WO2013108716A1 - Negative photosensitive resin composition - Google Patents

Negative photosensitive resin composition Download PDF

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Publication number
WO2013108716A1
WO2013108716A1 PCT/JP2013/050428 JP2013050428W WO2013108716A1 WO 2013108716 A1 WO2013108716 A1 WO 2013108716A1 JP 2013050428 W JP2013050428 W JP 2013050428W WO 2013108716 A1 WO2013108716 A1 WO 2013108716A1
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WO
WIPO (PCT)
Prior art keywords
component
photosensitive resin
resin composition
negative photosensitive
monomer
Prior art date
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PCT/JP2013/050428
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French (fr)
Japanese (ja)
Inventor
真 畑中
芽育 内山
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日産化学工業株式会社
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Filing date
Publication date
Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to KR1020147022183A priority Critical patent/KR102027756B1/en
Priority to CN201380004941.6A priority patent/CN104040432B/en
Priority to JP2013554281A priority patent/JP6150072B2/en
Publication of WO2013108716A1 publication Critical patent/WO2013108716A1/en

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Classifications

    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • 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
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • 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
    • C08F222/36—Amides or imides
    • C08F222/38—Amides

Definitions

  • the present invention relates to a negative photosensitive resin composition and a cured film obtained therefrom. More specifically, the present invention relates to a photosensitive resin composition suitable for use in display materials, a cured film thereof, and various materials using the cured film.
  • an epoxy cation polymerization UV curable resin containing an epoxy compound and a photoacid generator is highly transparent and can be made thick (for example, Patent Document 1).
  • Patent Document 1 Since the coating film has tack after application and before exposure, handling properties are poor.
  • development with an organic solvent is essential because development with an aqueous alkali solution is not possible.
  • Alkali development is considered possible by introducing a carboxyl group into the polymer.
  • the reaction between the epoxy group and the carboxyl group is likely to occur during the polymerization. It is difficult to control the synthesis of the polymer. Even if the reaction can be controlled to synthesize a polymer, the storage stability is low.
  • a radical polymerization negative material containing a polymer having an acryloyl group, a polyfunctional acrylic monomer, and a photo radical initiator is known (for example, Patent Document 2).
  • alkali development is possible by introducing a carboxyl group into the polymer, but in order to increase the film thickness, it is necessary to increase the viscosity and the handling property is poor.
  • polymerization is a radical system, it is easy to receive oxygen inhibition of the surface at the time of photocuring, and the film thickness reduction on the surface is a problem.
  • the positive type material has high resolution, but it is difficult to increase the film thickness and the transparency is low (for example, Patent Document 3).
  • the present invention has been made in view of the above circumstances, can be thickened, has no tack before exposure, can be patterned with high resolution by alkali development, and the resulting coating film has high transparency.
  • An object of the present invention is to provide a negative photosensitive resin composition having small shrinkage even after post-baking.
  • a negative photosensitive resin composition containing the following component (A), component (B) and solvent (C):
  • (C) component: solvent
  • the negative photosensitive resin composition according to the first aspect wherein (ii) the monomer having an alkali-soluble group of component (A) is maleimide
  • the negative photosensitive resin according to the first aspect or the second aspect further containing 0.1 to 10 parts by mass of a sensitizer as component (D) based on 100 parts by mass of the photosensitive resin composition.
  • the negative photosensitive resin composition As a 4th viewpoint, the negative photosensitive resin composition as described in a 1st viewpoint or a 2nd viewpoint containing the polymer which further has a hydroxyl group as (E) component, As a fifth aspect, the negative photosensitive resin composition according to the first aspect to the third aspect, wherein the component (A) is a copolymer obtained by copolymerizing a monomer mixture containing a monomer having a hydroxy group, As a sixth aspect, the negative photosensitive resin composition according to the first aspect to the fifth aspect, which further contains a crosslinking agent as the component (F), As a seventh aspect, a cured film obtained using the negative photosensitive resin composition according to any one of the first aspect to the sixth aspect, As an eighth aspect, an interlayer insulating film for a liquid crystal display comprising the cured film according to the seventh aspect, As a ninth aspect, an optical filter comprising the cured film according to the seventh aspect, It is about.
  • the photosensitive resin composition of the present invention has no tack before exposure, can be developed with alkali, and can form a coating film pattern with high transparency and resolution even with a thick film, and is therefore optimal for forming a structure as an optical member. .
  • the negative photosensitive resin composition of the present invention is a photosensitive resin composition containing the following component (A), component (B) and solvent (C).
  • component a copolymer obtained by copolymerizing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) a monomer mixture containing a monomer having an alkali-soluble group
  • component a photoacid generator
  • Solvent Solvent
  • Component (A) is a copolymer obtained by copolymerizing a monomer mixture containing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) a monomer having an alkali-soluble group.
  • the copolymer refers to a polymer obtained by copolymerization using a monomer having an unsaturated double bond, such as acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, and styrene.
  • the copolymer of component (A) may be any copolymer having such a structure, and is not particularly limited with respect to the main chain skeleton and side chain type of the polymer constituting the copolymer.
  • the number average molecular weight of the copolymer of component (A) is excessively greater than 100,000, the developability of the unexposed area is lowered, while the number average molecular weight is less than 2,000 and excessively low. If it is, the components may be eluted during development because the exposed area is not sufficiently cured. Therefore, the number average molecular weight is in the range of 2,000 to 100,000.
  • N-alkoxymethyl (meth) acrylamide used for component (A) is represented by the structure of formula (1): (Wherein R 1 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. In the formula, R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
  • these monomers include N- (methoxymethyl) acrylamide, N- (methoxymethyl) methacrylamide, N- (n-butoxymethyl) acrylamide, N- (n-butoxymethyl) methacrylamide, N- ( And isobutoxymethyl) acrylamide, N- (isobutoxymethyl) methacrylamide and the like.
  • Monomers having an alkali-soluble group used for the component (A) include monomers having a carboxyl group, a phenolic hydroxyl group, an acid anhydride group, and a maleimide group.
  • the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl).
  • Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like.
  • Examples of the monomer having an acid anhydride group include maleic anhydride and itaconic anhydride.
  • Examples of the monomer having a maleimide group include maleimide.
  • the monomer which can be copolymerized with the monomer which has a specific functional group can be used together.
  • Specific examples of such monomers include acrylic ester compounds, methacrylic ester compounds, N-substituted maleimide compounds, acrylonitrile, acrylamide compounds, methacrylamide compounds, styrene compounds and vinyl compounds.
  • acrylic ester compounds methacrylic ester compounds, N-substituted maleimide compounds, acrylonitrile, acrylamide compounds, methacrylamide compounds, styrene compounds and vinyl compounds.
  • acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert- Butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2 -Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3
  • methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert- Butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, ⁇ -Butyrolactone methacrylate, 2-propyl- -Adamantyl methacrylate, 8-methyl-8-tricyclodec
  • N-substituted maleimide compound examples include N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like.
  • styrene compound examples include styrene, methyl styrene, chlorostyrene, and bromostyrene.
  • vinyl compound examples include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
  • the method for obtaining a copolymer having a specific functional group used in the present invention is not particularly limited.
  • a monomer having a specific functional group, another monomer having a non-reactive functional group capable of copolymerization, and initiation of polymerization can be obtained by carrying out a polymerization reaction at a temperature of 50 to 110 ° C. in a solvent in which an agent or the like is present.
  • the solvent used will not be specifically limited if it dissolves the monomer which comprises the acrylic copolymer which has a specific functional group, and the acrylic copolymer which has a specific functional group.
  • the solvent described in the (C) solvent mentioned later is mentioned.
  • the acrylic copolymer having a specific functional group thus obtained is usually in a solution state dissolved in a solvent.
  • the copolymer solution obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the produced precipitate is filtered and washed, and then under normal pressure or reduced pressure.
  • the copolymer powder can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the copolymer can be removed, and as a result, a purified copolymer powder can be obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
  • the polymerization solution of the acrylic copolymer may be used as it is, or the powder thereof may be redissolved in a solvent (C) described later and used as a solution.
  • the copolymer of component (A) may be a mixture of a plurality of types of specific copolymers.
  • N-alkoxymethyl (meth) acrylamide / alkali-soluble monomer / others 10 to 60/10 to 40/0 to 80 parts by weight.
  • the component (B) is a photoacid generator.
  • the kind of acid used for the thermosetting resin composition of the present invention is not particularly limited. Specific examples of such a photoacid generator include the following.
  • the content of the component (B) in the negative photosensitive resin composition of the present invention is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is 2 to 10 parts by mass.
  • this ratio is less than 0.5 mass part, photoreactivity may fall and a sensitivity may fall.
  • permeability of the formed coating film may fall or the storage stability of a solution may fall.
  • Examples of such a solvent (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol.
  • solvents can be used alone or in combination of two or more.
  • solvents propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate and the like are preferable from the viewpoint of good coating properties and high safety.
  • These solvents are generally used as solvents for photoresist materials.
  • (D) component is a sensitizer.
  • the reaction rate of the photoacid generator as the component (B) is small with respect to the wavelength at which the coating film made of the negative photosensitive resin composition of the present invention is exposed, the reaction rate is improved by adding a sensitizer. be able to.
  • Such a sensitizer include 9,10-dibutoxyanthracene, 9-hydroxymethylanthracene, thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, Anthraquinone, 1,2-dihydroxyanthraquinone, 2-ethylanthraquinone, 1,4-diethoxynaphthalene and the like can be mentioned.
  • one or more of the sensitizers can be used in combination.
  • the addition amount of these sensitizers is usually preferably 0.1 to 10 parts by mass, more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the component (A). If the amount of the sensitizer is larger than the above, the transparency of the coating film may be lowered.
  • the component (E) is a polymer having a hydroxy group.
  • the polymer having a hydroxy group include a polymer obtained by polymerizing a monomer having a hydroxy group, cellulose, hydroxypropyl cellulose, a polymer obtained by copolymerizing diepoxy and dicarboxylic acid, and obtained by copolymerizing diepoxy and diphenol.
  • examples thereof include polymers, polyester polyols, polyether polyols, polycaprolactone polyols, and the like, and a polymer obtained by polymerizing a monomer having a hydroxy group, or hydroxypropyl cellulose is preferable.
  • polymer obtained by polymerizing the above-mentioned monomer having a hydroxy group a polymer obtained by copolymerizing a monomer having a hydroxy group alone or a copolymerizable monomer among the copolymerizable monomers mentioned in the component (A) described above. Can be mentioned.
  • monomers having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, and 5- Acryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate and 5-methacryloyloxy-6- Hydroxynorbornene-2-carboxyl-6-lactone and the like.
  • Examples of the copolymerizable monomer include the copolymerizable monomers listed in the component (A).
  • These polymers having a hydroxy group can be used alone or in combination of two or more.
  • the content of the polymer having a hydroxy group as the component (E) is preferably 5 to 150 parts by mass based on 100 parts by mass of the copolymer as the component (A). More preferably, it is 10 to 120 parts by mass. If this ratio is less than the above, the sensitivity of the negative photosensitive resin composition may be reduced. On the other hand, if it is more than the above, the developability of the unexposed area will be reduced and the remaining amount will be reduced. May cause film and residue.
  • the crosslinking agent that is the component (F) of the present invention may be any crosslinking agent that can react with the component (A) by the acid generated in the component (B).
  • Examples of such a crosslinking agent include compounds such as an epoxy compound and a methylol compound, and a methylol compound is preferred.
  • methylol compound described above examples include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
  • alkoxymethylated glycoluril examples include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 , 6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone.
  • glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resins (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin (high condensation type, commercial product) manufactured by Dainippon Ink & Chemicals, Inc. Name: Beccamine (registered trademark) J-300S, P-955, N) and the like.
  • alkoxymethylated benzoguanamine examples include tetramethoxymethylbenzoguanamine.
  • Commercially available products manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), manufactured by Sanwa Chemical Co., Ltd. (trade names: Nicalac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.
  • alkoxymethylated melamine examples include, for example, hexamethoxymethylmelamine.
  • methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade name: My Coat (registered trademark)) 506, 508), Sanwa Chemical's methoxymethyl-type melamine compound (trade names: Nicalak (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compounds (trade names: Nicalac (registered trademark) MX-45, MX-410, MX-302) and the like.
  • a compound obtained by condensing a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group may be used.
  • the high molecular weight compound manufactured from the melamine compound and the benzoguanamine compound which are described in US Patent 6,323,310 is mentioned.
  • Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.).
  • Examples of commercially available products of the benzoguanamine compound include product name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.).
  • cross-linking agents can be used alone or in combination of two or more.
  • the content of the crosslinking agent of the component (F) in the negative photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably based on 100 parts by mass of the copolymer of the component (A). Is 10 to 80 parts by mass. If this ratio is less than the above, the photo-curing property of the negative photosensitive resin composition may be reduced. On the other hand, if it is more than the above, the developability of the unexposed portion is reduced. This may cause residual film and residue.
  • the negative photosensitive resin composition of the present invention can be used as necessary as a quencher, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, as long as the effects of the present invention are not impaired.
  • a dissolution accelerator such as a polyhydric phenol or polyvalent carboxylic acid.
  • the negative photosensitive resin composition of the present invention is obtained by dissolving the polymer of component (A) and the photoacid generator of component (B) in solvent (C), and each component (D) as desired.
  • the preferable example of the negative photosensitive resin composition of this invention is as follows. [1]: A negative photosensitive resin composition containing 0.5 to 20 parts by mass of the component (B) based on 100 parts by mass of the component (A) and dissolving these components in the solvent (C). [2]: The negative photosensitive resin composition further comprising 0.1 to 10 parts by mass of component (D) based on 100 parts by mass of component (A) in the composition of [1] above. [3] A negative photosensitive resin composition containing 5 to 150 parts by mass of the component (E) based on 100 parts by mass of the component (A) in the composition of the above [1] or [2]. [4] A negative photosensitive resin composition containing 5 to 100 parts by mass of the component (F) based on 100 parts by mass of the component (A) in the compositions [1] to [3].
  • the ratio of the solid content in the negative photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1 to 80% by mass, It is 5 to 60% by mass, or 10 to 50% by mass.
  • solid content means what remove
  • the preparation method of the negative photosensitive resin composition of this invention is not specifically limited, As the preparation method, for example, (A) component (copolymer) is melt
  • A) component (copolymer) is melt
  • B) Component (photoacid generator) is mixed at a predetermined ratio to make a uniform solution, or at an appropriate stage of this preparation method, component (D) (sensitizer), ( E) Component (polymer having a hydroxy group), (F) component (crosslinking agent) and other additives may be further added and mixed.
  • the solution of the specific copolymer obtained by the polymerization reaction in the solvent (C) can be used as it is, and in this case, the solution of the component (A)
  • a solvent may be further added for the purpose of adjusting the concentration.
  • the (C) solvent used in the process of forming the specific copolymer and the (C) solvent used for concentration adjustment at the time of preparing the negative photosensitive resin composition may be the same, May be different.
  • the prepared negative photosensitive resin composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 ⁇ m.
  • the negative photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate. Etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., and then pre-dried in a hot plate or oven to form a coating film can do. Then, a negative photosensitive resin film is formed by heat-treating this coating film.
  • a semiconductor substrate for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate. Etc.
  • a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 160 ° C. and a time of 0.3 to 60 minutes are adopted.
  • the heating temperature and heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes.
  • the film thickness of the negative photosensitive resin film formed from the negative photosensitive resin composition is, for example, 0.1 to 30 ⁇ m, for example, 0.5 to 20 ⁇ m, and further, for example, 1 to 15 ⁇ m.
  • the negative photosensitive resin film formed from the negative photosensitive resin composition of the present invention is exposed to light such as ultraviolet rays, ArF, KrF, and F 2 laser light using a mask having a predetermined pattern, Due to the action of the acid generated from the photoacid generator (PAG) of the component (B) contained in the negative photosensitive resin film, the exposed portion of the film becomes insoluble in the alkaline developer.
  • light such as ultraviolet rays, ArF, KrF, and F 2 laser light using a mask having a predetermined pattern
  • PEB post-exposure heating
  • alkaline developer examples include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline.
  • Alkaline aqueous solutions such as amine aqueous solutions such as ethanolamine, propylamine, and ethylenediamine.
  • a surfactant or the like can be added to these developers.
  • a tetraethylammonium hydroxide 0.1 to 2.38 mass% aqueous solution is generally used as a photoresist developer, and the alkaline developer is also used in the photosensitive resin composition of the present invention. It can be developed satisfactorily without causing problems such as swelling.
  • any of a liquid piling method, a dipping method, a rocking dipping method and the like can be used as a developing method.
  • the development time at that time is usually 15 to 180 seconds.
  • the negative photosensitive resin film is washed with running water, for example, for 20 to 90 seconds, and then air-dried with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, and A patterned film is obtained.
  • the pattern forming film is subjected to post-baking for thermosetting, specifically by heating using a hot plate, an oven, etc., thereby providing heat resistance, transparency, and flatness.
  • a film having a good relief pattern with excellent water absorption and chemical resistance can be obtained.
  • the post-bake is generally processed at a heating temperature selected from the range of 140 ° C. to 250 ° C. for 5 to 30 minutes when on a hot plate and 30 to 90 minutes when in an oven. The method is taken.
  • a desired cured film having a good pattern shape can be obtained by such post-baking.
  • the film thickness of the exposed area is sufficient at the time of development, with sufficiently high sensitivity even at a film thickness of about 10 ⁇ m. Reduction is very small, and a coating film having a fine pattern can be formed. Furthermore, this cured film is excellent in transparency, heat resistance and solvent resistance. Therefore, it can be suitably used for various films in liquid crystal displays, organic EL displays, touch panel elements, etc., for example, interlayer insulating films, protective films, insulating films, optical films and the like.
  • Examples 1 to 7 and Comparative Examples 1 and 2 According to the composition shown in the following Table 1, the component (A) is mixed with the component (B), the solvent (C), the component (D), and the component (E) and the component (F) at a predetermined ratio.
  • the negative photosensitive resin composition of each Example and each Comparative Example was prepared by stirring at room temperature for 3 hours to obtain a uniform solution.
  • the negative photosensitive resin composition was applied onto a silicon wafer using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film.
  • the film thickness of this coating film was measured using F20 manufactured by FILMETRICS.
  • the negative photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film.
  • This coating film was irradiated with UV light having a light intensity at 365 nm of 5.5 mW / cm 2 for 36 seconds using a Canon UV irradiation device PLA-600FA.
  • This film was heated after exposure on a hot plate at a temperature of 95 ° C. for 120 seconds and then post-baked in an oven at a temperature of 150 ° C. for 15 minutes to form a cured film.
  • the cured film was measured for transmittance at a wavelength of 400 nm using a UV-visible spectrophotometer (SIMADSU UV-2550 model number, manufactured by Shimadzu Corporation).
  • the negative photosensitive resin composition was applied onto alkali-free glass using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film.
  • the coating light intensity at 365nm by UV irradiation apparatus PLA-600FA manufactured by Canon Inc. in was 190 mJ / cm 2 irradiation through a mask of the UV line and space pattern of 5.5 mW / cm 2. Thereafter, post-exposure heating was performed on a hot plate at a temperature of 110 ° C. for 120 seconds.
  • TMAH tetramethylammonium hydroxide
  • the negative photosensitive resin composition was applied onto alkali-free glass using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film.
  • This coating film was irradiated with ultraviolet rays having a light intensity of 365 m at 5.5 mW / cm 2 at a rate of 50 mJ / cm 2 through a 20 ⁇ m line & space pattern mask by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Thereafter, post-exposure heating was performed on a hot plate at a temperature of 110 ° C. for 120 seconds.
  • sensitivity The minimum exposure amount at which a 20 ⁇ m pattern was formed was defined as sensitivity.
  • each of the negative photosensitive resin compositions of Examples 1 to 7 can be applied with a thick film of 10 ⁇ m or more, and high transmittance and alkali development are possible even with a thick film. And maintained high resolution and sensitivity.
  • the film thickness could not be increased, and the remaining film ratio after post-baking was as low as 90% or less.
  • the tack entered after pre-baking, and development with an alkaline developer was not possible.
  • the negative photosensitive resin composition according to the present invention is a material for forming a cured film such as a protective film, a planarizing film, and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element, an organic EL element, and a touch panel element.
  • TFT thin film transistor
  • a protective film of a color filter e.g., a protective film of a color filter
  • an array flattening film e.g., an interlayer insulating film of a capacitive touch panel
  • an insulating film of an organic EL element e.g., a display surface antireflection layer

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Abstract

[Problem] To provide a negative photosensitive resin composition that can be made into a thick film, the composition being devoid of tackiness even before exposure, enabling a pattern to be formed at high resolution by alkali development, and yielding a high-transparency film that exhibits minimal shrinkage after post-baking. [Solution] A negative photosensitive resin composition containing components (A), (B), and (C). Component (A) is a copolymer obtained by copolymerizing a monomer mixture containing at least (i) N-alkoxymethyl(meth)acrylamide and (ii) a monomer having an alkali soluble group, component (B) is a photoacid generator, and component (C) is a solvent.

Description

ネガ型感光性樹脂組成物Negative photosensitive resin composition
　本発明は、ネガ型感光性樹脂組成物及びそれから得られる硬化膜に関する。より詳しくは、本発明は、ディスプレイ材料の用途において好適な感光性樹脂組成物及びその硬化膜、並びに該硬化膜を用いた各種材料に関する。 The present invention relates to a negative photosensitive resin composition and a cured film obtained therefrom. More specifically, the present invention relates to a photosensitive resin composition suitable for use in display materials, a cured film thereof, and various materials using the cured film.
　エポキシ化合物と光酸発生剤とを含有するエポキシカチオン重合系UV硬化樹脂は、透明性が高く、厚膜化が可能であることが知られている（例えば、特許文献１）。しかし、塗布後、露光前に塗膜にタックがあるため、ハンドリング性が悪い。また、アルカリ水溶液による現像ができないため有機溶剤による現像が必須である。アルカリ現像は、ポリマー中にカルボキシル基を導入することで可能と考えられるが、エポキシ基を有するモノマーとカルボキシル基を有するモノマーとの共重合では、重合中にエポキシ基とカルボキシル基の反応が起こりやすく、ポリマーの合成制御が難しい。また、反応を制御しポリマーが合成できても保存安定性が低い。 It is known that an epoxy cation polymerization UV curable resin containing an epoxy compound and a photoacid generator is highly transparent and can be made thick (for example, Patent Document 1). However, since the coating film has tack after application and before exposure, handling properties are poor. In addition, development with an organic solvent is essential because development with an aqueous alkali solution is not possible. Alkali development is considered possible by introducing a carboxyl group into the polymer. However, in the copolymerization of a monomer having an epoxy group and a monomer having a carboxyl group, the reaction between the epoxy group and the carboxyl group is likely to occur during the polymerization. It is difficult to control the synthesis of the polymer. Even if the reaction can be controlled to synthesize a polymer, the storage stability is low.
　アルカリ現像が可能なものとしては、アクリロイル基を有するポリマー、多官能アクリルモノマーおよび光ラジカル開始剤を含有するラジカル重合系のネガ型材料が知られている（例えば、特許文献２）。この発明においては、ポリマーにカルボキシル基を導入することでアルカリ現像が可能であるが、厚膜化するには高粘度化が必要でハンドリング性が悪い。また、重合がラジカル系なので光硬化時に表面の酸素阻害を受けやすく、表面の膜減りが大きくなることが問題であった。 As a material capable of alkali development, a radical polymerization negative material containing a polymer having an acryloyl group, a polyfunctional acrylic monomer, and a photo radical initiator is known (for example, Patent Document 2). In this invention, alkali development is possible by introducing a carboxyl group into the polymer, but in order to increase the film thickness, it is necessary to increase the viscosity and the handling property is poor. Moreover, since polymerization is a radical system, it is easy to receive oxygen inhibition of the surface at the time of photocuring, and the film thickness reduction on the surface is a problem.
　一方、ポジ型材料は、解像度は高いが、厚膜化が難しく透明性も低い（例えば、特許文献３）。 On the other hand, the positive type material has high resolution, but it is difficult to increase the film thickness and the transparency is low (for example, Patent Document 3).
　これらの点から透明性が高くアルカリ現像可能で厚膜化する際にもハンドリング性の高い材料が望まれている。 From these points, a material having high transparency, high alkali developability, and high handling properties even when thickening is desired.
国際特許出願公開ＷＯ２００８／００７７６４号パンフレットInternational Patent Application Publication WO2008 / 007764 Pamphlet 特開２００４－３０２３８９号公報JP 2004-302389 A 特開平８－３３９０８２号公報JP-A-8-339082
　本発明は、上記の事情に鑑みなされたものであって、厚膜化が可能で、露光前にもタックがなく、アルカリ現像により高解像度でパターン形成でき、出来た塗膜は透明性が高くポストベーク後もシュリンクの小さなネガ型感光性樹脂組成物を提供することにある。 The present invention has been made in view of the above circumstances, can be thickened, has no tack before exposure, can be patterned with high resolution by alkali development, and the resulting coating film has high transparency. An object of the present invention is to provide a negative photosensitive resin composition having small shrinkage even after post-baking.
　本発明者は、上記の課題を解決するべく鋭意研究を行った結果、本発明を見出すに至った。
すなわち、第１観点として、下記（Ａ）成分、（Ｂ）成分及び（Ｃ）溶剤を含有するネガ型感光性樹脂組成物：
（Ａ）成分：少なくとも（ｉ）N－アルコキシメチル（メタ）アクリルアミドと、（ｉｉ）アルカリ可溶性基を有するモノマーとを含有するモノマー混合物を共重合した共重合体、
（Ｂ）成分：光酸発生剤、
（Ｃ）成分：溶剤、
第２観点として、（Ａ）成分の（ｉｉ）アルカリ可溶性基を有するモノマーがマレイミドである第１観点に記載のネガ型感光性樹脂組成物、
第３観点として、（Ｄ）成分として、増感剤をさらに感光性樹脂組成物１００質量部に基づいて０．１乃至１０質量部含有する、第１観点または第２観点に記載のネガ型感光性樹脂組成物、
第４観点として、（Ｅ）成分として、さらにヒドロキシ基を有するポリマーを含有する、第１観点または第２観点に記載のネガ型感光性樹脂組成物、
第５観点として、（Ａ）成分はさらにヒドロキシ基を有するモノマーを含有するモノマー混合物を共重合した共重合体である、第１観点乃至第３観点に記載のネガ型感光性樹脂組成物、
第６観点として、（Ｆ）成分として、さらに架橋剤を含有する、第１観点乃至第５観点に記載のネガ型感光性樹脂組成物、
第７観点として、第１観点乃至第６観点のうちいずれかに記載のネガ型感光性樹脂組成物を用いて得られる硬化膜、
第８観点として、第７観点に記載の硬化膜からなる液晶ディスプレイ用層間絶縁膜、
第９観点として、第７観点に記載の硬化膜からなる光学フィルタ、
に関するものである。 As a result of intensive studies to solve the above problems, the present inventors have found the present invention.
That is, as a first aspect, a negative photosensitive resin composition containing the following component (A), component (B) and solvent (C):
(A) component: a copolymer obtained by copolymerizing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) a monomer mixture containing a monomer having an alkali-soluble group,
(B) component: a photoacid generator,
(C) component: solvent,
As a second aspect, the negative photosensitive resin composition according to the first aspect, wherein (ii) the monomer having an alkali-soluble group of component (A) is maleimide,
As a third aspect, the negative photosensitive resin according to the first aspect or the second aspect, further containing 0.1 to 10 parts by mass of a sensitizer as component (D) based on 100 parts by mass of the photosensitive resin composition. Functional resin composition,
As a 4th viewpoint, the negative photosensitive resin composition as described in a 1st viewpoint or a 2nd viewpoint containing the polymer which further has a hydroxyl group as (E) component,
As a fifth aspect, the negative photosensitive resin composition according to the first aspect to the third aspect, wherein the component (A) is a copolymer obtained by copolymerizing a monomer mixture containing a monomer having a hydroxy group,
As a sixth aspect, the negative photosensitive resin composition according to the first aspect to the fifth aspect, which further contains a crosslinking agent as the component (F),
As a seventh aspect, a cured film obtained using the negative photosensitive resin composition according to any one of the first aspect to the sixth aspect,
As an eighth aspect, an interlayer insulating film for a liquid crystal display comprising the cured film according to the seventh aspect,
As a ninth aspect, an optical filter comprising the cured film according to the seventh aspect,
It is about.
　本発明の感光性樹脂組成物は、露光前のタックがなく、アルカリ現像が可能で、厚膜でも透明性、解像度が高い塗膜パターンを形成できることから光学部材としての構造体形成に最適である。 The photosensitive resin composition of the present invention has no tack before exposure, can be developed with alkali, and can form a coating film pattern with high transparency and resolution even with a thick film, and is therefore optimal for forming a structure as an optical member. .
　本発明のネガ型感光性樹脂組成物は、下記（Ａ）成分、（Ｂ）成分及び（Ｃ）溶剤を含有する感光性樹脂組成物である。
（Ａ）成分：少なくとも（ｉ）N－アルコキシメチル（メタ）アクリルアミドと、（ｉｉ）アルカリ可溶性基を有するモノマーとを含有するモノマー混合物を共重合した共重合体、
（Ｂ）成分：光酸発生剤、
（Ｃ）溶剤。 The negative photosensitive resin composition of the present invention is a photosensitive resin composition containing the following component (A), component (B) and solvent (C).
(A) component: a copolymer obtained by copolymerizing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) a monomer mixture containing a monomer having an alkali-soluble group,
(B) component: a photoacid generator,
(C) Solvent.
＜（Ａ）成分＞
　（Ａ）成分は、少なくとも（ｉ）N－アルコキシメチル（メタ）アクリルアミドと、（ｉｉ）アルカリ可溶性基を有するモノマーとを含有するモノマー混合物を共重合した共重合体である。 <(A) component>
Component (A) is a copolymer obtained by copolymerizing a monomer mixture containing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) a monomer having an alkali-soluble group.
　本発明において、共重合体とはアクリル酸エステル、メタクリル酸エステル、アクリルアミド、メタクリルアミド、スチレン等の不飽和二重結合を有するモノマーを用いて共重合して得られる重合体を指す。
　（Ａ）成分の共重合体は、斯かる構造を有する共重合体であればよく、共重合体を構成する高分子の主鎖の骨格及び側鎖の種類などについて特に限定されない。 In the present invention, the copolymer refers to a polymer obtained by copolymerization using a monomer having an unsaturated double bond, such as acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, and styrene.
The copolymer of component (A) may be any copolymer having such a structure, and is not particularly limited with respect to the main chain skeleton and side chain type of the polymer constituting the copolymer.
　然しながら、（Ａ）成分の共重合体は、数平均分子量が１００，０００を超えて過大なものであると、未露光部の現像性が低下する一方、数平均分子量が２，０００未満で過小なものであると、露光部の硬化が不十分なため現像時に成分が溶出する場合がある。従って、数平均分子量が２，０００乃至１００，０００の範囲内にあるものである。 However, if the number average molecular weight of the copolymer of component (A) is excessively greater than 100,000, the developability of the unexposed area is lowered, while the number average molecular weight is less than 2,000 and excessively low. If it is, the components may be eluted during development because the exposed area is not sufficiently cured. Therefore, the number average molecular weight is in the range of 2,000 to 100,000.
　（Ａ）成分に用いる（ｉ）Ｎ－アルコキシメチル（メタ）アクリルアミドは式（１）の構造で表される：
Figure JPOXMLDOC01-appb-C000001
（式中Ｒ１は水素原子、ハロゲン原子または炭素数１乃至６のアルキル基を表す。式中Ｒ2は水素原子または炭素数１乃至１０のアルキル基を表す。） (I) N-alkoxymethyl (meth) acrylamide used for component (A) is represented by the structure of formula (1):
Figure JPOXMLDOC01-appb-C000001
(Wherein R 1 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. In the formula, R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
　これらのモノマーの具体例としては、N－(メトキシメチル)アクリルアミド、N－(メトキシメチル)メタクリルアミド、N－(n-ブトキシメチル)アクリルアミド、N－(n-ブトキシメチル)メタクリルアミド、N－(イソブトキシメチル)アクリルアミド、N－(イソブトキシメチル)メタクリルアミド等が挙げられる。 Specific examples of these monomers include N- (methoxymethyl) acrylamide, N- (methoxymethyl) methacrylamide, N- (n-butoxymethyl) acrylamide, N- (n-butoxymethyl) methacrylamide, N- ( And isobutoxymethyl) acrylamide, N- (isobutoxymethyl) methacrylamide and the like.
　（Ａ）成分に用いる（ｉｉ）アルカリ可溶性基を有するモノマーとしては、カルボキシル基、フェノール性水酸基、酸無水物基、マレイミド基を有するモノマーが挙げられる。
カルボキシル基を有するモノマーとしては、例えば、アクリル酸、メタクリル酸、クロトン酸、モノ－（２－（アクリロイルオキシ）エチル）フタレート、モノ－（２－（メタクリロイルオキシ）エチル）フタレート、Ｎ－（カルボキシフェニル）マレイミド、Ｎ－（カルボキシフェニル）メタクリルアミド、Ｎ－（カルボキシフェニル）アクリルアミド、４ビニル安息香酸等が挙げられる。
　フェノール性水酸基を有するモノマーとしては、例えば、ヒドロキシスチレン、Ｎ－（ヒドロキシフェニル）アクリルアミド、Ｎ－（ヒドロキシフェニル）メタクリルアミド、Ｎ－（ヒドロキシフェニル）マレイミド等が挙げられる。
　酸無水物基を有するモノマーとしては、例えば、無水マレイン酸、無水イタコン酸等が挙げられる。
マレイミド基を有するモノマーとしては、例えば、マレイミドが挙げられる。 (Ii) Monomers having an alkali-soluble group used for the component (A) include monomers having a carboxyl group, a phenolic hydroxyl group, an acid anhydride group, and a maleimide group.
Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl). ) Maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, 4-vinylbenzoic acid and the like.
Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like.
Examples of the monomer having an acid anhydride group include maleic anhydride and itaconic anhydride.
Examples of the monomer having a maleimide group include maleimide.
　また、本発明においては、特定官能基を有する共重合体を得る際に、特定官能基を有するモノマーと共重合可能な、モノマーを併用することができる。
　そのようなモノマーの具体例としては、アクリル酸エステル化合物、メタクリル酸エステル化合物、Ｎ－置換マレイミド化合物、アクリロニトリル、アクリルアミド化合物、メタクリルアミド化合物、スチレン化合物及びビニル化合物等が挙げられる。
　以下、上記モノマーの具体例を挙げるが、これらに限定されるものではない。 Moreover, in this invention, when obtaining the copolymer which has a specific functional group, the monomer which can be copolymerized with the monomer which has a specific functional group can be used together.
Specific examples of such monomers include acrylic ester compounds, methacrylic ester compounds, N-substituted maleimide compounds, acrylonitrile, acrylamide compounds, methacrylamide compounds, styrene compounds and vinyl compounds.
Hereinafter, although the specific example of the said monomer is given, it is not limited to these.
　前記アクリル酸エステル化合物としては、例えば、メチルアクリレート、エチルアクリレート、イソプロピルアクリレート、ベンジルアクリレート、ナフチルアクリレート、アントリルアクリレート、アントリルメチルアクリレート、フェニルアクリレート、２，２，２－トリフルオロエチルアクリレート、ｔｅｒｔ－ブチルアクリレート、シクロヘキシルアクリレート、イソボルニルアクリレート、２－メトキシエチルアクリレート、メトキシトリエチレングリコールアクリレート、２－エトキシエチルアクリレート、テトラヒドロフルフリルアクリレート、３－メトキシブチルアクリレート、２－メチル－２－アダマンチルアクリレート、２－プロピル－２－アダマンチルアクリレート、８－メチル－８－トリシクロデシルアクリレート、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、４－ヒドロキシブチルアクリレート、２，３－ジヒドロキシプロピルアクリレート、ジエチレングリコールモノアクリレート、カプロラクトン２－（アクリロイルオキシ）エチルエステル、ポリ（エチレングリコール）エチルエーテルアクリレート、５－アクリロイルオキシ－６－ヒドロキシノルボルネン－２－カルボキシリック－６－ラクトン、アクリロイルエチルイソシアネート、及び、８－エチル－８－トリシクロデシルアクリレート、グリシジルアクリレート、等が挙げられる。 Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert- Butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2 -Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, diethylene glycol monoacrylate, caprolactone 2- (acryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, Examples include 5-acryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone, acryloylethyl isocyanate, and 8-ethyl-8-tricyclodecyl acrylate, glycidyl acrylate, and the like.
　前記メタクリル酸エステル化合物としては、例えば、メチルメタクリレート、エチルメタクリレート、イソプロピルメタクリレート、ベンジルメタクリレート、ナフチルメタクリレート、アントリルメタクリレート、アントリルメチルメタクリレート、フェニルメタクリレート、２，２，２－トリフルオロエチルメタクリレート、ｔｅｒｔ－ブチルメタクリレート、シクロヘキシルメタクリレート、イソボルニルメタクリレート、２－メトキシエチルメタクリレート、メトキシトリエチレングリコールメタクリレート、２－エトキシエチルメタクリレート、テトラヒドロフルフリルメタクリレート、３－メトキシブチルメタクリレート、２－メチル－２－アダマンチルメタクリレート、γ－ブチロラクトンメタクリレート、２－プロピル－２－アダマンチルメタクリレート、８－メチル－８－トリシクロデシルメタクリレート、２－ヒドロキシエチルメタクリレート、２－ヒドロキシプロピルメタクリレート、４－ヒドロキシブチルメタクリレート、２，３－ジヒドロキシプロピルメタクリレート、ジエチレングリコールモノメタクリレート、カプロラクトン２－（メタクリロイルオキシ）エチルエステル、ポリ（エチレングリコール）エチルエーテルメタクリレート、５－メタクリロイルオキシ－６－ヒドロキシノルボルネン－２－カルボキシリック－６－ラクトン、メタクリロイルエチルイソシアネート、及び、８－エチル－８－トリシクロデシルメタクリレートグリシジルメタクリレート、等が挙げられる。 Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert- Butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ -Butyrolactone methacrylate, 2-propyl- -Adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2- (methacryloyl) Oxy) ethyl ester, poly (ethylene glycol) ethyl ether methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone, methacryloylethyl isocyanate, and 8-ethyl-8-tricyclodecyl methacrylate glycidyl And methacrylate.
　前記Ｎ－置換マレイミド化合物としては、例えば、Ｎ－メチルマレイミド、Ｎ－フェニルマレイミド、及びＮ－シクロヘキシルマレイミド等が挙げられる。 Examples of the N-substituted maleimide compound include N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like.
　前記スチレン化合物としては、例えば、スチレン、メチルスチレン、クロロスチレン、ブロモスチレン等が挙げられる。 Examples of the styrene compound include styrene, methyl styrene, chlorostyrene, and bromostyrene.
　前記ビニル化合物としては、例えば、メチルビニルエーテル、ベンジルビニルエーテル、ビニルナフタレン、ビニルアントラセン、ビニルビフェニル、ビニルカルバゾール、２－ヒドロキシエチルビニルエーテル、フェニルビニルエーテル、及び、プロピルビニルエーテル等が挙げられる。 Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
　本発明に用いる特定官能基を有する共重合体を得る方法は特に限定されないが、例えば、特定官能基を有するモノマー、それ以外の共重合可能な非反応性官能基を有するモノマー及び所望により重合開始剤等を共存させた溶剤中において、５０乃至１１０℃の温度下で重合反応させることにより、得られる。その際、用いられる溶剤は、特定官能基を有するアクリル共重合体を構成するモノマー及び特定官能基を有するアクリル共重合体を溶解するものであれば特に限定されない。具体例としては、後述する（C）溶剤に記載する溶剤が挙げられる。 The method for obtaining a copolymer having a specific functional group used in the present invention is not particularly limited. For example, a monomer having a specific functional group, another monomer having a non-reactive functional group capable of copolymerization, and initiation of polymerization if desired. It can be obtained by carrying out a polymerization reaction at a temperature of 50 to 110 ° C. in a solvent in which an agent or the like is present. In that case, the solvent used will not be specifically limited if it dissolves the monomer which comprises the acrylic copolymer which has a specific functional group, and the acrylic copolymer which has a specific functional group. As a specific example, the solvent described in the (C) solvent mentioned later is mentioned.
　このようにして得られる特定官能基を有するアクリル共重合体は、通常、溶剤に溶解した溶液の状態である。 The acrylic copolymer having a specific functional group thus obtained is usually in a solution state dissolved in a solvent.
　また、上記のようにして得られた共重合体の溶液を、ジエチルエーテルや水等の撹拌下に投入して再沈殿させ、生成した沈殿物を濾過・洗浄した後、常圧又は減圧下で、常温あるいは加熱乾燥することで、共重合体の粉体とすることができる。このような操作により、共重合体と共存する重合開始剤や未反応モノマーを除去することができ、その結果、精製した共重合体の粉体を得られる。一度の操作で充分に精製できない場合は、得られた粉体を溶剤に再溶解して、上記の操作を繰り返し行えば良い。 In addition, the copolymer solution obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the produced precipitate is filtered and washed, and then under normal pressure or reduced pressure. The copolymer powder can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the copolymer can be removed, and as a result, a purified copolymer powder can be obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
　本発明においては、上記アクリル共重合体の重合溶液をそのまま用いても良く、あるいはその粉体を、たとえば後述する（C）溶剤に再溶解して溶液の状態として用いても良い。 In the present invention, the polymerization solution of the acrylic copolymer may be used as it is, or the powder thereof may be redissolved in a solvent (C) described later and used as a solution.
　また、本発明においては、（Ａ）成分の共重合体は、複数種の特定共重合体の混合物であってもよい。 In the present invention, the copolymer of component (A) may be a mixture of a plurality of types of specific copolymers.
　モノマーの共重合比としては、Ｎ－アルコキシメチル（メタ）アクリルアミド/アルカリ可溶性モノマー/その他=１０乃至６０/１０乃至４０/０乃至８０重量部が好ましい。アルカリ可溶性モノマーが少なすぎる場合、未露光部が現像液に溶解せず残膜や残渣の原因となりやすい。多すぎる場合、露光部の硬化性が不足しパターンが形成できない可能性がある。Ｎ－アルコキシメチル（メタ）アクリルアミドが少なすぎる場合、光硬化性が不足し露光部が現像時に溶解してしまう可能性がある。多すぎる場合、未露光部の溶解性が不足し残膜や残渣の原因となる可能性がある。 The copolymerization ratio of the monomers is preferably N-alkoxymethyl (meth) acrylamide / alkali-soluble monomer / others = 10 to 60/10 to 40/0 to 80 parts by weight. When there are too few alkali-soluble monomers, an unexposed part does not melt | dissolve in a developing solution, and tends to cause a residual film and a residue. If it is too much, the curability of the exposed area is insufficient and a pattern may not be formed. If the amount of N-alkoxymethyl (meth) acrylamide is too small, the photocurability is insufficient and the exposed area may be dissolved during development. If the amount is too large, the solubility of the unexposed area is insufficient, which may cause a residual film or residue.
＜（Ｂ）成分＞
　（Ｂ）成分は光酸発生剤である。本発明の熱硬化性樹脂組成物に用いられる酸の種類は特に限定されない。このような光酸発生剤の具体例としては、以下のものが挙げられる。 <(B) component>
The component (B) is a photoacid generator. The kind of acid used for the thermosetting resin composition of the present invention is not particularly limited. Specific examples of such a photoacid generator include the following.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　さらに、（Ｂ）成分の光酸発生剤として、ジフェニルヨードニウムクロリド、ジフェニルヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウムメシレート、ジフェニルヨードニウムトシレート、ジフェニルヨードニウムブロミド、ジフェニルヨードニウムテトラフルオロボレート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムヘキサフルオロアルセネート、ビス（ｐ－ｔｅｒｔ－ブチルフェニル）ヨードニウムヘキサフルオロホスフェート、ビス（ｐ－ｔｅｒｔ－ブチルフェニル）ヨードニウムメシレート、ビス（ｐ－ｔｅｒｔ－ブチルフェニル）ヨードニウムトシレート、ビス（ｐ－ｔｅｒｔ－ブチルフェニル）ヨードニウムトリフルオロメタンスルホネート、ビス（ｐ－ｔｅｒｔ－ブチルフェニル）ヨードニウムテトラフルオロボレート、ビス（ｐ－ｔｅｒｔ－ブチルフェニル）ヨードニウムクロリド、ビス（ｐ－クロロフェニル）ヨードニウムクロリド、ビス（ｐ－クロロフェニル）ヨードニウムテトラフルオロボレート、トリフェニルスルホニウムクロリド、トリフェニルスルホニウムブロミド、トリフェニルスルホニウムトリフルオロメタンスルホネート、トリ（ｐ－メトキシフェニル）スルホニウムテトラフルオロボレート、トリ（ｐ－メトキシフェニル）スルホニウムヘキサフルオロホスホネート、トリ（ｐ－エトキシフェニル）スルホニウムテトラフルオロボレート、トリフェニルホスホニウムクロリド、トリフェニルホスホニウムブロミド、トリ（ｐ－メトキシフェニル）ホスホニウムテトラフルオロボレート、トリ（ｐ－メトキシフェニル）ホスホニウムヘキサフルオロホスホネート、トリ（ｐ－エトキシフェニル）ホスホニウムテトラフルオロボレート、等が挙げられる。 Furthermore, as the photoacid generator of component (B), diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, Diphenyliodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p -Tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (p-ter -Butylphenyl) iodonium tetrafluoroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide , Triphenylsulfonium trifluoromethanesulfonate, tri (p-methoxyphenyl) sulfonium tetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p-ethoxyphenyl) sulfonium tetrafluoroborate, triphenylphosphonium chloride, tri Phenylphosphonium bromide, tri (p-methoxyphenyl) phosphonium tetrafluoro Rate, tri (p- methoxyphenyl) phosphonium hexafluorophosphonate, tri (p- ethoxyphenyl) phosphonium tetrafluoroborate, and the like.
　本発明のネガ型感光性樹脂組成物における（Ｂ）成分の含有量は、（Ａ）成分の１００質量部に対して、好ましくは０．５乃至２０質量部、より好ましくは１乃至１５質量部、更に好ましくは２乃至１０質量部である。この割合が０．５質量部未満の場合、光反応性が低下し感度が低下する場合がある。また、２０質量部を超えると、形成した塗膜の透過率が低下したり、溶液の保存安定性が低下する場合がある。
The content of the component (B) in the negative photosensitive resin composition of the present invention is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is 2 to 10 parts by mass. When this ratio is less than 0.5 mass part, photoreactivity may fall and a sensitivity may fall. Moreover, when it exceeds 20 mass parts, the transmittance | permeability of the formed coating film may fall or the storage stability of a solution may fall.
＜（Ｃ）溶剤＞
　本発明に用いる（Ａ）成分および（Ｂ）成分を溶解し、且つ所望により添加される後述の（Ｄ）成分、（Ｅ）成分、（Ｆ）成分などを溶解するものであり、斯様な溶解能を有する溶剤であれば、その種類及び構造などは特に限定されるものでない。 <(C) Solvent>
The (A) component and the (B) component used in the present invention are dissolved, and the (D) component, (E) component, (F) component, etc., which will be added as required, are dissolved. If it is a solvent having solubility, its type and structure are not particularly limited.
　斯様な（Ｃ）溶剤としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、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、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメ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、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、２－ブタノン、３－メチル－２－ペンタノン、２－ペンタノン、２-ヘプタノン、γ―ブチロラクトン、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エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、及びＮ－メチルピロリドン等が挙げられる。 Examples of such a solvent (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol. Monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2-hydroxypropion Ethyl acetate, ethyl 2-hydroxy-2-methylpropionate, ethoxy vinegar Ethyl, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, pyruvate Examples include ethyl, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
　これらの溶剤は、一種単独で、または二種以上の組合せで使用することができる。 These solvents can be used alone or in combination of two or more.
　これら（Ｃ）溶剤の中、プロピ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メチルエーテル、プロピレングリコールモノメチルエーテルアセテート、乳酸エチル、乳酸ブチル等が、塗膜性が良好で安全性が高いという観点より好ましい。これら溶剤は、一般にフォトレジスト材料のための溶剤として用いられている。 Among these (C) solvents, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate and the like are preferable from the viewpoint of good coating properties and high safety. These solvents are generally used as solvents for photoresist materials.
＜（Ｄ）成分＞
　（Ｄ）成分は、増感剤である。本発明のネガ型感光性樹脂組成物からなる塗膜を露光する波長に対し（Ｂ）成分である光酸発生剤の反応率が小さい場合、増感剤を添加することで反応率を向上させることができる。このような増感剤の具体例としては、９，１０－ジブトキシアントラセン、９－ヒドロキシメチルアントラセン、チオキサントン、２－イソプロピルチオキサントン、４－イソプロピルチオキサントン、２－クロロチオキサントン、２，４－ジエチルチオキサントン、アントラキノン、１，２－ジヒドロキシアントラキノン、２－エチルアントラキノン、１，４－ジエトキシナフタレン等が挙げられる。 <(D) component>
(D) component is a sensitizer. When the reaction rate of the photoacid generator as the component (B) is small with respect to the wavelength at which the coating film made of the negative photosensitive resin composition of the present invention is exposed, the reaction rate is improved by adding a sensitizer. be able to. Specific examples of such a sensitizer include 9,10-dibutoxyanthracene, 9-hydroxymethylanthracene, thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, Anthraquinone, 1,2-dihydroxyanthraquinone, 2-ethylanthraquinone, 1,4-diethoxynaphthalene and the like can be mentioned.
　（Ｄ）成分として、前記増感剤のうち１種又は２種類以上を組み合わせて用いることができる。 As the component (D), one or more of the sensitizers can be used in combination.
　これらの増感剤の添加量は、（Ａ）成分の１００質量部に対して、通常、０．１ないし１０質量部であることが好ましく、より好ましくは０．１ないし８質量部である。増感剤の量が前記よりも過大であると塗膜の透明性が低下する場合がある。 The addition amount of these sensitizers is usually preferably 0.1 to 10 parts by mass, more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the component (A). If the amount of the sensitizer is larger than the above, the transparency of the coating film may be lowered.
＜（Ｅ）成分＞
　（Ｅ）成分は、ヒドロキシ基を有するポリマーである。ヒドロキシ基を有するポリマーとしては例えば、ヒドロキシ基を有するモノマーを重合した重合体、セルロース、ヒドロキシプロピルセルロース、ジエポキシとジカルボン酸を共重合して得られるポリマー、ジエポキシとジフェノールを共重合して得られるポリマー、ポリエステルポリオール、ポリエーテルポリオール、ポリカプロラクトンポリオール等が挙げられるが、好ましくはヒドロキシ基を有するモノマーを重合した重合体、またはヒドロキシプロピルセルロースである。 <(E) component>
The component (E) is a polymer having a hydroxy group. Examples of the polymer having a hydroxy group include a polymer obtained by polymerizing a monomer having a hydroxy group, cellulose, hydroxypropyl cellulose, a polymer obtained by copolymerizing diepoxy and dicarboxylic acid, and obtained by copolymerizing diepoxy and diphenol. Examples thereof include polymers, polyester polyols, polyether polyols, polycaprolactone polyols, and the like, and a polymer obtained by polymerizing a monomer having a hydroxy group, or hydroxypropyl cellulose is preferable.
　上述したヒドロキシ基を有するモノマーを重合した重合体としては上述した（Ａ）成分で挙げた共重合可能なモノマーのうちヒドロキシ基を有するモノマーを単独または共重合可能なモノマーと共重合した重合体が挙げられる。 As the polymer obtained by polymerizing the above-mentioned monomer having a hydroxy group, a polymer obtained by copolymerizing a monomer having a hydroxy group alone or a copolymerizable monomer among the copolymerizable monomers mentioned in the component (A) described above. Can be mentioned.
　（Ａ）成分で挙げた共重合可能なモノマーのうちヒドロキシ基を有するモノマーとしては、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、４－ヒドロキシブチルアクリレート、２，３－ジヒドロキシプロピルアクリレート及び５－アクリロイルオキシ－６－ヒドロキシノルボルネン－２－カルボキシリック－６－ラクトン、２－ヒドロキシエチルメタクリレート、２－ヒドロキシプロピルメタクリレート、４－ヒドロキシブチルメタクリレート、２，３－ジヒドロキシプロピルメタクリレート及び５－メタクリロイルオキシ－６－ヒドロキシノルボルネン－２－カルボキシリック－６－ラクトン等が挙げられる。 Among the copolymerizable monomers listed as the component (A), monomers having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, and 5- Acryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate and 5-methacryloyloxy-6- Hydroxynorbornene-2-carboxyl-6-lactone and the like.
　共重合可能なモノマーとしては、例えば、（Ａ）成分で挙げた共重合可能なモノマーが挙げられる。 Examples of the copolymerizable monomer include the copolymerizable monomers listed in the component (A).
　これらのヒドロキシ基を有するポリマーは、単独でまたは２種以上を組み合わせて使用することができる。 These polymers having a hydroxy group can be used alone or in combination of two or more.
　本発明のネガ型感光性樹脂組成物における（Ｅ）成分のヒドロキシ基を有するポリマーの含有量は、（Ａ）成分の共重合体１００質量部に基づいて５乃至１５０質量部であることが好ましく、より好ましくは１０乃至１２０質量部である。この割合が前記よりも過小である場合には、ネガ型感光性樹脂組成物の感度が低下する場合があり、他方、前記よりも過大である場合には未露光部の現像性が低下し残膜や残渣の原因となる場合がある。 In the negative photosensitive resin composition of the present invention, the content of the polymer having a hydroxy group as the component (E) is preferably 5 to 150 parts by mass based on 100 parts by mass of the copolymer as the component (A). More preferably, it is 10 to 120 parts by mass. If this ratio is less than the above, the sensitivity of the negative photosensitive resin composition may be reduced. On the other hand, if it is more than the above, the developability of the unexposed area will be reduced and the remaining amount will be reduced. May cause film and residue.
＜（Ｆ）成分＞
本発明の（Ｆ）成分である架橋剤としては（Ｂ）成分で発生した酸により（Ａ）成分と反応し得る架橋剤であればよい。このような架橋剤としてはエポキシ化合物、メチロール化合物等の化合物が挙げられるが、好ましくはメチロール化合物である。 <(F) component>
The crosslinking agent that is the component (F) of the present invention may be any crosslinking agent that can react with the component (A) by the acid generated in the component (B). Examples of such a crosslinking agent include compounds such as an epoxy compound and a methylol compound, and a methylol compound is preferred.
　上述したメチロール化合物の具体例としては、アルコキシメチル化グリコールウリル、アルコキシメチル化ベンゾグアナミンおよびアルコキシメチル化メラミン等の化合物が挙げられる。 Specific examples of the methylol compound described above include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
　アルコキシメチル化グリコールウリルの具体例としては、例えば、１，３，４，６－テトラキス（メトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ブトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ヒドロキシメチル）グリコールウリル、１，３－ビス（ヒドロキシメチル）尿素、１，１，３，３－テトラキス（ブトキシメチル）尿素、１，１，３，３－テトラキス（メトキシメチル）尿素、１，３－ビス（ヒドロキシメチル）－４，５－ジヒドロキシ－２－イミダゾリノン、および１，３－ビス（メトキシメチル）－４，５－ジメトキシ－２－イミダゾリノン等が挙げられる。市販品として、三井サイテック（株）製グリコールウリル化合物（商品名：サイメル（登録商標）１１７０、パウダーリンク（登録商標）１１７４）等の化合物、メチル化尿素樹脂（商品名：ＵＦＲ（登録商標）６５）、ブチル化尿素樹脂（商品名：ＵＦＲ（登録商標）３００、Ｕ－ＶＡＮ１０Ｓ６０、Ｕ－ＶＡＮ１０Ｒ、Ｕ－ＶＡＮ１１ＨＶ）、大日本インキ化学工業（株）製尿素／ホルムアルデヒド系樹脂（高縮合型、商品名：ベッカミン（登録商標）Ｊ－３００Ｓ、同Ｐ－９５５、同Ｎ）等が挙げられる。 Specific examples of the alkoxymethylated glycoluril include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 , 6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercially available products, compounds such as glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resins (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin (high condensation type, commercial product) manufactured by Dainippon Ink & Chemicals, Inc. Name: Beccamine (registered trademark) J-300S, P-955, N) and the like.
　アルコキシメチル化ベンゾグアナミンの具体例としてはテトラメトキシメチルベンゾグアナミン等が挙げられる。市販品として、三井サイテック（株）製（商品名：サイメル（登録商標）１１２３）、（株）三和ケミカル製（商品名：ニカラック（登録商標）ＢＸ－４０００、同ＢＸ－３７、同ＢＬ－６０、同ＢＸ－５５Ｈ）等が挙げられる。 Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. Commercially available products manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), manufactured by Sanwa Chemical Co., Ltd. (trade names: Nicalac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.
　アルコキシメチル化メラミンの具体例としては、例えば、ヘキサメトキシメチルメラミン等が挙げられる。市販品として、三井サイテック（株）製メトキシメチルタイプメラミン化合物（商品名：サイメル（登録商標）３００、同３０１、同３０３、同３５０）、ブトキシメチルタイプメラミン化合物（商品名：マイコート（登録商標）５０６、同５０８）、三和ケミカル製メトキシメチルタイプメラミン化合物（商品名：ニカラック（登録商標）ＭＷ－３０、同ＭＷ－２２、同ＭＷ－１１、同ＭＳ－００１、同ＭＸ－００２、同ＭＸ－７３０、同ＭＸ－７５０、同ＭＸ－０３５）、ブトキシメチルタイプメラミン化合物（商品名：ニカラック（登録商標）ＭＸ－４５、同ＭＸ－４１０、同ＭＸ－３０２）等が挙げられる。 Specific examples of alkoxymethylated melamine include, for example, hexamethoxymethylmelamine. As commercially available products, methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade name: My Coat (registered trademark)) 506, 508), Sanwa Chemical's methoxymethyl-type melamine compound (trade names: Nicalak (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compounds (trade names: Nicalac (registered trademark) MX-45, MX-410, MX-302) and the like.
　また、このようなアミノ基の水素原子がメチロール基またはアルコキシメチル基で置換されたメラミン化合物、尿素化合物、グリコールウリル化合物及びベンゾグアナミン化合物を縮合させて得られる化合物であってもよい。例えば、米国特許第６３２３３１０号に記載されているメラミン化合物およびベンゾグアナミン化合物から製造される高分子量の化合物が挙げられる。前記メラミン化合物の市販品としては、商品名：サイメル（登録商標）３０３（三井サイテック（株）製）等が挙げられ、前記ベンゾグアナミン化合物の市販品としては、商品名：サイメル（登録商標）１１２３（三井サイテック（株）製）等が挙げられる。 Also, a compound obtained by condensing a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group may be used. For example, the high molecular weight compound manufactured from the melamine compound and the benzoguanamine compound which are described in US Patent 6,323,310 is mentioned. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.). Examples of commercially available products of the benzoguanamine compound include product name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.).
　これらの架橋剤は、単独でまたは２種以上を組み合わせて使用することができる。 These cross-linking agents can be used alone or in combination of two or more.
　本発明のネガ型感光性樹脂組成物における（Ｆ）成分の架橋剤の含有量は、（Ａ）成分の共重合体１００質量部に基づいて５乃至１００質量部であることが好ましく、より好ましくは１０乃至８０質量部である。この割合が前記よりも過小である場合には、ネガ型感光性樹脂組成物の光硬化性が低下する場合があり、他方、前記よりも過大である場合には未露光部の現像性が低下し残膜や残渣の原因となる場合がある。 The content of the crosslinking agent of the component (F) in the negative photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably based on 100 parts by mass of the copolymer of the component (A). Is 10 to 80 parts by mass. If this ratio is less than the above, the photo-curing property of the negative photosensitive resin composition may be reduced. On the other hand, if it is more than the above, the developability of the unexposed portion is reduced. This may cause residual film and residue.
＜その他添加剤＞
　更に、本発明のネガ型感光性樹脂組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、クエンチャー、界面活性剤、レオロジー調整剤、顔料、染料、保存安定剤、消泡剤、または多価フェノール、多価カルボン酸等の溶解促進剤等を含有することができる。 <Other additives>
Furthermore, the negative photosensitive resin composition of the present invention can be used as necessary as a quencher, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, as long as the effects of the present invention are not impaired. Or a dissolution accelerator such as a polyhydric phenol or polyvalent carboxylic acid.
＜ネガ型感光性樹脂組成物＞
　本発明のネガ型感光性樹脂組成物は、（Ａ）成分の重合体及び（Ｂ）成分の光酸発生剤を（Ｃ）溶剤に溶解したものであり、且つ、それぞれ所望により（Ｄ）成分の増感剤、（Ｅ）成分のヒドロキシ基を有するポリマー、（Ｆ）成分の架橋剤、及びその他添加剤のうち一種以上を更に含有することができる組成物である。
<Negative photosensitive resin composition>
The negative photosensitive resin composition of the present invention is obtained by dissolving the polymer of component (A) and the photoacid generator of component (B) in solvent (C), and each component (D) as desired. (E) component-containing polymer having a hydroxy group, component (F) a cross-linking agent, and other additives.
　中でも、本発明のネガ型感光性樹脂組成物の好ましい例は、以下のとおりである。
［１］：（Ａ）成分１００質量部に基づいて、０．５乃至２０質量部の（Ｂ）成分を含有し、これら成分が（Ｃ）溶剤に溶解されたネガ型感光性樹脂組成物。
［２］：上記［１］の組成物において、更に（Ｄ）成分を（Ａ）成分１００質量部に基づいて、０．１乃至１０質量部含有するネガ型感光性樹脂組成物。
［３］：上記［１］又は［２］の組成物において、更に（Ｅ）成分を（Ａ）成分１００質量部に基づいて、５乃至１５０質量部含有するネガ型感光性樹脂組成物。
［４］：上記［１］乃至［３］の組成物において、更に（Ｆ）成分を（Ａ）成分１００質量部に基づいて５乃至１００質量部含有するネガ型感光性樹脂組成物。 Especially, the preferable example of the negative photosensitive resin composition of this invention is as follows.
[1]: A negative photosensitive resin composition containing 0.5 to 20 parts by mass of the component (B) based on 100 parts by mass of the component (A) and dissolving these components in the solvent (C).
[2]: The negative photosensitive resin composition further comprising 0.1 to 10 parts by mass of component (D) based on 100 parts by mass of component (A) in the composition of [1] above.
[3] A negative photosensitive resin composition containing 5 to 150 parts by mass of the component (E) based on 100 parts by mass of the component (A) in the composition of the above [1] or [2].
[4] A negative photosensitive resin composition containing 5 to 100 parts by mass of the component (F) based on 100 parts by mass of the component (A) in the compositions [1] to [3].
　本発明のネガ型感光性樹脂組成物における固形分の割合は、各成分が均一に溶剤に溶解している限り、特に限定されるものではないが、例えば１乃至８０質量％であり、また例えば５乃至６０質量％であり、または１０乃至５０質量％である。ここで、固形分とは、ネガ型感光性樹脂組成物の全成分から（Ｃ）溶剤を除いたものをいう。 The ratio of the solid content in the negative photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1 to 80% by mass, It is 5 to 60% by mass, or 10 to 50% by mass. Here, solid content means what remove | excluded the (C) solvent from all the components of the negative photosensitive resin composition.
　本発明のネガ型感光性樹脂組成物の調製方法は、特に限定されないが、その調製法としては、例えば、（Ａ）成分（共重合体）を（Ｃ）溶剤に溶解し、この溶液に（Ｂ）成分（光酸発生剤）を所定の割合で混合し、均一な溶液とする方法、或いは、この調製法の適当な段階において、必要に応じて（Ｄ）成分（増感剤）、（Ｅ）成分（ヒドロキシ基を有するポリマー）、（Ｆ）成分（架橋剤）及びその他添加剤を更に添加して混合する方法が挙げられる。 Although the preparation method of the negative photosensitive resin composition of this invention is not specifically limited, As the preparation method, for example, (A) component (copolymer) is melt | dissolved in (C) solvent, B) Component (photoacid generator) is mixed at a predetermined ratio to make a uniform solution, or at an appropriate stage of this preparation method, component (D) (sensitizer), ( E) Component (polymer having a hydroxy group), (F) component (crosslinking agent) and other additives may be further added and mixed.
　本発明のネガ型感光性樹脂組成物の調製にあたっては、（Ｃ）溶剤中における重合反応によって得られる特定共重合体の溶液をそのまま使用することができ、この場合、この（Ａ）成分の溶液に前記と同様に（Ｂ）成分などを入れて均一な溶液とする際に、濃度調整を目的としてさらに（Ｃ）溶剤を追加投入してもよい。このとき、特定共重合体の形成過程で用いられる（Ｃ）溶剤と、ネガ型感光性樹脂組成物の調製時に濃度調整のために用いられる（Ｃ）溶剤とは同一であってもよいし、異なってもよい。 In preparing the negative photosensitive resin composition of the present invention, the solution of the specific copolymer obtained by the polymerization reaction in the solvent (C) can be used as it is, and in this case, the solution of the component (A) In the same manner as above, when the component (B) is added to obtain a uniform solution, (C) a solvent may be further added for the purpose of adjusting the concentration. At this time, the (C) solvent used in the process of forming the specific copolymer and the (C) solvent used for concentration adjustment at the time of preparing the negative photosensitive resin composition may be the same, May be different.
　而して、調製されたネガ型感光性樹脂組成物の溶液は、孔径が０.２μｍ程度のフィルタなどを用いて濾過した後、使用することが好ましい。 Thus, the prepared negative photosensitive resin composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 μm.
＜塗膜及び硬化膜＞
　本発明のネガ型感光性樹脂組成物を半導体基板（例えば、シリコン／二酸化シリコン被覆基板、シリコンナイトライド基板、金属例えばアルミニウム、モリブデン、クロムなどが被覆された基板、ガラス基板、石英基板、ＩＴＯ基板等）の上に、回転塗布、流し塗布、ロール塗布、スリット塗布、スリットに続いた回転塗布、インクジェット塗布などによって塗布し、その後、ホットプレートまたはオーブン等で予備乾燥することにより、塗膜を形成することができる。その後、この塗膜を加熱処理することにより、ネガ型感光性樹脂膜が形成される。 <Coating film and cured film>
The negative photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate. Etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., and then pre-dried in a hot plate or oven to form a coating film can do. Then, a negative photosensitive resin film is formed by heat-treating this coating film.
　この加熱処理の条件としては、例えば、温度７０℃乃至１６０℃、時間０．３乃至６０分間の範囲の中から適宜選択された加熱温度及び加熱時間が採用される。加熱温度及び加熱時間は、好ましくは８０℃乃至１４０℃、０．５乃至１０分間である。 As the heat treatment conditions, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 160 ° C. and a time of 0.3 to 60 minutes are adopted. The heating temperature and heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes.
　またネガ型感光性樹脂組成物から形成されるネガ型感光性樹脂膜の膜厚は、例えば０．１乃至３０μｍであり、また例えば０．５乃至２０μｍであり、更に例えば１乃至１５μｍである。 The film thickness of the negative photosensitive resin film formed from the negative photosensitive resin composition is, for example, 0.1 to 30 μm, for example, 0.5 to 20 μm, and further, for example, 1 to 15 μm.
　本発明のネガ型感光性樹脂組成物から形成されるネガ型感光性樹脂膜は、所定のパターンを有するマスクを用いて紫外線、ＡｒＦ、ＫｒＦ、Ｆ２レーザー光等の光で露光されると、ネガ型感光性樹脂膜中に含まれる（Ｂ）成分の光酸発生剤（ＰＡＧ）から発生する酸の作用によって、該膜のうち露光部はアルカリ性現像液に不溶なものとなる。 When the negative photosensitive resin film formed from the negative photosensitive resin composition of the present invention is exposed to light such as ultraviolet rays, ArF, KrF, and F 2 laser light using a mask having a predetermined pattern, Due to the action of the acid generated from the photoacid generator (PAG) of the component (B) contained in the negative photosensitive resin film, the exposed portion of the film becomes insoluble in the alkaline developer.
　次いで、ネガ型感光性樹脂膜に対して露光後加熱（ＰＥＢ）が行われる。この場合の加熱の条件としては、温度７０℃乃至１５０℃、時間０．３乃至６０分間の範囲の中から適宜選択された加熱温度及び加熱時間が採用される。 Next, post-exposure heating (PEB) is performed on the negative photosensitive resin film. As heating conditions in this case, a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 150 ° C. and a time of 0.3 to 60 minutes are employed.
　その後、アルカリ性現像液を用いて現像が行われる。これにより、ネガ型感光性樹脂膜のうち、露光されていない部分が除去され、パターン様のレリーフが形成される。 Thereafter, development is performed using an alkaline developer. Thereby, the part which is not exposed among negative photosensitive resin films is removed, and a pattern-like relief is formed.
　使用されうるアルカリ性現像液としては、例えば、水酸化カリウム、水酸化ナトリウムなどのアルカリ金属水酸化物の水溶液、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、コリンなどの水酸化第四級アンモニウムの水溶液、エタノールアミン、プロピルアミン、エチレンジアミンなどのアミン水溶液等のアルカリ性水溶液が挙げられる。さらに、これらの現像液には、界面活性剤などを加えることもできる。 Examples of the alkaline developer that can be used include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline. Alkaline aqueous solutions such as amine aqueous solutions such as ethanolamine, propylamine, and ethylenediamine. Further, a surfactant or the like can be added to these developers.
　上記の中、水酸化テトラエチルアンモニウム０．１乃至２．３８質量％水溶液は、フォトレジストの現像液として一般に使用されており、本発明の感光性樹脂組成物においても、このアルカリ性現像液を用いて、膨潤などの問題をひき起こすことなく良好に現像することができる。 Among the above, a tetraethylammonium hydroxide 0.1 to 2.38 mass% aqueous solution is generally used as a photoresist developer, and the alkaline developer is also used in the photosensitive resin composition of the present invention. It can be developed satisfactorily without causing problems such as swelling.
　また、現像方法としては、液盛り法、ディッピング法、揺動浸漬法など、いずれも用いることができる。その際の現像時間は、通常、１５乃至１８０秒間である。 Further, as a developing method, any of a liquid piling method, a dipping method, a rocking dipping method and the like can be used. The development time at that time is usually 15 to 180 seconds.
　現像後、ネガ型感光性樹脂膜に対して流水による洗浄を例えば２０乃至９０秒間行い、続いて圧縮空気もしくは圧縮窒素を用いてまたはスピニングにより風乾することにより、基板上の水分が除去され、そしてパターン形成された膜が得られる。 After development, the negative photosensitive resin film is washed with running water, for example, for 20 to 90 seconds, and then air-dried with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, and A patterned film is obtained.
　続いて、斯かるパターン形成膜に対して、熱硬化のためにポストベークを行うことにより、具体的にはホットプレート、オーブンなどを用いて加熱することにより、耐熱性、透明性、平坦化性、低吸水性、耐薬品性などに優れ、良好なレリーフパターンを有する膜が得られる。 Subsequently, the pattern forming film is subjected to post-baking for thermosetting, specifically by heating using a hot plate, an oven, etc., thereby providing heat resistance, transparency, and flatness. In addition, a film having a good relief pattern with excellent water absorption and chemical resistance can be obtained.
　ポストベークとしては、一般に、温度１４０℃乃至２５０℃の範囲の中から選択された加熱温度にて、ホットプレート上の場合には５乃至３０分間、オーブン中の場合には３０乃至９０分間処理するという方法が採られる。 The post-bake is generally processed at a heating temperature selected from the range of 140 ° C. to 250 ° C. for 5 to 30 minutes when on a hot plate and 30 to 90 minutes when in an oven. The method is taken.
　而して、斯かるポストベークにより、目的とする、良好なパターン形状を有する硬化膜を得ることができる。 Thus, a desired cured film having a good pattern shape can be obtained by such post-baking.
　以上のように、本発明のネガ型感光性樹脂組成物により、露光前にタックがなく、アルカリ現像が可能で、１０μｍ程度の膜厚でも十分高感度であり且つ現像の際に露光部の膜減りが非常に小さく、微細なパターンを有する塗膜を形成することができる。さらに、この硬化膜は、透明性、耐熱性及び耐溶剤性に優れる。そのため、液晶ディスプレイや有機ＥＬディスプレイ、タッチパネル素子等における各種の膜、例えば層間絶縁膜、保護膜、絶縁膜、光学フィルムなどに好適に用いることができる。 As described above, with the negative photosensitive resin composition of the present invention, there is no tack before exposure, alkali development is possible, the film thickness of the exposed area is sufficient at the time of development, with sufficiently high sensitivity even at a film thickness of about 10 μm. Reduction is very small, and a coating film having a fine pattern can be formed. Furthermore, this cured film is excellent in transparency, heat resistance and solvent resistance. Therefore, it can be suitably used for various films in liquid crystal displays, organic EL displays, touch panel elements, etc., for example, interlayer insulating films, protective films, insulating films, optical films and the like.
　以下、実施例を挙げて、本発明を更に詳しく説明するが、本発明は、これら実施例に限定されるものでない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
［実施例で用いる略記号］
　以下の実施例で用いる略記号の意味は、次のとおりである。
ＭＡＡ：メタクリル酸
ＭＩ：マレイミド
ＭＭＡ：メタクリル酸メチル
ＢＭＡＡ：N－(n-ブトキシメチル)アクリルアミド
ＨＥＭＡ：２－ヒドロキシエチルメタクリレート
ＧＭＡ：グリシジルメタクリレート
ＳＴ：スチレン
ＡＩＢＮ：アゾビスイソブチロニトリル
ＰＡＧ１：ＴＰＳ－ＴＦ（東洋合成(株)製）（化合物名：トリフェニルスルホニウムトリフルオロメタンスルホネート）
ＰＡＧ２： GSID-26-1（BASF製）（前記式(79)で表される化合物）
ＰＡＧ３：イルガキュア369（BASF製）（光重合開始剤）
ＣＹＭ：サイテックジャパン製サイメル３０３（製品名）（化合物名：ヘキサメトキシメチルメラミン）
ＨＭＡ：９－ヒドロキシメチルアントラセン
ＨＰＣ：ヒドロキシプロピルセルロース
ＤＰＨＡ：ジペンタエリスリトールペンタ／ヘキサアクリレート
ＢＴＥＡＣ：ベンジルトリエチルアンモニウムクロライド
ＰＧＭＥ：プロピレングリコールモノメチルエーテル
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＪＥ：ジャパンエポキシレジン(株)製　JER157S70 [Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
MAA: methacrylic acid MI: maleimide MMA: methyl methacrylate BMAA: N- (n-butoxymethyl) acrylamide HEMA: 2-hydroxyethyl methacrylate GMA: glycidyl methacrylate ST: styrene AIBN: azobisisobutyronitrile PAG1: TPS-TF (Toyo Gosei Co., Ltd.) (Compound name: Triphenylsulfonium trifluoromethanesulfonate)
PAG2: GSID-26-1 (manufactured by BASF) (compound represented by the formula (79))
PAG3: Irgacure 369 (manufactured by BASF) (photopolymerization initiator)
CYM: Cytech Japan-made Cymel 303 (product name) (compound name: hexamethoxymethylmelamine)
HMA: 9-hydroxymethylanthracene HPC: hydroxypropyl cellulose DPHA: dipentaerythritol penta / hexaacrylate BTEAC: benzyltriethylammonium chloride PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate JE: manufactured by Japan Epoxy Resins Co., Ltd. JER157S70
［数平均分子量及び重量平均分子量の測定］
　以下の合成例に従い得られた特定共重合体及び特定架橋体の数平均分子量及び重量平均分子量を、日本分光（株）製ＧＰＣ装置（Ｓｈｏｄｅｘ（登録商標）カラムＫＦ８０３ＬおよびＫＦ８０４Ｌ）を用い、溶出溶媒テトラヒドロフランを流量１ｍｌ／分でカラム中に（カラム温度４０℃）流して溶離させるという条件で測定した。なお、下記の数平均分子量（以下、Ｍｎと称す。）及び重量平均分子量（以下、Ｍｗと称す。）は、ポリスチレン換算値にて表される。 [Measurement of number average molecular weight and weight average molecular weight]
The number average molecular weight and weight average molecular weight of the specific copolymer and specific cross-linked product obtained in accordance with the following synthesis examples were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation. Tetrahydrofuran was flowed through the column at a flow rate of 1 ml / min (column temperature: 40 ° C.) for elution. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.
＜合成例１＞
　共重合体を構成するモノマー成分として、ＭＩ（２６．０ｇ）、ＢＭＡＡ（４５．０ｇ）、ＳＴ（２９．０ｇ）を使用し、ラジカル重合開始剤としてＡＩＢＮ（２ｇ）を使用し、これらを溶剤ＰＧＭＥ（２３８ｇ）中において重合反応させることにより、Ｍｎ４，３００、Ｍｗ９，８００である共重合体溶液（共重合体濃度：３０質量％）を得た（Ｐ１）。なお、重合温度は、温度６０℃乃至９０℃に調整した。 <Synthesis Example 1>
MI (26.0 g), BMAA (45.0 g), ST (29.0 g) are used as monomer components constituting the copolymer, and AIBN (2 g) is used as a radical polymerization initiator. By carrying out a polymerization reaction in PGME (238 g), a copolymer solution (copolymer concentration: 30% by mass) as Mn 4,300 and Mw 9,800 was obtained (P1). The polymerization temperature was adjusted to a temperature of 60 ° C to 90 ° C.
＜合成例２＞
　共重合体を構成するモノマー成分として、ＭＡＡ（２０．０ｇ）、ＢＭＡＡ（５０．０ｇ）、ＳＴ（３０．０ｇ）を使用し、ラジカル重合開始剤としてＡＩＢＮ（２ｇ）を使用し、これらを溶剤ＰＧＭＥ（２３８ｇ）中において重合反応させることにより、Ｍｎ４，０００、Ｍｗ９，２００である共重合体溶液（共重合体濃度：３０質量％）を得た（Ｐ２）。なお、重合温度は、温度６０℃乃至９０℃に調整した。 <Synthesis Example 2>
MAA (20.0 g), BMAA (50.0 g), and ST (30.0 g) are used as monomer components constituting the copolymer, and AIBN (2 g) is used as a radical polymerization initiator. By carrying out a polymerization reaction in PGME (238 g), a copolymer solution (copolymer concentration: 30% by mass) of Mn 4,000 and Mw 9,200 was obtained (P2). The polymerization temperature was adjusted to a temperature of 60 ° C to 90 ° C.
＜合成例３＞
　共重合体を構成するモノマー成分として、ＭＡＡ（２０．０ｇ）、ＢＭＡＡ（５０．０ｇ）、ＨＥＭＡ（３０．０ｇ）を使用し、ラジカル重合開始剤としてＡＩＢＮ（２ｇ）を使用し、これらを溶剤ＰＧＭＥ（２３８ｇ）中において重合反応させることにより、Ｍｎ４，８００、Ｍｗ１０，５００である共重合体溶液（共重合体濃度：３０質量％）を得た（Ｐ３）。なお、重合温度は、温度６０℃乃至９０℃に調整した。 <Synthesis Example 3>
MAA (20.0 g), BMAA (50.0 g) and HEMA (30.0 g) are used as monomer components constituting the copolymer, and AIBN (2 g) is used as a radical polymerization initiator, and these are used as solvents. By carrying out a polymerization reaction in PGME (238 g), a copolymer solution (copolymer concentration: 30% by mass) having Mn 4,800 and Mw 10,500 was obtained (P3). The polymerization temperature was adjusted to a temperature of 60 ° C to 90 ° C.
＜合成例４＞
　共重合体を構成するモノマー成分として、ＭＡＡ（２０．０ｇ）、ＨＥＭＡ（４０．０ｇ）ＭＭＡ（４０．０ｇ）を使用し、ラジカル重合開始剤としてＡＩＢＮ（２ｇ）を使用し、これらを溶剤ＰＧＭＥ（２３８ｇ）中において重合反応させることにより、Ｍｎ３，９００、Ｍｗ８，５００である共重合体溶液（共重合体濃度：３０質量％）を得た（Ｐ４）。なお、重合温度は、温度６０℃乃至９０℃に調整した。
<Synthesis Example 4>
MAA (20.0 g), HEMA (40.0 g), MMA (40.0 g) are used as monomer components constituting the copolymer, AIBN (2 g) is used as a radical polymerization initiator, and these are used as a solvent PGME. (238 g) was subjected to a polymerization reaction to obtain a copolymer solution (copolymer concentration: 30% by mass) of Mn 3,900 and Mw 8,500 (P4). The polymerization temperature was adjusted to a temperature of 60 ° C to 90 ° C.
＜比較合成例１＞
　共重合体を構成するモノマー成分として、ＭＡＡ（５０．０ｇ）、ＭＭＡ（５０．０ｇ）を使用し、ラジカル重合開始剤としてＡＩＢＮ（２ｇ）を使用し、これらを溶剤ＰＧＭＥＡ（１２０ｇ）中において重合反応させることにより共重合体溶液（共重合体濃度：４０質量％）を得た。なお、重合温度は、温度６０℃乃至９０℃に調整した。この共重合体２００ｇにＧＭＡ（３３．０ｇ）、ＢＴＥＡＣ（１．１ｇ）、ＰＧＭＥＡ（４９．５ｇ）を加えて反応させることによりＭｎ８，７００、Ｍｗ２２，０００の（Ａ）成分（特定共重合体）の溶液（特定共重合体濃度：４０．５質量％）を得た（Ｐ５）。なお、反応温度を９０乃至１２０℃に調整した。 <Comparative Synthesis Example 1>
MAA (50.0 g) and MMA (50.0 g) are used as monomer components constituting the copolymer, AIBN (2 g) is used as a radical polymerization initiator, and these are polymerized in a solvent PGMEA (120 g). By reacting, a copolymer solution (copolymer concentration: 40% by mass) was obtained. The polymerization temperature was adjusted to a temperature of 60 ° C to 90 ° C. By adding GMA (33.0 g), BTEAC (1.1 g), and PGMEA (49.5 g) to 200 g of this copolymer and reacting them, the (A) component of Mn8,700 and Mw22,000 (specific copolymer) ) (Specific copolymer concentration: 40.5% by mass) was obtained (P5). The reaction temperature was adjusted to 90 to 120 ° C.
＜比較合成例２＞
　共重合体を構成するモノマー成分として、ＭＡＡ（３０．０ｇ）、ＧＭＡ（５０．０ｇ）、ＳＴ（２０．０ｇ）を使用し、ラジカル重合開始剤としてＡＩＢＮ（２ｇ）を使用し、これらを溶剤ＰＧＭＥ（２３８ｇ）中において温度６０℃乃至９０℃にて重合反応させたが、重合反応中にゲル化してしまいその後の評価に使用することが出来なかった。 <Comparative Synthesis Example 2>
MAA (30.0 g), GMA (50.0 g), and ST (20.0 g) are used as monomer components constituting the copolymer, and AIBN (2 g) is used as a radical polymerization initiator. The polymerization reaction was carried out at a temperature of 60 ° C. to 90 ° C. in PGME (238 g), but it was gelled during the polymerization reaction and could not be used for subsequent evaluation.
＜実施例１乃至７及び比較例１乃至２＞
　次の表１に示す組成に従い、（Ａ）成分の溶液に、（Ｂ）成分、（Ｃ）溶剤、及び（Ｄ）成分、更に（Ｅ）成分及び（Ｆ）成分を所定の割合で混合し、室温で３時間撹拌して均一な溶液とすることにより、各実施例及び各比較例のネガ型感光性樹脂組成物を調製した。 <Examples 1 to 7 and Comparative Examples 1 and 2>
According to the composition shown in the following Table 1, the component (A) is mixed with the component (B), the solvent (C), the component (D), and the component (E) and the component (F) at a predetermined ratio. The negative photosensitive resin composition of each Example and each Comparative Example was prepared by stirring at room temperature for 3 hours to obtain a uniform solution.
Figure JPOXMLDOC01-appb-I000011
Figure JPOXMLDOC01-appb-I000011
　得られた実施例１乃至７並びに比較例１及２の各ネガ型感光性樹脂組成物について、それぞれ、プリベーク後膜厚、タックの有無、透過率、解像度、感度を測定した。  For each of the obtained negative photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2, the film thickness after pre-baking, the presence or absence of tack, the transmittance, the resolution, and the sensitivity were measured.
[プリベーク後膜厚の評価］
　ネガ型感光性樹脂組成物をシリコンウェハ上にスピンコーターを用いて塗布した後、温度１１０℃で１２０秒間ホットプレート上においてプリベークを行い、塗膜を形成した。この塗膜の膜厚をＦＩＬＭＥＴＲＩＣＳ製　Ｆ２０を用いて測定した。 [Evaluation of film thickness after pre-baking]
The negative photosensitive resin composition was applied onto a silicon wafer using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film. The film thickness of this coating film was measured using F20 manufactured by FILMETRICS.
[透過率の評価］
　ネガ型感光性樹脂組成物を石英基板上にスピンコーターを用いて塗布した後、温度１１０℃で１２０秒間ホットプレート上においてプリベークを行い塗膜を形成した。この塗膜にキャノン製紫外線照射装置ＰＬＡ－６００ＦＡにより３６５ｎｍにおける光強度が５．５ｍＷ／ｃｍ２の紫外線を３６秒間照射した。この膜を温度９５℃にて１２０秒間ホットプレート上にて露光後加熱を行った後、温度１５０℃で１５分間オーブン中においてポストベークを行い硬化膜を形成した。この硬化膜を紫外線可視分光光度計（（株）島津製作所製ＳＩＭＡＤＳＵ　ＵＶ－２５５０型番）を用いて４００ｎｍの波長の透過率を測定した。 [Evaluation of transmittance]
The negative photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film. This coating film was irradiated with UV light having a light intensity at 365 nm of 5.5 mW / cm 2 for 36 seconds using a Canon UV irradiation device PLA-600FA. This film was heated after exposure on a hot plate at a temperature of 95 ° C. for 120 seconds and then post-baked in an oven at a temperature of 150 ° C. for 15 minutes to form a cured film. The cured film was measured for transmittance at a wavelength of 400 nm using a UV-visible spectrophotometer (SIMADSU UV-2550 model number, manufactured by Shimadzu Corporation).
[解像度の評価］
ネガ型感光性樹脂組成物を無アルカリガラス上にスピンコーターを用いて塗布した後、温度１１０℃で１２０秒間ホットプレート上においてプリベークを行い塗膜を形成した。この塗膜にキヤノン（株）製紫外線照射装置ＰＬＡ－６００ＦＡにより３６５ｎｍにおける光強度が５．５ｍＷ／ｃｍ２の紫外線をライン＆スペースパターンのマスクを介して１９０ｍＪ／ｃｍ２照射した。その後温度１１０℃で１２０秒間ホットプレート上において露光後加熱を行った。その後２．３８質量％の水酸化テトラメチルアンモニウム（以下、ＴＭＡＨと称す）水溶液に６０秒間浸漬することで現像を行った後、超純水で２０秒間流水洗浄を行うことでパターンを形成した。作製したパターンを１５０℃のオーブンにて１５分焼成したものについてＳＥＭ観察し、パターンの線幅がマスクの線幅と一致する最小パターンサイズを解像度とした。 [Resolution Evaluation]
The negative photosensitive resin composition was applied onto alkali-free glass using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film. The coating light intensity at 365nm by UV irradiation apparatus PLA-600FA manufactured by Canon Inc. in was 190 mJ / cm 2 irradiation through a mask of the UV line and space pattern of 5.5 mW / cm 2. Thereafter, post-exposure heating was performed on a hot plate at a temperature of 110 ° C. for 120 seconds. Thereafter, development was performed by immersing in a 2.38% by mass tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution for 60 seconds, and then washing was performed with ultrapure water for 20 seconds to form a pattern. SEM observation was performed on the prepared pattern that was baked in an oven at 150 ° C. for 15 minutes, and the minimum pattern size at which the line width of the pattern coincided with the line width of the mask was defined as the resolution.
[感度の評価］
　ネガ型感光性樹脂組成物を無アルカリガラス上にスピンコーターを用いて塗布した後、温度１１０℃で１２０秒間ホットプレート上においてプリベークを行い塗膜を形成した。この塗膜にキヤノン（株）製紫外線照射装置ＰＬＡ－６００ＦＡにより３６５ｎｍにおける光強度が５．５ｍＷ／ｃｍ２の紫外線を２０μｍのライン＆スペースパターンのマスクを介して５０ｍＪ／ｃｍ２刻みで照射した。その後温度１１０℃で１２０秒間ホットプレート上において露光後加熱を行った。その後２．３８質量％のＴＭＡＨ水溶液に６０秒間浸漬することで現像を行った後、超純水で２０秒間流水洗浄を行うことでパターンを形成した。２０μｍのパターンが形成できている最低の露光量を感度とした。 [Evaluation of sensitivity]
The negative photosensitive resin composition was applied onto alkali-free glass using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film. This coating film was irradiated with ultraviolet rays having a light intensity of 365 m at 5.5 mW / cm 2 at a rate of 50 mJ / cm 2 through a 20 μm line & space pattern mask by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Thereafter, post-exposure heating was performed on a hot plate at a temperature of 110 ° C. for 120 seconds. Thereafter, development was performed by immersing in a 2.38 mass% TMAH aqueous solution for 60 seconds, and then washing was performed with ultrapure water for 20 seconds to form a pattern. The minimum exposure amount at which a 20 μm pattern was formed was defined as sensitivity.
［評価の結果］
　以上の評価を行った結果を、次の表２に示す。 [Evaluation results]
The results of the above evaluation are shown in Table 2 below.
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000012
　表２に示す結果より判るように、実施例１乃至７のネガ型感光性樹脂組成物はいずれも１０μｍ以上の厚膜での塗布が可能であり、厚膜でも高い透過率とアルカリ現像が可能であり高い解像度、感度を維持していた。
比較例１については、厚膜化できず、ポストベーク後の残膜率も９０％以下と低かった。比較例２についてはプリベーク後にタックが入り、アルカリ現像液で現像することも出来なかった。 As can be seen from the results shown in Table 2, each of the negative photosensitive resin compositions of Examples 1 to 7 can be applied with a thick film of 10 μm or more, and high transmittance and alkali development are possible even with a thick film. And maintained high resolution and sensitivity.
In Comparative Example 1, the film thickness could not be increased, and the remaining film ratio after post-baking was as low as 90% or less. In Comparative Example 2, the tack entered after pre-baking, and development with an alkaline developer was not possible.
　本発明によるネガ型感光性樹脂組成物は、薄膜トランジスタ（ＴＦＴ）型液晶表示素子、有機ＥＬ素子、タッチパネル素子等の各種ディスプレイにおける保護膜、平坦化膜、絶縁膜等の硬化膜を形成する材料として好適であり、特に、ＴＦＴ型液晶素子の層間絶縁膜、カラーフィルターの保護膜、アレイ平坦化膜、静電容量式タッチパネルの層間絶縁膜、有機ＥＬ素子の絶縁膜、ディスプレイ表面反射防止層としての構造体シート等を形成する材料としても好適である。 The negative photosensitive resin composition according to the present invention is a material for forming a cured film such as a protective film, a planarizing film, and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element, an organic EL element, and a touch panel element. Particularly suitable as an interlayer insulating film of a TFT type liquid crystal element, a protective film of a color filter, an array flattening film, an interlayer insulating film of a capacitive touch panel, an insulating film of an organic EL element, a display surface antireflection layer It is also suitable as a material for forming a structure sheet or the like.

Claims (9)

  1. 下記（Ａ）成分、（Ｂ）成分及び（Ｃ）溶剤を含有するネガ型感光性樹脂組成物。
    （Ａ）成分：少なくとも（ｉ）N－アルコキシメチル（メタ）アクリルアミドと、（ｉｉ）アルカリ可溶性基を有するモノマーとを含有するモノマー混合物を共重合した共重合体、
    （Ｂ）成分：光酸発生剤、
    （Ｃ）溶剤。     Negative photosensitive resin composition containing the following (A) component, (B) component, and (C) solvent.
    (A) component: a copolymer obtained by copolymerizing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) a monomer mixture containing a monomer having an alkali-soluble group,
    (B) component: a photoacid generator,
    (C) Solvent.
  2. （Ａ）成分の（ｉｉ）アルカリ可溶性基を有するモノマーがマレイミドである請求項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 the monomer (A) of component (A) having an alkali-soluble group is maleimide.
  3. （Ｄ）成分として、増感剤をさらに感光性樹脂組成物１００質量部に基づいて０．１乃至１０質量部含有する、請求項１または２に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to claim 1 or 2, further comprising 0.1 to 10 parts by mass of a sensitizer as a component based on 100 parts by mass of the photosensitive resin composition.
  4. （Ｅ）成分として、さらにヒドロキシ基を有するポリマーを含有する、請求項１乃至３に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to claim 1, further comprising a polymer having a hydroxy group as component (E).
  5. （Ａ）成分はさらにヒドロキシ基を有するモノマーを含有するモノマー混合物を共重合した共重合体である、請求項１乃至３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 the component (A) is a copolymer obtained by copolymerizing a monomer mixture containing a monomer having a hydroxy group.
  6. （Ｆ）成分として、さらに架橋剤を含有する、請求項１乃至５のいずれか一項に記載のネガ型感光性樹脂組成物。 The negative photosensitive resin composition according to any one of claims 1 to 5, further comprising a crosslinking agent as the component (F).
  7. 請求項１乃至６のうちいずれか一項に記載のネガ型感光性樹脂組成物を用いて得られる硬化膜。 The cured film obtained using the negative photosensitive resin composition as described in any one of Claims 1 thru | or 6.
  8. 請求項７に記載の硬化膜からなる液晶ディスプレイ用層間絶縁膜。 The interlayer insulation film for liquid crystal displays which consists of a cured film of Claim 7.
  9. 請求項７に記載の硬化膜からなる光学フィルタ。 An optical filter comprising the cured film according to claim 7.
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