Curable composition

Abstract

The object of the present invention is to provide a curable composition that exhibits excellent curing reactivity by energy ray curing or thermal curing. The present invention relates to a curable composition comprising a polymer (A) and a polymerizable compound (B) and / or a curing catalyst (C), wherein the polymer (A) has a structural unit represented by the following general formula (1) and a molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.0 to 4.0. In the following formula, R 1 represents a hydrogen atom or a methyl group. 2 and R 3 The same or different, represents a hydrogen atom or an organic group. 4 represents a hydrogen atom or an organic group. n represents an integer greater than 2.

Description

Technical Field

[0001] The present invention relates to a curable composition and more particularly to a curable composition having excellent curing reactivity. Background Art

[0002] Polymer compounds having reactive functional groups in their side chains undergo crosslinking reactions by energy rays or heat to provide good cured products. They are therefore highly versatile and useful in industry and are used in a wide range of applications such as adhesives / adhesives, coatings, paints, inks, and resists.

[0003] For example, it is known that a polymer compound having a cyclic ether group or (meth) acryloyl group such as an epoxy group is cured in the presence of a compound that generates cations or free radicals by irradiation with energy rays or heating. In addition, it is known that a hydroxyl group and an isocyanate group or a carboxyl group and an oxazole group undergo a crosslinking reaction by heating.

[0004] It is also mentioned that it is known that a polymer compound having a vinyl ether group in a side chain also provides a cured product by undergoing a crosslinking reaction by irradiation with energy rays or heating.

[0005] For example, Patent Document 1 describes a curable composition which includes a vinyl ether group-containing polymer having a specific structure and a specific compound that generates cations or free radicals when irradiated with energy rays. The composition does not generate bubbles even during curing by irradiation with energy rays, and the curing performance based on irradiation with energy rays is significantly improved, thereby obtaining a high-quality cured product.

[0006] In addition, for example, Patent Document 2 describes a photocurable resin composition that has sufficient photocurability by containing a cationically polymerizable compound, an acrylic resin having a cationically polymerizable functional group, and a photocationic polymerization initiator in amounts within a specified range, and has sufficient adhesion to hard plastics such as polycarbonate and PET that are difficult to bond.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 6-298884

[0010] Patent Document 2: Japanese Patent Application Publication No. 2006-57078 Summary of the invention

[0011] Problems to be solved by the invention

[0012] As mentioned above, various curable compositions have been proposed so far. However, in existing curable compositions, there is still room for improvement in curing reactivity. In addition, if the above-mentioned curable composition can fully cure in energy ray curing and heat curing to provide a desired cured product, the above-mentioned curable composition can be applied to a wider range of uses.

[0013] The present invention has been made in view of the above-mentioned current situation, and an object of the present invention is to provide a curable composition that exhibits excellent curing reactivity by energy ray curing or thermal curing.

[0014] Means for solving problems

[0015] The present inventors have conducted various studies on curable compositions and have found that a curable composition having excellent curing reactivity can be obtained by including a polymer having a specific structural unit and a molecular weight distribution (weight average molecular weight / number average molecular weight) in a specific range, as well as a polymerizable compound and / or a curing catalyst, thereby completing the present invention.

[0016] That is, the present invention relates to a curable composition comprising a polymer (A) and a polymerizable compound (B) and / or a curing catalyst (C), characterized in that the polymer (A) has a structural unit represented by the following general formula (1) and has a molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.0 to 4.0.

[0017] [Chemistry 1]

[0018]

[0019] (Where R 1 represents a hydrogen atom or a methyl group. 2 and R 3 The same or different, represents a hydrogen atom or an organic group. 4 represents a hydrogen atom or an organic group. n represents an integer greater than 2.)

[0020] In addition, the present invention relates to a curable composition comprising a polymer (A) and a polymerizable compound (B) and / or a curing catalyst (C), characterized in that the polymer (A) is a group transfer polymer containing a monomer component of a vinyl ether group-containing (meth)acrylate represented by the following general formula (2).

[0021] [Chemistry 2]

[0022]

[0023] (Where R 1 represents a hydrogen atom or a methyl group. 2 and R 3The same or different, represents a hydrogen atom or an organic group. 4 represents a hydrogen atom or an organic group. n represents an integer greater than 1.)

[0024] In the curable composition, the weight average molecular weight of the polymer (A) is preferably 5,000 to 1,000,000.

[0025] In the curable composition, the curing catalyst (C) is preferably at least one selected from the group consisting of a cationic curing catalyst and a radical curing catalyst.

[0026] In the curable composition, the polymerizable compound (B) is preferably at least one selected from the group consisting of vinyl ether compounds, cyclic ether compounds, (meth)acrylates, carboxylic acid compounds, maleimide compounds, alcohols, and thiols.

[0027] In the curable composition, the polymerizable compound (B) is preferably at least one selected from the group consisting of methylene malonate diester compounds and α-cyanoacrylates.

[0028] In the curable composition, the polymerizable compound (B) is preferably an acid group-containing alkali-soluble resin and / or a resin having a group that generates an acid group by heat or acid.

[0029] The above-mentioned curable composition is preferably at least one selected from the group consisting of a curable composition for a coating agent, a curable composition for a binder, a curable composition for an adhesive, a curable composition for a resist, a curable composition for a coating, a curable composition for a printing ink composition, a curable composition for electronic components, and a curable composition for optical components.

[0030] The present invention also relates to use of the curable composition for producing at least one selected from the group consisting of a coating agent, a binder, an adhesive, a resist, a coating, a printing ink composition, an electronic component, and an optical component.

[0031] Effects of the Invention

[0032] Since the curable composition of the present invention has the above-mentioned constitution, it is excellent in curing reactivity. The curable composition of the present invention is suitable for various applications such as adhesives, bonding agents, printing ink compositions, resist compositions, coating agents, and molding materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is a schematic diagram of a differential molecular weight distribution curve obtained by GPC measurement.

[0034] Figure 2is a graph showing DSC curves of photocationically cured samples in Examples.

[0035] Figure 3 : is a graph showing the DSC curve of the photoradical curing sample in the example. DETAILED DESCRIPTION

[0036] The present invention is described in detail below.

[0037] In addition, the embodiment in which two or more of the preferred embodiments of the present invention described below are combined is also a preferred embodiment of the present invention.

[0038] In addition, in this specification, "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid", and "(meth)acrylate" means "acrylate and / or methacrylate".

[0039] Curable composition (1)

[0040] The first curable composition of the present invention (hereinafter also referred to as "curable composition (1)") is characterized in that it contains a polymer (A) and a polymerizable compound (B) and / or a curing catalyst (C), and the above-mentioned polymer (A) has a structural unit represented by the following general formula (1) and has a molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.0 to 4.0.

[0041] [Chemistry 3]

[0042]

[0043] (Where R 1 represents a hydrogen atom or a methyl group. 2 and R 3 The same or different, represents a hydrogen atom or an organic group. 4 represents a hydrogen atom or an organic group. n represents an integer greater than 2.)

[0044] The reason why the curable composition (1) of the present invention has excellent curing reactivity is presumably due to the presence of a sufficient amount of vinyl ether groups in the polymer to effectively carry out the curing reaction, in addition to containing a highly reactive polymer having a vinyl ether group. In the past, a part of the vinyl ether groups in the polymer having a vinyl ether group in the side chain reacted when the polymer was manufactured, and coupling of polymers occurred from this point, or macromolecular chains were grafted from the main chain, so that the molecular weight distribution became larger. In this case, the vinyl ether groups are consumed in the polymer, so the content of the vinyl ether groups in the polymer is insufficient. That is, the polymer whose molecular weight distribution is controlled within the above-mentioned specified range is a polymer having a sufficient content of the vinyl ether groups in the polymer, and it is believed that by using such a polymer, the curable composition can exert excellent curing reactivity.

[0045] In addition, the above-mentioned polymer (A) contains a gel component, for example, when synthesized by free radical polymerization, and therefore it may be impossible to obtain a flat coating film, etc. and thus it may be impossible to obtain a cured product of the desired shape, or the strength of the cured product may be reduced. However, a polymer in which the molecular weight distribution of the above-mentioned polymer (A) is controlled within a specified range can suppress the generation of the gel component, and thus a good cured product can be obtained.

[0046] Hereinafter, each component contained in the curable composition (1) of the present invention will be described.

[0047] <Polymer (A)>

[0048] The polymer (A) used in the curable composition (1) of the present invention has a structural unit represented by the above general formula (1) (hereinafter also referred to as "structural unit (a1)") and has a molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.0 to 4.0.

[0049] In the above general formula (1), R 1 represents a hydrogen atom or a methyl group.

[0050] In the above general formula (1), R 2 and R 3 The same or different represent a hydrogen atom or an organic group.

[0051] As R 2 or R 3 Examples of the organic group include chain or cyclic monovalent hydrocarbon groups having 1 to 20 carbon atoms, and groups in which at least a part of the atoms constituting the hydrocarbon groups are replaced with halogen atoms, oxygen atoms, nitrogen atoms or sulfur atoms.

[0052] Examples of the chain hydrocarbon group include linear or branched aliphatic hydrocarbon groups.

[0053] Examples of the aliphatic hydrocarbon group include saturated hydrocarbon groups such as an alkyl group and unsaturated hydrocarbon groups such as an alkenyl group, and preferably a saturated hydrocarbon group is used.

[0054] Specific examples of the aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, octyl, methylheptyl, dimethylhexyl, 2-ethylhexyl, 3-ethylhexyl, trimethylpentyl, 3-ethyl-2-methylpentyl, 2-ethyl-3-methylpentyl, 2,2,3,3-tetramethylbutyl, Alkyl groups such as methylbutyl, nonyl, methyloctyl, 3,7-dimethyloctyl, dimethylheptyl, 3-ethylheptyl, 4-ethylheptyl, trimethylhexyl, 3,3-diethylpentyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl; alkenyl groups such as vinyl, n-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 3-methyl-1-butenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl or 2-octenyl; and the like.

[0055] Examples of the cyclic hydrocarbon group include an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

[0056] Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, adamantyl, and norbornyl.

[0057] Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups such as phenyl, naphthyl, biphenyl, methoxyphenyl, trichlorophenyl, ethylphenyl, tolyl, xylyl, and benzyl.

[0058] The halogen atom is preferably chlorine, bromine or fluorine, more preferably fluorine.

[0059] Among them, as the above-mentioned organic group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 11 carbon atoms is more preferred, and an alkyl group having 1 to 2 carbon atoms, a haloalkyl group having 1 to 2 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms is further preferred.

[0060] In the above general formula (1), R 4 represents a hydrogen atom or an organic group.

[0061] As R 4 The organic group shown in the formula may be, for example, 2 and R 3 The same group as the organic group shown. 4 It is preferably a chain or cyclic hydrocarbon group having 1 to 11 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 11 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms.

[0062] In the above general formula (1), n ​​is an integer of 2 or more.

[0063] The polymer having the structural unit (a1) is obtained, for example, by polymerizing a monomer component containing a vinyl ether group-containing (meth)acrylic acid ester represented by the following general formula (2).

[0064] [Chemistry 4]

[0065]

[0066] In the above general formula (2), R 1 , R 2 , R 3 and R 4 R in the above general formula (1) 1 , R 2 , R 3 and R 4 n represents an integer greater than 2.

[0067] Specific preferred examples of the vinyl ether group-containing (meth)acrylic acid esters represented by the general formula (2) include 2-(2-vinyloxyethoxy)ethyl (meth)acrylate and the like.

[0068] The polymer (A) may have only one type of the structural unit (a1), or may have two or more types of the structural unit (a1).

[0069] The content of the structural unit (a1) in the polymer (A) is preferably 1 mol% to 100 mol% relative to 100 mol% of all structural units. From the perspective of being able to increase the crosslinking density and impart solvent resistance and hardness to the cured product, the content of the structural unit (a1) is more preferably 4 mol% or more, and further preferably 8 mol% or more. In addition, the content of the structural unit (a1) is preferably 95 mol% or less, and more preferably 90 mol% or less.

[0070] In addition, when two or more types are contained as the said structural unit (a1), the said content ratio is the total content ratio of these two or more types.

[0071] The polymer (A) may further have other structural units (a2). Examples of the other structural units (a2) include structural units derived from other polymerizable monomers other than the vinyl ether group-containing (meth)acrylates.

[0072] Examples of the other polymerizable monomers include polymerizable monomers having an electron-deficient double bond, and these can be appropriately selected depending on the purpose and use of the polymer to be produced.

[0073] Specific examples of the polymerizable monomer having an electron-deficient double bond include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, sec-pentyl (meth)acrylate, tert-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, decadecyl (meth)acrylate, tert-butyl (meth)acrylate, tert-butyl (meth)acrylate, tert-pentyl (meth)acrylate, tert-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tert-butyl ... (Meth)acrylates such as trialkyl esters, octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexyl methyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, 2-(acetoacetoxy)ethyl (meth)acrylate, and allyl (meth)acrylate;

[0074] (meth)acrylates containing hydroxyl groups, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy (meth)acrylate, and 4-hydroxymethylcyclohexylmethyl (meth)acrylate;

[0075] (Meth)acrylates containing cyclic ether groups, such as glycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and (3-ethyloxetan-3-yl)methyl (meth)acrylate;

[0076] Halogen-containing (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, and perfluorooctylethyl (meth)acrylate;

[0077] (Meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N,N'-dimethylaminoethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, 2-isopropenyl-2-oxazoline and other polymerizable monomers containing nitrogen atoms;

[0078] Multifunctional polymerizable monomers such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and pentaerythritol tri(meth)acrylate;

[0079] Isocyanate group-containing polymerizable monomers such as 2-(meth)acryloyloxyethyl isocyanate and (meth)acryloyl isocyanate;

[0080] UV-stable polymerizable monomers such as 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acrylamido-2,2,6,6-tetramethylpiperidine;

[0081] Polymerizable cyclic lactone monomers such as methylene butyrolactone and methyl methylene butyrolactone; (meth) acrylonitrile; maleic anhydride;

[0082] 1,4-dioxaspiro[4,5]dec-2-yl methacrylic acid, (meth)acryloylmorpholine, tetrahydrofurfuryl acrylate, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, alkoxylated phenylphenol (meth)acrylate; and the like.

[0083] The number of carbon atoms in the other polymerizable monomer is preferably 1-22, more preferably 1-18, and even more preferably 3-15.

[0084] The polymer (A) may have only one type of the other structural unit (a2), or may have two or more types of the other structural unit (a2).

[0085] The content of the structural unit (a2) in the polymer (A) is preferably 0 to 99 mol% relative to 100 mol% of all structural units. From the perspective of being able to impart various physical properties such as flexibility, adhesion, stability, and heat resistance to the cured product from the structural unit (a2), the content of the structural unit (a2) is more preferably 5 mol% or more, further preferably 10 mol% or more, more preferably 96 mol% or less, further preferably 92 mol% or less.

[0086] In addition, when two or more types are contained as the said structural unit (a2), the said content ratio is the total content ratio of these two or more types.

[0087] The content ratio of the structural units (a1) and (a2) can be determined by gas chromatography or liquid chromatography. 1 H-HMR, etc. are based on the reaction ratio of the vinyl ether group-containing (meth)acrylate and other monomers. 1 The results were obtained by comparing the corresponding integrated values ​​of H-NMR.

[0088] The polymer (A) preferably has a terminal group derived from a silane compound having a carbon-carbon double bond at the end of the main chain. As described later, when the polymer (A) is produced by group transfer polymerization using a silane compound having a carbon-carbon double bond as a polymerization initiator, a group derived from the silane compound having a carbon-carbon double bond is formed at the polymerization initiation side end of the main chain of the polymer.

[0089] As described later, group transfer polymerization is a type of anionic polymerization in which the above-mentioned silane compound having a carbon-carbon double bond is used as a polymerization initiator to polymerize the monomer. The above-mentioned silane compound having a carbon-carbon double bond is added to the (meth)acryloyl group of the above-mentioned (meth)acrylate containing a vinyl ether group or the polymerizable monomer having an electron-deficient double bond providing the above-mentioned structural unit (a2), thereby forming a structure derived from the silane compound having a carbon-carbon double bond described later at the terminal, and simultaneously forming a new silyl ketene acetal on the growing terminal side of the polymer. Then, the (meth)acrylate containing a vinyl ether group or the polymerizable monomer having an electron-deficient double bond providing the above-mentioned structural unit (a2) is further polymerized on the formed silyl ketene acetal. In this way, in the polymerization of the monomer components, it is considered that the silyl ketene acetal at the growing terminal is continuously transferred to the terminal of the polymer molecule, thereby obtaining a polymer.

[0090] Preferred examples of the terminal group derived from the silane compound having a carbon-carbon double bond include structures represented by the following general formula (3), (4) or (5).

[0091] [Chemistry 5]

[0092]

[0093] (Where R 5 and R 6 The same or different, represents a hydrogen atom or an organic group. 7 represents an organic group. )

[0094] [Chemistry 6]

[0095]

[0096] (Where R 5 , R 6 and R 7’ The same or different, represents a hydrogen atom or an organic group. )

[0097] [Chemistry 7]

[0098]

[0099] (Where R 5 , R 6 and R 7’ The same or different, represents a hydrogen atom or an organic group. )

[0100] In the above general formulas (3), (4) and (5), R 5 and R 6 The organic group shown in the formula (a) includes the same organic groups as those mentioned above, and among them, a hydrocarbon group having 1 to 12 carbon atoms is preferred.

[0101] Examples of the hydrocarbon group include alkyl, alkenyl, cycloalkyl, cycloalkenyl, aromatic hydrocarbon groups, etc. In the hydrocarbon group, at least a part of the atoms constituting the hydrocarbon group may be replaced by oxygen atoms, nitrogen atoms, or sulfur atoms, and one or more of the hydrogen atoms constituting the hydrocarbon group may be replaced by halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms; hydroxyl groups; alkoxy groups, and the like.

[0102] Among them, R 5 and R 6 The hydrocarbon group is more preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, a halogenated alkyl group or an aromatic hydrocarbon group, further preferably an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group or an ethyl group.

[0103] As R 7 and R 7’The organic group shown may include, for example, the same groups as the above-mentioned organic groups, among which a hydrocarbon group having 1 to 22 carbon atoms is preferred, an alkyl group, a cycloalkyl group, or an aromatic hydrocarbon group having 1 to 12 carbon atoms is more preferred, a methyl group, an ethyl group, a propyl group, a butyl group, a tert-butyl group, an adamantyl group, a cyclohexyl group, a 2-ethylhexyl group, or a phenyl group is further preferred, and a methyl group, an ethyl group, or a tert-butyl group is particularly preferred.

[0104] R 7 and R 7’ In the above-mentioned hydrocarbon groups shown, at least a part of the atoms constituting the above-mentioned hydrocarbon groups can be replaced by oxygen atoms, nitrogen atoms or sulfur atoms, and one or more of the hydrogen atoms constituting the above-mentioned hydrocarbon groups can be replaced by halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms; hydroxyl groups; alkoxy groups and other substituents.

[0105] Multiple R 7’ It can be the same or different.

[0106] In addition, R 5 With R 6 , or R 6 With R 7 or R 7’ The ring structure may be bonded to form a ring structure. Examples of the ring structure include alicyclic hydrocarbon structures such as cycloalkyl groups such as cyclohexyl and cyclopentyl groups; oxygen-containing heterocyclic structures such as dihydrofuran rings, tetrahydrofuran rings, dihydropyran rings, and tetrahydropyran rings; and the like.

[0107] It should be noted that when the above-mentioned group transfer polymerization is used to produce the above-mentioned polymer (A), if a silyl ketene acetal represented by the general formula (7), a vinyl silane compound represented by the general formula (8), or an allyl silane compound represented by the general formula (9) described later is used as a polymerization initiator, the resulting polymer has a main chain end having a structure represented by the above-mentioned general formula (3), general formula (4), or general formula (5), respectively.

[0108] Among them, the polymer (A) preferably has a terminal group derived from silylketene acetal represented by the general formula (3) in the main chain, from the viewpoint of easily controlling the molecular weight distribution when obtained by group transfer polymerization.

[0109] In addition, the polymer (A) may further have a terminal structure represented by the following general formula (6). If the terminal structure represented by the following general formula (6) is present at one end of the main chain, the desired function can be imparted to the polymer. The polymer (A) preferably has the terminal group from the silane compound having a carbon-carbon double bond at one end (first end) of the main chain, and has the terminal structure represented by the following general formula (6) at the other end (second end).

[0110] [Chemistry 8]

[0111]

[0112] (Where R 1 represents a hydrogen atom or a methyl group. 2 and R 3 The same or different, represents a hydrogen atom or an organic group. 4 represents a hydrogen atom or an organic group. X represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxymethyl group, an allyl group or a propargyl group.

[0113] n represents an integer greater than or equal to 2. )

[0114] In the above general formula (6), R 1 , R 2 , R 3 and R 4 R in the above general formula (1) 1 , R 2 , R 3 and R 4 Respectively the same.

[0115] In the general formula (6), X represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxymethyl group, an allyl group or a propargyl group. The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.

[0116] Among them, X is preferably a hydrogen atom from the viewpoint of unifying the terminal groups of the polymer, preferably a propargyl group from the viewpoint of easily imparting functions to the polymer, and preferably an alkyl group from the viewpoint of improving the stability of the polymer.

[0117] The molecular weight distribution (weight average molecular weight / number average molecular weight) of the polymer (A) is 1.0 to 4.0. When the polymer (A) has the structural unit (a1) and the molecular weight distribution, the curing reactivity is excellent and the variation in various physical properties of the cured product can be suppressed.

[0118] The molecular weight distribution of the polymer (A) is preferably 3.5 or less, more preferably 3.0 or less, and even more preferably 2.0 or less. The molecular weight distribution is also referred to as "dispersity".

[0119] The weight average molecular weight of the polymer (A) has an appropriate range in various applications, but is preferably 5,000 to 1,000,000.

[0120] From the viewpoint of durability, the weight average molecular weight of the polymer (A) is more preferably 10,000 or more, and further preferably 20,000 or more. From the viewpoint of polymer handleability, it is more preferably 800,000 or less, and further preferably 600,000 or less.

[0121] The weight average molecular weight and number average molecular weight of the polymer (A) can be measured by gel permeation chromatography (GPC), and specifically, can be determined by the method described in Examples below. The molecular weight distribution can be calculated by dividing the weight average molecular weight by the number average molecular weight.

[0122] The amount of the insoluble component in the polymer (A) is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 1% by mass or less, particularly preferably 0.5% by mass or less, based on 100% by mass of the polymer.

[0123] When the amount of the insoluble component increases, a flat coating film cannot be obtained, and the shape of the cured product of the curable composition may be deteriorated, or the strength of the cured product may be reduced.

[0124] The insoluble component is a gel component contained in the polymer, and is preferably a component insoluble in ethyl acetate, toluene or tetrahydrofuran, and has a solubility at 25° C. of 0.5 g or less, preferably 0.1 g or less, per 100 g of ethyl acetate, toluene or tetrahydrofuran.

[0125] The amount of the above-mentioned insoluble component can be calculated as follows: ethyl acetate, toluene or tetrahydrofuran is added in such a manner that the concentration of the above-mentioned polymer becomes about 33% by mass, and after sufficient stirring at room temperature, the mixture is passed through a filter with a pore size of 4 μm, and the mass of the insoluble component remaining on the filter after drying is defined as (b), and the mass of the initial polymer is defined as (a), and the amount can be calculated by (b) / (a)×100.

[0126] Regarding the above-mentioned polymer (A), in the differential molecular weight distribution curve obtained by measuring the above-mentioned polymer (A) by gel permeation chromatography (GPC), when the point of the maximum value of the above-mentioned differential molecular weight distribution curve is set as T, and the point of 5% height of T on the above-mentioned differential molecular weight distribution curve is set as L0 and L1 from the low molecular weight side, the ratio (X / Y) of the area (X) of the triangle surrounded by T-L0-L1 and the area (Y) of the part surrounded by the differential molecular weight distribution curve and the line connecting L0-L1 is preferably 0.8 to 2.0. By making the above-mentioned polymer satisfy the ratio in the above-mentioned range, it can be said that the gelation of the polymer is suppressed. The above-mentioned ratio (X / Y) is more preferably 0.8 to 1.5.

[0127] It should be noted that Figure 1 Schematic diagram of a differential molecular weight distribution curve obtained by GPC method and the above-mentioned T, L0, and L1 are shown in FIG.

[0128] The measurement conditions of the above GPC are the same as those described in the following Examples.

[0129] The content of the polymer (A) is preferably 5% to 100% by mass relative to the total solid content of the curable composition (100% by mass), and is more preferably 10% by mass or more, and further preferably 15% by mass or more, from the perspective of being able to increase the crosslinking density, impart solvent resistance or hardness to the cured product, etc. In addition, the content of the polymer (A) is more preferably 99.9% by mass or less, and further preferably 95% by mass or less relative to the total solid content of the curable composition (100% by mass).

[0130] In addition, in this specification, "total solid content" means the total amount of components forming a cured product (components excluding the solvent and the curing catalyst which volatilize when forming the cured product).

[0131] In addition, when the curable composition of the present invention is a curable composition for a resist, from the perspective of being able to improve solvent resistance, the content of the above-mentioned polymer (A) is preferably 1% by mass to 50% by mass, more preferably 2% by mass to 40% by mass, and even more preferably 5% by mass to 30% by mass relative to 100% by mass of the total solid content of the curable composition.

[0132] (Method for producing polymer (A))

[0133] The method for producing the polymer (A) is not particularly limited as long as it is a method capable of producing the polymer (A) having the above-mentioned structure. From the aspect of being able to efficiently produce the polymer (A), a method of producing the polymer by subjecting a monomer component containing the above-mentioned vinyl ether group-containing (meth) acrylic ester to group transfer polymerization is preferred. By subjecting the monomer component containing the above-mentioned vinyl ether group-containing (meth) acrylic ester to group transfer polymerization, a polymer obtained by subjecting only the (meth) acryloyl group of the vinyl ether group-containing (meth) acrylic ester to polymerization reaction can be efficiently produced. In addition, according to this method, the amount of gel component (insoluble component) contained in the obtained polymer can be suppressed to a low level.

[0134] Group transfer polymerization is a type of anionic polymerization in which a silane compound having a carbon-carbon double bond, such as silyl ketene acetal, is used as a polymerization initiator to polymerize a monomer. A silane compound having a carbon-carbon double bond is added to the (meth)acryloyl group of a (meth)acrylate containing a vinyl ether group, and the silyl ketene acetal at the growing end of the newly formed polymer is continuously transferred to the end of the polymer molecule, thereby obtaining a polymer.

[0135] By using such group transfer polymerization, the polymerization reaction of vinyl ether group-containing (meth) acrylates can be carried out in a temperature range that is relatively easy to control, such as room temperature. In addition, the above polymerization reaction can be carried out without strictly controlling the water content in the reaction system. In addition, when the above polymerization is applied, the generation of impurities is small, and the vinyl ether group-containing (meth) acrylate polymer can be produced at a high conversion rate while the vinyl ether group remains.

[0136] As a preferred method for producing the polymer (A), a method using the above-mentioned group transfer polymerization will be described below.

[0137] The method for producing the polymer (A) preferably includes a step of subjecting a monomer component containing the vinyl ether group-containing (meth)acrylate to group transfer polymerization in the presence of a silane compound having a carbon-carbon double bond and a catalyst.

[0138] In the above polymerization reaction, specifically, before the reaction, any two of the above monomer components, the catalyst, and the silane compound having a carbon-carbon double bond are put into a reaction container, and the remaining one is added to start polymerization. There is no particular limitation on the order of their addition, and polymerization can be started after adding them in any method.

[0139] The silane compound having a carbon-carbon double bond, the catalyst, and the monomer component may be added in their entirety at once, added in small amounts continuously, or added in several portions.

[0140] The molecular weight of the polymer obtained by polymerizing the above-mentioned monomer components can be appropriately controlled by the type and amount of the above-mentioned monomer components, the type and amount of the above-mentioned silane compound having a carbon-carbon double bond, the type and amount of the above-mentioned catalyst, and the type and amount of the solvent used.

[0141] The amount of the silane compound having a carbon-carbon double bond used is not particularly limited as long as the desired polymer can be obtained. From the perspective of more efficient production of the polymer, it is preferably 1×10 -4 mol% to 10 mol%, more preferably 1×10 -3 mol% to 5 mol%, more preferably 1×10 -2 Mol % to 1 mol %.

[0142] The amount of the catalyst used is not particularly limited as long as the desired polymer can be obtained. From the perspective of more efficient production of the polymer, it is preferably 1×10 -4 mol% to 10 mol%, more preferably 1×10 -3 mol% to 5 mol%, more preferably 1×10-2 Mol % to 1 mol %.

[0143] The above-mentioned polyreaction can also be carried out under the condition of not using a solvent, but preferably uses a solvent. As the solvent used, there is no restriction as long as it is a solvent that can dissolve raw materials, catalysts, polymerization initiators, and polymers, and from the aspect that can efficiently carry out polyreaction, a preferred aprotic solvent is used.

[0144] The solvent used in the present invention specifically includes, for example, aromatic hydrocarbon solvents such as toluene, xylene, and benzene; aliphatic hydrocarbon solvents such as hexane, pentane, heptane, and cyclohexane; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated hydrocarbon solvents such as chlorobenzene, dichloromethane, chloroform, and 1,2-dichloroethane; nitrile solvents such as acetonitrile, propionitrile, and valeronitrile; ester solvents such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; dimethylformamide (DMF), Amide solvents such as dimethylacetamide and N-methylpyrrolidone; ether solvents such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme), diethylene glycol ethyl ether (carbitol), cyclopentyl methyl ether (CPME); fluorine solvents such as perfluorohexane, perfluorocyclohexane, pentafluorobenzene, octafluorotoluene; DMSO, nitromethane, etc.

[0145] Among them, from the perspective of being able to carry out the polymerization reaction more efficiently, the above-mentioned solvent is preferably at least one selected from the group consisting of aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ketone solvents, halogenated hydrocarbon solvents, ether solvents, ester solvents and nitrile solvents, and more preferably aromatic hydrocarbon solvents, ether solvents and ester solvents.

[0146] The above solvents may be used alone or in combination of two or more.

[0147] The amount of the solvent used is preferably 10% by mass to 10,000% by mass, more preferably 50% by mass to 5,000% by mass, and even more preferably 100% by mass to 1,000% by mass, based on 100% by mass of the total amount of the monomer components used.

[0148] In addition, in the above-mentioned polymerization, the oxygen concentration in the solvent at the start of the polymerization is preferably 1000 ppm or less. When the oxygen concentration in the solvent at the start of the polymerization is within the above-mentioned range, the activity of the silane compound having a carbon-carbon double bond and the catalyst is less likely to decrease, so the polymerization reaction proceeds more smoothly and the desired polymer can be produced more efficiently. The above-mentioned oxygen concentration is more preferably 800 ppm or less, and further preferably 0 to 500 ppm.

[0149] The above oxygen concentration can be measured using a polarographic dissolved oxygen meter.

[0150] In addition, in the above-mentioned polymerization, the water content in the solvent at the start of the polymerization is preferably 1000 ppm or less. When the water content in the solvent at the start of the polymerization is within the above-mentioned range, the silane compound having a carbon-carbon double bond is not easily decomposed, and the activity of the catalyst is less likely to decrease, so the polymerization reaction proceeds more smoothly, and the desired polymer can be produced more efficiently. The above-mentioned water content is more preferably 500 ppm or less, and further preferably 300 ppm or less.

[0151] The water content can be measured by Karl Fischer water content determination.

[0152] The reaction temperature in the above-mentioned polymerization is not particularly limited, but is preferably -20°C to 100°C, more preferably -10°C to 50°C, and even more preferably 0 to 30°C, from the perspective of being able to control the molecular weight and molecular weight distribution and maintain the catalyst activity. In addition, from the perspective of reducing the production cost, including a step of performing the polymerization at room temperature ±20°C is also one of the preferred aspects of the production method of the present invention.

[0153] The reaction time is not particularly limited, but is preferably 10 minutes to 48 hours, more preferably 30 minutes to 36 hours, and even more preferably 1 hour to 24 hours.

[0154] The reaction atmosphere in the above-mentioned polymerization may be the air, but is preferably an atmosphere of an inert gas such as nitrogen or argon.

[0155] The oxygen concentration in the atmosphere during the polymerization is preferably 10000 ppm or less, more preferably 1000 ppm or less, and even more preferably 100 ppm or less.

[0156] The polymer obtained by the above polymerization reaction forms a silyl ketene acetal structure or an enolate anion structure containing a silyl group of a polymerization initiator at the end of the main chain. The polymerization reaction can be stopped by adding water, alcohol or acid to the reaction system to convert the silyl ketene acetal or enolate anion at one end of the polymer into a carboxylic acid or ester.

[0157] Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol.

[0158] Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as acetic acid and benzoic acid.

[0159] The amount of water, alcohol or acid used is not particularly limited, but is preferably 1 mol to 1000 mol, more preferably 1 mol to 100 mol, and even more preferably 1 mol to 10 mol, based on 1 mol of the silane compound having a carbon-carbon double bond used.

[0160] In addition, an electrophilic reagent may be added instead of the above water, alcohol or acid. By adding an electrophilic reagent, the target functional group can be introduced and the polymerization reaction can be stopped. Examples of the above electrophilic reagent include halogens such as iodine or bromine, halogenated succinimide compounds, alkyl halides, allyl halides, propargyl halides, aldehydes, and acyl chlorides.

[0161] The amount of the electrophilic reagent used is not particularly limited, but is preferably 0.5 mol to 1.5 mol, more preferably 0.6 mol to 1.3 mol, and even more preferably 0.8 mol to 1.2 mol, based on 1 mol of the silylketene acetal used.

[0162] The monomer components, the silane compound having a carbon-carbon double bond, and the catalyst used in the above-mentioned production method are described.

[0163] As the monomer component, there can be mentioned a monomer capable of introducing the structural unit (a1) and a monomer capable of introducing the structural unit (a2). As the monomer capable of introducing the structural unit (a1), there can be mentioned the above-mentioned vinyl ether group-containing (meth)acrylates. As the monomer capable of introducing the structural unit (a2), there can be mentioned the above-mentioned other polymerizable monomers.

[0164] The content of each of the above monomers can be appropriately set so as to obtain a polymer having a structural unit within a desired content ratio range.

[0165] Preferred examples of the silane compound having a carbon-carbon double bond include the following general formula (7):

[0166] [Chemistry 9]

[0167]

[0168] (Where R 5 and R 6 The same or different, represents a hydrogen atom or an organic group. 7 , R 8 , R 9 and R 10 The same or different, represents an organic group. 5 With R 6 or R 6 With R 7 Can be bonded to form a ring structure. 8 , R9 and R 10 Two or more of them may be bonded to form a ring structure. ) represented by silyl ketene acetal, the following general formula (8):

[0169] [Chemistry 10]

[0170]

[0171] (Where R 5 , R 6 and R 7’ The same or different, represents a hydrogen atom or an organic group. 8 , R 9 and R 10 The same or different, represents an organic group. 5 With R 6 or R 6 With R 7’ Can be bonded to form a ring structure. 8 , R 9 and R 10 Two or more of them may be bonded to form a ring structure. ) and the following general formula (9):

[0172] [Chemistry 11]

[0173]

[0174] (Where R 5 , R 6 and R 7’ The same or different, represents a hydrogen atom or an organic group. 8 , R 9 and R 10 The same or different, represents an organic group. 5 With R 6 or R 6 With R 7’ Can be bonded to form a ring structure. 8 , R 9 and R 10 Two or more of the above may be bonded to form a ring structure. One or more of the allylsilane compounds shown in ).

[0175] Among them, silylketene acetal is more preferred because polymerization can be easily and efficiently performed.

[0176] In the above general formulas (7), (8) and (9), R 5 and R 6 The same or different represent a hydrogen atom or an organic group.

[0177] As the above R 5and R 6 , which may be the same as R in the above general formula (3), (4), (5) 5 and R 6 The same atoms or groups.

[0178] As the above R 7 and R 7’ , which may be the same as R in the above general formula (3), (4), (5) 7 and R 7’ The same atoms or groups.

[0179] In the above general formulas (7), (8) and (9), R 8 , R 9 and R 10 The same or different, represent an organic group.

[0180] As R 8 , R 9 and R 10 The organic groups shown include the same groups as the above-mentioned organic groups, among which hydrocarbon groups and alkoxy groups having 1 to 12 carbon atoms are preferred, hydrocarbon groups and alkoxy groups having 1 to 6 carbon atoms are more preferred, and methyl, ethyl, isopropyl, tert-butyl, phenyl, methoxy and ethoxy groups are further preferred.

[0181] In addition, the above R 8 , R 9 and R 10 In the hydrocarbon groups shown, at least a part of the atoms constituting the above hydrocarbon groups can be replaced by oxygen atoms, nitrogen atoms or sulfur atoms, and one or more of the hydrogen atoms constituting the above hydrocarbon groups can be replaced by halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms; hydroxyl groups; alkoxy groups and other substituents.

[0182] As -SiR in the above general formulas (7), (8) and (9) 8 R 9 R 10 Specifically, the group shown in the formula (I) includes, for example, trimethylsilyl, triethylsilyl, triisopropylsilyl, triisobutylsilyl, tert-butyldimethylsilyl, triphenylsilyl, methyldiphenylsilyl, dimethylphenylsilyl, trimethoxysilyl, triethoxysilyl, etc. Among them, trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, triethoxysilyl, and triphenylsilyl are preferred from the perspective of easy availability and easy synthesis.

[0183] Specific examples of the silylketene acetal represented by the general formula (7) include methyl (trimethylsilyl) dimethylketene acetal, methyl (trimethylsilyl) diisopropylketene acetal, methyl (triethylsilyl) dimethylketene acetal, methyl (triisopropylsilyl) dimethylketene acetal, methyl (tert-butyldimethylsilyl) dimethylketene acetal, methyl (trimethylsilyl) diethylketene acetal, methyl (triphenylsilyl) dimethyl Ketene acetal, methyl (methyldiphenylsilyl) dimethyl ketene acetal, methyl (dimethylphenylsilyl) dimethyl ketene acetal, methyl (triethoxysilyl) dimethyl ketene acetal, ethyl (trimethylsilyl) dimethyl ketene acetal, 2-ethylhexyl (trimethylsilyl) dimethyl ketene acetal, tert-butyl (trimethylsilyl) dimethyl ketene acetal, 1-[(1-methoxy-2-methyl-1-propenyl) oxy]-1-methylsilacyclobutane, and the like.

[0184] Among these, methyl(trimethylsilyl)dimethylketene acetal, methyl(triisopropylsilyl)dimethylketene acetal, and ethyl(trimethylsilyl)dimethylketene acetal are preferred from the viewpoints of easy availability, easy synthesis, and stability.

[0185] The above-mentioned silylketene acetal may be used alone or in combination of two or more.

[0186] Specific examples of the vinylsilane compound represented by the general formula (8) include vinyltrimethylsilane, 1-trimethylsilylhexene, 1-trimethylsilyloctene, 1-trimethylsilyl-1-phenylethylene, 1-trimethylsilyl-2-phenylethylene, vinyl-tert-butyldimethylsilane, 1-tert-butyldimethylsilylhexene, 1-tert-butyldimethylsilyloctene, 1-tert-butyldimethylsilyl-2-phenylethylene, vinyltris(trimethylsilyl)silane, 1-tris(trimethylsilyl)silylhexene, 1-tris(trimethylsilyl)silyloctene, and 1-tris(trimethylsilyl)silyl-2-phenylethylene.

[0187] Specific examples of the allylsilane compound represented by the general formula (9) include 3-(trimethylsilyl)-1-propylene, 3-(triethylsilyl)-1-propylene, 3-(dimethylethylsilyl)-1-propylene, 3-(triisopropylsilyl)-1-propylene, 3-(dimethylisopropylsilyl)-1-propylene, 3-(tri-n-propylsilyl)-1-propylene, 3-(dimethyl-n-propylsilyl)-1-propylene, and 3-(tri-n-propylsilyl)-1-propylene. 1-propylene, 3-(tri-n-butylsilyl)-1-propylene, 3-(tri-n-butylsilyl)-1-propylene, 3-(triphenylsilyl)-1-propylene, 3-(dimethylphenylsilyl)-1-propylene, 2-methyl-3-(trimethylsilyl)-1-propylene, 3-(trimethylsilyl)-2-methyl-1-propylene, 3-(triphenylsilyl)-2-methyl-1-propylene and the like.

[0188] Preferred examples of the catalyst include those that function as a basic catalyst such as a Bronsted base or a Lewis base, and examples thereof include inorganic bases such as alkali metal hydroxides and alkaline earth metal hydroxides; and organic bases such as trialkylamines and pyridine.

[0189] Among them, as the above-mentioned catalyst, from the aspect of being able to more efficiently polymerize the above-mentioned vinyl ether group-containing (meth)acrylates, it is preferred that at least one selected from the group consisting of organic phosphorus compounds, N-heterocyclic carbenes, fluorine-containing ion compounds, cyclic amine compounds and ammonium salt compounds. When these specific catalysts are used, cationic polymerization of vinyl ether groups or decomposition of vinyl ethers is less likely to occur in vinyl ether group-containing (meth)acrylates, and only (meth)acryloyl groups can be polymerized more efficiently.

[0190] Examples of the organic phosphorus compound include 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphoranylideneamino]-2λ 5 , 4λ 5 -bis(phosphazene) (phosphazene base P4-t-BuP4), 1-tert-octyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphoranylideneamino]-2λ 5 , 4λ 5 -bis(phosphazene) (phosphazene base P4-tOct), 1-tert-butyl-2,2,4,4,4-penta(dimethylamino)-2λ 5 , -4λ 5 -bis(phosphazene) (phosphazene base P2-t-Bu), 1-ethyl-2,2,4,4,4-penta(dimethylamino)-2λ 5 , 4λ 5-bis(phosphazene) (phosphazene base P2-t-Et), tert-butyliminotri(dimethylamino)phosphorane (phosphazene base P1-t-Bu), tert-butyliminotri(pyrrolidinyl)phosphorane (BTPP), 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphabenzene and other phosphazene bases; tri(2,4,6-trimethoxyphenyl)phosphine, tributylphosphine, tri(dimethylaminophosphine), 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phosphabicyclo[3,3,3]undecane, 2,8,9-trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo[3,3,3]undecane, 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo[3,3,3]undecane; and the like. Among them, phosphazene bases P4-t-BuP4 and 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phosphabicyclo[3,3,3]undecane are preferred because they have strong basicity and can effectively activate silylketene acetal.

[0191] Examples of the N-heterocyclic carbene include 1,3-dimethylimidazol-2-ylidene, 1,3-diethylimidazol-2-ylidene, 1,3-di-tert-butylimidazol-2-ylidene, 1,3-dicyclohexylimidazol-2-ylidene, 1,3-diisopropylimidazol-2-ylidene, 1,3-di(1-adamantyl)imidazol-2-ylidene, and 1,3-dimesityl imidazol-2-ylidene. Among them, 1,3-di-tert-butylimidazol-2-ylidene and 1,3-diisopropylimidazol-2-ylidene are preferred because they can effectively activate silylketene acetal.

[0192] As the fluorine-containing ion compound, for example, tetra-n-butylammonium fluoride (TBAF), tris(dimethylamino)sulfonium difluoride (TASHF2), hydrogen fluoride-pyridine, tetrabutylammonium difluoride, potassium hydrogen fluoride, etc. Among them, tetra-n-butylammonium fluoride (TBAF), tetrabutylammonium difluoride, and tris(dimethylamino)sulfonium difluoride (TASHF2) are preferred from the perspective of easy availability and the ability to effectively activate silyl ketene acetal.

[0193] Examples of the cyclic amine compound include 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0194] Examples of the ammonium salt compounds include tetrabutylammonium diacetate, tetrabutylammonium acetate, tetrabutylammonium benzoate, tetrabutylammonium dibenzoate, tetrabutylammonium m-chlorobenzoate, tetrabutylammonium cyanate, tetrabutylammonium methanolate, tetrabutylammonium mercaptide, tetrabutylammonium dibromide, and compounds obtained by changing the ammonium cations of these ammonium salt compounds to tetramethylammonium, triethylammonium, benzyltributylammonium, N-methyl-N-butylpiperidinium, N-methyl-N-butylpyrrolidinium cations or compounds obtained by changing the ammonium cations to pyridinium cations.

[0195] In addition to the above compounds, a nitrogen-containing heterocyclic compound having a strong basicity such as 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene can also be used.

[0196] The above catalysts may be used alone or in combination of two or more.

[0197] In the above-mentioned polymerization, in addition to the above-mentioned components, other components can also be further used within the scope that will not affect the effect of the present invention. As the above-mentioned other components, known additives such as polymerization initiators, chain transfer agents, polymerization accelerators, polymerization inhibitors, etc. commonly used in the polymerization reaction can be enumerated. They can be appropriately selected as needed.

[0198] The above-mentioned production method may include other steps in addition to the above-mentioned polymerization reaction step. Examples of the above-mentioned other steps include an aging step, a neutralization step, a deactivation step of a polymerization initiator or a chain transfer agent, a dilution step, a drying step, a concentration step, a purification step, etc. These steps may be carried out by known methods.

[0199] The polymer (A) is preferably produced by the above production method. That is, the polymer (A) is preferably a group transfer polymer containing a monomer component of a vinyl ether group-containing (meth)acrylic acid ester represented by the above general formula (2).

[0200] When the polymer (A) is produced by the above production method, the conversion rate of the monomer components used in the polymerization is very high, and the amount of residual monomers can be made very small.

[0201] On the other hand, when the polymer (A) is produced by free radical polymerization, even if a polymer having a molecular weight distribution controlled within the above-specified range can be obtained without gelation, monomer residues will remain and their amount is difficult to control, so the reproducibility of the physical properties of the resulting cured product may be reduced.

[0202] The content of the residual monomers in the polymer (A) is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 0 to 3% by mass, based on 100% by mass of the polymer.

[0203] The residual monomer content can be determined by 1 H-NMR, gas chromatography, liquid chromatography, and gel permeation chromatography were used for determination.

[0204] <Polymerizable Compound (B)>

[0205] The polymerizable compound used in the present invention is not particularly limited as long as it is a compound capable of crosslinking the polymer (A), and is preferably at least one selected from the group consisting of vinyl ether compounds, cyclic ether compounds, (meth)acrylates, carboxylic acid compounds, maleimide compounds, alcohols, and thiols from the perspective of being able to react efficiently with a vinyl ether group. Among them, as the polymerizable compound, vinyl ether compounds, cyclic ether compounds, and thiols are more preferred, and vinyl ether compounds and cyclic ether compounds are further preferred.

[0206] The above polymerizable compounds may be used alone or in combination of two or more.

[0207] Examples of the vinyl ether compound include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl Alkyl vinyl ethers such as vinyl ether and tetrahydrofurfuryl vinyl ether; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthracenyl ether; vinyl ethers containing alicyclic compounds such as cyclohexyl vinyl ether and cyclohexanedimethanol monovinyl ether; vinyl ethers containing allyl groups such as allyl vinyl ether; polyfunctional divinyl ethers such as diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, and 1,4-cyclohexanedimethanol divinyl ether; etc.

[0208] The molecular weight of the vinyl ether compound is preferably 10,000 or less.

[0209] Examples of the cyclic ether compound include epoxy group-containing compounds, oxetane compounds, compounds having a tetrahydrofuran ring, and (meth)acrylates containing a cyclic ether group similar to the above-mentioned polymerizable monomer.

[0210] Specific examples of the cyclic ether compound include: monofunctional epoxy resins such as n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and 1,2-epoxycyclohexane; bifunctional epoxy resins such as hexanediol diglycidyl ether, tetraethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, monoallyl diglycidyl isocyanurate, and glycidyl methacrylate; trifunctional epoxy resins such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and 1,2-epoxycyclohexane; Multifunctional epoxy resins such as hydroxymethylpropane triglycidyl ether, sorbitol polyglycidyl ether, 1,3-bis(N,N-diglycidylaminoethyl)benzene, novolac epoxy resins, tetraphenolethane epoxy resins; alicyclic epoxy resins such as 1,2-epoxy-4-vinylcyclohexane, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylmethyl methacrylate Epoxy resins containing alkyl rings; monofunctional oxetane resins such as 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl(triethoxysilylpropoxymethyl)oxetane, 3-cyclohexyloxymethyl-3-ethyl-oxetane; bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-dimethoxy-1-nitroprop ... - Bifunctional oxetane resins such as bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene; polyfunctional oxetane resins such as trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetra(3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol penta(3-ethyl-3-oxetanylmethyl) ether.

[0211] The molecular weight of the cyclic ether compound is preferably 10,000 or less.

[0212] Examples of the (meth)acrylate include monofunctional (meth)acrylates such as methyl (meth)acrylate, butyl (meth)acrylate, isoamyl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hexafluoropropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate; and 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, and the like. Polyfunctional (meth)acrylates such as acrylate, polyethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tri((meth)acryloyloxyethyl)isocyanurate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; macromonomers having a (meth)acryloyl group such as epoxy (meth)acrylate, urethane (meth)acrylate, and polyester (meth)acrylate, etc.

[0213] The molecular weight of the (meth)acrylate is preferably 10,000 or less.

[0214] Examples of the carboxylic acid compounds include compounds having two or more functional groups in the molecule, such as succinic acid, malonic acid, maleic acid, adipic acid, malic acid, tartaric acid, azobenzene-4,4'-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, citric acid, trimellitic acid, and 1,3,5-tricarboxylic acid benzene; and polymers containing a carboxyl group in the side chain, such as poly(meth)acrylic acid.

[0215] The molecular weight of the carboxylic acid compound is preferably 10,000 or less.

[0216] Examples of the maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N,N'-tetramethylenebismaleimide, bisphenol A bis(4-maleimide phenyl ether), 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, and 1,3-bis(3-maleimidephenoxy)benzene.

[0217] The molecular weight of the maleimide compound is preferably 10,000 or less.

[0218] Examples of the alcohol include compounds having two or more hydroxyl groups in the molecule, such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,7-heptanediol, pentaerythritol, trimethylolpropane, trimethylolethane, dihydroxynaphthalene, 2,4-diethyl-1,5-pentanediol, 4,4'-(hexafluoroisopropylidene)biphenol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 4,4'-biphenyldimethanol, 9,9-bis(4-hydroxyphenyl)fluorene, 2,2-bis(4-hydroxyphenyl)propane, and dipentaerythritol.

[0219] The molecular weight of the alcohol is preferably 10,000 or less.

[0220] Examples of the thiol include compounds having two or more thiol groups in the molecule, such as 1,2-ethanedithiol, 1,3-propanedithiol, 2,4,6-trimercaptotriazine, 2-dibutylamino-4,6-dimercaptotriazine, 1,4-bis(3-mercaptobutyryloxy)butane, and pentaerythritol tetrakis(3-mercaptobutyrate). In addition, compounds having at least one carboxyl group and one thiol group in the molecule, such as thioglycolic acid and 3-mercaptopropionic acid, may also be used.

[0221] The molecular weight of the thiol is preferably 10,000 or less.

[0222] Furthermore, the polymerizable compound is preferably a methylene malonate diester compound from the viewpoint of being curable at a low temperature.

[0223] Examples of the methylene malonate diester compound include a diester compound represented by the following general formula (10) and a polyfunctional methylene malonate diester in which a plurality of methylene malonate diesters are bonded.

[0224] [Chemistry 12]

[0225]

[0226] (In formula (10), R 11 and R 12 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, or R 11 and R 12 Together, they form a divalent hydrocarbon group having 3 to 15 carbon atoms. 13 and R 14 are the same or different and represent a monovalent organic group having 1 to 30 carbon atoms.

[0227] Examples of the polyfunctional methylene malonate diester include reaction products obtained by reacting the diester compound represented by the general formula (10) with a polyol under conditions where an ester exchange reaction occurs between the two, such as compounds represented by the following general formula (11) or (12).

[0228] [Chemistry 13]

[0229]

[0230] (In formula (11), R 11 and R 12 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, or R 11 and R 12 Together, they form a divalent hydrocarbon group having 3 to 15 carbon atoms. 13 represents a monovalent organic group having 1 to 30 carbon atoms. 15 represents an n-valent organic group. n represents the number of structural units in parentheses in formula (11), and represents an integer greater than 2. In formula (11), a plurality of R 11 , R 12 and R 13 They may be the same as or different from each other.)

[0231] [Chemistry 14]

[0232]

[0233] (In formula (12), R 11 and R 12 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, or R 11 and R 12 Together, they form a divalent hydrocarbon group having 3 to 15 carbon atoms. 13 represents a monovalent organic group having 1 to 30 carbon atoms. 16 represents a divalent organic group. 17 represents a hydroxyl group or a monovalent organic group. m represents the number of the structural units in the brackets in formula (12), and represents an integer greater than 2. 11 , R 12 and R 16 They may be the same as or different from each other.)

[0234] In the above general formulae (10), (11) and (12), R 11 and R 12 The number of carbon atoms of the hydrocarbon group represented by is preferably 1-10, more preferably 1-5.

[0235] As R 11 and R12 The hydrocarbon group represented by the above-mentioned group includes, for example, methyl, ethyl, n-butyl, n-pentyl (amyl), n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, isopropyl, 2-methylbutyl, isopentyl, 3,3-dimethylbutyl, 2-ethylbutyl, 2-ethyl-2-methylpropyl, isoheptyl, isooctyl, 2-ethylhexyl, 2-propylpentyl, neononyl, 2-ethylheptyl, 2-propylhexyl, 2-butylpentyl, isodecyl, neodecyl, 2-ethyloctyl, 2-propylheptyl, 2-butylhexyl ...heptyl, 2-propylheptyl, 2-butylhexyl, isoheptyl, isooctyl, 2-ethylheptyl, 2-propylheptyl, 2-butylhexyl, isoheptyl, isooctyl, 2-ethylheptyl, 2-propylheptyl, 2-butylhexyl, isoheptyl, isooctyl, 2-ethylheptyl, 2- Undecyl, neoundecyl, 2-ethylnonyl, 2-propyloctyl, 2-butylheptyl, 2-pentylhexyl, isododecyl, neododecyl, 2-ethyldecyl, 2-propylnonyl, 2-butyloctyl, 2-pentylheptyl, isotridecyl, neotridecyl, 2-ethylundecyl, 2-propyldecyl, 2-butyloctyl, 2-pentyloctyl, 2-hexylheptyl, isotetradecyl, neotetradecyl, 2-ethyldodecyl, 2-propylundecyl, 2-butyldecyl, 2-pentylnonyl, 2-hexyloctyl, isopentadecyl, neopentadecyl, cyclohexylmethyl, benzyl, and the like.

[0236] In the above general formulas (10), (11) and (12), R 11 and R 12 At least one of them may be a hydrogen atom, or both of them may be hydrogen atoms. Preferably, R 11 and R 12 Both are hydrogen atoms.

[0237] In addition, the above R 11 and R 12 It can be R 11 and R 12 Together, they form a divalent hydrocarbon group having 3 to 15 carbon atoms. The divalent hydrocarbon group in this case preferably has 4 to 12 carbon atoms, and more preferably has 5 to 9 carbon atoms.

[0238] Specific examples of the divalent hydrocarbon group include 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, and 1,5-hexylene.

[0239] In the above general formulas (10), (11) and (12), R 13 and R 14 are the same or different and are monovalent organic groups. Examples of the organic groups include monovalent hydrocarbon groups and monovalent heteroatom-containing groups, which may have one or more substituents. Examples of the substituents include alkoxy groups, hydroxyl groups, nitro groups, azido groups, cyano groups, acyl groups, acyloxy groups, carboxyl groups, heterocyclic groups, ester groups, etc., which may be further substituted by substituents.

[0240] R13 and R 14 The number of substituents possessed is not limited, but is preferably 5 or less, more preferably 3 or less.

[0241] R 13 and R 14 The carbon number of each of them is 1 to 30, preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 6.

[0242] R 13 and R 14 When having one or two or more substituents, the number of carbon atoms including the substituents is preferably within the above range.

[0243] The monovalent hydrocarbon group may be any one of a monovalent aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be any one of a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group and an alicyclic hydrocarbon group. In addition, the aliphatic hydrocarbon group may be any one of a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group.

[0244] The alicyclic hydrocarbon group is a group having a cyclic aliphatic hydrocarbon portion, and may have a linear or branched aliphatic hydrocarbon portion.

[0245] The above-mentioned aromatic hydrocarbon group is a group having an aromatic ring, and may have an aliphatic part.

[0246] Examples of the aliphatic hydrocarbon group include the same groups as those described above for the aliphatic hydrocarbon group and alicyclic hydrocarbon group.

[0247] In addition, examples of the aromatic hydrocarbon group include the same groups as those described above.

[0248] Among them, an aliphatic hydrocarbon group is preferred, and a saturated aliphatic hydrocarbon group is more preferred.

[0249] Examples of the monovalent heteroatom-containing group include a polyoxyalkylene group and a polyester group.

[0250] The above R 13 and R 14 It can also be R 13 and R 14 Together, they form a divalent organic group having 3 to 30 carbon atoms. The divalent organic group in this case preferably has 3 to 10 carbon atoms, and more preferably has 3 to 6 carbon atoms.

[0251] Examples of the divalent organic group include divalent hydrocarbon groups, and specific examples of the divalent hydrocarbon group include 2,2-propylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, and 1,5-hexylene.

[0252] The divalent organic group may be a group in which one or more hydrogen atoms of a divalent hydrocarbon group having 3 to 15 carbon atoms are replaced by a substituent. Examples of the substituent include the same group as R 13 and R 14 The divalent organic group preferably has 1 to 5 substituents, more preferably 1 to 3 substituents.

[0253] The divalent organic group may be a divalent heteroatom-containing group. Examples of the divalent heteroatom-containing group include polyalkylene oxide and polyester groups.

[0254] In the above general formula (11), R 15 It is an n-valent organic group, a divalent or higher valent organic group, and preferably is a residue obtained by removing two or more hydroxyl groups from a polyol, for example.

[0255] Examples of the polyol include glycerin, polyglycerin, compounds obtained by adding alkylene glycol to glycerin, erythritol, xylitol, sorbitol, trimethylolpropane, pentaerythritol, and dipentaerythritol.

[0256] The upper limit of n is not particularly limited, but is preferably 100 or less, more preferably 12 or less, and further preferably 6 or less.

[0257] R 15 The number of carbon atoms in the n-valent organic group is preferably 1-30, more preferably 1-20, further preferably 1-15, and particularly preferably 1-10.

[0258] In the above general formula (12), R 16 It is a divalent organic group.

[0259] As R 16 Examples of the divalent organic group include the same groups as those described above, and preferably a residue obtained by removing two hydroxyl groups from a diol or a residue obtained by removing two hydroxyl groups from a polyalkylene glycol.

[0260] Examples of the diol or polyalkylene glycol include ethylene glycol, butanediol, polyethylene glycol, and polypropylene glycol.

[0261] R 16 The number of carbon atoms in the divalent organic group is preferably 1-30, more preferably 1-20, further preferably 1-15, and particularly preferably 1-10.

[0262] In the above general formula (12), R 17 represents a hydroxyl group or a monovalent organic group.

[0263] As R17 The monovalent organic group shown in the formula is not particularly limited, and examples thereof include the monovalent organic group 13 and R 14 The same groups as the monovalent organic groups shown above, etc.

[0264] R 17 It is preferably a hydroxyl group or a group represented by the following general formula (13).

[0265] [Chemistry 15]

[0266]

[0267] (In formula (13), R 11 and R 12 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, or R 11 and R 12 Together, they form a divalent hydrocarbon group having 3 to 15 carbon atoms. 14 It represents a monovalent organic group having 1 to 30 carbon atoms.

[0268] As R in the above general formula (13) 11 , R 12 and R 14 , respectively, can be cited with the above R 11 , R 12 , R 14 The same atoms or groups.

[0269] Specific examples of the diester compound represented by the general formula (10) include methyl propyl methylene malonate, dihexyl methylene malonate, dicyclohexyl methylene malonate, diisopropyl methylene malonate, butyl methyl methylene malonate, ethoxyethyl ethyl methylene malonate, methoxyethyl methyl methylene malonate, hexyl ethyl methylene malonate, dipentyl methylene malonate, ethyl pentyl methylene malonate, methyl pentyl methylene malonate, ethyl ethyl methyl methylene malonate, Oxyesters, ethoxyethyl methyl methylenemalonate, butyl ethyl methylenemalonate, dibutyl methylenemalonate, diethyl methylenemalonate (DEMM), diethoxyethyl methylenemalonate, dimethyl methylenemalonate, di-n-propyl methylenemalonate, ethylhexyl methylenemalonate, fenchyl methyl methylenemalonate, menthyl methyl methylenemalonate, 2-phenylpropyl ethyl methylenemalonate, 3-phenylpropyl methylenemalonate, dimethoxyethyl methylenemalonate, and the like.

[0270] The molecular weight of the methylene malonate diester compound is preferably 10,000 or less.

[0271] Moreover, as the polymerizable compound, α-cyanoacrylate can also be preferably used.

[0272] As the α-cyanoacrylate, any known α-cyanoacrylate can be used, and specifically, alkyl-α-cyanoacrylates and cycloalkyl-α-cyanoacrylates such as methyl-α-cyanoacrylate, ethyl-α-cyanoacrylate, propyl-α-cyanoacrylate, butyl-α-cyanoacrylate, and cyclohexyl-α-cyanoacrylate; alkenyl-α-cyanoacrylates and cycloalkenyl-α-cyanoacrylates such as allyl-α-cyanoacrylate, methallyl-α-cyanoacrylate, and cyclohexenyl-α-cyanoacrylate can be mentioned. ; Alkynyl-α-cyanoacrylates such as propynyl-α-cyanoacrylate; aryl-α-cyanoacrylates such as phenyl-α-cyanoacrylate and tolyl-α-cyanoacrylate; methoxyethyl-α-cyanoacrylate, ethoxyethyl-α-cyanoacrylate, and furfuryl-α-cyanoacrylate containing heteroatoms; silicon-containing trimethylsilylmethyl-α-cyanoacrylate, trimethylsilylethyl-α-cyanoacrylate, trimethylsilylpropyl-α-cyanoacrylate, and dimethylvinylsilylmethyl-α-cyanoacrylate; etc. Among them, alkyl-α-cyanoacrylate and cycloalkyl-α-cyanoacrylate are preferred from the aspects of performance and cost, and ethyl-α-cyanoacrylate is more preferred.

[0273] The molecular weight of the α-cyanoacrylate is preferably 10,000 or less.

[0274] In addition, as the above-mentioned polymerizable compound, a compound that can react with a vinyl ether group to form a cross-linked structure can also be used. For example, aliphatic alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, propylene glycol, dipropylene glycol, polyethylene glycol, polycarbonate diol, and glycerol; aromatic alcohols such as 4,4'-biphenol and bisphenol A; acid anhydrides such as maleic anhydride; and the like can be mentioned.

[0275] When the curable composition of the present invention contains the polymerizable compound (B), the content of the polymerizable compound (B) is preferably 1 to 95% by mass, more preferably 10 to 90% by mass, based on 100% by mass of the total solid content of the curable composition.

[0276] In addition, as the above-mentioned polymerizable compound (B), an alkali-soluble resin (b1) containing an acid group and / or a resin (b2) having a group that generates an acid group by heat or acid can also be preferably used. By including these resins, the above-mentioned polymer (A) can react with the acid group contained in the resin, and the curable composition of the present invention can fully undergo a curing reaction even under relatively low curing conditions at a temperature below 200°C. In addition, a cured product with excellent solvent resistance can be provided, which can be suitable for various uses such as various optical components or components of electrical / electronic equipment used in liquid crystal / organic EL / quantum dot / microLED liquid crystal display devices or solid-state imaging elements, touch panel display devices, etc.

[0277] Alkali-soluble resin containing acid groups (b1)

[0278] The acid group-containing alkali-soluble resin (b1) (hereinafter also referred to as "resin (b1)") is a polymer having an acid group. The presence of the acid group makes the resin alkali-soluble.

[0279] As the acid group, for example, functional groups that react with alkaline water to neutralize, such as carboxyl, phenolic hydroxyl, carboxylic acid anhydride, phosphoric acid, and sulfonic acid, may be mentioned, and only one of them may be present, or two or more thereof may be present. Among them, a carboxyl or carboxylic acid anhydride group is preferred, and a carboxyl group is more preferred.

[0280] (b1-1) Structural unit having an acid group

[0281] The resin (b1) preferably has the structural unit (b1-1) having an acid group.

[0282] As methods for obtaining a polymer having the above-mentioned structural unit (b1-1), for example, there can be cited: a method (1) of polymerizing a monomer component including an acid group-containing monomer; a method (2) of polymerizing a monomer component including an epoxy group-containing monomer to obtain a polymer including an epoxy group, and then causing the acid group of the acid group-containing monomer to undergo an addition reaction with the epoxy group to open the epoxy group, and causing a polybasic acid or a polybasic acid anhydride to react with the hydroxyl group generated at this time to produce a carboxyl group; etc., or a method in which these methods are combined.

[0283] In the above method (1), the structural unit (b1-1) is a structural unit derived from an acid group-containing monomer. In the above method (2), the structural unit (b1-1) is a structural unit containing a carboxyl group generated by reacting an acid group-containing monomer with a structural unit derived from an epoxy group-containing monomer and further reacting a polybasic acid or a polybasic acid anhydride.

[0284] Among them, the structural unit (b1-1) is preferably a structural unit derived from an acid group-containing monomer.

[0285] Examples of the acid group-containing monomer include compounds having the acid group and a polymerizable double bond (carbon-carbon double bond) in the molecule. Examples of the polymerizable double bond include (meth)acryloyl, vinyl, allyl, methallyl, etc. Among them, (meth)acryloyl is preferred.

[0286] Specific examples of the above-mentioned acid group-containing monomers include: unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and vinyl benzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; long-chain unsaturated monocarboxylic acids in which chain extension occurs between unsaturated groups and carboxyl groups such as (meth) acrylate β-carboxyethyl, succinic acid mono-2-(2-acryloyloxyethyl) ester, and succinic acid mono-2-(2-methacryloyloxyethyl) ester; unsaturated anhydrides such as maleic anhydride and itaconic anhydride; unsaturated compounds containing phosphoric acid groups such as LIGHT ESTER P-1M (manufactured by Kyoei Chemicals); etc. Among these, carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, long-chain unsaturated monocarboxylic acids, and unsaturated anhydrides) are preferred from the perspectives of versatility and availability. From the perspectives of reactivity and alkali solubility, the above-mentioned acid group-containing monomers are more preferably unsaturated monocarboxylic acids, and more preferably (meth) acrylic acid.

[0287] Examples of the epoxy group-containing monomer include compounds having an epoxy group and the polymerizable double bond in the molecule, and preferably include epoxy group-containing (meth)acrylates.

[0288] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, vinyl benzyl glycidyl ether, allyl glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and vinyl cyclohexene oxide. Among them, glycidyl (meth)acrylate and (3,4-epoxycyclohexyl)methyl (meth)acrylate are preferred, and glycidyl (meth)acrylate is more preferred.

[0289] As the above-mentioned polybasic acid or polybasic acid anhydride, for example, polybasic acids such as succinic acid, maleic acid, phthalic acid, and tetrahydrophthalic acid; dibasic acid anhydrides such as succinic anhydride (also known as succinic anhydride), maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, itaconic anhydride, and polybasic acid anhydrides such as trimellitic anhydride can be mentioned. Among them, polybasic acid anhydrides are preferred.

[0290] The resin (b1) may have only one type of the structural unit (b1-1), or may have two or more types of the structural unit (b1-1).

[0291] From the perspective of maintaining appropriate developability, the content ratio of the above-mentioned structural unit (b1-1) is preferably 3 mass% or more, more preferably 5 mass% or more, and further preferably 7 mass% or more, relative to 100 mass% of all structural units of the above-mentioned resin (b1), and is preferably 40 mass% or less, more preferably 30 mass% or less, and further preferably 20 mass% or less.

[0292] (b1-2) Structural unit having a ring structure in the main chain

[0293] The resin (b1) is preferably a polymer having a ring structure in the main chain. By having a ring structure in the main chain, the heat resistance of the resin (b1) can be improved. As the ring structure, an imide ring, a tetrahydrofuran ring, a lactone ring, etc. can be cited. In order to have these ring structures, the resin (b1) preferably further has a structural unit (b1-2) having a ring structure in the main chain.

[0294] Examples of monomers capable of introducing the structural unit (b1-2) include: monomers having a ring structure containing a double bond in the molecule; monomers that undergo cyclopolymerization to form a polymer having a ring structure in the main chain; monomers that form a ring structure after polymerization; etc. Among them, from the perspective of good heat resistance, solvent resistance, hardness, colorant dispersibility, etc., it is preferred to select at least one monomer from the group consisting of N-substituted maleimide monomers, dialkyl-2,2'-(oxydimethylene) diacrylate monomers, and α-(unsaturated alkoxyalkyl) acrylate monomers. From the perspective of better heat resistance and coloration, it is more preferred to select at least one monomer from the group consisting of N-substituted maleimide monomers and dialkyl-2,2'-(oxydimethylene) diacrylate monomers.

[0295] As the above-mentioned N-substituted maleimide monomer, for example, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-tert-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide, etc. can be mentioned, and one or more of them can be used. Among them, from the aspect of transparency, N-phenylmaleimide and N-benzylmaleimide are preferred, and N-benzylmaleimide is particularly preferred.

[0296] Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; halogen-substituted benzylmaleimide such as o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide; and the like.

[0297] Examples of the dialkyl-2,2'-(oxydimethylene) diacrylate monomers include compounds containing a tertiary carbon at at least one ester site, such as 2,2'-[oxybis(methylene)] diacrylate, dialkyl-2,2'-[oxybis(methylene)] bis-2-acrylate, and dialkyl-2,2'-[oxybis(methylene)] bis-2-acrylate. Among these, dimethyl-2,2'-[oxybis(methylene)] bis-2-acrylate is preferably used in view of transparency, dispersibility, ease of industrial availability, and the like.

[0298] As the above-mentioned α-(unsaturated alkoxyalkyl) acrylate monomers, for example, α-allyloxy methacrylic acid, α-allyloxy methacrylate methyl, α-allyloxy methacrylate ethyl, α-allyloxy methacrylate n-propyl, α-allyloxy methacrylate isopropyl, α-allyloxy methacrylate n-butyl, α-allyloxy methacrylate sec-butyl, α-allyloxy methacrylate tert-butyl, α-allyloxy methacrylate n-pentyl, α-allyloxy methacrylate sec-pentyl, α-allyloxy methacrylate tert-pentyl, α-allyloxy methacrylate neopentyl, etc. can be cited. Among them, alkyl-(α-allyloxymethyl) acrylate monomers are preferred. As alkyl-(α-allyloxymethyl) acrylate monomers, methyl-(α-allyloxymethyl) acrylate is preferably used from the aspects of transparency, dispersibility, ease of industrial acquisition, etc.

[0299] The α-(unsaturated alkoxyalkyl)acrylate monomer can be produced by, for example, the production method disclosed in International Publication No. 2010 / 114077.

[0300] In addition, as the monomer providing the structural unit (b1-2), 2-(hydroxyalkyl) alkyl acrylate is also preferably mentioned. 2-(Hydroxyalkyl) alkyl acrylate can react with (meth)acrylic acid to form a lactone ring structure in the main chain.

[0301] Examples of the alkyl 2-(hydroxyalkyl)acrylate include alkyl 2-(1-hydroxyalkyl)acrylate and alkyl 2-(2-hydroxyalkyl)acrylate. Specifically, examples include methyl 2-(1-hydroxymethyl)acrylate, ethyl 2-(1-hydroxymethyl)acrylate, isopropyl 2-(1-hydroxymethyl)acrylate, n-butyl 2-(1-hydroxymethyl)acrylate, tert-butyl 2-(1-hydroxymethyl)acrylate, and 2-ethylhexyl 2-(1-hydroxymethyl)acrylate. Among them, methyl 2-(1-hydroxymethyl)acrylate and ethyl 2-(1-hydroxymethyl)acrylate are preferred.

[0302] The resin (b1) may have only one type of the structural unit (b1-2), or may have two or more types of the structural unit (b1-2).

[0303] From the perspective of improving heat resistance and solvent resistance, the content ratio of the above-mentioned structural unit (b1-2) is preferably 5 mass% or more, more preferably 8 mass% or more, and further preferably 10 mass% or more, and is preferably 35 mass% or less, more preferably 30 mass% or less, and further preferably 25 mass% or less, relative to 100 mass% of all structural units of the above-mentioned resin (b1).

[0304] (b1-3) Other structural units

[0305] The resin (b1) may have another structural unit (b1-3) in addition to the structural units (b1-1) and (b1-2).

[0306] Examples of the other structural units (b1-3) include structural units derived from the following monomers.

[0307] Hydroxyl-containing monomers such as hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2,3-hydroxypropyl (meth)acrylate;

[0308] Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, n-pentyl (meth)acrylate, sec-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecyl (meth)acrylate, cyclohexyl (meth)acrylate, (Meth)acrylate monomers such as dicyclopentanyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, 1,4-dioxaspiro[4,5]dec-2-yl methacrylic acid, (meth)acryloylmorpholine, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, and 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane;

[0309] Aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, and methoxystyrene;

[0310] Epoxy-containing monomers such as (meth) glycidyl acrylate, (meth) acrylate-β-methyl glycidyl acrylate, (meth) acrylate-β-ethyl glycidyl ester, vinyl benzyl glycidyl ether, allyl glycidyl ether, (meth) acrylate (3,4-epoxycyclohexyl) methyl ester, and vinyl epoxycyclohexane;

[0311] (Meth)acrylamides such as N,N-dimethyl (meth)acrylamide and N-hydroxymethyl (meth)acrylamide;

[0312] Macromonomers having a (meth)acryloyl group at one end of the polymer molecular chain, such as polystyrene, poly(methyl)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, and polycaprolactam;

[0313] Conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene;

[0314] Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate;

[0315] Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether;

[0316] N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, and N-vinylacetamide;

[0317] Unsaturated isocyanates such as isocyanatoethyl (meth)acrylate and allyl isocyanate; etc.

[0318] Among them, the structural unit (b1-3) is preferably a structural unit derived from at least one monomer selected from the group consisting of the hydroxyl group-containing monomer, the (meth)acrylate monomer, the aromatic vinyl monomer, and the epoxy group-containing monomer.

[0319] The resin (b1) may have only one type of the structural unit (b1-3), or may have two or more types of the structural unit (b1-3).

[0320] From the perspective of good developability, the content ratio of the above-mentioned structural unit (b1-3) is preferably 50 mass% or more, more preferably 60 mass% or more, and further preferably 70 mass% or more, and is preferably 92 mass% or less, more preferably 90 mass% or less, and further preferably 85 mass% or less, relative to 100 mass% of all structural units of the above-mentioned resin (b1).

[0321] When the resin (b1) contains two or more of the structural units (b1-3), the content ratio of each structural unit can be appropriately set according to the use and purpose of the curable composition of the present invention.

[0322] The resin (b1) preferably further has an epoxy group. When the resin (b1) further has an epoxy group, the curability of the curable composition of the present invention can be improved, and a cured product having better solvent resistance can be provided.

[0323] The resin (b1) having an epoxy group can be obtained by polymerizing the monomer components including the epoxy group-containing monomer.

[0324] When the resin (b1) has an epoxy group, the epoxy equivalent of the resin (b1) is preferably 100 to 20,000, more preferably 200 to 8,000, and even more preferably 500 to 5000, from the viewpoint of good solvent resistance. The epoxy equivalent can be obtained by dividing the amount of the resin by the number of moles of the epoxy group contained in the resin.

[0325] The acid value of the resin (b1) is preferably 20 mgKOH / g to 230 mgKOH / g. When the acid value is within the above range, a cured film having good developability and excellent solvent resistance can be provided. It is more preferably 30 mgKOH / g to 200 mgKOH / g, and even more preferably 40 mgKOH / g to 180 mgKOH / g.

[0326] The above-mentioned acid value is a value measured by a neutralization titration method using a KOH solution.

[0327] The weight average molecular weight of the resin (b1) is not particularly limited and may be appropriately set depending on the purpose and application of the curable composition, but is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 30,000.

[0328] The molecular weight distribution (weight average molecular weight / number average molecular weight) of the resin (b1) is preferably 1.0 to 4.0, more preferably 1.1 to 3.5, and even more preferably 1.5 to 3.0.

[0329] The weight average molecular weight and molecular weight distribution are values ​​measured by gel permeation chromatography (GPC), and can be specifically determined by the method described in Examples below.

[0330] The resin (b1) may have a polymerizable double bond in the side chain. By having a polymerizable double bond in the side chain, the curability of the resin (b1) can be improved. As the polymerizable double bond, the above-mentioned polymerizable double bond can be cited. Among them, from the aspect of reactivity, (meth)acryloyl is preferred.

[0331] When the resin (b1) has a polymerizable double bond in a side chain, the double bond equivalent is preferably 200 to 8000 g / equivalent, more preferably 250 to 5000 g / equivalent, and even more preferably 300 to 1500 g / equivalent.

[0332] The double bond equivalent refers to the mass of the solid content of the resin solution relative to each 1 mol of double bonds of the resin (b1). The mass of the solid content of the resin solution refers to the total mass of the mass of the monomer components constituting the resin (b1) and the mass of the polymerization inhibitor. The double bond equivalent can be calculated by dividing the mass (g) of the resin solid content of the resin solution by the amount of double bonds (mol) of the resin. The amount of double bonds of the resin can be calculated from the amount of the acid group-containing monomer used during polymerization and the compound having a functional group capable of bonding to the acid group and a polymerizable double bond. As the functional group capable of bonding to the acid group, hydroxyl group, epoxy group, etc. can be cited. In addition, various analyses such as titration and elemental analysis, NMR, IR, or differential scanning calorimetry can also be used for measurement.

[0333] The method for producing the resin (b1) is not particularly limited as long as it is a method that can produce a polymer having at least the structural unit (b1-1) and, as required, the structural units (b1-2) and (b1-3). Examples include a method of polymerizing monomer components containing monomers capable of introducing the structural units (b1-1) to (b1-3) using a known method, and examples include the production methods described in paragraphs

[0039] to

[0062] of Japanese Patent Gazette No. 2015-42697.

[0334] The content of the resin (b1) in 100% by mass of the total solid content of the curable composition is preferably 10% to 60% by mass, more preferably 20% to 50% by mass, and even more preferably 30% to 45% by mass.

[0335] Resin (b2) having a group that generates an acid group by heat or acid

[0336] Examples of the resin (b2) having a group that generates an acid group by heat or acid include resins having a structure or group that generates an acid group by the action of heat or acid.

[0337] Examples of the structure or group that generates an acid group by the action of heat or acid include a tertiary carbon-containing group, a group in which an acid group is blocked by a vinyl ether compound, and a group in which a phenolic hydroxyl group is protected by a protecting group such as a tert-butyl group or an acetyl group.

[0338] As the tertiary carbon-containing group, preferably, -COO * R 18 (R 18 Represents a monovalent organic group, with O * The carbon atom to which the bond is attached is a tertiary carbon atom).

[0339] Above-COO * R 18 R 18Represents a monovalent organic group, with O * The carbon atom to which the carbon atom is bonded is a tertiary carbon atom. A tertiary carbon atom refers to a carbon atom to which three other carbon atoms are bonded.

[0340] Preferred examples of the monovalent organic group include monovalent chain, branched or cyclic saturated or unsaturated hydrocarbon groups having a carbon number of 1 to 91. The organic group may have a substituent.

[0341] About R 18 The number of carbon atoms is preferably 1 to 50, more preferably 1 to 35, still more preferably 1 to 20, particularly preferably 1 to 12, and most preferably 1 to 9.

[0342] R 18 Preferably, -C(R 19 )(R 20 )( R21 ). In this case, R 19 , R 20 and R 21 The same or different, preferably a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, may have a cyclic structure, or may have a substituent. 19 , R 20 and R 21 They can be linked to each other at the end to form a ring structure.

[0343] Here, in the above-mentioned tertiary carbon-containing group, it is preferred that at least one of the adjacent carbon atoms of the above-mentioned tertiary carbon atom is bonded to a hydrogen atom. 18 -C(R 19 )(R 20 )(R 21 ) is preferably R 19 , R 20 and R 21 At least one of the carbon atoms contains a carbon atom having one or more hydrogen atoms, and the carbon atom is bonded to a tertiary carbon atom.

[0344] The above R 19 , R 20 and R 31 The groups are the same or different and are preferably a saturated hydrocarbon group having 1 to 15 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, further preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and particularly preferably a saturated hydrocarbon group having 1 to 3 carbon atoms.

[0345] The above R 18 Preferred are tert-butyl and tert-pentyl.

[0346] In order to obtain the polymer having a tertiary carbon-containing group, a tertiary carbon-containing monomer may be used as a monomer component. Preferred examples of the tertiary carbon-containing monomer include tert-butyl (meth)acrylate and tert-amyl (meth)acrylate.

[0347] Examples of the group in which the acid group is blocked with a vinyl ether compound include a group in which a vinyl ether compound is bonded to the acid group such as a carboxyl group.

[0348] Examples of the vinyl ether compounds include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; cyclic ether compounds such as dihydropyran that can open the ring to generate vinyl ethers; and the like.

[0349] Among the above vinyl ether compounds, dihydropyran is preferred because the protective group can be easily removed at a lower temperature.

[0350] Preferred examples of the group in which the acid group is blocked with dihydropyran include groups represented by the following formula.

[0351] [Chemistry 16]

[0352]

[0353] As the group in which the phenolic hydroxyl group is protected by a protecting group such as a tert-butyl group or an acetyl group, preferably there can be mentioned groups represented by the following formula.

[0354] [Chemistry 17]

[0355]

[0356] (In the formula, n represents the number of substituents, which is an integer from 1 to 5.)

[0357] The group represented by the above formula can be reacted in a solvent in the presence of an acid catalyst such as hydrochloric acid or sulfuric acid at 50 to 150° C. for 1 to 30 hours to remove the protecting group and generate an acid group.

[0358] Among them, groups in which the acid groups are blocked with dihydropyran are preferred because they can generate acid groups at lower temperatures.

[0359] (b2-1) Structural unit represented by general formula (14)

[0360] Preferred examples of the resin (b2) include resins having a structural unit (b2-1) represented by the following general formula (14).

[0361] [Chemistry 18]

[0362]

[0363] (Where R 22 represents a hydrogen atom or a methyl group. Y represents a direct bond or a divalent organic group. A represents a group that generates an acid group by heat or acid.

[0364] In the above general formula (14), R 22 represents a hydrogen atom or a methyl group. Among them, R 22 Preferred is methyl.

[0365] Y represents a direct bond or a divalent organic group.

[0366] Examples of the divalent organic group include a divalent hydrocarbon group which may have a substituent.

[0367] Examples of the divalent hydrocarbon group include an alkylene group, a cycloalkylene group, and an arylene group.

[0368] In the above-mentioned divalent hydrocarbon group, at least one of the atoms constituting the hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom.

[0369] Examples of the substituent include a hydroxyl group, an alkoxy group, and a halogen atom.

[0370] Y is preferably a direct bond.

[0371] In the above general formula (14), A represents a group that generates an acid group by heat or acid.

[0372] Examples of the group that generates an acid group by heat or acid include the same structures or groups as those that generate an acid group by the action of heat or acid.

[0373] The resin (b2) may have only one type of the structural unit (b2-1), or may have two or more types of the structural unit (b2-1).

[0374] From the perspective of good solvent resistance, the content ratio of the above-mentioned structural unit (b2-1) is preferably 5 mass% or more, more preferably 10 mass% or more, and further preferably 15 mass% or more, and is preferably 80 mass% or less, more preferably 70 mass% or less, and further preferably 60 mass% or less, relative to 100 mass% of all structural units of the above-mentioned resin (b2).

[0375] (b2-2) Structural unit having a ring structure in the main chain

[0376] The resin (b2) is preferably a polymer having a ring structure in the main chain. By having a ring structure in the main chain, the heat resistance of the resin (b2) can be improved. As the ring structure, the same ring structure as the ring structure described in the structural unit (b1-2) can be cited. The resin (b2) preferably further has a structural unit (b2-2) having a ring structure in the main chain.

[0377] Examples of the monomer that can introduce the structural unit (b2-2) include the same monomers as those that can introduce the structural unit (b1-2).

[0378] The resin (b2) may have only one type of the structural unit (b2-2), or may have two or more types of the structural unit (b2-2).

[0379] From the perspective of good heat resistance and solvent resistance, the content ratio of the above-mentioned structural unit (b2-2) relative to 100% by mass of all structural units of the above-mentioned resin (b2) is preferably 5% by mass or more, more preferably 8% by mass or more, and further preferably 10% by mass or more, and is preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.

[0380] (b2-3) Other structural units

[0381] The resin (b2) may further have another structural unit (b2-3) in addition to the structural units (b2-1) and (b2-2).

[0382] Examples of the other structural unit (b2-3) include the same structural units as those described above for the other structural unit (b1-3).

[0383] Among them, the structural unit (b2-3) is preferably a structural unit derived from at least one monomer selected from the group consisting of a hydroxyl group-containing monomer, a (meth)acrylate monomer, an aromatic vinyl monomer, and an epoxy group-containing monomer.

[0384] The resin (b2) may have only one type of the structural unit (b2-3), or may have two or more types of the structural unit (b2-3).

[0385] From the perspective of good developability, the content ratio of the above-mentioned structural unit (b2-3) is preferably 15 mass% or more, more preferably 20 mass% or more, and further preferably 30 mass% or more, and is preferably 95 mass% or less, more preferably 90 mass% or less, and further preferably 85 mass% or less, relative to 100 mass% of all structural units of the above-mentioned resin (b2).

[0386] When the resin (b2) contains two or more of the structural units (b2-3), the content ratio of each structural unit can be appropriately designed according to the use and purpose of the curable composition of the present invention.

[0387] The resin (b2) preferably further has an epoxy group. When the resin (b2) further has an epoxy group, the curability of the curable composition can be improved, and a cured product having better solvent resistance can be provided.

[0388] The resin (b2) having an epoxy group can be obtained by polymerizing the monomer components including the epoxy group-containing monomer.

[0389] The acid value of the resin (b2) is preferably 20 mgKOH / g to 230 mgKOH / g. When the acid value is within the above range, a cured film having good developability and excellent solvent resistance can be provided. It is more preferably 30 mgKOH / g to 200 mgKOH / g, and even more preferably 40 mgKOH / g to 180 mgKOH / g.

[0390] The above-mentioned acid value is a value measured by a neutralization titration method using a KOH solution.

[0391] The weight average molecular weight of the resin (b2) is not particularly limited and may be appropriately set according to the purpose and use of the curable composition of the present invention, but is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 30,000.

[0392] The molecular weight distribution (weight average molecular weight / number average molecular weight) of the resin (b2) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.1 to 3.5, and even more preferably 1.5 to 3.0.

[0393] The weight average molecular weight and molecular weight distribution of the above-mentioned polymer are values ​​measured by gel permeation chromatography (GPC), and can be specifically determined by the method described in Examples below.

[0394] The resin (b2) may have a polymerizable double bond in the side chain. The resin (b2) may have a polymerizable double bond in the side chain, thereby improving the curability of the resin (b2).

[0395] The polymerizable double bonds include the same ones as those in the resin (b1). When the resin (b2) has a polymerizable double bond in the side chain, the double bond equivalent is preferably in the same range as that of the resin (b1).

[0396] The method for producing the resin (b2) is not particularly limited as long as it is a method that can obtain a polymer having at least the structural unit (b2-1) and, as required, the structural units (b2-2) and (b2-3). Examples include a method in which a monomer component containing a monomer capable of introducing each of the structural units (b2-1) to (b2-3) is polymerized using a known method. In addition, after the monomer component containing an acid group-containing monomer is polymerized, a protective group may be added to the acid group.

[0397] The amount of each monomer can be appropriately adjusted so that the content of each structural unit in the polymer is within a desired range.

[0398] The polymerization method is not particularly limited, and examples thereof include the same methods as those for producing the resin (b1).

[0399] The content of the resin (b2) in 100% by mass of the total solid content of the curable composition is preferably 10% to 60% by mass, more preferably 20% to 50% by mass, and even more preferably 30% to 45% by mass.

[0400] When the above-mentioned resin (b1) and resin (b2) are used in combination, the total content of the above-mentioned resin (b1) and resin (b2) is preferably 1% by mass to 50% by mass, more preferably 3% by mass to 40% by mass, and further preferably 5% by mass to 35% by mass in 100% by mass of the total solid content of the curable composition.

[0401] The resin (b2) may have the acid group. The resin (b) may have the group that generates an acid group by heat or acid and the acid group.

[0402] The polymerizable compound is preferably at least one selected from the group consisting of the vinyl ether compounds, cyclic ether compounds, (meth)acrylates, carboxylic acid compounds, acid group-containing alkali-soluble resins, resins having groups that generate acid groups by heat or acid, maleimide compounds, alcohols, and thiols.

[0403] <Curing Catalyst (C)>

[0404] The curing catalyst used in the present invention is not particularly limited, but preferably at least one selected from the group consisting of a cationic curing catalyst and a radical curing catalyst can be cited. Among them, a cationic curing catalyst is preferred because the crosslinking reaction of the vinyl ether group proceeds rapidly.

[0405] In the case of any one of a cationic curing catalyst and a free radical curing catalyst, a thermal latent or photolatent curing catalyst can be used according to the embodiment. In addition, Lewis acid or Bronsted acid itself can also be used as a cationic curing catalyst. These catalysts can be used only one, or two or more can be used in combination.

[0406] (Thermolatent cationic curing catalyst)

[0407] The above-mentioned thermolatent cationic curing catalyst is not particularly limited, and a known thermolatent cationic curing catalyst can be used. These are compounds that cannot generate a practical amount of cationic active species by light irradiation, and the temperature for generating cationic active species is preferably 40°C to 200°C, more preferably 60°C to 180°C, and further preferably 80°C to 150°C. Examples of the above-mentioned thermolatent cationic curing catalyst include nonionic curing catalysts and ionic curing catalysts.

[0408] Examples of the nonionic curing catalyst in the thermolatent cationic curing catalyst include compounds composed of a Lewis acid portion such as an organic boron compound and a Lewis base portion such as an amine, a nitrogen-containing compound such as pyridine, a phosphorus-containing compound such as phosphine, or a sulfur-containing compound such as sulfide.

[0409] Examples of the ionic curing catalyst in the above-mentioned thermolatent cationic curing catalyst include compounds composed of a combination of cations such as (4-hydroxyphenyl)benzylmethylsulfonium, (4-hydroxyphenyl)methyl-o-tolylsulfonium, (4-acetoxyphenyl)benzylmethylsulfonium, and diphenylmethylsulfonium, and anions such as tetrafluoroborate, hexafluorophosphate, triphenylhexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, tetrakis(pentafluorophenyl)borate, bis(trifluoromethanesulfonyl)imide, and tricyanomethane.

[0410] (Photolatent cationic curing catalyst)

[0411] The photolatent cationic curing catalyst is not particularly limited, and known photolatent cationic curing catalysts can be used, and nonionic curing catalysts and ionic curing catalysts can be mentioned. Examples of the nonionic curing catalyst include nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, naphthoquinone diazide, and N-hydroxyimide phosphonic acid esters. Examples of the ionic curing catalyst include diphenyliodonium, 4-methoxydiphenyliodonium, bis(4-methylphenyl)iodonium, 4-isopropyl-4′-methyldiphenyliodonium, bis(4-tert-butylphenyl)iodonium, bis(dodecylphenyl)iodonium, diphenyl-4-thiophenoxyphenylsulfonium, bis[4-(diphenylsulfonyl)phenyl]sulfide, bis[4-(di(4-(2-hydroxyethyl)phenyl)sulfonyl)phenyl]sulfide, 4-chlorophenyldiphenylsulfonium, triphenylsulfonium, η5-2,4-(cyclopentadienyl)[1,2,3,4,5,6-η-(methylethyl)benzene]-Fe(1+) and a compound consisting of a combination of a cation such as tetrafluoroborate, hexafluorophosphate, triphenylhexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, tetrakis(pentafluorophenyl)borate and an anion such as salt. In addition, a photosensitizer such as thioxanthone may be added as needed.

[0412] As the photolatent cationic curing catalyst, a photoacid generator may be used. Examples of such a compound include onium salt compounds, sulfone compounds, sulfonate compounds, quinonediazide compounds, sulfonimide compounds, and diazomethane compounds.

[0413] Among them, at least one selected from the group consisting of onium salt compounds, sulfonimide compounds and diazomethane compounds is preferred, an onium salt compound is more preferred, and a triarylsulfonium salt is further preferred.

[0414] Examples of the onium salt compound include diaryliodonium salts, triarylsulfonium salts, and triarylphosphonium salts.

[0415] Specific examples of the diaryliodonium salt include Bluesil PI2074 (manufactured by Elkem), diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, and diphenyliodonium p-toluenesulfonate; 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphate, 4-methoxyphenylphenyliodonium hexafluoroantimonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium salts such as 4-methoxyphenylphenyl iodonium trifluoroacetate and 4-methoxyphenylphenyl iodonium p-toluenesulfonate; bis(4-tert-butylphenyl)iodonium tetrafluoroborate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium hexafluoroantimonate, bis(4-tert-butylphenyl)iodonium hexafluoroarsenate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium trifluoroacetate, bis(4-tert-butylphenyl)iodonium p-toluenesulfonate and the like.

[0416] Examples of the triarylsulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, and triphenylsulfonium p-toluenesulfonate; 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, and 4-methoxyphenyldiphenylsulfonium p-toluenesulfonate; 4-methoxyphenyldiphenylsulfonium salts such as 4-methoxyphenyldiphenylsulfonium trifluoroacetate and 4-methoxyphenyldiphenylsulfonium p-toluenesulfonate; 4-phenylthienyldiphenylsulfonium tetrafluoroborate, 4-phenylthienyldiphenylsulfonium hexafluorophosphate, 4-phenylthienyldiphenylsulfonium hexafluoroantimonate, 4-phenylthienyldiphenylsulfonium hexafluoroarsenate, 4-phenylthienyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthienyldiphenylsulfonium trifluoroacetate and 4-phenylthienyldiphenylsulfonium p-toluenesulfonate; and the like.

[0417] Examples of the triarylphosphonium salt include triphenylphosphonium tetrafluoroborate, triphenylphosphonium hexafluorophosphate, triphenylphosphonium hexafluoroantimonate, triphenylphosphonium hexafluoroarsenate, triphenylphosphonium trifluoromethanesulfonate, triphenylphosphonium trifluoroacetate, and triphenylphosphonium p-toluenesulfonate; 4-methoxyphenyldiphenylphosphonium tetrafluoroborate, 4-methoxyphenyldiphenylphosphonium hexafluorophosphate, 4-methoxyphenyldiphenylphosphonium hexafluoroantimonate, 4-methoxyphenyldiphenylphosphonium hexafluoroarsenate, 4-methoxyphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylphosphonium trifluoroacetate, and 4-methoxyphenyldiphenylphosphonium p-toluenesulfonate; 4-methoxyphenyldiphenylphosphonium salts such as 4-methoxyphenyldiphenylphosphonium trifluoroacetate and 4-methoxyphenyldiphenylphosphonium p-toluenesulfonate; tris(4-methoxyphenyl)phosphonium tetrafluoroborate, tris(4-methoxyphenyl)phosphonium hexafluorophosphate, tris(4-methoxyphenyl)phosphonium hexafluoroantimonate, tris(4-methoxyphenyl)phosphonium hexafluoroarsenate, tris(4-methoxyphenyl)phosphonium trifluoromethanesulfonate, tris(4-methoxyphenyl)phosphonium trifluoroacetate and tris(4-methoxyphenyl)phosphonium p-toluenesulfonate.

[0418] Examples of the sulfonyl imide compound include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)bicyclo[2,2,1]-heptane-5,6-oxy-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)naphthyl imide, and the like. ) sulfonyl imide compounds having an N-(bornylsulfonyloxy) group, such as N-(bornylsulfonyloxy) succinimide, N-(bornylsulfonyloxy) phthalimide, N-(bornylsulfonyloxy) diphenylmaleimide, N-(bornylsulfonyloxy) bicyclo[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(bornylsulfonyloxy)-7-oxabicyclo[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(bornylsulfonyloxy) bicyclo[2,2,1]-heptane-5,6-oxy-2,3-dicarboximide, and N-(bornylsulfonyloxy) naphthyl imide; sulfonyl imide compounds having an N-(bornylsulfonyloxy) group, such as N-(4-methylbenzenesulfonyloxy) succinimide, N-(bornylsulfonyloxy) phthalimide, N-(bornylsulfonyloxy) diphenylmaleimide, N-(bornylsulfonyloxy) bicyclo[2,2,1]-hept-5-ene-2,3-dicarboximide, Sulfonyl imide compounds having an N-(4-methylbenzenesulfonyloxy) group, such as N-(4-methylbenzenesulfonyloxy)phthalimide, N-(4-methylbenzenesulfonyloxy)diphenylmaleimide, N-(4-methylbenzenesulfonyloxy)bicyclo[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(4-methylbenzenesulfonyloxy)-7-oxabicyclo[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(4-methylbenzenesulfonyloxy)bicyclo[2,2,1]-heptane-5,6-oxo-2,3-dicarboximide, and N-(4-methylbenzenesulfonyloxy)naphthyl imide; and N-(2-trifluoromethylbenzenesulfonyloxy)succinimide. Sulfonyl imide compounds having an N-(2-trifluoromethylbenzenesulfonyloxy group) such as acrylamide, N-(2-trifluoromethylbenzenesulfonyloxy)phthalimide, N-(2-trifluoromethylbenzenesulfonyloxy)diphenylmaleimide, N-(2-trifluoromethylbenzenesulfonyloxy)bicyclo[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(2-trifluoromethylbenzenesulfonyloxy)-7-oxabicyclo[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(2-trifluoromethylbenzenesulfonyloxy)bicyclo[2,2,1]-heptane-5,6-oxo-2,3-dicarboximide, and N-(2-trifluoromethylbenzenesulfonyloxy)naphthyl imide.

[0419] Examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1-(1,1-dimethylethylsulfonyl)diazomethane, and bis(1,1-dimethylethylsulfonyl)diazomethane.

[0420] (Thermolatent free radical curing catalyst)

[0421] Examples of the thermolatent free radical curing catalyst include organic peroxides such as cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene peroxide, di-tert-butyl peroxide, lauryl peroxide, benzoyl peroxide, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy(2-ethylhexanoate), and tert-amyl peroxy-2-ethylhexanoate; and azo compounds such as 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(2-methylpropionic acid)dimethyl ester.

[0422] (Photolatent free radical curing catalyst)

[0423] Examples of the photolatent free radical curing catalyst include alkyl phenones such as 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone ("IRGACURE 184", manufactured by BASF), 2-hydroxy-2-methyl-1-phenylacetone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone, and 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone; acyl phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)diphenylphosphine oxide; and methyl benzoylformate.

[0424] Aminoketone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone ("IRGACURE 907", manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone ("IRGACURE 369", manufactured by BASF), 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)butan-1-one ("IRGACURE 379", manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethane-1-one ("IRGACURE 651", manufactured by BASF), methyl phenylglyoxylate ("DAROCURE 651", manufactured by BASF); MBF, manufactured by BASF) and the like; benzyl ketal compounds; hydroxyketone compounds such as 1-hydroxycyclohexyl phenyl ketone ("IRGACURE 184", manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propane-1-one ("DAROCUR 1173", manufactured by BASF), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one ("IRGACURE 2959", manufactured by BASF), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methyl-propane-1-one ("IRGACURE 127", manufactured by BASF), [1-hydroxycyclohexyl phenyl ketone + benzophenone] ("IRGACURE 500", manufactured by BASF); 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-hydroxy-2-methyl-1-propane-1-one ("IRGACURE 2959", manufactured by BASF), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methyl-propane-1-one ("IRGACURE 127", manufactured by BASF), and [1-hydroxycyclohexyl phenyl ketone + benzophenone] ("IRGACURE 500", manufactured by BASF); ]-, 2-(O-benzoyl oxime)] ("OXE01", manufactured by BASF), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime) ("OXE02", manufactured by BASF), 1,2-octanedione, 1-[4-(phenylthio)-, 2-, (O-benzoyl oxime)], ethyl ketone ("OXE03", manufactured by BASF), Oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime) ("OXE04", manufactured by BASF)); benzophenone compounds; benzoin compounds; thioxanthone compounds; halomethylated triazine compounds; halomethylated oxadiazole compounds; biimidazole compounds; cyclopentadienyl titanium compounds; benzoate compounds; acridine compounds; etc.

[0425] When the curable composition of the present invention contains the curing catalyst (C), the content of the curing catalyst (C) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the polymer (A).

[0426] In addition, particularly when the above-mentioned photolatent free radical curing catalyst is used as the above-mentioned curing catalyst (C), the content of the above-mentioned curing catalyst (C) is preferably 0.3% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, and further preferably 1% by mass to 8% by mass relative to 100% by mass of the total solid content of the curable composition of the present invention.

[0427] In addition, particularly when a photolatent cationic curing catalyst of the photoacid generator is used as the curing catalyst (C), the content of the curing catalyst (C) is preferably 0.3% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, and even more preferably 1% by mass to 8% by mass, based on 100% by mass of the total solid content of the curable composition of the present invention.

[0428] In addition to the above-mentioned components, the curable composition (1) of the present invention may further include other components. As the above-mentioned other components, for example, other polymerizable compounds, epoxides, solvents, chain transfer agents, dispersants, antioxidants, leveling agents, inorganic particles, coupling agents, curing agents, curing aids, plasticizers, inhibitors, ultraviolet light absorbers, defoamers, antistatic agents, anti-aging agents, wettability improvers, close fit imparting agents, colorants (pigments, dyes), heat-resistant improvers, developing aids, fillers, thermosetting resins, matting agents, slip agents, surface modifiers, thixotropic aids, quinone diazide compounds, polyphenol compounds, cationic polymerizable compounds, thermal acid generators, etc., other than the above-mentioned optional components can be cited. They can be appropriately selected from known materials according to the purpose and purpose of the curable composition. In addition, its dosage can also be appropriately set.

[0429] (Other polymerizable compounds)

[0430] The curable composition (1) of the present invention preferably contains the above-mentioned other polymerizable compound. By further containing the above-mentioned other polymerizable compound, a cured product having excellent various physical properties such as solvent resistance, mechanical strength, and heat resistance in addition to curability can be provided.

[0431] The above-mentioned other polymerizable compounds are low molecular weight compounds having polymerizable unsaturated bonds (also referred to as polymerizable unsaturated groups) that can be polymerized by irradiation with free radicals, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays, etc.), electron beams, and other active energy rays, and examples thereof include monofunctional compounds having one polymerizable unsaturated group in the molecule and polyfunctional compounds having two or more polymerizable unsaturated groups.

[0432] Specific examples of the other polymerizable compounds include monofunctional polymerizable compounds and polyfunctional polymerizable compounds other than the polymerizable compound (B) described in paragraphs

[0077] to

[0085] of JP-A-2015-42697.

[0433] As the above-mentioned multifunctional polymerizable compound, from the aspects of reactivity, economy, availability, etc., preferably, a compound having a (meth)acryloyl group such as a multifunctional (meth)acrylate compound, a multifunctional urethane (meth)acrylate compound, an isocyanurate compound containing a (meth)acryloyl group, etc. can be cited, and more preferably, a multifunctional (meth)acrylate compound can be cited. By including a compound having a (meth)acryloyl group, the photosensitivity and curability of the curable composition are more excellent, and a cured product with higher hardness and higher transparency can be obtained. As the above-mentioned multifunctional polymerizable compound, it is further preferred to use a multifunctional (meth)acrylate compound having more than three functions.

[0434] The content of the above-mentioned other polymerizable compounds can be appropriately set without particular limitation as long as it is within the range where the effect of the present invention is exerted. From the perspective of being able to make the viscosity of the curable composition appropriate, it is preferably 5% by mass to 60% by mass, and more preferably 10% by mass to 50% by mass, relative to 100% by mass of the total solid content of the curable composition.

[0435] (Epoxide)

[0436] The curable composition (1) of the present invention preferably contains an epoxide. When an epoxide is contained, cationic polymerization proceeds, a crosslinking reaction proceeds more easily, and a cured product having excellent solvent resistance can be provided.

[0437] Examples of the epoxide include compounds having an epoxy group and a polymerizable double bond, and examples thereof include the epoxy group-containing monomers described above.

[0438] The content of the epoxide is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and even more preferably 5 to 30% by mass, based on 100% by mass of the total solid content of the curable composition.

[0439] Curable composition (2)

[0440] The second curable composition of the present invention (hereinafter also referred to as "curable composition (2)") is a curable composition comprising a polymer (A) and a polymerizable compound (B) and / or a curing catalyst (C), characterized in that the above-mentioned polymer (A) is a group transfer polymer comprising a monomer component of a (meth)acrylate containing a vinyl ether group represented by the following general formula (2).

[0441] [Chemistry 19]

[0442]

[0443] (Where R 1 represents a hydrogen atom or a methyl group. 2 and R 3 The same or different, represents a hydrogen atom or an organic group. 4 represents a hydrogen atom or an organic group. n represents an integer greater than 1.)

[0444] In addition, a curable composition containing such a group transfer polymer is also excellent in curing reactivity.

[0445] In addition, as described above, since the group transfer polymer is obtained by group transfer polymerization, a cured product having a desired shape and good strength with a small amount of insoluble components can be obtained. In addition, since the amount of residual monomers is small, the reproducibility of the physical property performance of the obtained cured product is improved.

[0446] The group transfer polymer preferably has the same structural unit as the structural unit (a1) except that n is an integer of 1 or more in the structural unit (a1) represented by the general formula (1).

[0447] The polymer (A) used in the curable composition (2) may further have the same structural units as the polymer (A) used in the curable composition (1) in addition to the above structural units. In addition, the polymer (A) used in the curable composition (2) preferably has the same physical properties such as various molecular weights, insoluble content, residual monomer content, and content in the curable composition as the polymer (A) used in the curable composition (1).

[0448] As a method for producing the polymer (A) used in the above-mentioned curable composition (2), there can be mentioned a method similar to the method of group transfer polymerization described in the method for producing the polymer (A) used in the above-mentioned curable composition (1), except that a substance in which n is an integer of 1 or more among the vinyl ether group-containing (meth)acrylates represented by the above-mentioned general formula (2) is used as a monomer component.

[0449] Preferred examples of the vinyl ether group-containing (meth)acrylates wherein n is an integer of 1 or more in the general formula (2) include 2-(2-vinyloxyethoxy)ethyl (meth)acrylate and 2-vinyloxyethyl (meth)acrylate.

[0450] Examples of the polymerizable compound (B) and the curing catalyst (C) used in the curable composition (2) include the same ones as those used in the curable composition (1), and their contents are also the same.

[0451] The curable composition (2) may further contain other components. Examples of the other components include the same components as those used in the curable composition (1).

[0452] <Method for producing curable composition>

[0453] The manufacturing method of the curable composition (1) and (2) of the present invention is not particularly limited, and for example, the above-mentioned components can be mixed and dispersed by using various known mixers or dispersers such as a bead mill, a ball mill, a kneader, a stirrer, etc. In addition, the solvent used in the manufacture can be desolvated after the polymer is manufactured, and other solvents are added to the resulting product and mixed with the components. In addition, other steps that are usually performed can also be further included. For example, in the case of including a colorant, a colorant composition can be prepared in advance using a solvent or a dispersant, and then mixed with the above-mentioned components.

[0454] <How to use>

[0455] Examples of methods for using the curable compositions (1) and (2) of the present invention include a method in which the curable composition is applied to a substrate and the applied material is dried, heated or irradiated with active energy rays, or a combination of these methods to cure the applied material to form a cured film.

[0456] The substrate is not particularly limited, and examples thereof include known substrates made of wood, glass, various plastics, or a combination thereof.

[0457] The coating method is not particularly limited, and the coating can be carried out by a known method such as gravure printing, roll coating, bar coating, coater, ink jet, or the like.

[0458] The drying or heating method may be appropriately selected from known methods depending on the composition, purpose, and application of the curable composition, and is preferably carried out at 50° C. to 300° C., more preferably 60° C. to 200° C. The drying and heating time is preferably 1 minute to 72 hours, more preferably 20 minutes to 24 hours.

[0459] The active energy ray irradiation can be performed by a known method using active energy rays such as infrared rays, ultraviolet rays, X-rays, electron beams, etc. The irradiation amount can be appropriately set according to the composition and application of the curable composition.

[0460] In addition, the curable compositions (1) and (2) of the present invention can also be used as molding materials. The molding method is not particularly limited and can be appropriately selected from known methods such as injection molding, extrusion molding, 3D printing, etc. according to the composition, purpose or use of the curable composition.

[0461] When the cured product of the curable composition is a cured film, the thickness thereof may be appropriately designed depending on the purpose and application, and is usually preferably 1 μm to 5 mm.

[0462] <Purpose>

[0463] The curable compositions (1) and (2) of the present invention are excellent in curing reactivity when cured by active energy rays or heat. The curable compositions (1) and (2) of the present invention can be suitably used in adhesives, bonding agents, printing ink compositions, 3D printing compositions, resist compositions, sealing materials, various coating agents imparting anti-stickiness, anti-fingerprint adhesion, waterproofing, hydrophilicity, hard coating, antifouling, antistatic, insulation and other functions, various functional coatings for automobiles, buildings / structures, industry, packaging, etc., surface protection sheets, substrates, lenses, electronic components, optical films, optical components and other molding materials.

[0464] The curable compositions (1) and (2) of the present invention can be suitably used as compositions for resists, and can be more suitably used as compositions for color filters. As methods for producing and using the curable compositions (1) and (2) of the present invention suitable as compositions for resists, the methods described in paragraphs

[0120] to

[0140] of Japanese Patent Application Laid-Open No. 2015-42697 can be cited.

[0465] Example

[0466] The present invention is described in more detail below with reference to Examples, but the present invention is not limited to these Examples. It should be noted that, unless otherwise stated, "parts" means "parts by mass" and "%" means "% by mass".

[0467] Various physical properties of the polymer were measured by the following methods.

[0468] <Weight Average Molecular Weight (Mw), Number Average Molecular Weight (Mn) and Molecular Weight Distribution (Mw / Mn)>

[0469] The obtained polymer was dissolved / diluted with tetrahydrofuran and filtered through a filter having a pore size of 0.45 μm. The obtained filtrate was measured using the following gel permeation chromatography (GPC) apparatus and conditions.

[0470] Equipment: HLC-8020GPC (manufactured by Tosoh Corporation)

[0471] Elution solvent: Tetrahydrofuran

[0472] Standard substance: Standard polystyrene (manufactured by Tosoh Corporation)

[0473] Separation column: TSKgel SuperHM-M, TSKgel SuperH-RC (manufactured by Tosoh Corporation)

[0474] It should be noted that for polymers B-1 and B-2, TSKgel SuperHZM-M and TSKgel SuperH-RC (manufactured by Tosoh Corporation) are used as the separation columns.

[0475] < I 1H-NMR measurement

[0476] For the obtained polymers, 1H-NMR measurement is carried out under the following conditions. 1 1H-NMR measurement.

[0477] Apparatus: Nuclear magnetic resonance apparatus (600 MHz) manufactured by Agilent Technologies

[0478] Measurement solvent: Deuterochloroform

[0479] Sample preparation: Dissolve several mg to several tens of mg of the obtained polymer in the measurement solvent.

[0480] <Insoluble component content>

[0481] Add ethyl acetate to about 2 g to 3 g of the obtained polymer in such a way that the solid content is about 33% by mass. After stirring well at room temperature, pass the obtained solution through a filter with a pore size of 4 μm. Further wash the residue on the filter with about 7 g to 10 g of ethyl acetate, and then dry the residue at room temperature for 5 minutes. Measure the mass (b) of the dried residue. Let the mass of the polymer be (a), and calculate the insoluble component content by the following formula.

[0482] Insoluble component content (% by mass) = (b) / (a) × 100

[0483] <X / Y ratio>

[0484] In the differential molecular weight distribution curve obtained by measuring the molecular weight of the above polymer using the GPC method, as Figure 1 shown, when the point of the maximum value is set as T and the points at 5% height of T on the above differential molecular weight distribution curve are set as L0 and L1 from the low molecular weight side, find the area (X) of the triangle surrounded by T-L0-L1 and the area (Y) of the part surrounded by the above differential molecular weight distribution curve and the line connecting L0-L1, and calculate the ratio (X / Y).

[0485] <Solid content>

[0486] About 1 g of the polymer solution was weighed in an aluminum cup, and about 3 g of acetone was added to dissolve it, and then dried naturally at room temperature. Then, it was dried at 170°C under vacuum for 1.5 hours using a hot air dryer (trade name: PHH-101, manufactured by Espec), and then naturally cooled in a dryer and the mass was measured. The solid content (mass %) of the polymer solution was calculated from the mass loss.

[0487] <Acid value>

[0488] 3 g of the polymer solution was accurately weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated using a 0.1 N aqueous KOH solution as a titrant. The titration was performed using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value (mgKOH / g) per 1 g of the solid content was determined from the acid value of the solution and the solid content of the solution.

[0489] Polymer Manufacturing

[0490] (Production Example 1)

[0491] <Production of 2-(2-vinyloxyethoxy)ethyl methacrylate polymer>

[0492] Dehydrated tetrahydrofuran (230 parts by mass), methyl (trimethylsilyl) dimethyl ketene acetal (0.9 parts by mass), and tetrabutylammonium benzoate (0.02 parts by mass) were added to a 50 mL Schlenk bottle, and 2-(2-vinyloxyethoxy)ethyl methacrylate (hereinafter referred to as "VEEM") (100 parts by mass) was added dropwise over 10 minutes while stirring at room temperature under a nitrogen flow. After the addition was completed, the reaction solution was stirred at room temperature for 5 hours, and then the catalyst was removed by passing it through a silica gel column. The obtained solution was concentrated to obtain a VEEM polymer. Utilization 1 The obtained polymer was analyzed by H-NMR. As a result, a peak derived from vinyl ether was observed at around 6.5 ppm, and the integrated value showed that all vinyl ether groups remained.

[0493] VEEM as a monomer was not observed, and the insoluble component contained in the polymer was 0%.

[0494] The obtained polymer had a weight average molecular weight of 42,000, a number average molecular weight of 25,000, and a molecular weight distribution (Mw / Mn) of 1.7. The X / Y value of the polymer was 1.16.

[0495] 100 parts by mass of ethyl acetate was added thereto to prepare a 50% by mass polymer solution.

[0496] (Production Example 2)

[0497] <Production of 2-(2-vinyloxyethoxy)ethyl methacrylate-methyl methacrylate copolymer>

[0498] In a 500 mL flask, add dehydrated tetrahydrofuran (200 parts by mass), methyl (trimethylsilyl) dimethyl ketene acetal (1.7 parts by mass), and tetrabutylammonium benzoate (0.02 parts by mass). Under a nitrogen stream, slowly dropwise add a monomer mixture (VEEM (20 parts by mass), methyl methacrylate (hereinafter referred to as "MMA") (90 parts by mass)) at 20°C while stirring. After stirring for 5 hours, dilute with ethyl acetate and pass through a short silica gel column to remove the catalyst. The polymer concentration of the obtained solution is concentrated / adjusted to obtain a VEEM-MMA copolymer solution with a polymer concentration of 50%. Utilize 1 The obtained copolymer was confirmed by H-NMR, and the peak from vinyl ether was confirmed. From the integral value, it can be seen that all vinyl ether groups remain. VEEM and MMA as monomers were not observed, and the insoluble components contained in the copolymer were 0%. The ratio of the structural units of the above copolymer was VEEM / MMA=11 / 89 (mol%). In addition, the weight average molecular weight of the above copolymer was 15000, the number average molecular weight was 12800, and the molecular weight distribution (weight average molecular weight / number average molecular weight) was 1.17. The X / Y value of the above copolymer was 1.37.

[0499] (Production Example 3)

[0500] <Production of 2-(2-vinyloxyethoxy)ethyl methacrylate-methyl methacrylate copolymer>

[0501] VEEM (100 parts by mass), MMA (50 parts by mass), dehydrated tetrahydrofuran (350 parts by mass), methyl (trimethylsilyl) dimethyl ketene acetal (2 parts by mass) were added to a flask, and phosphazene base P4-t-Bu (0.8 M toluene solution, 2.5 parts by mass) was added while stirring at room temperature under a nitrogen stream. After stirring overnight (about 20 hours) at room temperature, a small amount of methanol was added, and the reaction solution was concentrated to obtain a polymer composition containing a VEEM-MMA copolymer.

[0502] use 1The obtained polymer composition was confirmed by H-NMR. As a result, a peak derived from vinyl ether was confirmed at around 6.5 ppm. From the integral value, it was known that all vinyl ether groups remained. It was thus confirmed that a polymer in which only the methacryloyl group of VEEM was polymerized was obtained. On the other hand, no peak of VEEM as a monomer was confirmed. The insoluble component contained in the copolymer was 0%. The ratio of the structural units of the above copolymer was VEEM / MMA=50 / 50 (mol%).

[0503] The weight average molecular weight of the obtained copolymer was 27600, the number average molecular weight was 10600, and the molecular weight distribution (Mw / Mn) was 2.61. The X / Y value of the above copolymer was 1.11.

[0504] (Production Example 4)

[0505] <Production of 2-(2-vinyloxyethoxy)ethyl acrylate polymer>

[0506] 2-(2-vinyloxyethoxy)ethyl acrylate (hereinafter referred to as "VEEA") (100 parts by mass), dehydrated toluene (180 parts by mass), and methyl (trimethylsilyl) dimethyl ketene acetal (1 part by mass) were added to a flask, and phosphazene base P4-t-Bu (0.8 M toluene solution, 2 parts by mass) was added while stirring at 30° C. under a nitrogen stream. After stirring at 30° C. overnight (about 24 hours), a small amount of methanol was added, and the reaction solution was concentrated to obtain a polymer composition containing a VEEA polymer.

[0507] use 1 The obtained polymer composition was confirmed by H-NMR, and the result showed that the peak from vinyl ether was confirmed near 6.5ppm, and the integral value showed that all the vinyl ether groups remained. It was thus confirmed that a polymer in which only the acryloyl group of VEEA was polymerized was obtained. On the other hand, the peak of VEEA as a monomer was not confirmed (peaks near 6.5ppm, 6.2ppm and 5.8ppm). The insoluble components contained in the polymer were 0%. In addition, the weight average molecular weight of the obtained VEEA polymer was 19400, the number average molecular weight was 7600, and the molecular weight distribution (Mw / Mn) was 2.57. The X / Y value of the above VEEA polymer was 1.04.

[0508] (Production Example 5)

[0509] <Production of 2-(2-vinyloxyethoxy)ethyl methacrylate-cyclohexyl methacrylate copolymer>

[0510] In a flask immersed in a thermostatic bath at 20° C., a mixture of VEEM (100 parts by mass) and cyclohexyl methacrylate (hereinafter referred to as “CHMA”) (100 parts by mass) was added dropwise to a mixture of dehydrated tetrahydrofuran (400 parts by mass), methyl (trimethylsilyl) dimethyl ketene acetal (6 parts by mass), and tetrabutylammonium benzoate (0.1 parts by mass) under a nitrogen stream over 10 minutes. After the addition was completed, the reaction solution was stirred for 5 hours under the same conditions. The obtained solution was diluted with ethyl acetate, passed through a short silica gel column, and then concentrated under reduced pressure to obtain a polymer composition containing a VEEM-CHMA copolymer.

[0511] use 1 The obtained polymer composition was confirmed by H-NMR, and as a result, VEEM and CHMA used in the polymerization were completely consumed. The insoluble components contained in the obtained copolymer were 0%.

[0512] The weight average molecular weight of the copolymer was 6900, the number average molecular weight was 6272, and the molecular weight distribution (Mw / Mn) was 1.1. The X / Y value of the VEEM-CHMA copolymer was 1.20.

[0513] (Production Example 6)

[0514] <Production of Glycidyl Methacrylate Polymer>

[0515] Glycidyl methacrylate (hereinafter referred to as "GMA") (30 parts by mass) and methyl ethyl ketone (hereinafter referred to as "MEK") (70 parts by mass) were added to a four-necked flask equipped with a thermometer, an inert gas introduction tube, and a reflux condenser as a reaction solution. Nitrogen was introduced into the reaction solution by bubbling, and after degassing for 3 hours, the reaction solution was heated to 70°C while nitrogen was introduced from the inert gas introduction tube, and a MEK solution (5 parts by mass) of a polymerization initiator (azobisisobutyronitrile: AIBN) (0.34 parts by mass) was slowly added to the reaction solution. After that, the mixture was stirred at the same temperature for 20 hours, cooled naturally to room temperature, and MEK (100 parts by mass) was added to obtain a polymer solution. The polymer solution was reprecipitated using hexane to obtain a GMA polymer. The weight average molecular weight of the obtained polymer was 125,800, the number average molecular weight was 23,200, and the molecular weight distribution (Mw / Mn) was 5.42.

[0516] (Production Example 7)

[0517] <Production of Polymer B-1>

[0518] Into a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a condenser, and a drop tank inlet, 81.9 parts of propylene glycol monomethyl ether acetate and 37.7 parts of propylene glycol monomethyl ether were added, and after nitrogen substitution, the temperature was raised to 90°C. On the other hand, as a drop tank (A), a mixture of 10.0 parts of N-benzylmaleimide, 70.0 parts of tert-butyl methacrylate, 20.0 parts of methacrylic acid, 34.2 parts of propylene glycol monomethyl ether acetate, 14.7 parts of propylene glycol monomethyl ether, and 2.0 parts of tert-butyl peroxy (2-ethylhexanoate) was prepared, and a stirred mixture of 1.0 parts of n-dodecyl mercaptan and 6.1 parts of propylene glycol monomethyl ether acetate was prepared in a drop tank (B). After the temperature of the reaction tank reached 90°C, the polymerization was carried out by dropping from the drop tank over 3 hours while maintaining the temperature. After the addition was completed, the temperature was maintained at 90°C for 30 minutes, then raised to 115°C and aged for 90 minutes. After cooling to room temperature, 16.5 parts of GMA, 0.4 parts of dimethylbenzylamine as a catalyst, and 0.2 parts of Topanol as a polymerization inhibitor were added, and the mixture was reacted at 110°C for 7 hours to obtain a polymer solution B-1 (solid content 39.8%). The weight average molecular weight of the obtained polymer was 15,000, the molecular weight distribution (Mw / Mn) was 2.5, and the acid value was 60 mgKOH / g.

[0519] (Production Example 8)

[0520] <Production of Polymer B-2>

[0521] 201.0 parts of propylene glycol monomethyl ether acetate were added to a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a condenser and a dropping tank inlet, and after nitrogen substitution, the temperature was raised to 90°C. On the other hand, as a dropping tank (A), 10.0 parts of N-benzylmaleimide, 43.6 parts of CHMA, 30.0 parts of 2-hydroxyethyl methacrylate, 16.4 parts of GMA, 30.0 parts of propylene glycol monomethyl ether acetate and 2.0 parts of tert-butyl peroxy (2-ethylhexanoate) were stirred and mixed in a beaker, and a stirred mixture of 2.0 parts of n-dodecyl mercaptan and 31.3 parts of propylene glycol monomethyl ether acetate was prepared in a dropping tank (B). After the temperature of the reaction tank reached 90°C, the polymerization was carried out by dropping from the dropping tank over 3 hours while maintaining the temperature. After the addition was completed, the temperature was maintained at 90°C for 30 minutes, then the temperature was raised to 115°C and aged for 90 minutes. After cooling to room temperature, 11.5 parts of succinic anhydride and 0.3 parts of dimethylbenzylamine as a catalyst were added and reacted at 60°C for 3 hours to obtain a polymer solution B-2 (solid content 28.8%). The weight average molecular weight of the obtained polymer was 10,000, the molecular weight distribution (Mw / Mn) was 2.8, and the acid value was 68 mgKOH / g.

[0522] (Examples 1 to 28, Comparative Examples 1 to 9)

[0523] <Manufacturing of Curable Composition>

[0524] The polymer solution, polymerizable compound and curing catalyst obtained above were mixed in the proportions shown in Tables 1 to 3 to obtain curable compositions. The blending amounts in the tables are based on solid content.

[0525] <Evaluation of curability (acetone friction test)>

[0526] The obtained curable composition was applied to a PET film (7 cm × 21 cm) with a single-sided easy-adhesion treatment in a thickness of 25 μm using a bar coater, and left at room temperature for about 10 to 20 minutes. The coated material was then cured by ultraviolet light using the ultraviolet irradiation device FUSION UV manufactured by Heraeus under the irradiation energy conditions described in Table 1, or thermally cured under the curing conditions described in Tables 2 to 3 to obtain a cured coating film. The obtained cured coating film was rubbed 20 times using a Kimwipe (manufactured by NIPPON PAPER CRECIA CO., LTD.) impregnated with acetone, and the degree of curing was confirmed according to the following evaluation criteria. The results are shown in Tables 1 to 3.

[0527] (Evaluation Criteria)

[0528] ○: The cured coating film does not dissolve.

[0529] △: The cured coating film has residual friction marks or swelling.

[0530] ×: The cured coating film whitened or dissolved.

[0531] In addition, the compounds described in Tables 1 to 3 are as follows.

[0532] BMI-2300: Phenylmethane maleimide, manufactured by Yamato Chemical Industry Co., Ltd.

[0533] PI2074: Bluesil TM PI2074, manufactured by Elkem

[0534] Irg184: IRUGACURE184 (1-hydroxycyclohexyl phenyl ketone, manufactured by BASF)

[0535] Polyacrylic acid (Mw 5000): manufactured by Aldrich

[0536] FRONZA B5200XP: Made by SIRRUS

[0537] San-Aid SI150L: Made by Sanshin Chemical Industry Co., Ltd.

[0538] San-Aid SI110L: Made by Sanshin Chemical Industry Co., Ltd.

[0539] San-Aid SI100L: Made by Sanshin Chemical Industry Co., Ltd.

[0540] Organic boron compound: FX-TP-BC-PC-AD-57103, Nippon Shokubai Manufacturing Co., Ltd.

[0541]

[0542]

[0543] [Table 3]

[0544]

[0545] As can be seen from Tables 1 to 3, the curable compositions of Examples are excellent in curing reactivity in both ultraviolet curing and thermal curing, and provide good cured products with less energy.

[0546] It is also found that the curable compositions of Examples are superior in curing reactivity compared to the curable compositions of Comparative Examples containing a polymer (GMA) having an epoxy group in a side chain which is common among cationic curable compounds.

[0547] <Photocuring Reactivity Evaluation>

[0548] The photocuring reactivity of the VEEM polymer obtained in Production Example 1 and the VEEM-MMA copolymer obtained in Production Example 2 was evaluated by the following method. In addition, as a control, Celloxide 2021P (3,4-epoxycyclohexylcarboxylic acid 3',4'-epoxycyclohexylmethyl ester, manufactured by Daicel Corporation) and trimethylolpropane triacrylate (TMPTA) were used to similarly evaluate the photocuring reactivity.

[0549] Device: NETZSCH DSC 204F1 Phoenix

[0550] Method: Weigh 1 mg to 2 mg of sample in a container, place it in the device, and irradiate with 10 mW / cm2 while keeping the sample temperature at 25°C in a nitrogen atmosphere. 2 The reaction mixture was exposed to light (light source: xenon lamp, no filter) for 5 minutes, and the change in the heat released by the reaction during this period was measured.

[0551] As the photocationic curing sample, a propylene carbonate solution containing 40% by mass of VEEM-MMA copolymer or a solution prepared by mixing 1% by mass of Bluesil as a photocationic curing catalyst with epoxide (Celloxide 2021P) relative to the solid content was used. TM A sample of PI2074 (manufactured by Elkem).

[0552] In addition, as a photo-radical curing sample, a 50% by mass propylene carbonate solution of VEEM polymer or a sample in which 2% by mass of Irg184 as a photo-radical initiator was mixed with TMPTA relative to the solid content was used. The measurement results are shown in Figure 2 and Figure 3 middle.

[0553] Figure 2 The DSC curve of the photocationic curing sample is shown. Figure 2 , heat release began sharply 3.5 minutes after the light irradiation started, indicating that a curing reaction had taken place. After the heat release of the epoxy used as a comparative control reached a peak, the heat release caused by the curing reaction continued for a period of time. On the other hand, the heat release peak of the VEEM-MMA copolymer was steep, and the curing reaction was terminated in a short time. It can be seen from this that the curing reactivity of the polymer containing the vinyl ether group is excellent.

[0554] Figure 3 The DSC curve of the photo-radical cured sample is shown in FIG. Figure 3 It is found that the VEEM polymer has photoradical curability at the same level as that of the multifunctional acrylate compound.

[0555] The curability of the curable composition was evaluated above, but the physical properties of the coating film formed by the curable composition are also important in actual use. Therefore, the curable composition of the example was used to evaluate the adhesion and pencil hardness of the cured coating film by the following method.

[0556] In addition, the cured coating film used for evaluation used the cured coating film formed by the same method as the cured coating film used in the above-mentioned <Acetone Friction Test>.

[0557] <Adhesion Evaluation (Cross Cut Test)>

[0558] Using the cured coating film for evaluation, the adhesion of the cured coating film to the PET film was evaluated in accordance with the old JIS-K5400. That is, after 11 cuts were made from the top of the cured coating film at intervals of 1 mm, the direction was changed by 90°, and 11 cuts were made in the same way to form a checkerboard of 10 squares. The cuts were to the extent of penetrating the coating film but not the PET film. Paste the cellophane tape in a way that completely covers the checkerboard, and rub it thoroughly to make it fit. After that, grab the end of the tape and peel it off at an angle of 45 degrees. After peeling off the tape, count the number of squares remaining on the PET film. The more squares that remain, the higher the adhesion is judged to be. The results are shown in Table 4.

[0559] <Pencil hardness test>

[0560] The scratch hardness of the coating film was evaluated using the cured coating film for evaluation according to JIS K5600-5-4. As a measuring device, an electric pencil hardness tester No. 553-M (manufactured by Yasuda Seiki Co., Ltd.) was used, and a pencil manufactured by Mitsubishi Pencil Co., Ltd. was used. The hardness of the hardest pencil that did not produce a scratch (plastic deformation) is shown in Table 4.

[0561] [Table 4]

[0562] Example 1 8 9 12 16 19 20 21 27 28 Adhesion 100 / 100 100 / 100 96 / 100 100 / 100 100 / 100 100 / 100 100 / 100 100 / 100 100 / 100 100 / 100 Pencil hardness F 2H H F H 2H H 2H H F

[0563] From Table 4, it was confirmed that the cured coating film formed using the curable composition of the example had excellent adhesion to the PET film and good pencil hardness, and showed excellent performance.

[0564] (Examples 29 to 30, Comparative Example 10)

[0565] The components were mixed in the proportions shown in Table 5 to obtain a curable composition. It should be noted that the mixing amounts in the table are solid content conversion amounts. In addition, the pigment dispersion 1 in the table was prepared by the following method.

[0566] (Preparation Example 1)

[0567] Preparation of pigment dispersion 1

[0568] 12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparlon DA-7301 as a dispersant, 2.25 parts of CI Pigment Green 58 as a colorant, and 1.5 parts of CI Pigment Yellow 138 were mixed and dispersed in a paint shaker for 3 hours to obtain a pigment dispersion 1 (solid content 22 mass %).

[0569] The compounds described in Table 5 are as follows.

[0570] Irgacure OXE02: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyl oxime) (manufactured by BASF)

[0571] The solvent resistance of the obtained curable composition was evaluated by the following method.

[0572] <Solvent resistance>

[0573] The curable composition was spin-coated onto a 5 cm square glass substrate, dried at 100 ° C for 3 minutes, exposed to 60 mJ using a high pressure mercury lamp, and heat treated (post-cured) at 110 ° C for 40 minutes to obtain a cured film with a film thickness of 5 μm. Then, the cured film was taken out after being immersed in 1-methyl-2-pyrrolidone (NMP) 20g at 40 ° C for 10 minutes. The absorbance of the immersion liquid (NMP) after taking out the cured film was measured using a spectrophotometer UV3100 (manufactured by Shimadzu Corporation). The larger the absorbance value, the more colorants dissolved in the immersion liquid, and the lower the solvent resistance of the curable composition.

[0574] [Table 5]

[0575]

[0576] From Table 5, it was confirmed that the curable compositions of Examples can provide cured products having excellent curing reactivity and excellent solvent resistance.

[0577] Explanation of symbols

[0578] 1 Differential molecular weight distribution curve.

Claims

1. A curable composition comprising a polymer (A) and a polymerizable compound (B) and / or a curing catalyst (C), characterized in that: The polymer (A) has a structural unit (a1) represented by the following general formula (1), has a structure represented by the following general formula (3), (4) or (5) at the end of the main chain, and has a molecular weight distribution, that is, weight average molecular weight / number average molecular weight of 1.0 to 4.

0. The content of the structural unit (a1) in the polymer (A) is 8 mol% to 100 mol% relative to 100 mol% of all structural units. In formula (1), R 1 Represents a hydrogen atom or a methyl group; R 2 and R 3 The same or different, represents a hydrogen atom or an organic group; R 4 represents a hydrogen atom or an organic group; n represents an integer greater than 2, In formula (3), R 5 and R 6 The same or different, represents a hydrogen atom or an organic group; R 7 represents an organic group, In formula (4), R 5 , R 6 and R 7’ The same or different, representing a hydrogen atom or an organic group, In formula (5), R 5 , R 6 and R 7’ The same or different represent a hydrogen atom or an organic group.

2. A curable composition comprising a polymer (A) and a polymerizable compound (B) and / or a curing catalyst (C), characterized in that: The polymer (A) is a group transfer polymer containing a monomer component of a vinyl ether group-containing (meth)acrylate represented by the following general formula (2), obtained by using a silyl ketene acetal represented by the general formula (7), a vinyl silane compound represented by the general formula (8), or an allyl silane compound represented by the general formula (9) as a polymerization initiator. The content ratio of the structural unit (a1) derived from the vinyl ether group-containing (meth)acrylate in the polymer (A) is 8 mol% to 100 mol% based on 100 mol% of all structural units. In formula (7), R 5 and R 6 The same or different, represents a hydrogen atom or an organic group; R 7 , R 8 , R 9 and R 10 The same or different, representing an organic group; R 5 With R 6 or R 6 With R 7 Can bond to form a ring structure; R 8 , R 9 and R 10 Two or more of them may be bonded to form a ring structure, In formula (8), R 5 , R 6 and R 7’ The same or different, represents a hydrogen atom or an organic group; R 8 , R 9 and R 10 The same or different, representing an organic group; R 5 With R 6 or R 6 With R 7’ Can bond to form a ring structure; R 8 , R 9 and R 10 Two or more of them may be bonded to form a ring structure, In formula (9), R 5 , R 6 and R 7’ The same or different, represents a hydrogen atom or an organic group; R 8 , R 9 and R 10 The same or different, representing an organic group; R 5 With R 6 or R 6 With R 7’ Can bond to form a ring structure; R 8 , R 9 and R 10 Two or more of them may be bonded to form a ring structure, In formula (2), R 1 Represents a hydrogen atom or a methyl group; R 2 and R 3 The same or different, represents a hydrogen atom or an organic group; R 4 represents a hydrogen atom or an organic group; and n represents an integer greater than 1.

3. The curable composition according to claim 1, wherein The weight average molecular weight of the polymer (A) is 5,000 to 1,000,000.

4. The curable composition according to claim 2, characterized in that The weight average molecular weight of the polymer (A) is 5,000 to 1,000,000.

5. The curable composition according to any one of claims 1 to 4, wherein The curing catalyst (C) is at least one selected from the group consisting of a cationic curing catalyst and a radical curing catalyst.

6. The curable composition according to any one of claims 1 to 4, wherein The polymerizable compound (B) is at least one selected from the group consisting of vinyl ether compounds, cyclic ether compounds, (meth)acrylates, carboxylic acid compounds, maleimide compounds, alcohols, and thiols.

7. The curable composition according to any one of claims 1 to 4, wherein The polymerizable compound (B) is at least one selected from the group consisting of methylene malonate diester compounds and α-cyanoacrylate.

8. The curable composition according to any one of claims 1 to 4, wherein The polymerizable compound (B) is at least one selected from the group consisting of an alkali-soluble resin containing an acid group and / or a resin having a group that generates an acid group by heat or acid.

9. The curable composition according to any one of claims 1 to 4, wherein The composition is at least one selected from the group consisting of curable compositions for coating agents, curable compositions for adhesives, curable compositions for resists, curable compositions for printing ink compositions, curable compositions for electronic components, and curable compositions for optical components.

10. Use of the curable composition according to any one of claims 1 to 4 for producing at least one selected from the group consisting of a coating agent, an adhesive, a resist, a printing ink composition, an electronic component, and an optical component.

11. The curable composition according to claim 5, characterized in that The composition is at least one selected from the group consisting of curable compositions for coating agents, curable compositions for adhesives, curable compositions for resists, curable compositions for printing ink compositions, curable compositions for electronic components, and curable compositions for optical components.

12. The curable composition according to claim 6, wherein The composition is at least one selected from the group consisting of curable compositions for coating agents, curable compositions for adhesives, curable compositions for resists, curable compositions for printing ink compositions, curable compositions for electronic components, and curable compositions for optical components.

13. The curable composition according to claim 7, characterized in that The composition is at least one selected from the group consisting of curable compositions for coating agents, curable compositions for adhesives, curable compositions for resists, curable compositions for printing ink compositions, curable compositions for electronic components, and curable compositions for optical components.

14. The curable composition according to claim 8, wherein The composition is at least one selected from the group consisting of curable compositions for coating agents, curable compositions for adhesives, curable compositions for resists, curable compositions for printing ink compositions, curable compositions for electronic components, and curable compositions for optical components.

15. The curable composition according to claim 1, wherein The molecular weight distribution of the polymer (A), that is, weight average molecular weight / number average molecular weight, is 3.5 or less.

16. The curable composition according to claim 1, wherein The molecular weight distribution of the polymer (A), that is, weight average molecular weight / number average molecular weight, is 3.0 or less.

17. The curable composition according to claim 1, wherein The molecular weight distribution of the polymer (A), that is, weight average molecular weight / number average molecular weight, is 2.0 or less.

18. The curable composition according to claim 1, wherein The amount of the insoluble component of the polymer (A) is 10% by mass or less based on 100% by mass of the polymer (A), and the insoluble component is a component having a solubility of 0.5 g or less in 100 g of ethyl acetate, toluene or tetrahydrofuran at 25°C.

19. The curable composition according to claim 1, wherein The amount of the insoluble component of the polymer (A) is 5% by mass or less based on 100% by mass of the polymer (A), and the insoluble component is a component having a solubility of 0.5 g or less in 100 g of ethyl acetate, toluene or tetrahydrofuran at 25°C.

20. The curable composition according to claim 1, wherein The amount of the insoluble component of the polymer (A) is 1% by mass or less based on 100% by mass of the polymer (A), and the insoluble component is a component having a solubility of 0.5g or less in 100g of ethyl acetate, toluene or tetrahydrofuran at 25°C.

21. The curable composition according to claim 1, wherein The amount of the insoluble component of the polymer (A) is 0.5 mass% or less based on 100 mass% of the polymer (A), and the insoluble component is a component having a solubility of 0.5 g or less in 100 g of ethyl acetate, toluene or tetrahydrofuran at 25°C.

22. The curable composition according to claim 1, wherein In a differential molecular weight distribution curve of the polymer (A) obtained by measuring the polymer (A) by gel permeation chromatography (GPC), when the point of the maximum value of the differential molecular weight distribution curve is set as T and the points at 5% height of T on the differential molecular weight distribution curve are set as L0 and L1 from the low molecular weight side, the ratio X / Y of the area X of the triangle enclosed by T-L0-L1 to the area Y of the part enclosed by the differential molecular weight distribution curve and the line connecting L0-L1 is 0.8 to 2.

0.

23. The curable composition according to claim 1, wherein In a differential molecular weight distribution curve of the polymer (A) obtained by measuring the polymer (A) by gel permeation chromatography (GPC), when the point of the maximum value of the differential molecular weight distribution curve is set as T and the points at 5% height of T on the differential molecular weight distribution curve are set as L0 and L1 from the low molecular weight side, the ratio X / Y of the area X of the triangle enclosed by T-L0-L1 to the area Y of the part enclosed by the differential molecular weight distribution curve and the line connecting L0-L1 is 0.8 to 1.

5.

24. The curable composition according to claim 1, wherein The content of the structural unit (a1) is 95 mol% or less.

25. The curable composition according to claim 1, wherein The content of the structural unit (a1) is 90 mol% or less.

26. The curable composition according to claim 1, wherein The polymer (A) has another structural unit (a2), and the other structural unit (a2) is a structural unit derived from another polymerizable monomer other than the vinyl ether group-containing (meth)acrylic acid ester.

27. The curable composition according to claim 26, wherein The other polymerizable monomer is a polymerizable monomer having an electron-deficient double bond.

28. The curable composition according to claim 26, wherein The content ratio of the structural unit (a2) in the polymer (A) is 0 to 99 mol% based on 100 mol% of all structural units.

29. The curable composition according to claim 28, wherein The content of the structural unit (a2) is 5 mol% or more.

30. The curable composition according to claim 28, wherein The content of the structural unit (a2) is 10 mol% or more.

31. The curable composition according to claim 28, wherein The content of the structural unit (a2) is 96 mol% or less.

32. The curable composition according to claim 28, wherein The content of the structural unit (a2) is 92 mol% or less.

33. The curable composition according to claim 1, wherein The content of the polymer (A) is 5% by mass to 100% by mass based on 100% by mass of the total solid content of the curable composition.

34. The curable composition according to claim 33, wherein The content of the polymer (A) is 10% by mass or more.

35. The curable composition according to claim 33, wherein The content of the polymer (A) is 15% by mass or more.

36. The curable composition according to claim 33, wherein The content of the polymer (A) is 99.9% by mass or less.

37. The curable composition according to claim 33, wherein The content of the polymer (A) is 95% by mass or less.

38. The curable composition according to claim 1, wherein The curable composition is a curable composition for a resist.

39. The curable composition according to claim 38, wherein The content of the polymer (A) is 1% by mass to 50% by mass based on 100% by mass of the total solid content of the curable composition.

40. The curable composition according to claim 38, wherein The content of the polymer (A) is 2% by mass to 40% by mass based on 100% by mass of the total solid content of the curable composition.

41. The curable composition according to claim 38, wherein The content of the polymer (A) is 5% by mass to 30% by mass based on 100% by mass of the total solid content of the curable composition.

42. The curable composition according to claim 2, wherein The amount of the insoluble component of the polymer (A) is 10% by mass or less based on 100% by mass of the polymer (A), and the insoluble component is a component having a solubility of 0.5 g or less in 100 g of ethyl acetate, toluene or tetrahydrofuran at 25°C.

43. The curable composition according to claim 2, wherein The amount of the insoluble component of the polymer (A) is 5% by mass or less based on 100% by mass of the polymer (A), and the insoluble component is a component having a solubility of 0.5 g or less in 100 g of ethyl acetate, toluene or tetrahydrofuran at 25°C.

44. The curable composition according to claim 2, wherein The amount of the insoluble component of the polymer (A) is 1% by mass or less based on 100% by mass of the polymer (A), and the insoluble component is a component having a solubility of 0.5g or less in 100g of ethyl acetate, toluene or tetrahydrofuran at 25°C.

45. The curable composition according to claim 2, wherein The amount of the insoluble component of the polymer (A) is 0.5 mass% or less based on 100 mass% of the polymer (A), and the insoluble component is a component having a solubility of 0.5 g or less in 100 g of ethyl acetate, toluene or tetrahydrofuran at 25°C.

46. ​​The curable composition according to claim 2, wherein In a differential molecular weight distribution curve of the polymer (A) obtained by measuring the polymer (A) by gel permeation chromatography (GPC), when the point of the maximum value of the differential molecular weight distribution curve is set as T and the points at 5% height of T on the differential molecular weight distribution curve are set as L0 and L1 from the low molecular weight side, the ratio X / Y of the area X of the triangle enclosed by T-L0-L1 to the area Y of the part enclosed by the differential molecular weight distribution curve and the line connecting L0-L1 is 0.8 to 2.

0.

47. The curable composition according to claim 2, wherein In a differential molecular weight distribution curve of the polymer (A) obtained by measuring the polymer (A) by gel permeation chromatography (GPC), when the point of the maximum value of the differential molecular weight distribution curve is set as T and the points at 5% height of T on the differential molecular weight distribution curve are set as L0 and L1 from the low molecular weight side, the ratio X / Y of the area X of the triangle enclosed by T-L0-L1 to the area Y of the part enclosed by the differential molecular weight distribution curve and the line connecting L0-L1 is 0.8 to 1.

5.

48. The curable composition according to claim 2, wherein The content of the structural unit (a1) is 95 mol% or less.

49. The curable composition according to claim 2, wherein The content of the structural unit (a1) is 90 mol% or less.

50. The curable composition according to claim 2, wherein The polymer (A) has another structural unit (a2), and the other structural unit (a2) is a structural unit derived from another polymerizable monomer other than the vinyl ether group-containing (meth)acrylic acid ester.

51. The curable composition according to claim 50, wherein The other polymerizable monomer is a polymerizable monomer having an electron-deficient double bond.

52. The curable composition according to claim 50, wherein The content ratio of the structural unit (a2) in the polymer (A) is 0 to 99 mol% based on 100 mol% of all structural units.

53. The curable composition according to claim 52, wherein The content of the structural unit (a2) is 5 mol% or more.

54. The curable composition according to claim 52, wherein The content of the structural unit (a2) is 10 mol% or more.

55. The curable composition according to claim 52, wherein The content of the structural unit (a2) is 96 mol% or less.

56. The curable composition of claim 52, wherein The content of the structural unit (a2) is 92 mol% or less.

57. The curable composition of claim 2, wherein: The content of the polymer (A) is 5% by mass to 100% by mass based on 100% by mass of the total solid content of the curable composition.

58. The curable composition according to claim 57, wherein The content of the polymer (A) is 10% by mass or more.

59. The curable composition according to claim 57, wherein The content of the polymer (A) is 15% by mass or more.

60. The curable composition according to claim 57, wherein The content of the polymer (A) is 99.9% by mass or less.

61. The curable composition according to claim 57, wherein The content of the polymer (A) is 95% by mass or less.

62. The curable composition according to claim 2, wherein: The curable composition is a curable composition for a resist.

63. The curable composition according to claim 62, wherein The content of the polymer (A) is 1% by mass to 50% by mass based on 100% by mass of the total solid content of the curable composition.

64. The curable composition of claim 62, wherein The content of the polymer (A) is 2% by mass to 40% by mass based on 100% by mass of the total solid content of the curable composition.

65. The curable composition of claim 62, wherein The content of the polymer (A) is 5% by mass to 30% by mass based on 100% by mass of the total solid content of the curable composition.

66. The curable composition of claim 3, wherein: The weight average molecular weight of the polymer (A) is 10,000 or more.

67. The curable composition of claim 3, wherein: The weight average molecular weight of the polymer (A) is 20,000 or more.

68. The curable composition of claim 3, wherein: The weight average molecular weight of the polymer (A) is 800,000 or less.

69. The curable composition according to claim 3, wherein The weight average molecular weight of the polymer (A) is 600,000 or less.

70. The curable composition of claim 4, wherein: The weight average molecular weight of the polymer (A) is 10,000 or more.

71. The curable composition of claim 4, wherein: The weight average molecular weight of the polymer (A) is 20,000 or more.

72. The curable composition of claim 4, wherein: The weight average molecular weight of the polymer (A) is 800,000 or less.

73. The curable composition of claim 4, wherein: The weight average molecular weight of the polymer (A) is 600,000 or less.

74. The curable composition of claim 8, wherein The acid group-containing alkali-soluble resin is a resin (b1) having an acid group, and the acid group is any one of a carboxyl group, a phenolic hydroxyl group, a carboxylic anhydride group, a phosphoric acid group, and a sulfonic acid group.

75. The curable composition of claim 74, wherein The weight average molecular weight of the resin (b1) is 1,000 to 100,000.

76. The curable composition of claim 74, wherein The weight average molecular weight of the resin (b1) is 2,000 to 50,000.

77. The curable composition of claim 74, wherein The weight average molecular weight of the resin (b1) is 4,000 to 30,000.

78. The curable composition of claim 74, wherein The molecular weight distribution of the resin (b1), that is, weight average molecular weight / number average molecular weight, is 1.0 to 4.

0.

79. The curable composition of claim 74, wherein The molecular weight distribution of the resin (b1), that is, weight average molecular weight / number average molecular weight, is 1.1 to 3.

5.

80. The curable composition of claim 74, wherein The molecular weight distribution of the resin (b1), that is, weight average molecular weight / number average molecular weight, is 1.5 to 3.

0.

81. The curable composition of claim 74, wherein The content of the resin (b1) is 10% by mass to 60% by mass in 100% by mass of the total solid content of the curable composition.

82. The curable composition of claim 74, wherein The content of the resin (b1) is 20% to 50% by mass in 100% by mass of the total solid content of the curable composition.

83. The curable composition of claim 74, wherein The content of the resin (b1) is 30% by mass to 45% by mass in 100% by mass of the total solid content of the curable composition.

84. The curable composition of claim 8, wherein The resin having a group that generates an acid group by heat or acid is a resin (b2) having a group that generates an acid group by heat or acid, wherein the group that generates an acid group by heat or acid is a tertiary carbon-containing group, a group in which the acid group is blocked by a vinyl ether compound, or a group in which a phenolic hydroxyl group is protected by a tert-butyl group or an acetyl group.

85. The curable composition of claim 84, wherein The weight average molecular weight of the resin (b2) is 1,000 to 100,000.

86. The curable composition of claim 84, wherein The weight average molecular weight of the resin (b2) is 2,000 to 50,000.

87. The curable composition of claim 84, wherein The weight average molecular weight of the resin (b2) is 4,000 to 30,000.

88. The curable composition of claim 84, wherein The molecular weight distribution of the resin (b2), that is, weight average molecular weight / number average molecular weight, is 1.0 to 4.

0.

89. The curable composition of claim 84, wherein The molecular weight distribution of the resin (b2), that is, weight average molecular weight / number average molecular weight, is 1.1 to 3.

5.

90. The curable composition of claim 84, wherein The molecular weight distribution of the resin (b2), that is, weight average molecular weight / number average molecular weight, is 1.5 to 3.

0.

91. The curable composition of claim 84, wherein The content of the resin (b2) is 10% to 60% by mass in 100% by mass of the total solid content of the curable composition.

92. The curable composition of claim 84, wherein The content of the resin (b2) is 20% to 50% by mass in 100% by mass of the total solid content of the curable composition.

93. The curable composition of claim 84, wherein The content of the resin (b2) is 30% by mass to 45% by mass in 100% by mass of the total solid content of the curable composition.

94. The curable composition of claim 5, wherein The content of the curing catalyst (C) is 0.01 to 10 parts by mass based on 100 parts by mass of the polymer (A).

95. The curable composition of claim 5, wherein The content of the curing catalyst (C) is 0.1 to 5 parts by mass based on 100 parts by mass of the polymer (A).

96. The curable composition of claim 5, wherein The content of the curing catalyst (C) is 0.5 to 3 parts by mass based on 100 parts by mass of the polymer (A).

97. The curable composition of claim 5, wherein The curing catalyst (C) is a thermolatent cationic curing catalyst or a thermolatent free radical curing catalyst.

98. The curable composition of claim 5, wherein The curing catalyst (C) is a photolatent cationic curing catalyst or a photolatent free radical curing catalyst.

99. The curable composition of claim 98, wherein The content of the curing catalyst (C) is 0.3% by mass to 20% by mass based on 100% by mass of the total solid content of the curable composition.

100. The curable composition of claim 98, wherein The content of the curing catalyst (C) is 0.5% by mass to 10% by mass based on 100% by mass of the total solid content of the curable composition.

101. The curable composition of claim 98, wherein The content of the curing catalyst (C) is 1% by mass to 8% by mass based on 100% by mass of the total solid content of the curable composition.

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