JP2010197568A - Photosensitive resin composition, dry film, and method for forming pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition, which is to be used for a permanent film and does not use a photosensitive agent containing a halogen, and to provide a dry film and a method for forming a pattern using the dry film. <P>SOLUTION: The photosensitive resin composition contains (A) a polymer having an alicyclic epoxy group, (B) a monomer having a radical polymerizable group, (C) a radical polymerization initiator and (D) a photosensitive agent generating sulfonic acid by irradiation with light. As the photosensitive resin composition does not corrode a material to be used for microcomponents even when the composition is used for a permanent film, the composition can be suitably used as a photosensitive resin composition for a permanent film. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, a dry film, and a pattern forming method using the dry film.

  MEMS (Micro Electro Mechanical System), which is attracting attention as a mass-productivity system that integrates fine parts in the same chip using semiconductor manufacturing technology and realizes high performance and high integration, It is used in various fields such as consumer electronics, medical and biotechnology.

  By the way, although the photosensitive resin composition is used for various uses, the use as what is called a permanent film is mentioned as one of such uses. A permanent film is a film formed by a photosensitive resin composition on or between parts constituting a product, and is a generic term for a film that remains even after the product is completed. It is also often used during manufacturing.

  As a photosensitive resin composition used for permanent film applications, for example, Patent Document 1 discloses a solid polyfunctional epoxy resin (A) having a predetermined epoxy equivalent and a predetermined softening point, and phenol having a predetermined hydroxyl equivalent. A photosensitive resin composition containing a photo-curing polymerization initiator that is a system curing agent and sulfonium tris (pentafluoroethyl) trifluorophosphate is disclosed.

JP 2008-026660 A

  However, since the photosensitive resin composition described in Patent Document 1 uses a halogen-containing photosensitive agent, when it is used for permanent film applications, the halogen remaining in the permanent film is fine. There is a problem of corroding materials used for parts and the like.

  Accordingly, an object of the present invention is to provide a photosensitive resin composition, a dry film, and a pattern forming method using this dry film, which are used for permanent films and do not use a halogen-containing photosensitizer. .

  In view of the above problems, the present inventors conducted extensive research. As a result, by using a photosensitive resin composition containing a polymer having an alicyclic epoxy group, a monomer having a radical polymerizable group, a radical polymerization initiator, and a photosensitive agent that generates sulfonic acid by light irradiation, As a result, the present invention has been completed.

  Specifically, the present invention provides the following.

  In the first aspect of the present invention, (A) a polymer having an alicyclic epoxy group, (B) a monomer having a radical polymerizable group, (C) a radical polymerization initiator, and (D) sulfonic acid by light irradiation. It is the photosensitive resin composition containing the photosensitizer to generate | occur | produce.

  The 2nd aspect of this invention is a dry film formed by forming a protective film on both surfaces of the layer formed from the photosensitive resin composition of this invention.

  In the third aspect of the present invention, the photosensitive resin composition of the present invention is coated on a support, dried, exposed to a predetermined pattern, and then developed to heat-treat the resin pattern obtained. This is a pattern forming method for obtaining a cured resin pattern having a predetermined shape.

  According to a fourth aspect of the present invention, the protective film of the dry film of the present invention is peeled off, attached to a support, exposed to a predetermined pattern, and then developed to heat a resin pattern to obtain a predetermined shape. This is a pattern forming method for obtaining a cured resin pattern.

  According to a fifth aspect of the present invention, the protective film on one side of the dry film of the present invention is peeled off, attached to a support so that the exposed photosensitive resin layer is in contact, and exposed to a predetermined pattern. In this pattern forming method, the protective film on the other surface of the dry film is peeled and developed, and the resulting resin pattern is heated to obtain a cured resin pattern having a predetermined shape.

  Since the photosensitive resin composition of the present invention uses a photosensitive agent that generates sulfonic acid by light irradiation instead of a halogen-containing photosensitive agent, even if it is used for permanent film applications, it is a material used for fine parts and the like Will not corrode. Therefore, the photosensitive resin composition of the present invention can be suitably used as a photosensitive resin composition for permanent film applications.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention comprises (A) a polymer having an alicyclic epoxy group (hereinafter sometimes referred to as (A) component), (B) a monomer having a radical polymerizable group (hereinafter referred to as (B). Component)), (C) radical polymerization initiator (hereinafter also referred to as component (C)), and (D) a photosensitizer that generates sulfonic acid by light irradiation (hereinafter referred to as component (D)). Is included).

[(A) Polymer having alicyclic epoxy group]
In the photosensitive resin composition of the present invention, (A) a monomer having an alicyclic group is used. Here, by using the component (A), the curing reaction of the photosensitive resin layer by heating can be satisfactorily progressed even when the photosensitive agent that generates sulfonic acid by light irradiation is used as the acid catalyst (D). it can.

  Although it does not specifically limit as (A) component, For example, the polymer synthesize | combined from the monomer composition containing the unsaturated compound which has an alicyclic epoxy group can be used. As an unsaturated compound which has such an alicyclic epoxy group, the unsaturated compound shown by the following general formula (A1) to (A31) can be mentioned, for example.

［上記一般式（Ａ１）から（Ａ３１）において、Ｒ^１は水素原子又はメチル基を示し、Ｒ^２は炭素数１以上８以下の二価の炭化水素基を示し、Ｒ^３は炭素数１以上２０以下の二価の炭化水素基を示し、Ｒ^１からＲ^３は、互いに同一であっても、異なっていてもよく、ｗは０以上１０以下の整数を示す。］

[In the above general formulas (A1) to (A31), R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent hydrocarbon group having 1 to 8 carbon atoms, and R ³ represents 1 or more carbon atoms. 20 or less divalent hydrocarbon group, R ¹ to R ³ may be the same or different from each other, and w represents an integer of 0 or more and 10 or less. ]

  Among these unsaturated compounds having an alicyclic epoxy group, from the general formulas (A3), (A4), (A16), (A17), (A21), (A22), (A24), (A26) to ( It is preferable to use unsaturated compounds represented by A28), (A30), and (A31), and (A3), (A17), (A21), (A24) such as 3,4-epoxycyclohexyl (meth) acrylate , (A26), (A28), and (A30) are more preferable. These compounds may be used alone or in combination of two or more.

  The component (A) may have only a structural unit derived from an unsaturated compound having an alicyclic epoxy group, and may be a structural unit derived from an unsaturated compound having an alicyclic epoxy group; And structural units derived from other unsaturated compounds. In the latter case, the proportion of the structural unit derived from the unsaturated compound having an alicyclic epoxy group is preferably 20 mol% or more and 95 mol% or less, and 40 mol% or more and 90 mol% or less. Is more preferable. When the proportion of the structural unit derived from the unsaturated compound having an alicyclic epoxy group is within the above range, heat resistance and dissolution resistance can be kept good.

  Although it does not specifically limit as said other unsaturated compound, For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) (Meth) acrylic acid alkyl esters such as acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate; hydroxy (such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate) (Meth) acrylic acid alkyl ester; (meth) acrylic acid cyclic alkyl ester such as cyclohexyl (meth) acrylate and dicyclopentanyl (meth) acrylate; styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, -Vinyl compounds such as methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate; and (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyl Methyldimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltris (methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, etc. And siloxane compounds.

  Of these, styrene, (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, and the like are preferably used. These unsaturated compounds may be used alone or in combination of two or more.

  The component (A) may have a radical polymerizable group in addition to the epoxy group. In such a case, for example, a radical polymerizable group may be introduced into the component (A) by reacting a compound having a radical polymerizable group with the component (A).

  The molecular weight of the component (A) is preferably 4000 or more and 150,000 or less, and more preferably 8000 or more and 80000 or less. Moreover, as content of (A) component in the photosensitive resin composition of this invention, it is preferable that it is 30 to 65 mass%, and it is still more preferable that it is 40 to 60 mass%. When the molecular weight and content of the component (A) are within the above range, the film forming property and the coating property of the photosensitive resin composition of the present invention can be favorably maintained.

[(B) Monomer Having Radical Polymerizable Group]
Examples of the component (B) include unsaturated compounds having at least one ethylenically unsaturated bond, which may be monofunctional unsaturated compounds or polyfunctional unsaturated compounds.

  Monofunctional unsaturated compounds include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N -Methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2 Acrylamide-2-methylpropane sulfonic acid, tert-butyl acrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) a Relate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( Examples include meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, phthalic acid derivative half (meth) acrylate, and (meth) acryloxypropyltrimethoxysilane. Door can be.

  Polyfunctional unsaturated compounds include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate. , Butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol diacrylate (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryl Roxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di ( (Meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether Poly (meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate and 2-bidoxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) Examples thereof include acrylamide methylene ether, a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, and triacryl formal.

  These unsaturated compounds may be used alone or in combination of two or more, regardless of whether they are monofunctional or polyfunctional.

  The content of the component (B) in the photosensitive resin composition of the present invention is preferably 50 parts by mass or more and 200 parts by mass or less, and 60 parts by mass or more and 150 parts by mass or less per 100 parts by mass of the component (A). More preferably it is. When the content of the component (B) is within the above range, a good balance of sensitivity, developability, and resolution can be maintained.

[(B ′) Polymer having radical polymerizable group]
The photosensitive resin composition of the present invention may have (B ′) a polymer having a radical polymerizable group (hereinafter sometimes referred to as “component (B ′)”). As the component (B ′), (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl Ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol diacrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, butylene glycol dimethacrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and cardoepoxy diacrylate, etc .; A polyester (meth) acrylate obtained by reacting a (meth) acrylic acid with a polyester prepolymer obtained by condensation with a basic acid or a polybasic acid, and After reacting with a compound having polyol and two isocyanate groups, and (meth) polyurethane obtained by reacting acrylic acid (meth) acrylate.

  In addition, as a resin having a radical polymerizable group, a reaction product of an epoxy compound (B′1) and an ethylenically unsaturated group-containing carboxylic acid compound (B′2), a polybasic acid anhydride (B ′ Resins obtained by reacting with 3) can also be used.

(Epoxy compound (B'1))
Epoxy compounds (B'1) include glycidyl ether type, glycidyl ester type, glycidyl amine type, alicyclic type, bisphenol A type, bisphenol F type, bisphenol S type, biphenyl type, naphthalene type, fluorene type, phenol novolak type And ortho-cresol type epoxy resin.

(Ethylenically unsaturated group-containing carboxylic acid compound (B'2))
As the ethylenically unsaturated group-containing carboxylic acid compound (B′2), a monocarboxylic acid compound containing a reactive ethylenic double bond such as an acrylic group or a methacryl group in the molecule is preferable. Examples of such ethylenically unsaturated group-containing carboxylic acid compounds include acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, α-cyanocinnamic acid, and cinnamic acid. These ethylenically unsaturated group-containing carboxylic acid compounds may be used alone or in combination of two or more.

(Polybasic acid anhydride (B'3))
Examples of the polybasic acid anhydride (B′3) include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydro Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, Examples include 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic anhydride, and 4-ethyltetrahydrophthalic anhydride. it can. These polybasic acid anhydrides may be used alone or in combination of two or more.

  When the photosensitive resin composition of the present invention contains the component (B ′), the content of the component (B ′) is 5 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the component (A). Preferably, it is 10 parts by mass or more and 30 parts by mass or less. When the content of the component (B ′) is within the above range, it is possible to maintain a good balance of sensitivity, developability, and resolution. In addition, when the above-mentioned component (A) has a radical polymerizable group, the component (B ′) is not necessarily contained.

[(C) radical polymerization initiator]
As the component (C), 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2 -Methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane -1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpho Linopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone-1- [9 Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethyl Sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2 -Isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl O-benzoylbenzoate, 2,4-diethyl Thioxanthone, 2-chlorothioxanthone, 2, -Dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidar, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (O-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'- Sudiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin Butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloro Acetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetate Phenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (Trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2) -Yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino) 2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2 , 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-me Carboxymethyl) styryl phenyl -s- triazine, and 2,4-bis - can be exemplified trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl -s- triazine. These photopolymerization initiators may be used alone or in combination of two or more.

  The content of the component (C) is preferably 0.1% by mass or more and 10% by mass or less, and preferably 0.5% by mass or more and 5% by mass or less based on the solid content of the photosensitive resin composition of the present invention. More preferably it is. By setting the content of the component (C) within the above range, the sensitivity of the photosensitive resin composition can be improved, and poor photocuring can be suppressed.

[(D) Photosensitive agent that generates sulfonic acid by light irradiation]
The photosensitive resin composition of this invention contains the photosensitive agent ((D) component) which generate | occur | produces a sulfonic acid by light irradiation. Examples of such a component (D) include (D1) a quinonediazide compound that generates sulfonic acid by light irradiation (hereinafter sometimes referred to as (D1) component), and (D2) an oxime-based photoacid generator (hereinafter referred to as “D1”). (D2) component) and (D3) sulfonium salt acid generator (hereinafter also referred to as (D3) component).

((D1) quinonediazide compound that generates sulfonic acid by light irradiation)
Examples of the quinonediazide compound that generates sulfonic acid upon irradiation with light include an esterified product of a naphthoquinone-1,2-diazide-4-sulfonyl halide and a phenolic hydroxyl group-containing compound. As the quinonediazide compound, a compound having a naphthoquinone-1,2-diazide-4-sulfonyl group and a compound having a naphthoquinone-1,2-diazide-5-sulfonyl group are generally known. In contrast, the latter generates an indenecarboxylic acid compound by light irradiation and does not generate a sulfonic acid. For this reason, in the photosensitive resin composition of the present invention, a compound having a naphthoquinone-1,2-diazide-5-sulfonyl group cannot be used as the quinonediazide compound that generates sulfonic acid by light irradiation.

［上記一般式（Ｄ１１）において、Ｒ^ｄ１からＲ^ｄ４は、同一であっても異なっていてもよく、それぞれ、水素原子、置換基を有していてもよい炭素数１以上６以下のアルキル基、アルコキシ基、シアノ基、ニトロ基、カルボニル基、アリール基を示し、Ｘはハロゲン原子である。］ Here, examples of naphthoquinone-1,2-diazide-4-sulfonyl halide include compounds represented by the following general formula (D11).

[In General Formula (D11), R ^d1 to R ^d4 may be the same or different, and each may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. , An alkoxy group, a cyano group, a nitro group, a carbonyl group, and an aryl group, and X is a halogen atom. ]

［上記一般式（Ｄ１１−１）及び（Ｄ１１−２）において、Ｘはハロゲン原子である。］ Specifically, the compound represented by the following general formula (D11-1) and (D11-2) can be mentioned, for example.

[In the above general formulas (D11-1) and (D11-2), X represents a halogen atom. ]

  Specific examples of the phenolic hydroxyl group-containing compound include 2,3,4-trihydroxybenzophenone and trihydroxybenzophenone such as 2,4,6-trihydroxybenzophenone; 2,2 ′, 4,4′-tetra Hydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4,2′-tetrahydroxybenzophenone, and 2,3,4,4 Tetrahydroxybenzophenones such as' -tetradroxy-3'-methobenzophenone; 2,3,4,2 ', 4'-pentahydroxybenzophenone, 2,3,4,2', 6'-pentahydroxybenzophenone, etc. Pentahydroxybenzophenone; 2,4,6,3 ′, 4 ′, 5′-hexahydroxy Hexahydroxybenzophenones such as nzophenone and 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone; 2,2′-dihydroxydiphenylmethane, 2,4′-dihydroxydiphenylmethane, and 4,4′-dihydroxy Dihydroxydiphenylmethane, such as diphenylmethane;

  1- (2-hydroxyphenyl) -1- (2′-hydroxyphenyl) ethane, 1- (2-hydroxyphenyl) -1- (4′-hydroxyphenyl) ethane, 1- (4-hydroxyphenyl) -1 -(4'-hydroxyphenyl) ethane, 1-phenyl-1- (2,4-dihydroxyphenyl) ethane, 1-phenyl-1- (2,6-dihydroxyphenyl) ethane, 1- (2-hydroxyphenyl) -2- (2′-hydroxyphenyl) ethane, 1- (2-hydroxyphenyl) -2- (4′-hydroxyphenyl) ethane, 1- (4-hydroxyphenyl) -2- (4′-hydroxyphenyl) Ethane, 1-phenyl-2- (2,4-dihydroxyphenyl) ethane, and 1-phenyl-2- (2,6-dihydroxyphenyl) ethane Diphenyl-hydroxy-ethane;

  1- (2-hydroxyphenyl) -1- (2′-hydroxyphenyl) propane, 1- (2-hydroxyphenyl) -1- (4′-hydroxyphenyl) propane, 1- (4-hydroxyphenyl) -1 -(4'-hydroxyphenyl) propane, 1-phenyl-1- (2,4-dihydroxyphenyl) propane, 1-phenyl-1- (2,6-dihydroxyphenyl) propane, 1- (2-dihydroxyphenyl) -2- (2′-hydroxyphenyl) propane, 1- (2-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (2-hydroxyphenyl) -1- (4′-hydroxyphenyl) Propane, 1- (4-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 1-phenyl-2- (2,4 Dihydroxyphenyl) propane, 2-phenyl-1- (2,4-dihydroxyphenyl) propane, 1-phenyl-2- (2,6-dihydroxyphenyl) propane, 2-phenyl-1- (2,6-dihydroxyphenyl) ) Propane, 2- (2-hydroxyphenyl) -2- (2′-hydroxyphenyl) propane, 2- (2-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) ) -2- (4′-hydroxyphenyl) propane, 2-phenyl-2- (2,4-dihydroxyphenyl) propane, 2-phenyl-2- (2,6-dihydroxyphenyl) propane, 1- (2- Hydroxyphenyl) -3- (2'-hydroxyphenyl) propane, 1- (2-hydroxyphenyl) -3- 4′-hydroxyphenyl) propane, 1- (4-hydroxyphenyl) -3- (4′-hydroxyphenyl) propane, 1-phenyl-3- (2,4-dihydroxyphenyl) propane, and 1-phenyl-3 -Dihydroxyphenylpropane such as (2,6-dihydroxyphenyl) propane; and

  2,2 ′, 2 ″ -trihydroxytriphenylmethane, 2,2 ′, 4 ″ -trihydroxytriphenylmethane, 2,4 ′, 4 ″ -trihydroxytriphenylmethane, 4,4 ′, 4 ″ -trihydroxytriphenylmethane, 2,2 ′, 2 ″ -trihydroxytriphenylethane, 2,2 ′, 4 ″ -trihydroxytriphenylethane, 2,4 ′, 4 ″ -tri Hydroxytriphenylethane, 4,4 ′, 4 ″ -trihydroxytriphenylethane, 2,2 ′, 2 ″ -trihydroxytriphenylpropane, 2,2 ′, 4 ″ -trihydroxytriphenylpropane, 2,4 ′, 4 ″ -trihydroxytriphenylpropane, 4,4 ′, 4 ″ -trihydroxytriphenylpropane, 4- [1,1-dimethyl-1- (o- Droxymethyl) phenyl] -bis (o-hydroxyphenyl) methane, 4- [1,1-dimethyl-1- (o-hydroxymethyl) phenyl] -bis (p-hydroxyphenyl) methane, 4- [1,1- Dimethyl-1- (p-hydroxymethyl) phenyl] -bis (o-hydroxyphenyl) methane, 4- [1,1-dimethyl-1- (p-hydroxymethyl) phenyl] -bis (p-hydroxyphenyl) methane [4- (o-hydroxyphenylmethyl) phenyl] -bis (o-hydroxyphenyl) methane, [4- (o-hydroxyphenylmethyl) phenyl] -bis (p-hydroxyphenyl) methane, [4- (p -Hydroxyphenylmethyl) phenyl] -bis (o-hydroxyphenyl) methane, [4- (p-hydroxyphenyl) Methyl) phenyl] -bis (p-hydroxyphenyl) methane, 1- {4- [1,1-dimethyl-1- (o-hydroxyphenyl) methyl] phenyl} -1,1-bis (o-hydroxyphenyl) Ethane, 1- {4- [1,1-dimethyl-1- (o-hydroxyphenyl) methyl] phenyl} -1,1-bis (p-hydroxyphenyl) ethane, 1- {4- [1,1- Dimethyl-1- (p-hydroxyphenyl) methyl] phenyl} -1,1-bis (o-hydroxyphenyl) ethane, 1- {4- [1,1-dimethyl-1- (p-hydroxyphenyl) methyl] Phenyl} -1,1-bis (p-hydroxyphenyl) ethane, 1- [4- (o-hydroxyphenylmethyl) phenyl] -1,1-bis (o-hydroxyphenyl) ethane, 1- [4- (o-hydroxyphenylmethyl) phenyl] -1,1-bis (p-hydroxyphenyl) ethane, 1- [4- (p-hydroxyphenylmethyl) phenyl] -1,1-bis (o-hydroxy) Phenyl) ethane, 1- [4- (p-hydroxyphenylmethyl) phenyl] -1,1-bis (p-hydroxyphenyl) ethane, 1- {4- [1,1-dimethyl-1- (o-hydroxy) Phenyl) methyl] phenyl} -2,2-bis (o-hydroxyphenyl) ethane, 1- {4- [1,1-dimethyl-1- (o-hydroxyphenyl) methyl] phenyl} -2,2-bis (P-hydroxyphenyl) ethane, 1- {4- [1,1-dimethyl-1- (p-hydroxyphenyl) methyl] phenyl} -2,2-bis (o-hydroxyphenyl) 1- {4- [1,1-dimethyl-1- (p-hydroxyphenyl) methyl] phenyl} -2,2-bis (p-hydroxyphenyl) ethane, 1- [4- (o-hydroxyphenyl) Methyl) phenyl] -2,2-bis (o-hydroxyphenyl) ethane, 1- [4- (o-hydroxyphenylmethyl) phenyl] -2,2-bis (p-hydroxyphenyl) ethane, 1- [4 -(P-hydroxyphenylmethyl) phenyl] -2,2-bis (o-hydroxyphenyl) ethane and 1- [4- (p-hydroxyphenylmethyl) phenyl] -2,2-bis (p-hydroxyphenyl) ) Ethane and the like can be mentioned.

  The quinonediazide compound which generates sulfonic acid by light irradiation and is contained in the photosensitive resin composition of the present invention may contain a single quinonediazide compound derived from a single phenolic hydroxyl group-containing compound, or a plurality of phenols A plurality of quinonediazide compounds derived from a functional hydroxyl group-containing compound may be included.

  In the photosensitive resin composition of the present invention, the quinonediazide compound is preferably a compound in which 65% or more of the phenolic hydroxyl group of the phenolic hydroxyl group-containing compound is substituted with a 1,2-naphthoquinonediazide-4-sulfonyl group. . Photocuring by polymerization of the component (B) and the component (B ′) by replacing 65% or more of the phenolic hydroxyl group of the phenolic hydroxyl group-containing compound with a 1,2-naphthoquinonediazide-4-sulfonyl group And thermal curing due to a crosslinking reaction of the alicyclic epoxy group in the presence of an acid catalyst occurs, and a cured resin pattern can be obtained.

((D2) Oxime-based photoacid generator)
The oxime photoacid generator (component (D2)) contained in the photosensitive resin composition of the present invention is not particularly limited. For example, α- (p-toluenesulfonyloxyimino) -phenylacetonitrile. , Α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, Examples include α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile and a compound represented by the following general formula (D21) containing an oxime sulfonate group.

［一般式（Ｄ２１）において、Ｒ^４は、１価以上６価以下の有機基を表し、Ｒ^５は、置換又は未置換の飽和炭化水素基、不飽和炭化水素基、若しくは芳香族性化合物基を表し、ｍは１以上６以下の整数である。］

[In General Formula (D21), R ⁴ represents a monovalent to hexavalent organic group, and R ⁵ represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic compound group. M is an integer of 1-6. ]

In the general formula (D21), R ⁴ is particularly preferably an aromatic compound group. Examples of such an aromatic compound group include an aromatic hydrocarbon group such as a phenyl group and a naphthyl group, Heterocyclic groups such as a furyl group and a thienyl group can be exemplified. These may have one or more suitable substituents such as an alkyl group, an alkoxy group, or a nitro group on the ring. R ⁵ is particularly preferably a lower alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.

As the photoacid generator represented by the general formula (D21), when m = 1, R ⁴ is any one of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R ⁵ is a methyl group. Compounds; specifically α- (methylsulfonyloxyimino) -1-phenylacetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- (P-methoxyphenyl) acetonitrile, [2- (propylsulfonyloxyimino) -2,3-dihydroxythiophene-3-ylidene] (o-tolyl) acetonitrile and the like can be mentioned. Specific examples of the photoacid generator represented by the above general formula when m = 2 include photoacid generators represented by the following chemical formulas (D21-1) to (D21-6). .

  These oxime photoacid generators may be used alone or in combination of two or more.

((D3) sulfonium salt acid generator)
As the component (D) used in the photosensitive resin composition of the present invention, the sulfonium salt acid generator (component (D3)) is more thermally stable than the components (D1) and (D2). The process margin can be improved by using the component (D3).

［一般式（Ｄ３１）において、Ｒ^１’’からＲ^３’’は、それぞれ独立に、置換基を有していてもよいアリール基、又は置換基を有していてもよいアルキル基であり、Ｒ^１’’からＲ^３’’のうち、いずれか２つが互いに結合して上記一般式中の硫黄原子と共に環を形成していてもよく、Ｒ^０は置換基を有していてもよい炭素数１以上１２以下の炭化水素基である。］ As (D3), the compound shown by the following general formula (D31) can be mentioned, for example.

[In General Formula (D31), R ^{1 ″} to R ^{3 ″} are each independently an aryl group which may have a substituent, or an alkyl group which may have a substituent, Any two of R ^{1 ″} to R ^{3 ″} may be bonded to each other to form a ring together with the sulfur atom in the above general formula, and R ⁰ is a carbon that may have a substituent. A hydrocarbon group having a number of 1 or more and 12 or less. ]

(Cation part of the compound represented by the general formula (D31))
The aryl group which may have a substituent represented by R ^{1 ″} to R ^{3 ″} is not particularly limited, and examples thereof include an unsubstituted aryl group having 6 to 20 carbon atoms; A substituted aryl group in which part or all of the hydrogen atoms of the unsubstituted aryl group are substituted with an alkyl group, an alkoxy group, an alkoxyalkyloxy group, an alkoxycarbonylalkyloxy group, a hydroxyl group, a thiophenyl group, or the like; and — (R ^{4 A group represented by '} ) -C (= O) -R ^5' (where R ^{4 '} is an alkylene chain having 1 to 5 carbon atoms, R ^5' is an aryl group, and an aryl group of R ^{5 '} ) Can include the same groups as the unsubstituted aryl group and the substituted aryl group in the aryl groups of R ^{1 ″} to R ^{3 ″} .

  The unsubstituted aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at low cost. Specific examples include a phenyl group and a naphthyl group.

  As the alkyl group which may substitute part or all of the hydrogen atoms of the unsubstituted aryl group, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, or an n-butyl group. And tert-butyl groups are most preferred.

  As an alkoxy group which may substitute a part or all of hydrogen atoms of an unsubstituted aryl group, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso- Most preferred are propoxy, n-butoxy, and tert-butoxy.

［一般式（Ｄ３２）において、Ｒ^４７及びＲ^４８はそれぞれ独立して水素原子、又は直鎖状若しくは分岐鎖状のアルキル基であり、Ｒ^４９はアルキル基である。］ Examples of the alkoxyalkyloxy group which may substitute part or all of the hydrogen atoms of the unsubstituted aryl group include a group represented by the following general formula (D32).

[In General Formula (D32), R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom or a linear or branched alkyl group, and R ⁴⁹ is an alkyl group. ]

In R ⁴⁷ and R ⁴⁸ , the alkyl group preferably has 1 to 5 carbon atoms, and may be linear or branched, preferably a methyl group or an ethyl group, and most preferably a methyl group. Moreover, it is preferable that at least one of R ⁴⁷ and R ⁴⁸ is a hydrogen atom. In particular, it is more preferable that one is a hydrogen atom and the other is a hydrogen atom or a methyl group.

The alkyl group for R ⁴⁹ preferably has 1 to 15 carbon atoms, and may be linear, branched, or cyclic.

The linear or branched alkyl group for R ⁴⁹ preferably has 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group. Etc.

The cyclic alkyl group for R ⁴⁹ preferably has 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, one hydrogen atom is removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane, which may be substituted with an alkyl group having 1 to 5 carbon atoms. The group etc. can be mentioned. Among these, examples of the monocycloalkane include cyclopentane and cyclohexane. Examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among these, a group in which one hydrogen atom is removed from adamantane is preferable.

［一般式（Ｄ３３）において、Ｒ^５０は直鎖状又は分岐鎖状のアルキレン鎖であり、Ｒ^５１は第３級アルキル基である。］ Examples of the alkoxycarbonylalkyloxy group which may substitute part or all of the hydrogen atoms of the unsubstituted aryl group include a group represented by the following general formula (D33).

[In General Formula (D33), R ⁵⁰ represents a linear or branched alkylene chain, and R ⁵¹ represents a tertiary alkyl group. ]

The linear or branched alkylene chain represented by R ⁵⁰ preferably has 1 to 5 carbon atoms, such as a methylene chain, an ethylene chain, a trimethylene chain, a tetramethylene chain, or 1,1-dimethylethylene. A chain etc. can be mentioned.

As the tertiary alkyl group for R ⁵¹ , 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, 1-methyl -1-cyclohexyl group, 1-ethyl-1-cyclohexyl group, 1- (1-adamantyl) -1-methylethyl group, 1- (1-adamantyl) -1-methylpropyl group, 1- (1-adamantyl) -1-methylbutyl group and 1- (1-adamantyl) -1-methylpentyl group; 1- (1-cyclopentyl) -1-methylethyl group, 1- (1-cyclopentyl) -1-methylpropyl group, -(1-cyclopentyl) -1-methylbutyl group and 1- (1-cyclopentyl) -1-methylpentyl group; 1- (1-cyclohexyl) -1-me A tilethyl group, a 1- (1-cyclohexyl) -1-methylpropyl group, a 1- (1-cyclohexyl) -1-methylbutyl group, and a 1- (1-cyclohexyl) -1-methylpentyl group; and a tert-butyl group , Tert-pentyl group, and tert-hexyl group.

The alkyl group represented by R ^{1 ″} to R ^{3 ″} is not particularly limited, and examples thereof include linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms. be able to. Among these alkyl groups, an alkyl group having 1 to 5 carbon atoms is preferable from the viewpoint of excellent resolution. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, and a decanyl group. The methyl group can be most preferably used because it is excellent in resolution and can be synthesized at low cost.

When any two of R ^{1 ″} to R ^{3 ″} are bonded to each other to form a ring together with the sulfur atom in the general formula (D31), a 3-membered ring to a 10-membered ring including the sulfur atom It is preferable to form a 5-membered ring to a 7-membered ring.

When any two of R ^{1 ″} to R ^{3 ″} are bonded to each other to form a ring together with the sulfur atom in the general formula (D31), the remaining one is preferably an aryl group. Examples of the aryl group include the same groups as the aryl group which may have a substituent represented by R ^{1 ″} to R ^{3 ″} .

  Specific examples of suitable cation moieties in general formula (D31) are shown below.

  Among these, the cation moiety represented by the chemical formula (D31-1-20) to the chemical formula (D31-1-22) is particularly preferable, and the cation moiety represented by the chemical formula (D31-1-20) is most preferable. The cation moiety represented by the chemical formula (D31-1-22) is generated, for example, in the process of synthesizing the cation moiety represented by the chemical formula (D31-1-20).

(Anion part of the compound represented by the general formula (D31))
The hydrocarbon group having 1 to 12 carbon atoms represented by R ⁰ may have a substituent but does not have a halogen atom. Examples of the substituent include a lower alkyl group having 1 to 5 carbon atoms and an oxygen atom (═O).

The hydrocarbon group having 1 to 12 carbon atoms which may have a substituent represented by R ⁰ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. When the hydrocarbon group having 1 to 12 carbon atoms which may have a substituent represented by R ⁰ is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may be a saturated hydrocarbon group An unsaturated hydrocarbon group may be used, and a saturated hydrocarbon group is usually preferred.

  Further, the aliphatic hydrocarbon group may be any of linear, branched, and cyclic. The linear or branched hydrocarbon group is preferably a linear or branched alkyl group, and the alkyl group preferably has 1 to 10 carbon atoms, and has 1 to 8 carbon atoms. More preferably, it is more preferably 3 or more and 8 or less.

Specific examples of the linear or branched alkyl group represented by R ⁰ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and a pentyl group. , Isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, and n-octyl group. Among these alkyl groups, a methyl group, an n-propyl group, an n-butyl group, and an n-octyl group are preferable, and an n-octyl group is particularly preferable.

［一般式（Ｄ３１−２−１）において、ａは１以上１０以下の整数であり、好ましくは１以上８以下の整数である。］ In the anion portion of the compound represented by the general formula (D31), specific examples of the sulfonate ion in which R ⁰ is a linear or branched alkyl group include, for example, the following general formula (D31-2-1) The sulfonate ion shown by this can be mentioned.

[In general formula (D31-2-1), a is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less. ]

  Specific examples of the sulfonate ion represented by the general formula (D31-2-1) include, for example, methanesulfonate ion, ethanesulfonate ion, n-propanesulfonate ion, n-butanesulfonate ion, and n-octanesulfonate ion. Etc.

As the cyclic hydrocarbon group represented by R ⁰ , an aliphatic cyclic group or a group in which at least one hydrogen atom of a chain hydrocarbon group is substituted with an aliphatic cyclic group (including an aliphatic cyclic group) Group) and the like.

  The “aliphatic cyclic group” refers to a monocyclic group or polycyclic group having no aromaticity. The “aliphatic cyclic group” may have a substituent. Examples of the substituent include a lower alkyl group having 1 to 5 carbon atoms and an oxygen atom (═O). In the “aliphatic cyclic group”, the basic ring structure excluding the substituent is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but is preferably a hydrocarbon group.

  Further, the “hydrocarbon group” may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group, but is usually preferably a saturated hydrocarbon group. The “aliphatic cyclic group” is preferably a polycyclic group.

  Examples of the aliphatic cyclic group include one monocycloalkane which may be substituted with an alkyl group having 1 to 5 carbon atoms and one polycycloalkane such as bicycloalkane, tricycloalkane, and tetracycloalkane. The group etc. which remove | excluded the hydrogen atom can be mentioned. More specifically, examples include monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. be able to.

  Of these aliphatic cyclic groups, an aliphatic cyclic group having 3 to 12 carbon atoms is preferable, and an aliphatic cyclic group having 4 to 10 carbon atoms is more preferable.

  In particular, the monocyclic group that can be adopted by the aliphatic cyclic group is preferably a group in which one hydrogen atom is removed from the monocycloalkane having 3 to 6 carbon atoms, specifically, a cyclopentyl group and A cyclohexyl group etc. can be illustrated.

  Further, the polycyclic group that can be adopted by the aliphatic cyclic group is preferably a group in which one hydrogen is removed from the above polycycloalkane having 7 to 12 carbon atoms, specifically, an adamantyl group, norbornyl Group, isobornyl group, tricyclodecanyl group, tetracyclododecanyl group and the like.

  As described above, the aliphatic cyclic group is preferably a polycyclic group, and an adamantyl group, a norbornyl group, and a tetracyclododecanyl group are preferable from an industrial viewpoint. Further, these aliphatic cyclic groups may have a substituent as described above.

Examples of the aliphatic cyclic group in the “aliphatic cyclic group-containing group” include those similar to the “aliphatic cyclic group” as R ⁰ . In the “aliphatic cyclic group-containing group”, the linear hydrocarbon chain to which the aliphatic cyclic group is bonded is preferably a linear or branched alkylene chain, and is a lower alkyl having 1 to 5 carbon atoms. More preferably, it is a group. Specific examples include a methylene chain, ethylene chain, propylene chain, isopropylene chain, n-butylene chain, isobutylene chain, tert-butylene chain, pentylene chain, isopentylene chain, and neopentylene chain. Among these, a linear alkylene chain is preferable, and a methylene chain or an ethylene chain is preferable from an industrial viewpoint.

Specific examples of the sulfonate ion in which R ⁰ is a cyclic hydrocarbon group include groups represented by the following chemical formulas (D3-3-1) to (D3-3-7).

  In the present invention, the anion moiety of the compound represented by the general formula (D31) is preferably an anion moiety represented by the chemical formula (D3-3-1).

Examples of the aromatic hydrocarbon group which is a hydrocarbon group represented by R ⁰ include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a phenethyl group, and a naphthyl group. As described above, the aromatic hydrocarbon group may have a substituent. The aromatic hydrocarbon group may have a hetero atom such as a nitrogen atom in the ring.

［一般式（Ｄ３−４−１）から（Ｄ３−４−３）において、Ｒ^６１からＲ^６３は、それぞれ独立に炭素数１以上５以下のアルキル基、及び炭素数１以上５以下のアルコキシ基であり、ｄ及びｅは、それぞれ独立に０以上４以下の整数であり、ｆは、０以上３以下の整数である。］ Examples of the aromatic hydrocarbon group which is a hydrocarbon group represented by R ⁰ include groups represented by the following general formulas (D3-4-1) to (D3-4-3).

[In General Formulas (D3-4-1) to (D3-4-3), R ⁶¹ to R ⁶³ are each independently an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms. D and e are each independently an integer of 0 or more and 4 or less, and f is an integer of 0 or more and 3 or less. ]

Examples of the alkyl group represented by R ⁶¹ and R ⁶² include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. In particular, a methyl group is preferred.

Examples of the alkoxy group represented by R ⁶¹ and R ⁶² include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group. Groups are preferred.

d and e are each independently an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 2 or less, and most preferably 0. d and / or e is an integer of 2 or ^{more, if R 61} and / or ^{R 62} there are a plurality, a plurality of ^{R 61} and / or ^{R 62} may be identical to each other, be different Good.

^Examples of the alkyl group represented by R ⁶³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. A methyl group is particularly preferred.

^Examples of the alkoxy group represented by R ⁶³ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group, and a methoxy group and an ethoxy group are particularly preferable. .

f is an integer of 0 or more and 3 or less, preferably 1 or 2, and most preferably 1. A f is an integer of 2 or more, if R ⁶³ there are a plurality, a plurality of R ⁶³ may be the same as each other or may be different.

As the anion moiety of the compound represented by the general formula (D31), the most preferable one is methanesulfonate ion, butanesulfonate ion, an anion represented by the following chemical formula (D3-4-21), and the following chemical formula (D3-4-31). ) And the like.

  These sulfonium salt acid generators may be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, only one of the quinonediazide compound, the oxime photoacid generator, and the sulfonium salt acid generator may be used, or selected from the three. However, when using copper and a copper alloy for the substrate, it is preferable to use only a quinonediazide compound.

  The content of the component (D) in the photosensitive resin composition of the present invention is preferably 0.01 parts by weight or more and 5 parts by weight or less, and 0.1 parts by weight or more and 3 parts by weight per 100 parts by weight of the component (A). It is still more preferable that it is below mass parts. By making content of (D) component into the said range, the adhesiveness to the board | substrate of the coating film after hardening and the hardness of the said coating film can be made favorable.

[(E) Solvent]
The photosensitive resin composition of the present invention can be used by dissolving the above components in a solvent (E) (hereinafter sometimes referred to as component (E)). Such a component (E) is not particularly limited, and a conventionally known solvent can be used. Examples include γ-butyrolactone, ethyl lactate, propylene carbonate, propylene glycol monomethyl ether acetate (PGMEA), methyl isobutyl ketone, butyl acetate, methyl amyl ketone, 2-heptanone, ethyl acetate, and methyl ethyl ketone. Among these, it is preferable to use propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl lactate, and methyl ethyl ketone. (E) A component may be used independently and may mix 2 or more types.

  The amount of component (E) used is preferably within a range where the solid content concentration is 30% by mass or more and 70% by mass or less in consideration of applicability and the like.

[Other ingredients]
The photosensitive resin composition of the present invention may optionally contain miscible additives such as additional resins, plasticizers, stabilizers, sensitizers, leveling agents, and coupling agents for improving pattern performance. Conventionally known materials such as these can be appropriately contained.

[Method for Preparing Photosensitive Resin Composition]
The photosensitive resin composition of the present invention can be prepared, for example, by mixing and stirring each of the above components by a usual method, and using a disperser such as a dissolver, a homogenizer, and a three-roll mill as necessary. , May be mixed. Moreover, after mixing, you may filter using a mesh, a membrane filter, etc. further.

<Dry film>
The photosensitive resin composition of the present invention may be used in the form of a solution, but may also be used in the form of a dry film by forming protective films on both sides of the photosensitive resin layer formed from the photosensitive resin composition. Good. By setting it as such a dry film, the application | coating on a support body and a drying process can be skipped, and pattern formation becomes possible more simply.

  As the protective film, it is preferable to use a polymer film of any of a polyethylene terephthalate film, a polypropylene film, and a polyethylene film.

<Pattern formation method>
When the photosensitive resin composition of the present invention is used in the form of a solution, the photosensitive resin composition is applied onto a support by a spin coater or the like, dried, and exposed to a predetermined pattern using actinic rays or radiation. Thereafter, development is performed, and the obtained resin pattern is subjected to heat treatment, whereby a cured resin pattern having a predetermined shape can be obtained.

  On the other hand, when using the photosensitive resin composition of the present invention in the form of a dry film, after removing the protective film on both sides of the dry film and pasting it on the support, after exposing the photosensitive resin layer to a predetermined pattern, By developing and heat-treating the obtained resin pattern, a cured resin pattern having a predetermined shape can be obtained.

  In addition, when affixing on a support body, you may make it remove only the protective film of one surface instead of removing the protective film of both surfaces of a dry film. In this case, a dry film is stuck on the support so that the exposed photosensitive resin layer is in contact, and after exposing the photosensitive resin layer to a predetermined pattern, the protective film on the other surface of the photosensitive resin laminate is removed. do it.

[Support]
The support is not particularly limited, and a conventionally known one can be used, and examples thereof include a substrate for electronic components and a substrate on which a predetermined wiring pattern is formed. Examples of the substrate include a metal substrate such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, and aluminum, a glass substrate, and the like. As a material for the wiring pattern, for example, copper, solder, chromium, aluminum, nickel, gold or the like is used.

[exposure]
The photosensitive resin layer is exposed through a predetermined mask. This exposure is performed by irradiating active energy rays such as ultraviolet rays and excimer laser light. Examples of the active energy ray light source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, and an excimer laser generator. Energy dose to be irradiated may differ depending on the composition of the photosensitive resin composition may be a 2000 mJ / cm ^2, for example, about from 30 mJ / cm ^2.

[developing]
Examples of the developer include conventionally known ones. When developing the photosensitive resin composition of this invention, it is preferable to use the solvent used for preparation of the photosensitive resin composition as a developing solution.

[Heat treatment]
The heat treatment performed after development is usually performed within a range of 140 ° C to 300 ° C. In the present invention, the heat treatment is preferably performed at a resin pattern of 140 ° C. or higher, more preferably 200 ° C. or higher and 30 minutes or longer and 180 minutes or shorter.

  The photosensitive resin composition of the present invention is a cured resin pattern in which photocuring due to polymerization of a compound having a radical polymerizable group and thermal curing due to a crosslinking reaction of an alicyclic epoxy group in the presence of an acid catalyst occur. Is obtained. In the photosensitive resin composition of the present invention, since it contains a photosensitizer that generates sulfonic acid by light irradiation, thermosetting proceeds well even under low temperature conditions, A cured resin pattern having sufficient hardness can be obtained.

  Hereinafter, the present invention will be described in detail with reference to examples. In addition, this invention is not limited to the Example shown below at all.

<Examples 1 to 13, Comparative Examples 1 to 5>
A photosensitive resin composition was prepared according to the composition shown in Tables 1 and 2.

  In addition, each component used by each said Example and comparative example is as follows.

[Polymer having epoxy group]
(A-1); 3,4-epoxycyclohexylmethyl methacrylate homopolymer, molecular weight 40000
(A-2); 3,4-epoxycyclohexylmethyl methacrylate: styrene = 60: 40 copolymer, molecular weight 40000
(A-3); 3,4-epoxycyclohexylmethyl methacrylate: styrene: methacryloxypropyltrimethoxysilane = 60: 35: 5 copolymer, molecular weight 40000
(A-4); “Epicoat 1007” (trade name, manufactured by Japan Epoxy Resin Co., Ltd., glycidyl ether type epoxy resin)

[Monomer having radical polymerizable group]
(B-1); Dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)
(B-2); methacryloxypropyltrimethoxysilane (Toray Dow Corning)
(B-3); 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., EO 2 mol)
(B-4); N-acryloyloxyethyl hexahydrophthalimide (manufactured by Toa Gosei Co., Ltd.)

[Polymer having radically polymerizable group]
(B′-1); methacrylic acid-modified acryloyl: styrene = 50: 50 copolymer, molecular weight 20000

[Radical polymerization initiator]
(C-1); 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (o-acetyloxime) (manufactured by Ciba Specialty Chemicals)
(C-2); 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals)
(C-3); 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by Ciba Specialty Chemicals)

[Quinonediazide compound]
(D1-1); 2 mol of all hydroxyl groups of 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene is 1,2-naphthoquinonediazide Compound substituted with -4-sulfonyl group (d1-2); all hydroxyl groups of 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene In which 2 moles of the above are substituted with a 1,2-naphthoquinonediazide-5-sulfonyl group

[Photoacid generator]
(D2-1); [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] (o-tolyl) acetonitrile (manufactured by Ciba Specialty Chemicals)
(D-2); diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate (manufactured by San Apro)
(D3-1); a compound represented by the following chemical formula (D34)

<Evaluation>
[Fine wire adhesion]
The photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 5 were applied to a silicon wafer having a diameter of 12.5 cm using a spin coater (manufactured by Mikasa) and dried on a hot plate at 100 ° C. for 10 minutes. A photosensitive resin layer having a thickness of 30 μm was obtained. After exposure using an exposure apparatus “PLA-501F” (manufactured by Canon Inc.) at an exposure amount of 400 mJ / cm ² , post-exposure heating was performed at 130 ° C. for 5 minutes on a hot plate. The layered product after exposure was dip developed for 3.5 minutes using PGMEA as a developer. After development, the width of the finest adhered pattern was measured to evaluate fine line adhesion. In addition, when the pattern after development was post-baked at 200 ° C. for 2 hours and immersed in N-methylpyrrolidone at 60 ° C. for 30 minutes, the pattern state was changed before and after immersion in each example. On the other hand, in each of the comparative examples, the pattern did not remain. The results are shown in Tables 3 and 4.

[Glass-transition temperature]
The photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 5 were applied to a silicon wafer having a diameter of 12.5 cm using a spin coater (manufactured by Mikasa) and dried on a hot plate at 100 ° C. for 10 minutes. A photosensitive resin layer having a thickness of 30 μm was obtained. After exposure using an exposure apparatus “PLA-501F” (manufactured by Canon Inc.) at an exposure amount of 400 mJ / cm ² , post-exposure heating was performed at 130 ° C. for 5 minutes on a hot plate. The layered product after exposure was dip developed for 3.5 minutes using PGMEA as a developer. This was post-baked at 200 ° C. or 250 ° C. for 2 hours, and the glass transition point of the obtained cured resin pattern was measured. The results are shown in Tables 3 and 4.

  As can be seen from Tables 3 and 4, when the photosensitive resin compositions of Examples 1 to 13 were used, unlike Comparative Examples 1 and 3 to 4, it was comparable to Comparative Example 2 using a halogen-containing photosensitive agent. Good fine wire adhesion is obtained. Moreover, about the baking temperature, when using the photosensitive resin composition of Examples 1-13, even when it heat-processes at 200 degreeC, it is 250 in the comparative example 1 which does not contain (D) component. It can be seen that a glass transition point comparable to that obtained when heat treatment is performed at 0 ° C. is obtained, and that a cured resin pattern having sufficient hardness is obtained under low temperature conditions.

  Based on the above, the photosensitive resin composition of the present invention can be suitably used in permanent film applications without using a halogen-containing photosensitive agent.

Claims (9)

  (A) a photosensitive resin containing a polymer having an alicyclic epoxy group, (B) a monomer having a radical polymerizable group, (C) a radical polymerization initiator, and (D) a photosensitive agent that generates sulfonic acid by light irradiation. Composition.   The photosensitive resin composition according to claim 1, further comprising (B ′) a polymer having a radical polymerizable group.   The photosensitive resin composition according to claim 1, wherein the polymer having an alicyclic epoxy group further has a radical polymerizable group.   The photosensitive resin composition according to any one of claims 1 to 3, wherein the photosensitive agent that generates sulfonic acid upon irradiation with light is a quinonediazide compound having a 1,2-naphthoquinonediazide-4-sulfonyl group.   The photosensitive resin composition according to claim 4, wherein the quinonediazide compound is a compound in which 65% or more of the phenolic hydroxyl group of the phenolic hydroxyl group-containing compound is substituted with a 1,2-naphthoquinonediazide-4-sulfonyl group.   The dry film formed by forming a protective film on both surfaces of the layer formed from the photosensitive resin composition in any one of Claim 1 to 5.   The photosensitive resin composition according to any one of claims 1 to 5 is applied on a support, dried, exposed to a predetermined pattern, and then developed to heat-treat the resin pattern, A pattern forming method for obtaining a cured resin pattern having a predetermined shape.   The protective film of the dry film according to claim 6 is peeled off, attached to a support and exposed to a predetermined pattern, and then a resin pattern obtained by development is heated to obtain a cured resin pattern having a predetermined shape. Pattern formation method.   The protective film on one side of the dry film according to claim 6 is peeled off, attached to a support so that the exposed photosensitive resin layer is in contact with it, and exposed to a predetermined pattern, and then the other side of the dry film The pattern formation method which peels and develops the protective film and heats the obtained resin pattern to obtain a cured resin pattern having a predetermined shape.