WO2022210268A1 - Resin composition, film, and copolymer - Google Patents

Resin composition, film, and copolymer Download PDF

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Publication number
WO2022210268A1
WO2022210268A1 PCT/JP2022/014025 JP2022014025W WO2022210268A1 WO 2022210268 A1 WO2022210268 A1 WO 2022210268A1 JP 2022014025 W JP2022014025 W JP 2022014025W WO 2022210268 A1 WO2022210268 A1 WO 2022210268A1
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WIPO (PCT)
Prior art keywords
structural unit
group
resin
carbon atoms
resin composition
Prior art date
Application number
PCT/JP2022/014025
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French (fr)
Japanese (ja)
Inventor
裕 河西
Original Assignee
住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to KR1020237026060A priority Critical patent/KR20230161421A/en
Priority to CN202280025393.4A priority patent/CN117098788A/en
Publication of WO2022210268A1 publication Critical patent/WO2022210268A1/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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • 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
    • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • 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
    • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/12—N-Vinylcarbazole
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D139/00—Coating compositions based on homopolymers or 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member

Definitions

  • the present invention relates to resin compositions, membranes and copolymers.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2006-171160 discloses polymerizing methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate.
  • a resin composition is described that includes a copolymer of
  • Patent Document 2 International Publication No. 2012/053377 describes a high refractive index resin composition for electronic devices containing a carbazole compound.
  • the present invention was made based on the discovery of the problem that a resin composition containing a copolymer having a structural unit having a carbazole ring has low solvent solubility. Resin compositions with low solvent solubility have problems such as difficulty in forming a uniform film and difficulty in wiping off with a solvent.
  • the present invention is a resin composition containing a copolymer having a structural unit having a carbazole ring, the resin composition having excellent solvent solubility, a film formed from the resin composition, and the resin composition
  • An object is to provide a copolymer that can be used.
  • the present invention includes the following inventions.
  • the resin (A) comprises a structural unit (Aa) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms, and a structural unit (Ab) having a carbazole ring which may have a substituent.
  • a copolymer containing a structural unit (Ac) derived from an unsaturated compound having a (meth) acrylic acid ester structure A resin composition in which the structural unit (Ac) is represented by the following formula (Ac).
  • R a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R a2 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
  • the structure obtained by epoxidizing the unsaturated alicyclic hydrocarbon is selected from the group consisting of structural units represented by formula (Aa-1) and structural units represented by formula (Aa-2).
  • X b1 and X b2 each represent a single bond, *-R b3 -, *-R b3 -O-, *-R b3 -S- or *-R b3 -NH-.
  • R b3 represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond with O. ]
  • R 1 represents a hydrogen atom, a methyl group, or a hydroxymethyl group.
  • R 2 to R 9 each independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is , an alkoxy group or an aryl group.
  • X represents a single bond, an alkanediyl group having 1 or more carbon atoms, or a linear or branched group represented by the following formula (V).
  • the structural unit (Ac) is a copolymer represented by the following formula (Ac).
  • R a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R a2 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
  • the resin composition of the present invention it is possible to provide a resin composition with excellent solvent solubility.
  • the resin composition of the present invention contains a resin (hereinafter referred to as resin (A)) and a solvent (hereinafter referred to as solvent (E)), and the resin (A) is a cyclic ether having 2 to 4 carbon atoms.
  • (meth)acrylic acid represents at least one compound selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth)acryloyl” and “(meth)acrylate” have the same meaning.
  • the resin composition of the present invention has excellent solvent solubility because the resin (A) is a copolymer containing the structural unit (Aa), the structural unit (Ab), and the structural unit (Ac). can be provided.
  • the resin composition of the present invention may contain a polymerizable compound (hereinafter referred to as polymerizable compound (C)).
  • a polymerizable compound hereinafter referred to as polymerizable compound (C)
  • polymerization initiator hereinafter referred to as polymerization initiator (D)
  • the resin composition of the present invention also contains other components such as a polymerization initiation aid (hereinafter referred to as polymerization initiation aid (H)), a leveling agent (hereinafter referred to as a leveling agent (B)), It may contain an antioxidant (hereinafter referred to as antioxidant (F)), a curing agent (hereinafter referred to as curing agent (G)), and the like.
  • the curing agent (G) include polycarboxylic acids (hereinafter referred to as polycarboxylic acids (G1)), imidazole compounds (hereinafter referred to as imidazole compounds (G2)), and the like.
  • the resin (A) is a copolymer containing a structural unit (Aa), a structural unit (Ab) and a structural unit (Ac).
  • the copolymer is further copolymerizable with the structural unit (Aa), the structural unit (Ab) or the structural unit (Ac), and the structural unit (Aa), the structural unit (Ab) and the structural unit (Ac ) (hereinafter referred to as a structural unit (Ad)).
  • the resin (A) may contain two or more kinds of each of the structural units (Aa), the structural units (Ab) and the structural units (Ac).
  • the structural unit (Aa) can be derived from an unsaturated compound having a cyclic ether structure with 2 to 4 carbon atoms (eg, at least one selected from the group consisting of oxirane ring, oxetane ring and tetrahydrofuran ring).
  • a structural unit derived from an unsaturated compound having a cyclic ether structure with 2 to 4 carbon atoms can be obtained by producing a copolymer using the unsaturated compound as a monomer. Alternatively, it can be obtained by reacting another structural unit (hereinafter referred to as structural unit (Aa')) with a compound having a cyclic ether structure having 2 to 4 carbon atoms.
  • the unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms leading to the structural unit (Aa) is, for example, a monomer having an oxiranyl group and an ethylenically unsaturated bond (hereinafter, monomer (Aa1) and ), a monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter referred to as monomer (Aa2)), a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as referred to as a monomer (Aa3)).
  • the monomer (Aa1) is, for example, a monomer having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter referred to as monomer (Aa1-1). ), and a monomer having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter referred to as monomer (Aa1-2)).
  • monomer (Aa1) is preferable in that the heat resistance, chemical resistance, etc. of the obtained film can be further enhanced.
  • the monomer (Aa1-2) is more preferable in terms of excellent storage stability of the resin composition.
  • Examples of the monomer (Aa1-1) include glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, ⁇ -ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether and m-vinylbenzyl glycidyl.
  • Examples of the monomer (Aa1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, Celoxide 2000; manufactured by Daicel Corporation), and 3,4-epoxycyclohexylmethyl (meth)acrylate.
  • vinylcyclohexene monoxide 1,2-epoxy-4-vinylcyclohexane
  • Celoxide 2000 manufactured by Daicel Corporation
  • 3,4-epoxycyclohexylmethyl (meth)acrylate for example, Cychromer M100; manufactured by Daicel Corporation
  • the compound represented by formula (I) and the formula A compound represented by (II) and the like can be mentioned.
  • R b1 and R b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group.
  • X b1 and X b2 each represent a single bond, *-R b3 -, *-R b3 -O-, *-R b3 -S- or *-R b3 -NH-.
  • R b3 represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond with O.
  • alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.
  • Alkyl groups in which hydrogen atoms are substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.
  • R b1 and R b2 preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.
  • the alkanediyl group includes methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane- A 1,6-diyl group and the like can be mentioned.
  • X b1 and X b2 are preferably single bond, methylene group, ethylene group, *-CH 2 -O- and *-CH 2 CH 2 -O-, more preferably single bond and *-CH 2 CH 2 —O— is included. * represents a bond with O.
  • Examples of the compound represented by formula (I) include compounds represented by any one of formulas (I-1) to (I-15), preferably formula (I-1), formula (I -3), formula (I-5), formula (I-7), formula (I-9) or compounds represented by formulas (I-11) to (I-15), more preferably Examples include compounds represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).
  • Examples of the compound represented by formula (II) include compounds represented by any one of formulas (II-1) to (II-15), preferably formula (II-1), formula (II -3), formula (II-5), formula (II-7), formula (II-9) or compounds represented by formulas (II-11) to (II-15), more preferably Examples include compounds represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).
  • the compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination of two or more. When these are used in combination, the content ratio of these [compound represented by formula (I): compound represented by formula (II)] is on a molar basis, preferably 5:95 to 95:5, more preferably 20 :80 to 80:20. For example, a mixture containing a compound represented by formula (I-1) and a compound represented by formula (II-1) at a ratio of 50:50 can be used.
  • a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable as the monomer (Aa2).
  • Examples of the monomer (Aa2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyl Oxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane and the like. be done.
  • the monomer (Aa3) a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is preferable.
  • the monomer (Aa3) include tetrahydrofurfuryl acrylate (eg, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.
  • the structural unit (Aa) is a structure derived from the monomer (Aa1-2) in that the solvent solubility and storage stability of the resin composition and the chemical resistance, heat resistance and mechanical strength of the obtained film are excellent. It is preferably a unit, more preferably a structural unit represented by formula (Aa-1) or formula (Aa-2).
  • the structural unit represented by formula (Aa-1) is derived from the compound represented by formula (I)
  • the structural unit represented by formula (Aa-2) is derived from the compound represented by formula (II). be killed.
  • R b1 and R b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. may be substituted.
  • X b1 and X b2 each represent a single bond, *-R b3 -, *-R b3 -O-, *-R b3 -S- or *-R b3 -NH-.
  • R b3 represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond with O.
  • the structural unit (Ab) can be derived from an unsaturated compound having an optionally substituted carbazole ring.
  • a structural unit derived from the unsaturated compound can be obtained by producing a copolymer using the unsaturated compound as a monomer. Alternatively, it can be obtained by reacting another structural unit (Ab') with a compound (Ab'') having a carbazole ring which may have a substituent.
  • the resin (A) can improve the refractive index of the resulting film.
  • the unsaturated compound leading to the structural unit (Ab) is preferably a compound represented by formula (III).
  • R 1 represents a hydrogen atom, a methyl group, or a hydroxymethyl group.
  • R 2 to R 9 each independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is , an alkoxy group or an aryl group.
  • X represents a single bond, an alkanediyl group having 1 or more carbon atoms, or a linear or branched group represented by the following formula (V).
  • Compounds represented by formula (III) include N-vinylcarbazole, N-allylcarbazole, N-(meth)acryloylcarbazole, 2-(9-carbazolyl)ethyl (meth)acrylate, 2-(9-carbazolyl) ethoxyethyl (meth)acrylate, 2-(9-carbazolyl)-2-methylethyl (meth)acrylate, 2-(9-carbazolyl)-1-methylethyl (meth)acrylate and the like.
  • N-vinylcarbazole, N-allylcarbazole and 2-(9-carbazolyl)ethyl (meth)acrylate are preferred.
  • the structural unit (Ac) can be derived from an unsaturated compound having a (meth)acrylic acid ester structure.
  • a structural unit derived from the unsaturated compound can be obtained by producing a copolymer using the unsaturated compound as a monomer. Alternatively, it can be obtained by reacting another structural unit (Ac') with a compound (Ac'') having a (meth)acrylate structure.
  • the resin (A) can improve the solvent solubility of the resin composition.
  • the structural unit (Ac) is represented by the following formula (Ac).
  • R a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R a2 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
  • Examples of the alkyl group having 1 to 4 carbon atoms representing R a1 include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group.
  • R a1 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
  • the aliphatic hydrocarbon group having 1 to 20 carbon atoms representing R a2 includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group.
  • R a2 is preferably a hydrogen atom or an aliphatic hydrocarbon group having 4 to 20 carbon atoms, more preferably an aliphatic hydrocarbon group having 4 to 12 carbon atoms, and still more preferably an aliphatic hydrocarbon group having 4 to 10 carbon atoms.
  • R a2 may be an aliphatic hydrocarbon group having 5 or more carbon atoms, may be an aliphatic hydrocarbon group having 6 to 18 carbon atoms, or may be an aliphatic hydrocarbon group having 7 to 18 carbon atoms. may be an aliphatic hydrocarbon group having 7 to 9 carbon atoms, or may be an aliphatic hydrocarbon group having 8 carbon atoms.
  • R a2 may be an aliphatic hydrocarbon group having 5 or more carbon atoms, may be an aliphatic hydrocarbon group having 6 to 18 carbon atoms, or may be an aliphatic hydrocarbon group having 7 to 18 carbon atoms. may be an aliphatic hydrocarbon group having 7 to 9 carbon atoms, or may be an aliphatic hydrocarbon group having 8 carbon atoms.
  • the monomer (Ac) is an unsaturated compound having a (meth)acrylic acid ester structure that leads to the structural unit (Ac).
  • Examples of the monomer (Ac) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, 2,4,6-trimethylheptyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, propargyl ( meth)acrylate and the like.
  • Structural unit (Ad) examples include a structural unit derived from a compound belonging to the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as "structural unit (Ad1)").
  • Examples of compounds belonging to the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m- and p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicy
  • structural unit (Ad2) examples include the following compounds: Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5- Hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2′-hydroxyethyl)bicyclo[2.2.1] Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]h
  • the resin (A) is the following resin [K1] or [K2].
  • Resin [K1] a copolymer composed of a structural unit (Aa), a structural unit (Ab) and a structural unit (Ac);
  • Resin [K2] A copolymer composed of a structural unit (Aa), a structural unit (Ab), a structural unit (Ac) and a structural unit (Ad).
  • Resin (A) is preferably resin [K2]. Further, among the resin [K2], it is preferable that the structural unit (Ad1) is included as the structural unit (Ad), and the structural unit (Aa), the structural unit (Ab), the structural unit (Ac), and the structural unit ( Ad1) is preferred.
  • the resin (A) contains the structural unit (Ad1)
  • its content is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, based on the total structural units constituting the resin (A).
  • the resin (A) contains a structural unit (Ab), and the content thereof is preferably 5 to 98 mol%, preferably 5 to 90 mol%, based on the total structural units constituting the resin (A). It is more preferable to have The content of the structural unit (Ab) may be 50 mol% or more, 65 mol% or more, 70 mol% or more, or 75 mol% or more.
  • the ratio of each structural unit is, with respect to all structural units constituting resin [K1], Structural unit (Aa); 5 to 95 mol%, Structural unit (Ab); 5 to 95 mol%, Structural unit (Ac); preferably 0.001 to 10 mol%, Structural unit (Aa); 10 to 70 mol%, Structural unit (Ab); 30 to 90 mol%, Structural unit (Ac); more preferably 0.01 to 1 mol %.
  • the ratio of the structural units constituting the resin [K1] is within the above range, the solvent solubility and storage stability of the resin composition, and the chemical resistance, heat resistance, and mechanical strength of the resulting film are excellent, which is preferable. .
  • the resin [K1] is, for example, the method described in the document "Experimental Method for Polymer Synthesis” (written by Takayuki Otsu, published by Kagaku Doujin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the It can be manufactured with reference to the cited document described in the literature. Specifically, predetermined amounts of the structural unit (Aa) and the structural unit (Ab), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and, for example, oxygen is replaced with nitrogen to create a deoxygenated atmosphere, A method of heating and keeping warm while stirring can be used.
  • the polymerization initiator, solvent, and the like are not particularly limited, and those commonly used in the field can be used.
  • examples of polymerization initiators include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.).
  • the solvent any solvent can be used as long as it dissolves each monomer.
  • the resin solution obtained by the reaction may be used as it is, or a concentrated or diluted solution may be used. ) may be used.
  • the solvent included in the resin composition of the present invention as the polymerization solvent, the solution after the reaction can be used as it is for the production of the resin composition, thereby simplifying the production process of the resin composition. be able to.
  • the proportion of each structural unit in the total structural units constituting the resin [K2] is the structural unit (Aa): 1 to 90 mol% Structural unit (Ab); 5 to 98 mol%, Structural unit (Ac); 0.001 to 10 mol%, Structural unit (Ad); preferably 1 to 50 mol%, Structural unit (Aa); 3 to 80 mol%, Structural unit (Ab); 17 to 90 mol%, Structural unit (Ac); 0.005 to 5 mol%, Structural unit (Ad); more preferably 3 to 40 mol%, Structural unit (Aa); 3 to 80 mol%, Structural unit (Ab); 50 to 90 mol%, Structural unit (Ac): 0.01 to 1 mol%, Structural unit (Ad); more preferably 3 to 40 mol %.
  • the resin [K2] contains only the structural unit (Ad1) as the structural unit (Ad), Structural unit (Aa); 1 to 70 mol%, Structural unit (Ab); 5 to 90 mol%, Structural unit (Ac); 0.001 to 10 mol%, Structural unit (Ad1); preferably 1 to 50 mol%, Structural unit (Aa); 3 to 50 mol%, Structural unit (Ab); 20 to 90 mol%, Structural unit (Ac); 0.005 to 5 mol%, Structural unit (Ad1); more preferably 5 to 40 mol%, Structural unit (Aa); 3 to 50 mol%, Structural unit (Ab); 50 to 90 mol%, Structural unit (Ac): 0.01 to 1 mol%, Structural unit (Ad1); more preferably 5 to 40 mol %.
  • the resin [K2] contains only the structural unit (Ad2) as the structural unit (Ad), Structural unit (Aa); 1 to 90 mol%, Structural unit (Ab); 5 to 98 mol%, Structural unit (Ac); 0.001 to 10 mol%, Structural unit (Ad2); preferably 1 to 50 mol%, Structural unit (Aa); 3 to 70 mol%, Structural unit (Ab); 20 to 90 mol%, Structural unit (Ac); 0.005 to 5 mol%, Structural unit (Ad2); more preferably 3 to 40 mol%, Structural unit (Aa); 3 to 70 mol%, Structural unit (Ab); 50 to 90 mol%, Structural unit (Ac): 0.01 to 1 mol%, Structural unit (Ad2); more preferably 3 to 40 mol %.
  • Resin [K2] can be produced by the same method as resin [K1].
  • the polystyrene equivalent weight average molecular weight (Mw) of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 20,000, and particularly preferably is between 5,000 and 10,000.
  • Mw weight-average molecular weight
  • the dispersion degree [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the degree of dispersion is within the above range, the obtained film tends to have excellent chemical resistance.
  • the resin (A) contains the structural unit (Ad1)
  • its acid value is preferably 30 mg-KOH/g or more and 180 mg-KOH/g or less, more preferably 40 mg-KOH/g or more and 150 mg-KOH/g or less, More preferably, it is 50 mg-KOH/g or more and 135 mg-KOH/g or less.
  • the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin, and can be determined by titration using an aqueous potassium hydroxide solution. When the acid value of the resin (A) is within the above range, the obtained film tends to have excellent adhesion to the substrate.
  • the content of the resin (A) is preferably 30 to 99 with respect to the solid content of the resin composition of the present invention. % by mass, more preferably 35 to 80% by mass, and even more preferably 40 to 70% by mass.
  • the content of the resin (A) is within the above range, the resulting film tends to be excellent in heat resistance, adhesion to the substrate, and chemical resistance.
  • the solid content of the resin composition refers to the amount obtained by subtracting the content of the solvent (E) from the total amount of the resin composition of the present invention.
  • the polymerizable compound (C) is a monomer that reacts with heat or the action of the polymerization initiator (D).
  • the monomer include compounds having an ethylenically unsaturated bond, preferably (meth)acrylic compounds. and more preferably a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group.
  • the (meth)acrylic compound having one (meth)acryloyl group includes the same compounds as the monomers leading to the structural unit (Aa), the structural unit (Ab) and the structural unit (Ac) of the resin (A). mentioned.
  • the (meth)acrylic compounds having two (meth)acryloyl groups include 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, 1,6-hexanediol di(meth) Acrylates, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol Bis (acryloyloxyethyl) ether of A, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, ethylene oxide-modified neopentyl glycol di(meth)acrylate, 3-methylpentanediol diol (Meth)acrylate and
  • Examples of (meth)acrylic compounds having three or more (meth)acryloyl groups include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, Ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri Pentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hept
  • the (meth)acrylic compound is preferably a (meth)acrylic compound having three or more (meth)acryloyl groups, more preferably dipentaerythritol hexa(meth)acrylate.
  • the resin composition of the present invention contains a polymerizable compound (C)
  • its content is preferably 20 to 200 parts by mass, more preferably 30 to 150 parts by mass, relative to 100 parts by mass of the resin (A). be.
  • the content of the polymerizable compound (C) is within the above range, the resulting film can have good chemical resistance and mechanical strength.
  • the polymerization initiator (D) is not particularly limited as long as it is a compound that generates an active radical, an acid, etc. by the action of light or heat and can initiate the polymerization of the polymerizable compound (C). agent can be used.
  • a polymerization initiator containing at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds is preferred, and O-acyloxy More preferred is a polymerization initiator containing a chromium compound. These polymerization initiators tend to have high sensitivity and high transmittance in the visible light region.
  • O-acyloxime compound is a compound having a structure represented by formula (D1). Below, * represents a bond.
  • O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane- 1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6- ⁇ 2-methyl-4-(3,3-dimethyl-2,4 -dioxacyclopentanylmethyloxy)benzoyl ⁇ -9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)
  • An alkylphenone compound is a compound having a structure represented by formula (D2-1) or a structure represented by formula (D2-2). In these structures, the benzene ring may have a substituent.
  • Examples of compounds having a structure represented by formula (D2-1) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-( 4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1- On is mentioned.
  • Commercially available products such as Irgacure (registered trademark) 369, 907 and 379 (manufactured by BASF Corporation) may also be used.
  • a polymerization initiator having a group capable of causing chain transfer which is described in JP-T-2002-544205, may be used.
  • Examples of compounds having a structure represented by formula (D2-2) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-( 2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, ⁇ , ⁇ -di ethoxyacetophenone, benzyl dimethyl ketal; From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (D2-1).
  • triazine compounds examples include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxy naphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl )-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4- Bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri
  • Acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. Commercially available products such as Irgacure 819 (manufactured by BASF Japan Ltd.) may also be used.
  • Biimidazole compounds include, for example, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2,3-dichlorophenyl)-4 ,4′,5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis(2-chlorophenyl)-4, 4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetra(alkoxyphenyl)biimidazole, 2,2′-bis( 2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra
  • the polymerization initiator (D) includes benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like.
  • H polymerization initiation aid
  • An acid generator can also be used as the polymerization initiator (D).
  • acid generators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl-methyl- Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, and benzoin tosylate.
  • the content of the polymerization initiator (D) is the total content of the resin (A) and the polymerizable compound (C). It is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 1 to 8 parts by mass, based on 100 parts by mass.
  • the content of the polymerization initiator (D) is within the above range, the resulting pattern tends to have a high visible light transmittance.
  • the polymerization initiation aid (H) is a compound used together with the polymerization initiator (D) to accelerate the polymerization of the polymerizable compound (C) whose polymerization is initiated by the polymerization initiator (D), or a sensitizer. is.
  • polymerization initiation aids examples include thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.
  • Examples of thiazoline compounds include compounds represented by formulas (H1-1) to (H1-3), compounds described in JP-A-2008-65319, and the like.
  • amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N,N-dimethyl p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis( ethylmethylamino)benzophenone and the like, among which 4,4'-bis(diethylamino)benzophenone is preferred.
  • EAB-F manufactured by Hodogaya Chemical Industry Co., Ltd.
  • Alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxy anthracene, 2-ethyl-9,10-dibutoxyanthracene and the like.
  • Thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
  • Carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N -phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.
  • the content of the polymerization initiation aid (H) is It is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 10 parts by mass, per 100 parts by mass of the total content of the compound (C).
  • the amount of the polymerization initiation aid (H) is within the above range, the pattern tends to be formed with higher sensitivity.
  • Leveling agent (B) examples include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.
  • silicone-based surfactants include surfactants that have siloxane bonds in their molecules.
  • Toray Silicone DC3PA, Toray SH7PA, Toray DC11PA, Toray SH21PA, Toray SH28PA, Toray SH29PA, Toray SH30PA, Toray SH8400 (trade name: Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC), etc. .
  • fluorine-based surfactants examples include surfactants having a fluorocarbon chain in the molecule.
  • silicone-based surfactants having fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in the molecule.
  • Megafac registered trademark
  • Megafac BL20 Megafac F475, F477 and F443 (manufactured by DIC Corporation) and the like can be mentioned.
  • the leveling agent (B) When the leveling agent (B) is contained, its content is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more, relative to the total amount of the resin composition. It is 0.1% by mass or less, more preferably 0.005% by mass or more and 0.07% by mass or less.
  • Antioxidants (F) include phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, and amine antioxidants. Among them, phenol-based antioxidants are preferable because the resulting film is less colored.
  • Phenolic antioxidants include, for example, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy -3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 3,9-bis[2- ⁇ 3-(3-tert-butyl-4-hydroxy-5 -methylphenyl)propionyloxy ⁇ -1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2′-methylenebis(6-tert-butyl-4-methyl phenol), 4,4′-butylidenebis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(2-tert-butyl-5-methylphenol), 2,2′-thiobis(6- tert-butyl
  • sulfur-based antioxidants examples include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3 - lauryl thiopropionate).
  • a commercially available product may be used as the sulfur-based antioxidant.
  • Examples of commercially available sulfur-based antioxidants include Sumilizer (registered trademark) TPL-R and TP-D (all manufactured by Sumitomo Chemical Co., Ltd.).
  • Phosphorus antioxidants include, for example, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra(tridecyl)-1,1, 3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite.
  • a commercially available product may be used as the phosphorus antioxidant.
  • phosphorus-based antioxidants include, for example, Irgafos (registered trademark) 168, 12, 38 (all manufactured by BASF Corporation), ADEKA STAB 329K, and ADEKA STAB PEP36 (all manufactured by ADEKA Corporation). is mentioned.
  • amine antioxidants examples include N,N'-di-sec-butyl-p-phenylenediamine, N,N'-diisopropyl-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine.
  • Commercially available products may be used as the amine-based antioxidant.
  • Commercially available amine-based antioxidants include, for example, Sumilizer (registered trademark) BPA, BPA-M1, and 4ML (all manufactured by Sumitomo Chemical Co., Ltd.).
  • the resin composition of the present invention contains an antioxidant (F)
  • its content is preferably 0.1 per 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). More than 5 parts by mass and less than 5 parts by mass, more preferably more than 0.5 parts by mass and less than 3 parts by mass.
  • the content of the antioxidant (F) is within the above range, the obtained film tends to be excellent in heat resistance and pencil hardness.
  • the polycarboxylic acid (G1) is at least one compound selected from the group consisting of polycarboxylic anhydrides and polycarboxylic acids.
  • a polyvalent carboxylic acid is a compound having two or more carboxy groups, and a polyvalent carboxylic acid anhydride is an anhydride of a polyvalent carboxylic acid.
  • the molecular weight of the polycarboxylic acid (G1) is preferably 3000 or less, more preferably 1000 or less.
  • polyvalent carboxylic acid anhydrides examples include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecylsuccinic anhydride, 2-(2-octa -3-enyl)succinic anhydride, 2-(2,4,6-trimethylnon-3-enyl)succinic anhydride, tricarballylic anhydride, 1,2,3,4-butanetetracarboxylic acid di Chain polyvalent carboxylic anhydride such as anhydride; 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydro Phthalic anhydride, 4-methylhexahydrophthalic anhydride, norbornene dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic
  • polyvalent carboxylic acid examples include chain polyvalent carboxylic acids such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and polyvalent carboxylic acids leading to chain polyvalent carboxylic acid anhydrides.
  • chain carboxylic acid anhydrides and alicyclic polyvalent carboxylic acid anhydrides are preferable, and alicyclic polyvalent Carboxylic anhydrides are more preferred.
  • the resin composition of the present invention contains a polyvalent carboxylic acid (G1)
  • its content is preferably 1 to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). 30 parts by mass, more preferably 2 to 20 parts by mass, and even more preferably 2 to 15 parts by mass.
  • the content of the polycarboxylic acid (G1) is within the above range, the heat resistance and adhesion of the obtained film are excellent.
  • the imidazole compound (G2) is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include compounds known as epoxy curing agents. Among them, the compound represented by formula (G2-1) is preferable.
  • R 31 represents an alkyl group having 1 to 20 carbon atoms, a phenyl group, a benzyl group, or a cyanoalkyl group having 2 to 5 carbon atoms.
  • R 32 to R 34 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group or an acyl group having 1 to 20 carbon atoms, and the alkyl group and the phenyl group; A hydrogen atom contained in may be substituted with a hydroxy group.
  • alkyl groups having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isobutyl group, butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and heptadecyl group. , an undecyl group.
  • Examples of the cyanoalkyl group having 2 to 5 carbon atoms include cyanomethyl group, cyanoethyl group, cyanopropyl group, cyanobutyl group and cyanopentyl group.
  • Halogen atoms include, for example, fluorine, chlorine and bromine atoms.
  • acyl groups having 1 to 20 carbon atoms include formyl, acetyl, propionyl, isobutyryl, valeryl, isovaleryl, pivaloyl, lauroyl, myristoyl and stearoyl groups.
  • imidazole compounds (G2) include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl-4-methylimidazole, and 2-ethylimidazole.
  • the content thereof is preferably 0.1 mass parts per 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). parts or more and 25 parts by mass or less, more preferably 0.2 parts by mass or more and 15 parts by mass or less, and even more preferably 0.5 parts by mass or more and 5 parts by mass or less.
  • the content of the imidazole compound (G2) is within the above range, the resulting film tends to have excellent transparency in the visible light region.
  • the resin composition of the present invention contains a solvent (E).
  • the solvent (E) is not particularly limited, and solvents commonly used in the field can be mentioned.
  • ester solvent solvent (solvent containing -COO- in the molecule but not containing -O-)
  • ether solvent solvent containing -O- in the molecule but not containing -COO-
  • ether ester solvent solvent containing -COO- in the molecule solvent containing -COO- and -O-
  • ketone solvent solvent containing -CO- in the molecule and not containing -COO-
  • alcohol solvent containing OH in the molecule, -O-, - solvents containing no CO- and -COO-
  • aromatic hydrocarbon solvents amide solvents, dimethyl sulfoxide and the like.
  • Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and ⁇ -butyrolactone.
  • Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.
  • propylene glycol monopropyl ether propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol and methylanisole and the like.
  • Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether a
  • Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. etc.
  • Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.
  • Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.
  • Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.
  • organic solvents having a boiling point of 100°C or higher and 200°C or lower at 1 atm are preferable from the viewpoint of coating properties and drying properties.
  • Preferred solvents are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol ethyl methyl ether, cyclohexanone, methoxybutanol and methoxybutyl acetate, and propylene glycol monomethyl ether. More preferred are acetate, propylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, methoxybutanol and methoxybutyl acetate.
  • the content of the solvent (E) in the resin composition of the present invention is preferably 60-95% by mass, more preferably 70-95% by mass, relative to the total amount of the resin composition.
  • the solid content of the resin composition of the present invention is preferably 5-40 mass %, more preferably 5-30 mass %.
  • the resin composition of the present invention may contain additives known in the art such as fillers, other polymer compounds, ultraviolet absorbers, chain transfer agents, adhesion promoters, etc. good.
  • the average transmittance is preferably 70% or more, more preferably 80% or more.
  • the average transmittance of the film is preferably 90% or higher, more preferably 95% or higher.
  • This average transmittance was measured on a film having a thickness of 2 ⁇ m after heat curing (100 to 250° C., 5 minutes to 3 hours) using a spectrophotometer under the conditions of a measurement wavelength of 400 to 700 nm. is the average value for the case. Thereby, a film having excellent transparency in the visible light region can be provided.
  • the resin composition of the present invention comprises a resin (A) and a solvent (E), and optionally a polymerizable compound (C), a polymerization initiator (D), a polymerization initiation aid (H), and a leveling agent. (B), antioxidant (F), curing agent (G) and other components can be mixed by a known method. After mixing, it is preferable to filter with a filter having a pore size of about 0.05 to 1.0 ⁇ m.
  • the resin composition of the present invention has excellent solvent solubility, it can be used to form a uniform film.
  • a film can be produced by coating the resin composition of the present invention on a substrate, drying it, and then heating it. More specifically, the film production method of the present invention includes the following steps (1) to (3). Step (1): a step of applying the resin composition of the present invention to a substrate; Step (2): a step of drying the resin composition after application under reduced pressure and/or heating to form a composition layer; Step (3): A step of heating the composition layer.
  • a patterned film can be produced by performing the following steps.
  • Step (1) is a step of applying the resin composition of the present invention to a substrate (underlying substrate).
  • the substrate include glass, metal, plastic, and the like, and a color filter, an insulating film, a conductive film, a driving circuit, and the like may be formed on the substrate.
  • Coating onto the substrate is preferably carried out using a coating device such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.
  • the resin composition may swell around the outer periphery of the substrate, or the resin composition may wrap around the back surface of the substrate.
  • the resin composition that forms a bulge or runs around to the back surface of the substrate causes contamination of equipment and lowers the accuracy of exposure and heating in subsequent steps. Since the resin composition of the present invention has excellent solvent solubility, it is possible to cleanly remove unnecessary resin compositions and to suppress problems caused by unnecessary resin compositions. Moreover, a resin composition having poor solubility in a solvent is not preferred because it may cause clogging of pipes in equipment.
  • Step (2) is a step of drying the applied resin composition under reduced pressure and/or by heating to form a composition layer. By performing this step, volatile components such as solvents in the resin composition are removed. Vacuum drying is preferably carried out under a pressure of 50-150 Pa in a temperature range of 20-25°C. Heat drying (pre-baking) may be performed before or after vacuum drying. Heat drying is usually performed using a heating device such as an oven or a hot plate. The temperature for drying by heating is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
  • Step (3) is a step of heating the composition layer (post-baking). Heating is usually performed using a heating device such as an oven or a hot plate.
  • the heating temperature is preferably 130 to 270°C, more preferably 150 to 260°C, still more preferably 200 to 250°C. A heating temperature of 200 to 250° C. can prevent unnecessary solvent from remaining in the film.
  • the heating time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.
  • Step (2a) is a step of exposing the composition layer formed in step (2) through a photomask.
  • the photomask used has a light-shielding portion corresponding to a portion of the composition layer to be removed.
  • the shape of the light shielding portion is not particularly limited, and can be selected according to the intended use.
  • the light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges.
  • Light sources include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like. It is preferable to use an exposure apparatus such as a mask aligner, a stepper, etc., because it is possible to uniformly irradiate the entire exposure surface with parallel rays and to perform accurate alignment between the photomask and the composition layer.
  • the step (2b) is a step of developing the composition layer after exposure.
  • a developer for development By contacting the exposed composition layer with a developer for development, the unexposed portion of the composition layer is dissolved in the developer and removed, thereby forming a patterned composition layer on the substrate.
  • the developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide.
  • the concentration of these alkaline compounds in the aqueous solution is preferably 0.01-10 mass %, more preferably 0.03-5 mass %.
  • the developer may contain a surfactant.
  • the development method may be any of the puddle method, dipping method, spray method, and the like.
  • the substrate may be tilted at any angle during development. It is preferable to wash with water after development.
  • the step (3a) is a step of heating the composition layer after development. By heating in the same manner as in step (3), the patterned composition layer is cured to form a patterned film on the substrate.
  • the film thus obtained is useful, for example, as a color filter substrate used in liquid crystal display devices, organic EL display devices, and electronic paper. This makes it possible to manufacture display devices with high-quality films.
  • the resin composition of the present invention can be used to form an overcoat layer even on a color filter substrate having a colored pattern on its surface.
  • the film thickness of the overcoat layer (the film thickness from the surface of the projections when the surface to be coated has an uneven shape) is preferably 0.5 ⁇ m or more and 5 ⁇ m or less, more preferably 0.5 ⁇ m or more and 3 ⁇ m or less.
  • the width of the concave portion is 1 to 500 ⁇ m
  • the height from the surface of the concave portion to the surface of the convex portion is 0.1 to 20 ⁇ m.
  • the copolymer of the present invention comprises a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms, a structural unit (Ab) having a carbazole ring, and an unsaturated compound having a (meth)acrylic acid ester structure. It is a resin (A) containing a structural unit (Ac) derived from.
  • the above description of the resin (A) contained in the resin composition applies to the copolymer of the present invention.
  • Resin (a1) Resin obtained in Synthesis Example 1
  • Resin (a2) Resin obtained in Synthesis Example 2
  • Resin (a3) Resin obtained in Synthesis Example 3
  • Resin (a4) Obtained in Synthesis Example 4
  • Resin Resin (a5) Resin obtained in Synthesis Example 5
  • Resin (a6) Resin obtained in Synthesis Example 6
  • Resin (a7) Resin obtained in Synthesis Example 7
  • Resin (a8) According to Synthesis Example 8 Obtained Resin Resin (a9): Resin obtained in Synthesis Example 9
  • Resin (a10) Resin obtained in Synthesis Example 10
  • the structural unit (AaI) (3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-9-yl acrylate), building block (AbI) (9-vinylcarbazole), and building block ( AdI) (acrylic acid)
  • the resin (a2) contains the structural unit (AcI) (2-ethylhexyl acrylate)
  • the resin (a3) contains the structural unit (AcII) (butyl acrylate)
  • the resin (a4) to (a6) contains structural unit (AcIII) (tert-butyl acrylate)
  • resin (a7) contains structural unit (AcIV) (isodecyl acrylate).
  • Table 2 shows the ratio of each structural unit in each resin.
  • Resin (a1) a copolymer (resin (a1)) solution having a B-type viscosity (23°C) of 379 mPas and a solid content of 33.4%.
  • the obtained resin (a1) had a weight average molecular weight (Mw) of 21080, a dispersity (Mw/Mn) of 2.76, and an acid value in terms of solid content of 33 mg-KOH/g.
  • Resin (a1) has the following structural units.
  • Resin (a2) a copolymer (resin (a2)) solution having a B-type viscosity (23°C) of 76 mPas and a solid content of 30.5%.
  • the obtained resin (a2) had a weight average molecular weight (Mw) of 19420, a dispersity (Mw/Mn) of 2.86, and an acid value in terms of solid content of 32 mg-KOH/g.
  • Resin (a2) has the following structural units.
  • Resin (a3) a copolymer (resin (a3)) solution having a B-type viscosity (23°C) of 84 mPas and a solid content of 31.0%.
  • the obtained resin (a3) had a weight average molecular weight (Mw) of 20520, a dispersity (Mw/Mn) of 3.02, and an acid value in terms of solid content of 31 mg-KOH/g.
  • Resin (a3) has the following structural units.
  • Resin (a4) a copolymer (resin (a4)) solution having a B-type viscosity (23°C) of 85 mPas and a solid content of 31.7%.
  • the obtained resin (a4) had a weight average molecular weight (Mw) of 19,900, a dispersity (Mw/Mn) of 2.96, and an acid value in terms of solid content of 30 mg-KOH/g.
  • Resin (a4) has the following structural units.
  • Resin (a4) a copolymer (resin (a4)) solution having a B-type viscosity (23°C) of 98 mPas and a solid content of 31.8%.
  • the obtained resin (a7) had a weight average molecular weight (Mw) of 18590, a dispersity (Mw/Mn) of 2.89, and an acid value in terms of solid content of 30 mg-KOH/g.
  • Resin (a7) has the following structural units.
  • resin (a8) a copolymer (resin (a8)) solution having a B-type viscosity (23°C) of 98 mPas and a solid content of 31.8%.
  • the obtained resin (a8) had a weight average molecular weight (Mw) of 20590, a dispersity (Mw/Mn) of 2.98, and an acid value of 37 mg-KOH/g in terms of solid content.
  • Resin (a8) has the same structural units as resin (a4).
  • resin (a9) a copolymer (resin (a9)) solution having a B-type viscosity (23°C) of 143 mPas and a solid content of 32.5%.
  • the obtained resin (a9) had a weight average molecular weight (Mw) of 23320, a dispersity (Mw/Mn) of 3.11, and an acid value of 44 mg-KOH/g in terms of solid content.
  • Resin (a9) has the same structural units as resin (a4).
  • resin (a10) a copolymer (resin (a10)) solution having a B-type viscosity (23°C) of 125 mPas and a solid content of 31.8%.
  • the obtained resin (a10) had a weight average molecular weight (Mw) of 22640, a dispersity (Mw/Mn) of 3.11, and an acid value of 44 mg-KOH/g in terms of solid content.
  • Resin (a10) has the same structural units as resin (a4).
  • HLC-8120GPC manufactured by Tosoh Corporation
  • the ratio (Mw/Mn) of the polystyrene equivalent weight average molecular weight (Mw) to the number average molecular weight (Mn) obtained above was taken as the degree of dispersion.

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Abstract

The purpose of the present invention is to provide a resin composition comprising a copolymer that has a constituent unit which has a carbazole ring, said resin composition having excellent solvent solubility.　A resin composition according to the present invention comprises a resin (A) and a solvent. The resin (A) is a copolymer including: a constituent unit (Aa) which is derived from an unsaturated compound having a cyclic ether structure with 2-4 carbon atoms; a constituent unit (Ab) which has a carbazole ring that may have a substituent; and a constituent unit (Ac) which is derived from an unsaturated compound that has a (meth)acrylic acid ester structure.

Description

樹脂組成物、膜及び共重合体Resin composition, membrane and copolymer
　本発明は、樹脂組成物、膜及び共重合体に関する。 The present invention relates to resin compositions, membranes and copolymers.
　近年の液晶表示装置では、オーバーコートなどの膜を形成するために、樹脂組成物が用いられる。このような樹脂組成物として、特許文献１（特開２００６－１７１１６０号公報）には、メタクリル酸及び３，４－エポキシトリシクロ［５．２．１．０２，６］デシルアクリレートを重合させた共重合体を含む樹脂組成物が記載されている。 In recent liquid crystal display devices, a resin composition is used to form a film such as an overcoat. As such a resin composition, Patent Document 1 (Japanese Unexamined Patent Application Publication No. 2006-171160) discloses polymerizing methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate. A resin composition is described that includes a copolymer of
　特許文献２（国際公開第２０１２／０５３３７７号）には、カルバゾール化合物を含む、電子デバイス用高屈折率樹脂組成物が記載されている。 Patent Document 2 (International Publication No. 2012/053377) describes a high refractive index resin composition for electronic devices containing a carbazole compound.
特開２００６－１７１１６０号公報JP 2006-171160 A 国際公開第２０１２／０５３３７７号WO2012/053377
　本発明は、カルバゾール環を有する構成単位を有する共重合体を含む樹脂組成物は、溶剤溶解性が低いとの問題を知見してなされたものである。溶剤溶解性が低い樹脂組成物は、均一な膜形成が難しい、溶剤による拭き取りが難しい、等の問題がある。 The present invention was made based on the discovery of the problem that a resin composition containing a copolymer having a structural unit having a carbazole ring has low solvent solubility. Resin compositions with low solvent solubility have problems such as difficulty in forming a uniform film and difficulty in wiping off with a solvent.
　本発明は、カルバゾール環を有する構成単位を有する共重合体を含む樹脂組成物であって、溶剤溶解性に優れた樹脂組成物、当該樹脂組成物により形成された膜、及び当該樹脂組成物に用いることができる共重合体を提供することを目的とする。 The present invention is a resin composition containing a copolymer having a structural unit having a carbazole ring, the resin composition having excellent solvent solubility, a film formed from the resin composition, and the resin composition An object is to provide a copolymer that can be used.
　本発明は、以下の発明を含む。
　〔１〕　樹脂（Ａ）及び溶剤を含み、
　前記樹脂（Ａ）は、炭素数２～４の環状エーテル構造を有する不飽和化合物に由来する構成単位（Ａａ）と、置換基を有していてもよいカルバゾール環を有する構成単位（Ａｂ）と、（メタ）アクリル酸エステル構造を有する不飽和化合物に由来する構成単位（Ａｃ）と、含む共重合体であり、
　前記構成単位（Ａｃ）は、下記式（Ａｃ）で表される、樹脂組成物。
Figure JPOXMLDOC01-appb-I000006
［式（Ａｃ）中、Ｒａ１は、水素原子又は炭素数１～４のアルキル基を表す。
　Ｒａ２は、炭素数１～２０の脂肪族炭化水素基を表す。］ The present invention includes the following inventions.
[1] containing a resin (A) and a solvent,
The resin (A) comprises a structural unit (Aa) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms, and a structural unit (Ab) having a carbazole ring which may have a substituent. , A copolymer containing a structural unit (Ac) derived from an unsaturated compound having a (meth) acrylic acid ester structure,
A resin composition in which the structural unit (Ac) is represented by the following formula (Ac).
Figure JPOXMLDOC01-appb-I000006
[In formula (Ac), R a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R a2 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms. ]
　〔２〕　前記構成単位（Ａａ）は、不飽和脂環式炭化水素がエポキシ化された構造を有する、〔１〕に記載の樹脂組成物。
　〔３〕　前記不飽和脂環式炭化水素がエポキシ化された構造は、式（Ａａ－１）で表される構成単位及び式（Ａａ－２）で表される構成単位からなる群から選択される少なくとも１種を含む、〔２〕に記載の樹脂組成物。
Figure JPOXMLDOC01-appb-I000007
［式（Ａａ－１）及び式（Ａａ－２）中、Ｒｂ１及びＲｂ２は、水素原子又は炭素数１～４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
　Ｘｂ１及びＸｂ２は、単結合、＊－Ｒｂ３－、＊－Ｒｂ３－Ｏ－、＊－Ｒｂ３－Ｓ－又は＊－Ｒｂ３－ＮＨ－を表す。
　Ｒｂ３は、炭素数１～６のアルカンジイル基を表す。
　＊は、Ｏとの結合手を表す。］ [2] The resin composition according to [1], wherein the structural unit (Aa) has a structure in which an unsaturated alicyclic hydrocarbon is epoxidized.
[3] The structure obtained by epoxidizing the unsaturated alicyclic hydrocarbon is selected from the group consisting of structural units represented by formula (Aa-1) and structural units represented by formula (Aa-2). The resin composition according to [2], comprising at least one of
Figure JPOXMLDOC01-appb-I000007
[In the formulas (Aa-1) and (Aa-2), R b1 and R b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. may be substituted.
X b1 and X b2 each represent a single bond, *-R b3 -, *-R b3 -O-, *-R b3 -S- or *-R b3 -NH-.
R b3 represents an alkanediyl group having 1 to 6 carbon atoms.
* represents a bond with O. ]
　〔４〕　前記構成単位（Ａｂ）は、式（Ａｂ－１）で表される構成単位である、〔１〕～〔３〕のいずれか１項に記載の樹脂組成物。
Figure JPOXMLDOC01-appb-I000008
［式（Ａｂ－１）中、Ｒ１は、水素原子、メチル基、またはヒドロキシメチル基を表す。
　Ｒ２～Ｒ９は、互いに独立に、水素原子、ハロゲン原子、炭素数１～２０の飽和炭化水素基又は炭素数６～２０のアリール基を表し、該飽和炭化水素基に含まれる水素原子は、アルコキシ基又はアリール基で置換されていてもよい。
　Ｘは、単結合、炭素数１以上のアルカンジイル基、もしくは直鎖状又は分枝鎖状の下記の式（Ｖ）で表される基を表す。
Figure JPOXMLDOC01-appb-I000009
（式（Ｖ）中、前記ｌは、０以上の整数を表す。ｍは、１以上の整数を表す。）］
　〔５〕　重合開始剤を含む、〔１〕～〔４〕のいずれか１項に記載の樹脂組成物。
　〔６〕　〔１〕～〔５〕のいずれか１項に記載の樹脂組成物から形成された膜。
　〔７〕　炭素数２～４の環状エーテル構造を有する不飽和化合物に由来する構成単位（Ａａ）と、置換基を有していてもよいカルバゾール環を有する構成単位（Ａｂ）と、アルキル（メタ）アクリレートを有する不飽和化合物に由来する構成単位（Ａｃ）と、含む共重合体であり、
　前記構成単位（Ａｃ）は、下記式（Ａｃ）で表される、共重合体。
Figure JPOXMLDOC01-appb-I000010
［式（Ａｃ）中、Ｒａ１は、水素原子又は炭素数１～４のアルキル基を表す。
　Ｒａ２は、炭素数１～２０の脂肪族炭化水素基を表す。］ [4] The resin composition according to any one of [1] to [3], wherein the structural unit (Ab) is a structural unit represented by formula (Ab-1).
Figure JPOXMLDOC01-appb-I000008
[In formula (Ab-1), R 1 represents a hydrogen atom, a methyl group, or a hydroxymethyl group.
R 2 to R 9 each independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is , an alkoxy group or an aryl group.
X represents a single bond, an alkanediyl group having 1 or more carbon atoms, or a linear or branched group represented by the following formula (V).
Figure JPOXMLDOC01-appb-I000009
(In formula (V), l represents an integer of 0 or more. m represents an integer of 1 or more.)]
[5] The resin composition according to any one of [1] to [4], which contains a polymerization initiator.
[6] A film formed from the resin composition according to any one of [1] to [5].
[7] A structural unit (Aa) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms, a structural unit (Ab) having an optionally substituted carbazole ring, and an alkyl (meth ) a structural unit (Ac) derived from an unsaturated compound having an acrylate, and a copolymer containing
The structural unit (Ac) is a copolymer represented by the following formula (Ac).
Figure JPOXMLDOC01-appb-I000010
[In formula (Ac), R a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R a2 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms. ]
　本発明の樹脂組成物によれば、溶剤溶解性に優れた樹脂組成物を提供することができる。 According to the resin composition of the present invention, it is possible to provide a resin composition with excellent solvent solubility.
　本明細書において、各成分として例示する化合物は、特に断りのない限り、単独で又は複数種を組合せて使用することができる。 Unless otherwise specified, the compounds exemplified as components in this specification can be used alone or in combination.
　［樹脂組成物］
　本発明の樹脂組成物は、樹脂（以下、樹脂（Ａ）と称する。）及び溶剤（以下、溶剤（Ｅ）と称する。）を含み、樹脂（Ａ）は、炭素数２～４の環状エーテル構造を有する構成単位（Ａａ）（以下「構成単位（Ａａ）」と称する。）と、置換基を有していてもよいカルバゾール環を有する構成単位（Ａｂ）（以下「構成単位（Ａｂ）」と称する。）と、（メタ）アクリル酸エステル構造を有する不飽和化合物に由来する構成単位（Ａｃ）（以下「構成単位（Ａｃ）」と称する。）、を含む共重合体である。本明細書において、「（メタ）アクリル酸」とは、アクリル酸及びメタクリル酸よりなる群から選ばれる少なくとも１種の化合物を表す。「（メタ）アクリロイル」及び「（メタ）アクリレート」等の表記も、同様の意味を有する。本発明の樹脂組成物は、樹脂（Ａ）が構成単位（Ａａ）と構成単位（Ａｂ）と構成単位（Ａｃ）とを含む共重合体であることにより、溶剤溶解性に優れた樹脂組成物を提供することができる。 [Resin composition]
The resin composition of the present invention contains a resin (hereinafter referred to as resin (A)) and a solvent (hereinafter referred to as solvent (E)), and the resin (A) is a cyclic ether having 2 to 4 carbon atoms. A structural unit (Aa) having a structure (hereinafter referred to as "structural unit (Aa)") and a structural unit (Ab) having an optionally substituted carbazole ring (hereinafter referred to as "structural unit (Ab)" and a structural unit (Ac) derived from an unsaturated compound having a (meth)acrylic acid ester structure (hereinafter referred to as “structural unit (Ac)”). As used herein, "(meth)acrylic acid" represents at least one compound selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth)acryloyl" and "(meth)acrylate" have the same meaning. The resin composition of the present invention has excellent solvent solubility because the resin (A) is a copolymer containing the structural unit (Aa), the structural unit (Ab), and the structural unit (Ac). can be provided.
　本発明の樹脂組成物は、重合性化合物（以下、重合性化合物（Ｃ）と称する。）を含んでいてもよい。重合性化合物（Ｃ）を含む場合には、重合開始剤（以下、重合開始剤（Ｄ）と称する。）も含むことが好ましい。また、本発明の樹脂組成物は、他の成分、例えば、重合開始助剤（以下、重合開始助剤（Ｈ）と称する。）、レベリング剤（以下、レベリング剤（Ｂ）と称する。）、酸化防止剤（以下、酸化防止剤（Ｆ）と称する。）、硬化剤（以下、硬化剤（Ｇ）と称する。）等を含んでいてもよい。硬化剤（Ｇ）としては、多価カルボン酸（以下、多価カルボン酸（Ｇ１）と称する。）、イミダゾール化合物（以下、イミダゾール化合物（Ｇ２）と称する。）等が例示される。 The resin composition of the present invention may contain a polymerizable compound (hereinafter referred to as polymerizable compound (C)). When the polymerizable compound (C) is contained, it is preferable to also contain a polymerization initiator (hereinafter referred to as polymerization initiator (D)). The resin composition of the present invention also contains other components such as a polymerization initiation aid (hereinafter referred to as polymerization initiation aid (H)), a leveling agent (hereinafter referred to as a leveling agent (B)), It may contain an antioxidant (hereinafter referred to as antioxidant (F)), a curing agent (hereinafter referred to as curing agent (G)), and the like. Examples of the curing agent (G) include polycarboxylic acids (hereinafter referred to as polycarboxylic acids (G1)), imidazole compounds (hereinafter referred to as imidazole compounds (G2)), and the like.
　＜樹脂（Ａ）＞
　樹脂（Ａ）は、構成単位（Ａａ）と、構成単位（Ａｂ）と、構成単位（Ａｃ）と、を含む共重合体である。該共重合体は、さらに、構成単位（Ａａ）、構成単位（Ａｂ）又は構成単位（Ａｃ）と共重合可能であり、かつ、構成単位（Ａａ）、構成単位（Ａｂ）及び構成単位（Ａｃ）以外の構成単位（以下、構成単位（Ａｄ）と称する。）をさらに含んでもよい。樹脂（Ａ）は、構成単位（Ａａ）、構成単位（Ａｂ）及び構成単位（Ａｃ）を、それぞれ２種以上含んでいてもよい。 <Resin (A)>
The resin (A) is a copolymer containing a structural unit (Aa), a structural unit (Ab) and a structural unit (Ac). The copolymer is further copolymerizable with the structural unit (Aa), the structural unit (Ab) or the structural unit (Ac), and the structural unit (Aa), the structural unit (Ab) and the structural unit (Ac ) (hereinafter referred to as a structural unit (Ad)). The resin (A) may contain two or more kinds of each of the structural units (Aa), the structural units (Ab) and the structural units (Ac).
　〔１〕　構成単位（Ａａ）
　構成単位（Ａａ）は、炭素数２～４の環状エーテル構造（例えば、オキシラン環、オキセタン環及びテトラヒドロフラン環からなる群から選ばれる少なくとも１種）を有する不飽和化合物から導くことができる。炭素数２～４の環状エーテル構造を有する不飽和化合物から導かれる構成単位とは、該不飽和化合物を単量体として用いて共重合体を製造することによって得ることができる。あるいは、他の構成単位（以下、構成単位（Ａａ’）と称する。）に、炭素数２～４の環状エーテル構造を有する化合物を反応させることによって得ることもできる。 [1] Structural unit (Aa)
The structural unit (Aa) can be derived from an unsaturated compound having a cyclic ether structure with 2 to 4 carbon atoms (eg, at least one selected from the group consisting of oxirane ring, oxetane ring and tetrahydrofuran ring). A structural unit derived from an unsaturated compound having a cyclic ether structure with 2 to 4 carbon atoms can be obtained by producing a copolymer using the unsaturated compound as a monomer. Alternatively, it can be obtained by reacting another structural unit (hereinafter referred to as structural unit (Aa')) with a compound having a cyclic ether structure having 2 to 4 carbon atoms.
　構成単位（Ａａ）を導く、炭素数２～４の環状エーテル構造を有する不飽和化合物は、例えば、オキシラニル基とエチレン性不飽和結合とを有する単量体（以下、単量体（Ａａ１）と称する。）、オキセタニル基とエチレン性不飽和結合とを有する単量体（以下、単量体（Ａａ２）と称する。）、テトラヒドロフリル基とエチレン性不飽和結合とを有する単量体（以下、単量体（Ａａ３）と称する。）が挙げられる。 The unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms leading to the structural unit (Aa) is, for example, a monomer having an oxiranyl group and an ethylenically unsaturated bond (hereinafter, monomer (Aa1) and ), a monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter referred to as monomer (Aa2)), a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as referred to as a monomer (Aa3)).
　単量体（Ａａ１）は、例えば、直鎖状又は分枝鎖状の不飽和脂肪族炭化水素がエポキシ化された構造を有する単量体（以下、単量体（Ａａ１－１）と称する。）、及び不飽和脂環式炭化水素がエポキシ化された構造を有する単量体（以下、単量体（Ａａ１－２）と称する。）が挙げられる。構成単位（Ａａ）を導く単量体としては、得られる膜の耐熱性、耐薬品性等の信頼性をより高くすることができる点で、単量体（Ａａ１）であることが好ましい。さらに、樹脂組成物の保存安定性が優れるという点で、単量体（Ａａ１－２）がより好ましい。 The monomer (Aa1) is, for example, a monomer having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter referred to as monomer (Aa1-1). ), and a monomer having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter referred to as monomer (Aa1-2)). As the monomer leading to the structural unit (Aa), the monomer (Aa1) is preferable in that the heat resistance, chemical resistance, etc. of the obtained film can be further enhanced. Furthermore, the monomer (Aa1-2) is more preferable in terms of excellent storage stability of the resin composition.
　単量体（Ａａ１－１）としては、グリシジル（メタ）アクリレート、β－メチルグリシジル（メタ）アクリレート、β－エチルグリシジル（メタ）アクリレート、グリシジルビニルエーテル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、α－メチル－ｏ－ビニルベンジルグリシジルエーテル、α－メチル－ｍ－ビニルベンジルグリシジルエーテル、α－メチル－ｐ－ビニルベンジルグリシジルエーテル、２，３－ビス（グリシジルオキシメチル）スチレン、２，４－ビス（グリシジルオキシメチル）スチレン、２，５－ビス（グリシジルオキシメチル）スチレン、２，６－ビス（グリシジルオキシメチル）スチレン、２，３，４－トリス（グリシジルオキシメチル）スチレン、２，３，５－トリス（グリシジルオキシメチル）スチレン、２，３，６－トリス（グリシジルオキシメチル）スチレン、３，４，５－トリス（グリシジルオキシメチル）スチレン、２，４，６－トリス（グリシジルオキシメチル）スチレン等が挙げられる。 Examples of the monomer (Aa1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether and m-vinylbenzyl glycidyl. ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxy methyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxy methyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4, 6-tris(glycidyloxymethyl)styrene and the like.
　単量体（Ａａ１－２）としては、ビニルシクロヘキセンモノオキサイド、１，２－エポキシ－４－ビニルシクロヘキサン（例えば、セロキサイド２０００；（株）ダイセル製）、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート（例えば、サイクロマーＡ４００；（株）ダイセル製）、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート（例えば、サイクロマーＭ１００；（株）ダイセル製）、式（Ｉ）で表される化合物及び式（ＩＩ）で表される化合物等が挙げられる。 Examples of the monomer (Aa1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, Celoxide 2000; manufactured by Daicel Corporation), and 3,4-epoxycyclohexylmethyl (meth)acrylate. (for example, Cychromer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cychromer M100; manufactured by Daicel Corporation), the compound represented by formula (I) and the formula A compound represented by (II) and the like can be mentioned.
Figure JPOXMLDOC01-appb-I000011
Figure JPOXMLDOC01-appb-I000011
［式（Ｉ）及び式（ＩＩ）中、Ｒb1及びＲb2は、水素原子又は炭素数１～４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
　Ｘb1及びＸb2は、単結合、＊－Ｒb3－、＊－Ｒb3－Ｏ－、＊－Ｒb3－Ｓ－又は＊－Ｒb3－ＮＨ－を表す。
　Ｒb3は、炭素数１～６のアルカンジイル基を表す。
　＊は、Ｏとの結合手を表す。］ [In formula (I) and formula (II), R b1 and R b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. good too.
X b1 and X b2 each represent a single bond, *-R b3 -, *-R b3 -O-, *-R b3 -S- or *-R b3 -NH-.
R b3 represents an alkanediyl group having 1 to 6 carbon atoms.
* represents a bond with O. ]
　炭素数１～４のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等が挙げられる。
　水素原子がヒドロキシで置換されたアルキル基としては、ヒドロキシメチル基、１－ヒドロキシエチル基、２－ヒドロキシエチル基、１－ヒドロキシプロピル基、２－ヒドロキシプロピル基、３－ヒドロキシプロピル基、１－ヒドロキシ－１－メチルエチル基、２－ヒドロキシ－１－メチルエチル基、１－ヒドロキシブチル基、２－ヒドロキシブチル基、３－ヒドロキシブチル基、４－ヒドロキシブチル基等が挙げられる。 Examples of alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.
Alkyl groups in which hydrogen atoms are substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.
　Ｒb1及びＲb2としては、好ましくは水素原子、メチル基、ヒドロキシメチル基、１－ヒドロキシエチル基及び２－ヒドロキシエチル基が挙げられ、より好ましくは水素原子及びメチル基が挙げられる。 R b1 and R b2 preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.
　アルカンジイル基としては、メチレン基、エチレン基、プロパン－１，２－ジイル基、プロパン－１，３－ジイル基、ブタン－１，４－ジイル基、ペンタン－１，５－ジイル基、ヘキサン－１，６－ジイル基等が挙げられる。 The alkanediyl group includes methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane- A 1,6-diyl group and the like can be mentioned.
　Ｘb1及びＸb2としては、好ましくは単結合、メチレン基、エチレン基、＊－ＣＨ２－Ｏ－、＊－ＣＨ２ＣＨ２－Ｏ－が挙げられ、より好ましくは単結合、＊－ＣＨ２ＣＨ２－Ｏ－が挙げられる。＊はＯとの結合手を表す。 X b1 and X b2 are preferably single bond, methylene group, ethylene group, *-CH 2 -O- and *-CH 2 CH 2 -O-, more preferably single bond and *-CH 2 CH 2 —O— is included. * represents a bond with O.
　式（Ｉ）で表される化合物としては、式（Ｉ－１）～式（Ｉ－１５）のいずれかで表される化合物等が挙げられ、好ましくは式（Ｉ－１）、式（Ｉ－３）、式（Ｉ－５）、式（Ｉ－７）、式（Ｉ－９）又は式（Ｉ－１１）～式（Ｉ－１５）で表される化合物が挙げられ、より好ましくは式（Ｉ－１）、式（Ｉ－７）、式（Ｉ－９）又は式（Ｉ－１５）で表される化合物が挙げられる。 Examples of the compound represented by formula (I) include compounds represented by any one of formulas (I-1) to (I-15), preferably formula (I-1), formula (I -3), formula (I-5), formula (I-7), formula (I-9) or compounds represented by formulas (I-11) to (I-15), more preferably Examples include compounds represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000013
　式（ＩＩ）で表される化合物としては、式（ＩＩ－１）～式（ＩＩ－１５）のいずれかで表される化合物等が挙げられ、好ましくは式（ＩＩ－１）、式（ＩＩ－３）、式（ＩＩ－５）、式（ＩＩ－７）、式（ＩＩ－９）又は式（ＩＩ－１１）～式（ＩＩ－１５）で表される化合物が挙げられ、より好ましくは式（ＩＩ－１）、式（ＩＩ－７）、式（ＩＩ－９）又は式（ＩＩ－１５）で表される化合物が挙げられる。 Examples of the compound represented by formula (II) include compounds represented by any one of formulas (II-1) to (II-15), preferably formula (II-1), formula (II -3), formula (II-5), formula (II-7), formula (II-9) or compounds represented by formulas (II-11) to (II-15), more preferably Examples include compounds represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000014
Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000015
　式（Ｉ）で表される化合物及び式（ＩＩ）で表される化合物は、それぞれ単独で用いても、２種以上を併用してもよい。これらを併用する場合、これらの含有比率〔式（Ｉ）で表される化合物：式（ＩＩ）で表される化合物〕はモル基準で、好ましくは５：９５～９５：５、より好ましくは２０：８０～８０：２０である。例えば、式（Ｉ－１）で表される化合物と、式（ＩＩ－１）で表される化合物とを５０：５０で含む混合物を用いることができる。 The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination of two or more. When these are used in combination, the content ratio of these [compound represented by formula (I): compound represented by formula (II)] is on a molar basis, preferably 5:95 to 95:5, more preferably 20 :80 to 80:20. For example, a mixture containing a compound represented by formula (I-1) and a compound represented by formula (II-1) at a ratio of 50:50 can be used.
　単量体（Ａａ２）としては、オキセタニル基と（メタ）アクリロイルオキシ基とを有する単量体がより好ましい。単量体（Ａａ２）としては、３－メチル－３－メタクリルロイルオキシメチルオキセタン、３－メチル－３－アクリロイルオキシメチルオキセタン、３－エチル－３－メタクリロイルオキシメチルオキセタン、３－エチル－３－アクリロイルオキシメチルオキセタン、３－メチル－３－メタクリロイルオキシエチルオキセタン、３－メチル－３－アクリロイルオキシエチルオキセタン、３－エチル－３－メタクリロイルオキシエチルオキセタン、３－エチル－３－アクリロイルオキシエチルオキセタン等が挙げられる。 A monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable as the monomer (Aa2). Examples of the monomer (Aa2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyl Oxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane and the like. be done.
　単量体（Ａａ３）としては、テトラヒドロフリル基と（メタ）アクリロイルオキシ基とを有する単量体が好ましい。単量体（Ａａ３）としては、テトラヒドロフルフリルアクリレート（例えば、ビスコートＶ＃１５０、大阪有機化学工業（株）製）、テトラヒドロフルフリルメタクリレート等が挙げられる。 As the monomer (Aa3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is preferable. Examples of the monomer (Aa3) include tetrahydrofurfuryl acrylate (eg, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.
　構成単位（Ａａ）としては、樹脂組成物の溶剤溶解性、保存安定性、得られる膜の耐薬品性、耐熱性及び機械強度に優れる点で、単量体（Ａａ１－２）から導かれる構成単位であることが好ましく、式（Ａａ－１）又は式（Ａａ－２）で表される構成単位であることがより好ましい。式（Ａａ－１）で表される構成単位は式（Ｉ）で表される化合物より導かれ、式（Ａａ－２）で表される構成単位は式（ＩＩ）で表される化合物より導かれる。 The structural unit (Aa) is a structure derived from the monomer (Aa1-2) in that the solvent solubility and storage stability of the resin composition and the chemical resistance, heat resistance and mechanical strength of the obtained film are excellent. It is preferably a unit, more preferably a structural unit represented by formula (Aa-1) or formula (Aa-2). The structural unit represented by formula (Aa-1) is derived from the compound represented by formula (I), and the structural unit represented by formula (Aa-2) is derived from the compound represented by formula (II). be killed.
Figure JPOXMLDOC01-appb-I000016
［式（Ａａ－１）及び式（Ａａ－２）中、Ｒb１及びＲb２は、水素原子又は炭素数１～４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
　Ｘb１及びＸb２は、単結合、＊－Ｒb３－、＊－Ｒb３－Ｏ－、＊－Ｒb３－Ｓ－又は＊－Ｒb３－ＮＨ－を表す。
　Ｒb３は、炭素数１～６のアルカンジイル基を表す。
　＊は、Ｏとの結合手を表す。］
Figure JPOXMLDOC01-appb-I000016
[In the formulas (Aa-1) and (Aa-2), R b1 and R b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. may be substituted.
X b1 and X b2 each represent a single bond, *-R b3 -, *-R b3 -O-, *-R b3 -S- or *-R b3 -NH-.
R b3 represents an alkanediyl group having 1 to 6 carbon atoms.
* represents a bond with O. ]
　〔２〕　構成単位（Ａｂ）
　構成単位（Ａｂ）は、置換基を有していてもよいカルバゾール環を有する不飽和化合物から導くことができる。該不飽和化合物から導かれる構成単位は、該不飽和化合物を単量体として用いて共重合体を製造することによって得ることができる。
あるいは、他の構成単位（Ａｂ’）に、置換基を有していてもよいカルバゾール環を有する化合物（Ａｂ’’）を反応させることによって得ることもできる。
　樹脂（Ａ）は、構成単位（Ａｂ）を有することにより、得られる膜の屈折率を向上させることができる。 [2] Structural unit (Ab)
The structural unit (Ab) can be derived from an unsaturated compound having an optionally substituted carbazole ring. A structural unit derived from the unsaturated compound can be obtained by producing a copolymer using the unsaturated compound as a monomer.
Alternatively, it can be obtained by reacting another structural unit (Ab') with a compound (Ab'') having a carbazole ring which may have a substituent.
By having the structural unit (Ab), the resin (A) can improve the refractive index of the resulting film.
　構成単位（Ａｂ）を導く不飽和化合物は、好ましくは式（ＩＩＩ）で表される化合物である。 The unsaturated compound leading to the structural unit (Ab) is preferably a compound represented by formula (III).
Figure JPOXMLDOC01-appb-I000017
　［式（ＩＩＩ）中、Ｒ１は、水素原子、メチル基、またはヒドロキシメチル基を表す。
　Ｒ２～Ｒ９は、互いに独立に、水素原子、ハロゲン原子、炭素数１～２０の飽和炭化水素基又は炭素数６～２０のアリール基を表し、該飽和炭化水素基に含まれる水素原子は、アルコキシ基又はアリール基で置換されていてもよい。
　Ｘは、単結合、炭素数１以上のアルカンジイル基、もしくは直鎖状又は分枝鎖状の下記の式（Ｖ）で表される基を表す。
Figure JPOXMLDOC01-appb-I000017
[In formula (III), R 1 represents a hydrogen atom, a methyl group, or a hydroxymethyl group.
R 2 to R 9 each independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is , an alkoxy group or an aryl group.
X represents a single bond, an alkanediyl group having 1 or more carbon atoms, or a linear or branched group represented by the following formula (V).
Figure JPOXMLDOC01-appb-I000018
（式（Ｖ）中、前記ｌは、０以上の整数を表す。ｍは、１以上の整数を表す。）］
Figure JPOXMLDOC01-appb-I000018
(In formula (V), l represents an integer of 0 or more. m represents an integer of 1 or more.)]
　式（ＩＩＩ）で表される化合物としては、Ｎ－ビニルカルバゾール、Ｎ－アリルカルバゾール、Ｎ－（メタ）アクリロイルカルバゾール、２－（９－カルバゾリル）エチル（メタ）アクリレート、２－（９－カルバゾリル）エトキシエチル（メタ）アクリレート、２－（９－カルバゾリル）－２－メチルエチル（メタ）アクリレート、２－（９－カルバゾリル）－１－メチルエチル（メタ）アクリレート等が挙げられる。中でも、Ｎ－ビニルカルバゾール、Ｎ－アリルカルバゾール、２－（９－カルバゾリル）エチル（メタ）アクリレートが好ましい。 Compounds represented by formula (III) include N-vinylcarbazole, N-allylcarbazole, N-(meth)acryloylcarbazole, 2-(9-carbazolyl)ethyl (meth)acrylate, 2-(9-carbazolyl) ethoxyethyl (meth)acrylate, 2-(9-carbazolyl)-2-methylethyl (meth)acrylate, 2-(9-carbazolyl)-1-methylethyl (meth)acrylate and the like. Among them, N-vinylcarbazole, N-allylcarbazole and 2-(9-carbazolyl)ethyl (meth)acrylate are preferred.
　〔３〕　構成単位（Ａｃ）
　構成単位（Ａｃ）は、（メタ）アクリル酸エステル構造を有する不飽和化合物から導くことができる。該不飽和化合物から導かれる構成単位は、該不飽和化合物を単量体として用いて共重合体を製造することによって得ることができる。
　あるいは、他の構成単位（Ａｃ’）に、（メタ）アクリル酸エステル構造を有する化合物（Ａｃ’’）を反応させることによって得ることもできる。
　樹脂（Ａ）は、構成単位（Ａｃ）を有することにより、樹脂組成物の溶剤溶解性を向上させることができる。 [3] Structural unit (Ac)
The structural unit (Ac) can be derived from an unsaturated compound having a (meth)acrylic acid ester structure. A structural unit derived from the unsaturated compound can be obtained by producing a copolymer using the unsaturated compound as a monomer.
Alternatively, it can be obtained by reacting another structural unit (Ac') with a compound (Ac'') having a (meth)acrylate structure.
By having the structural unit (Ac), the resin (A) can improve the solvent solubility of the resin composition.
　構成単位（Ａｃ）は、下記式（Ａｃ）で表される。 The structural unit (Ac) is represented by the following formula (Ac).
Figure JPOXMLDOC01-appb-I000019
Figure JPOXMLDOC01-appb-I000019
　式（Ａｃ）中、Ｒａ１は、水素原子又は炭素数１～４のアルキル基を表す。
　Ｒａ２は、炭素数１～２０の脂肪族炭化水素基を表す。 In formula (Ac), R a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R a2 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
　Ｒａ１を表す炭素数１～４のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基及びブチル基等が挙げられる。
　Ｒａ１は、水素原子又はメチル基であることが好ましく、水素原子であることがより好ましい。 Examples of the alkyl group having 1 to 4 carbon atoms representing R a1 include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group.
R a1 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
　Ｒａ２を表す炭素数１～２０の脂肪族炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、オクタデセニル基、イコシル基等の直鎖状脂肪族炭化水素基；イソプロピル基、イソブチル基、ｔｅｒｔ－ブチル基、イソペンチル基、イソデシル基、ネオペンチル基、２－エチルヘキシル基等の分岐鎖状脂肪族炭化水素基；が挙げられる。
　Ｒａ２は、水素原子又は炭素数４～２０の脂肪族炭化水素基が好ましく、炭素数４～１２の脂肪族炭化水素基がより好ましく、炭素数４～１０の脂肪族炭化水素基がさらに好ましい。具体的には、ブチル基、ｔｅｒｔ－ブチル基、２－エチルヘキシル基、及びイソデシル基が挙げられる。Ｒａ２は、炭素数５以上の脂肪族炭化水素基であってもよく、炭素数６～１８の脂肪族炭化水素基であってもよく、炭素数７～１８の脂肪族炭化水素基であってもよく、炭素数７～９の脂肪族炭化水素基であってもよく、炭素数８の脂肪族炭化水素基であってもよい。
　また、Ｒａ２としては、 The aliphatic hydrocarbon group having 1 to 20 carbon atoms representing R a2 includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group. , tetradecyl group, hexadecyl group, octadecyl group, octadecenyl group, icosyl group, and other linear aliphatic hydrocarbon groups; isopropyl group, isobutyl group, tert-butyl group, isopentyl group, isodecyl group, neopentyl group, 2-ethylhexyl group branched chain aliphatic hydrocarbon groups;
R a2 is preferably a hydrogen atom or an aliphatic hydrocarbon group having 4 to 20 carbon atoms, more preferably an aliphatic hydrocarbon group having 4 to 12 carbon atoms, and still more preferably an aliphatic hydrocarbon group having 4 to 10 carbon atoms. . Specific examples include butyl, tert-butyl, 2-ethylhexyl, and isodecyl groups. R a2 may be an aliphatic hydrocarbon group having 5 or more carbon atoms, may be an aliphatic hydrocarbon group having 6 to 18 carbon atoms, or may be an aliphatic hydrocarbon group having 7 to 18 carbon atoms. may be an aliphatic hydrocarbon group having 7 to 9 carbon atoms, or may be an aliphatic hydrocarbon group having 8 carbon atoms.
In addition, as R a2 ,
　構成単位（Ａｃ）を導く、（メタ）アクリル酸エステル構造を有する不飽和化合物を単量体（Ａｃ）とする。単量体（Ａｃ）としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレート、２，４，６－トリメチルヘプチル（メタ）アクリレート、ドデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、アリル（メタ）アクリレート、プロパルギル（メタ）アクリレート等が挙げられる。 The monomer (Ac) is an unsaturated compound having a (meth)acrylic acid ester structure that leads to the structural unit (Ac). Examples of the monomer (Ac) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, 2,4,6-trimethylheptyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, propargyl ( meth)acrylate and the like.
　〔４〕　構成単位（Ａｄ）
　構成単位（Ａｄ）としては、不飽和カルボン酸及び不飽和カルボン酸無水物からなる群に属する化合物によって導かれる構成単位（以下「構成単位（Ａｄ１）」と称する。）が挙げられる。不飽和カルボン酸及び不飽和カルボン酸無水物からなる群に属する化合物としては、例えば、アクリル酸、メタクリル酸、クロトン酸、ｏ－、ｍ－、ｐ－ビニル安息香酸等の不飽和モノカルボン酸；
　マレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸、３－ビニルフタル酸、４－ビニルフタル酸、３，４，５，６－テトラヒドロフタル酸、１，２，３，６－テトラヒドロフタル酸、ジメチルテトラヒドロフタル酸、１，４－シクロヘキセンジカルボン酸等の不飽和ジカルボン酸；
　メチル－５－ノルボルネン－２，３－ジカルボン酸、５－カルボキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジカルボキシビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシ－５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシ－５－エチルビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシ－６－メチルビシクロ［２．２．１］ヘプト－２－エン、５－カルボキシ－６－エチルビシクロ［２．２．１］ヘプト－２－エン等のカルボキシ基を含有するビシクロ不飽和化合物；
　無水マレイン酸、シトラコン酸無水物、イタコン酸無水物、３－ビニルフタル酸無水物、４－ビニルフタル酸無水物、３，４，５，６－テトラヒドロフタル酸無水物、１，２，３，６－テトラヒドロフタル酸無水物、ジメチルテトラヒドロフタル酸無水物、５，６－ジカルボキシビシクロ［２．２．１］ヘプト－２－エン無水物等の不飽和ジカルボン酸無水物；こはく酸モノ〔２－（メタ）アクリロイルオキシエチル〕、フタル酸モノ〔２－（メタ）アクリロイルオキシエチル〕等の２価以上の多価カルボン酸の不飽和モノ〔（メタ）アクリロイルオキシアルキル〕エステル；
　α－（ヒドロキシメチル）アクリル酸などの、同一分子中にヒドロキシ基及びカルボキシ基を含有する不飽和アクリレート等が挙げられる。 [4] Structural unit (Ad)
Examples of the structural unit (Ad) include a structural unit derived from a compound belonging to the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as "structural unit (Ad1)"). Examples of compounds belonging to the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m- and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;
methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclounsaturated compounds containing a carboxy group;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinic mono[2-( meth)acryloyloxyethyl], unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl] phthalate;
Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid.
　構成単位（Ａｄ１）以外の構成単位（Ａｄ）（以下「構成単位（Ａｄ２）」と称する。）としては、例えば、次の化合物：
　２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート等のヒドロキシ基含有（メタ）アクリル酸エステル；
　マレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジエチル等のジカルボン酸ジエステル；
　ビシクロ［２．２．１］ヘプト－２－エン、５－メチルビシクロ［２．２．１］ヘプト－２－エン、５－エチルビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシビシクロ［２．２．１］ヘプト－２－エン、５－ヒドロキシメチルビシクロ［２．２．１］ヘプト－２－エン、５－（２’－ヒドロキシエチル）ビシクロ［２．２．１］ヘプト－２－エン、５－メトキシビシクロ［２．２．１］ヘプト－２－エン、５－エトキシビシクロ［２．２．１］ヘプト－２－エン、５，６－ジヒドロキシビシクロ［２．２．１］ヘプト－２－エン等のビシクロ不飽和化合物；
　Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－ベンジルマレイミド、Ｎ－スクシンイミジル－３－マレイミドベンゾエート、Ｎ－スクシンイミジル－４－マレイミドブチレート等のジカルボニルイミド誘導体；
　スチレン、α－メチルスチレン、ｏ－ビニルトルエン、ｍ－ビニルトルエン、ｐ－ビニルトルエン、ｐ－メトキシスチレン、（メタ）アクリロニトリル、塩化ビニル、塩化ビニリデン、（メタ）アクリルアミド、酢酸ビニル、１，３－ブタジエン、イソプレン及び２，３－ジメチル－１，３－ブタジエン等から導かれる構成単位が挙げられる。樹脂（Ａ）は、構成単位（Ａｄ１）を有していることが好ましい。 Examples of the structural unit (Ad) other than the structural unit (Ad1) (hereinafter referred to as "structural unit (Ad2)") include the following compounds:
Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;
bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5- Hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2′-hydroxyethyl)bicyclo[2.2.1] Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2 .1] Bicyclounsaturated compounds such as hept-2-ene;
Dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate;
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, (meth)acrylonitrile, vinyl chloride, vinylidene chloride, (meth)acrylamide, vinyl acetate, 1,3- Structural units derived from butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like are included. The resin (A) preferably has a structural unit (Ad1).
　〔５〕　各構成単位の比率
　樹脂（Ａ）は、以下の樹脂［Ｋ１］または［Ｋ２］である。
樹脂［Ｋ１］：構成単位（Ａａ）、構成単位（Ａｂ）及び構成単位（Ａｃ）から構成される共重合体；
樹脂［Ｋ２］：構成単位（Ａａ）、構成単位（Ａｂ）、構成単位（Ａｃ）及び構成単位（Ａｄ）から構成される共重合体。
　樹脂（Ａ）は、樹脂［Ｋ２］であることが好ましい。さらに、樹脂［Ｋ２］の中でも、構成単位（Ａｄ）として構成単位（Ａｄ１）を含むことが好ましく、構成単位（Ａａ）と、構成単位（Ａｂ）と、構成単位（Ａｃ）と、構成単位（Ａｄ１）とからなる樹脂が好ましい。
　樹脂（Ａ）が構成単位（Ａｄ１）を含む場合、その含有率は、樹脂（Ａ）を構成する全構成単位に対して、１～５０モル％が好ましく、２～４０モル％がより好ましい。
　樹脂（Ａ）は、構成単位（Ａｂ）を含み、その含有率は、樹脂（Ａ）を構成する全構成単位に対して、５～９８モル％であることが好ましく、５～９０モル％であることがより好ましい。構成単位（Ａｂ）の含有率は、５０モル％以上、６５モル％以上、７０モル％以上、７５モル％以上であってもよい。 [5] Ratio of Each Structural Unit The resin (A) is the following resin [K1] or [K2].
Resin [K1]: a copolymer composed of a structural unit (Aa), a structural unit (Ab) and a structural unit (Ac);
Resin [K2]: A copolymer composed of a structural unit (Aa), a structural unit (Ab), a structural unit (Ac) and a structural unit (Ad).
Resin (A) is preferably resin [K2]. Further, among the resin [K2], it is preferable that the structural unit (Ad1) is included as the structural unit (Ad), and the structural unit (Aa), the structural unit (Ab), the structural unit (Ac), and the structural unit ( Ad1) is preferred.
When the resin (A) contains the structural unit (Ad1), its content is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, based on the total structural units constituting the resin (A).
The resin (A) contains a structural unit (Ab), and the content thereof is preferably 5 to 98 mol%, preferably 5 to 90 mol%, based on the total structural units constituting the resin (A). It is more preferable to have The content of the structural unit (Ab) may be 50 mol% or more, 65 mol% or more, 70 mol% or more, or 75 mol% or more.
　樹脂［Ｋ１］において、各構成単位の比率は、樹脂［Ｋ１］を構成する全構成単位に対して、
構成単位（Ａａ）；５～９５モル％、
構成単位（Ａｂ）；５～９５モル％、
構成単位（Ａｃ）；０．００１～１０モル％、であることが好ましく、
構成単位（Ａａ）；１０～７０モル％、
構成単位（Ａｂ）；３０～９０モル％、
構成単位（Ａｃ）；０．０１～１モル％、であることがより好ましい。 In resin [K1], the ratio of each structural unit is, with respect to all structural units constituting resin [K1],
Structural unit (Aa); 5 to 95 mol%,
Structural unit (Ab); 5 to 95 mol%,
Structural unit (Ac); preferably 0.001 to 10 mol%,
Structural unit (Aa); 10 to 70 mol%,
Structural unit (Ab); 30 to 90 mol%,
Structural unit (Ac); more preferably 0.01 to 1 mol %.
　樹脂［Ｋ１］を構成する構成単位の比率が、上記の範囲内にあると、樹脂組成物の溶剤溶解性、保存安定性、得られる膜の耐薬品性、耐熱性及び機械強度に優れるので好ましい。 When the ratio of the structural units constituting the resin [K1] is within the above range, the solvent solubility and storage stability of the resin composition, and the chemical resistance, heat resistance, and mechanical strength of the resulting film are excellent, which is preferable. .
　樹脂［Ｋ１］は、例えば、文献「高分子合成の実験法」（大津隆行著　発行所：（株）化学同人　第１版第１刷　１９７２年３月１日発行）に記載された方法及び当該文献に記載された引用文献を参考にして製造することができる。
　具体的には、構成単位（Ａａ）及び構成単位（Ａｂ）の所定量、重合開始剤及び溶剤等を反応容器中に入れて、例えば、窒素により酸素を置換することにより、脱酸素雰囲気にし、攪拌しながら、加熱及び保温する方法が挙げられる。なお、重合開始剤及び溶剤等は、特に限定されず、当該分野で通常使用されているものを使用することができる。重合開始剤としては、例えば、アゾ化合物（２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２，４－ジメチルバレロニトリル）等）や有機過酸化物（ベンゾイルペルオキシド等）が挙げられ、溶剤としては、各モノマーを溶解するものであればよく、樹脂組成物に用いられる後述の溶剤等が挙げられる。 The resin [K1] is, for example, the method described in the document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Doujin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the It can be manufactured with reference to the cited document described in the literature.
Specifically, predetermined amounts of the structural unit (Aa) and the structural unit (Ab), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and, for example, oxygen is replaced with nitrogen to create a deoxygenated atmosphere, A method of heating and keeping warm while stirring can be used. The polymerization initiator, solvent, and the like are not particularly limited, and those commonly used in the field can be used. Examples of polymerization initiators include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). As the solvent, any solvent can be used as long as it dissolves each monomer.
　本発明の樹脂組成物を調製する際、反応により得られた樹脂溶液をそのまま使用してもよいし、濃縮あるいは希釈した溶液を使用してもよいし、再沈殿等の方法で固体（粉体）として取り出したものを使用してもよい。特に、重合溶剤として、本発明の樹脂組成物に含める溶剤を使用することにより、反応後の溶液を樹脂組成物の製造にそのまま使用することができるため、樹脂組成物の製造工程を簡略化することができる。 When preparing the resin composition of the present invention, the resin solution obtained by the reaction may be used as it is, or a concentrated or diluted solution may be used. ) may be used. In particular, by using the solvent included in the resin composition of the present invention as the polymerization solvent, the solution after the reaction can be used as it is for the production of the resin composition, thereby simplifying the production process of the resin composition. be able to.
　樹脂［Ｋ２］において、各構成単位の比率は、樹脂［Ｋ２］を構成する全構成単位中、構成単位（Ａａ）；１～９０モル％、
構成単位（Ａｂ）；５～９８モル％、
構成単位（Ａｃ）；０．００１～１０モル％、
構成単位（Ａｄ）；１～５０モル％、であることが好ましく、
構成単位（Ａａ）；３～８０モル％、
構成単位（Ａｂ）；１７～９０モル％、
構成単位（Ａｃ）；０．００５～５モル％、
構成単位（Ａｄ）；３～４０モル％、であることがより好ましく、
構成単位（Ａａ）；３～８０モル％、
構成単位（Ａｂ）；５０～９０モル％、
構成単位（Ａｃ）；０．０１～１モル％、
構成単位（Ａｄ）；３～４０モル％、であることがさらに好ましい。 In the resin [K2], the proportion of each structural unit in the total structural units constituting the resin [K2] is the structural unit (Aa): 1 to 90 mol%
Structural unit (Ab); 5 to 98 mol%,
Structural unit (Ac); 0.001 to 10 mol%,
Structural unit (Ad); preferably 1 to 50 mol%,
Structural unit (Aa); 3 to 80 mol%,
Structural unit (Ab); 17 to 90 mol%,
Structural unit (Ac); 0.005 to 5 mol%,
Structural unit (Ad); more preferably 3 to 40 mol%,
Structural unit (Aa); 3 to 80 mol%,
Structural unit (Ab); 50 to 90 mol%,
Structural unit (Ac): 0.01 to 1 mol%,
Structural unit (Ad); more preferably 3 to 40 mol %.
　樹脂［Ｋ２］のうち、構成単位（Ａｄ）として構成単位（Ａｄ１）のみを含む場合、
構成単位（Ａａ）；１～７０モル％、
構成単位（Ａｂ）；５～９０モル％、
構成単位（Ａｃ）；０．００１～１０モル％、
構成単位（Ａｄ１）；１～５０モル％、であることが好ましく、
構成単位（Ａａ）；３～５０モル％、
構成単位（Ａｂ）；２０～９０モル％、
構成単位（Ａｃ）；０．００５～５モル％、
構成単位（Ａｄ１）；５～４０モル％、であることがより好ましく、
構成単位（Ａａ）；３～５０モル％、
構成単位（Ａｂ）；５０～９０モル％、
構成単位（Ａｃ）；０．０１～１モル％、
構成単位（Ａｄ１）；５～４０モル％、であることがさらに好ましい。 When the resin [K2] contains only the structural unit (Ad1) as the structural unit (Ad),
Structural unit (Aa); 1 to 70 mol%,
Structural unit (Ab); 5 to 90 mol%,
Structural unit (Ac); 0.001 to 10 mol%,
Structural unit (Ad1); preferably 1 to 50 mol%,
Structural unit (Aa); 3 to 50 mol%,
Structural unit (Ab); 20 to 90 mol%,
Structural unit (Ac); 0.005 to 5 mol%,
Structural unit (Ad1); more preferably 5 to 40 mol%,
Structural unit (Aa); 3 to 50 mol%,
Structural unit (Ab); 50 to 90 mol%,
Structural unit (Ac): 0.01 to 1 mol%,
Structural unit (Ad1); more preferably 5 to 40 mol %.
　樹脂［Ｋ２］のうち、構成単位（Ａｄ）として構成単位（Ａｄ２）のみを含む場合、
構成単位（Ａａ）；１～９０モル％、
構成単位（Ａｂ）；５～９８モル％、
構成単位（Ａｃ）；０．００１～１０モル％、
構成単位（Ａｄ２）；１～５０モル％、であることが好ましく、
構成単位（Ａａ）；３～７０モル％、
構成単位（Ａｂ）；２０～９０モル％、
構成単位（Ａｃ）；０．００５～５モル％、
構成単位（Ａｄ２）；３～４０モル％、であることがより好ましく、
構成単位（Ａａ）；３～７０モル％、
構成単位（Ａｂ）；５０～９０モル％、
構成単位（Ａｃ）；０．０１～１モル％、
構成単位（Ａｄ２）；３～４０モル％、であることがさらに好ましい。 When the resin [K2] contains only the structural unit (Ad2) as the structural unit (Ad),
Structural unit (Aa); 1 to 90 mol%,
Structural unit (Ab); 5 to 98 mol%,
Structural unit (Ac); 0.001 to 10 mol%,
Structural unit (Ad2); preferably 1 to 50 mol%,
Structural unit (Aa); 3 to 70 mol%,
Structural unit (Ab); 20 to 90 mol%,
Structural unit (Ac); 0.005 to 5 mol%,
Structural unit (Ad2); more preferably 3 to 40 mol%,
Structural unit (Aa); 3 to 70 mol%,
Structural unit (Ab); 50 to 90 mol%,
Structural unit (Ac): 0.01 to 1 mol%,
Structural unit (Ad2); more preferably 3 to 40 mol %.
　樹脂［Ｋ２］のうち、構成単位（Ａｄ）として構成単位（Ａｄ１）と構成単位（Ａｄ２）との両者を含む場合、
構成単位（Ａａ）；１～７０モル％、
構成単位（Ａｂ）；５～９０モル％、
構成単位（Ａｃ）；０．００１～１０モル％、
構成単位（Ａｄ１）；１～５０モル％、
構成単位（Ａｄ２）；１～４０モル％、であることが好ましく、
構成単位（Ａａ）；３～５０モル％、
構成単位（Ａｂ）；１０～９０モル％、
構成単位（Ａｃ）；０．００５～５モル％、
構成単位（Ａｄ１）；５～３５モル％、
構成単位（Ａｄ２）；１～３０モル％、であることがより好ましく、
構成単位（Ａａ）；３～５０モル％、
構成単位（Ａｂ）；５０～９０モル％、
構成単位（Ａｃ）；０．０１～１モル％、
構成単位（Ａｄ１）；５～３５モル％、
構成単位（Ａｄ２）；１～３０モル％、であることがより好ましい。 When both the structural unit (Ad1) and the structural unit (Ad2) are included as the structural unit (Ad) in the resin [K2],
Structural unit (Aa); 1 to 70 mol%,
Structural unit (Ab); 5 to 90 mol%,
Structural unit (Ac); 0.001 to 10 mol%,
Structural unit (Ad1); 1 to 50 mol%,
Structural unit (Ad2); preferably 1 to 40 mol%,
Structural unit (Aa); 3 to 50 mol%,
Structural unit (Ab); 10 to 90 mol%,
Structural unit (Ac); 0.005 to 5 mol%,
Structural unit (Ad1); 5 to 35 mol%,
Structural unit (Ad2); more preferably 1 to 30 mol%,
Structural unit (Aa); 3 to 50 mol%,
Structural unit (Ab); 50 to 90 mol%,
Structural unit (Ac): 0.01 to 1 mol%,
Structural unit (Ad1); 5 to 35 mol%,
Structural unit (Ad2); more preferably 1 to 30 mol %.
　樹脂［Ｋ２］の構成単位の比率が、上記の範囲内にあると、溶剤溶解性、保存安定性に優れた樹脂組成物が得られ、樹脂組成物を用いて得られる膜の耐薬品性、耐熱性及び機械強度に優れる点で好ましい。樹脂［Ｋ２］は、樹脂［Ｋ１］と同様の方法により製造することができる。 When the ratio of the structural units of the resin [K2] is within the above range, a resin composition having excellent solvent solubility and storage stability is obtained, and the film obtained using the resin composition has chemical resistance, It is preferable in terms of excellent heat resistance and mechanical strength. Resin [K2] can be produced by the same method as resin [K1].
　樹脂（Ａ）のポリスチレン換算の重量平均分子量（Ｍｗ）は、好ましくは３，０００～１００，０００、より好ましくは５，０００～５０，０００、さらに好ましくは５，０００～２０，０００、とりわけ好ましくは５，０００～１０，０００である。樹脂（Ａ）の重量平均分子量（Ｍｗ）が前記の範囲内にあると、樹脂組成物の塗布性が良好となる傾向がある。 The polystyrene equivalent weight average molecular weight (Mw) of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 20,000, and particularly preferably is between 5,000 and 10,000. When the weight-average molecular weight (Mw) of the resin (A) is within the above range, the coating properties of the resin composition tend to be good.
　樹脂（Ａ）の分散度［重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）］は、好ましくは１．１～６．０、より好ましくは１．２～４．０である。分散度が前記の範囲内にあると、得られる膜は耐薬品性に優れる傾向がある。 The dispersion degree [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the degree of dispersion is within the above range, the obtained film tends to have excellent chemical resistance.
　樹脂（Ａ）が構成単位（Ａｄ１）を含む場合、その酸価は、好ましくは３０ｍｇ－ＫＯＨ／ｇ以上１８０ｍｇ－ＫＯＨ／ｇ以下、より好ましくは４０ｍｇ－ＫＯＨ／ｇ以上１５０ｍｇ－ＫＯＨ／ｇ以下、さらに好ましくは５０ｍｇ－ＫＯＨ／ｇ以上１３５ｍｇ－ＫＯＨ／ｇ以下である。ここで酸価は樹脂１ｇを中和するために必要な水酸化カリウムの量（ｍｇ）として測定される値であり、水酸化カリウム水溶液を用いて滴定することにより求めることができる。樹脂（Ａ）の酸価が前記の範囲内にあると、得られる膜は基板との密着性に優れる傾向がある。 When the resin (A) contains the structural unit (Ad1), its acid value is preferably 30 mg-KOH/g or more and 180 mg-KOH/g or less, more preferably 40 mg-KOH/g or more and 150 mg-KOH/g or less, More preferably, it is 50 mg-KOH/g or more and 135 mg-KOH/g or less. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin, and can be determined by titration using an aqueous potassium hydroxide solution. When the acid value of the resin (A) is within the above range, the obtained film tends to have excellent adhesion to the substrate.
　本発明の樹脂組成物が樹脂（Ａ）及び溶剤（Ｅ）以外の成分を含む場合、樹脂（Ａ）の含有率は、本発明の樹脂組成物の固形分に対して、好ましくは３０～９９質量％、より好ましくは３５～８０質量％、さらに好ましくは４０～７０質量％である。樹脂（Ａ）の含有率が前記の範囲内にあると、得られる膜は耐熱性に優れ、かつ基板との密着性及び耐薬品性に優れる傾向がある。ここで、樹脂組成物の固形分とは、本発明の樹脂組成物の総量から溶剤（Ｅ）の含有量を除いた量のことをいう。 When the resin composition of the present invention contains components other than the resin (A) and the solvent (E), the content of the resin (A) is preferably 30 to 99 with respect to the solid content of the resin composition of the present invention. % by mass, more preferably 35 to 80% by mass, and even more preferably 40 to 70% by mass. When the content of the resin (A) is within the above range, the resulting film tends to be excellent in heat resistance, adhesion to the substrate, and chemical resistance. Here, the solid content of the resin composition refers to the amount obtained by subtracting the content of the solvent (E) from the total amount of the resin composition of the present invention.
　＜重合性化合物（Ｃ）＞
　重合性化合物（Ｃ）は、熱又は重合開始剤（Ｄ）の作用により反応するモノマーであり、該モノマーとして、例えば、エチレン性不飽和結合を有する化合物が挙げられ、好ましくは（メタ）アクリル化合物が挙げられ、より好ましくはアクリロイル基及びメタクリロイル基からなる群から選ばれる少なくとも１種の基を有する化合物が挙げられる。 <Polymerizable compound (C)>
The polymerizable compound (C) is a monomer that reacts with heat or the action of the polymerization initiator (D). Examples of the monomer include compounds having an ethylenically unsaturated bond, preferably (meth)acrylic compounds. and more preferably a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group.
　（メタ）アクリロイル基を１つ有する（メタ）アクリル化合物としては、樹脂（Ａ）の、構成単位（Ａａ）、構成単位（Ａｂ）及び構成単位（Ａｃ）を導く単量体と同様の化合物が挙げられる。 The (meth)acrylic compound having one (meth)acryloyl group includes the same compounds as the monomers leading to the structural unit (Aa), the structural unit (Ab) and the structural unit (Ac) of the resin (A). mentioned.
　（メタ）アクリロイル基を２つ有する（メタ）アクリル化合物としては、１，３－ブタンジオールジ（メタ）アクリレート、１，３－ブタンジオール（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジアクリレート、ビスフェノールＡのビス（アクリロイロキシエチル）エーテル、エチレンオキシド変性ビスフェノールＡジ（メタ）アクリレート、プロピレンオキシド変性ネオペンチルグリコールジ（メタ）アクリレート、エチレンオキシド変性ネオペンチルグリコールジ（メタ）アクリレート、３－メチルペンタンジオールジ（メタ）アクリレート等が挙げられる。 The (meth)acrylic compounds having two (meth)acryloyl groups include 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, 1,6-hexanediol di(meth) Acrylates, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol Bis (acryloyloxyethyl) ether of A, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, ethylene oxide-modified neopentyl glycol di(meth)acrylate, 3-methylpentanediol diol (Meth)acrylate and the like.
　（メタ）アクリロイル基を３つ以上有する（メタ）アクリル化合物としては、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリス（２－ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、エチレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールテトラ（メタ）アクリレート、トリペンタエリスリトールペンタ（メタ）アクリレート、トリペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールヘプタ（メタ）アクリレート、トリペンタエリスリトールオクタ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートと酸無水物との反応物、ジペンタエリスリトールペンタ（メタ）アクリレートと酸無水物との反応物、トリペンタエリスリトールヘプタ（メタ）アクリレートと酸無水物との反応物、カプロラクトン変性トリメチロールプロパントリ（メタ）アクリレート、カプロラクトン変性ペンタエリスリトールトリ（メタ）アクリレート、カプロラクトン変性トリス（２－ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、カプロラクトン変性ペンタエリスリトールテトラ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールペンタ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性トリペンタエリスリトールテトラ（メタ）アクリレート、カプロラクトン変性トリペンタエリスリトールペンタ（メタ）アクリレート、カプロラクトン変性トリペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性トリペンタエリスリトールヘプタ（メタ）アクリレート、カプロラクトン変性トリペンタエリスリトールオクタ（メタ）アクリレート、カプロラクトン変性ペンタエリスリトールトリ（メタ）アクリレートと酸無水物との反応物、カプロラクトン変性ジペンタエリスリトールペンタ（メタ）アクリレートと酸無水物との反応物、カプロラクトン変性トリペンタエリスリトールヘプタ（メタ）アクリレートと酸無水物との反応物等が挙げられる。 Examples of (meth)acrylic compounds having three or more (meth)acryloyl groups include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, Ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri Pentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, pentaerythritol tri(meth)acrylate Reaction product of acrylate and acid anhydride, reaction product of dipentaerythritol penta(meth)acrylate and acid anhydride, reaction product of tripentaerythritol hepta(meth)acrylate and acid anhydride, caprolactone-modified trimethylolpropane tri (Meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) ) acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified tripentaerythritol tetra(meth)acrylate, caprolactone-modified tripentaerythritol penta(meth)acrylate, caprolactone-modified tripentaerythritol hexa(meth)acrylate, caprolactone-modified tripentaerythritol hexa(meth)acrylate Pentaerythritol hepta(meth)acrylate, caprolactone-modified tripentaerythritol octa(meth)acrylate, reaction product of caprolactone-modified pentaerythritol tri(meth)acrylate and acid anhydride, caprolactone-modified dipentaerythritol penta(meth)acrylate and acid anhydride caprolactone-modified tripentaerythritol hepta(meth)acrylate reaction products of salts and acid anhydrides, and the like.
　（メタ）アクリル化合物としては、（メタ）アクリルロイル基を３つ以上有する（メタ）アクリル化合物が好ましく、ジペンタエリスリトールヘキサ（メタ）アクリレートがより好ましい。 The (meth)acrylic compound is preferably a (meth)acrylic compound having three or more (meth)acryloyl groups, more preferably dipentaerythritol hexa(meth)acrylate.
　本発明の樹脂組成物が重合性化合物（Ｃ）を含む場合、その含有量は、樹脂（Ａ）１００質量部に対して、好ましくは２０～２００質量部、より好ましくは３０～１５０質量部である。重合性化合物（Ｃ）の含有量が前記の範囲内にあると、得られる膜の耐薬品性及び機械強度を良好にすることができる。 When the resin composition of the present invention contains a polymerizable compound (C), its content is preferably 20 to 200 parts by mass, more preferably 30 to 150 parts by mass, relative to 100 parts by mass of the resin (A). be. When the content of the polymerizable compound (C) is within the above range, the resulting film can have good chemical resistance and mechanical strength.
　＜重合開始剤（Ｄ）＞
　重合開始剤（Ｄ）は、光や熱の作用により活性ラジカル、酸等を発生し、重合性化合物（Ｃ）の重合を開始しうる化合物であれば特に限定されることなく、公知の重合開始剤を用いることができる。重合開始剤（Ｄ）としては、Ｏ－アシルオキシム化合物、アルキルフェノン化合物、トリアジン化合物、アシルホスフィンオキサイド化合物及びビイミダゾール化合物からなる群から選ばれる少なくとも１種を含む重合開始剤が好ましく、Ｏ－アシルオキシム化合物を含む重合開始剤がより好ましい。これらの重合開始剤であると、高感度であり、かつ可視光領域における透過率が高くなる傾向がある。 <Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that generates an active radical, an acid, etc. by the action of light or heat and can initiate the polymerization of the polymerizable compound (C). agent can be used. As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds is preferred, and O-acyloxy More preferred is a polymerization initiator containing a chromium compound. These polymerization initiators tend to have high sensitivity and high transmittance in the visible light region.
　Ｏ－アシルオキシム化合物は、式（Ｄ１）で表される構造を有する化合物である。
以下、＊は結合手を表す。 An O-acyloxime compound is a compound having a structure represented by formula (D1).
Below, * represents a bond.
Figure JPOXMLDOC01-appb-I000020
Figure JPOXMLDOC01-appb-I000020
　Ｏ－アシルオキシム化合物としては、例えば、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）ブタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）オクタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロペンチルプロパン－１－オン－２－イミン、Ｎ－アセトキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタン－１－イミン、Ｎ－アセトキシ－１－［９－エチル－６－｛２－メチル－４－（３，３－ジメチル－２，４－ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝－９Ｈ－カルバゾール－３－イル］エタン－１－イミン、Ｎ－アセトキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－３－シクロペンチルプロパン－１－イミン、Ｎ－ベンゾイルオキシ－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－３－シクロペンチルプロパン－１－オン－２－イミンが挙げられる。イルガキュア（登録商標）ＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ（株）製）、Ｎ－１９１９（（株）ＡＤＥＫＡ製）等の市販品を用いてもよい。 Examples of O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane- 1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4 -dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- 3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1 -on-2-imine. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) may also be used.
　アルキルフェノン化合物は、式（Ｄ２－１）で表される構造又は式（Ｄ２－２）で表される構造を有する化合物である。これらの構造中、ベンゼン環は置換基を有していてもよい。 An alkylphenone compound is a compound having a structure represented by formula (D2-1) or a structure represented by formula (D2-2). In these structures, the benzene ring may have a substituent.
Figure JPOXMLDOC01-appb-I000021
Figure JPOXMLDOC01-appb-I000021
　式（Ｄ２－１）で表される構造を有する化合物としては、例えば、２－メチル－２－モルホリノ－１－（４－メチルスルファニルフェニル）プロパン－１－オン、２－ジメチルアミノ－１－（４－モルホリノフェニル）－２－ベンジルブタン－１－オン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］ブタン－１－オンが挙げられる。イルガキュア（登録商標）３６９、９０７及び３７９（以上、ＢＡＳＦ（株）製）等の市販品を用いてもよい。また、特表２００２－５４４２０５号公報に記載されている、連鎖移動を起こしうる基を有する重合開始剤を用いてもよい。式（Ｄ２－２）で表される構造を有する化合物としては、例えば、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、２－ヒドロキシ－２－メチル－１－〔４－（２－ヒドロキシエトキシ）フェニル〕プロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－（４－イソプロペニルフェニル）プロパン－１－オンのオリゴマー、α，α－ジエトキシアセトフェノン、ベンジルジメチルケタールが挙げられる。感度の点で、アルキルフェノン化合物としては、式（Ｄ２－１）で表される構造を有する化合物が好ましい。 Examples of compounds having a structure represented by formula (D2-1) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-( 4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1- On is mentioned. Commercially available products such as Irgacure (registered trademark) 369, 907 and 379 (manufactured by BASF Corporation) may also be used. Also, a polymerization initiator having a group capable of causing chain transfer, which is described in JP-T-2002-544205, may be used. Examples of compounds having a structure represented by formula (D2-2) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-( 2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-di ethoxyacetophenone, benzyl dimethyl ketal; From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (D2-1).
　トリアジン化合物としては、例えば、２，４－ビス（トリクロロメチル）－６－（４－メトキシフェニル）－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－（４－メトキシナフチル）－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－ピペロニル－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－（４－メトキシスチリル）－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（５－メチルフラン－２－イル）エテニル〕－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（フラン－２－イル）エテニル〕－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（４－ジエチルアミノ－２－メチルフェニル）エテニル〕－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（３，４－ジメトキシフェニル）エテニル〕－１，３，５－トリアジンが挙げられる。 Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxy naphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl )-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4- Bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2 -methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine. be done.
　アシルホスフィンオキサイド化合物としては、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド等が挙げられる。イルガキュア８１９（ＢＡＳＦ・ジャパン（株）製）等の市販品を用いてもよい。 Acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. Commercially available products such as Irgacure 819 (manufactured by BASF Japan Ltd.) may also be used.
　ビイミダゾール化合物としては、例えば、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール、２，２’－ビス（２，３－ジクロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール（例えば、特開平６－７５３７２号公報、特開平６－７５３７３号公報等参照。）、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラ（アルコキシフェニル）ビイミダゾール、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラ（ジアルコキシフェニル）ビイミダゾール、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラ（トリアルコキシフェニル）ビイミダゾール（例えば、特公昭４８－３８４０３号公報、特開昭６２－１７４２０４号公報等参照。）、４，４’，５，５’－位のフェニル基がカルボアルコキシ基により置換されているビイミダゾール化合物（例えば、特開平７－１０９１３号公報等参照）が挙げられる。 Biimidazole compounds include, for example, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2,3-dichlorophenyl)-4 ,4′,5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis(2-chlorophenyl)-4, 4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetra(alkoxyphenyl)biimidazole, 2,2′-bis( 2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxy phenyl)biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.), the phenyl groups at the 4,4′,5,5′-positions are substituted with carboalkoxy groups; and biimidazole compounds (see, for example, JP-A-7-10913).
　さらに重合開始剤（Ｄ）としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン化合物；ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルサルファイド、３，３’，４，４’－テトラ（ｔｅｒｔ－ブチルパーオキシカルボニル）ベンゾフェノン、２，４，６－トリメチルベンゾフェノン等のベンゾフェノン化合物；９，１０－フェナンスレンキノン、２－エチルアントラキノン、カンファーキノン等のキノン化合物；１０－ブチル－２－クロロアクリドン、ベンジル、フェニルグリオキシル酸メチル、チタノセン化合物等が挙げられる。これらは、後述の重合開始助剤（Ｈ）（特にアミン化合物）と組合せて用いることができる。 Furthermore, the polymerization initiator (D) includes benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. These can be used in combination with a polymerization initiation aid (H) (especially an amine compound) described below.
　重合開始剤（Ｄ）としては、酸発生剤も用いることができる。酸発生剤としては、例えば、４－ヒドロキシフェニルジメチルスルホニウムｐ－トルエンスルホナート、４－ヒドロキシフェニルジメチルスルホニウムヘキサフルオロアンチモネート、４－アセトキシフェニルジメチルスルホニウムｐ－トルエンスルホナート、４－アセトキシフェニル・メチル・ベンジルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムｐ－トルエンスルホナート、トリフェニルスルホ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ｐ－トルエンスルホナート、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等のオニウム塩や、ニトロベンジルトシレート、ベンゾイントシレートが挙げられる。 An acid generator can also be used as the polymerization initiator (D). Examples of acid generators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl-methyl- Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, and benzoin tosylate.
　本発明の樹脂組成物が重合性化合物（Ｃ）及び重合開始剤（Ｄ）を含む場合、重合開始剤（Ｄ）の含有量は、樹脂（Ａ）と重合性化合物（Ｃ）との合計含有量１００質量部に対して、好ましくは０．１～３０質量部、より好ましくは０．５～１５質量部、さらに好ましくは１～８質量部である。重合開始剤（Ｄ）の含有量が前記の範囲内にあると、得られるパターンの可視光透過率が高い傾向がある。 When the resin composition of the present invention contains the polymerizable compound (C) and the polymerization initiator (D), the content of the polymerization initiator (D) is the total content of the resin (A) and the polymerizable compound (C). It is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 1 to 8 parts by mass, based on 100 parts by mass. When the content of the polymerization initiator (D) is within the above range, the resulting pattern tends to have a high visible light transmittance.
　＜重合開始助剤（Ｈ）＞
　重合開始助剤（Ｈ）は、重合開始剤（Ｄ）とともに、重合開始剤（Ｄ）によって重合が開始された重合性化合物（Ｃ）の重合を促進するために用いられる化合物、もしくは増感剤である。 <Polymerization initiation aid (H)>
The polymerization initiation aid (H) is a compound used together with the polymerization initiator (D) to accelerate the polymerization of the polymerizable compound (C) whose polymerization is initiated by the polymerization initiator (D), or a sensitizer. is.
　重合開始助剤（Ｈ）としては、チアゾリン化合物、アミン化合物、アルコキシアントラセン化合物、チオキサントン化合物、カルボン酸化合物等が挙げられる。 Examples of polymerization initiation aids (H) include thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.
　チアゾリン化合物としては、式（Ｈ１－１）～式（Ｈ１－３）で表される化合物、特開２００８－６５３１９号公報記載の化合物等が挙げられる。 Examples of thiazoline compounds include compounds represented by formulas (H1-1) to (H1-3), compounds described in JP-A-2008-65319, and the like.
Figure JPOXMLDOC01-appb-I000022
Figure JPOXMLDOC01-appb-I000022
　アミン化合物としては、トリエタノールアミン、メチルジエタノールアミン、トリイソプロパノールアミン、４－ジメチルアミノ安息香酸メチル、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸イソアミル、安息香酸２－ジメチルアミノエチル、４－ジメチルアミノ安息香酸２－エチルヘキシル、Ｎ，Ｎ－ジメチルパラトルイジン、４，４’－ビス（ジメチルアミノ）ベンゾフェノン（通称ミヒラーズケトン）、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、４，４’－ビス（エチルメチルアミノ）ベンゾフェノン等が挙げられ、中でも４，４’－ビス（ジエチルアミノ）ベンゾフェノンが好ましい。ＥＡＢ－Ｆ（保土谷化学工業（株）製）等の市販品を用いてもよい。 Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N,N-dimethyl p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis( ethylmethylamino)benzophenone and the like, among which 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may also be used.
　アルコキシアントラセン化合物としては、９，１０－ジメトキシアントラセン、２－エチル－９，１０－ジメトキシアントラセン、９，１０－ジエトキシアントラセン、２－エチル－９，１０－ジエトキシアントラセン、９，１０－ジブトキシアントラセン、２－エチル－９，１０－ジブトキシアントラセン等が挙げられる。 Alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxy anthracene, 2-ethyl-9,10-dibutoxyanthracene and the like.
　チオキサントン化合物としては、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、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン、１－クロロ－４－プロポキシチオキサントン等が挙げられる。 Thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
　カルボン酸化合物としては、フェニルスルファニル酢酸、メチルフェニルスルファニル酢酸、エチルフェニルスルファニル酢酸、メチルエチルフェニルスルファニル酢酸、ジメチルフェニルスルファニル酢酸、メトキシフェニルスルファニル酢酸、ジメトキシフェニルスルファニル酢酸、クロロフェニルスルファニル酢酸、ジクロロフェニルスルファニル酢酸、Ｎ－フェニルグリシン、フェノキシ酢酸、ナフチルチオ酢酸、Ｎ－ナフチルグリシン、ナフトキシ酢酸等が挙げられる。 Carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N -phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.
　本発明の樹脂組成物が重合性化合物（Ｃ）、重合開始剤（Ｄ）及び重合開始助剤（Ｈ）を含む場合、重合開始助剤（Ｈ）の含有量は、樹脂（Ａ）と重合性化合物（Ｃ）との合計含有量１００質量部に対して、好ましくは０．１～３０質量部、より好ましくは０．２～１０質量部である。重合開始助剤（Ｈ）の量が前記の範囲内にあると、パターンを形成する際、さらに高感度になる傾向にある。 When the resin composition of the present invention contains a polymerizable compound (C), a polymerization initiator (D) and a polymerization initiation aid (H), the content of the polymerization initiation aid (H) is It is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 10 parts by mass, per 100 parts by mass of the total content of the compound (C). When the amount of the polymerization initiation aid (H) is within the above range, the pattern tends to be formed with higher sensitivity.
　＜レベリング剤（Ｂ）＞
　レベリング剤（Ｂ）としては、シリコーン系界面活性剤、フッ素系界面活性剤及びフッ素原子を有するシリコーン系界面活性剤等が挙げられる。これらは、側鎖に重合性基を有していてもよい。 <Leveling agent (B)>
Examples of the leveling agent (B) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.
　シリコーン系界面活性剤としては、分子内にシロキサン結合を有する界面活性剤等が挙げられる。具体的には、トーレシリコーンＤＣ３ＰＡ、同ＳＨ７ＰＡ、同ＤＣ１１ＰＡ、同ＳＨ２１ＰＡ、同ＳＨ２８ＰＡ、同ＳＨ２９ＰＡ、同ＳＨ３０ＰＡ、同ＳＨ８４００（商品名：東レ・ダウコーニング（株）製）、ＫＰ３２１、ＫＰ３２２、ＫＰ３２３、ＫＰ３２４、ＫＰ３２６、ＫＰ３４０、ＫＰ３４１（信越化学工業（株）製）、ＴＳＦ４００、ＴＳＦ４０１、ＴＳＦ４１０、ＴＳＦ４３００、ＴＳＦ４４４０、ＴＳＦ４４４５、ＴＳＦ４４４６、ＴＳＦ４４５２及びＴＳＦ４４６０（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製）等が挙げられる。 Examples of silicone-based surfactants include surfactants that have siloxane bonds in their molecules. Specifically, Toray Silicone DC3PA, Toray SH7PA, Toray DC11PA, Toray SH21PA, Toray SH28PA, Toray SH29PA, Toray SH30PA, Toray SH8400 (trade name: Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC), etc. .
　前記のフッ素系界面活性剤としては、分子内にフルオロカーボン鎖を有する界面活性剤等が挙げられる。具体的には、フロラード（登録商標）ＦＣ４３０、同ＦＣ４３１（住友スリーエム（株）製）、メガファック（登録商標）Ｆ１４２Ｄ、同Ｆ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７７、同Ｆ１８３、同Ｆ５５４、同Ｒ３０、同ＲＳ－７１８－Ｋ（ＤＩＣ（株）製）、エフトップ（登録商標）ＥＦ３０１、同ＥＦ３０３、同ＥＦ３５１、同ＥＦ３５２（三菱マテリアル電子化成（株）製）、サーフロン（登録商標）Ｓ３８１、同Ｓ３８２、同ＳＣ１０１、同ＳＣ１０５（旭硝子（株）製）及びＥ５８４４（（株）ダイキンファインケミカル研究所製）等が挙げられる。 Examples of the fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, Florard FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Florado F171, Flora F172, Flora F173, Flora F177, Flora F183, Flora F554 R30, RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Examples include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Laboratory Co., Ltd.).
　前記のフッ素原子を有するシリコーン系界面活性剤としては、分子内にシロキサン結合及びフルオロカーボン鎖を有する界面活性剤等が挙げられる。具体的には、メガファック（登録商標）Ｒ０８、同ＢＬ２０、同Ｆ４７５、同Ｆ４７７及び同Ｆ４４３（ＤＩＣ（株）製）等が挙げられる。 Examples of the silicone-based surfactants having fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, F477 and F443 (manufactured by DIC Corporation) and the like can be mentioned.
　レベリング剤（Ｂ）を含有する場合、その含有率は、樹脂組成物の総量に対して、好ましくは０．００１質量％以上０.２質量％以下であり、より好ましくは０.００２質量％以上０．１質量％以下であり、さらに好ましくは０.００５質量％以上０．０７質量％以下である。 When the leveling agent (B) is contained, its content is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more, relative to the total amount of the resin composition. It is 0.1% by mass or less, more preferably 0.005% by mass or more and 0.07% by mass or less.
　＜酸化防止剤（Ｆ）＞
　酸化防止剤（Ｆ）としては、フェノール系酸化防止剤、イオウ系酸化防止剤、リン系酸化防止剤、アミン系酸化防止剤が挙げられる。中でも、得られる膜の着色が少ないという点で、フェノール系酸化防止剤が好ましい。 <Antioxidant (F)>
Antioxidants (F) include phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, and amine antioxidants. Among them, phenol-based antioxidants are preferable because the resulting film is less colored.
　フェノール系酸化防止剤としては、例えば、２－ｔｅｒｔ－ブチル－６－（３－ｔｅｒｔ－ブチル－２－ヒドロキシ－５－メチルベンジル）－４－メチルフェニルアクリレート、２－［１－（２－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ペンチルフェニル）エチル］－４，６－ジ－ｔｅｒｔ－ペンチルフェニルアクリレート、３，９－ビス［２－｛３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ｝－１，１－ジメチルエチル］－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン、２，２’－メチレンビス（６－ｔｅｒｔ－ブチル－４－メチルフェノール）、４，４’－ブチリデンビス（６－ｔｅｒｔ－ブチル－３－メチルフェノール）、４，４’－チオビス（２－ｔｅｒｔ－ブチル－５－メチルフェノール）、２，２’－チオビス（６－ｔｅｒｔ－ブチル－４－メチルフェノール）、１，３，５－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、３，３’，３”，５，５’，５”－ヘキサ－ｔｅｒｔ－ブチル－ａ，ａ’，ａ”－（メシチレン－２，４，６－トリイル）トリ－ｐ－クレゾール、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール及び６－［３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロポキシ］－２，４，８，１０－テトラ－ｔｅｒｔ－ブチルジベンズ［ｄ，ｆ］［１，３，２］ジオキサホスフェピンが挙げられる。 前記フェノール系酸化防止剤としては、市販品を使用してもよい。市販されているフェノール系酸化防止剤としては、例えば、スミライザー（登録商標）ＢＨＴ、ＧＭ、ＧＳ、ＧＰ（以上、全て住友化学（株）製）、イルガノックス（登録商標）１０１０、１０７６、１３３０、３１１４（以上、全てＢＡＳＦ（株）製）が挙げられる。 Phenolic antioxidants include, for example, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy -3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5 -methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2′-methylenebis(6-tert-butyl-4-methyl phenol), 4,4′-butylidenebis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(2-tert-butyl-5-methylphenol), 2,2′-thiobis(6- tert-butyl-4-methylphenol), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H, 3H,5H)-trione, 3,3′,3″,5,5′,5″-hexa-tert-butyl-a,a′,a″-(mesitylene-2,4,6-triyl)tri- p-cresol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methylphenol and 6-[3-( 3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepine As the phenolic antioxidant, a commercially available product may be used.As a commercially available phenolic antioxidant, for example, Sumilizer (registered trademark) BHT, GM, GS, GP (all of the above Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) 1010, 1076, 1330, 3114 (all of which are manufactured by BASF Corporation).
　イオウ系酸化防止剤としては、例えば、ジラウリル３，３’－チオジプロピオネート、ジミリスチル３，３’－チオジプロピオネート、ジステアリル３，３’－チオジプロピオネート、ペンタエリスリチルテトラキス（３－ラウリルチオプロピオネート）が挙げられる。前記イオウ系酸化防止剤としては、市販品を使用してもよい。市販されているイオウ系酸化防止剤としては、例えば、スミライザー（登録商標）ＴＰＬ－Ｒ、ＴＰ－Ｄ（以上、全て住友化学（株）製）が挙げられる。 Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3 - lauryl thiopropionate). A commercially available product may be used as the sulfur-based antioxidant. Examples of commercially available sulfur-based antioxidants include Sumilizer (registered trademark) TPL-R and TP-D (all manufactured by Sumitomo Chemical Co., Ltd.).
　リン系酸化防止剤としては、例えば、トリオクチルホスファイト、トリラウリルホスファイト、トリデシルホスファイト、トリス（ノニルフェニル）ホスファイト、ジステアリルペンタエリスリトールジホスファイト、テトラ（トリデシル）－１，１，３－トリス（２－メチル－５－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）ブタンジホスファイトが挙げられる。前記リン系酸化防止剤としては、市販品を使用してもよい。市販されているリン系酸化防止剤としては、例えば、イルガフォス（登録商標）１６８、１２、３８（以上、全てＢＡＳＦ（株）製）、アデカスタブ３２９Ｋ、アデカスタブＰＥＰ３６（以上、全て（株）ＡＤＥＫＡ製）が挙げられる。 Phosphorus antioxidants include, for example, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra(tridecyl)-1,1, 3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite. A commercially available product may be used as the phosphorus antioxidant. Commercially available phosphorus-based antioxidants include, for example, Irgafos (registered trademark) 168, 12, 38 (all manufactured by BASF Corporation), ADEKA STAB 329K, and ADEKA STAB PEP36 (all manufactured by ADEKA Corporation). is mentioned.
　アミン系酸化防止剤としては、例えば、Ｎ，Ｎ’－ジ－ｓｅｃ－ブチル－ｐ－フェニレンジアミン、Ｎ，Ｎ’－ジイソプロピル－ｐ－フェニレンジアミン、Ｎ，Ｎ’－ジシクロヘキシル－ｐ－フェニレンジアミン、Ｎ，Ｎ’－ジフェニル－ｐ－フェニレンジアミン、Ｎ，Ｎ’－ビス（２－ナフチル）－ｐ－フェニレンジアミンが挙げられる。前記アミン系酸化防止剤としては、市販品を使用してもよい。市販されているアミン系酸化防止剤としては、例えば、スミライザー（登録商標）ＢＰＡ、ＢＰＡ－Ｍ１、４ＭＬ（以上、全て住友化学（株）製）が挙げられる。 Examples of amine antioxidants include N,N'-di-sec-butyl-p-phenylenediamine, N,N'-diisopropyl-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine. Commercially available products may be used as the amine-based antioxidant. Commercially available amine-based antioxidants include, for example, Sumilizer (registered trademark) BPA, BPA-M1, and 4ML (all manufactured by Sumitomo Chemical Co., Ltd.).
　本発明の樹脂組成物が酸化防止剤（Ｆ）を含む場合、その含有量は、樹脂（Ａ）と重合性化合物（Ｃ）との合計含有量１００質量部に対して、好ましくは０．１質量部以上５質量部以下、より好ましくは０．５質量部以上３質量部以下である。酸化防止剤（Ｆ）の含有量が前記の範囲内にあると、得られる膜は耐熱性及び鉛筆硬度に優れる傾向がある。 When the resin composition of the present invention contains an antioxidant (F), its content is preferably 0.1 per 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). More than 5 parts by mass and less than 5 parts by mass, more preferably more than 0.5 parts by mass and less than 3 parts by mass. When the content of the antioxidant (F) is within the above range, the obtained film tends to be excellent in heat resistance and pencil hardness.
　＜硬化剤（Ｇ）＞
　＜多価カルボン酸（Ｇ１）＞
　多価カルボン酸（Ｇ１）は、多価カルボン酸無水物及び多価カルボン酸からなる群から選ばれる少なくとも１種の化合物である。多価カルボン酸とは、２つ以上のカルボキシ基を有する化合物であり、多価カルボン酸無水物とは、多価カルボン酸の無水物である。多価カルボン酸（Ｇ１）の分子量は、好ましくは３０００以下、より好ましくは１０００以下である。 <Curing agent (G)>
<Polyvalent carboxylic acid (G1)>
The polycarboxylic acid (G1) is at least one compound selected from the group consisting of polycarboxylic anhydrides and polycarboxylic acids. A polyvalent carboxylic acid is a compound having two or more carboxy groups, and a polyvalent carboxylic acid anhydride is an anhydride of a polyvalent carboxylic acid. The molecular weight of the polycarboxylic acid (G1) is preferably 3000 or less, more preferably 1000 or less.
　前記の多価カルボン酸無水物としては、例えば、無水マレイン酸、無水コハク酸、グルタル酸無水物、シトラコン酸無水物、イタコン酸無水物、２－ドデシルコハク酸無水物、２－（２－オクタ－３－エニル）コハク酸無水物、２－（２，４，６－トリメチルノナ－３－エニル）コハク酸無水物、トリカルバリル酸無水物、１，２，３，４－ブタンテトラカルボン酸二無水物等の鎖状多価カルボン酸無水物；３，４，５，６－テトラヒドロフタル酸無水物、１，２，３，６－テトラヒドロフタル酸無水物、ジメチルテトラヒドロフタル酸無水物、ヘキサヒドロフタル酸無水物、４－メチルヘキサヒドロフタル酸無水物、ノルボルネンジカルボン酸無水物、メチルビシクロ［２．２．１］ヘプタン－２，３－ジカルボン酸無水物、ビシクロ［２．２．１］ヘプタン－２，３－ジカルボン酸無水物、ビシクロ［２．２．１］ヘプタ－５－エン－２，３－ジカルボン酸無水物、メチルビシクロ［２．２．１］ヘプタ－５－エン－２，３－ジカルボン酸無水物、シクロペンタンテトラカルボン酸二無水物等の脂環式多価カルボン酸無水物；無水フタル酸、３－ビニルフタル酸無水物、４－ビニルフタル酸無水物、ピロメリット酸無水物、トリメリット酸無水物、ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物、エチレングリコールビス（アンヒドロトリメリテート）、グリセリントリス（アンヒドロトリメリテート）、グリセリンビス（アンヒドロトリメリテート）モノアセテート、１，３，３ａ，４，５，９ｂ－ヘキサヒドロ－５－（テトラヒドロ－２，５－ジオキソ－３－フラニル）ナフト［１，２－ｃ］フラン－１，３－ジオン等の芳香族多価カルボン酸無水物；が挙げられる。アデカハードナ（登録商標）－ＥＨ－７００（商品名（以下同様）、（株）ＡＤＥＫＡ製）、リカシッド（登録商標）－ＨＨ、同－ＴＨ、同－ＭＨ、同ＭＨ－７００（新日本理化（株）製）、エピキニア１２６、同ＹＨ－３０６、同ＤＸ－１２６（油化シェルエポキシ（株）製）等の市販品を用いてもよい。 Examples of the polyvalent carboxylic acid anhydrides include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecylsuccinic anhydride, 2-(2-octa -3-enyl)succinic anhydride, 2-(2,4,6-trimethylnon-3-enyl)succinic anhydride, tricarballylic anhydride, 1,2,3,4-butanetetracarboxylic acid di Chain polyvalent carboxylic anhydride such as anhydride; 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydro Phthalic anhydride, 4-methylhexahydrophthalic anhydride, norbornene dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane -2,3-dicarboxylic anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]hept-5-ene-2, Alicyclic polyvalent carboxylic anhydrides such as 3-dicarboxylic anhydride and cyclopentanetetracarboxylic dianhydride; phthalic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, pyromellitic anhydride , trimellitic anhydride, benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, ethylene glycol bis(anhydro trimellitate), glyceryl tris (anhydro trimellitate), glycerin bis(anhydrotrimellitate) monoacetate, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1, 2-c] aromatic polyvalent carboxylic acid anhydrides such as furan-1,3-dione; Adeka Hardner (registered trademark) -EH-700 (trade name (hereinafter the same), manufactured by ADEKA Co., Ltd.), Rikacid (registered trademark) -HH, -TH, -MH, -MH-700 (Shin Nippon Chemical Co., Ltd. ), Epicinia 126, YH-306, and DX-126 (manufactured by Yuka Shell Epoxy Co., Ltd.).
　前記の多価カルボン酸としては、シュウ酸、マロン酸、アジピン酸、セバシン酸、フマル酸、酒石酸、クエン酸、鎖状多価カルボン酸無水物を導く多価カルボン酸等の鎖状多価カルボン酸；シクロヘキサンジカルボン酸、脂環式多価カルボン酸無水物を導く多価カルボン酸等の脂環式多価カルボン酸；イソフタル酸、テレフタル酸、１，４，５，８－ナフタレンテトラカルボン酸、芳香族多価カルボン酸無水物を導く多価カルボン酸等の芳香族多価カルボン酸；等が挙げられる。 Examples of the polyvalent carboxylic acid include chain polyvalent carboxylic acids such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and polyvalent carboxylic acids leading to chain polyvalent carboxylic acid anhydrides. Acid; cyclohexanedicarboxylic acid, alicyclic polycarboxylic acid such as polycarboxylic acid leading to alicyclic polycarboxylic acid anhydride; isophthalic acid, terephthalic acid, 1,4,5,8-naphthalenetetracarboxylic acid, aromatic polycarboxylic acids such as polycarboxylic acids leading to aromatic polycarboxylic anhydrides; and the like.
　中でも、得られる膜の耐熱性に優れ、特に可視光領域での透明性が低下しにくい点から、鎖状カルボン酸無水物、脂環式多価カルボン酸無水物が好ましく、脂環式多価カルボン酸無水物がより好ましい。 Among them, chain carboxylic acid anhydrides and alicyclic polyvalent carboxylic acid anhydrides are preferable, and alicyclic polyvalent Carboxylic anhydrides are more preferred.
　本発明の樹脂組成物が多価カルボン酸（Ｇ１）を含む場合、その含有量は、樹脂（Ａ）と重合性化合物（Ｃ）との合計含有量１００質量部に対して、好ましくは１～３０質量部、より好ましくは２～２０質量部、さらに好ましくは２～１５質量部である。多価カルボン酸（Ｇ１）の含有量が前記の範囲内にあると、得られる膜の耐熱性及び密着性に優れる。 When the resin composition of the present invention contains a polyvalent carboxylic acid (G1), its content is preferably 1 to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). 30 parts by mass, more preferably 2 to 20 parts by mass, and even more preferably 2 to 15 parts by mass. When the content of the polycarboxylic acid (G1) is within the above range, the heat resistance and adhesion of the obtained film are excellent.
　＜イミダゾール化合物（Ｇ２）＞
　イミダゾール化合物（Ｇ２）は、イミダゾール骨格を有する化合物であれば特に限定されず、例えば、エポキシ硬化剤として知られている化合物が挙げられる。中でも、式（Ｇ２－１）で表される化合物が好ましい。 <Imidazole compound (G2)>
The imidazole compound (G2) is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include compounds known as epoxy curing agents. Among them, the compound represented by formula (G2-1) is preferable.
Figure JPOXMLDOC01-appb-I000023
Figure JPOXMLDOC01-appb-I000023
［式（G２－１）中、Ｒ31は、炭素数１～２０のアルキル基、フェニル基、ベンジル基又は炭素数２～５のシアノアルキル基を表す。
　Ｒ3２～Ｒ34は、互いに独立に、水素原子、ハロゲン原子、炭素数１～２０のアルキル基、フェニル基、ニトロ基又は炭素数１～２０のアシル基を表し、該アルキル基及び該フェニル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。］ [In formula (G2-1), R 31 represents an alkyl group having 1 to 20 carbon atoms, a phenyl group, a benzyl group, or a cyanoalkyl group having 2 to 5 carbon atoms.
R 32 to R 34 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group or an acyl group having 1 to 20 carbon atoms, and the alkyl group and the phenyl group; A hydrogen atom contained in may be substituted with a hydroxy group. ]
　炭素数１～２０のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソブチル基、ブチル基、ｔｅｒｔ－ブチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ヘプタデシル基、ウンデシル基が挙げられる。
　炭素数２～５のシアノアルキル基としては、例えば、シアノメチル基、シアノエチル基、シアノプロピル基、シアノブチル基、シアノペンチル基が挙げられる。 Examples of alkyl groups having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isobutyl group, butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and heptadecyl group. , an undecyl group.
Examples of the cyanoalkyl group having 2 to 5 carbon atoms include cyanomethyl group, cyanoethyl group, cyanopropyl group, cyanobutyl group and cyanopentyl group.
　ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子が挙げられる。
　炭素数１～２０のアシル基としては、例えば、ホルミル基、アセチル基、プロピオニル基、イソブチリル基、バレリル基、イソバレリル基、ピバロイル基、ラウロイル基、ミリストイル基、ステアロイル基が挙げられる。 Halogen atoms include, for example, fluorine, chlorine and bromine atoms.
Examples of acyl groups having 1 to 20 carbon atoms include formyl, acetyl, propionyl, isobutyryl, valeryl, isovaleryl, pivaloyl, lauroyl, myristoyl and stearoyl groups.
　イミダゾール化合物（Ｇ２）としては、例えば、１－メチルイミダゾール、２－メチルイミダゾール、２－ヒドロキシメチルイミダゾール、２－メチル－４－ヒドロキシメチルイミダゾール、５－ヒドロキシメチル－４－メチルイミダゾール、２－エチルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、１，２－ジメチルイミダゾール、２－エチル－４－メチルイミダゾール、４－ヒドロキシメチル－２－フェニルイミダゾール、２－フェニルイミダゾール、２－フェニル－２－ヒドロキシメチルイミダゾール、１－ベンジル－４－メチルイミダゾール、１－ベンジル－４－フェニルイミダゾール、１－ベンジル－５－ヒドロキシメチルイミダゾール、２－（ｐ－ヒドロキシフェニル）イミダゾール、１－シアノメチル－２－メチルイミダゾール、１－（２－シアノエチル）－２－ヒドロキシメチルイミダゾール、２，４－ジフェニルイミダゾール、１－シアノメチル－２－ウンデシルイミダゾール、１－シアノメチル－２－エチル－４－メチルイミダゾール、１－シアノメチル－２－フェニルイミダゾール、１－（２－シアノエチル）－２－エチル－４－メチルイミダゾールが挙げられる。中でも１－ベンジル－４－フェニルイミダゾール、２－エチル－４－メチルイミダゾール、１－（２－シアノエチル）－２－エチル－４－メチルイミダゾールが好ましい。 Examples of imidazole compounds (G2) include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl-4-methylimidazole, and 2-ethylimidazole. , 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-hydroxymethyl-2-phenylimidazole, 2-phenylimidazole, 2-phenyl-2- Hydroxymethylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-phenylimidazole, 1-benzyl-5-hydroxymethylimidazole, 2-(p-hydroxyphenyl)imidazole, 1-cyanomethyl-2-methylimidazole , 1-(2-cyanoethyl)-2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2-ethyl-4-methylimidazole, 1-cyanomethyl-2 -phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole. Among them, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole are preferred.
　本発明の樹脂組成物がイミダゾール化合物（Ｇ２）を含む場合、その含有量は、樹脂（Ａ）と重合性化合物（Ｃ）との合計含有量１００質量部に対して、好ましくは０．１質量部以上２５質量部以下、より好ましくは０．２質量部以上１５質量部以下、さらに好ましくは０．５質量部以上５質量部以下である。イミダゾール化合物（Ｇ２）の含有量が前記の範囲にあると、得られる膜は可視光領域における透明性に優れる傾向がある。 When the resin composition of the present invention contains the imidazole compound (G2), the content thereof is preferably 0.1 mass parts per 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). parts or more and 25 parts by mass or less, more preferably 0.2 parts by mass or more and 15 parts by mass or less, and even more preferably 0.5 parts by mass or more and 5 parts by mass or less. When the content of the imidazole compound (G2) is within the above range, the resulting film tends to have excellent transparency in the visible light region.
　＜溶剤（Ｅ）＞
　本発明の樹脂組成物は、溶剤（Ｅ）を含有する。溶剤（Ｅ）としては、特に限定されず、当該分野で通常使用される溶剤を挙げることができる。例えば、エステル溶剤（分子内に－ＣＯＯ－を含み、－Ｏ－を含まない溶剤）、エーテル溶剤（分子内に－Ｏ－を含み、－ＣＯＯ－を含まない溶剤）、エーテルエステル溶剤（分子内に－ＣＯＯ－と－Ｏ－とを含む溶剤）、ケトン溶剤（分子内に－ＣＯ－を含み、－ＣＯＯ－を含まない溶剤）、アルコール溶剤（分子内にＯＨを含み、－Ｏ－、－ＣＯ－及び－ＣＯＯ－を含まない溶剤）、芳香族炭化水素溶剤、アミド溶剤、ジメチルスルホキシド等が挙げられる。 <Solvent (E)>
The resin composition of the present invention contains a solvent (E). The solvent (E) is not particularly limited, and solvents commonly used in the field can be mentioned. For example, ester solvent (solvent containing -COO- in the molecule but not containing -O-), ether solvent (solvent containing -O- in the molecule but not containing -COO-), ether ester solvent (solvent containing -COO- in the molecule solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-, - solvents containing no CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.
　エステル溶剤としては、乳酸メチル、乳酸エチル、乳酸ブチル、２－ヒドロキシイソブタン酸メチル、酢酸エチル、酢酸ｎ－ブチル、酢酸イソブチル、ギ酸ペンチル、酢酸イソペンチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、シクロヘキサノールアセテート及びγ－ブチロラクトンなどが挙げられる。 Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.
　エーテル溶剤としては、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、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピ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モノプロピルエーテル、プロピレングリコールモノブチルエーテル、３－メトキシ－１－ブタノール、３－メトキシ－３－メチルブタノール、テトラヒドロフラン、テトラヒドロピラン、１，４－ジオキサン、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、アニソール、フェネトール及びメチルアニソールなどが挙げられる。 Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. , propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol and methylanisole and the like.
　エーテルエステル溶剤としては、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル、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メチル、３－エトキシプロピオン酸エチル、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル、３－メトキシブチルアセテート、３－メチル－３－メトキシブチルアセテート、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モノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート及びジエチレングリコールモノブチルエーテルアセテートなどが挙げられる。 Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl Ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.
　ケトン溶剤としては、４－ヒドロキシ－４－メチル－２－ペンタノン、アセトン、２－ブタノン、２－ヘプタノン、３－ヘプタノン、４－ヘプタノン、４－メチル－２－ペンタノン、シクロペンタノン、シクロヘキサノン及びイソホロンなどが挙げられる。 Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. etc.
　アルコール溶剤としては、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール及びグリセリンなどが挙げられる。 Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.
　芳香族炭化水素溶剤としては、ベンゼン、トルエン、キシレン及びメシチレンなどが挙げられる。アミド溶剤としては、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－メチルピロリドンなどが挙げられる。 　Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene. Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.
　上記の溶剤のうち、塗布性、乾燥性の点から、１ａｔｍにおける沸点が１００℃以上２００℃以下である有機溶剤が好ましい。溶剤としては、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モノメチルエーテル、３－メトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチレングリコールエチルメチルエーテル、シクロヘキサノン、メトキシブタノール及びメトキシブチルアセテートが好ましく、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モノメチルエーテル、エチレングリコールエチルメチルエーテル、メトキシブタノール及びメトキシブチルアセテートがより好ましい。 Among the above solvents, organic solvents having a boiling point of 100°C or higher and 200°C or lower at 1 atm are preferable from the viewpoint of coating properties and drying properties. Preferred solvents are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol ethyl methyl ether, cyclohexanone, methoxybutanol and methoxybutyl acetate, and propylene glycol monomethyl ether. More preferred are acetate, propylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, methoxybutanol and methoxybutyl acetate.
　本発明の樹脂組成物における溶剤（Ｅ）の含有率は、樹脂組成物の総量に対して、好ましくは６０～９５質量％、より好ましくは７０～９５質量％である。言い換えると、本発明の樹脂組成物の固形分は、好ましくは５～４０質量％、より好ましくは５～３０質量％である。溶剤（Ｅ）の含有率が、前記の範囲にあると、樹脂組成物の均一性を向上させることができる傾向がある。 The content of the solvent (E) in the resin composition of the present invention is preferably 60-95% by mass, more preferably 70-95% by mass, relative to the total amount of the resin composition. In other words, the solid content of the resin composition of the present invention is preferably 5-40 mass %, more preferably 5-30 mass %. When the content of the solvent (E) is within the above range, there is a tendency that the uniformity of the resin composition can be improved.
　＜その他の成分＞
　本発明の樹脂組成物には、必要に応じて、充填剤、その他の高分子化合物、紫外線吸収剤、連鎖移動剤、密着促進剤等、当該技術分野において公知の添加剤を含有していてもよい。 <Other ingredients>
If necessary, the resin composition of the present invention may contain additives known in the art such as fillers, other polymer compounds, ultraviolet absorbers, chain transfer agents, adhesion promoters, etc. good.
　本発明の樹脂組成物は、光路長が１ｃｍの石英セルに充填し、分光光度計を使用して、測定波長４００～７００ｎｍの条件下で透過率を測定した場合、その平均透過率は好ましくは７０％以上、より好ましくは８０％以上である。 When the resin composition of the present invention is filled in a quartz cell having an optical path length of 1 cm and the transmittance is measured using a spectrophotometer under the conditions of a measurement wavelength of 400 to 700 nm, the average transmittance is preferably 70% or more, more preferably 80% or more.
　本発明の樹脂組成物から膜を形成した際に、膜の平均透過率が好ましくは９０％以上、より好ましくは９５％以上である。この平均透過率は、加熱硬化（１００～２５０℃、５分～３時間）後の厚みが２μｍの膜に対して、分光光度計を使用して、測定波長４００～７００ｎｍの条件下で測定した場合の平均値である。これにより、可視光領域での透明性に優れた膜を提供することができる。 When a film is formed from the resin composition of the present invention, the average transmittance of the film is preferably 90% or higher, more preferably 95% or higher. This average transmittance was measured on a film having a thickness of 2 μm after heat curing (100 to 250° C., 5 minutes to 3 hours) using a spectrophotometer under the conditions of a measurement wavelength of 400 to 700 nm. is the average value for the case. Thereby, a film having excellent transparency in the visible light region can be provided.
　＜樹脂組成物の製造方法＞
　本発明の樹脂組成物は、樹脂（Ａ）及び溶剤（Ｅ）、並びに、必要に応じて用いられる重合性化合物（Ｃ）、重合開始剤（Ｄ）、重合開始助剤（Ｈ）、レベリング剤（Ｂ）、酸化防止剤（Ｆ）、硬化剤（Ｇ）及びその他の成分を、公知の方法で混合することにより製造することができる。混合後は、孔径０．０５～１．０μｍ程度のフィルタでろ過することが好ましい。 <Method for producing resin composition>
The resin composition of the present invention comprises a resin (A) and a solvent (E), and optionally a polymerizable compound (C), a polymerization initiator (D), a polymerization initiation aid (H), and a leveling agent. (B), antioxidant (F), curing agent (G) and other components can be mixed by a known method. After mixing, it is preferable to filter with a filter having a pore size of about 0.05 to 1.0 μm.
　本発明の樹脂組成物は、優れた溶剤溶解性を有するので、これを用いて均一な膜を形成することができる。 Since the resin composition of the present invention has excellent solvent solubility, it can be used to form a uniform film.
　＜膜の製造方法＞
　膜は、本発明の樹脂組成物を基板上に塗布し、乾燥後、加熱することにより製造することができる。より具体的には、本発明の膜の製造方法は、以下の工程（１）～（３）を含む。
工程（１）：本発明の樹脂組成物を基板に塗布する工程、
工程（２）：塗布後の樹脂組成物を減圧乾燥及び／又は加熱乾燥させて、組成物層を形成する工程、
工程（３）：組成物層を加熱する工程。 <Method for producing membrane>
A film can be produced by coating the resin composition of the present invention on a substrate, drying it, and then heating it. More specifically, the film production method of the present invention includes the following steps (1) to (3).
Step (1): a step of applying the resin composition of the present invention to a substrate;
Step (2): a step of drying the resin composition after application under reduced pressure and/or heating to form a composition layer;
Step (3): A step of heating the composition layer.
　また、本発明の樹脂組成物が重合性化合物（Ｃ）及び重合開始剤（Ｄ）を含む場合、下記の工程を行うことにより、パターンを有する膜を製造することができる。
工程（１）：本発明の樹脂組成物を基板に塗布する工程、
工程（２）：塗布後の樹脂組成物を減圧乾燥及び／又は加熱乾燥させて、組成物層を形成する工程、
工程（２ａ）：組成物層を、フォトマスクを介して露光する工程、
工程（２ｂ）：露光後の組成物層を現像する工程、
工程（３ａ）：現像後の組成物層を加熱する工程。 Moreover, when the resin composition of the present invention contains the polymerizable compound (C) and the polymerization initiator (D), a patterned film can be produced by performing the following steps.
Step (1): a step of applying the resin composition of the present invention to a substrate;
Step (2): a step of drying the resin composition after application under reduced pressure and/or heating to form a composition layer;
Step (2a): a step of exposing the composition layer through a photomask;
Step (2b): a step of developing the composition layer after exposure;
Step (3a): A step of heating the composition layer after development.
　工程（１）は、本発明の樹脂組成物を基板（下地基板）に塗布する工程である。基板としては、ガラス、金属、プラスチック等が挙げられ、基板上にカラーフィルタ、絶縁膜、導電膜及び／又は駆動回路等が形成されていてもよい。基板上への塗布は、スピンコーター、スリット＆スピンコーター、スリットコーター、インクジェット、ロールコータ、ディップコーター等の塗布装置を用いて行うことが好ましい。 Step (1) is a step of applying the resin composition of the present invention to a substrate (underlying substrate). Examples of the substrate include glass, metal, plastic, and the like, and a color filter, an insulating film, a conductive film, a driving circuit, and the like may be formed on the substrate. Coating onto the substrate is preferably carried out using a coating device such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.
　工程（１）においては、基板の外周部に樹脂組成物の盛り上がりが発生したり、基板の裏面に樹脂組成物が回り込んだりすることがある。盛り上がりを形成したり、基板の裏面に回り込んだりした樹脂組成物は、後段の工程において、設備を汚したり、露光や加熱の精度を低下させる原因となる。本発明の樹脂組成物は、溶剤溶解性に優れるので、不要な樹脂組成物をきれいに除去することができ、不要な樹脂組成物に起因する問題を抑制することができる。また溶剤溶解性に難がある樹脂組成物は設備の配管閉塞の原因になることがあり好ましくない。 In step (1), the resin composition may swell around the outer periphery of the substrate, or the resin composition may wrap around the back surface of the substrate. The resin composition that forms a bulge or runs around to the back surface of the substrate causes contamination of equipment and lowers the accuracy of exposure and heating in subsequent steps. Since the resin composition of the present invention has excellent solvent solubility, it is possible to cleanly remove unnecessary resin compositions and to suppress problems caused by unnecessary resin compositions. Moreover, a resin composition having poor solubility in a solvent is not preferred because it may cause clogging of pipes in equipment.
　工程（２）は、塗布後の樹脂組成物を減圧乾燥及び／又は加熱乾燥させて、組成物層を形成する工程である。該工程を行うことにより、樹脂組成物中の溶剤等の揮発成分を除去する。減圧乾燥は、５０～１５０Ｐａの圧力の下で、２０～２５℃の温度範囲で行うことが好ましい。減圧乾燥の前又は後に、加熱乾燥（プリベーク）を行ってもよい。加熱乾燥は、通常、オーブン、ホットプレート等の加熱装置を用いて行う。加熱乾燥の温度は、好ましくは３０～１２０℃、より好ましくは５０～１１０℃である。また加熱時間は、好ましくは１０秒間～６０分間、より好ましくは３０秒間～３０分間である。 Step (2) is a step of drying the applied resin composition under reduced pressure and/or by heating to form a composition layer. By performing this step, volatile components such as solvents in the resin composition are removed. Vacuum drying is preferably carried out under a pressure of 50-150 Pa in a temperature range of 20-25°C. Heat drying (pre-baking) may be performed before or after vacuum drying. Heat drying is usually performed using a heating device such as an oven or a hot plate. The temperature for drying by heating is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.
　工程（３）は、組成物層を加熱する工程（ポストベーク）である。加熱は、通常、オーブン、ホットプレート等の加熱装置を用いて行う。加熱温度は、好ましくは１３０～２７０℃、より好ましくは１５０～２６０℃、さらに好ましくは２００～２５０℃である。加熱温度が、２００～２５０℃であると、膜中に不要な溶剤が残存することを防ぐことができる。加熱時間は、好ましくは１～１２０分間、より好ましくは１０～６０分間である。 Step (3) is a step of heating the composition layer (post-baking). Heating is usually performed using a heating device such as an oven or a hot plate. The heating temperature is preferably 130 to 270°C, more preferably 150 to 260°C, still more preferably 200 to 250°C. A heating temperature of 200 to 250° C. can prevent unnecessary solvent from remaining in the film. The heating time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.
　工程（２ａ）は、工程（２）により形成された組成物層を、フォトマスクを介して露光する工程である。該フォトマスクは、組成物層の除去したい部分に対応して、遮光部が形成されたものを用いる。遮光部の形状は、特に限定されず、目的とする用途に応じて選択できる。露光に用いられる光源としては、２５０～４５０ｎｍの波長の光を発生する光源が好ましい。例えば、３５０ｎｍ未満の光を、この波長域をカットするフィルタを用いてカットしたり、４３６ｎｍ付近、４０８ｎｍ付近、３６５ｎｍ付近の光を、これらの波長域を取り出すバンドパスフィルタを用いて選択的に取り出したりしてもよい。光源としては、水銀灯、発光ダイオード、メタルハライドランプ、ハロゲンランプ等が挙げられる。
露光面全体に均一に平行光線を照射することや、フォトマスクと組成物層との正確な位置合わせを行うことができるため、マスクアライナ、ステッパ等の露光装置を用いることが好ましい。 Step (2a) is a step of exposing the composition layer formed in step (2) through a photomask. The photomask used has a light-shielding portion corresponding to a portion of the composition layer to be removed. The shape of the light shielding portion is not particularly limited, and can be selected according to the intended use. The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You can Light sources include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
It is preferable to use an exposure apparatus such as a mask aligner, a stepper, etc., because it is possible to uniformly irradiate the entire exposure surface with parallel rays and to perform accurate alignment between the photomask and the composition layer.
　工程（２ｂ）は、露光後の組成物層を現像する工程である。露光後の組成物層を現像液に接触させて現像することにより、組成物層の未露光部が現像液に溶解して除去されて、基板上にパターンを有する組成物層が形成される。現像液としては、水酸化カリウム、炭酸水素ナトリウム、炭酸ナトリウム、水酸化テトラメチルアンモニウム等のアルカリ性化合物の水溶液が好ましい。これらのアルカリ性化合物の水溶液中の濃度は、好ましくは０．０１～１０質量％、より好ましくは０．０３～５質量％である。さらに、現像液は、界面活性剤を含んでいてもよい。 現像方法は、パドル法、ディッピング法及びスプレー法等のいずれでもよい。さらに現像時に基板を任意の角度に傾けてもよい。現像後は、水洗することが好ましい。 The step (2b) is a step of developing the composition layer after exposure. By contacting the exposed composition layer with a developer for development, the unexposed portion of the composition layer is dissolved in the developer and removed, thereby forming a patterned composition layer on the substrate. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01-10 mass %, more preferably 0.03-5 mass %. Furthermore, the developer may contain a surfactant. The development method may be any of the puddle method, dipping method, spray method, and the like. Furthermore, the substrate may be tilted at any angle during development. It is preferable to wash with water after development.
　工程（３ａ）は、現像後の組成物層を加熱する工程である。前記工程（３）と同様にして加熱を行うことにより、パターンを有する組成物層が硬化して、パターンを有する膜が基板上に形成される。 The step (3a) is a step of heating the composition layer after development. By heating in the same manner as in step (3), the patterned composition layer is cured to form a patterned film on the substrate.
　このようにして得られる膜は、例えば、液晶表示装置、有機ＥＬ表示装置や電子ペーパーに用いられるカラーフィルタ基板として有用である。これにより、高品質の膜を備えた表示装置を製造することが可能となる。着色パターンの凹凸形状を表面に有するカラーフィルタ基板においても、本発明の樹脂組成物によりオーバーコート層を形成することができる。 The film thus obtained is useful, for example, as a color filter substrate used in liquid crystal display devices, organic EL display devices, and electronic paper. This makes it possible to manufacture display devices with high-quality films. The resin composition of the present invention can be used to form an overcoat layer even on a color filter substrate having a colored pattern on its surface.
　オーバーコート層の膜厚（被塗布面が凹凸形状を有する場合は凸部の表面からの膜厚）は、好ましくは０．５μｍ以上５μｍ以下、より好ましくは０．５μｍ以上３μｍ以下である。本発明の樹脂組成物は、被塗布面が凹凸形状を有する場合、例えば、凹部の幅が１～５００μｍ、凹部の表面から凸部の表面までの高さが０．１～２０μｍである凹凸形状を有する下地基板に用いることができる。 The film thickness of the overcoat layer (the film thickness from the surface of the projections when the surface to be coated has an uneven shape) is preferably 0.5 μm or more and 5 μm or less, more preferably 0.5 μm or more and 3 μm or less. When the surface to be coated of the resin composition of the present invention has an uneven shape, for example, the width of the concave portion is 1 to 500 μm, and the height from the surface of the concave portion to the surface of the convex portion is 0.1 to 20 μm. can be used for a base substrate having
　［共重合体］
　本発明の共重合体は、炭素数２～４の環状エーテル構造を有する構成単位（Ａａ）と、カルバゾール環を有する構成単位（Ａｂ）と、（メタ）アクリル酸エステル構造を有する不飽和化合物に由来する構成単位（Ａｃ）と、を含む樹脂（Ａ）である。本発明の共重合体については、樹脂組成物に含まれる樹脂（Ａ）についての上記説明が適用される。 [Copolymer]
The copolymer of the present invention comprises a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms, a structural unit (Ab) having a carbazole ring, and an unsaturated compound having a (meth)acrylic acid ester structure. It is a resin (A) containing a structural unit (Ac) derived from. The above description of the resin (A) contained in the resin composition applies to the copolymer of the present invention.
　以下、実施例によって本発明をより詳細に説明する。例中の「％」及び「部」は、特記しない限り、質量％及び質量部である。 The present invention will be described in more detail below with reference to examples. Unless otherwise specified, "%" and "parts" in the examples are % by mass and parts by mass.
　［実施例１～６、比較例１］
　＜樹脂組成物の調製＞
　表１に示す固形分濃度になるように、表１に示す樹脂（Ａ）と、溶剤（Ｅ）であるプロピレングリコールモノメチルエーテルアセテート（以下「ＰＥＧＭＥＡ」とも称する。）とを混合して樹脂組成物を調製した。表１において、各成分の部数は、固形分換算の質量部を表す。この際、樹脂組成物の溶剤ＰＥＧＭＥＡとシクロペンタノンの比は６５／３５になるように調整した。 [Examples 1 to 6, Comparative Example 1]
<Preparation of resin composition>
Resin (A) shown in Table 1 and propylene glycol monomethyl ether acetate (hereinafter also referred to as "PEGMEA") as a solvent (E) are mixed so as to have a solid content concentration shown in Table 1 to prepare a resin composition. was prepared. In Table 1, the number of parts of each component represents parts by mass in terms of solid content. At this time, the ratio of the solvent PEGMEA and cyclopentanone in the resin composition was adjusted to 65/35.
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
　表１における各成分は、以下の通りである。
　樹脂（ａ１）：合成例１により得られた樹脂
　樹脂（ａ２）：合成例２により得られた樹脂
　樹脂（ａ３）：合成例３により得られた樹脂
　樹脂（ａ４）：合成例４により得られた樹脂
　樹脂（ａ５）：合成例５により得られた樹脂
　樹脂（ａ６）：合成例６により得られた樹脂
　樹脂（ａ７）：合成例７により得られた樹脂
　樹脂（ａ８）：合成例８により得られた樹脂
　樹脂（ａ９）：合成例９により得られた樹脂
　樹脂（ａ１０）：合成例１０により得られた樹脂 Each component in Table 1 is as follows.
Resin (a1): Resin obtained in Synthesis Example 1 Resin (a2): Resin obtained in Synthesis Example 2 Resin (a3): Resin obtained in Synthesis Example 3 Resin (a4): Obtained in Synthesis Example 4 Resin Resin (a5): Resin obtained in Synthesis Example 5 Resin (a6): Resin obtained in Synthesis Example 6 Resin (a7): Resin obtained in Synthesis Example 7 Resin (a8): According to Synthesis Example 8 Obtained Resin Resin (a9): Resin obtained in Synthesis Example 9 Resin (a10): Resin obtained in Synthesis Example 10
　樹脂（ａ１）～（ａ７）は、構成単位として、以下に式を示す構成単位（ＡａＩ）（３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－９－イルアクリレートの１：１の混合物）、構成単位（ＡｂＩ）（９－ビニルカルバゾール）、及び構成単位（ＡｄＩ）（アクリル酸）を含み、さらに、樹脂（ａ２）は構成単位（ＡｃＩ）（２－エチルヘキシルアクリレート）を、樹脂（ａ３）は構成単位（ＡｃＩＩ）（ブチルアクリレート）を、樹脂（ａ４）～（ａ６）は構成単位（ＡｃＩＩＩ）（ｔｅｒｔ―ブチルアクリレート）を、樹脂（ａ７）は構成単位（ＡｃＩＶ）（イソデシルアクリレート）を含む。各樹脂における、各構成単位の比率は、表２に示すとおりである。 In the resins (a1) to (a7), the structural unit (AaI) (3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-9-yl acrylate), building block (AbI) (9-vinylcarbazole), and building block ( AdI) (acrylic acid), the resin (a2) contains the structural unit (AcI) (2-ethylhexyl acrylate), the resin (a3) contains the structural unit (AcII) (butyl acrylate), and the resin (a4) to (a6) contains structural unit (AcIII) (tert-butyl acrylate), and resin (a7) contains structural unit (AcIV) (isodecyl acrylate). Table 2 shows the ratio of each structural unit in each resin.
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
　（合成例１：樹脂（ａ１）の調製）
　還流冷却器、滴下ロート及び攪拌機を備えたフラスコ内に窒素を適量流し窒素雰囲気に置換し、ＰＥＧＭＥＡ３４８部を入れ、攪拌しながら８５℃まで加熱した。次いで、アクリル酸１６部、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－９－イルアクリレートの混合物（混合割合は１：１）３２部、９－ビニルカルバゾール２７２部、シクロペンタノン１０３重量部、プロピレングリコールモノメチルエーテルアセテート１０５部の混合溶液を５時間かけて滴下した。一方、２，２－アゾビス（２，４－ジメチルバレロニトリル）６部をプロピレングリコールモノメチルエーテルアセテート１１８部に溶解した混合溶液を５時間かけて滴下した。滴下終了後、３時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）３７９ｍＰａｓ、固形分３３．４％の共重合体（樹脂（ａ１））溶液を得た。得られた樹脂（ａ１）の重量平均分子量（Ｍｗ）は２１０８０、分散度（Ｍｗ／Ｍｎ）は２．７６、固形分換算の酸価は３３ｍｇ－ＫＯＨ／ｇであった。樹脂（ａ１）は、下記の構成単位を有する。 (Synthesis Example 1: Preparation of resin (a1))
A proper amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 348 parts of PEGMEA was added, and the flask was heated to 85°C while stirring. Then 16 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2, 6 ] A mixed solution of 32 parts of a mixture of decan-9-yl acrylate (mixing ratio is 1:1), 272 parts by weight of 9-vinylcarbazole, 103 parts by weight of cyclopentanone, and 105 parts by weight of propylene glycol monomethyl ether acetate was added over 5 hours. Dripped. On the other hand, a mixed solution of 6 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 118 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of dropping, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (a1)) solution having a B-type viscosity (23°C) of 379 mPas and a solid content of 33.4%. The obtained resin (a1) had a weight average molecular weight (Mw) of 21080, a dispersity (Mw/Mn) of 2.76, and an acid value in terms of solid content of 33 mg-KOH/g. Resin (a1) has the following structural units.
Figure JPOXMLDOC01-appb-I000026
Figure JPOXMLDOC01-appb-I000026
　（合成例２：樹脂（ａ２）の調製）
　還流冷却器、滴下ロート及び攪拌機を備えたフラスコ内に窒素を適量流し窒素雰囲気に置換し、ＰＥＧＭＥＡ３４８部を入れ、攪拌しながら８５℃まで加熱した。次いで、アクリル酸１６部、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－９－イルアクリレートの混合物（混合割合は１：１）３２部、９－ビニルカルバゾール２６９部、２－エチルヘキシルアクリレート３．２部、シクロペンタノン１０３重量部、プロピレングリコールモノメチルエーテルアセテート１０５部の混合溶液を５時間かけて滴下した。一方、２，２－アゾビス（２，４－ジメチルバレロニトリル）６部をプロピレングリコールモノメチルエーテルアセテート１１８部に溶解した混合溶液を５時間かけて滴下した。滴下終了後、３時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）７６ｍＰａｓ、固形分３０．５％の共重合体（樹脂（ａ２））溶液を得た。得られた樹脂（ａ２）の重量平均分子量（Ｍｗ）は１９４２０、分散度（Ｍｗ／Ｍｎ）は２．８６、固形分換算の酸価は３２ｍｇ－ＫＯＨ／ｇであった。樹脂（ａ２）は、下記の構成単位を有する。 (Synthesis Example 2: Preparation of resin (a2))
A proper amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 348 parts of PEGMEA was added, and the flask was heated to 85°C while stirring. Then 16 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.02,6]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02,6] 32 parts of a mixture of decan-9-yl acrylate (mixing ratio is 1:1), 269 parts of 9-vinylcarbazole, 3.2 parts of 2-ethylhexyl acrylate, 103 parts by weight of cyclopentanone, and 105 parts of propylene glycol monomethyl ether acetate. The mixed solution was added dropwise over 5 hours. On the other hand, a mixed solution of 6 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 118 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of dropping, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (a2)) solution having a B-type viscosity (23°C) of 76 mPas and a solid content of 30.5%. The obtained resin (a2) had a weight average molecular weight (Mw) of 19420, a dispersity (Mw/Mn) of 2.86, and an acid value in terms of solid content of 32 mg-KOH/g. Resin (a2) has the following structural units.
Figure JPOXMLDOC01-appb-I000027
Figure JPOXMLDOC01-appb-I000027
　（合成例３：樹脂（ａ３）の調製）
　還流冷却器、滴下ロート及び攪拌機を備えたフラスコ内に窒素を適量流し窒素雰囲気に置換し、ＰＥＧＭＥＡ３４８部を入れ、攪拌しながら８５℃まで加熱した。次いで、アクリル酸１６部、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－９－イルアクリレートの混合物（混合割合は１：１）３２部、９－ビニルカルバゾール２６９部、ブチルアクリレート３．２部、シクロペンタノン１０３重量部、プロピレングリコールモノメチルエーテルアセテート１０５部の混合溶液を５時間かけて滴下した。一方、２，２－アゾビス（２，４－ジメチルバレロニトリル）６部をプロピレングリコールモノメチルエーテルアセテート１１８部に溶解した混合溶液を５時間かけて滴下した。滴下終了後、３時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）８４ｍＰａｓ、固形分３１．０％の共重合体（樹脂（ａ３））溶液を得た。得られた樹脂（ａ３）の重量平均分子量（Ｍｗ）は２０５２０、分散度（Ｍｗ／Ｍｎ）は３．０２、固形分換算の酸価は３１ｍｇ－ＫＯＨ／ｇであった。樹脂（ａ３）は、下記の構成単位を有する。 (Synthesis Example 3: Preparation of resin (a3))
A proper amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 348 parts of PEGMEA was added, and the flask was heated to 85°C while stirring. Then 16 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.02,6]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02,6] A mixed solution of 32 parts of a mixture of decan-9-yl acrylate (mixing ratio is 1:1), 269 parts of 9-vinylcarbazole, 3.2 parts of butyl acrylate, 103 parts by weight of cyclopentanone, and 105 parts of propylene glycol monomethyl ether acetate. was added dropwise over 5 hours. On the other hand, a mixed solution of 6 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 118 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of dropping, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (a3)) solution having a B-type viscosity (23°C) of 84 mPas and a solid content of 31.0%. The obtained resin (a3) had a weight average molecular weight (Mw) of 20520, a dispersity (Mw/Mn) of 3.02, and an acid value in terms of solid content of 31 mg-KOH/g. Resin (a3) has the following structural units.
Figure JPOXMLDOC01-appb-I000028
Figure JPOXMLDOC01-appb-I000028
　（合成例４：樹脂（ａ４）の調製）
　還流冷却器、滴下ロート及び攪拌機を備えたフラスコ内に窒素を適量流し窒素雰囲気に置換し、ＰＥＧＭＥＡ３４８部を入れ、攪拌しながら８５℃まで加熱した。次いで、アクリル酸１６部、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－９－イルアクリレートの混合物（混合割合は１：１）３２部、９－ビニルカルバゾール２６９部、ｔｅｒｔ―ブチルアクリレート３．２部、シクロペンタノン１０３重量部、プロピレングリコールモノメチルエーテルアセテート１０５部の混合溶液を５時間かけて滴下した。一方、２，２－アゾビス（２，４－ジメチルバレロニトリル）６部をプロピレングリコールモノメチルエーテルアセテート１１８部に溶解した混合溶液を５時間かけて滴下した。滴下終了後、３時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）８５ｍＰａｓ、固形分３１．７％の共重合体（樹脂（ａ４））溶液を得た。得られた樹脂（ａ４）の重量平均分子量（Ｍｗ）は１９９００、分散度（Ｍｗ／Ｍｎ）は２．９６、固形分換算の酸価は３０ｍｇ－ＫＯＨ／ｇであった。樹脂（ａ４）は、下記の構成単位を有する。 (Synthesis Example 4: Preparation of resin (a4))
A proper amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 348 parts of PEGMEA was added, and the flask was heated to 85°C while stirring. Then 16 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.02,6]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02,6] 32 parts of a mixture of decan-9-yl acrylate (mixing ratio is 1:1), 269 parts of 9-vinylcarbazole, 3.2 parts of tert-butyl acrylate, 103 parts by weight of cyclopentanone, and 105 parts of propylene glycol monomethyl ether acetate. The mixed solution was added dropwise over 5 hours. On the other hand, a mixed solution of 6 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 118 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of dropping, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (a4)) solution having a B-type viscosity (23°C) of 85 mPas and a solid content of 31.7%. The obtained resin (a4) had a weight average molecular weight (Mw) of 19,900, a dispersity (Mw/Mn) of 2.96, and an acid value in terms of solid content of 30 mg-KOH/g. Resin (a4) has the following structural units.
Figure JPOXMLDOC01-appb-I000029
Figure JPOXMLDOC01-appb-I000029
　（合成例５：樹脂（ａ５）の調製）
　合成例４とは、９－ビニルカルバゾール２７０．４部、ｔｅｒｔ―ブチルアクリレート１．６部、とした点のみ異なる。滴下終了後、３時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）７６ｍＰａｓ、固形分３０．３％の共重合体（樹脂（ａ５））溶液を得た。得られた樹脂（ａ５）の重量平均分子量（Ｍｗ）は１９７９０、分散度（Ｍｗ／Ｍｎ）は２．８９、固形分換算の酸価は３０ｍｇ－ＫＯＨ／ｇであった。樹脂（ａ５）は、樹脂（ａ４）と同じ構成単位を有する。 (Synthesis Example 5: Preparation of resin (a5))
The only difference from Synthesis Example 4 is that 270.4 parts of 9-vinylcarbazole and 1.6 parts of tert-butyl acrylate were used. After completion of dropping, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (a5)) solution having a B-type viscosity (23°C) of 76 mPas and a solid content of 30.3%. The obtained resin (a5) had a weight average molecular weight (Mw) of 19790, a dispersity (Mw/Mn) of 2.89, and an acid value converted to solid content of 30 mg-KOH/g. Resin (a5) has the same structural units as resin (a4).
　（合成例６：樹脂（ａ６）の調製）
　合成例４とは、９－ビニルカルバゾール２７１．４部、ｔｅｒｔ―ブチルアクリレート０．６４部、とした点のみ異なる。滴下終了後、３時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）３１３ｍＰａｓ、固形分３６．１％の共重合体（樹脂（ａ６））溶液を得た。得られた樹脂（ａ６）の重量平均分子量（Ｍｗ）は１８８３０、分散度（Ｍｗ／Ｍｎ）は２．８５、固形分換算の酸価は３０ｍｇ－ＫＯＨ／ｇであった。樹脂（ａ６）は、樹脂（ａ４）と同じ構成単位を有する。 (Synthesis Example 6: Preparation of resin (a6))
The only difference from Synthesis Example 4 is that 271.4 parts of 9-vinylcarbazole and 0.64 parts of tert-butyl acrylate are used. After completion of dropping, the mixture was held at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (a6)) solution having a B-type viscosity (23°C) of 313 mPas and a solid content of 36.1%. The obtained resin (a6) had a weight average molecular weight (Mw) of 18830, a dispersity (Mw/Mn) of 2.85, and an acid value of 30 mg-KOH/g in terms of solid content. Resin (a6) has the same structural units as resin (a4).
　（合成例７：樹脂（ａ７）の調製）
　還流冷却器、滴下ロート及び攪拌機を備えたフラスコ内に窒素を適量流し窒素雰囲気に置換し、ＰＥＧＭＥＡ２３７部を入れ、攪拌しながら８５℃まで加熱した。次いで、アクリル酸１７部、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－９－イルアクリレートの混合物（混合割合は１：１）３４部、９－ビニルカルバゾール２８８．３部、イソデシルメタクリレート０．７部、シクロペンタノン２６２重量部の混合溶液を５時間かけて滴下した。一方、２，２－アゾビス（２，４－ジメチルバレロニトリル）５部をプロピレングリコールモノメチルエーテルアセテート１５６部に溶解した混合溶液を５時間かけて滴下した。
　滴下終了後、３時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）９８ｍＰａｓ、固形分３１．８％の共重合体（樹脂（ａ４））溶液を得た。得られた樹脂（ａ７）の重量平均分子量（Ｍｗ）は１８５９０、分散度（Ｍｗ／Ｍｎ）は２．８９、固形分換算の酸価は３０ｍｇ－ＫＯＨ／ｇであった。樹脂（ａ７）は、下記の構成単位を有する。 (Synthesis Example 7: Preparation of resin (a7))
A proper amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 237 parts of PEGMEA was added, and the flask was heated to 85° C. while stirring. Then, 17 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.02,6]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02,6] A mixed solution of 34 parts of a mixture of decane-9-yl acrylate (mixing ratio is 1:1), 288.3 parts of 9-vinylcarbazole, 0.7 parts of isodecyl methacrylate, and 262 parts by weight of cyclopentanone was added over 5 hours. Dripped. On the other hand, a mixed solution of 5 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 156 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours.
After completion of dropping, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (a4)) solution having a B-type viscosity (23°C) of 98 mPas and a solid content of 31.8%. The obtained resin (a7) had a weight average molecular weight (Mw) of 18590, a dispersity (Mw/Mn) of 2.89, and an acid value in terms of solid content of 30 mg-KOH/g. Resin (a7) has the following structural units.
Figure JPOXMLDOC01-appb-I000030
Figure JPOXMLDOC01-appb-I000030
　（合成例８：樹脂（ａ８）の調製）
　合成例４とは、仕込み比をアクリル酸１９．２部、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－９－イルアクリレートの混合物（商品名「Ｅ－ＤＣＰＡ」、（株）ダイセル製））３８．４部、９－ビニルカルバゾール２５８部、ｔｅｒｔ―ブチルアクリレート１．６部とした点が異なる。滴下終了後、３時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）９８ｍＰａｓ、固形分３１．８％の共重合体（樹脂（ａ８））溶液を得た。得られた樹脂（ａ８）の重量平均分子量（Ｍｗ）は２０５９０、分散度（Ｍｗ／Ｍｎ）は２．９８、固形分換算の酸価は３７ｍｇ－ＫＯＨ／ｇであった。樹脂（ａ８）は、樹脂（ａ４）と同じ構成単位を有する。 (Synthesis Example 8: Preparation of resin (a8))
In Synthesis Example 4, the charging ratio is 19.2 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.02,6]decan-8-yl acrylate and 3,4-epoxytricyclo[5 .2.1.02,6]Decan-9-yl acrylate mixture (trade name “E-DCPA”, manufactured by Daicel Corporation)) 38.4 parts, 9-vinylcarbazole 258 parts, tert-butyl acrylate 1 .6 is different. After completion of dropping, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (a8)) solution having a B-type viscosity (23°C) of 98 mPas and a solid content of 31.8%. The obtained resin (a8) had a weight average molecular weight (Mw) of 20590, a dispersity (Mw/Mn) of 2.98, and an acid value of 37 mg-KOH/g in terms of solid content. Resin (a8) has the same structural units as resin (a4).
　(合成例９：樹脂（ａ９）の調製)
　合成例４とは、仕込み比をアクリル酸２２．４部、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－９－イルアクリレートの混合物（商品名「Ｅ－ＤＣＰＡ」、（株）ダイセル製））４８部、９－ビニルカルバゾール２４７部、ｔｅｒｔ―ブチルアクリレート１．６部とした点が異なる。滴下終了後、３時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）１４３ｍＰａｓ、固形分３２．５％の共重合体（樹脂（ａ９））溶液を得た。得られた樹脂（ａ９）の重量平均分子量（Ｍｗ）は２３３２０、分散度（Ｍｗ／Ｍｎ）は３．１１、固形分換算の酸価は４４ｍｇ－ＫＯＨ／ｇであった。樹脂（ａ９）は、樹脂（ａ４）と同じ構成単位を有する。 (Synthesis Example 9: Preparation of resin (a9))
In Synthesis Example 4, the charging ratio is 22.4 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.02,6]decan-8-yl acrylate and 3,4-epoxytricyclo[5 .2.1.02,6] Decane-9-yl acrylate mixture (trade name “E-DCPA”, manufactured by Daicel Corporation)) 48 parts, 9-vinylcarbazole 247 parts, tert-butyl acrylate 1.6 The difference is that it is divided into parts. After completion of dropping, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (a9)) solution having a B-type viscosity (23°C) of 143 mPas and a solid content of 32.5%. The obtained resin (a9) had a weight average molecular weight (Mw) of 23320, a dispersity (Mw/Mn) of 3.11, and an acid value of 44 mg-KOH/g in terms of solid content. Resin (a9) has the same structural units as resin (a4).
　（合成例１０：樹脂(ａ１０)の調製）
　合成例４とは、仕込み比をアクリル酸２２．４部、３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０２，６］デカン－９－イルアクリレートの混合物（商品名「Ｅ－ＤＣＰＡ」、（株）ダイセル製））４８部、９－ビニルカルバゾール２４８部、ｔｅｒｔ―ブチルアクリレート０．６４部とした点が異なる。滴下終了後、３時間同温度で保持した後、室温まで冷却して、Ｂ型粘度（２３℃）１２５ｍＰａｓ、固形分３１．８％の共重合体（樹脂（ａ１０））溶液を得た。得られた樹脂（ａ１０）の重量平均分子量（Ｍｗ）は２２６４０、分散度（Ｍｗ／Ｍｎ）は３．１１、固形分換算の酸価は４４ｍｇ－ＫＯＨ／ｇであった。樹脂（ａ１０）は、樹脂（ａ４）と同じ構成単位を有する。 (Synthesis Example 10: Preparation of resin (a10))
In Synthesis Example 4, the charging ratio is 22.4 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.02,6]decan-8-yl acrylate and 3,4-epoxytricyclo[5 .2.1.02,6]Decan-9-yl acrylate mixture (trade name “E-DCPA”, manufactured by Daicel Corporation)) 48 parts, 9-vinylcarbazole 248 parts, tert-butyl acrylate 0.64 The difference is that it is divided into parts. After completion of dropping, the mixture was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (a10)) solution having a B-type viscosity (23°C) of 125 mPas and a solid content of 31.8%. The obtained resin (a10) had a weight average molecular weight (Mw) of 22640, a dispersity (Mw/Mn) of 3.11, and an acid value of 44 mg-KOH/g in terms of solid content. Resin (a10) has the same structural units as resin (a4).
　＜重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）の測定＞
　得られた樹脂の重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）の測定は、ＧＰＣ法を用いて、以下の条件で行った。
　装置：ＨＬＣ－８１２０ＧＰＣ（東ソー（株）製）
　カラム：ＴＳＫ－ＧＥＬＧ２０００ＨＸＬ
　カラム温度：４０℃
　溶媒：ＴＨＦ（テトラヒドロフラン）
　流速：１．０ｍＬ／ｍｉｎ
　被検液固形分濃度：０．００１～０．０１質量％
　注入量：５０μＬ
　検出器：ＲＩ
　較正用標準物質：ＴＳＫ　ＳＴＡＮＤＡＲＤ　ＰＯＬＹＳＴＹＲＥＮＥ　Ｆ－４０、Ｆ－４、Ｆ－２８８、Ａ－２５００、Ａ－５００（東ソー（株）製）
　上記で得られたポリスチレン換算の重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）を分散度とした。 <Measurement of Weight Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn)>
The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the obtained resin were measured using the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40°C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL/min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw/Mn) of the polystyrene equivalent weight average molecular weight (Mw) to the number average molecular weight (Mn) obtained above was taken as the degree of dispersion.
　＜評価用溶液の作製＞
　実施例１～９、比較例１の樹脂組成物のそれぞれ１ｇを１０ｇのＰＧＭＥＡで希釈し、評価用溶液を得た。各評価用溶液を、光路長が１ｃｍの石英セルに充填し、分光光度計を使用して、測定波長４００～７００ｎｍの条件下で透過率を測定し、その平均透過率を求めた。結果を表１に示す。実施例１～９については、平均透過率が９０％以上であり、ＰＥＧＭＥＡを溶剤とした場合の溶剤溶解性に優れていることがわかる。 <Preparation of solution for evaluation>
1 g of each of the resin compositions of Examples 1 to 9 and Comparative Example 1 was diluted with 10 g of PGMEA to obtain solutions for evaluation. Each solution for evaluation was filled in a quartz cell with an optical path length of 1 cm, and the transmittance was measured using a spectrophotometer under conditions of a measurement wavelength of 400 to 700 nm to obtain the average transmittance. Table 1 shows the results. For Examples 1 to 9, the average transmittance was 90% or more, and it can be seen that the solvent solubility is excellent when PEGMEA is used as the solvent.

Claims (7)

  1. 　樹脂（Ａ）及び溶剤を含み、
    　前記樹脂（Ａ）は、炭素数２～４の環状エーテル構造を有する不飽和化合物に由来する構成単位（Ａａ）と、置換基を有していてもよいカルバゾール環を有する構成単位（Ａｂ）と、（メタ）アクリル酸エステル構造を有する不飽和化合物に由来する構成単位（Ａｃ）と、含む共重合体であり、
    　前記構成単位（Ａｃ）は、下記式（Ａｃ）で表される、樹脂組成物。
    Figure JPOXMLDOC01-appb-I000001
    ［式（Ａｃ）中、Ｒａ１は、水素原子又は炭素数１～４のアルキル基を表す。
    　Ｒａ２は、炭素数１～２０の脂肪族炭化水素基を表す。］     including a resin (A) and a solvent,
    The resin (A) comprises a structural unit (Aa) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms, and a structural unit (Ab) having a carbazole ring which may have a substituent. , A copolymer containing a structural unit (Ac) derived from an unsaturated compound having a (meth) acrylic acid ester structure,
    A resin composition in which the structural unit (Ac) is represented by the following formula (Ac).
    Figure JPOXMLDOC01-appb-I000001
    [In formula (Ac), R a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
    R a2 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms. ]
  2. 　前記構成単位（Ａａ）は、不飽和脂環式炭化水素がエポキシ化された構造を有する、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the structural unit (Aa) has a structure in which an unsaturated alicyclic hydrocarbon is epoxidized.
  3. 　前記不飽和脂環式炭化水素がエポキシ化された構造は、式（Ａａ－１）で表される構成単位及び式（Ａａ－２）で表される構成単位からなる群から選択される少なくとも１種を含む、請求項２に記載の樹脂組成物。
    Figure JPOXMLDOC01-appb-I000002
    ［式（Ａａ－１）及び式（Ａａ－２）中、Ｒｂ１及びＲｂ２は、水素原子又は炭素数１～４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
    　Ｘｂ１及びＸｂ２は、単結合、＊－Ｒｂ３－、＊－Ｒｂ３－Ｏ－、＊－Ｒｂ３－Ｓ－又は＊－Ｒｂ３－ＮＨ－を表す。
    　Ｒｂ３は、炭素数１～６のアルカンジイル基を表す。
    　＊は、Ｏとの結合手を表す。］     The structure in which the unsaturated alicyclic hydrocarbon is epoxidized is at least one selected from the group consisting of a structural unit represented by formula (Aa-1) and a structural unit represented by formula (Aa-2) 3. The resin composition of claim 2, comprising seeds.
    Figure JPOXMLDOC01-appb-I000002
    [In the formulas (Aa-1) and (Aa-2), R b1 and R b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. may be substituted.
    X b1 and X b2 each represent a single bond, *-R b3 -, *-R b3 -O-, *-R b3 -S- or *-R b3 -NH-.
    R b3 represents an alkanediyl group having 1 to 6 carbon atoms.
    * represents a bond with O. ]
  4. 　前記構成単位（Ａｂ）は、式（Ａｂ－１）で表される構成単位である、請求項１～３のいずれか１項に記載の樹脂組成物。
    Figure JPOXMLDOC01-appb-I000003
    ［式（Ａｂ－１）中、Ｒ１は、水素原子、メチル基、またはヒドロキシメチル基を表す。
    　Ｒ２～Ｒ９は、互いに独立に、水素原子、ハロゲン原子、炭素数１～２０の飽和炭化水素基又は炭素数６～２０のアリール基を表し、該飽和炭化水素基に含まれる水素原子は、アルコキシ基又はアリール基で置換されていてもよい。
    　Ｘは、単結合、炭素数１以上のアルカンジイル基、もしくは直鎖状又は分枝鎖状の下記の式（Ｖ）で表される基を表す。
    Figure JPOXMLDOC01-appb-I000004
    （式（Ｖ）中、前記ｌは、０以上の整数を表す。ｍは、１以上の整数を表す。）］     The resin composition according to any one of claims 1 to 3, wherein the structural unit (Ab) is a structural unit represented by formula (Ab-1).
    Figure JPOXMLDOC01-appb-I000003
    [In formula (Ab-1), R 1 represents a hydrogen atom, a methyl group, or a hydroxymethyl group.
    R 2 to R 9 each independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is , an alkoxy group or an aryl group.
    X represents a single bond, an alkanediyl group having 1 or more carbon atoms, or a linear or branched group represented by the following formula (V).
    Figure JPOXMLDOC01-appb-I000004
    (In formula (V), l represents an integer of 0 or more. m represents an integer of 1 or more.)]
  5. 　重合開始剤を含む、請求項１～４のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 4, which contains a polymerization initiator.
  6. 　請求項１～５のいずれか１項に記載の樹脂組成物から形成された膜。 A film formed from the resin composition according to any one of claims 1 to 5.
  7. 　炭素数２～４の環状エーテル構造を有する不飽和化合物に由来する構成単位（Ａａ）と、置換基を有していてもよいカルバゾール環を有する構成単位（Ａｂ）と、アルキル（メタ）アクリレートを有する不飽和化合物に由来する構成単位（Ａｃ）と、含む共重合体であり、
    　前記構成単位（Ａｃ）は、下記式（Ａｃ）で表される、共重合体。
    Figure JPOXMLDOC01-appb-I000005
    ［式（Ａｃ）中、Ｒａ１は、水素原子又は炭素数１～４のアルキル基を表す。
    　Ｒａ２は、炭素数１～２０の脂肪族炭化水素基を表す。］     A structural unit (Aa) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms, a structural unit (Ab) having a carbazole ring which may have a substituent, and an alkyl (meth)acrylate. A structural unit (Ac) derived from an unsaturated compound having and a copolymer containing
    The structural unit (Ac) is a copolymer represented by the following formula (Ac).
    Figure JPOXMLDOC01-appb-I000005
    [In formula (Ac), R a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
    R a2 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms. ]
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WO2008069047A1 (en) * 2006-11-28 2008-06-12 Nissan Chemical Industries, Ltd. Resist underlayer film forming composition for lithography, containing aromatic fused ring-containing resin
JP2012078501A (en) * 2010-09-30 2012-04-19 Fujifilm Corp Alignment layer, optical film, polarizing plate and liquid crystal display device
JP2020128494A (en) * 2019-02-08 2020-08-27 住友化学株式会社 Coloring curable resin composition

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JP4501665B2 (en) 2004-12-14 2010-07-14 住友化学株式会社 Photosensitive resin composition
WO2012053377A1 (en) 2010-10-18 2012-04-26 株式会社ダイセル High refractive index resin composition and cured resin

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008069047A1 (en) * 2006-11-28 2008-06-12 Nissan Chemical Industries, Ltd. Resist underlayer film forming composition for lithography, containing aromatic fused ring-containing resin
JP2012078501A (en) * 2010-09-30 2012-04-19 Fujifilm Corp Alignment layer, optical film, polarizing plate and liquid crystal display device
JP2020128494A (en) * 2019-02-08 2020-08-27 住友化学株式会社 Coloring curable resin composition

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