上記ネガ型感光性樹脂組成物は、好適には、適当な溶媒に溶解して溶液状態で用いられる。例えば（Ａ）環状オレフィン樹脂、（Ｂ）多官能性アクリルモノマー、（Ｃ）光重合開始剤、及び必要に応じ、その他の配合剤を、所定の割合で混合することによって、溶液状態のネガ型感光性樹脂組成物を調製することができる。 -Preparation of negative photosensitive resin composition-
The negative photosensitive resin composition according to this embodiment is prepared by mixing the components of (A) cyclic olefin resin, (B) polyfunctional acrylic monomer, and (C) photopolymerization initiator. The negative photosensitive resin composition is preferably used in the form of a solution after being dissolved in an appropriate solvent. For example, (A) a cyclic olefin resin, (B) a polyfunctional acrylic monomer, (C) a photopolymerization initiator, and, if necessary, other compounding agents are mixed at a predetermined ratio to obtain a negative type solution. A photosensitive resin composition can be prepared.
　本実施形態に係るネガ型感光性樹脂組成物は、（Ａ）環状オレフィン樹脂１０重量部に対して、（Ｂ）多官能性アクリルモノマーを、好ましくは１０～１５０重量部、より好ましくは４０～１２０重量部の割合で含有する。（Ｂ）多官能性アクリルモノマーが１０重量部未満の場合は、感光性が十分得られない傾向にある。一方、１５０重量部を超える場合は、破断強度が低下する傾向にある。また（Ｃ）光重合開始剤は、好ましくは１～４０重量部、より好ましくは３～３５重量部の割合で含有する。（Ｃ）光重合開始剤が１重量部未満の場合は、耐熱性、表面硬度及び耐薬品性が得られない傾向にある。一方、４０重量部を超える場合は、透明性が低下する傾向にある。 In the negative photosensitive resin composition according to this embodiment, the polyfunctional acrylic monomer is preferably 10 to 150 parts by weight, more preferably 40 to 40 parts by weight with respect to 10 parts by weight of the (A) cyclic olefin resin. It is contained at a ratio of 120 parts by weight. (B) When the polyfunctional acrylic monomer is less than 10 parts by weight, sufficient photosensitivity tends not to be obtained. On the other hand, when it exceeds 150 parts by weight, the breaking strength tends to decrease. The (C) photopolymerization initiator is preferably contained in an amount of 1 to 40 parts by weight, more preferably 3 to 35 parts by weight. (C) When the photopolymerization initiator is less than 1 part by weight, heat resistance, surface hardness and chemical resistance tend not to be obtained. On the other hand, when it exceeds 40 weight part, it exists in the tendency for transparency to fall.
　本実施形態に係るネガ型感光性樹脂組成物の調製に用いられる溶媒としては、（Ａ）環状オレフィン樹脂、（Ｂ）多官能性アクリルモノマー及び（Ｃ）光重合開始剤の各成分を溶解し、各成分と反応しないものが用いられる。具体的には、メタノール及びエタノール等のアルコール類、テトラヒドロフラン等のエーテル類、エチレングリコールモノメチルエーテル及びエチレングリコールモノエチルエーテル等のグリコールエーテル類、メチルセロソルブアセテート及びエチルセロソルブアセテート等のエチレングリコールアルキルエーテルアセテート類、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールエチルメチルエーテル及びジエチレングリコールジエチルエーテル等のジエチレングリコール類、プロピレングリコールメチルエーテル、プロピレングリコールエチルエーテル、プロピレングリコールプロピルエーテル及びプロピレングリコールブチルエーテル等のプロピレングリコールモノアルキルエーテル類、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート及びプロピレングリコールブチルエーテルアセテート等のプロピレングリコールアルキルエーテルアセテート類、プロピレングリコールメチルエーテルプロピオネート、プロピレングリコールエチルエーテルプロピオネート、プロピレングリコールプロピルエーテルプロピオネート及びプロピレングリコールブチルエーテルプロピオネート等のプロピレングリコールアルキルエーテルアセテート類、トルエン及びキシレン等の芳香族炭化水素類、メチルエチルケトン、シクロヘキサノン及び４－ヒドロキシ－４－メチル－２－ペンタノン等のケトン類、並びに、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、２－ヒドロキシプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸メチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、ヒドロキシ酢酸メチル、ヒドロキシ酢酸エチル、ヒドロキシ酢酸ブチル、乳酸メチル、乳酸エチル、乳酸プロピル、乳酸ブチル、３－ヒドロキシプロピオン酸メチル、３－ヒドロキシプロピオン酸エチル、３－ヒドロキシプロピオン酸プロピル、３－ヒドロキシプロピオン酸メチル、３－ブトキシプロピオン酸エチル、３－ブトキシプロピオン酸プロピル及び３－ブトキシプロピオン酸ブチル等のエステル類が挙げられる。 As a solvent used for the preparation of the negative photosensitive resin composition according to this embodiment, (A) a cyclic olefin resin, (B) a polyfunctional acrylic monomer, and (C) a photopolymerization initiator are dissolved. Those that do not react with each component are used. Specifically, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether and diethylene glycol diethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether Propylene glycol monoalkyl ethers, such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol alkyl ether acetates such as propylene glycol propyl ether acetate and propylene glycol butyl ether acetate, propylene glycol methyl ether propionate, propylene Propylene glycol alkyl ether acetates such as glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate, aromatic hydrocarbons such as toluene and xylene, methyl ethyl ketone, cyclohexanone and 4-hydroxy-4 -Methyl-2-pen Ketones such as non-methyl, ethyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, hydroxy Methyl acetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, methyl 3-hydroxypropionate And esters such as ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate.
　これらの溶媒の中で、溶解性、各成分との反応性及び塗膜の形成のしやすさから、プロピレングリコールアルキルエーテルアセテート類、プロピレングリコールアルキルエーテルアセテート類及び芳香族炭化水素類が好ましく用いられる。 Of these solvents, propylene glycol alkyl ether acetates, propylene glycol alkyl ether acetates and aromatic hydrocarbons are preferably used because of their solubility, reactivity with each component, and ease of formation of a coating film. .
　さらに上記溶媒と共に高沸点溶媒を併用することもできる。併用できる高沸点溶媒としては、例えば、Ｎ－メチルホルムアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチルホルムアニリド、Ｎ－メチルアセトアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン、ジメチルスルホキシド、ベンジルエチルエーテル、ジヘキシルエーテル、アセトニルアセトン、イソホロン、カプロン酸、カプリル酸、１－オクタノール、１－ノナノール、ベンジルアルコール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジエチル、γ－ブチロラクトン、炭酸エチレン、炭酸プロピレン及びフェニルセロソルブアセテートが挙げられる。本実施形態のネガ型感光性樹脂組成物は、本発明の目的を損なわない範囲で、必要に応じて上記以外に他の成分を含有していてもよい。 Further, a high boiling point solvent can be used in combination with the above solvent. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl. Ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, Examples include propylene carbonate and phenyl cellosolve acetate. The negative photosensitive resin composition of the present embodiment may contain other components in addition to the above as necessary, as long as the object of the present invention is not impaired.
　上記のように調製されたネガ型感光性樹脂組成物は、孔径０．２～０．５μｍ程度のミリポアフィルタ等を用いて濾過した後、使用に供することもできる。 The negative photosensitive resin composition prepared as described above can be used after being filtered using a Millipore filter having a pore diameter of about 0.2 to 0.5 μm.
－層間絶縁膜の形成方法－
　本実施形態に係る層間絶縁膜の形成方法は、少なくとも下記の工程を含んでいる。（１）上記ネガ型感光性樹脂組成物の膜を基板上に形成する工程、（２）上記膜の少なくとも一部に光を照射（以下、「露光」という場合がある。）する工程、（３）露光後の上記膜を現像する工程、（４）現像後の上記膜を焼成し（以下、「ベーク」という場合がある。）、層間絶縁膜を形成する工程。 -Formation method of interlayer insulation film-
The method for forming an interlayer insulating film according to the present embodiment includes at least the following steps. (1) a step of forming a film of the negative photosensitive resin composition on a substrate, (2) a step of irradiating at least a part of the film with light (hereinafter sometimes referred to as “exposure”); 3) a step of developing the film after exposure, and (4) a step of baking the film after development (hereinafter sometimes referred to as “baking”) to form an interlayer insulating film.
　ここで、本実施形態でいう「光」とは、紫外線、遠紫外線、Ｘ線、電子線、分子線、γ線、シンクロトロン光及びプロトンビーム等を含むものを意味する。 Here, “light” in the present embodiment means light including ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ rays, synchrotron light, proton beams, and the like.
　以下、これらの工程について詳細に説明する。 Hereinafter, these steps will be described in detail.
－（１）工程－
　（１）工程においては、ネガ型感光性樹脂組成物を、好ましくは液状組成物として、基板表面に膜を形成し、プレベークを行うことによって溶媒を除去して、ネガ型感光性樹脂組成物の膜を形成する。 -(1) Process-
In the step (1), the negative photosensitive resin composition is preferably formed as a liquid composition, a film is formed on the substrate surface, the solvent is removed by pre-baking, and the negative photosensitive resin composition A film is formed.
　使用できる基板の種類としては、ガラス基板、シリコンウエハー及びこれらの表面に各種金属が形成された基板等を挙げることができる。組成物溶液の膜形成方法としては、特に限定されるものではないが、塗布による方法が好ましい。塗布方法としては、スプレー法、ロールコート法、回転塗布法、スリットダイ塗布法、バー塗布法及びインクジェット法等の適宜の方法を採用することができる。 Examples of the types of substrates that can be used include glass substrates, silicon wafers, and substrates on which various metals are formed. The film forming method of the composition solution is not particularly limited, but a method by coating is preferable. As a coating method, an appropriate method such as a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, and an ink jet method can be employed.
　プレベークの条件は、ネガ型感光性樹脂組成物の構成成分の種類及び使用割合等によっても異なるが、例えば、６０～１３０℃で３０秒間～１５分間とすることができる。形成される上記膜の膜厚としては、プレベーク後の値として、５～２０μｍが好ましい。 The pre-baking conditions vary depending on the types of constituent components of the negative photosensitive resin composition and the usage ratio, but can be, for example, 60 to 130 ° C. for 30 seconds to 15 minutes. The film thickness of the film to be formed is preferably 5 to 20 μm after pre-baking.
－（２）工程－
　（２）工程においては、形成された上記膜の少なくとも一部に露光する。この場合、上記膜の一部のみに露光する際には、通常、所定形状のパターンを有するフォトマスクを介して露光する。 -(2) Process-
(2) In the step, at least a part of the formed film is exposed. In this case, when exposing only a part of the film, the exposure is usually performed through a photomask having a pattern of a predetermined shape.
　露光に用いられる光としては、例えば、ｉ線（波長３６５ｎｍ）等の紫外線、ＫｒＦエキシマレーザー及びＡｒＦエキシマレーザー等の遠紫外線、シンクロトロン光等のＸ線、並びに、電子線等の荷電粒子線を挙げることができる。これらの光のうち、紫外線が好ましく、波長４００ｎｍ以下の紫外線がより好ましく、ｉ線を含む紫外線が更により好ましい。露光量は、５０～１００００Ｊ／ｍ２程度とすることが好ましい。 Examples of light used for exposure include ultraviolet rays such as i-rays (wavelength 365 nm), far ultraviolet rays such as KrF excimer laser and ArF excimer laser, X-rays such as synchrotron light, and charged particle beams such as electron beams. Can be mentioned. Of these lights, ultraviolet rays are preferred, ultraviolet rays having a wavelength of 400 nm or less are more preferred, and ultraviolet rays containing i-rays are even more preferred. The exposure amount is preferably about 50 to 10,000 J / m 2 .
－（３）工程－
　（３）工程においては、露光後の上記膜を現像して、未露光部を除去することによって、所定形状のパターンを形成する。 -(3) Process-
In step (3), the film after exposure is developed to remove unexposed portions, thereby forming a pattern having a predetermined shape.
　現像に用いられる現像液としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア、エチルアミン、ｎ－プロピルアミン、ジエチルアミン、ジエチルアミノエタノール、ジ－ｎ－プロピルアミン、トリエチルアミン、メチルジエチルアミン、ジメチルエタノールアミン、トリエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、ピロール、ピペリジン、１，８－ジアザビシクロ［５，４，０］－７－ウンデセン及び１，５－ジアザビシクロ［４，３，０］－５－ノネン等のアルカリ性化合物の水溶液が好ましい。上記アルカリ性化合物の水溶液には、メタノール及びエタノール等の水溶性有機溶媒、並びに、界面活性剤を適量添加することができる。 Developers used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene and 1,5-diazabicyclo [ An aqueous solution of an alkaline compound such as 4,3,0] -5-nonene is preferred. An appropriate amount of a water-soluble organic solvent such as methanol and ethanol and a surfactant can be added to the aqueous solution of the alkaline compound.
　また、本実施形態においては、ネガ型感光性樹脂組成物が充填材や顔料等の不溶性成分を含有しない場合、現像液として、構成成分を溶解する各種の有機溶媒を使用することもできる。 In this embodiment, when the negative photosensitive resin composition does not contain insoluble components such as fillers and pigments, various organic solvents that dissolve the constituent components can also be used as the developer.
　現像方法としては、液盛り法、ディッピング法、揺動浸漬法及びシャワー法等の適宜の方法を採用することができる。 As a developing method, an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, a shower method, or the like can be employed.
　現像時間は、ネガ型感光性樹脂組成物の配合組成によっても異なるが、例えば、３０～３００秒間とすることができる。なお、従来から層間絶縁膜の形成に使用されているネガ型感光性樹脂組成物は、現像時間が最適条件から２０秒以上超過すると、形成されたパターンに剥がれ等の不具合が生じるため、現像時間を厳密に制御する必要があったが、本発明のネガ型感光性樹脂組成物の場合、最適現像時間からの超過時間が３０秒以上となっても、良好なパターンを形成でき、製品歩留まりが向上する。 The development time varies depending on the composition of the negative photosensitive resin composition, but can be, for example, 30 to 300 seconds. In addition, since the negative photosensitive resin composition conventionally used for forming an interlayer insulating film has a development time of more than 20 seconds from the optimum condition, a defect such as peeling occurs in the formed pattern. However, in the case of the negative photosensitive resin composition of the present invention, a good pattern can be formed even if the excess time from the optimum development time is 30 seconds or more, and the product yield is increased. improves.
－（４）工程－
　（４）工程においては、現像後の上記膜を、必要に応じて後露光したのち、ホットプレート及びオーブン等の加熱装置によってベークすることで、上記膜を硬化させ、層間絶縁膜を形成する。後露光に用いられる光としては、例えば、ｉ線（波長３６５ｎｍ）等の紫外線、ＫｒＦエキシマレーザー及びＡｒＦエキシマレーザー等の遠紫外線、シンクロトロン光等のＸ線、並びに、電子線等の荷電粒子線を挙げることができる。 -(4) Process-
In the step (4), the film after development is post-exposed as necessary, and then baked by a heating device such as a hot plate and an oven to cure the film and form an interlayer insulating film. Examples of the light used for the post-exposure include ultraviolet rays such as i-rays (wavelength 365 nm), far ultraviolet rays such as KrF excimer laser and ArF excimer laser, X-rays such as synchrotron light, and charged particle beams such as electron beams. Can be mentioned.
　これらの光のうち、紫外線が好ましく、波長４００ｎｍ以下の紫外線がより好ましく、ｉ線を含む紫外線が更により好ましい。後露光の露光量は、５０～１００００Ｊ／ｍ２とすることが好ましい。ベーク条件は、ネガ型感光性樹脂組成物の構成成分の種類及び使用割合、所望のパターン形状、並びに、使用される加熱装置等によっても異なるが、ホットプレートの場合は、例えば、１５０～２４０℃で１０～３０分間であり、オーブンの場合は、例えば、１５０～２４０℃で３０～９０分間である。また、ベークに際しては、２回以上加熱処理するステップベーク法等を採用することもできる。 Of these lights, ultraviolet rays are preferred, ultraviolet rays having a wavelength of 400 nm or less are more preferred, and ultraviolet rays containing i-rays are even more preferred. The exposure amount for post-exposure is preferably 50 to 10,000 J / m 2 . The baking conditions vary depending on the types and proportions of the constituent components of the negative photosensitive resin composition, the desired pattern shape, and the heating device used. In the case of a hot plate, for example, 150 to 240 ° C. In the case of an oven, for example, the temperature is 150 to 240 ° C. for 30 to 90 minutes. Moreover, the step baking method etc. which heat-process twice or more can also be employ | adopted at the time of baking.
　このようにして、目的とする層間絶縁膜を基板上に形成することができる。得られた層間絶縁膜は、厚膜化しても、解像度、透明性、耐熱性、耐熱変色性及び耐溶媒性等の諸特性に優れており、例えば、ＴＦＴ型液晶表示素子を含む各種の液晶表示素子、磁気ヘッド素子、集積回路素子及び固体撮像素子等の電子部品等に極めて好適に使用することができる。また、本実施形態の層間絶縁膜の形成方法によると、優れた特性を有する層間絶縁膜を高い製品歩留まりで簡便に形成することができる。 In this way, the desired interlayer insulating film can be formed on the substrate. The obtained interlayer insulating film is excellent in various properties such as resolution, transparency, heat resistance, heat discoloration resistance and solvent resistance even when it is thickened. For example, various liquid crystals including TFT-type liquid crystal display elements It can be used very suitably for electronic components such as display elements, magnetic head elements, integrated circuit elements, and solid-state imaging elements. Moreover, according to the method for forming an interlayer insulating film of this embodiment, an interlayer insulating film having excellent characteristics can be easily formed with a high product yield.
　以下に実施例を示して、本発明を更に具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
（実施例１）
－ネガ型感光性樹脂組成物の調製－
　（Ｂ）多官能性アクリルモノマーとしてアロニックスＭ－３０５（東亞合成（株）製、商品名）１０ｇをトルエン３６．４ｇに溶解し、得られた溶液に、Ｒ１、Ｒ２及びＲ４が水素原子であり、Ｒ３がメチルエステル基であるモノマーと、Ｒ１、Ｒ２、Ｒ３及びＲ４が水素原子であるモノマーと、を１：１（モル比）で共重合させた（Ａ）環状オレフィン樹脂１ｇと、（Ｃ）光重合開始剤として２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン（チバ・スペシャルティ・ケミカルズ社製、商品名：ＩＲＧＡＣＵＲＥ－９０７）０．６ｇと、を加え、孔径０．５μｍのメンブランフィルターでろ過して、全体の固形分濃度が３０質量％であるような溶液状態のネガ型感光性樹脂組成物（Ｓ－１）を調製した。 Example 1
-Preparation of negative photosensitive resin composition-
(B) 10 g of Aronix M-305 (trade name, manufactured by Toagosei Co., Ltd.) as a polyfunctional acrylic monomer is dissolved in 36.4 g of toluene, and R 1 , R 2 and R 4 are hydrogenated in the resulting solution. A monomer in which R 3 is a methyl ester group and a monomer in which R 1 , R 2 , R 3 and R 4 are hydrogen atoms were copolymerized at a 1: 1 (molar ratio) (A) 1 g of cyclic olefin resin and (C) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals, trade name: IRGACURE- as photopolymerization initiator) 907) 0.6 g is added, and filtered through a membrane filter having a pore size of 0.5 μm, and the negative photosensitive resin composition (S-1) in a solution state in which the total solid content concentration is 30% by mass Adjust Made.
－層間絶縁膜の形成－
　ネガ型感光性樹脂組成物（Ｓ－１）をガラス基板上に、卓上塗工機を用いて塗布した後、８０℃の防爆乾燥機内で１０分間プレベークして、塗膜を形成した。次いで、この塗膜に所定形状のパターンを有するフォトマスクを介して、波長３６５ｎｍの紫外線を積算露光量が１００ｍＪ／ｃｍ２となるように露光した。その後、２．３８質量％のテトラメチルアンモニウムヒドロキシド水溶液を用い、２５℃で５分間ディッピング現像したのち、純水で１分間洗浄することによって、不要な部分を除去して、パターン状薄膜を得た。 -Formation of interlayer insulation film-
The negative photosensitive resin composition (S-1) was applied on a glass substrate using a desktop coater, and then pre-baked in an explosion-proof dryer at 80 ° C. for 10 minutes to form a coating film. Next, the coating film was exposed to ultraviolet rays having a wavelength of 365 nm so that the integrated exposure amount was 100 mJ / cm 2 through a photomask having a pattern of a predetermined shape. Thereafter, a 2.38 mass% tetramethylammonium hydroxide aqueous solution is used for dipping development at 25 ° C. for 5 minutes, and then washed with pure water for 1 minute to remove unnecessary portions and obtain a patterned thin film. It was.
　次いで、得られたパターン状薄膜を２００℃のオーブン中で３０分間ベークして、硬化させることによって、所定のパターン形状を有する膜厚５０μｍの層間絶縁膜を得た。 Next, the obtained patterned thin film was baked in an oven at 200 ° C. for 30 minutes and cured to obtain an interlayer insulating film having a predetermined pattern shape and a film thickness of 50 μm.
－評価－
　次いで、下記の要領で評価を行った。評価結果を、層間絶縁膜の膜厚と併せて（以下同様）、表１に示す。 -Evaluation-
Subsequently, evaluation was performed in the following manner. The evaluation results are shown in Table 1 together with the thickness of the interlayer insulating film (the same applies hereinafter).
－解像度の評価－
　得られた層間絶縁膜において、直径５０μｍのマスクパターンを用いて解像度を評価した。５０μｍ平方のホールパターンが解像できる場合を良好（Ａ）、５０μｍ平方のホールパターンが解像できない場合を不良（Ｂ）として評価した。 -Resolution evaluation-
In the obtained interlayer insulating film, the resolution was evaluated using a mask pattern having a diameter of 50 μm. The case where a 50 μm square hole pattern could be resolved was evaluated as good (A), and the case where a 50 μm square hole pattern could not be resolved was evaluated as defective (B).
－透明性の評価－
　得られた層間絶縁膜の連続膜部分について、波長４００ｎｍにおける透過率を、ダブルビーム分光光度計　Ｕ－２９００（（株）日立製作所製、商品名）を用いて測定して評価した。この透過率が９０％を超えるとき、透明性が良好（Ａ）であるといえる。 -Evaluation of transparency-
With respect to the continuous film portion of the obtained interlayer insulating film, the transmittance at a wavelength of 400 nm was measured and evaluated using a double beam spectrophotometer U-2900 (trade name, manufactured by Hitachi, Ltd.). When this transmittance exceeds 90%, it can be said that the transparency is good (A).
－耐熱性の評価－
　得られた層間絶縁膜を、２２０℃のオーブン中で６０分加熱し、加熱前後での膜厚の変化率（％）〔＝（加熱前の膜厚－加熱後の膜厚）×１００／加熱前の膜厚〕を（株）ミツトヨ製デジマチックインジケーターを用いて測定して評価した。この変化率が５％以内のとき、耐熱性が良好（Ａ）であるといえる。 -Evaluation of heat resistance-
The obtained interlayer insulating film was heated in an oven at 220 ° C. for 60 minutes, and the rate of change in film thickness before and after heating (%) [= (film thickness before heating−film thickness after heating) × 100 / heating The previous film thickness] was measured and evaluated using a Digimatic indicator manufactured by Mitutoyo Corporation. When this rate of change is within 5%, it can be said that the heat resistance is good (A).
－耐熱変色性の評価－
　得られた層間絶縁膜を、２５０℃のオーブンを窒素パージし、その中で６０分加熱し、層間絶縁膜の連続膜部分について、波長４００ｎｍにおける透過率を、ダブルビーム分光光度計　Ｕ－２９００（商品名、（株）日立製作所製）を用いて測定して、加熱前後での透過率の変化率（％）〔＝（加熱前の透過率－加熱後の透過率）×１００／加熱前の透過率〕によって評価した。この変化率が５％以内のとき、耐熱変色性が良好（Ａ）であるといえる。 -Evaluation of heat discoloration-
The obtained interlayer insulating film was purged with an oven at 250 ° C. with nitrogen and heated therein for 60 minutes, and the transmittance at a wavelength of 400 nm of the continuous film portion of the interlayer insulating film was measured with a double beam spectrophotometer U-2900 ( The rate of change in transmittance before and after heating (%) [= (transmittance before heating−transmittance after heating) × 100 / before heating) The transmittance was evaluated. When this rate of change is within 5%, it can be said that the heat discoloration is good (A).
－耐溶媒性の評価－
　層間絶縁膜を形成したガラス基板を、５０℃のＮ－メチルピロリドン中に１５分間浸漬し、浸漬前後における層間絶縁膜の膜厚の変化率（％）〔＝（浸漬後の膜厚－浸漬前の膜厚）×１００／浸漬前の膜厚〕を（株）ミツトヨ製デジマチックインジケーターを用いて測定して評価した。この変化率が±１０％以内のとき、耐溶媒性が良好（Ａ）であるといえる。 -Evaluation of solvent resistance-
The glass substrate on which the interlayer insulating film is formed is immersed in N-methylpyrrolidone at 50 ° C. for 15 minutes, and the rate of change in film thickness of the interlayer insulating film before and after immersion (%) [= (film thickness after immersion−before immersion) Film thickness) × 100 / film thickness before immersion] was measured and evaluated using a Digimatic indicator manufactured by Mitutoyo Corporation. When this rate of change is within ± 10%, it can be said that the solvent resistance is good (A).
（実施例２）
　実施例１において、アロニックスＭ－３０５　１０ｇの代わりにアロニックスＭ－４０２（東亞合成（株）製、商品名）、１０ｇを用いたこと以外は、実施例１と同様にして、溶液状態のネガ型感光性樹脂組成物（Ｓ－２）を調製して、所定のパターン形状を有する膜厚４０μｍの層間絶縁膜を得た。評価結果を表１に示す。 (Example 2)
In Example 1, in the same manner as in Example 1 except that 10 g of Aronix M-402 (trade name, manufactured by Toagosei Co., Ltd.) was used instead of 10 g of Aronix M-305. A photosensitive resin composition (S-2) was prepared to obtain an interlayer insulating film having a predetermined pattern shape and a film thickness of 40 μm. The evaluation results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　実施例１及び２、どちらの層間絶縁膜も、厚膜化しても、解像度、透明性、耐熱性、耐熱変色性及び耐溶媒性に優れることが確認できた。 It was confirmed that both the interlayer insulating films of Examples 1 and 2 were excellent in resolution, transparency, heat resistance, heat discoloration resistance and solvent resistance even when the film thickness was increased.

Claims (7)

  1. 　下記一般式（１）で表される繰り返し単位：
    Figure JPOXMLDOC01-appb-C000001
     （式中Ｒ１、Ｒ２、Ｒ３及びＲ４は、各々独立して水素原子、炭素数１～１５のアルキル基、炭素数２～２０のアルケニル基、炭素数５～１５のシクロアルキル基、炭素数６～２０のアリール基若しくは炭素数１～２０のアルコキシ基、又は、加水分解性シリル基、炭素数２～２０のアルコキシカルボニル基、炭素数４～２０のトリアルキルシロキシカルボニル基、炭素数２～２０のアルキルカルボニルオキシ基、炭素数３～２０のアルケニルカルボニルオキシ基及びオキセタニル基から選ばれる置換基を示し、直接、又は、酸素原子、窒素原子若しくは硫黄原子を介して互いに連結されていてもよい。）を含む（Ａ）環状オレフィン樹脂と、
    　（Ｂ）多官能性アクリルモノマーと、
    　（Ｃ）光重合開始剤と、を含有するネガ型感光性樹脂組成物。     A repeating unit represented by the following general formula (1):
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a cycloalkyl group having 5 to 15 carbon atoms) An aryl group having 6 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, or a hydrolyzable silyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms, a trialkylsiloxycarbonyl group having 4 to 20 carbon atoms, carbon 1 represents a substituent selected from an alkylcarbonyloxy group having 2 to 20 carbon atoms, an alkenylcarbonyloxy group having 3 to 20 carbon atoms, and an oxetanyl group, and is connected to each other directly or through an oxygen atom, a nitrogen atom, or a sulfur atom. (A) a cyclic olefin resin containing
    (B) a polyfunctional acrylic monomer;
    (C) A negative photosensitive resin composition containing a photopolymerization initiator.
  2. 　（Ａ）環状オレフィン樹脂が、前記一般式（１）で表され、Ｒ１、Ｒ２、Ｒ３及びＲ４が水素原子である構成単位を含む請求項１に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to claim 1, wherein (A) the cyclic olefin resin includes a structural unit represented by the general formula (1), wherein R 1 , R 2 , R 3, and R 4 are hydrogen atoms. object.
  3. 　（Ａ）環状オレフィン樹脂が、前記一般式（１）で表され、Ｒ１、Ｒ２、Ｒ３及びＲ４のいずれか一つが炭素数２～２０のアルキルカルボニルオキシ基である構成単位を含む請求項１又は２に記載のネガ型感光性樹脂組成物。 (A) The cyclic olefin resin includes the structural unit represented by the general formula (1), and any one of R 1 , R 2 , R 3, and R 4 is an alkylcarbonyloxy group having 2 to 20 carbon atoms. The negative photosensitive resin composition of Claim 1 or 2.
  4. 　当該ネガ型感光性樹脂組成物から形成された膜の少なくとも一部に波長４００ｎｍ以下の紫外線を照射する工程を有する層間絶縁膜の形成方法に用いられる、請求項１～３のいずれか１項に記載のネガ型感光性樹脂組成物。 The method according to any one of claims 1 to 3, which is used in a method for forming an interlayer insulating film, which includes a step of irradiating at least a part of a film formed from the negative photosensitive resin composition with an ultraviolet ray having a wavelength of 400 nm or less. The negative photosensitive resin composition as described.
  5. 　（Ｄ）アルカリ可溶性樹脂を更に含有する請求項１～４のいずれか１項に記載のネガ型感光性樹脂組成物。 5. The negative photosensitive resin composition according to claim 1, further comprising (D) an alkali-soluble resin.
  6. 　請求項１～５のいずれか１項に記載のネガ型感光性樹脂組成物から形成された層間絶縁膜。 An interlayer insulating film formed from the negative photosensitive resin composition according to any one of claims 1 to 5.
  7. 　請求項１～５のいずれか１項に記載のネガ型感光性樹脂組成物から形成された膜の少なくとも一部に光を照射する工程と、
    　光が照射された後の前記膜を現像する工程と、
    　現像後の前記膜を焼成し、層間絶縁膜を形成する工程と、を有する層間絶縁膜の形成方法。     Irradiating at least part of a film formed from the negative photosensitive resin composition according to any one of claims 1 to 5;
    Developing the film after being irradiated with light;
    Baking the film after development to form an interlayer insulating film, and forming an interlayer insulating film.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012211988A (en) * 2011-03-31 2012-11-01 Nippon Zeon Co Ltd Negative photosensitive resin composition and electronic component
JP2014232232A (en) * 2013-05-29 2014-12-11 住友ベークライト株式会社 Photosensitive resin composition and electronic device
JP2014232233A (en) * 2013-05-29 2014-12-11 住友ベークライト株式会社 Photosensitive resin composition and electronic device
WO2015080073A1 (en) * 2013-11-28 2015-06-04 日本ゼオン株式会社 Laminate
JPWO2015083395A1 (en) * 2013-12-03 2017-03-16 住友ベークライト株式会社 Negative photoresist resin composition, cured film and electronic device

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6183029B2 (en) * 2013-07-25 2017-08-23 日本ゼオン株式会社 Negative photosensitive resin composition and electronic component
KR101564872B1 (en) * 2015-02-10 2015-10-30 동우 화인켐 주식회사 Negative-type photosensitive resin composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005531680A (en) * 2002-07-03 2005-10-20 住友ベークライト株式会社 Photosensitive compositions based on polycyclic copolymers
JP2006293094A (en) * 2005-04-12 2006-10-26 Mitsubishi Chemicals Corp Photopolymerizable composition, image forming material and imaging material
JP2008076860A (en) * 2006-09-22 2008-04-03 Showa Highpolymer Co Ltd Photosensitive resin composition
JP2009216728A (en) * 2008-03-06 2009-09-24 Sumitomo Chemical Co Ltd Photosensitive resin composition, pattern obtained from it, and display device

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200628981A (en) * 2004-09-29 2006-08-16 Sumitomo Bakelite Co Semiconductor device
JP4905700B2 (en) * 2007-05-16 2012-03-28 Ｊｓｒ株式会社 Radiation-sensitive resin composition, interlayer insulating film, microlens and method for forming them
JP5224764B2 (en) * 2007-09-28 2013-07-03 富士フイルム株式会社 Pigment dispersion composition, photocurable composition, color filter, liquid crystal display device and solid-state imaging device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005531680A (en) * 2002-07-03 2005-10-20 住友ベークライト株式会社 Photosensitive compositions based on polycyclic copolymers
JP2006293094A (en) * 2005-04-12 2006-10-26 Mitsubishi Chemicals Corp Photopolymerizable composition, image forming material and imaging material
JP2008076860A (en) * 2006-09-22 2008-04-03 Showa Highpolymer Co Ltd Photosensitive resin composition
JP2009216728A (en) * 2008-03-06 2009-09-24 Sumitomo Chemical Co Ltd Photosensitive resin composition, pattern obtained from it, and display device

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012211988A (en) * 2011-03-31 2012-11-01 Nippon Zeon Co Ltd Negative photosensitive resin composition and electronic component
JP2014232232A (en) * 2013-05-29 2014-12-11 住友ベークライト株式会社 Photosensitive resin composition and electronic device
JP2014232233A (en) * 2013-05-29 2014-12-11 住友ベークライト株式会社 Photosensitive resin composition and electronic device
WO2015080073A1 (en) * 2013-11-28 2015-06-04 日本ゼオン株式会社 Laminate
KR20160090826A (en) * 2013-11-28 2016-08-01 제온 코포레이션 Laminate
JPWO2015080073A1 (en) * 2013-11-28 2017-03-16 日本ゼオン株式会社 Laminate
KR102406577B1 (en) 2013-11-28 2022-06-07 제온 코포레이션 Laminate
JPWO2015083395A1 (en) * 2013-12-03 2017-03-16 住友ベークライト株式会社 Negative photoresist resin composition, cured film and electronic device

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