WO2011105443A1 - Composition de résine photosensible négative, film isolant intercouche et procédé de formation de ceux-ci - Google Patents

Composition de résine photosensible négative, film isolant intercouche et procédé de formation de ceux-ci 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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group
carbon atoms
resin composition
photosensitive resin
negative photosensitive
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PCT/JP2011/054019
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English (en)
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
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日立化成工業株式会社
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Priority to CN2011800109403A priority Critical patent/CN102782579A/zh
Priority to JP2011509751A priority patent/JP5333581B2/ja
Priority to KR1020127024435A priority patent/KR20120132509A/ko
Publication of WO2011105443A1 publication Critical patent/WO2011105443A1/fr

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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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  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne une composition de résine photosensible négative constituée de : (A) une résine oléfinique cyclique contenant des motifs répétés représentés par la formule générale (1) (dans laquelle R1, R2, R3 et R4 représentent chacun un groupe substituant indépendant choisi dans le groupe comprenant un atome d'hydrogène, un groupe alkyle doté de 1 à 15 atomes de carbone, un groupe alcényle doté de 2 à 20 atomes de carbone, un groupe cycloalkyle doté de 5 à 15 atomes de carbone, un groupe aryle doté de 6 à 20 atomes de carbone ou un groupe alcoxy doté de 1 à 20 atomes de carbone; ou un groupe silyle hydrolysable, un groupe alcoxycarbonyle doté de 2 à 20 atomes de carbone, un groupe carbonyle trialkylsiloxy doté de 4 à 20 atomes de carbone, un groupe alkyle carbonyloxy doté de 2 à 20 atomes de carbone, un groupe alcényle carbonyloxy doté de 3 à 20 atomes de carbone et un groupe oxétanyle, qui sont fixés directement ou par l'intermédiaire de l'atome d'oxygène, d'azote ou de soufre auquel ils sont liés); (B) un monomère acrylique polyfonctionnel et (C) un photoinitiateur.
PCT/JP2011/054019 2010-02-25 2011-02-23 Composition de résine photosensible négative, film isolant intercouche et procédé de formation de ceux-ci WO2011105443A1 (fr)

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JP2012211988A (ja) * 2011-03-31 2012-11-01 Nippon Zeon Co Ltd ネガ型感光性樹脂組成物および電子部品
JP2014232233A (ja) * 2013-05-29 2014-12-11 住友ベークライト株式会社 感光性樹脂組成物および電子装置
JP2014232232A (ja) * 2013-05-29 2014-12-11 住友ベークライト株式会社 感光性樹脂組成物および電子装置
WO2015080073A1 (fr) * 2013-11-28 2015-06-04 日本ゼオン株式会社 Laminé
JPWO2015083395A1 (ja) * 2013-12-03 2017-03-16 住友ベークライト株式会社 ネガ型フォトレジスト用樹脂組成物、硬化膜及び電子装置

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JP6183029B2 (ja) * 2013-07-25 2017-08-23 日本ゼオン株式会社 ネガ型感光性樹脂組成物および電子部品
KR101564872B1 (ko) * 2015-02-10 2015-10-30 동우 화인켐 주식회사 네가티브형 감광성 수지 조성물

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JP2006293094A (ja) * 2005-04-12 2006-10-26 Mitsubishi Chemicals Corp 光重合性組成物、画像形成材料及び画像形成材
JP2008076860A (ja) * 2006-09-22 2008-04-03 Showa Highpolymer Co Ltd 感光性樹脂組成物
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JP5224764B2 (ja) * 2007-09-28 2013-07-03 富士フイルム株式会社 顔料分散組成物、光硬化性組成物、カラーフィルタ、液晶表示素子および固体撮像素子

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JP2005531680A (ja) * 2002-07-03 2005-10-20 住友ベークライト株式会社 多環式コポリマーに基づく感光性組成物
JP2006293094A (ja) * 2005-04-12 2006-10-26 Mitsubishi Chemicals Corp 光重合性組成物、画像形成材料及び画像形成材
JP2008076860A (ja) * 2006-09-22 2008-04-03 Showa Highpolymer Co Ltd 感光性樹脂組成物
JP2009216728A (ja) * 2008-03-06 2009-09-24 Sumitomo Chemical Co Ltd 感光性樹脂組成物、これから得られるパターン、及び表示装置

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012211988A (ja) * 2011-03-31 2012-11-01 Nippon Zeon Co Ltd ネガ型感光性樹脂組成物および電子部品
JP2014232233A (ja) * 2013-05-29 2014-12-11 住友ベークライト株式会社 感光性樹脂組成物および電子装置
JP2014232232A (ja) * 2013-05-29 2014-12-11 住友ベークライト株式会社 感光性樹脂組成物および電子装置
WO2015080073A1 (fr) * 2013-11-28 2015-06-04 日本ゼオン株式会社 Laminé
KR20160090826A (ko) * 2013-11-28 2016-08-01 제온 코포레이션 적층체
JPWO2015080073A1 (ja) * 2013-11-28 2017-03-16 日本ゼオン株式会社 積層体
KR102406577B1 (ko) 2013-11-28 2022-06-07 제온 코포레이션 적층체
JPWO2015083395A1 (ja) * 2013-12-03 2017-03-16 住友ベークライト株式会社 ネガ型フォトレジスト用樹脂組成物、硬化膜及び電子装置

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CN104597712A (zh) 2015-05-06
JP2013101365A (ja) 2013-05-23
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