Polymerizable unsaturated group-containing resin, curable resin composition, cured product and article

Abstract

To provide: a polymerizable unsaturated group-containing resin having a low elastic modulus, excellent toughness, and excellent adhesiveness in cured state; a curable resin composition; and a cured product and an article thereof.SOLUTION: A production method of a polymerizable unsaturated group-containing resin includes: a first step of mixing a (meth)acrylate compound (a1) and a compound (a2) having one or more of first polymerizable unsaturated group and one or more of first reactive functional group in the presence of an alcohol solvent having a biomass carbon content (%) (pMC%) of 30% or more and having an oxygen atom-containing alicyclic group represented by the general formula (1) so as to obtain a (meth)acrylic copolymer (A); and a second step of mixing the (meth)acrylic copolymer (A) and a compound (B) having a second reactive functional group capable of reacting with the first reactive functional group in the presence of the alcohol solvent so as to obtain the polymerizable unsaturated group-containing resin.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to polymerizable unsaturated group-containing resins, curable resin compositions, cured products, and articles. [Background technology]

[0002] 2. Description of the Related Art In recent years, curable resin compositions, such as active energy ray-curable resin compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting resin compositions that can be cured by heat, have been widely used in the fields of inks, paints, coating agents, adhesives, optical members, and the like. In particular, since various properties such as elastic modulus (toughness), adhesion, curability, heat resistance, and low dielectric properties are required for the above coating agents depending on the application, it is essential to manufacture the coating agents using materials appropriate for the above properties. For example, Patent Document 1 discloses a photosensitive resin composition containing an acid group-containing epoxy acrylate resin obtained by further reacting an intermediate obtained by reacting a cresol novolac epoxy resin with acrylic acid and phthalic anhydride with tetrahydrophthalic anhydride. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 96 / 011239 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the technology of Patent Document 1 above has problems in terms of various resin properties required for the cured product. Therefore, the technical problem that the present disclosure aims to solve is to provide a polymerizable unsaturated group-containing resin, a curable resin composition, and a cured product and article thereof, which have a low elastic modulus and excellent toughness when cured, and also have excellent adhesion. [Means for solving the problem]

[0005] As a result of intensive research to solve the above problems, the inventors focused on the solvent in the manufacturing stage of the resin and its cured product. They then found that when a solvent having a specific structure is used, the toughness and adhesion of the resulting cured resin can be improved. Furthermore, they found that since this solvent with a specific structure is naturally derived, the environmental load during resin production can be reduced. Based on this knowledge, they found that the above problems can be solved by using a solvent with a specific structure, and completed the present invention. That is, the gist of the present invention that solves the above problems is as follows.

[0006] [1] A first step of obtaining a (meth)acrylic copolymer (A) by mixing a (meth)acrylate compound (a1) and a compound (a2) having one or more first polymerizable unsaturated groups and first reactive functional groups in the presence of an alcohol solvent having a biomass carbon content (%) (pMC%) of 30% or more and having an oxygen atom-containing alicyclic group represented by the following general formula (1); and a second step of mixing, in the presence of the alcohol solvent, the (meth)acrylic copolymer (A) and a compound (B) having a second reactive functional group capable of reacting with the first reactive functional group to obtain a polymerizable unsaturated group-containing resin. [ka] (In the above general formula (1), R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; M 1 ~M 5 each independently represents a meidine group, a methylene group, an oxygen atom, or a single bond; M 1 ~M 5 One or two of the groups are oxygen atoms, and M 1 ~M 5 is a mezine group, and the mezine group is -(CH 2 ) n -OH and M 1 ~M 5Of these, 0 to 2 are single bonds, and n is an integer of 0 to 10. 1 ~M 5 are oxygen atoms, the oxygen atoms are not adjacent to each other.)

[0007] [2] The method for producing a polymerizable unsaturated group-containing resin according to [1], wherein the alcohol solvent is 2,2-dimethyl-1,3-dioxolane-4-methanol.

[0008] [3] The method for producing a polymerizable unsaturated group-containing resin according to [1] or [2], wherein in the first step, 1 to 60 parts by mass of the (meth)acrylate compound (a1) and 40 to 99 parts by mass of the compound (a2) having one or more first polymerizable unsaturated groups and first reactive functional groups are mixed with each other relative to 100 parts by mass of the (meth)acrylic copolymer (A).

[0009] [4] The method for producing a polymerizable unsaturated group-containing resin according to any one of [1] to [3], wherein the first reactive functional group is one or more selected from the group consisting of a hydroxyl group, an epoxy group, an isocyanate group, a carboxyl group, and an acrylamide group.

[0010] [5] The method for producing a polymerizable unsaturated group-containing resin according to any one of [1] to [4], wherein the first polymerizable unsaturated group is one or more selected from the group consisting of a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, a vinyl ether group, and a (meth)acrylamide group.

[0011] [6] The method for producing a polymerizable unsaturated group-containing resin according to any one of [1] to [5], wherein a mixing ratio of the (meth)acrylic copolymer (A) and the compound (B) is in a range of 0.3 to 1.05 mol of the second reactive functional group contained in the compound (B) per 1 mol of the first reactive functional group contained in the (meth)acrylic copolymer (A).

[0012] [7] A (meth)acrylic copolymer (A) containing, as essential reaction raw materials (C), a (meth)acrylate compound (a1) and a compound (a2) having one or more first polymerizable unsaturated groups and first reactive functional groups; an alcohol solvent represented by the following general formula (1) having an oxygen atom-containing alicyclic group; A compound (B) having a second reactive functional group capable of reacting with the first reactive functional group; The above is used as a synthetic raw material (D) serving as a reaction raw material and an auxiliary for chemical reactions, and the biomass carbon content (%) (pMC%) of the entire resin is 20% or more. [ka] (In the above general formula (1), R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; M 1 ~M 5 each independently represents a meidine group, a methylene group, an oxygen atom, or a single bond; M 1 ~M 5 One or two of the groups are oxygen atoms, and M 1 ~M 5 is a mezine group, and the mezine group is -(CH 2 ) n -OH and M 1 ~M 5 Of these, 0 to 2 are single bonds, and n is an integer of 0 to 10. 1 ~M 5 are oxygen atoms, the oxygen atoms are not adjacent to each other.)

[0013] [8] The polymerizable unsaturated group-containing resin according to [7], wherein the alcohol solvent is 2,2-dimethyl-1,3-dioxolane-4-methanol.

[0014] [9] A curable resin composition comprising the polymerizable unsaturated group-containing resin according to [7] or [8] and a photopolymerization initiator.

[0015]

[10] The curable resin composition according to [9], further comprising a resin (X) having a polymerizable unsaturated group other than the polymerizable unsaturated group-containing resin.

[0016]

[11] A resin material for a solder resist, comprising the curable resin composition according to [9] or

[10] .

[0017]

[12] A cured product of the curable resin composition described in [9] or

[10] .

[0018]

[13] An insulating material comprising the cured product described in

[12] .

[0019]

[14] A resist member comprising the cured product according to

[12] . Effect of the Invention

[0020] According to the present disclosure, it is possible to provide a polymerizable unsaturated group-containing resin, a curable resin composition, and a cured product and article thereof, which have a low elastic modulus, excellent toughness, and excellent adhesion when cured. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Below, an embodiment of the present invention (hereinafter referred to as the "present embodiment") will be described in detail, but the present disclosure is not limited to the description below and can be implemented in various modifications within the scope of its gist.

[0022] <Terminology> In this specification, the term "reaction raw material" refers to a compound that is used to obtain a target compound by a chemical reaction such as synthesis or decomposition and that partially constitutes the chemical structure of the target compound, excluding catalysts and solvents. In particular, in this specification, the term "reaction raw material" refers to a precursor for obtaining the target polymerizable unsaturated group-containing resin or (meth)acrylic copolymer (A) by a chemical reaction. Meanwhile, in this specification, the term "synthesis raw materials" broadly includes substances that play the role of assistants in chemical reactions, such as solvents and catalysts, etc. These also include compounds that are used as reaction raw materials to obtain a target compound (including intermediate compounds) through chemical reactions such as synthesis or decomposition, and that partially constitute the chemical structure of the target compound. The term "synthetic starting material" is used herein because it is often impractical to directly identify a compound of interest by its structure. The term "structural unit" as used herein refers to a (repeating) unit of a chemical structure formed during a reaction or polymerization, in other words, refers to a partial structure other than the structure of the chemical bonds involved in the reaction or polymerization in a compound formed by a reaction or polymerization, i.e., a so-called residue. The "aromatic group" in this specification preferably has an aromatic ring having 3 to 30 carbon atoms, and more preferably has an aromatic ring having 4 to 26 carbon atoms. In addition, the "aromatic group" in this specification may have a hydrogen atom of the aromatic ring in the aromatic group substituted with a substituent, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. In addition, the "aromatic group" includes heteroaromatic groups, and the -CH in the "aromatic group" may be substituted with a substituent such as an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. 2 -O-(-CH 2 -), -S-(-CH 2 -), -N=(substituted with -CH=) or -NH-(-CH 2-) may be substituted. Examples of the aromatic ring include a monocyclic aromatic ring, a condensed aromatic ring, and an assembled aromatic ring. Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Examples of the condensed aromatic ring include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. Examples of the assembled aromatic ring include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. In addition, a hydrogen atom of an aromatic ring in the aromatic group may be substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. The divalent aromatic group refers to a group in which two hydrogen atoms have been removed from an "aromatic group". In the present specification, examples of the "aryl group" include a phenyl group, a naphthyl group, a phenalenyl group, a phenanthrenyl group, an anthryl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group. In addition, the "aryl group" may have a hydrogen atom of an aromatic ring in the aryl group substituted with, for example, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a halogen atom. In addition, examples of the "arylene group" include a divalent group obtained by removing any one hydrogen atom from the "aryl group". In the present specification, examples of the "aralkyl group" include a benzyl group, a diphenylmethyl group, a biphenyl group, and a naphthylmethyl group. A hydrogen atom of an aromatic ring in the aralkyl group may be substituted with, for example, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom. An example of the "aralkylene group" is a divalent group obtained by removing any one hydrogen atom from the "aralkyl group". In the present specification, examples of the "aryloxy group" include a phenoxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, and a pyrenyloxy group. As used herein, the term "arylthio group" includes arylthio groups such as a phenylthio group, a naphthylthio group, an anthrylthio group, a phenanthrylthio group, or a pyrenylthio group. In the present specification, the "alkyl group" may be linear, branched or cyclic, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, (n-)heptyl, (n-)octyl, (n-)nonyl, (n-)decyl, (n-)undecyl, (n-)dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclononyl. The alkylene group is a group obtained by removing one hydrogen atom from the above alkyl group. Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, and a pentylene oxide group. In the present specification, examples of a "cycloalkyl group" include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, and an adamantyl group. As used herein, the term "alkylthio group" includes a methylthio group, an ethylthio group, a propylthio group, a butylthio group, an octylthio group, and a 2-ethylhexylthio group. In the present specification, examples of the "alkenyl group" include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a pentynyl group, a hexynyl group, a vinyl group, an allyl group, and an isopropenyl group. In the present specification, examples of the "alkoxy group" include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group. As used herein, the term "halogen atom" includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. In the present specification, the "monovalent organic group" is preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. In addition, one or two or more non-adjacent -CH 2 - may be substituted with -O-, -COO-, or -OCO-. In addition, the "divalent organic group" refers to a group obtained by removing any one hydrogen atom from the above monovalent organic group. In addition, the "trivalent organic group" refers to a group obtained by removing any two hydrogen atoms from the above monovalent organic group. In addition, the "hexavalent organic group" refers to a group obtained by removing any five hydrogen atoms from the above monovalent organic group.

[0023] In this specification, the term "resin" includes not only solid matter but also a mixture of solid matter and a solvent.

[0024] [Polymerizable unsaturated group-containing resin] The polymerizable unsaturated group-containing resin of the present embodiment (hereinafter, sometimes simply referred to as "the resin of the present embodiment") is a polymerizable unsaturated group-containing resin which comprises a (meth)acrylic copolymer (A) having a (meth)acrylate compound (a1) and a compound (a2) having one or more first polymerizable unsaturated groups and first reactive functional groups as essential reaction raw materials (C), an alcohol solvent represented by the following general formula (1) having an oxygen atom-containing alicyclic group, and a compound (B) having a second reactive functional group capable of reacting with the first reactive functional group as synthesis raw materials (D) serving as reaction raw materials and chemical reaction assistants, and has a biomass carbon content (%) (pMC%) in the entire resin of 20% or more. [ka] In addition, in the above general formula (1), R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; M 1 ~M 5 each independently represents a meidine group, a methylene group, an oxygen atom, or a single bond; M 1 ~M 5 One or two of the groups are oxygen atoms, and M 1 ~M 5 is a mezine group, and the mezine group is -(CH 2 ) n -OH and M 1 ~M 5 Of these, 0 to 2 are single bonds, and n is an integer of 0 to 10. 1 ~M 5 When two of M are oxygen atoms, the oxygen atoms are not adjacent to each other. 1 ~M 5 When two of the groups are single bonds, it means that the moieties form a four-membered ring.

[0025] In this embodiment, the alcohol solvent represented by the above general formula (1) is preferably 2,2-dimethyl-1,3-dioxolane-4-methanol. Hereinafter, the components of the synthesis raw material (D) for the polymerizable unsaturated group-containing resin of this embodiment, that is, the (meth)acrylic copolymer (A) and the compound (B) having a second reactive functional group capable of reacting with the first reactive functional group, will be described.

[0026] ((Meth)acrylic copolymer (A)) The (meth)acrylic copolymer (A) of the present embodiment is a copolymer having a (meth)acrylate compound (a1) and a compound (a2) having a first polymerizable unsaturated group and one or more of the first reactive functional groups as essential reaction raw materials (C). By including a structural unit derived from the (meth)acrylic copolymer (A) as a structural unit constituting the polymerizable unsaturated group-containing resin of the present disclosure, the resin can exhibit the effects of having a low elastic modulus, excellent toughness, and excellent adhesion. The lower limit of the biomass carbon content (%) of the (meth)acrylic copolymer (A) (solid content) of this embodiment may be, for example, preferably 1% or more, more preferably 3% or more, even more preferably 5% or more, even more preferably 9% or more, and even more preferably 12% or more. On the other hand, the upper limit of the biomass carbon content (%) may be preferably 100% or less, more preferably 90% or less, even more preferably 80% or less, and even more preferably 70% or less. The upper and lower limits may be appropriately combined.

[0027] Hereinafter, each component of the reaction raw material (C) for the (meth)acrylic copolymer (A) of this embodiment will be described. <(Meth)acrylate Compound (a1) (hereinafter, also referred to as compound (a1))> By including a structural unit derived from the (meth)acrylate compound (a1) as a structural unit constituting the (meth)acrylic copolymer (A) of the present disclosure, the copolymer can exhibit the effects of having a low elastic modulus, excellent toughness, and excellent adhesion. The (meth)acrylate compound (a1) of this embodiment may be a monofunctional or difunctional (meth)acrylate monomer having one or two (meth)acryloyloxy groups in the molecule.

[0028] The (meth)acrylate compound (a1) of this embodiment may be a non-aromatic compound (so-called aliphatic compound) having a (meth)acrylate group ((meth)acrylo group) and no aromatic ring, or an aromatic compound having a (meth)acrylate group and an aromatic ring. When heat yellowing resistance is important, non-aromatic compounds, particularly aliphatic compounds or alicyclic compounds, are generally preferred (however, benzyl methacrylate has excellent heat yellowing resistance). On the other hand, when heat resistance (high glass transition temperature Tg) and the like are important, aromatic compounds having an aromatic ring are generally preferred. The non-aromatic compound may be linear, branched, or cyclic. In this specification, "(meth)acrylate" means acrylate and / or methacrylate. "(meth)acryloyl" means acryloyl and / or methacryloyl. "(meth)acrylic" means acrylic and / or methacrylic.

[0029] When the (meth)acrylate compound (a1) is a monofunctional (meth)acrylate monomer, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, octa ... (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl mono(meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, N-[2-(acryloyloxy)ethyl]phthalimide, N-[2-(acryloyloxy)ethyl]tetrahydrophthalimide, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, ω-carboxy-polycaprolactone mono Noacrylate, benzyl acrylate, benzyl methacrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, phenylbenzyl acrylate, phenoxy acrylate, phenoxyethyl acrylate, phenoxyethoxyethyl acrylate, phenoxybenzyl acrylate, phenylphenoxyethyl acrylate, phenyl methacrylate, phenylbenzyl methacrylate, phenoxybenzyl methacrylate, biphenyl methyl methacrylate, phenol EO modified methacrylate, phenol PO modified methacrylate,Examples of the methacrylate include nonylphenol EO-modified methacrylate, nonylphenol PO-modified methacrylate, phenylphenol EO-modified methacrylate, phenylphenol PO-modified methacrylate, monohydroxyethyl phthalate methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, and N-phenylmethacrylamide.

[0030] When the (meth)acrylate compound (a1) is a bifunctional (meth)acrylate monomer, for example, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalic acid ester di(meth)acrylate, di(meth)acrylate in which two hydroxyl groups of tris(2-hydroxyethyl)isocyanurate are substituted with (meth)acryloyloxy groups, di(meth)acrylate in which two hydroxyl groups of diol obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol are substituted with (meth)acryloyloxy groups, bisphenol A Examples of the di(meth)acrylate include a diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A, in which the two hydroxyl groups are substituted with (meth)acryloyloxy groups; bisphenol A type EO modified dimethacrylate; bisphenol A type PO modified dimethacrylate; bisphenol F type EO modified dimethacrylate; bisphenol F type PO modified dimethacrylate; biphenol dimethacrylate; a triol obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane, in which the two hydroxyl groups are substituted with (meth)acryloyloxy groups; and a di(meth)acrylate obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of bisphenol A, in which the two hydroxyl groups are substituted with (meth)acryloyloxy groups. (Poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butadiene glycol di(meth)acrylate, aliphatic di(meth)acrylate compounds such as hexanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate; biphenol diacrylate aromatic diacrylate compounds such as bisphenol diacrylate and bisphenol diacrylate; polyoxyalkylene-modified di(meth)acrylate compounds obtained by introducing a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain into the molecular structure of the above-mentioned various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds obtained by introducing a (poly)lactone structure into the molecular structure of the above-mentioned various di(meth)acrylate compounds; trimethylolpropane tri(meth)acrylate; aliphatic tri(meth)acrylate compounds such as acrylate and glycerin tri(meth)acrylate; (poly)oxyalkylene-modified tri(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds;Examples of such compounds include tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds; and tetrafunctional or higher lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds. The above (meth)acrylate compound (a1) may be used alone or in combination of two or more. Among these, monofunctional methacrylates are preferred, and benzyl (meth)acrylate, phenyl (meth)acrylate, or methyl (meth)acrylate are more preferred, since they can provide a polymerizable unsaturated group-containing resin capable of forming a cured product having excellent toughness and adhesion.

[0031] In this embodiment, the content of the (meth)acrylate compound (a1) (in other words, the content of the structural unit of the (meth)acrylate compound (a1)) in the entire (meth)acrylic copolymer (A) is preferably 1% by mass or more and 40% by mass or less in the copolymer (A) because a polymerizable unsaturated group-containing resin capable of forming a cured product excellent in toughness and adhesion can be obtained. In particular, when an aromatic compound having an aromatic ring such as benzyl (meth)acrylate or phenyl (meth)acrylate is selected as the (meth)acrylate compound (a1), the content of the aromatic compound having an aromatic ring (e.g., benzyl (meth)acrylate) in the copolymer (A) is preferably 3% by mass or more and 15% by mass or less, more preferably 3% by mass or more and 10% by mass or less. On the other hand, when methyl (meth)acrylate is selected as the (meth)acrylate compound (a1), the content of methyl (meth)acrylate in the copolymer (A) is preferably 1% by mass or more and 40% by mass or less, more preferably more than 5% by mass or less and 38% by mass or less. The lower limit of the biomass carbon content (%) of the compound (a1) (solid content) of this embodiment may be, for example, preferably 0% or more, more preferably 3% or more, even more preferably 5% or more, even more preferably 9% or more, and even more preferably 12% or more. On the other hand, the upper limit of the biomass carbon content (%) may be preferably 100% or less, more preferably 98% or less, even more preferably 95% or less, and even more preferably 90% or less. The upper and lower limits may be appropriately combined.

[0032] <Compound (a2) Having One or More First Polymerizable Unsaturated Groups and One or More First Reactive Functional Groups (hereinafter also referred to as compound (a2))> By including a structural unit derived from the compound (a2) as a structural unit constituting the (meth)acrylic copolymer (A) of the present disclosure, the amount of unsaturated bonds can be easily adjusted, and as a result, excellent effects in toughness and adhesion can be exhibited. The compound (a2) having one or more first polymerizable unsaturated groups and one or more first reactive functional groups in this embodiment has one or two first polymerizable unsaturated groups and one or more first reactive functional groups in the molecule, and has a chemical structure different from that of the (meth)acrylate compound (a1). In this embodiment, the compound (a2) is preferably one having a first reactive functional group and a first polymerizable unsaturated group in one molecule. In this specification, the term "polymerizable unsaturated group" refers to an unsaturated group that can be radically polymerized. Examples of the first reactive functional group include a hydroxyl group, an epoxy group, an isocyanate group, a carboxyl group, and an alkoxy group. These first reactive functional groups may be present alone or in combination. However, the compound (a2) has a different chemical structure from the (meth)acrylate compound (a1). When the compound (a2) has two or more first reactive functional groups, the first reactive functional groups may have the same chemical structure as any one of the other reactive functional groups or may have a different chemical structure. When the compound (a2) has two or more first reactive functional groups, the first reactive functional groups may have a different chemical structure from the (meth)acrylate compound (a1).

[0033] In this embodiment, examples of the first polymerizable unsaturated group include a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, a vinyl ether group, and a (meth)acrylamide group. Among these, a (meth)acryloyl group and a styryl group are preferred from the viewpoint of easily adjusting the amount of unsaturated bonds in the molecule and thus exhibiting excellent effects in terms of toughness and adhesion.

[0034] In this embodiment, the preferred aspects of the compound (a2) having one or more first polymerizable unsaturated groups and first reactive functional groups are as follows: the compound (a2) has a hydroxyl group as the first reactive functional group, the compound (a2) has an epoxy group as the first reactive functional group, the compound (a2) has an isocyanate group as the first reactive functional group, the compound (a2) has a carboxyl group as the first reactive functional group, and the compound (a2) has an alkoxy group as the first reactive functional group. The five aspects are described below.

[0035] When the compound (a2) of this embodiment has a hydroxyl group as the first reactive functional group, examples of the compound (a2) include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and (meth)acrylic acid. In addition, (poly)oxyalkylene modified compounds obtained by introducing a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain into the molecular structure of the above-mentioned various compounds, and lactone modified compounds obtained by introducing a (poly)lactone structure into the molecular structure of the above-mentioned various compounds, etc. can also be used. These compounds can be used alone or in combination of two or more kinds. Among these, the compound (a2) of the present embodiment is preferably hydroxyethyl(meth)acrylate, pentaerythritol di(meth)acrylate, or pentaerythritol tri(meth)acrylate, and more preferably pentaerythritol tri(meth)acrylate.

[0036] When the compound (a2) of this embodiment has an epoxy group as the first reactive functional group, the compound (a2) may be, for example, a glycidyl group-containing (meth)acrylate monomer such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, or epoxycyclohexylmethyl (meth)acrylate; or a mono(meth)acrylate of a diglycidyl ether compound such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, or bisphenol diglycidyl ether. Among them, the compound (a2) of this embodiment is preferably a glycidyl group-containing (meth)acrylate monomer, and more preferably glycidyl (meth)acrylate. These compounds may be used alone or in combination of two or more.

[0037] When the compound (a2) of the present embodiment has an isocyanate group as the first reactive functional group, examples of the compound (a2) include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, etc. These compounds can be used alone or in combination of two or more kinds. Moreover, as the (meth)acrylate compound having an isocyanate group, a compound obtained by adding a (meth)acrylate compound having a hydroxyl group to one of the isocyanate groups of a diisocyanate compound can also be used. Examples of the diisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; and aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate. In addition, as the compound (a2) having an isocyanate group, a commercially available product can also be used. Examples of the commercially available product include Karenz AOI, Karenz MOI, and Karenz BEI manufactured by Showa Denko K.K.

[0038] When the compound (a2) of this embodiment has a carboxyl group as the first reactive functional group, other specific structures are not particularly limited as long as the compound has a carboxyl group and a first polymerizable unsaturated group in the molecular structure, and a wide variety of compounds can be used.Specific examples thereof include those having a (meth)acryloyl group as the first polymerizable unsaturated group, such as (meth)acrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid, or their esters, acid halides, or acid anhydrides.

[0039] Further, as the compound having a carboxyl group and a (meth)acryloyl group as the first polymerizable unsaturated group, for example, a compound represented by the following general formula (2) can also be used. [ka] (In the above general formula (2), X 1represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain; X 1 The hydrogen atoms in the structure of Y may be substituted with halogen atoms, alkoxy groups, etc. 1 is a hydrogen atom or a methyl group.

[0040] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

[0041] An example of the (poly)ester chain is a (poly)ester chain represented by the following general formula (3-1).

[0042] [ka] (In the above general formula (3-1), R 2 are each independently an alkylene group having 1 to 10 carbon atoms, 2 is an integer between 1 and 5.)

[0043] An example of the (poly)carbonate chain is a (poly)carbonate chain represented by the following general formula (3-2). [ka] In the above general formula (3-2), R 3 represents an alkylene group having 1 to 10 carbon atoms, 3 represents an integer from 1 to 5.)

[0044] Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. Furthermore, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used.

[0045] Further, as the compound having a carboxyl group and a (meth)acryloyl group as the first polymerizable unsaturated group, for example, a compound represented by the following general formula (4) can also be used. [ka] In the above general formula (4), X 4 represents an alkylene chain having 1 to 10 carbon atoms, which may contain a halogen atom or the like in the structure. 4 is a hydrogen atom or a methyl group. 4 is an integer between 1 and 5.)

[0046] These compounds having a carboxyl group and a first polymerizable unsaturated group can be used alone or in combination of two or more. Among these, acrylic acid, methacrylic acid, and ω-carboxy-polycaprolactone mono(meth)acrylate are preferred because they tend to produce a polymerizable unsaturated group-containing resin capable of forming a cured product having excellent photosensitivity, elongation, heat yellowing resistance, and adhesion.

[0047] When the compound (a2) of the present embodiment has an alkoxy group as the first reactive functional group, examples of the compound (a2) include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide, etc. These compounds can be used alone or in combination of two or more kinds.

[0048] In this embodiment, examples of compound (a2) other than the exemplified compound (a2) include unsaturated acids such as cinnamic acid, acid anhydrides having an unsaturated bond in the molecule such as tetrahydrophthalic anhydride and maleic anhydride, allyl compounds having a reactive functional group such as allyl alcohol, vinyl ether compounds having a first reactive functional group such as 2-hydroxyethyl vinyl ether, maleimide compounds having a first reactive functional group such as N-(4-aminophenyl)maleimide, and styryl compounds having a second reactive functional group such as 4-vinylbenzoic acid.

[0049] In the present embodiment, since a polymerizable unsaturated group-containing resin capable of forming a cured product is obtained, the content of the compound (a2) in the (meth)acrylic copolymer (A) is preferably in the range of 50 to 95 mass %, more preferably in the range of 60 to 90 mass %. In the reaction raw material (C) according to the present embodiment, the ratio of the amount of compound (a1) to the amount of compound (a2) (amount of compound (a1) / amount of compound (a2)) is preferably 5 / 95 to 50 / 50. The lower limit of the biomass carbon content (%) of the compound (a2) (solid content) of this embodiment may be, for example, preferably 0% or more, more preferably 3% or more, even more preferably 5% or more, even more preferably 9% or more, and even more preferably 12% or more. On the other hand, the upper limit of the biomass carbon content (%) may be preferably 100% or less, more preferably 98% or less, even more preferably 95% or less, and even more preferably 90% or less. The upper and lower limits may be appropriately combined.

[0050] <Other polymerization components that may be contained in the reaction material (C)> In this embodiment, the reaction raw material (C) of the (meth)acrylic copolymer (A) may contain other polymerization components, if necessary, in addition to the compound (a1) and the compound (a2). Examples of the other polymerization components include a compound (a3) ​​having a polymerizable unsaturated group other than the (meth)acrylate compound (a1) and the compound (a2) having one or more first polymerizable unsaturated groups and first reactive functional groups.

[0051] The compound (a3) ​​having a polymerizable unsaturated group other than the (meth)acrylate compound (a1) and the compound (a2) having one or more first polymerizable unsaturated groups and one or more first reactive functional groups is not particularly limited as long as it is a compound having one or more polymerizable unsaturated groups in the molecule. Examples of the polymerizable unsaturated group include an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, and a vinyl ether group. These compounds (a3) ​​can be used alone or in combination of two or more kinds. The compound (a3) ​​has a different chemical structure from the compound (a2), and is a different compound from the compound (a1) and the compound (a2). In the reaction raw material (C) according to the present embodiment, the amount of compound (a3) ​​per 100 parts by mass of compound (a1) is preferably 0 parts by mass or more and 20 parts by mass or less, more preferably 0 to 10 parts by mass, and even more preferably 0 to 8 parts by mass.

[0052] <Method for producing (meth)acrylic copolymer (A)> The method for producing the (meth)acrylic copolymer (A) of the present embodiment is not particularly limited, and may be produced by any method. For example, the polymerization components containing the compound (a1), the compound (a2), and other compounds (a3) ​​that are mixed as necessary are polymerized at 50 to 200° C. at once. In this case, if the reaction is carried out in an oxygen atmosphere, the polymerization reaction may be stopped due to the polymerization inhibition effect, so it is preferable to carry out the polymerization in an inert gas or nitrogen atmosphere.

[0053] In the step of polymerizing the (meth)acrylic copolymer (A) of this embodiment, a polymerization initiator can be used as necessary. Examples of the polymerization initiator include persulfates, organic peroxides, hydrogen peroxide, and azo-based polymerization initiators such as 4,4'-azobis(4-cyanovaleric acid) and 2,2'-azobis(2-amidinopropane) dihydrochloride. The polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent such as ascorbic acid. These polymerization initiators may be used alone or in combination of two or more.

[0054] Examples of the persulfate include potassium persulfate, sodium persulfate, ammonium persulfate, etc. These persulfates can be used alone or in combination of two or more kinds.

[0055] Examples of the organic peroxide include diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, and decanoyl peroxide, dialkyl peroxides such as t-butyl cumyl peroxide and dicumyl peroxide, peroxy esters such as t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy laurate, and t-butyl peroxy benzoate, and hydroperoxides such as cumene hydroperoxide, paramenthane hydroperoxide, and t-butyl hydroperoxide. These organic peroxides can be used alone or in combination of two or more. Among these, peroxy esters are preferred because they can provide a polymerizable unsaturated group-containing resin capable of forming a cured product having excellent toughness and adhesion.

[0056] The amount of the polymerization initiator used may be an amount that allows the polymerization to proceed smoothly, and is preferably in the range of 0.1 to 20 parts by mass, and more preferably in the range of 0.5 to 10 parts by mass, relative to 100 parts by mass of the total of the polymerization components containing the compound (a1) and the compound (a2).

[0057] In the reaction raw material (C) according to the present embodiment, a preferred blending ratio of the compound (a1) to the compound (a2) is, relative to the total amount of the reaction raw material (C), 1 mass % to 60 mass % of the compound (a1) and 20 mass % to 99 mass % of the compound (a2), more preferably 5 mass % to 40 mass % of the compound (a1) and 30 mass % to 90 mass % of the compound (a2), even more preferably 5 mass % to 35 mass % of the compound (a1) and 50 mass % to 90 mass % of the compound (a2), and particularly preferably 5 mass % to 30 mass % of the compound (a1) and 60 mass % to 90 mass % of the compound (a2). In addition, when the reaction raw material (C) according to the present embodiment contains the compound (a3), the preferred compounding ratios of the compound (a1) and the compound (a3) ​​relative to the amount of the reaction raw material (C) may be 50% by mass to 99% by mass of the compound (a1) and 1% by mass to 50% by mass of the compound (a3), more preferably 70% by mass to 99% by mass of the compound (a1) and 1% by mass to 30% by mass of the compound (a3), even more preferably 80% by mass to 99% by mass of the compound (a1) and 1% by mass to 20% by mass of the compound (a3), and particularly preferably 90% by mass to 99% by mass of the compound (a1) and 1% by mass to 10% by mass of the compound (a3).

[0058] (Compound (B) Having a Second Reactive Functional Group (Hereinafter, referred to as compound (B))) By including a structural unit derived from the compound (B) having a second reactive functional group as a structural unit constituting the polymerizable unsaturated group-containing resin of the present disclosure, excellent effects in terms of toughness and adhesion can be exhibited. The compound (B) of the present embodiment is a compound having a second reactive functional group, and the second reactive functional group in the compound (B) is a functional group capable of reacting with a first reactive functional group in a structural unit derived from the compound (a2) contained in the (meth)acrylic copolymer (A). Examples of the second reactive functional group in this embodiment include a hydroxyl group, an amino group, an epoxy group, an isocyanate group, a carboxyl group, an alkoxy group, etc. Compound (B) may have one type of these second reactive functional groups, or two or more types of them. Furthermore, the number of these second reactive functional groups in compound (B) may be one or two or more. As described above, the second reactive functional group in this embodiment is a functional group that can react with the first reactive functional group, and therefore can be appropriately selected from the group consisting of a hydroxyl group, an amino group, an epoxy group, an isocyanate group, a carboxyl group, and an alkoxy group, which can react with the first reactive functional group, depending on the type of the first reactive functional group.

[0059] In the present embodiment, examples of the polymerizable unsaturated group that can react with the first reactive functional group include (meth)acryloyl group, allyl group, isopropenyl group, 1-propenyl group, styryl group, styrylmethyl group, maleimide group, vinyl ether group, and (meth)acrylamide group. The polymerizable unsaturated group may be the same as or different from the first polymerizable unsaturated group. The preferred polymerizable unsaturated group is one or more groups selected from the group consisting of (meth)acryloyl group, allyl group, isopropenyl group, 1-propenyl group, styryl group, maleimide group, vinyl ether group, and (meth)acrylamide group.

[0060] As described above, the compound (B) having a second reactive functional group of this embodiment has a different chemical structure from the (meth)acrylate compound (a1) and the compound (a2). Therefore, when the compound (B) having a second reactive functional group is compared with the (meth)acrylate compound (a1), the compound (B) has a group that does not exist in the (meth)acrylate compound (a1), or the (meth)acrylate compound (a1) has a group that does not exist in the compound (B). Furthermore, when the compound (B) having a second reactive functional group is compared with the compound (a2), the compound (B) has a group that does not exist in the compound (a2), or the compound (a2) has a group that does not exist in the compound (B). Hereinafter, in this embodiment, the form of the combination of the compound (a2) and the compound (B) having a second reactive functional group will be described.

[0061] Examples of the compound (B) include the same compounds as those exemplified as the compound (a2) described above. When a compound having a hydroxyl group and a (meth)acryloyl group is used as the compound (a2), it is preferable to use a compound having an isocyanate group and a (meth)acryloyl group and / or a compound having an alkoxy group and a (meth)acrylamide group as the compound (B). When a compound having an epoxy group and a (meth)acryloyl group is used as the compound (a2), it is preferable to use a compound having a carboxyl group and a (meth)acryloyl group as the compound (B). When a compound having an isocyanate group and a (meth)acryloyl group is used as (a2), it is preferable to use a compound having a hydroxyl group and a (meth)acryloyl group as compound (B), when a compound having a carboxyl group and a (meth)acryloyl group is used as compound (a2), it is preferable to use a compound having an epoxy group and a (meth)acryloyl group as compound (B), and when a compound having an alkoxy group and a (meth)acrylamide group is used as compound (a2), it is preferable to use a compound having a hydroxyl group and a (meth)acryloyl group as compound (B). These compounds (B) can be used alone or in combination of two or more kinds. Among these, it is preferable to use a compound having an epoxy group and a (meth)acryloyl group as the compound (a2) and a compound having a carboxyl group and a (meth)acryloyl group as the compound (B), because a polymerizable unsaturated group-containing resin capable of forming a cured product excellent in toughness and adhesion can be obtained. It is also preferable to use a compound having a carboxyl group as the compound (a2) and a compound having an epoxy group as the compound (B).

[0062] The compound (B) having a second reactive functional group in this embodiment is preferably represented by the following general formula (5). [ka] (In the above general formula (5), R b1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; L b1represents -O- or -NH-; P b1 represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, provided that the alkyl group has one or more -CH 2 - represents -O-, -C(=O)O-, -O(C=O)-, -C(=O)- or a cyclic group (e.g., a divalent aromatic group (particularly, a phenylene group) or a divalent alicyclic group). b1 -P b1 In the above, the second reactive functional group is one or more selected from the group consisting of a hydroxyl group, an amino group, an epoxy group, an isocyanate group, a carboxyl group, and an alkoxy group. In the above general formula (5), R b1 preferably represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom, a methyl group, or a fluoromethyl group. In the above general formula (5), the alicyclic group is preferably a 4- to 7-membered alicyclic group which may contain at least one nitrogen atom, oxygen atom or sulfur atom. The alicyclic group may have a hydroxyl group, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, or one or more -CH 2 - may be substituted with -C(=O)-. The divalent alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic divalent alicyclic group include monocyclic cycloalkylene groups such as a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group. Examples of the polycyclic divalent alicyclic group include polycyclic cycloalkylene groups such as a norbornylene group, a tricyclodecanylene group, a tetracyclodecanylene group, a tetracyclododecanylene group, and an adamantylene group. In the above general formula (5), P b1 is more preferably a hydrogen atom or any of the following general formulae (5-1) to (5-4). [ka] (In the above formulas (5-1) to (5-4), A 51 is unsubstituted or one or more hydrogen atoms are substituted by R b2A represents a divalent aromatic group (preferably a 1,2-phenylene group, a 1,3-phenylene group, or a 1,4-phenylene group) optionally substituted by 52 is unsubstituted or one or more hydrogen atoms are substituted by R b2 represents a divalent alicyclic group (preferably a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a norbornylene group, a tricyclodecanylene group, a tetracyclodecanylene group, a tetracyclododecanylene group, or an adamantylene group) optionally substituted by b1 represents an integer from 1 to 10, and n b2 represents an integer from 1 to 10, m b1 represents an integer between 1 and 10, and Y 51 , Y 52 and Y 53 each independently represents a hydroxyl group, an epoxy group, an isocyanate group, a carboxyl group, or an alkoxy group; R b2 represents a halogen atom, a cyano group, an amino group, or an alkyl or alkoxy group having 1 to 5 carbon atoms. It is preferable that the compound (B) having a second reactive functional group is a compound represented by the above general formula (5), from the viewpoint of exerting excellent effects in toughness and adhesion.

[0063] In this embodiment, the compound (B) having a second reactive functional group is preferably one or more selected from the group consisting of glycidyl methacrylate, (meth)acrylic acid, 2-(trifluoromethyl)acrylic acid, mono(2-acryloyloxyethyl) succinate, mono-2-(methacryloyloxy)ethyl phthalate, monohydroxyethyl phthalate acrylate, ω-carboxy-polycaprolactone monoacrylate, and 6-acrylamidohexanoic acid. The compound (B) having a second reactive functional group in this embodiment is preferably two or more compounds having different chemical structures. When the compound (B) having a second reactive functional group is two or more compounds, it is preferable from the viewpoint of exhibiting excellent effects in toughness and adhesion.

[0064] In this embodiment, the mixing ratio of the (meth)acrylic copolymer (A) using a compound having an epoxy group and a (meth)acryloyl group as the compound (a2) to the compound (B) using a carboxyl group and a (meth)acryloyl group is preferably in the range of 0.3 to 1.05 mol, more preferably 0.3 to 1.03 mol, and further preferably 0.4 to 1.03 mol of the second reactive functional group of the compound (B) per 1 mol of the first reactive functional group of the (meth)acrylic copolymer (A).

[0065] In addition, the mixing ratio of the (meth)acrylic copolymer (A) using a compound having a carboxyl group and a (meth)acryloyl group as the compound (a2) to the compound (B) using an epoxy group and a (meth)acryloyl group is preferably in the range of 0.2 to 1.1 mol, more preferably 0.3 to 0.9, and even more preferably 0.4 to 0.8, of the second reactive functional group contained in the compound (B) relative to 1 mol of the first reactive functional group contained in the (meth)acrylic copolymer (A).

[0066] The lower limit of the biomass carbon content (%) of the compound (B) (solid content) of this embodiment may be, for example, preferably 0% or more, more preferably 3% or more, even more preferably 5% or more, even more preferably 9% or more, and even more preferably 12% or more. On the other hand, the upper limit of the biomass carbon content (%) may be preferably 100% or less, more preferably 98% or less, even more preferably 95% or less, and even more preferably 90% or less. The upper and lower limits may be appropriately combined.

[0067] (Preferred embodiment of polymerizable unsaturated group-containing resin) Since the polymerizable unsaturated group-containing resin of the present embodiment can form a cured product excellent in toughness and adhesion, the total content of the (meth)acrylic copolymer (A) and the compound (B) (the structural units of the (meth)acrylic copolymer (A) and the structural units of the compound (B)) in the polymerizable unsaturated group-containing resin is preferably 35 mass% or more, more preferably 40 mass% or more, and still more preferably 45 mass% or more.

[0068] The polymerizable unsaturated group-containing resin of this embodiment may further contain, as the synthesis raw material (D), a compound (E) having a phenolic hydroxyl group and a tert-butyl group, if necessary. Examples of the compound (E) include tert-butylcatechol, tert-butylhydroquinone, tert-butylresorcinol, 2,5-di-tert-amylhydroquinone, tert-butyl-p-benzoquinone, 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-methylphenol (dibutylhydroxytoluene), 2,6-di-tert-butyl-4-ethylphenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2 ,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), N,N'-bis{2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl}oxamide, octyl-3,5-di-tert-butyl-4-hydroxyphenyl Hydroxy-hydrocinnamic acid, 3,6-dioxaoctamethylene bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 2,2'-dimethyl-2,2'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dipropane-1,1'-diyl bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate], 3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate stearyl, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylene bis(oxyethylene)]triethylene glycol-bis-[3-(3-tert-butyl-5-methyl-4 hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-Triazine, pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethylene ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl)calcium, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)isocyanuric acid, N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, tris(2,4-di-tert-butylphenyl)phosphite, 2-(3,5-di-tert-butylphenyl)phosphonic acid ethyl)calcium 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl), 2,4-di-tert-butylphenyl -3,5-di-t-butyl-4-hydroxybenzoate, pentaerythritol tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 2,4.6-tri-tert-butylnitrobenzene, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,4,8,10-tetra-tert-butyl-6-[(2-ethylhexyl)oxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, etc. These compounds can be used alone or in combination of two or more. Among these, 2,6-di-tert-butyl-p-cresol, pentaerythritol tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], and 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] are preferred because they are capable of forming a cured product with excellent toughness and adhesion. The content of the compound (E) in the polymerizable unsaturated group-containing resin of this embodiment is preferably in the range of 0.01 to 10% by mass, and more preferably in the range of 0.01 to 5% by mass. The amount of the compound (E) in the polymerizable unsaturated group-containing resin of this embodiment is preferably within a range from 0.01 to 10% by mass, and more preferably within a range from 0.01 to 5% by mass.

[0069] In addition, since it is possible to form a cured product with excellent toughness and adhesion, the double bond equivalent (g / equivalent) of the polymerizable unsaturated group-containing resin of this embodiment is preferably 500 or less, more preferably 450 or less. In this specification, the "double bond equivalent" is an amount that is an index of the amount of double bonds contained in a molecule, and if the compounds have the same molecular weight, the smaller the double bond equivalent value, the more double bonds are introduced. The "double bond equivalent" is a calculated value calculated from the amount of raw materials charged, as described in the Examples section. The acid value of the solid content of the polymerizable unsaturated group-containing resin of this embodiment is preferably in the range of 50 to 130 mgKOH / g, more preferably 55 to 120 mgKOH / g, as measured under neutral conditions. The "acid value of the solid content" was calculated by the method described in the Examples section.

[0070] [Biomass carbon content (%)] In this specification, "biomass carbon content (%)" refers to the radioactive carbon ( 14 C) content ratio (pMC%) multiplied by 0.93, which is the correction ratio, and when the correction value is 100% or more, it is regarded as 100%. In this specification, radiocarbon14 The content ratio (pMC%) of radioactive carbon (C) in the biomass-derived component indicates the carbon concentration (mass ratio) of the biomass-derived component, and is related to the so-called biomass blending ratio. More specifically, the content ratio of radioactive carbon ( 14 C) Radiocarbon obtained by the measurement method ( 14 C) content ratio. 14 C) has a half-life of 5730 years, and nitrogen ( 14 It is known that radioactive carbon ( 14 C) Carbon dioxide 14 CO 2 It is oxidized to carbon dioxide and diffuses into the atmosphere, then is taken up by animals and plants through the food chain, and disappears according to its half-life as it circulates through the environment via the food chain. 14 C) The measurement method is that fossil fuels are radiocarbon ( 14 C), and biomass (or biological carbon) is essentially free of radioactive carbon ( 14 C) in the carbon contained in biomass materials (or living organisms), 14 C) Ratio to radiocarbon ( 14 C) content (pMC%). 14 The higher the ratio of radioactive carbon (pMC%), the less fossil fuels are used, which can reduce the environmental impact. 14 The value of the carbon content ratio (pMC%) of carbon dioxide (CO2) is related to the index showing the blend ratio of biomass, which is a renewable, biologically derived organic resource (=biomass carbon content (%)).

[0071] And the radioactive carbon ( 14 By measuring the ratio of radioactive carbon (C) in the sample to be measured, the ratio of carbon derived from biomass can be calculated. 14 C) content (pMC%) can be calculated. Formula (A): Radiocarbon ( 14 C) content ratio (pMC%) = [{radioactive carbon ( 14 C) ÷ Carbon in the sample to be measured ( 12 C)} / {Radiocarbon of standard material ( 14 C) / Standard Carbon ( 12 C)}×100 (In the above formula, the standard substance is oxalic acid (SRM4990C) supplied by the National Institute of Standards and Technology as a standard substance for dating, which has been converted to graphite using the same pretreatment method (described below) as for the graphite used for measurement.)

[0072] Next, the radioactive carbon ( 14 The biomass carbon content (%) can be calculated by multiplying the biomass carbon content (pMC%) by 0.93, taking into account the effects of atmospheric nuclear testing from 1950 to the present. Formula (B): Biomass carbon content (%) = Radiocarbon ( 14 C) content ratio (pMC%) x 0.93

[0073] As a supplementary note, radioactive carbon ( 14 C), which produces about 1.5 times the usual amount of radioactive carbon ( 14 C) has been observed. However, it has gradually decreased over time, and the current value is around 107.5 (pMC%). Therefore, in this embodiment, radiocarbon ( 14 The content ratio (pMC%) of carbon monoxide (C) is multiplied by 0.93 (=100 / 107.5) to define the biomass carbon content (%). However, even when the method using the above formula (B) is adopted, there are cases where a value of 100% or more is calculated. Therefore, in this embodiment, as in the ASTM standard, when the value calculated by the above formula (B) is 100% or more, the biomass carbon content (%) is regarded as 100%.

[0074] Radiocarbon (14 The concentration of C is measured by accelerator mass spectrometry (AMS), which combines a tandem accelerator and a mass spectrometer, to measure the isotopes of carbon atoms (specifically, 12 C, 13 C, 14 Examples of isotopes include C. This can be done by using a method in which the isotopes are physically separated using an accelerator, taking advantage of the weight difference between the atoms, and the abundance of each atom of the isotope is measured. The sample to be measured requires pretreatment. Specifically, as described in the Examples section below, the carbon contained in the sample to be measured is oxidized and converted into carbon dioxide. The resulting carbon dioxide is then separated from water and nitrogen, reduced, and converted into graphite for measurement, which is solid carbon. Then, Cs is added to this graphite for measurement. + The carbon ions are accelerated using a 3MV tandem accelerator, and the negative ions are converted to positive ions. The negative ions are then converted to positive ions using a mass analysis magnet. 12 C 3+ , 13 C 3+ , 14 C 3+ Separating the traveling orbit of 14 C 3+ is measured using an electrostatic analyzer. The carbon isotopes contained in the graphite obtained in the pretreatment 12 C. 13 C and 14 C is accelerated at the same speed and its flight path is bent by the magnetic field of the mass analysis electromagnet. 12 C. 13 C is on the inside, the heaviest 14 C flies on the outermost side of the bend. 12 C. 13 Since the amount of C is large, it is detected as a current by a Faraday cup detector. 14 C are counted one by one by an ionization chamber type ion detector.

[0075] In this embodiment, examples of the measurement sample (the subject for measuring the biomass carbon content) include, in addition to the polymerizable unsaturated group-containing resin, various reaction raw materials such as the (meth)acrylic copolymer (A) and the compound (B) having a second reactive functional group, and a curable resin composition.

[0076] [Method of producing polymerizable unsaturated group-containing resin] The method for producing the polymerizable unsaturated group-containing resin of the present embodiment is not particularly limited, and may include a first step of mixing a (meth)acrylate compound (a1) and a compound (a2) having one or more first polymerizable unsaturated groups and a first reactive functional group in the presence of an alcohol solvent represented by the following general formula (1) having a biomass carbon content (%) (pMC%) of 30% or more and an oxygen atom-containing alicyclic group to obtain a (meth)acrylic copolymer (A), and a second step of mixing a (meth)acrylic copolymer (A) and a compound (B) having a second reactive functional group capable of reacting with the first reactive functional group in the presence of an alcohol solvent to obtain a polymerizable unsaturated group-containing resin, and other points are not particularly limited. For example, the polymerizable unsaturated group-containing resin may be produced by a method in which all of the raw materials containing the (meth)acrylic copolymer (A) and the compound (B) are reacted at once (hereinafter referred to as the "production method according to the present embodiment"). [ka]

[0077] In the above general formula (1), R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; M 1 ~M 5 each independently represents a meidine group, a methylene group, an oxygen atom, or a single bond; M 1 ~M 5 One or two of the groups are oxygen atoms, and M 1 ~M 5 is a mezine group, and the mezine group is -(CH 2 ) n -OH and M 1 ~M5 Of these, 0 to 2 are single bonds, and n is an integer of 0 to 10. 1 ~M 5 When two of are oxygen atoms, the oxygen atoms are not adjacent to each other. In this case, the alcohol solvent represented by the above general formula (1) is preferably 2,2-dimethyl-1,3-dioxolane-4-methanol.

[0078] In the first step, it is preferable to mix 1 to 60 parts by mass of the (meth)acrylate compound (a1) and 40 to 99 parts by mass of the compound (a2) having one or more first polymerizable unsaturated groups and first reactive functional groups with respect to 100 parts by mass of the (meth)acrylic copolymer (A), and it is preferable that the first reactive functional groups are one or more types selected from the group consisting of hydroxyl groups, epoxy groups, isocyanate groups, carboxyl groups, and acrylamide groups.

[0079] The first polymerizable unsaturated group is preferably one or more selected from the group consisting of a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, a vinyl ether group, and a (meth)acrylamide group.

[0080] The mixing ratio of the (meth)acrylic copolymer (A) and the compound (B) is preferably in the range of 0.3 to 1.05 mol of the second reactive functional group of the compound (B) per 1 mol of the first reactive functional group of the (meth)acrylic copolymer (A).

[0081] As a method for reacting the raw materials, for example, a method in which the reaction raw materials containing the (meth)acrylic copolymer (A) and the compound (B) are reacted at 50 to 150°C in the presence of a basic catalyst or an acidic catalyst can be mentioned.

[0082] Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, trimethylamine, dimethylethylamine, diethylmethylamine, triethylamine, dimethylpropylamine, diethylpropylamine, dipropylmethylamine, amine, dipropylethylamine, tripropylamine, dimethylbutylamine, diethylbutylamine, dibutylmethylamine, dibutylethylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4- amine compounds such as diethylimidazole, 2-ethyl-4-methylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and tetramethylammonium hydroxide; quaternary ammonium salts such as trioctylmethylammonium chloride and trioctylmethylammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride;Examples of the basic catalyst include organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octanoate; and inorganic metal compounds. In addition, alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides can also be used. These basic catalysts can be used alone or in combination of two or more. When used, these basic catalysts can be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid.

[0083] Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, etc., organic acids such as methanesulfonic acid, paratoluenesulfonic acid, oxalic acid, etc., Lewis acids such as boron trifluoride, anhydrous aluminum chloride, zinc chloride, etc. These acid catalysts can be used alone or in combination of two or more kinds.

[0084] The amount of the basic catalyst or acidic catalyst used in the production method according to this embodiment is preferably in the range of 0.01 to 5 parts by mass relative to 100 parts by mass in total of the (meth)acrylic copolymer (A) and the compound (B).

[0085] In the production method according to the present embodiment, when the (meth)acrylic copolymer (A) has an epoxy group derived from the compound (a2) and the compound (B) has a carboxyl group, or when the (meth)acrylic copolymer (A) has a carboxyl group derived from the compound (a2) and the compound (B) has an epoxy group, the catalyst used in the reaction is preferably a phosphorus-based catalyst such as a phosphine compound or a phosphonium salt, and more preferably a phosphine compound.

[0086] The phosphine compound may be the same as those exemplified above. These phosphine compounds may be used alone or in combination of two or more.

[0087] The phosphonium salt may be the same as those exemplified above as the phosphonium salt. These phosphonium salts may be used alone or in combination of two or more.

[0088] In the production of the polymerizable unsaturated group-containing resin of the present disclosure, a polymerization inhibitor, an antioxidant, etc. can be used as necessary. The polymerization inhibitor, the antioxidant, etc. can be used in place of the compound (E) or can be used in combination with or in overlap with the compound (E). Examples of the polymerization inhibitor include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethyl- Phenol compounds such as 1,2-dihydroquinoline, quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N.N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1.amine compounds such as 3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction products of styrenated diphenylamine and 2,4,4-trimethylpentene, reaction products of diphenylamine and 2,4,4-trimethylpentene, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecyl) thioether compounds such as N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso ... -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn -Propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds, esters of phosphoric acid and octadecane-1-ol, triphenyl phosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]Undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite and other phosphite compounds, bis(dimethyldithiocarbamato-κ(2)S,S')zinc, diethyldithiocarbamate , zinc compounds such as zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and distearyl 3,3'-thiodipropionate. These polymerization inhibitors can be used alone or in combination of two or more. As the antioxidant, the same compounds as those exemplified as the polymerization inhibitor can be used, and the antioxidants can be used alone or in combination of two or more kinds. In addition, examples of commercially available products of the polymerization inhibitor and the antioxidant include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.

[0089] [Curable resin composition] Another aspect of this embodiment may be a curable resin composition containing the polymerizable unsaturated group-containing resin of this embodiment and a polymerization initiator, preferably a photopolymerization initiator. More preferably, the curable resin composition of this embodiment essentially contains the polymerizable unsaturated group-containing resin of this embodiment and a polymerization initiator, preferably a photopolymerization initiator, and may contain optional additive components such as a resin (X) having a polymerizable unsaturated group, a curing agent, a solvent, other resins, and additives, if necessary. (Polymerization initiator) The polymerization initiator of the present embodiment may be one or more selected from the group consisting of thermal polymerization initiators and photopolymerization initiators. The polymerization initiator of the present embodiment is preferably a photopolymerization initiator. Examples of the thermal polymerization initiator include benzoyl peroxide and 2,2'-azobisisobutyronitrile. The content of the polymerization initiator in the curable resin composition of the present embodiment is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total of the polymerizable unsaturated group-containing resins.

[0090] <Photopolymerization initiator> Examples of the photopolymerization initiator of the present embodiment include photoradical polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone.

[0091] Commercially available photopolymerization initiators include, for example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", "Omnirad-500", and "Omnirad-81". Examples of commercially available photoradical polymerization initiators include KAYACURE-DETX, KAYACURE-MBP, KAYACURE-DMBI, KAYACURE-EPA, and KAYACURE-OA (manufactured by Nippon Kayaku Co., Ltd.), BICURE-10, BICURE-55 (manufactured by Stouffer Chemical Co., Ltd.), Trigonal P1 (manufactured by Akzo Corporation), Sandray 1000 (manufactured by Sandoz Corporation), Deep (manufactured by Upjohn Corporation), Quantacure-PDO, Quantacure-ITX, and Quantacure-EPD (manufactured by Ward Blenkinsop Co., Ltd.), and Runtecure-1104 (manufactured by Runtec Corporation). These photopolymerization initiators can be used alone or in combination of two or more kinds. The content of the photopolymerization initiator in the curable resin composition is preferably 0.5 to 20 mass%, more preferably 1 to 10 mass%, and even more preferably 2 to 10 mass%, relative to 100 mass% of the total components of the curable resin composition other than the solvent.

[0092] (Preferred embodiment of the curable resin composition) The curable resin composition of the present disclosure may contain other resin components other than the polymerizable unsaturated group-containing resin of the present embodiment and the polymerization initiator, preferably the photopolymerization initiator. The other resin components include a resin (X) having other polymerizable unsaturated groups. The curable resin composition of the present embodiment may contain any additive components such as a curing agent, a solvent, other resins, and additives in addition to the polymerizable unsaturated group-containing resin of the present embodiment, the polymerization initiator, and the resin (X) having other polymerizable unsaturated groups described above.

[0093] <Other resins having polymerizable unsaturated groups (X)> The curable resin composition of the present embodiment may contain a resin (X) having other polymerizable unsaturated groups as an optional component. The resin (X) having other polymerizable unsaturated groups may have a polymerizable unsaturated group, and other specific structures or molecular weights are not particularly limited, and a wide variety of resins can be used. The resin having other polymerizable unsaturated groups may be used alone or in combination of two or more. It is preferable that the resin (X) having other polymerizable unsaturated groups has a polymerizable unsaturated group but does not have an acid group.

[0094] In this embodiment, examples of the polymerizable unsaturated group contained in the resin (X) having another polymerizable unsaturated group include a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, and a vinyl ether group. Specific examples of the resin (X) having another polymerizable unsaturated group include a (meth)acrylate compound (X-1) and / or resins (I) to (VI) having an acid group and a polymerizable unsaturated group.

[0095] The (meth)acrylate compound (X-1) is not particularly limited as long as it has a (meth)acryloyl group, and examples thereof include aliphatic mono(meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate; cyclohexyl (meth)acrylate. alicyclic mono(meth)acrylate compounds such as isobornyl (meth)acrylate and adamantyl mono(meth)acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxyethoxyethyl (meth)acrylate mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzyl benzyl (meth)acrylate, and phenylphenoxyethyl (meth)acrylate; (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various mono(meth)acrylate monomers mentioned above; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various mono(meth)acrylate compounds mentioned above; aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate;Alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; and compounds having a (poly)oxyethylene group in the molecular structure of the above di(meth)acrylate compounds. polyoxyalkylene-modified di(meth)acrylate compounds having a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain introduced therein; lactone-modified di(meth)acrylate compounds having a (poly)lactone structure introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (Poly)oxyalkylene-modified tri(meth)acrylate compounds having a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain introduced into the structure; lactone-modified tri(meth)acrylate compounds having a (poly)lactone structure introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, aliphatic poly(meth)acrylate compounds having 4 or more functional groups, such as acrylate; (poly)oxyalkylene-modified poly(meth)acrylate compounds having 4 or more functional groups, in which a (poly)oxyalkylene chain, such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain, has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compound; and lactone-modified poly(meth)acrylate compounds having 4 or more functional groups, in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compound;Hydroxyethyl (meth)acrylate, Hydroxypropyl (meth)acrylate, Trimethylolpropane (meth)acrylate, Trimethylolpropane di(meth)acrylate, Pentaerythritol (meth)acrylate, Pentaerythritol di(meth)acrylate, Pentaerythritol tri(meth)acrylate, Dipentaerythritol (meth)acrylate, Dipentaerythritol di(meth)acrylate, Dipentaerythritol tri(meth)acrylate (meth)acrylate compounds having a hydroxyl group, such as dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate; (meth)acrylate compounds having a hydroxyl group, such as (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylolpropane chains, (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxyethylene ... (Poly)oxyalkylene modified products having a (poly)oxyalkylene chain such as a styrene chain introduced therein; lactone modified products having a (poly)lactone structure introduced into the molecular structure of the (meth)acrylate compound having a hydroxyl group; (meth)acrylate compounds having an isocyanate group such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate; (meth)acrylate monomers having a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate, and (meth)acrylate compounds having an epoxy group such as mono(meth)acrylates of diglycidyl ether compounds of hydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. The (meth)acrylate compounds (X-1) may be used alone or in combination of two or more.

[0096] <Resins Having Acid Groups and Polymerizable Unsaturated Groups (I) to (VI)> In the curable resin composition of the present embodiment, the other polymerizable unsaturated group-containing resin, which is an optional component, may be any resin other than the above-mentioned polymerizable unsaturated group-containing resin, and may have a polymerizable unsaturated group in the resin, such as an epoxy resin (I) having an acid group and a polymerizable unsaturated group, a urethane resin (II) having an acid group and a polymerizable unsaturated group, an acrylic resin (III) having an acid group and a polymerizable unsaturated group, an amide-imide resin (IV) having an acid group and a polymerizable unsaturated group, an acrylamide resin (V) having an acid group and a polymerizable unsaturated group, an ester resin (VI) having an acid group and a polymerizable unsaturated group, etc. However, the acrylic resin (III) having an acid group and a polymerizable unsaturated group does not include the polymerizable unsaturated group-containing resin of the present embodiment. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. Examples of the polymerizable unsaturated group include a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, a vinyl ether group, etc. Hereinafter, the epoxy resin (I) having an acid group and a polymerizable unsaturated group, the urethane resin (II) having an acid group and a polymerizable unsaturated group, the acrylic resin (III) having an acid group and a polymerizable unsaturated group, the amide-imide resin (IV) having an acid group and a polymerizable unsaturated group, the acrylamide resin (V) having an acid group and a polymerizable unsaturated group, the ester resin (VI) having an acid group and a polymerizable unsaturated group, and other various (meth)acrylate monomers will be described in this order. The amount of the other polymerizable unsaturated group-containing resin used in this embodiment is preferably in the range of 10 to 900 parts by mass with respect to 100 parts by mass of the polymerizable unsaturated group-containing resin in this embodiment.

[0097] <<Epoxy resin having acid group and polymerizable unsaturated group (I)>> Examples of the epoxy resin (I) having an acid group and a polymerizable unsaturated group of the present embodiment include an acid group-containing epoxy (meth)acrylate resin having an epoxy resin, an unsaturated monobasic acid, and a polybasic acid anhydride as essential raw materials, and an acid group- and urethane group-containing epoxy (meth)acrylate resin having an epoxy resin, an unsaturated monobasic acid, a polybasic acid anhydride, a polyisocyanate compound, and a hydroxyl group-containing (meth)acrylate compound as reaction raw materials.

[0098] Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin, etc. These epoxy resins can be used alone or in combination of two or more.

[0099] Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin.

[0100] Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'-biphenol type epoxy resin. Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, hydrogenated tetramethyl-4,4'-biphenol type epoxy resin, and hydrogenated tetramethyl-2,2'-biphenol type epoxy resin.

[0101] Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Esters, acid halides, and acid anhydrides of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following general formula (6) can also be used. [ka] [In the above general formula (6), X 61 represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain; X 61 A hydrogen atom in the structure of Y may be substituted with a halogen atom or an alkoxy group. 61 is a hydrogen atom or a methyl group.

[0102] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain. An example of the (poly)ester chain is a (poly)ester chain represented by the following general formula (7). [ka] (In the above general formula (7), R 71 and R 72represents an alkylene group having 1 to 10 carbon atoms, 71 represents an integer from 1 to 5.)

[0103] An example of the (poly)carbonate chain in the above general formula (6) is a (poly)carbonate chain represented by the following general formula (8). [ka] (In the above general formula (8), R 81 represents an alkylene group having 1 to 10 carbon atoms, 81 represents an integer from 1 to 5.) The molecular weight of the compound represented by formula (6) is preferably in the range of 100-500, and more preferably in the range of 150-400.

[0104] Examples of the aromatic hydrocarbon chain in the above general formula (6) include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. In addition, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used.

[0105] Examples of the polybasic acid anhydride include saturated polybasic acid anhydrides, unsaturated polybasic acid anhydrides, etc. In this specification, the saturated polybasic acid anhydride means a polybasic acid anhydride having no carbon-carbon double bond, and the unsaturated polybasic acid anhydride means a polybasic acid anhydride having a carbon-carbon double bond.

[0106] Examples of the saturated polybasic acid anhydride include acid anhydrides such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,2,3,4-butanetetracarboxylic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid. Among these, hexahydrophthalic anhydride (hexahydroisobenzofuran-1,3-dione), methylhexahydrophthalic anhydride (3-methyl-8-oxabicyclo[4.3.0]nonane-7,9-dione), and the like are more preferable.

[0107] Examples of the unsaturated polybasic acid anhydride include acid anhydrides such as maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, tetrahydrophthalic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid.

[0108] These polybasic acid anhydrides may be used alone or in combination of two or more. Among these, saturated polybasic acid anhydrides are preferred, and saturated polybasic acid anhydrides having an alicyclic structure are more preferred, since they can provide an acid group- and polymerizable unsaturated group-containing resin capable of forming a cured product having excellent toughness and adhesion.

[0109] Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, cyclohexane diisocyanate, and cyclohexane diisocyanate; Examples of the polyisocyanate include aromatic diisocyanate compounds such as silylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following general formula (9); and isocyanurate modified products, biuret modified products, and allophanate modified products of these. These polyisocyanate compounds can be used alone or in combination of two or more kinds. [ka] [In the above general formula (9), R 92 and R 93 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. 91 are each independently either an alkyl group having 1 to 4 carbon atoms or a bonding point connecting the structural portion represented by general formula (9) via a methylene group marked with an *. l is 0 or an integer of 1 to 3, and m is an integer of 1 to 15.]

[0110] As the hydroxyl group-containing (meth)acrylate compound, the same compounds as those exemplified above as compounds having a hydroxyl group and a (meth)acryloyl group can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more kinds.

[0111] The method for producing the epoxy resin (I) having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the epoxy resin (I) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary.

[0112] Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination of two or more. The amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, since this improves the reaction efficiency.

[0113] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0114] <<Urethane resin having acid groups and polymerizable unsaturated groups (II)>> Examples of the urethane resin (II) having an acid group and a polymerizable unsaturated group in this embodiment include those obtained by reacting a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, a carboxyl group-containing polyol compound, and, if necessary, a polybasic acid anhydride with a polyol compound other than the carboxyl group-containing polyol compound; and those obtained by reacting a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, a polybasic acid anhydride, and a polyol compound other than the carboxyl group-containing polyol compound.

[0115] As the polyisocyanate compound, the same compounds as those exemplified above as the polyisocyanate compounds can be used, and the polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0116] As the hydroxyl group-containing (meth)acrylate compound, the same compounds as those exemplified above as compounds having a hydroxyl group and a (meth)acryloyl group can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more kinds.

[0117] Examples of the carboxyl group-containing polyol compound include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, etc. The carboxyl group-containing polyol compound can be used alone or in combination of two or more kinds.

[0118] As the polybasic acid anhydride, the same ones as those exemplified for the epoxy resin (I) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0119] Examples of the polyol compounds other than the carboxyl group-containing polyol compounds include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified products in which (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are introduced into the molecular structure of the various polyol compounds; lactone modified products in which (poly)lactone structures are introduced into the molecular structure of the various polyol compounds. The polyol compounds other than the carboxyl group-containing polyol compounds can be used alone or in combination of two or more.

[0120] The method for producing the urethane resin (II) having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the urethane resin (II) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and may also use a basic catalyst as necessary.

[0121] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds. As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0122] <<Acrylic resin having an acid group and a polymerizable unsaturated group (III)>> Examples of the acrylic resin (III) having an acid group and a polymerizable unsaturated group include a reaction product obtained by further reacting an acrylic resin intermediate obtained by polymerizing a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group as an essential component with a (meth)acrylate compound (β) having a reactive functional group that can react with these functional groups to introduce a (meth)acryloyl group, and a reaction product obtained by reacting a polybasic acid anhydride with a hydroxyl group in the reaction product. However, the acrylic resin (III) having an acid group and a polymerizable unsaturated group is a resin synthesized without using a solvent of general formula (1).

[0123] The acrylic resin intermediate may be a copolymer of the (meth)acrylate compound (α) and other polymerizable unsaturated group-containing compounds as necessary. Examples of the other polymerizable unsaturated group-containing compounds include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These compounds may be used alone or in combination of two or more.

[0124] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but the following combinations are preferable from the viewpoint of reactivity. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate compound (β). When a carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When an isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a hydroxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), the (meth)acrylate compound (β) may be used alone or in combination of two or more kinds.

[0125] The polybasic acid anhydride may be the same as those exemplified for the above epoxy resin (I), and the polybasic acid anhydride may be used alone or in combination of two or more kinds.

[0126] The method for producing the acrylic resin (III) having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylic resin (III) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and may also use a basic catalyst as necessary.

[0127] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds. As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0128] <<Amide-imide resin having an acid group and a polymerizable unsaturated group (IV)>> The amide-imide resin having an acid group and a polymerizable unsaturated group may be, for example, a product obtained by reacting an amide-imide resin having an acid group and / or an acid anhydride group with a hydroxyl group-containing (meth)acrylate compound and / or an epoxy group-containing (meth)acrylate compound, and, if necessary, a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. The compound having a reactive functional group may or may not have a (meth)acryloyl group.

[0129] The amide-imide resin may have either an acid group or an acid anhydride group, or may have both. From the viewpoint of reactivity and reaction control with a hydroxyl group-containing (meth)acrylate compound or a (meth)acryloyl group-containing epoxy compound, it is preferable that the resin has an acid anhydride group, and it is more preferable that the resin has both an acid group and an acid anhydride group. The solid content acid value of the amide-imide resin is preferably in the range of 60 to 350 mgKOH / g under neutral conditions, i.e., conditions in which the acid anhydride group is not ring-opened. On the other hand, it is preferably in the range of 61 to 360 mgKOH / g under conditions in which the acid anhydride group is ring-opened, such as in the presence of water.

[0130] The amide-imide resin may be, for example, one obtained by reacting a polyisocyanate compound with a polybasic acid anhydride as raw materials. As the polyisocyanate compound, the same compounds as those exemplified above as the polyisocyanate compounds can be used, and the polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0131] As the polybasic acid anhydride, the same ones as those exemplified for the above epoxy resin (I) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds. Furthermore, the amide-imide resin may contain, as necessary, a polybasic acid as a reaction raw material in addition to the polyisocyanate compound and the polybasic acid anhydride.

[0132] The polybasic acid may be any compound having two or more carboxyl groups in one molecule. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3- Examples of the polybasic acid include dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, and benzophenone tetracarboxylic acid. In addition, examples of the polybasic acid include a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in the molecule. These polybasic acids can be used alone or in combination of two or more.

[0133] As the hydroxyl group-containing (meth)acrylate compound, the same compounds as those exemplified above as compounds having a hydroxyl group and a (meth)acryloyl group can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more kinds.

[0134] As the epoxy group-containing (meth)acrylate compound, the same compounds as those exemplified as the compounds having an epoxy group and a (meth)acryloyl group described above can be used, and the epoxy group-containing (meth)acrylate compound can be used alone or in combination of two or more kinds.

[0135] In the present embodiment, the method for producing the amide-imide resin (IV) having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the amide-imide resin (IV) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst may be used as necessary. As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds. As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0136] <<Acrylamide resin having an acid group and a polymerizable unsaturated group (V)>> Examples of the acrylamide resin having an acid group and a polymerizable unsaturated group of the present embodiment include those obtained by reacting a phenolic hydroxyl group-containing compound, an alkylene oxide or alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, a polybasic acid anhydride, and, as necessary, an unsaturated monobasic acid.

[0137] The phenolic hydroxyl group-containing compound refers to a compound containing a phenolic hydroxyl group having at least one phenolic hydroxyl group in the molecule. Examples of the phenolic hydroxyl group-containing compound include compounds represented by any of the following general formulas (10.1) to (10.5), reaction products in which an aromatic polyhydroxy compound and a compound represented by any of the following general formulas (11.1) to (11.5) are used as essential reaction raw materials, and novolac-type phenolic resins in which one or more aromatic polyhydroxy compounds or other compounds having one phenolic hydroxyl group in the molecule are used as reaction raw materials. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following general formulas (10.1) to (10.5). [ka]

[0138] (In the above general formulas (10.1) to (10.5), R 101 ~R 104 and R 107 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom; R 105 and R 106 j each independently represents a hydrogen atom or a methyl group; 101 ~j 105 Each independently represents an integer of 0 or 1 or more, preferably 0 or an integer of 1 to 3, and more preferably 0 or 1. 101 ~k 105 Each independently represents an integer of 1 or more, preferably 2 or 3. In the above general formulae (10.1) to (10.5), the position of the substituent on the aromatic ring is arbitrary. For example, in the naphthalene ring of the general formula (10.2), any hydrogen atom on the ring may be substituted; in the general formula (10.3), any hydrogen atom on the benzene ring present in one molecule of biphenyl may be substituted; in the general formula (10.4), any hydrogen atom on the benzene ring present in one molecule of aralkyl may be substituted; and in the general formula (10.5), any hydrogen atom on the benzene ring present in one molecule may be substituted. When the number of the substituents in one molecule is j, 101 ~j 105 and k 101 ~k 105 This shows that. [ka]

[0139] In the above general formulas (11.1) to (11.5), h 81 represents 0 or 1; R 111 ~R 116 each independently represents a monovalent aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group; k 111 ~k 116 each independently represents 0 or an integer of 1 to 4; Z 111 ~Z 116 each independently represents a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group; Y 111 represents an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group; n 111 represents an integer from 1 to 4.) The compounds represented by the above general formulas (11.1) to (11.5) can be used alone or in combination of two or more kinds.

[0140] Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred because it can provide a curable resin composition capable of forming a cured product having excellent toughness and adhesion. The alkylene oxides can be used alone or in combination of two or more kinds.

[0141] Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferred because it can provide a curable resin composition capable of forming a cured product having excellent toughness and adhesion. The alkylene carbonates can be used alone or in combination of two or more kinds.

[0142] Examples of the N-alkoxyalkyl(meth)acrylamide compound include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide, etc. The N-alkoxyalkyl(meth)acrylamide compound can be used alone or in combination of two or more kinds.

[0143] As the polybasic acid anhydride, the same ones as those exemplified for the above epoxy resin (I) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds. As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0144] The method for producing the acrylamide resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylamide resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst and an acid catalyst may be used as necessary.

[0145] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds. As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds. As the acid catalyst, the same as those exemplified above as the acid catalyst can be used, and the acid catalyst can be used alone or in combination of two or more kinds.

[0146] <<Ester resin having acid group and polymerizable unsaturated group (VI)>> Examples of the ester resin (VI) having an acid group and a polymerizable unsaturated group of the present embodiment include those obtained by reacting a phenolic hydroxyl group-containing compound with an alkylene oxide or alkylene carbonate, an unsaturated monobasic acid, and a polybasic acid anhydride.

[0147] As the phenolic hydroxyl group-containing compound, the same compounds as those exemplified above as the phenolic hydroxyl group-containing compound can be used, and the phenolic hydroxyl group-containing compound can be used alone or in combination of two or more kinds.

[0148] The alkylene oxide may be the same as those exemplified above. Among these, ethylene oxide or propylene oxide is preferred because it can provide a curable resin composition capable of forming a cured product having excellent toughness and adhesion. The alkylene oxide may be used alone or in combination of two or more kinds.

[0149] The alkylene carbonate may be the same as those exemplified above. Among these, ethylene carbonate or propylene carbonate is preferred because it can provide a curable resin composition capable of forming a cured product having excellent toughness and adhesion. The alkylene carbonate may be used alone or in combination of two or more kinds. As the unsaturated monobasic acid, the same as those exemplified above as the unsaturated monobasic acid can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds. As the polybasic acid anhydride, the same ones as those exemplified for the above epoxy resin (I) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0150] The method for producing the ester resin (VI) having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the ester resin (VI) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent as necessary, and a basic catalyst and an acid catalyst may be used as necessary.

[0151] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds. As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds. As the acid catalyst, the same as those exemplified above as the acid catalyst can be used, and the acid catalyst can be used alone or in combination of two or more kinds.

[0152] <<Other (meth)acrylate monomers>> Other various (meth)acrylate monomers of the present embodiment include, for example, aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; alicyclic mono(meth)acrylate compounds such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate; ) acrylate compounds; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds, for example: (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain, such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain, has been introduced into the molecular structure of the various mono(meth)acrylate monomers mentioned above; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various mono(meth)acrylate compounds mentioned above; ethylene glycol di(meth)acrylate aliphatic di(meth)acrylate compounds such as propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate;Aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyalkylene chains in which a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds Examples of the alkylene-modified tri(meth)acrylate compound include: a lactone-modified tri(meth)acrylate compound obtained by introducing a (poly)lactone structure into the molecular structure of the aliphatic tri(meth)acrylate compound; aliphatic poly(meth)acrylate compounds having 4 or more functional groups, such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; aliphatic poly(meth)acrylate compounds having 4 or more functional groups, such as (poly)oxyalkylene chains, such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains, obtained by introducing a (poly)oxyalkylene chain into the molecular structure of the aliphatic poly(meth)acrylate compound; and a lactone-modified poly(meth)acrylate compound having 4 or more functional groups, such as (poly)lactone structure into the molecular structure of the aliphatic poly(meth)acrylate compound. In addition, as other various (meth)acrylate monomers of this embodiment, in addition to those mentioned above, (meth)acrylate monomers having a phenol compound, a cyclic carbonate compound or a cyclic ether compound, and an unsaturated monocarboxylic acid as essential reaction raw materials can be used.

[0153] Examples of the phenol compound include cresol, xylenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, hydrogenated bisphenol, hydrogenated biphenol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and cyclo ring structure-containing phenol resin.

[0154] Examples of the cyclic carbonate compound include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, etc. These cyclic carbonate compounds can be used alone or in combination of two or more kinds. Examples of the cyclic ether compound include ethylene oxide, propylene oxide, tetrahydrofuran, etc. These cyclic ether compounds can be used alone or in combination of two or more kinds. As the unsaturated monocarboxylic acid, the same as those exemplified above as the unsaturated monobasic acid can be used. The content of the other (meth)acrylate monomers in the curable resin composition of this embodiment is preferably 90 mass % or less.

[0155] (optional ingredient) The curable resin composition in the present embodiment may contain optional additional components such as a curing agent, other resins, and additives in addition to the above-mentioned polymerizable unsaturated group-containing resin, polymerization initiator, and other resin (X) having a polymerizable unsaturated group. The method for producing the curable resin composition of the present embodiment is not particularly limited, and the composition can be produced by kneading the various components described above using a kneader such as a roll mixer. Hereinafter, each component that can be contained in the curable resin composition in the present embodiment, that is, optional added components such as a curing agent, other resins, and additives, will be described in detail.

[0156] <Hardening agent> Examples of the curing agent in this embodiment include epoxy resins, amine curing agents, acid anhydride curing agents, and phenolic resin curing agents, and epoxy resins and amine curing agents are preferred.

[0157] <<Epoxy resin>> The epoxy resin that is a suitable curing agent in this embodiment is not particularly limited, but is preferably, for example, a curable resin that contains two or more epoxy groups in the molecule and can be cured by forming a crosslinked network with the epoxy groups. The epoxy resin of the present embodiment is not particularly limited, but may be a novolac type epoxy resin such as a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, an α-naphthol novolac type epoxy resin, a β-naphthol novolac type epoxy resin, a bisphenol A novolac type epoxy resin, or a biphenyl novolac type epoxy resin; Aralkyl-type epoxy resins such as phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, and phenol biphenyl aralkyl-type epoxy resins; Bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and tetrabromobisphenol A type epoxy resin; biphenyl-type epoxy resins such as biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, and epoxy resins having a biphenyl skeleton and a diglycidyloxybenzene skeleton; Naphthalene type epoxy resin; Binaphthol type epoxy resin; Binaphthyl type epoxy resin; Dicyclopentadiene type epoxy resins such as dicyclopentadiene phenol type epoxy resins; glycidylamine-type epoxy resins such as tetraglycidyldiaminodiphenylmethane-type epoxy resins, triglycidyl-p-aminophenol-type epoxy resins, and diaminodiphenylsulfone-type glycidylamine-type epoxy resins; diglycidyl ester type epoxy resins such as 2,6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resins and hexahydrophthalic anhydride glycidyl ester type epoxy resins; Benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran are included. Among these epoxy resins, the so-called glycidyl ether type epoxy resins obtained by epoxidizing a phenolic compound are preferred, and among them, novolac type epoxy resins, aralkyl type epoxy resins, and dicyclopentadiene type epoxy resins are more preferred from the viewpoint of dielectric properties. The above-mentioned epoxy resins may be used alone or in combination of two or more kinds.

[0158] The epoxy equivalent of the epoxy resin in this embodiment is preferably 120 to 400 g / eq, and more preferably 150 to 300 g / eq. If the epoxy equivalent of the epoxy resin is 120 g / eq or more, the dielectric properties of the resulting cured product are more excellent, and if the epoxy equivalent of the epoxy resin is 400 g / eq or less, the balance between toughness and adhesion of the resulting cured product is excellent.

[0159] The softening point of the epoxy resin of the present embodiment is preferably 20 to 200°C, and more preferably 40 to 150°C, from the viewpoint of improving toughness and adhesion in a well-balanced manner.

[0160] In this embodiment, with respect to the amount of epoxy resin used, the equivalent ratio (polymerizable unsaturated group-containing resin / epoxy resin) of the (total) functional group in the resin (A+B) having a polymerizable unsaturated group to the functional group in the amount of epoxy resin used is preferably 0.2 to 2, more preferably 0.4 to 1.5. If the functional group equivalent ratio is 0.2 or more, the obtained cured product has a better balance of toughness and adhesion, which is preferable. If the functional group equivalent ratio exceeds 2, heat resistance and curability are reduced, so it is preferable to use within the above range.

[0161] <Other hardeners> The curable resin composition of the present embodiment may contain another curing agent together with the epoxy resin or in place of the epoxy resin. The other curing agent is not particularly limited, but may include an amine curing agent, an acid anhydride curing agent, a phenolic resin curing agent, etc. The amine curing agent is not particularly limited, but examples thereof include aliphatic amines such as diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine, menthenediamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N,-dimethylpiperazine, and triethylenediamine; and aromatic amines such as m-xylenediamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol.

[0162] Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, methylbutenyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, and methylcyclohexene dicarboxylic anhydride.

[0163] Examples of the phenol resin curing agent include phenol novolac resin, cresol novolac resin, naphthol novolac resin, bisphenol novolac resin, biphenyl novolac resin, dicyclopentadiene-phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, triphenol methane type resin, tetraphenol ethane type resin, aminotriazine modified phenol resin, and the like. Any of the other curing agents mentioned above may be used alone or in combination of two or more.

[0164] <Additives> The curable resin composition of the present embodiment may contain, as necessary, an additive selected from the group consisting of a curing accelerator, an ultraviolet absorber, an organic solvent, an inorganic filler or polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, a storage stabilizer, a polymerization inhibitor, and an antioxidant. The additive is preferably used in an amount of 0.01 to 30 mass % based on the total solid content of the curable resin composition. The curing accelerator is one that accelerates the curing reaction, and examples thereof include phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acids, and amine complex salts. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator added is preferably within a range of 0.01 to 10 mass % based on the solid content of the curable resin composition.

[0165] Examples of the ultraviolet absorbent include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, etc. These ultraviolet absorbents can be used alone or in combination of two or more.

[0166] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. As the pigment, known and commonly used inorganic pigments and organic pigments can be used. Examples of the inorganic pigment include white pigment, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, and graphite. These inorganic pigments can be used alone or in combination of two or more. The inorganic pigment is preferably a white pigment. Examples of the white pigment include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, zinc sulfide, etc. Among these, titanium oxide is preferred as the white pigment. Examples of the organic pigment include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments, etc. These organic pigments can be used alone or in combination of two or more kinds.

[0167] Examples of the flame retardant include inorganic phosphorus compounds such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides; phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxy, and the like. Examples of the flame retardant include organic phosphorus compounds such as cyclic organic phosphorus compounds such as 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof reacted with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oils, silicone rubbers, and silicone resins; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. These flame retardants can be used alone or in combination of two or more. In addition, when these flame retardants are used, the amount is preferably in the range of 0.1 to 20 mass% in the total curable resin composition. As the polymerization inhibitor, the same ones as those exemplified above as the polymerization inhibitor can be used, and the polymerization inhibitors can be used alone or in combination of two or more kinds. As the antioxidant, the same ones as those exemplified above as the antioxidant can be used, and the antioxidants can be used alone or in combination of two or more kinds. The method for producing the curable resin composition of the present disclosure is not particularly limited, and may be produced by any method. For example, a method of producing the composition by mixing each compounding component may be mentioned. The mixing method is not particularly limited, and a paint shaker, a disperser, a roll mill, a bead mill, a ball mill, an attritor, a sand mill, a bead mill, etc. may be used.

[0168] [Cured product] The present disclosure relates to a cured product obtained by subjecting a curable resin composition to a curing reaction. The cured product of the present embodiment is a cured product of the curable resin composition. The cured product can be obtained by irradiating the curable resin composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, irradiation may be performed under an inert gas atmosphere such as nitrogen gas, or under an air atmosphere in order to efficiently carry out a curing reaction by ultraviolet rays.

[0169] As a source of ultraviolet light, ultraviolet lamps are generally used from the viewpoints of practicality and economy, and specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc. The cumulative amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 is preferably 0.5 to 10 kJ / m 2 It is more preferable that the integrated light amount is within the above range, since it is possible to prevent or suppress the occurrence of uncured portions. The irradiation of the active energy rays may be carried out in one step or in two or more steps.

[0170] In addition, since the cured product of the present embodiment has excellent elongation, heat yellowing resistance, and adhesion, it can be suitably used, for example, in semiconductor device applications as solder resist, interlayer insulating material, packaging material, underfill material, package adhesive layer for circuit elements, and adhesive layer between integrated circuit elements and circuit boards. It can also be suitably used in thin display applications such as LCD and OELD as thin film transistor protective film, liquid crystal color filter protective film, pigment resist for color filters, resist for black matrix, spacer, and the like. Among these, it can be particularly suitably used as a solder resist.

[0171] [Goods] The article of the present embodiment is characterized by having a coating film made of the above-mentioned cured product. In such an article of the present embodiment, the coating film can function as an insulating material having excellent heat resistance and coating appearance. The article of this embodiment is typically a printed wiring board or a substrate for a semiconductor package having a solder resist film (the coating film) formed in appropriate positions on the surface layer.

[0172] [Insulating material] The insulating material in this embodiment is made of the above-mentioned curable resin composition. Examples of the insulating material include the above-mentioned interlayer insulating material for build-up boards, insulating materials for circuit boards such as adhesive films for build-up boards, insulating materials for circuit boards, and insulating materials for boards with built-in electronic components. For example, a method for producing a build-up board from the above-mentioned curable resin composition includes a method consisting of the following three steps. The first step is a step of applying the above-mentioned curable resin composition, which is appropriately blended with rubber, filler, etc., to a circuit board on which a circuit is formed using a spray coating method, a curtain coating method, etc., and then curing the applied curable resin composition. The second step is a step of forming a predetermined through-hole portion or the like as necessary, treating the surface with a roughening agent, washing the surface with hot water to form unevenness, and plating a metal such as copper. The third step is a step of repeating such operations in sequence as desired to alternately build up a resin insulating layer and a conductor layer of a predetermined circuit pattern. It is preferable to drill the through-hole portion after forming the outermost resin insulating layer. The first step can be performed by laminating a build-up film that has been applied to a desired thickness and dried in advance, in addition to the above-mentioned solution coating. The build-up board of the present invention can also be produced by forming a roughened surface and omitting the plating process by heating and pressing the resin-coated copper foil, which is a copper foil on which the curable resin composition is semi-cured, onto a wiring board on which a circuit is formed, at 170 to 250°C.

[0173] [Resist material] The resist member in this embodiment is made of the above-mentioned curable resin composition. The resist member can be obtained, for example, by applying the curable resin composition onto a substrate, evaporating and drying the organic solvent at a temperature range of about 60 to 100°C, exposing the composition to active energy rays through a photomask having a desired pattern formed thereon, developing the unexposed areas with an alkaline aqueous solution, and, if necessary, further heating and curing the composition at a temperature range of about 140 to 180°C. The resist member of this embodiment is excellent in low dielectric properties and elongation. EXAMPLES

[0174] The present invention will be described in detail with reference to examples and comparative examples. In the following, "parts" and "%" are by mass unless otherwise specified. The properties of the synthesized polyfunctional monomer compounds and polymerizable unsaturated group-containing resins were measured as follows, and the results are shown in Table 1.

[0175] [Method of measuring the acid value of solids (mgKOH / g)] The solid content acid value of the polymerizable unsaturated group-containing resin in the examples is the number of milligrams of potassium hydroxide required to neutralize the free fatty acid, resin acid, etc. contained in 1 g of a sample, and was calculated according to the following procedures 1) to 4) shown in JIS K0070-1992. 1) The reagents are as follows: 0.1 mol / L hydrochloric acid based on JIS K8001 standard 4.5 (5.5) [0.1 mol / L hydrochloric acid (3.646 g HCl / L)]. · 0.1 mol / L potassium hydroxide ethanol solution Dissolve 7 g of potassium hydroxide specified in JIS K8574 in 5 mL of water, add ethanol (95) specified in JIS K8102 to make 1 L, block out carbon dioxide, leave for 2-3 days, then remove the supernatant or filter and store in an alkali-resistant bottle. For standardization, use a volumetric pipette to transfer 25 mL of 0.1 mol / L hydrochloric acid into an Erlenmeyer flask, add phenolphthalein solution, and titrate with 0.1 mol / L potassium hydroxide ethanol solution to determine the factor from the amount required for neutralization. Phenolphthalein solution according to JIS K8001 4.3 (indicator). Solvent: A mixture of diethyl ether (specified in JIS K8103) and ethanol (99.5) (specified in JIS K8101) in a volume ratio of 1:1 or 2:1. Just before use, add a few drops of phenolphthalein solution as an indicator and neutralize with 0.1 mol / L potassium hydroxide ethanol solution. 2) Equipment and toolsThe equipment and tools shall be as follows: ·300ml Erlenmeyer flask Burette 25ml Water bath or hot plate 3) The operation is carried out as follows: -Weigh out an appropriate amount of sample into an Erlenmeyer flask. Add 100 mL of solvent and a few drops of phenolphthalein solution as an indicator, and shake thoroughly in a water bath until the sample is completely dissolved. Titrate with 0.1 mol / L potassium hydroxide ethanol solution, and the endpoint is when the indicator turns pale red for 30 seconds. 4) The calculated acid value is calculated by the following formula. A = (B × f × 5.611) / S Where: A: Acid value B: Amount of 0.1 mol / L potassium hydroxide ethanol solution used in titration (mL) f: Factor of 0.1 mol / L potassium hydroxide ethanol solution S: mass of sample (g) 5.611: Formula weight of potassium hydroxide 56.11 x 1 / 10

[0176] [Method of measuring elastic modulus] First, the curable resin compositions obtained in the examples and comparative examples were applied onto a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using a 50 μm applicator, and then heated at 10 kJ / m using a metal halide lamp. 2 After irradiating with ultraviolet light, the specimen was heated at 160°C for 1 hour. The cured product was peeled off from the copper foil to obtain a test piece 1 (cured product). The elastic modulus (MPa) of the test piece 1 (cured product) was measured at 2 mm / min in accordance with JIS K7181. Here, a smaller value indicates lower elasticity.

[0177] [Method of evaluating adhesion] Adhesion was evaluated by measuring peel strength using test piece 2 (cured product) prepared in the same manner as test piece 1 obtained when measuring elastic modulus. Test piece 2 was cut to a size of 1 cm wide and 12 cm long, and the 90° peel strength (N / cm) was measured using a peel tester (A&D Tensilon manufactured by A&D Co., Ltd., peel speed 50 mm / min). A higher value indicates better adhesion.

[0178] (Example 1: Production of polymerizable unsaturated group-containing resin (1)) 66.7 parts by mass of 2,2-dimethyl-1,3-dioxolane-4-methanol with a biomass carbon content (%) (pMC%) of 50% or more was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 70 parts by mass of methacrylic acid, 30 parts by mass of methyl methacrylate, 83.3 parts by mass of 2,2-dimethyl-1,3-dioxolane-4-methanol, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl)peroxide were mixed in advance and dropped over 3 hours. The mixture was held at 120°C for 10 hours to obtain an acrylic copolymer (A1). Next, 0.9 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 80.9 parts by mass of glycidyl methacrylate (total chlorine content: the total chlorine content of the glycidyl methacrylate was 10 ppm by mass or less. More specifically, the value could not be specified because it was below the lower limit of quantification, but it is thought to be approximately several ppm. Biomass carbon content (%): 43%), 0.9 parts by mass of triphenylphosphine, and 71.1 parts by mass of 2,2-dimethyl-1,3-dioxolane-4-methanol were charged, and the mixture was reacted at 100°C for 35 hours while blowing in air and stirring to obtain a polymerizable unsaturated group-containing resin (1) (here, resin means a mixture of solids and solvent). The nonvolatile content of this polymerizable unsaturated group-containing resin (1) was 45% by mass, and the acid value of the solids was 81 mgKOH / g. Moreover, the biomass carbon content (%) (pMC%) in the entire polymerizable unsaturated group-containing resin (1) was 33% or more, and the biomass carbon content (%) of the solid content was about 19%.

[0179] (Example 2: Production of polymerizable unsaturated group-containing resin (2)) 66.7 parts by mass of 2,2-dimethyl-1,3-dioxolane-4-methanol with a biomass carbon content (%) (pMC%) of 50% or more was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 70 parts by mass of methacrylic acid, 30 parts by mass of methyl methacrylate, 83.3 parts by mass of 2,2-dimethyl-1,3-dioxolane-4-methanol, and 5 parts by mass of (2-ethylhexanoyl)(tert-butyl)peroxide were mixed in advance and dropped over 3 hours. The mixture was held at 120°C for 10 hours to obtain an acrylic copolymer (A2). Next, 0.9 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 80.9 parts by mass of glycidyl methacrylate (total chlorine content: 30 ppm, biomass carbon content: 0 (%)), 0.9 parts by mass of triphenylphosphine, and 71.1 parts by mass of 2,2-dimethyl-1,3-dioxolane-4-methanol were charged, and the mixture was reacted at 100 ° C. for 35 hours while blowing in air and stirring to obtain a polymerizable unsaturated group-containing resin (2). The non-volatile content of this polymerizable unsaturated group-containing resin (2) was 45 mass%, and the solid content acid value was 80 mg KOH / g. In addition, the biomass carbon content (%) (pMC%) in the entire polymerizable unsaturated group-containing resin (2) was 22% or more, and the biomass carbon content (%) of the solid content was 0%.

[0180] (Example 3: Production of polymerizable unsaturated group-containing resin (3)) 66.7 parts by mass of 2,2-dimethyl-1,3-dioxolane-4-methanol with a biomass carbon content (%) (pMC%) of 50% or more was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 80 parts by mass of methacrylic acid, 20 parts by mass of methyl methacrylate, 83.3 parts by mass of 2,2-dimethyl-1,3-dioxolane-4-methanol, and 6 parts by mass of (2-ethylhexanoyl)(tert-butyl)peroxide were mixed in advance and dropped over 3 hours. The mixture was held at 120°C for 10 hours to obtain an acrylic copolymer (A3). Next, 1 part by mass of dibutylhydroxytoluene, 0.1 part by mass of methylhydroquinone, 93.8 parts by mass of glycidyl methacrylate (total chlorine content: the total chlorine content of the glycidyl methacrylate was 10 ppm by mass or less. More specifically, the value could not be specified because it was below the lower limit of quantification, but it is thought to be approximately several ppm. Biomass carbon content (%): 43%), 1 part by mass of triphenylphosphine, and 117.6 parts by mass of 2,2-dimethyl-1,3-dioxolane-4-methanol were charged, and the mixture was reacted at 100°C for 40 hours while blowing in air and stirring to obtain a polymerizable unsaturated group-containing resin (3). The nonvolatile content of this polymerizable unsaturated group-containing resin (3) was 45% by mass, and the solid content acid value was 80 mgKOH / g. In addition, the biomass carbon content (%) (pMC%) of the entire polymerizable unsaturated group-containing resin (3) was 38% or more, and the biomass carbon content (%) of the solid content was about 21%.

[0181] (Example 4: Production of polymerizable unsaturated group-containing resin (4)) 66.7 parts by mass of 2,2-dimethyl-1,3-dioxolane-4-methanol with a biomass carbon content (%) (pMC%) of 50% or more was added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 60 parts by mass of methacrylic acid, 40 parts by mass of methyl methacrylate, 83.3 parts by mass of 2,2-dimethyl-1,3-dioxolane-4-methanol, and 6 parts by mass of (2-ethylhexanoyl)(tert-butyl)peroxide were mixed in advance and dropped over 3 hours. The mixture was held at 120°C for 10 hours to obtain an acrylic copolymer (A4). Next, 0.8 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 66.4 parts by mass of glycidyl methacrylate (total chlorine content: the total chlorine content of the glycidyl methacrylate was 10 ppm by mass or less. More specifically, the value could not be specified because it was below the lower limit of quantification, but it is thought to be approximately several ppm. Biomass carbon content (%): 43%), 0.8 parts by mass of triphenylphosphine, and 37.6 parts by mass of 2,2-dimethyl-1,3-dioxolane-4-methanol were charged, and the mixture was reacted at 100°C for 32 hours while blowing in air and stirring, to obtain a polymerizable unsaturated group-containing resin (4). The nonvolatile content of this polymerizable unsaturated group-containing resin (4) was 45% by mass, and the solid content acid value was 81 mgKOH / g. Moreover, the biomass carbon content (%) (pMC%) in the entire polymerizable unsaturated group-containing resin (4) was 35% or more, and the biomass carbon content (%) in the solid matter was about 17%.

[0182] (Comparative Example 1: Production of polymerizable unsaturated group-containing resin (C1)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 66.7 parts by mass of dipropylene glycol monomethyl ether, and the temperature was raised to 120°C under a nitrogen atmosphere. Next, 70 parts by mass of methacrylic acid, 30 parts by mass of methyl methacrylate, 83.3 parts by mass of dipropylene glycol monomethyl ether, and 5 parts by mass of (2-ethylhexanoyl) (tert-butyl) peroxide were mixed in advance and dropped over 3 hours. The mixture was held at 120°C for 10 hours to obtain an acrylic copolymer (C1). Next, 0.9 parts by mass of dibutylhydroxytoluene, 0.1 parts by mass of methylhydroquinone, 80.9 parts by mass of glycidyl methacrylate (total chlorine content: 30 ppm, biomass carbon content: 0 (%)), and 0.9 parts by mass of triphenylphosphine were charged, and the mixture was reacted at 100°C for 24 hours while blowing in air and stirring to obtain a polymerizable unsaturated group-containing resin (C1). The non-volatile content of this polymerizable unsaturated group-containing resin (C1) was 54% by mass, the acid value of the solid content was 79 mgKOH / g, the biomass carbon content (%) in the whole (pMC%) was 0%, and the biomass carbon content (%) in the solid content was 0%.

[0183] (Examples 5 to 8 and Comparative Example 2: Preparation of Curable Resin Composition) The polymerizable unsaturated group-containing resins (1) to (4) and the polymerizable unsaturated group-containing resin (C1) prepared in the above Examples 1 to 4 and Comparative Example 1 were mixed with a bisphenol A type epoxy resin (EPICLON 850-S manufactured by DIC Corporation, epoxy equivalent: 188 g / equivalent) as a curing agent and a photopolymerization initiator (Omnirad907 manufactured by IGM) in the composition ratios shown in Table 1 to prepare the curable resin compositions (1) and (C1) according to Examples 5 to 8 and Comparative Example 2. The elastic modulus and adhesion were evaluated using Examples 5 to 8 and Comparative Example 2. The results are shown in Table 1.

[0184] [Table 1] From the experimental results in Table 1 above, it was confirmed that the curable resin composition of this example has a lower elastic modulus, better toughness, and better adhesion when cured than the curable resin composition of the comparative example. Therefore, it is considered that the polymerizable unsaturated group-containing resin of this example has a lower elastic modulus, better toughness, and better adhesion when cured, compared to the resin of the comparative example.

[0185] [Contribution to the United Nations-led Sustainable Development Goals (SDGs)] The SDGs have been proposed to realize a sustainable society. One embodiment of the present invention is considered to be a technology that can contribute to the achievement of goals such as "No. 7 - Affordable and clean energy for all," "No. 12 - Responsible consumption and production," and "No. 13 - Take concrete measures against climate change."

Claims

1. A first step of obtaining a (meth)acrylic copolymer (A) by mixing a (meth)acrylate compound (a1) and a compound (a2) having one or more first polymerizable unsaturated groups and first reactive functional groups in the presence of an alcohol solvent having a biomass carbon content (%) (pMC%) of 30% or more and having an oxygen atom-containing alicyclic group and represented by the following general formula (1); a second step of mixing, in the presence of the alcohol solvent, the (meth)acrylic copolymer (A) and a compound (B) having a second reactive functional group capable of reacting with the first reactive functional group to obtain a polymerizable unsaturated group-containing resin. 【Chemistry 1】 (In the above general formula (1), R １ and R ２ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; M １ ~M ５ each independently represents a meidine group, a methylene group, an oxygen atom, or a single bond; M １ ~M ５ One or two of M are oxygen atoms; １ ~M ５ is a medin group, and the medin group is -(CH ２ ) ｎ It is chemically bonded to —OH, and M １ ~M ５ Of these, 0 to 2 are single bonds, and n is an integer of 0 to 10. １ ~M ５ are oxygen atoms, the oxygen atoms are not adjacent to each other.)

2. 2. The method for producing a polymerizable unsaturated group-containing resin according to claim 1, wherein the alcohol solvent is 2,2-dimethyl-1,3-dioxolane-4-methanol.

3. 3. The method for producing a polymerizable unsaturated group-containing resin according to claim 1, wherein in the first step, 1 to 60 parts by mass of the (meth)acrylate compound (a1) and 40 to 99 parts by mass of the compound (a2) having one or more first polymerizable unsaturated groups and first reactive functional groups are mixed with each other relative to 100 parts by mass of the (meth)acrylic copolymer (A).

4. 3. The method for producing a polymerizable unsaturated group-containing resin according to claim 1, wherein the first reactive functional group is one or more selected from the group consisting of a hydroxyl group, an epoxy group, an isocyanate group, a carboxyl group and an acrylamide group.

5. 3. The method for producing a polymerizable unsaturated group-containing resin according to claim 1, wherein the first polymerizable unsaturated group is one or more selected from the group consisting of a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, a vinyl ether group, and a (meth)acrylamide group.

6. The method for producing a polymerizable unsaturated group-containing resin according to claim 1 or 2, wherein a mixing ratio of the (meth)acrylic copolymer (A) and the compound (B) is in a range of 0.3 to 1.05 mol of the second reactive functional group contained in the compound (B) relative to 1 mol of the first reactive functional group contained in the (meth)acrylic copolymer (A).

7. A (meth)acrylic copolymer (A) containing, as essential reaction raw materials (C), a (meth)acrylate compound (a1) and a compound (a2) having one or more first polymerizable unsaturated groups and first reactive functional groups; an alcohol solvent represented by the following general formula (1) having an oxygen atom-containing alicyclic group; A compound (B) having a second reactive functional group capable of reacting with the first reactive functional group; The polymerizable unsaturated group-containing resin has a biomass carbon content (%) (pMC%) of 20% or more in the entire resin, and is a synthetic raw material (D) that serves as a reaction raw material and an auxiliary for chemical reactions. 【Chemistry 2】 (In the above general formula (1), R １ and R ２ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; M １ ~M ５ each independently represents a meidine group, a methylene group, an oxygen atom, or a single bond; M １ ~M ５ One or two of M are oxygen atoms; １ ~M ５ is a medin group, and the medin group is -(CH ２ ) ｎ It is chemically bonded to —OH, and M １ ~M ５ Of these, 0 to 2 are single bonds, and n is an integer of 0 to 10. １ ~M ５ are oxygen atoms, the oxygen atoms are not adjacent to each other.)

8. 8. The polymerizable unsaturated group-containing resin according to claim 7, wherein the alcohol solvent is 2,2-dimethyl-1,3-dioxolane-4-methanol.

9. A curable resin composition comprising the polymerizable unsaturated group-containing resin according to claim 7 or 8 and a photopolymerization initiator.

10. The curable resin composition according to claim 9 , further comprising a resin (X) having a polymerizable unsaturated group other than the polymerizable unsaturated group-containing resin.

11. A resin material for a solder resist, comprising the curable resin composition according to claim 9.

12. A cured product of the curable resin composition according to claim 9.

13. An insulating material comprising the cured product according to claim 12.

14. A resist member comprising the cured product according to claim 12.

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