Resin having polymerizable unsaturated group, curable resin composition, cured product and article

Abstract

To provide a resin with high adhesion and a low linear expansion coefficient in a cured product, and also to provide a curable resin composition, a cured product and an article using the same.SOLUTION: A resin having a polymerizable unsaturated group includes, as essential raw materials: a calixarene body-containing phenolic resin (A) having a phenolic hydroxyl group-containing compound (a1) and a binding compound (a2) as essential raw materials; and a (meth)acrylate compound (B) having an epoxide group. The binding compound (a2) is: a compound (a2-1) containing a saturated hydrocarbon structure substituted with an ethylenic unsaturated bond or a binding functional group; and / or a compound (a2-2) containing an aldehyde group. A content ratio of a calixarene body in the calixarene type phenolic resin (A) is a specified value or higher.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a resin having a polymerizable unsaturated group, a curable resin composition, a cured product, and an article. [Background technology]

[0002] In recent years, curable compositions such as active energy ray curable compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting compositions that can be cured by heat have been widely used in the fields of inks, paints, coating agents, adhesives, optical components, etc. In particular, for the above-mentioned coating agent applications, it is generally required that the coating agent can impart design to the surfaces of various substrates, has excellent curability, and can form a coating film that can prevent deterioration of the substrate surface. Furthermore, in recent years, the industrial world has been demanding a material that has high adhesion and a low linear expansion coefficient in the obtained cured product.

[0003] As a conventional active energy ray-curable composition, a photosensitive resin composition containing an epoxy acrylate resin obtained by further reacting an intermediate obtained by reacting a cresol novolac epoxy resin with acrylic acid and phthalic anhydride with tetrahydrophthalic anhydride is known (see, for example, Patent Document 1). However, this composition is not sufficient in terms of high adhesion and low linear expansion coefficient to meet the market demands that will continue to increase in the future. Therefore, there has been a demand for a material capable of forming a cured product having high adhesion and a low linear expansion coefficient. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 8-259663 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a resin having a polymerizable unsaturated group capable of forming a cured product having high adhesion and a low linear expansion coefficient, a curable resin composition, a cured product, and an article. [Means for solving the problem]

[0006] As a result of intensive research into solving the above-mentioned problems, the inventors have found that the above-mentioned problems can be solved by using a resin having a polymerizable unsaturated group, in which a specific calixarene-containing phenolic resin and a (meth)acrylate compound having an epoxy group are essential reaction raw materials, as well as a curable resin composition, a cured product, and an article, and have thus completed the present invention.

[0007] Suitable forms of the resin of the present invention include the following [1] to [7]. [1] A calixarene-containing phenolic resin (A) containing a phenolic hydroxyl group-containing compound (a1) and a linking compound (a2) as essential reaction raw materials (1); (B) a (meth)acrylate compound having an epoxy group; is the essential reactant (2), A resin having a polymerizable unsaturated group, characterized in that the calixarene content in the calixarene-type phenolic resin (A) is 10% or more in terms of area ratio in gel permeation chromatography (GPC). [2] The resin having a polymerizable unsaturated group according to the above [1], wherein the ratio of the phenolic hydroxyl group-containing compound (a1) to the linking compound (a2) is such that the number of moles of the linking compound (a2) is in the range of 0.9 to 1.2 per mole of the phenolic hydroxyl group-containing compound (a1). [3] The resin having a polymerizable unsaturated group according to the above [1] or [2], wherein the amount of the (meth)acrylate compound (B) having an epoxy group used is within a range of 0.9 to 1.1 moles of the epoxy group per mole of the phenolic hydroxyl group in the phenolic hydroxyl group-containing compound (a1). [4] The resin having a polymerizable unsaturated group according to any one of the above [1] to [3], wherein the ratio of the phenolic hydroxyl group-containing compound (a1) to the linking compound (a2) is in the range of 0.9 to 1.2 moles of the linking compound (a2) per 1 mole of the phenolic hydroxyl group-containing compound (a1). [5] The resin having a polymerizable unsaturated group according to any one of the above [1] to [4], wherein the amount of the (meth)acrylate compound (B) having an epoxy group used is in the range of 0.9 to 1.1 moles of the epoxy group per mole of the phenolic hydroxyl group in the phenolic hydroxyl group-containing compound (a1). [6] The resin having an acid group and a polymerizable unsaturated group according to any one of the above [1] to [5], wherein the linking compound (a2) is one or more selected from the group consisting of the following (i) and (ii): (i) an organic compound (a2-1) which contains two or more ethylenically unsaturated bonds or linking functional groups as the electrophilic reactive groups and which may contain an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom; (ii) an organic compound (a2-2) which contains one or more aldehyde groups as the electrophilic reactive group and may contain an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom; The resin having an acid group and a polymerizable unsaturated group according to any one of the above [1] to [5], wherein the linking functional group is a haloalkyl group, a hydroxyalkyl group, or an alkoxyalkyl group. [7] A curable resin composition comprising the resin having a polymerizable unsaturated group according to any one of the above [1] to [6] and a photopolymerization initiator. [8] The curable resin composition according to the above [7], further comprising other resin components. [9] A cured product of the curable resin composition according to any one of the above [7] to [8].

[10] An article having a coating film made of the cured product described in [9] above. Effect of the Invention

[0008] The resin having a polymerizable unsaturated group of the present invention has high adhesion and a low linear expansion coefficient in a cured product, and therefore a curable resin composition containing the resin and a photopolymerization initiator can be used as a coating agent or an adhesive, and as a coating agent in particular, it can be suitably used for solder resist applications. [Brief description of the drawings]

[0009] [Figure 1] An example of a GPC chart of a phenolic resin obtained according to the method of the following synthesis example is shown below. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Below, an embodiment of the present invention (hereinafter referred to as the "present embodiment") will be described in detail, but the present disclosure is not limited to the description below and can be implemented in various modifications within the scope of its gist.

[0011] -term- In this specification, the term "raw material" refers to a compound that is used to obtain a target compound through a chemical reaction such as synthesis or decomposition and that partially constitutes the chemical structure of the target compound, and excludes substances that play the role of chemical reaction auxiliaries such as solvents and catalysts. In particular, in this specification, the term "reaction raw material" refers to a precursor compound for obtaining a resin having a target polymerizable unsaturated group or a precursor compound thereof (e.g., a calixarene-containing phenolic resin) through a chemical reaction (e.g., a polymerization reaction, an etherification reaction, etc.). For the sake of convenience in the present specification, the reaction raw material for the resin having a polymerizable unsaturated group is referred to as reaction raw material (2), and the reaction raw material for the calixarene-containing phenolic resin (A), which is a precursor compound for the resin having a polymerizable unsaturated group, is referred to as reaction raw material (1), and the two are distinguished from each other. In this specification, the term "phenolic resin" refers to a resin that contains a phenolic hydroxyl group in its structure. Examples of the "alkyl group" in this specification include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, a (n-)heptyl group, a (n-)octyl group, a (n-)nonyl group, a (n-)decyl group, a (n-)undecyl group, a (n-)dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group. In this specification, the "alkenyl group" includes a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 2-methylallyl group and the like. As used herein, the term "alkynyl group" includes an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a pentynyl group, a hexynyl group and the like. As used herein, the term "alkoxy group" includes, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, a nonyloxy group and the like. In this specification, examples of the "aryl group" include a phenyl group, a naphthyl group (1-naphthyl group or 2-naphthyl group), anthracenyl group, phenanthrenyl group, naphthacenyl group, chrysenyl group, triphenylenyl group, and pyrenyl group. As used herein, the term "halogen atom" includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. In this specification, the "organic group" is preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 1 to 10 carbon atoms. In addition, one or two or more non-adjacent -CH2- groups in the alkyl group, alkenyl group, or alkoxy group may be substituted with -O-, -COO-, or -OCO-. In this specification, "(meth)acrylate" means acrylate and / or methacrylate. In addition, "(meth)acryloyl" means acryloyl and / or methacryloyl. Furthermore, "(meth)acrylic" means acrylic and / or methacrylic.

[0012] (Resin having polymerizable unsaturated groups) The present disclosure relates to A calixarene-containing phenolic resin (A) containing a phenolic hydroxyl group-containing compound (a1) and a linking compound (a2) as essential reaction raw materials (1); (B) a (meth)acrylate compound having an epoxy group; is the essential reactant (2), The calixarene-type phenolic resin (A) has a calixarene content of 10% or more in terms of area ratio in gel permeation chromatography (GPC).

[0013] <Calixarene-containing phenolic resin (A)> The calixarene-containing phenolic resin (A) of this embodiment is a calixarene-containing phenolic resin obtained by a polymerization reaction using a phenolic hydroxyl group-containing compound (a1) and a linking compound (a2) as essential reaction raw materials (1). Alternatively, the calixarene-containing phenolic resin (A) of this embodiment can be expressed in another way other than as the essential reaction raw material (1) described above, as a polymer (or an inclusion compound) having a group having a repeating unit derived from the phenolic hydroxyl group-containing compound (a1) and a repeating unit derived from the linking compound (a2) chemically bonded to the repeating unit derived from the phenolic hydroxyl group-containing compound (a1). The linking compound (a2) may be an organic compound (a2-1) and / or an organic compound (a2-2) described below. The "calixarene compound" contained in the calixarene compound-containing phenolic resin (A) is a repeating unit U derived from a phenolic hydroxyl group-containing compound (a1). a1and a repeating unit U derived from the linking compound (a2). a2 The calixarene is a polymer in which the repeating units U and U are alternately linked in a ring shape, and can be represented by the following general formula (1). a1 and repeating unit U a2 It may further contain other repeating units other than the above. [ka] (In the above general formula (1), U a1 is a repeating unit derived from a phenolic hydroxyl group-containing compound (a1) described below, and U a2 is a repeating unit derived from a linking compound (a2) described below, and n1 is an integer of 2 or more. The structure of the calixarene will be described in more detail later.

[0014] The lower limit of the calixarene content in the calixarene-containing phenolic resin (A) is preferably 5% or more, 10% or more, 13% or more, 15% or more, and 18% or more, in terms of area ratio in gel permeation chromatography (GPC), relative to the entire resin having a polymerizable unsaturated group. The upper limit of the calixarene content is preferably 90% or less, 88% or less, and 78% or less, in terms of area ratio in gel permeation chromatography (GPC), relative to the entire resin having an acid group and a polymerizable unsaturated group. Since the calixarene molecules are uniform, it is considered that the resin having an acid group and a polymerizable unsaturated group formed from the calixarene-containing phenolic resin (A) has excellent alkali developability and a low linear expansion coefficient in the cured product.

[0015] <<Phenol-containing hydroxyl group compound (a1)>> The phenolic hydroxyl group-containing compound (a1) refers to a compound having at least one phenolic hydroxyl group in the molecule. The phenolic hydroxyl group-containing compound (a1) can be represented by the following general formula (a1). [ka] In the above general formula (a1), Ar represents a group having an aromatic ring-containing structure (main chain-forming structure), and R 1 each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group, q represents an integer, and p represents a natural number.

[0016] In the above general formula (a1), Ar is a group having a monovalent or higher aromatic ring-containing structure (main chain-forming structure). Examples of the aromatic ring include structures consisting of aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, naphthacene ring, chrysene ring, triphenylene ring, and pyrene ring; and structures consisting of aromatic heterocycles such as pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, indolizine ring, benzimidazole ring, 1H-indazole ring, purine ring, quinoline ring, isoquinoline ring, and 4H-quinolizine ring. Furthermore, the group having an aromatic ring-containing structure (main chain-forming structure) may be not only a monovalent or higher group obtained by removing one or more hydrogen atoms from the aromatic ring, but also a monovalent or higher group obtained by removing one or more hydrogen atoms from the aromatic ring, in which one or more hydrogen atoms in the monovalent or higher group obtained by removing one or more hydrogen atoms from the aromatic ring are each independently selected from the group consisting of a substituent (e.g., one or more selected from the group consisting of a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a carboxylic acid, and an amino group, and preferably R 1 )), or a structure in which two or more of the aromatic rings are linked together via a bond (such as a single bond) and / or a linker (for example, a divalent group such as an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, a carbonyl group (-C(=O)-O-), a ketone group, or a -SO2- group).

[0017] In the above general formula (a1), R 1 is any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, and a halogen atom, In the above general formula (a1), q is 0 or an integer of 1 or more, preferably 0 or an integer of 1 to 3, more preferably 0 or 1, and even more preferably 0. On the other hand, p is a natural number, i.e., an integer of 1 or more, and preferably 1 or 2. Preferred examples of the phenolic hydroxyl group-containing compound (a1) in this embodiment include compounds represented by any of the following formulas (a1-1) to (a1-5). [ka] In the above formulas (a1-1) to (a1-5), R 1 , p, and q are each independently the same as those in the above formula (a1), and the above description is incorporated herein by reference. 2 are each independently a hydrogen atom or a methyl group. 1 The position of the substituent (R ) is arbitrary. For example, in the naphthalene ring of formula (a1-2), it may be substituted on either of the benzene rings forming the condensed ring. In formulas (a1-3), (a1-4), and (a1-5), it may be substituted on either of the two benzene rings present in one molecule (i.e., when each of the two benzene rings has a substituent (R 1 ) may be substituted on any of the benzene rings present in one molecule in the formula (a1-4), and p and q represent the numbers of substituents in one molecule.

[0018] The number of phenolic hydroxyl groups in the phenolic hydroxyl group-containing compound (a1) may be 1 or more, but is preferably 1 or 2. When the number of phenolic hydroxyl groups is more than one, it is preferable that the ortho and para positions of each phenolic hydroxyl group coincide (i.e., each phenolic hydroxyl group is located at the meta position relative to each other), since this structure makes it easy to produce a calixarene compound.

[0019] Specific examples of the phenolic hydroxyl group-containing compound (a1) include dialkylphenols such as phenol, cresol, xylenol (dimethylphenol), and diethylphenol; trialkylphenols such as trimethylphenol and triethylphenol; diphenylphenol, triphenylphenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, tetramethylbisphenol A, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, naphthalenediol (e.g., 1,3-naphthalenediol, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,6-naphthalenediol, and 2,7-naphthalenediol), polyphenylene ether diol, polynaphthylene ether diol, and trihydroxynaphthalene. Among these, compounds having one phenolic hydroxyl group (phenol, cresol, xylenol, diethylphenol, trimethylphenol, triethylphenol, diphenylphenol, triphenylphenol, 1-naphthol, 2-naphthol); compounds having two phenolic hydroxyl groups, the phenolic hydroxyl groups being located at the meta position relative to each other (resorcinol, 1,6-naphthalenediol) are preferred, with resorcinol, 1-naphthol, and 1,6-naphthalenediol being more preferred. These phenolic hydroxyl group-containing compounds (a1) can be used alone or in combination of two or more kinds.

[0020] <<Connecting compound (a2)>> The "linking compound (a2)" is a compound that can link two or more phenolic hydroxyl group-containing compounds (a1) via the linking compound (a2) during a polymerization reaction with the phenolic hydroxyl group-containing compound (a1). Therefore, the linking compound (a2) preferably has an electrophilic reactive group that exhibits electrophilic reactivity with the aromatic ring in the phenolic hydroxyl group-containing compound (a1). In addition, the linking compound (a2) may contain oxygen atoms, nitrogen atoms, sulfur atoms, and / or halogen atoms in addition to carbon atoms and hydrogen atoms.

[0021] When the linking compound (a2) of the present embodiment has an electrophilic reactive group exhibiting electrophilic substitution reactivity or electrophilic addition reactivity, it is possible to easily react with the compound by electrophilic substitution reaction (ArS E ) or the like, the aromatic ring in the phenolic hydroxyl group-containing compound (a1) can react with the linking compound (a2) to link them together (in other words, one or more hydrogen atoms in the aromatic ring are substituted). In addition, when the linking compound (a2) has two or more electrophilic reactive groups, or when multiple electrophilic reactive bonding sites in the linking compound (a2) react successively, such as in the reaction between an aldehyde compound such as formaldehyde, as typified by novolac resin or resol resin, and a phenol, two or more phenolic hydroxyl group-containing compounds (a1) can be linked via the linking compound (a2). This allows the formation of a calixarene-containing phenolic resin (A).

[0022] If the electrophilic reactive group is a group that forms a cation such as a so-called cationoid, the aromatic ring in the phenolic hydroxyl group-containing compound (a1) and the linking compound (a2) can react with each other by electrophilic substitution reaction or electrophilic addition reaction, and thus the two can be linked together, and thus there is no particular limitation. Examples of the electrophilic reactive group include an ethylenically unsaturated bond group and a linking functional group (including, for example, an aldehyde group, a haloalkyl group, a hydroxyalkyl group, or an alkoxyalkyl group). The ethylenically unsaturated bond group preferably has a group represented by the following formula (i): The linking functional group preferably has a group represented by the following formula (ii): [ka] In the above formula (i) and formula (ii), * represents a bond to another atom, E represents an electron-withdrawing group, and is preferably a group selected from the group consisting of halogen atoms (e.g., fluorine, chlorine, bromine, iodine, etc.), a hydroxyl group, -O- (oxygen atom), and an alkoxy group having 1 to 20 carbon atoms, and R ii1 represents an absent hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, The dashed line in the above formula (ii) represents an optionally present bond. When E is -O- (oxygen atom), a bond represented by a double bond between E and C exists, and R ii1 Since there is no bond between and C, R ii1 represents that the compound represented by the formula (ii-1) below is not present. [ka] Represents.)

[0023] The ethylenically unsaturated bond group is not particularly limited, and examples thereof include alkenyl groups (e.g., alkenyl groups having 2 to 20 carbon atoms) such as vinyl, allyl, 1-propenyl, isopropenyl, butenyl (including 1-butenyl, 2-butenyl, and 3-butenyl), 2-methylallyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, and decenyl. In the ethylenically unsaturated bond group, the ethylenically unsaturated bond (double bond portion) is preferably located as close to the end as possible, and more preferably located closest to the end. During the polymerization reaction, the ethylenically unsaturated bond group in the linking compound (a2) and the aromatic ring in the phenolic hydroxyl group-containing compound (a1) are thought to undergo an electrophilic addition reaction to be linked. The linking functional group is preferably one or more groups selected from the group consisting of an aldehyde group, a halogenated sulfide group (-SX (X is a halogen atom)), a sulfide group (-S-), a haloalkyl group, a hydroxyalkyl group, and an alkoxyalkyl group.

[0024] The haloalkyl group is not particularly limited, but examples thereof include fluorinated alkyl groups such as fluoromethyl, fluoroethyl, fluoropropyl, fluorobutyl, 2,2-methylfluoropropyl, fluoropentyl, and fluorohexyl groups, chlorinated alkyl groups such as chloromethyl, chloroethyl, chloropropyl, chlorobutyl, 2,2-methylchloropropyl, chloropentyl, and chlorohexyl groups, brominated alkyl groups such as bromomethyl, bromoethyl, bromopropyl, bromobutyl, 2,2-methylbromopropyl, bromopentyl, and bromohexyl groups, and iodized alkyl groups such as iodomethyl, iodoethyl, iodopropyl, iodobutyl, 2,2-methyliodopropyl, iodopentyl, and iodohexyl groups. In the haloalkyl group, the halogen atom is preferably located as close to the end as possible, and more preferably located at the end. During the polymerization reaction, a cationoid is easily produced by the halogen atoms in the linking compound (a2), and therefore the linking compound (a2) and the phenolic hydroxyl group-containing compound (a1) are presumably linked together.

[0025] The hydroxyalkyl group is not particularly limited, and examples thereof include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, 2,2-methylhydroxypropyl, hydroxypentyl, hydroxyhexyl, etc. The hydroxy group is preferably located as close to the end as possible, and more preferably located at the end closest to the end. It is believed that since a cationoid is easily produced by the hydroxyl group in the linking compound (a2), the linking compound (a2) and the phenolic hydroxyl group-containing compound (a1) are linked together. The alkoxyalkyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group, an ethoxypropyl group, a methoxybutyl group, an ethoxybutyl group, a 2,2-methylmethoxypropyl group, a methoxypentyl group, a methoxyhexyl group, etc. The alkoxy group is preferably located as close to the end as possible, and more preferably located at the end closest to the end. It is believed that a cationoid is easily produced by the oxygen atom in the linking compound (a2), and therefore the linking compound (a2) and the phenolic hydroxyl group-containing compound (a1) are linked together.

[0026] The following description will be made by roughly dividing the linking compound (a2) of this embodiment into a case where it has two or more electrophilic reactive groups and a case where the electrophilic reactive binding sites undergo multiple successive reactions. That is, the linking compound (a2) of the present embodiment is preferably one or more compounds selected from the group consisting of the following (i) and (ii): (i) An organic compound (a2-1) which contains two or more ethylenically unsaturated bond groups or linking functional groups as electrophilic reactive groups and may contain an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom. (ii) an organic compound (a2-2) which contains one or more aldehyde groups as electrophilic reactive groups and may contain an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom; Here, the linking functional group is a haloalkyl group, a hydroxyalkyl group, or an alkoxyalkyl group.

[0027] - A linking compound (a2) having two or more electrophilic reactive groups (hereinafter also referred to as organic compound (a2-1)). The linking compound (a2) of the present embodiment is preferably represented by the following general formula (I): In other words, (i) the organic compound (a2-1) containing two or more ethylenically unsaturated bond groups or linking functional groups and which may contain an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom is preferably represented by the following general formula (I): [ka] (In the above general formula (I), Z 1 and Z 1 each independently represents an electrophilic reactive group, D represents a bond or a central structure, and the dashed line represents an optionally present bond. When the bond represented by the dashed line is present, Z 1 and / or Z 2 forms a ring structure together with D.

[0028] When the bond represented by the dashed line in the above general formula (I) is not present, the linking compound (a2) or the organic compound (a2-1) can be represented by the following general formula (I-1). That is, one aspect of the linking compound (a2) or the organic compound (a2-1) of the present embodiment is preferably represented by the following general formula (I-1). [ka] (In the above general formula (I-1), Z 1 and Z 2 each independently represents an electrophilic reactive group, specifically an ethylenically unsaturated bond-containing group or a linking functional group (a haloalkyl group, a hydroxyalkyl group, or an alkoxyalkyl group), and D is a single bond or a divalent group.

[0029] In the above general formula (I-1), the divalent group of D is not particularly limited, and examples thereof include divalent hydrocarbon groups which may contain oxygen atoms, nitrogen atoms, sulfur atoms, and / or halogen atoms, carbonyl groups, -O-, -S-, -SO2-, -NH-, -N=N-, and divalent groups formed by linking one or more of these. Examples of the "divalent (hydrocarbon) group which may contain oxygen atoms, nitrogen atoms, sulfur atoms, and / or halogen atoms" include linear or branched alkylene groups having 1 to 20 carbon atoms, arylene groups having 6 to 30 carbon atoms, divalent alicyclic groups having 3 to 30 carbon atoms, divalent aromatic heterocyclic groups having 1 to 30 carbon atoms, divalent non-aromatic heterocyclic groups having 1 to 30 carbon atoms, and divalent groups substituted with substituents such as alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups, halogen atoms, and hydroxyl groups. In the above general formula (I-1), preferred embodiments of the divalent group represented by D are an arylene group or aralkylene group having 6 to 30 carbon atoms which may be substituted by a substituent; or a divalent group formed by linking one or more arylene groups having 6 to 30 carbon atoms which may be substituted by a substituent and optionally one or more divalent groups other than the arylene groups, and more preferably a phenylene group, biphenylene group, or naphthalene group which may be substituted by a substituent; or a divalent group formed by linking one or more phenylene groups which may be substituted by a substituent and optionally one or more other divalent groups (i.e., a divalent group containing a benzene ring). It is particularly preferable that D in the above general formula (I-1) is one or more of the following formulae (iii-1) to (iii-3). [ka] (In the above formulas (iii-1) to (iii-3), R i3 , R i4 and R i5 are each independently a monovalent substituent, and are, for example, any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen atom, and an acid group; i1 is 0 or an integer of 1 to 4; L i1is a divalent linker, and is, for example, any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, a carbonyl group (-C(=O)-), -SO2-, -NH-, and -N=N-, and i2 and i3 are each independently an integer of 1 to 4.

[0030] In the above general formula (I-1), Z 1 and Z 2 Each of Z preferably independently represents an ethylenically unsaturated bond-containing group, a haloalkyl group, a hydroxyalkyl group, or an alkoxyalkyl group. 1 and Z 2 are preferably each independently one or more groups selected from the group consisting of the following formula (iv) and formula (v): [ka] (In the above formula (iv) and formula (v), R 21 , R 22 and R 23 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R 24 and R 25 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom (e.g., fluorine, chlorine, bromine, iodine, etc.), a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms, E represents a halogen atom (e.g., fluorine, chlorine, bromine, iodine, etc.), a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms.

[0031] The linking compound (a2) of this embodiment is preferably one or more compounds selected from the group consisting of compounds represented by the following general formula (I-1.1) and general formula (I-1.2). [ka] (In the above general formula (I-1.1), R 11 , R 12 and R 13 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R 21, R 22 and R 23 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; L 1 and L 2 each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and D represents the above-described divalent group. (In the above general formula (I-1.2), R 14 , R 15 , R 24 and R 25 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom (e.g., fluorine, chlorine, bromine, iodine, etc.), a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms; L 1 and L 2 each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, D represents a divalent group as described above, and E represents a halogen atom (e.g., fluorine, chlorine, bromine, iodine, etc.), a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms.

[0032] When the bond represented by the dashed line in the above general formula (I) is present, the linking compound (a2) can be represented by the following general formula (I-2): That is, the organic compound (a2-1), which is one aspect of the linking compound (a2) of the present embodiment, is preferably represented by the following general formula (I-2). [ka] (In the above general formula (I-2), Z 3 and Z 4 each independently represents an electrophilic reactive group; D 1 form a ring structure together with the structure, specifically, a divalent group having an ethylenically unsaturated bond group or a divalent group having a linking functional group (e.g., a haloalkylene group, a hydroxyalkylene group, or an alkoxyalkylene group), D 1 represents a central structure, preferably represents a tetravalent group, and specifically, preferably has an alicyclic group. In the above general formula (I-2), D 1represents a central structure. The central structure is not particularly limited, but examples thereof include cyclic groups such as alicyclic structures which may be substituted with a substituent. 1 The tetravalent group represented by the formula (I) preferably has an alicyclic structure. The alicyclic group is not particularly limited, but examples thereof include tetravalent groups obtained by removing four arbitrary hydrogen atoms from a cycloalkane monocyclic structure such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, and cyclodecane; and tetravalent groups obtained by removing four arbitrary hydrogen atoms from a condensed ring, a bridged ring (e.g., a bicyclo ring), a spiro ring, or a polycyclic structure formed by a combination of two or more of these monocyclic cycloalkanes. In addition, the alicyclic group may be substituted with one or more (e.g., 1 to 4) substituents as necessary. Examples of the substituents include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen atom, and a hydroxyl group.

[0033] In the above general formula (I-2), the divalent group containing an ethylenically unsaturated bond is not particularly limited, and examples thereof include alkenylene groups such as a vinylene group, an allylene group, a propenylene group, a butenylene group, a methylarylene group, a methylpropenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, a nonenylene group, and a decenylene group (e.g., an alkenylene group having 2 to 20 carbon atoms).

[0034] In the above general formula (I-2), the haloalkylene group is not particularly limited, but examples thereof include fluorinated alkylene groups such as fluoromethylene, fluoroethylene, fluoropropylene, fluorobutylene, methylfluoropropylene, fluoropentylene, and fluorohexylene; chlorinated alkylene groups such as chloromethylene, chloroethylene, chloropropylene, chlorobutylene, methylchloropropylene, chloropentylene, and chlorohexylene; brominated alkylene groups such as bromomethylene, bromoethylene, bromopropylene, bromobutylene, methylbromopropylene, bromopentylene, and bromohexylene; and iodinated alkylene groups such as iodomethylene, iodoethylene, iodopropylene, iodobutylene, methyliodopropylene, iodopentylene, and iodohexylene.

[0035] In the above general formula (I-2), the hydroxyalkylene group is not particularly limited, but examples thereof include hydroxymethylene, hydroxyethylene, hydroxypropylene, hydroxybutylene, 2,2-methylhydroxypropylene, hydroxypentylene, and hydroxyhexylene.

[0036] In the above general formula (I-2), the alkoxyalkylene group is not particularly limited, but examples thereof include methoxymethylene, ethoxymethylene, propoxymethylene, methoxyethylene, ethoxyethylene, methoxypropylene, ethoxypropylene, methoxybutylene, ethoxybutylene, methylmethoxypropylene, methoxypentylene, and methoxyhexylene.

[0037] The linking compound (a2) or organic compound (a2-1) of this embodiment is preferably one or more compounds selected from the group consisting of compounds represented by the following general formulas (I-2.1) and (I-2.2). [ka] (In the above general formula (I-2.1), L 3 , L 4 , L 5 and L 6each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms; R 26 , R 27 , R 28 and R 29 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; D 1 is the same as above. (In the above general formula (I-2.2), L 3 , L 4 , L 5 and L 6 each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms; R 30 and R 31 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom (e.g., fluorine, chlorine, bromine, iodine, etc.), a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms; E 3 and E 4 each independently represents a halogen atom (e.g., fluorine, chlorine, bromine, iodine, etc.), a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms; D 1 is the same as above.)

[0038] Specific examples of the linking compound (a2) of the present embodiment include octahydrobiphenylene, octahydroindacene, octahydrofluorene, decahydroanthracene, decahydrophenanthrene, tetradecahydronaphthacene, tetradecahydrochrysene, and compounds represented by the following structural formula: [ka] and the like.

[0039] Other specific examples of the linking compound (a2) of the present embodiment include dichlorododecahydrobiphenylene, dichlorododecahydroindacene, dichlorododecahydrofluorene, dichlorotetradecahydroanthracene, dichlorotetradecahydrophenanthrene, dichlorooctadecahydronaphthacene, dichlorooctadecahydrochrysene, difluorotetradecahydroanthracene, dibromotetradecahydroanthracene, and diiodotetradecahydroanthracene.

[0040] Other specific examples of the linking compound (a2) of this embodiment include dihydroxydodecahydrobiphenylene, dihydroxydodecahydroindacene, dihydroxydodecahydrofluorene, dihydroxytetradecahydroanthracene, dihydroxytetradecahydrophenanthrene, dihydroxyoctadecahydronaphthacene, and dihydroxyoctadecahydrochrysene.

[0041] Other specific examples of the linking compound (a2) of the present embodiment include dimethoxydodecahydrobiphenylene, dimethoxydodecahydroindacene, dimethoxydodecahydrofluorene, dimethoxytetradecahydroanthracene, dimethoxytetradecahydrophenanthrene, dimethoxyoctadecahydronaphthacene, dimethoxyoctadecahydrochrysene, and diethoxytetradecahydroanthracene.

[0042] - A linking compound (a2) in which an electrophilically reactive bonding site reacts successively multiple times (hereinafter, also referred to as organic compound (a2-2)) - The linking compound (a2) of the present embodiment preferably contains one or more ketone groups (preferably aldehyde groups) as electrophilic reactive groups. When the linking compound (a2) has an aldehyde group, two phenolic hydroxyl group-containing compounds (a1) can be linked to one aldehyde group in the linking compound (a2) during the polymerization reaction with the phenolic hydroxyl group-containing compound (a1), so that two or more phenolic hydroxyl group-containing compounds (a1) can be linked via the linking compound (a2). When the linking compound (a2) of this embodiment contains one or more aldehyde groups as electrophilic reactive groups, that is, the organic compound (a2-2) is preferably an aldehyde compound represented by the following general formula (II). [ka] (In the above general formula (II), D 2 are each independently a hydrogen atom or a monovalent substituent.

[0043] In the above general formula (II), D 2 are each independently a hydrogen atom or a monovalent substituent. Examples of the "monovalent substituent" include, but are not limited to, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alicyclic group having 3 to 30 carbon atoms, an aromatic heterocyclic group having 1 to 30 carbon atoms, a non-aromatic heterocyclic group having 1 to 30 carbon atoms, and groups substituted with a substituent such as an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a halogen atom, or a hydroxyl group, as well as a halogen atom, a hydroxyl group, or a carboxyl group.

[0044] The linking compound (a2) or the organic compound (a2-2) in this embodiment is preferably an aldehyde compound represented by the following formulas (II-1) to (II-4). [ka] (In the above formulas (II-1) to (II-4), k is an integer of 1 to 20. ii1 and R ii2 are each independently any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen atom, and a hydroxyl group, and nii1 is an integer of 0 to 4. nii2 is an integer of 0 to 7.

[0045] Specific examples of the organic compound (a2-2) include, but are not limited to, formaldehyde; aliphatic aldehydes such as acetaldehyde and propionaldehyde; aldehyde group-containing benzene compounds such as benzaldehyde and salicylaldehyde; aldehyde group-containing naphthalene compounds such as 1-naphthaldehyde, 2-naphthaldehyde, 2,3-naphthalenedicarboxyaldehyde and 2,6-naphthalenedicarboxyaldehyde. Among these, aldehyde group-containing benzene compounds and aldehyde group-containing naphthalene compounds are preferred, aldehyde group-containing benzene compounds are more preferred, and benzaldehyde and salicylaldehyde are even more preferred.

[0046] <<Preferable embodiment of the linking compound (a2) of the present embodiment>> A preferred embodiment of the linking compound (a2) of this embodiment is one or more selected from the group consisting of S8, SCl2, the compound represented by the above formula (I) (including the compounds represented by general formulas (I-1.1) and (I-1.2)), and the compound represented by the above formula (II) (including the compounds represented by formulas (II-1) to (II-4)).

[0047] <Ratio of phenolic hydroxyl group-containing compound (a1) and linking compound (a2)> The ratio of the phenolic hydroxyl group-containing compound (a1) to the linking compound (a2) used is preferably such that the number of moles of the organic compound (a2-1) and / or the organic compound (a2-2) per mole of the phenolic hydroxyl group-containing compound (a1) is in the range of 0.9 to 1.2, more preferably in the range of 0.9 to 1.1, and even more preferably in the range of 0.95 to 1.05, since a curable resin composition capable of forming a cured product having high adhesion and a low linear expansion coefficient can be obtained.

[0048] <Calixarene structure> The "calixarene compound" contained in the calixarene compound-containing phenolic resin (A) is a repeating unit U derived from the phenolic hydroxyl group-containing compound (a1). a1 and a repeating unit U derived from the linking compound (a2).a2 The calixarene is a polymer in which the repeating units U and U are alternately linked in a ring shape, and can be represented by the following general formula (1). a1 and repeating unit U a2 It may further contain other repeating units other than the above. [ka] In the above general formula (1), U a1 is a repeating unit derived from the phenolic hydroxyl group-containing compound (a1), U a2 is a repeating unit derived from the linking compound (a2), n1 is an integer of 2 or more, preferably 2 to 16, more preferably 4, 6, 8, 10, 12, 14, or 16, and further preferably 4, 6, or 8.

[0049] <<Repeating unit U derived from phenolic hydroxyl group-containing compound (a1) a1 >> The repeating unit U in the above general formula (1) a1 may have a structure represented by the following general formula (a1'). [ka]

[0050] In the above general formula (a1'), Ar represents a group having an aromatic ring-containing structure (main chain-forming structure), and R 1 each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group, q represents an integer, and p represents a natural number. In the above formula (a1'), * indicates an adjacent repeating unit U a2 Ar and R represent the linking site. 1 The preferred forms of p and q are the same as those explained above in the section entitled "Phenolic Hydroxyl Group-Containing Compound (a1)."

[0051] Repeating unit U a1Examples of structures that the compound may have include structures represented by the following structural formulas (3-1) to (3-5). [ka]

[0052] In the above general formulas (3-1) to (3-5), * indicates an adjacent repeating unit U a2 represents the linking site with R 1 , R 2 , p, and q are the same as those explained in the section on "phenolic hydroxyl group-containing compound (a1)". The position of the substituent on the aromatic ring in the above structural formula is arbitrary. For example, in the naphthalene ring of general formula (3-2), it may be substituted on any benzene ring forming a condensed ring. In general formulas (3-3), (3-4), and (3-5), U a1 p and q may be substituted on any benzene ring present in one repeating unit U a1 The number of substituents in each group is shown.

[0053] Repeating unit U a1 Specific examples of the repeating unit derived from the specific example of the phenolic hydroxyl group-containing compound (a1) shown in the item of <<Phenolic hydroxyl group-containing compound (a1)>> (two hydrogen atoms bonded to the aromatic ring in these compounds are adjacent to the repeating unit U a2 (a repeating unit having a structure converted into a linking site with the repeating unit).

[0054] <<Repeating unit U derived from linking compound (a2) a2 >> Repeating unit U a2 may have different structures depending on whether it is (i) the organic compound (a2-1) or (ii) the organic compound (a2-2). Preferred forms of (i) the organic compound (a2-1) or (ii) the organic compound (a2-2) will be described below.

[0055] - a repeating unit U derived from organic compound (a2-1) a2 - The linking compound (a2) is represented by the following general formula (I-1.1): [ka] In the case of the organic compound (a2-1) represented by the following formula, the repeating unit U a2 may have a structure represented by any one of the following general formulas (I'-1.1) to (I'''-1.1). [ka] [ka] [ka] (In the above general formulas (I-1.1) and (I'-1.1) to (I'''-1.1), R 11 , R 12 and R 13 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R 21 , R 22 and R 23 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; L 1 and L 2 each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and D represents a divalent group as described above.

[0056] For example, the linking compound (a2) is represented by the following formula (I-1-1): [ka] In the case of 1,4-divinylbenzene represented by the formula (I-1-1'), the repeating unit is mainly represented by the formula (I-1-1') [ka] (* indicates adjacent repeating units U a1 (representing a linkage site with

[0057] The linking compound (a2) is represented by the following general formula (I-1.2): [ka] In the case of the organic compound (a2-1) represented by the following formula, the repeating unit U a2 may have a structure represented by the following general formula (I'-1.2): [ka] (In the above general formula (I'-1.2), [E 1 -CR 14 R 15 One or more leaving groups are generated from the [E 2 -CR 24 R 25 -] produces one or more leaving groups. * indicates the adjacent repeating unit U a1 represents the linking site with R 14 , R 15 , R 24 and R 25 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom (e.g., fluorine, chlorine, bromine, iodine, etc.), a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms; L 1 and L 2 each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, D represents a divalent group as described above, and E represents a halogen atom (e.g., fluorine, chlorine, bromine, iodine, etc.), a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms. When the linking compound (a2) is one or more compounds selected from the group consisting of the compounds represented by the above general formula (I-2.1) and the above general formula (I-2.2), the repeating unit U a2 may have a structure represented by any one of the following general formulas (I'-2.1) to (I'''-2.1) and (I'-2.2). [ka] (In the above general formulae (I'-2.1) to (I''-2.1), L 3 , L 4 , L 5 and L 6each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms; R 26 , R 27 , R 28 and R 29 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; D 1 is the same as above. [ka] (In the above general formula (I'-2.2), L 3 , L 4 , L 5 and L 6 each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms; R 30 and R 31 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom (e.g., fluorine, chlorine, bromine, iodine, etc.), a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms; E 3 and E 4 each independently represents a halogen atom (e.g., fluorine, chlorine, bromine, iodine, etc.), a hydroxyl group, or an alkoxy group having 1 to 20 carbon atoms; D 1 is the same as above. In addition, * in the general formula (I'-2.2) is the same as the above [E 3 -CR 30 One or more leaving groups are generated from the [E =] moiety. 4 -CR 31 =] represents one or more leaving groups.)

[0058] - a repeating unit U derived from an organic compound (a2-2) a2 - When the linking compound (a2) is an organic compound represented by the following general formula (II), preferably an organic compound (a2-2) represented by the above general formulas (II-1) to (II-4), the repeating unit U a2 may have a structure represented by the following general formula (II'): [ka] (In the above general formulas (II) and (II'), D2 are each independently a hydrogen atom or a monovalent substituent, and represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alicyclic group having 1 to 30 carbon atoms, an aromatic heterocyclic group having 1 to 30 carbon atoms, a non-aromatic heterocyclic group having 1 to 30 carbon atoms, and groups substituted with a substituent such as an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a halogen atom, or a hydroxyl group, as well as a halogen atom, a hydroxyl group, or a carboxyl group.

[0059] The repeating unit U derived from the linking compound (a2) of this embodiment a2 The repeating units represented by the following formulae (II'-1) to (II'-4) are preferred. [ka] (In the above formulas (II'-1) to (II'-4), k is an integer of 1 to 20. ii1 and R ii2 are each independently any one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen atom, and a hydroxyl group, and nii1 is an integer of 0 to 4. nii2 is an integer of 0 to 7.

[0060] <(Meth)acrylate Compound Having Epoxy Group (B)> The (meth)acrylate compound (B) having an epoxy group in this embodiment is an essential component of the reaction raw material (2) for synthesizing a resin having an acid group and a polymerizable unsaturated group. The (meth)acrylate compound (B) having an epoxy group is not particularly limited in specific structure as long as it has a (meth)acryloyl group and an epoxy group in the molecular structure, and a wide variety of compounds can be used. For example, (meth)acrylate monomers having a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate (e.g., 3,4-epoxycyclohexylmethyl (meth)acrylate); mono(meth)acrylated products of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether can be mentioned. Among them, it is preferable to use glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate, and glycidyl (meth)acrylate is more preferable. These (meth)acrylate compounds having an epoxy group can be used alone or in combination of two or more kinds.

[0061] The amount of the (meth)acrylate compound (B) having an epoxy group used is preferably in the range of 0.9 to 1.1 moles of epoxy groups per mole of phenolic hydroxyl groups in the calixarene body-containing phenolic resin (A), and more preferably 0.95 to 1.1 moles, since a curable resin composition capable of forming a cured product having high adhesion and a low linear expansion coefficient can be obtained.

[0062] <Other compounds> The resin having a polymerizable unsaturated group of the present invention can also use compounds other than the calixarene body-containing phenolic resin (A) and the (meth)acrylate compound having an epoxy group (B) as raw materials or reaction raw materials, if necessary. Examples of the other compounds include unsaturated monobasic acid anhydrides.

[0063] Examples of the unsaturated monobasic acid anhydride include acrylic acid anhydride, methacrylic acid anhydride, etc. These unsaturated monobasic acid anhydrides can be used alone or in combination of two or more kinds.

[0064] The total mass ratio of the calixarene-containing phenolic resin (A) and the epoxy group-containing (meth)acrylate compound (B) in the raw material (solid content) of the resin having a polymerizable unsaturated group of the present invention is preferably 70 mass% or more, more preferably 80 mass% or more, since a curable resin composition capable of forming a cured product having high adhesion and a low linear expansion coefficient can be obtained. The upper limit of the total mass ratio can be 100 mass% or less, or 98 mass% or less.

[0065] <Method of producing resin having polymerizable unsaturated group> The method for producing the resin having a polymerizable unsaturated group of the present invention is not particularly limited, and any method may be used for production. The resin having a polymerizable unsaturated group of the present invention may be produced, for example, by a method in which the phenolic hydroxyl group-containing compound (a1) and the organic compound (a2-1) and / or (a2-2), which are essential reaction raw materials (1) for the calixarene-containing phenolic resin (A), and the reaction raw material (2) containing the epoxy group-containing (meth)acrylate compound (B) are all reacted at once, or by a method in which the reaction raw materials (1) are reacted sequentially to obtain the calixarene-containing phenolic resin (A), and then the calixarene-containing phenolic resin (A) is reacted with the reaction raw material (2) containing the epoxy group-containing (meth)acrylate compound (B). Among these, a method in which a phenolic hydroxyl group-containing compound (a1) is first reacted with the organic compound (a2-1) and / or (a2-2) in the presence of an acidic catalyst at a temperature in the range of 0 to 200°C to produce a calixarene-containing phenolic resin (A), and then the calixarene-containing phenolic resin (A) is reacted with a (meth)acrylate compound (B) having an epoxy group in the presence of a basic catalyst at a temperature in the range of 80 to 140°C to produce a resin having a polymerizable unsaturated group of the present invention is preferred, because the reaction can be easily controlled. In addition, when the calixarene-containing phenolic resin (A) is reacted with the (meth)acrylate compound (B) having an epoxy group in the presence of a basic catalyst, a step of neutralizing the basic catalyst may be further provided, if necessary. By neutralizing the basic catalyst, the amount of the basic catalyst (e.g., triethylamine in the examples) remaining in the final product can be reduced. It has been confirmed that if the basic catalyst (e.g., triethylamine in the examples) remains in the final product, the developability is significantly deteriorated. In the present embodiment, the amount of the basic catalyst (e.g., an amine compound, triethylamine is used in the embodiment) remaining in the resin having a polymerizable unsaturated group is preferably 100 μg or less per 1 g of the solid content of the resin having a polymerizable unsaturated group, more preferably 50 μg or less. In the curable resin composition described below, the amount is preferably 100 μg or less per 1 g of the solid content in the curable resin composition, more preferably 50 μg or less. When the amount of the basic catalyst (particularly an amine compound can be mentioned, and triethylamine is used in the examples) remaining in the resin having a polymerizable unsaturated group is within the above range, a significant deterioration in developability can be suppressed or prevented. On the other hand, when a phosphorus-based basic catalyst such as a phosphine compound remains in the resin having a polymerizable unsaturated group, it is less likely to cause deterioration in developability than when an amine compound such as triethylamine remains, so the amount of the phosphorus-based basic catalyst remaining does not need to be strictly specified. In addition, the neutralizing agent used in the step of neutralizing the basic catalyst is preferably an acidic compound. The acidic compound is not particularly limited as long as it is a compound that exhibits acidity, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid; and the like. These acidic compounds may be used alone or in combination of two or more.

[0066] The synthesis of the calixarene-containing phenolic resin (A) or the synthesis of the resin having a polymerizable unsaturated group may be carried out in an organic solvent, if necessary. The reaction of the phenolic hydroxyl group-containing compound (a1), the compound (a2-1) and / or (a2-2), and the (meth)acrylate compound having an epoxy group (B) may also be carried out in an organic solvent, if necessary. A polymerization inhibitor or an antioxidant may also be used, if necessary.

[0067] Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. In addition, solid acid catalysts having a strong acid such as a sulfonyl group can also be used. These acid catalysts can be used alone or in combination of two or more.

[0068] Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, trimethylamine, dimethylethylamine, diethylmethylamine, triethylamine, dimethylpropylamine, diethylpropylamine, dipropylmethylamine, and the like. ammine, dipropylethylamine, tripropylamine, dimethylbutylamine, diethylbutylamine, dibutylmethylamine, dibutylethylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4 -Amine compounds such as diethylimidazole, 2-ethyl-4-methylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and tetramethylammonium hydroxide; quaternary ammonium salts such as trioctylmethylammonium chloride and trioctylmethylammonium acetate; phosphine compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride;Examples of the basic catalyst include organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octanoate; and inorganic metal compounds. In addition, alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides can also be used. These basic catalysts can be used alone or in combination of two or more. When used, these basic catalysts can be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid.

[0069] The amount of the basic catalyst used is preferably in the range of 0.01 to 1 part by mass, and more preferably in the range of 0.05 to 0.8, relative to 100 parts by mass in total of the calixarene body-containing phenolic resin (A) and the (meth)acrylate compound (B) having an epoxy group, since a curable resin composition capable of forming a cured product having high adhesion and a low linear expansion coefficient can be obtained.

[0070] Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, cyclohexanone, and dimethylacetamide; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; carbitol, cellosolve, methanol, ethanol, propanol, isopropanol, and butanol (n-butanol, isobutanol, secondary butanol, Examples of the organic solvent include alcohol solvents such as tertiary butanol, cyclohexanol, and propylene glycol monomethyl ether; ether solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, and methyl carbitol; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; vegetable oils and fats such as soybean oil, linseed oil, rapeseed oil, and safflower oil; and methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination of two or more. For the reaction to produce the calixarene-containing phenolic resin (A) and the reaction to produce a resin having a polymerizable unsaturated group from the calixarene-containing phenolic resin (A), an organic solvent suitable for each reaction may be selected and used separately. Also, different organic solvents may be used before and after each reaction.

[0071] In addition, as the organic solvent, commercially available products can also be used. Examples of commercially available products include "No. 1 Spindle Oil," "No. 3 Solvent," "No. 4 Solvent," "No. 5 Solvent," "No. 6 Solvent," "Naphthesol H," "Alkene 56NT," "AF Solvent No. 4," "AF Solvent No. 5," "AF Solvent No. 6," and "AF Solvent No. 7" manufactured by ENEOS Corporation; "Diadol 13" and "Dialene 168" manufactured by Mitsubishi Chemical Corporation; "F Oxocol" and "F Oxocol 180" manufactured by Nissan Chemical Industries, Ltd.; "Supersol LA35" and "Supersol LA38" manufactured by Idemitsu Kosan Co., Ltd.; and ExxonMobil Examples include "Exxor D80", "Exxor D110", "Exxor D120", "Exxor D130", "Exxor D160", "Exxor D100K", "Exxor D120K", "Exxor D130K", "Exxor D280", "Exxor D300", and "Exxor D320" manufactured by Exxor Chemical Co., Ltd. The organic solvents can be used alone or in combination of two or more kinds. In the present embodiment, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, since this improves the reaction efficiency.

[0072] The organic solvent may be used in combination with water, and the ratio of water to be used in the mixed solvent is preferably within a range of 5 to 60 parts by mass, and more preferably 10 to 50 parts by mass, per 100 parts by mass of the mixed solvent.

[0073] Examples of the polymerization inhibitor include p-methoxyphenol, p-methoxycresol, dibutylhydroxytoluene, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4 -Phenol compounds such as trimethyl-1,2-dihydroquinoline, quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N.N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1.amine compounds such as 3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction products of styrenated diphenylamine and 2,4,4-trimethylpentene, reaction products of diphenylamine and 2,4,4-trimethylpentene, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecyl) thioether compounds such as N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso ... -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn -Propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds, esters of phosphoric acid and octadecane-1-ol, triphenyl phosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]Undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite and other phosphite compounds, bis(dimethyldithiocarbamato-κ(2)S,S')zinc, diethyldithiocarbamate , zinc compounds such as zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and distearyl 3,3'-thiodipropionate. These polymerization inhibitors can be used alone or in combination of two or more. As the antioxidant, the same compounds as those exemplified as the polymerization inhibitor can be used, and the antioxidants can be used alone or in combination of two or more kinds. In addition, examples of commercially available products of the polymerization inhibitor and the antioxidant include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.

[0074] <Curable resin composition> The resin having a polymerizable unsaturated group of the present invention can be used as a curable resin composition by adding a photopolymerization initiator. In other words, the curable resin composition of the present embodiment essentially contains a photopolymerization initiator and a resin having a polymerizable unsaturated group.

[0075] Examples of the photopolymerization initiator include photoradical polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone.

[0076] Examples of commercially available photopolymerization initiators include "Omnirad 1173", "Omnirad 184", "Omnirad 127", "Omnirad 2959", "Omnirad 369", "Omnirad 379", "Omnirad 907", "Omnirad 4265", "Omnirad 1000", "Omnirad 651", "Omnirad TPO", "Omnirad 819", "Omnirad 2022", "Omnirad 2100", "Omnirad 754", "Omnirad 784", "Omnirad 500", and "Omnirad 81" (manufactured by IGM Resins); "KAYACURE DETX", "KAYACURE MBP", "KAYACURE DMBI", "KAYACURE EPA", and "KAYACURE OA" (manufactured by Nippon Kayaku Co., Ltd.); and "Vicure 10" and "Vicure 55" (manufactured by Stoffa Examples of photopolymerization initiators include "Trigonal P1" (manufactured by Akzo Nobel), "SANDORAY 1000" (manufactured by SANDOZ), "DEAP" (manufactured by Upjohn Chemical), "Quantacure PDO", "Quantacure ITX", "Quantacure EPD" (manufactured by Ward Blenkinsop), and "Runtecure 1104" (manufactured by Runtec). These photopolymerization initiators can be used alone or in combination of two or more kinds. The amount of the photopolymerization initiator added is preferably within a range of, for example, 0.5 to 20% by mass in the curable resin composition.

[0077] <Other Resins Having Polymerizable Unsaturated Groups (D)> The curable resin composition of the present disclosure may further contain a resin (D) having a polymerizable unsaturated group other than the resin having a polymerizable unsaturated group of the present embodiment (hereinafter also referred to as "another resin (D) having a polymerizable unsaturated group").

[0078] Examples of the polymerizable unsaturated group contained in the resin (D) include (meth)acryloyl group, allyl group, isopropenyl group, 1-propenyl group, styryl group, styrylmethyl group, maleimide group, vinyl ether group, etc. In addition, the resin (D) having other polymerizable unsaturated groups may not contain an acid group. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc.

[0079] When the curable resin composition of the present invention contains another resin (D) having a polymerizable unsaturated group, the amount of the resin (D) having an acid group and a polymerizable unsaturated group added is preferably in the range of, for example, 0.5 to 20 mass % in the curable resin composition. The curable resin composition of the present embodiment may contain a resin (D) having other polymerizable unsaturated groups as an optional component. The resin (D) having other polymerizable unsaturated groups may have a polymerizable unsaturated group, and other specific structures or molecular weights are not particularly limited, and a wide variety of resins can be used. The resin (DX) having other polymerizable unsaturated groups may be used alone or in combination of two or more. It is preferable that the resin (D) having other polymerizable unsaturated groups has a polymerizable unsaturated group but does not have an acid group. Specific examples of the resin (D) having another polymerizable unsaturated group include a (meth)acrylate compound (D-1) and / or a resin (D-2) having a polymerizable unsaturated group. The (meth)acrylate compound (D-1) is not particularly limited as long as it has a (meth)acryloyl group, and examples thereof include aliphatic mono(meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate; cyclohexyl (meth)acrylate. alicyclic mono(meth)acrylate compounds such as isobornyl (meth)acrylate and adamantyl mono(meth)acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxyethoxyethyl (meth)acrylate mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzyl benzyl (meth)acrylate, and phenylphenoxyethyl (meth)acrylate; (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various mono(meth)acrylate monomers mentioned above; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various mono(meth)acrylate compounds mentioned above; aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate;Alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; and compounds having a (poly)oxyethylene group in the molecular structure of the above di(meth)acrylate compounds. polyoxyalkylene-modified di(meth)acrylate compounds having a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain introduced therein; lactone-modified di(meth)acrylate compounds having a (poly)lactone structure introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (Poly)oxyalkylene-modified tri(meth)acrylate compounds having a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain introduced into the structure; lactone-modified tri(meth)acrylate compounds having a (poly)lactone structure introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, aliphatic poly(meth)acrylate compounds having 4 or more functional groups, such as acrylate; (poly)oxyalkylene-modified poly(meth)acrylate compounds having 4 or more functional groups, in which a (poly)oxyalkylene chain, such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain, has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compound; and lactone-modified poly(meth)acrylate compounds having 4 or more functional groups, in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compound;Hydroxyethyl (meth)acrylate, Hydroxypropyl (meth)acrylate, Trimethylolpropane (meth)acrylate, Trimethylolpropane di(meth)acrylate, Pentaerythritol (meth)acrylate, Pentaerythritol di(meth)acrylate, Pentaerythritol tri(meth)acrylate, Dipentaerythritol (meth)acrylate, Dipentaerythritol di(meth)acrylate, Dipentaerythritol tri(meth)acrylate (meth)acrylate compounds having a hydroxyl group, such as dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate; (meth)acrylate compounds having a hydroxyl group, such as (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylolpropane chains, (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxyethylene ... (Poly)oxyalkylene modified products having a (poly)oxyalkylene chain such as a styrene chain introduced therein; lactone modified products having a (poly)lactone structure introduced into the molecular structure of the (meth)acrylate compound having a hydroxyl group; (meth)acrylate compounds having an isocyanate group such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate; (meth)acrylate monomers having a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate, and (meth)acrylate compounds having an epoxy group such as mono(meth)acrylates of diglycidyl ether compounds of hydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. The (meth)acrylate compounds (D-1) may be used alone or in combination of two or more.

[0080] The resin (D-2) having the other polymerizable unsaturated group may be any polymer material having a polymerizable unsaturated group in the resin, and examples thereof include the following [1] to [6]: [1] Epoxy resin having a polymerizable unsaturated group (D-2.1), [2] Urethane resin having a polymerizable unsaturated group (D-2.2), [3] Acrylic resin having a polymerizable unsaturated group (D-2.3), [4] Amide-imide resin having a polymerizable unsaturated group (D-2.4), [5] Acrylamide resin having a polymerizable unsaturated group (D-2.5), [6] Ester resin having a polymerizable unsaturated group (D-2.6), etc.

[0081] <Epoxy resin having polymerizable unsaturated group (D-2.1)> Examples of the epoxy resin (D-2.1) having a polymerizable unsaturated group of this embodiment (hereinafter also referred to as resin (D-2.1)) include an epoxy (meth)acrylate resin obtained by reacting an epoxy resin with an unsaturated monobasic acid, and optionally a polybasic acid anhydride; an epoxy (meth)acrylate resin having a urethane group obtained by reacting an epoxy resin, an unsaturated monobasic acid, a polyisocyanate compound, and a (meth)acrylate compound having a hydroxyl group, and optionally a polybasic acid anhydride; and the like. As described above, the polybasic acid anhydride can be used as a reaction raw material for the resin (D-2.1), but it is preferable not to use it. The resin (D-2.1) preferably has a polymerizable unsaturated group but does not have an acid group.

[0082] Examples of the epoxy resin include bisphenol type epoxy resin, hydrogenated bisphenol type epoxy resin, biphenol type epoxy resin, hydrogenated biphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin, etc. These epoxy resins may be used alone or in combination of two or more. Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin. Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'-biphenol type epoxy resin. Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, hydrogenated tetramethyl-4,4'-biphenol type epoxy resin, and hydrogenated tetramethyl-2,2'-biphenol type epoxy resin. Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Esters, acid halides, and acid anhydrides of the unsaturated monobasic acids can also be used. Examples of the unsaturated monobasic acid include those represented by the following general formula (6): [ka] (In the above general formula (6), X 61 represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain; X 61 A hydrogen atom in the structure of Y may be substituted with a halogen atom or an alkoxy group. 61 is a hydrogen atom or a methyl group. Compounds represented by the following formula: Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain. The (poly)ester chain may, for example, be represented by the following general formula (7): [ka] (In the above general formula (7), R 71 and R 72 represents an alkylene group having 1 to 10 carbon atoms, 71 represents an integer of 1 to 5. Examples of the (poly)ester chain include those represented by the following formula: These unsaturated monobasic acids may be used alone or in combination of two or more. Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. In addition, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used. The (poly)carbonate chain may, for example, be a chain represented by the following general formula (8): [ka] (In the above general formula (8), R 81 represents an alkylene group having 1 to 10 carbon atoms, 81 represents an integer of 1 to 5. Examples of the (poly)carbonate chain include those represented by the following formula:

[0083] Examples of the polybasic acid anhydride include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides. Examples of the aliphatic polybasic acid anhydride include anhydrides of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, etc. In addition, the aliphatic polybasic acid anhydride may have an aliphatic hydrocarbon group of either a straight-chain type or a branched type, and may have an unsaturated bond in the structure. In the present invention, the alicyclic polybasic acid anhydride is one in which an acid anhydride group is bonded to an alicyclic structure, and the presence or absence of aromatic rings in other structural parts is not important. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydrides. Examples of the aromatic polybasic acid anhydride include anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, and benzophenone tetracarboxylic acid. These polybasic acid anhydrides may be used alone or in combination of two or more. Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, cyclohexane diisocyanate, and cyclohexane diisocyanate; Examples of the polyisocyanate include aromatic diisocyanate compounds such as silylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following general formula (9); and isocyanurate-modified, biuret-modified, and allophanate-modified products thereof. These polyisocyanate compounds may be used alone or in combination of two or more. [ka] (In the above general formula (9), R 92 and R 93 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; R 91 each independently represents an alkyl group having 1 to 4 carbon atoms; k 91 is 0 or an integer of 1 to 3, and n 91 is an integer greater than or equal to 1.) Examples of the (meth)acrylate compound having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. In addition, (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds described above, and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds described above, and the like can also be used.

[0084] The method for producing the epoxy resin (D-2.1) having the polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the epoxy resin (D-2.1) having the polymerizable unsaturated group may be carried out in an organic solvent as necessary, and may also use a basic catalyst as necessary. Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, cyclohexanone, and dimethylacetamide; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; carbitol, cellosolve, methanol, ethanol, propanol, isopropanol, butanol, and cyclohexanol. Examples of the organic solvent include alcohol solvents such as propylene glycol monomethyl ether, propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol, and other ether solvents, glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether acetate, and other vegetable oils and fats such as soybean oil, linseed oil, rapeseed oil, and safflower oil, as well as methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents may be used alone or in combination of two or more. In addition, as the organic solvent, commercially available products can also be used. Examples of commercially available products include "No. 1 Spindle Oil," "No. 3 Solvent," "No. 4 Solvent," "No. 5 Solvent," "No. 6 Solvent," "Naphthesol H," "Alkene 56NT," "AF Solvent No. 4," "AF Solvent No. 5," "AF Solvent No. 6," and "AF Solvent No. 7" manufactured by ENEOS Corporation; "Diadol 13" and "Dialene 168" manufactured by Mitsubishi Chemical Corporation; "F Oxocol" and "F Oxocol 180" manufactured by Nissan Chemical Industries, Ltd.; "Supersol LA35" and "Supersol LA38" manufactured by Idemitsu Kosan Co., Ltd.; and ExxonMobil Examples include "Exxor D80", "Exxor D110", "Exxor D120", "Exxor D130", "Exxor D160", "Exxor D100K", "Exxor D120K", "Exxor D130K", "Exxor D280", "Exxor D300", and "Exxor D320" manufactured by Exxor Chemical Co., Ltd. Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and amine compounds such as tetramethylammonium hydroxide; trioctylmethylammonium chloride, tri quaternary ammonium salts such as octylmethylammonium acetate; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. In addition, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, etc. can also be used. The basic catalysts may be used alone or in combination of two or more.

[0085] <Urethane resin having polymerizable unsaturated group (D-2.2)> Examples of the urethane resin (D-2.2) having a polymerizable unsaturated group of this embodiment (hereinafter also referred to as resin (D-2.2)) include those obtained by reacting a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, and, if necessary, a polyol compound and / or a polybasic acid anhydride. As described above, a polybasic acid anhydride can be used as a reaction raw material for resin (D-2.2), but it is preferable not to use it. The above resin (D-2.2) preferably has a polymerizable unsaturated group but does not have an acid group. The polyisocyanate compound, the (meth)acrylate compound having a hydroxyl group, and the polybasic acid anhydride are the same as those described above for the resin (D-2.1) and the like. Examples of the polyol compounds include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified compounds in which (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are introduced into the molecular structure of the various polyol compounds; lactone modified compounds in which (poly)lactone structures are introduced into the molecular structure of the various polyol compounds, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The polyol compounds may be used alone or in combination of two or more. The method for producing the urethane resin (D-2.2) having the polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the urethane resin (D-2.2) having the polymerizable unsaturated group may be carried out in an organic solvent if necessary, and may also use a basic catalyst if necessary. In this case, the organic solvent and the basic catalyst are the same as those described above for the resin (D-2.1) and the like.

[0086] <Acrylic resin having polymerizable unsaturated group (D-2.3)> Examples of the acrylic resin (D-2.3) having a polymerizable unsaturated group of this embodiment (hereinafter also referred to as resin (D-2.3)) include a reaction product obtained by further reacting a (meth)acrylate compound (β) having a reactive functional group capable of reacting with a hydroxyl group, carboxyl group, isocyanate group, glycidyl group, or other reactive functional group with an acrylic resin intermediate obtained by polymerizing the (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, carboxyl group, isocyanate group, or glycidyl group as an essential component, to introduce a (meth)acryloyl group, and a reaction product obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product as necessary. As described above, the polybasic acid anhydride can be used as a reaction raw material for the resin (D-2.3), but it is preferable not to use it. The above resin (D-2.3) preferably has a polymerizable unsaturated group but does not have an acid group.

[0087] The acrylic resin intermediate may be a copolymer of the (meth)acrylate compound (α) and other compounds having polymerizable unsaturated groups as necessary. Examples of the compounds having other polymerizable unsaturated groups include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. The compound having an unsaturated group may be used alone or in combination of two or more kinds. The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but the following combinations are preferable from the viewpoint of reactivity. That is, when water (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having an isocyanate group as the (meth)acrylate compound (β). When a (meth)acrylate having a carboxyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a glycidyl group as the (meth)acrylate compound (β). When a (meth)acrylate having an isocyanate group is used as the (meth)acrylate compound (α), it is preferable to use water (meth)acrylate as the (meth)acrylate compound (β). When a (meth)acrylate having a glycidyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a carboxyl group as the (meth)acrylate compound (β). The (meth)acrylate compound (β) may be used alone or in combination of two or more kinds. The polybasic acid anhydride is the same as that described above with respect to the resin (D-2.1) and the like. The method for producing the acrylic resin (D-2.3) having the polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylic resin (D-2.3) having the polymerizable unsaturated group may be carried out in an organic solvent if necessary, and may also use a basic catalyst if necessary. In this case, the organic solvent and the basic catalyst are the same as those described above for the resin (D-2.1) and the like.

[0088] <Amide-imide resin having polymerizable unsaturated group (D-2.4)> The amide-imide resin (D-2.4) having a polymerizable unsaturated group of this embodiment (hereinafter also referred to as resin (D-2.4)) can be, for example, a resin obtained by reacting an amide-imide resin having an acid group and / or an acid anhydride group with a (meth)acrylate compound having a hydroxyl group and / or a (meth)acrylate compound having an epoxy group, and, if necessary, a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. The compound having the reactive functional group may or may not have a (meth)acryloyl group. It is preferable that the resin (D-2.4) has a polymerizable unsaturated group but does not have an acid group.

[0089] The amide-imide resin (D-2.4) having a polymerizable unsaturated group may have only one of an acid group or an acid anhydride group, or may have both. However, from the viewpoint of reactivity and reaction control with a (meth)acrylate compound having a hydroxyl group or an epoxy compound having a (meth)acryloyl group, the amide-imide resin (D-2.4) having a polymerizable unsaturated group is preferably one having an acid anhydride group, and more preferably one having both an acid group and an acid anhydride group. The solid content acid value of the amide-imide resin is preferably in the range of 60 to 350 mg KOH / g under neutral conditions, i.e., under conditions where the acid anhydride group is not ring-opened. On the other hand, it is preferably in the range of 61 to 360 mg KOH / g under conditions where the acid anhydride group is ring-opened, such as in the presence of water.

[0090] The amide-imide resin (D-2.4) having the above-mentioned polymerizable unsaturated group may be, for example, one obtained by using a polyisocyanate compound and a polybasic acid anhydride as reaction raw materials. In this case, the polyisocyanate compound and the polybasic acid anhydride are the same as those described above with respect to the resin (D-2.1). As mentioned above, the polybasic acid anhydride can be used as a reaction raw material for the resin (D-2.4), but it is preferable not to use it. As reaction raw materials for the amide-imide resin (D-2.4) having a polymerizable unsaturated group, a polybasic acid can be used in combination with the polyisocyanate compound and polybasic acid anhydride, if necessary. The polybasic acid may be any compound having two or more carboxyl groups in one molecule. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 -dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, etc. In addition, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in the molecule, can also be used. These polybasic acids may be used alone or in combination of two or more. The (meth)acrylate compound having a hydroxyl group is the same as that described above with respect to the resin (D-2.1) and the like. Examples of the (meth)acrylate compound having an epoxy group include (meth)acrylate monomers having a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and mono(meth)acrylates of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These (meth)acrylate compounds having an epoxy group may be used alone or in combination of two or more. The method for producing the amide-imide resin (D-2.4) having the polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the amide-imide resin (D-2.4) having the polymerizable unsaturated group may be carried out in an organic solvent if necessary, and may also use a basic catalyst if necessary. In this case, the organic solvent and the basic catalyst are the same as those described above for the resin (D-2.1) and the like.

[0091] <Acrylamide resin having polymerizable unsaturated group (D-2.5)> Examples of the acrylamide resin (D-2.5) having a polymerizable unsaturated group of this embodiment (hereinafter also referred to as resin (D-2.5)) include those obtained by reacting a compound having a phenolic hydroxyl group, an alkylene oxide or alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, and, if necessary, a polybasic acid anhydride and an unsaturated monobasic acid. As described above, the polybasic acid anhydride can be used as a reaction raw material for the resin (D-2.5), but it is preferable not to use it. The above resin (D-2.5) preferably has a polymerizable unsaturated group but does not have an acid group. The compound having a phenolic hydroxyl group refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following general formulas (10.1) to (10.5). [ka] (In the above general formulas (10.1) to (10.5), R 101 ~R 104 and R 107 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom; R 105 and R 106 j each independently represents a hydrogen atom or a methyl group; 101 ~j 105 Each independently represents an integer of 0 or 1 or more, preferably 0 or an integer of 1 to 3, and more preferably 0 or 1. 101 ~k 105 Each independently represents an integer of 1 or more, preferably 2 or 3.

[0092] In the above general formulae (10.1) to (10.5), the position of the substituent on the aromatic ring is arbitrary. For example, in the naphthalene ring of the general formula (10.2), the substituent may be substituted with any hydrogen atom on the ring. In the general formula (10.3), the substituent may be substituted with any hydrogen atom on the benzene ring present in one molecule of biphenyl. In the general formula (10.4), the substituent may be substituted with any hydrogen atom on the benzene ring present in one molecule of aralkyl. In the general formula (10.5), the substituent may be substituted with any hydrogen atom on the benzene ring present in one molecule. When the number of the substituents in one molecule is j, 101 ~j 105 and k 101 ~k 105 This shows that.

[0093] Examples of the compound having a phenolic hydroxyl group include reaction products obtained by using a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any one of the following general formulae (11.1) to (11.5) and / or formaldehyde as essential reaction raw materials. Novolac-type phenolic resins using one or more compounds having at least one phenolic hydroxyl group in the molecule as reaction raw materials can also be used. [ka] (In the above general formulas (11.1) to (11.5), h 111 represents 0 or 1; R 111 ~R 116 each independently represents a monovalent aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group; k 111 ~k 116 each independently represents 0 or an integer of 1 to 4; Z 111 ~Z 116 each independently represents a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group; Y 111 represents an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group; n 111 represents an integer from 1 to 4.)

[0094] Specific examples of the above compounds include phenol, cresol, xylenol; dialkylphenols such as dimethylphenol and diethylphenol; trialkylphenols such as trimethylphenol and triethylphenol; diphenylphenol, triphenylphenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, tetramethylbisphenol A, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and phenol resin having a cyclo ring structure. The above-mentioned compounds having a phenolic hydroxyl group may be used alone or in combination of two or more kinds.

[0095] Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. The alkylene oxide may be used alone or in combination of two or more. Among these, the alkylene oxide is preferably ethylene oxide or propylene oxide. Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. The alkylene carbonate may be used alone or in combination of two or more. Among these, the alkylene carbonate is preferably ethylene carbonate or propylene carbonate. Examples of the N-alkoxyalkyl(meth)acrylamide compound include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide, etc. The N-alkoxyalkyl(meth)acrylamide compound may be used alone or in combination of two or more. The polybasic acid anhydrides and unsaturated monobasic acids are the same as those described above for the resin (D-2.1) and the like.

[0096] The method for producing the acrylamide resin (D-2.5) having the polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylamide resin (D-2.5) having the polymerizable unsaturated group may be carried out in an organic solvent if necessary, and may also use a basic catalyst and an acid catalyst if necessary. In this case, the organic solvent and the basic catalyst are the same as those described above for the resin (D-2.1) and the like. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. In addition, solid acid catalysts having a strong acid such as a sulfonyl group can also be used. These acid catalysts may be used alone or in combination of two or more.

[0097] <Ester resin having polymerizable unsaturated group (D-2.6)> The ester resin (D-2.6) having a polymerizable unsaturated group of this embodiment (hereinafter also referred to as resin (D-2.6)) can be, for example, a compound having a phenolic hydroxyl group, an alkylene oxide or alkylene carbonate, an unsaturated monobasic acid, and, if necessary, a polybasic acid anhydride, which is obtained by reacting the compound. As described above, the polybasic acid anhydride can be used as a reaction raw material for the resin (D-2.6), but it is preferable not to use the polybasic acid anhydride. The resin (D-2.6) preferably has a polymerizable unsaturated group but does not have an acid group. The compounds having a phenolic hydroxyl group, the alkylene oxides, the alkylene carbonates, the unsaturated monobasic acids, and the polybasic acid anhydrides are the same as those described above for resins (D-2.1) and (D-2.5), etc. The method for producing the ester resin (D-2.6) having the polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the ester resin (D-2.6) having the polymerizable unsaturated group may be carried out in an organic solvent if necessary, and may also use a basic catalyst and an acid catalyst if necessary. In this case, the organic solvent, the basic catalyst, and the acid catalyst are the same as those described above for the resin (D-2.1) and the resin (D-2.5).

[0098] <Compound having a polymerizable unsaturated group> The curable resin composition of the present embodiment may further contain a compound having a polymerizable unsaturated group. The compound having such a polymerizable unsaturated group is typically a compound having no acid group.

[0099] The compound having a polymerizable unsaturated group includes the above-mentioned (meth)acrylate compound (D-1).

[0100] <Additives> In addition, the curable resin composition of the present invention may contain various additives, such as a curing accelerator, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, an organic solvent, an inorganic filler or polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, and a storage stabilizer, as necessary.

[0101] The curing accelerator is one that accelerates the curing reaction, and examples thereof include phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acids, and amine complex salts. These curing accelerators can be used alone or in combination of two or more. The amount of the curing accelerator added is preferably within a range of 0.01 to 10 mass % based on the solid content of the curable resin composition.

[0102] Examples of the ultraviolet absorbent include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbents can be used alone or in combination of two or more.

[0103] As the polymerization inhibitor, the same ones as those exemplified above as the polymerization inhibitor can be used, and the polymerization inhibitors can be used alone or in combination of two or more kinds.

[0104] As the antioxidant, the same ones as those exemplified above as the antioxidant can be used, and the antioxidants can be used alone or in combination of two or more kinds.

[0105] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. As the pigment, known and commonly used inorganic pigments and organic pigments can be used. Examples of the inorganic pigment include white pigments, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more kinds. Examples of the white pigment include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide. Examples of the organic pigment include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments, etc. These organic pigments can be used alone or in combination of two or more kinds.

[0106] Examples of the flame retardant include inorganic phosphorus compounds such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides; phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxy Examples of suitable flame retardants include organic phosphorus compounds such as cyclic organic phosphorus compounds such as 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof reacted with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oils, silicone rubbers, and silicone resins; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. These flame retardants can be used alone or in combination of two or more. When these flame retardants are used, the amount is preferably in the range of 0.1 to 20 mass% in the total resin composition.

[0107] The cured product of the present invention can be obtained by irradiating the curable resin composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, irradiation may be performed under an inert gas atmosphere such as nitrogen gas, or under an air atmosphere in order to efficiently carry out a curing reaction by ultraviolet rays.

[0108] As a source of ultraviolet light, ultraviolet lamps are generally used from the viewpoints of practicality and economy, and specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc.

[0109] The cumulative amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 is preferably 0.5 to 10 kJ / m 2 It is more preferable that the integrated light amount is within the above range, since it is possible to prevent or suppress the occurrence of uncured portions. The irradiation of the active energy rays may be carried out in one step or in two or more steps.

[0110] The cured product of the present invention can be used for coating materials in general. In addition, since the cured product of the present invention has excellent low elasticity and high adhesion, it can be suitably used, for example, in semiconductor device applications as solder resist, interlayer insulating material, packaging material, underfill material, package adhesive layer for circuit elements, and adhesive layer between integrated circuit elements and circuit boards. In addition, it can be suitably used for thin-film transistor protective film, liquid crystal color filter protective film, pigment resist for color filters, resist for black matrix, spacer, etc. in thin display applications represented by LCD and OELD. Among these, it can be suitably used for solder resist applications, particularly for inkjet solder resist applications.

[0111] The article of the present invention has a coating film made of the cured product. Examples of the article include plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, and office automation equipment, as well as semiconductor devices, display devices, and imaging devices. EXAMPLES

[0112] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples in any way. In the examples, the instruments and conditions employed for gel permeation chromatography (GPC) are as follows:

[0113] (GPC measurement) Measurements were performed using the following measuring equipment and conditions to obtain GPC charts for the phenolic resins obtained in the following synthesis examples. An example of a GPC chart for a phenolic resin obtained by a method conforming to the synthesis example is shown in FIG. 1. The arrow in the figure indicates the peak of the calixarene body. From the GPC chart, the content of the calixarene body in the phenolic resin was calculated as the area ratio in GPC of the calixarene body to the total phenolic resin. Measurement equipment: Tosoh Corporation "HLC-8420 GPC" Column: Tosoh Corporation guard column "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G3000HXL" + Tosoh Corporation "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40℃ Developing solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: In accordance with the measurement manual for the "GPC Workstation EcoSEC-WorkStation," the following monodisperse polystyrene with known molecular weight was used. (Polystyrene used) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation Sample: A tetrahydrofuran solution (1.0 mass % in terms of solid content) of the diphenyl isophthalate derivative, aromatic ester compound (A), and epoxy resin having a polymerizable unsaturated group (B) obtained in the Synthesis Examples and Examples was filtered through a microfilter (50 μl).

[0114] < 1 H-NMR measurement> 1 H-NMR: “JNM-ECA600” manufactured by JEOL RESONANCE Magnetic field strength: 600MHz Number of times: 32 Solvent: DMSO-d6 Sample concentration: 30% by mass 1 From the results of the H-NMR chart, peaks derived from the target products were confirmed, confirming that the target products were obtained in each reaction. < 13 C-NMR measurement> 13 C-NMR: “JNM-ECA600” manufactured by JEOL RESONANCE Magnetic field strength: 150MHz Number of times: 320 Solvent: DMSO-d6 Sample concentration: 30% by mass 13 From the results of the C-NMR chart, peaks derived from the target products were confirmed, confirming that the target products were obtained in each reaction.

[0115] (Synthesis Example 1: Production of phenolic resin (1)) 560 parts by mass of toluene, 110 parts by mass of resorcinol, and 7.2 parts by mass of paratoluenesulfonic acid were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was heated to 115°C under a nitrogen atmosphere. 130 parts by mass of 1,4-divinylbenzene were added dropwise over 2 hours, and the mixture was held at 115°C for 15 hours. 7.6 parts by mass of a 20% aqueous sodium hydroxide solution was added, and the toluene was removed at 170°C to obtain a phenolic resin (1). The hydroxyl equivalent of this phenolic resin (1) was 130 g / equivalent. The GPC chart of the phenolic resin (1) is shown in Figure 1. The arrow in the figure indicates the peak of the calixarene body. The area % of the calixarene body in the GPC of the phenolic resin (1) was 18%.

[0116] (Synthesis Example 2: Production of phenolic resin (2)) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 375 parts by mass of n-butanol, 144 parts by mass of α-naphthol (1-naphthol), and 12.5 parts by mass of paratoluenesulfonic acid were added, and the temperature was raised to 100°C under a nitrogen atmosphere. 106 parts by mass of benzaldehyde were added dropwise over 2 hours, and the mixture was held at 100°C for 24 hours. After adding 375 parts by mass of methyl isobutyl ketone, the mixture was washed with water, and after confirming that the pH became neutral, the butanol and methyl isobutyl ketone were removed at 170°C to obtain a phenolic resin (2). The hydroxyl group equivalent of this phenolic resin (2) was 257 g / equivalent. The area % of the calixarene body in the GPC of the phenolic resin (2) was 19%.

[0117] (Synthesis Example 3: Production of phenolic resin (3)) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 399 parts by mass of n-butanol, 144 parts by mass of α-naphthol (1-naphthol), and 26.6 parts by mass of paratoluenesulfonic acid were added, and the temperature was raised to 100°C under a nitrogen atmosphere. 122 parts by mass of salicylaldehyde were added dropwise over 2 hours, and the mixture was held at 100°C for 24 hours. After adding 399 parts by mass of methyl isobutyl ketone, the mixture was washed with water, and after confirming that the pH had become neutral, the butanol and methyl isobutyl ketone were removed at 170°C to obtain a phenolic resin (3). The hydroxyl equivalent of this phenolic resin (3) was 139 g / equivalent. The area % of the calixarene body in GPC of the phenolic resin (3) was 55%.

[0118] (Synthesis Example 4: Production of phenolic resin (4)) In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 423 parts by mass of n-butanol, 160 parts by mass of 1,6-dihydroxynaphthalene (1,6-naphthalenediol), and 28.2 parts by mass of paratoluenesulfonic acid were added, and the mixture was heated to 100°C under a nitrogen atmosphere. 122 parts by mass of salicylaldehyde were added dropwise over 2 hours, and the mixture was held at 100°C for 24 hours. After adding 423 parts by mass of methyl isobutyl ketone, the mixture was washed with water, and after confirming that the pH had become neutral, the butanol and methyl isobutyl ketone were removed at 170°C to obtain a phenolic resin (4). The hydroxyl group equivalent of this phenolic resin (4) was 101 g / equivalent. The area % of the calixarene body in the GPC of the phenolic resin (4) was 88%.

[0119] (Example 1): Synthesis of Resin (1) Having Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 116.6 parts by mass of butyl acetate, and 130 parts by mass of the phenolic resin (1) obtained in Synthesis Example 1 was dissolved therein. 0.7 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone (p-methoxyphenol) were then added, followed by the addition of 142 parts by mass of glycidyl methacrylate and 1.4 parts by mass of triethylamine. The mixture was reacted at 120°C for 20 hours while blowing in air, to obtain a resin (1) having a polymerizable unsaturated group. The non-volatile content of this resin (1) having a polymerizable unsaturated group was 70% by mass.

[0120] (Example 2): Synthesis of resin (2) having polymerizable unsaturated group In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 171 parts by mass of butyl acetate was placed, 257 parts by mass of the phenolic resin (2) obtained in Synthesis Example 2 was dissolved, 1.0 part by mass of dibutylhydroxytoluene and 0.2 parts by mass of methoquinone (p-methoxyphenol) were added, and then 142 parts by mass of glycidyl methacrylate and 2.0 parts by mass of triethylamine were added, and the reaction was carried out at 120°C for 20 hours while blowing in air, to obtain a resin (2) having a polymerizable unsaturated group. The non-volatile content of this resin (2) having a polymerizable unsaturated group was 70% by mass.

[0121] (Example 3): Synthesis of resin (3) having polymerizable unsaturated group In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 120.4 parts by mass of butyl acetate was placed, 139 parts by mass of the phenolic resin (3) obtained in Synthesis Example 3 was dissolved, 0.7 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone (p-methoxyphenol) were added, and then 142 parts by mass of glycidyl methacrylate and 1.4 parts by mass of triethylamine were added, and the mixture was reacted at 120°C for 20 hours while blowing in air to obtain a resin (3) having a polymerizable unsaturated group. The non-volatile content of this resin (3) having a polymerizable unsaturated group was 70% by mass.

[0122] (Example 4): Synthesis of Resin (4) Having Polymerizable Unsaturated Group In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 104.1 parts by mass of butyl acetate was placed, 101 parts by mass of the phenolic resin (4) obtained in Synthesis Example 4 was dissolved, 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone (p-methoxyphenol) were added, and then 142 parts by mass of glycidyl methacrylate and 1.2 parts by mass of triethylamine were added, and the reaction was carried out at 120°C for 20 hours while blowing in air, to obtain a resin (4) having a polymerizable unsaturated group. The non-volatile content of this resin (4) having a polymerizable unsaturated group was 70% by mass.

[0123] Comparative Example 1: Synthesis of Resin (C-1) Having Polymerizable Unsaturated Group In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 103.7 parts by mass of butyl acetate was placed, 100 parts by mass of phenol novolak resin "PHENOLITE TD-2093" (DIC Corporation, phenolic hydroxyl group equivalent weight 100g / equivalent) was dissolved, 0.6 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone (p-methoxyphenol) were added, and then 142 parts by mass of glycidyl methacrylate and 1.2 parts by mass of triethylamine were added. The reaction was carried out at 120°C for 20 hours while blowing in air, to obtain a resin (C-1) having a polymerizable unsaturated group. The non-volatile content of this resin (C-1) having a polymerizable unsaturated group was 70% by mass.

[0124] (Examples 5 to 8, Comparative Example 2): Preparation of curable resin composition and evaluation of linear expansion coefficient and adhesion <Preparation of Curable Resin Composition> Curable resin compositions (1) to (4) and (C1) were obtained by mixing the components shown in Table 1. The following tests were carried out on the curable resin compositions.

[0125] <Measurement and evaluation of linear expansion coefficient> The curable resin compositions (1) to (4) and (C1) obtained above were applied to a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Kaisha) using an applicator to a thickness of 50 μm, and dried at 80° C. for 30 minutes. Next, the dried coating film was irradiated with 10 kJ / m using a metal halide lamp. 2After irradiating the laminate with ultraviolet light, the laminate was cured at 160 degrees for 1 hour to harden the coating, obtaining a laminate. The laminate was cut into a size of 20 mm x 5 mm, which was used as a test piece. Using a thermomechanical analyzer (TMA: Shimadzu Corporation's "TMA-60"), the test piece was subjected to thermomechanical analysis in a nitrogen atmosphere in tension mode under the following measurement conditions. Measurement conditions Measurement load: 6mN Heating rate: 10℃ / min twice Measurement temperature range: 1st time: 0℃ to 220℃, 2nd time: -60℃ to 240℃ The measurement under the above conditions was carried out twice for the same sample, and the average linear expansion coefficient in the temperature range of 40°C to 60°C in the second measurement was evaluated as the linear expansion coefficient (linear expansion coefficient). The results are shown in Table 1. The lower the linear expansion coefficient, the more excellent the properties.

[0126] <Evaluation of Adhesion> The curable resin compositions (1) to (4) and (C1) obtained above were applied to a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Kaisha) using an applicator to a thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply the applied coating to the copper foil. 2 After irradiating with ultraviolet light of 1000 nm, the sample was heated at 160°C for 1 hour to obtain a test piece 2. The test piece 2 was cut into a size of 1 cm wide and 12 cm long, and the 90° peel strength was measured using a peel tester ("A&D Tensilon" manufactured by A&D Corporation, peel speed 50 mm / min). The results are shown in Table 1. A higher peel strength (N / cm) value indicates better adhesion. The peel strength was measured under the following conditions. Measuring equipment: "A&D Tensilon" manufactured by A&D Co., Ltd. Test piece: width 1cm, length 12cm Peel tester Test speed: 50mm / min Conditions: Temperature 23℃, humidity 50%

[0127] [Table 1]

[0128] The specifications of each component shown in Table 1 are as follows: Acrylate monomer (M-240): EO-modified diacrylate of bisphenol A (Miwon Specialty Chemical's "Miramaer M240") Photopolymerization initiator: IGM Resins, product name "Omnirad-907"

[0129] From Table 1, it can be seen that the curable resin compositions of the Examples can exhibit excellent adhesion and a low linear expansion coefficient in the obtained cured products, as compared with the Comparative Examples.

[0130] According to the present invention, it is possible to provide a curable resin composition which is capable of giving a cured product having high adhesion and a low linear expansion coefficient. Furthermore, according to the present invention, it is possible to provide a cured product having high adhesion and a low coefficient of linear expansion, and an article using the same.

Claims

1. A calixarene-containing phenolic resin (A) containing a phenolic hydroxyl group-containing compound (a1) and a linking compound (a2) as essential reaction raw materials (1); (B) a (meth)acrylate compound having an epoxy group; is used as the essential reactant (2), A resin having a polymerizable unsaturated group, characterized in that the calixarene content in the calixarene-type phenolic resin (A) is 10% or more in terms of area ratio in gel permeation chromatography (GPC).

2. 2. The resin having a polymerizable unsaturated group according to claim 1, wherein the phenolic hydroxyl group-containing compound (a1) has an aromatic ring, and the linking compound (a2) has an electrophilic reactive group that shows electrophilic reactivity with the aromatic ring.

3. The resin having a polymerizable unsaturated group according to claim 2 , wherein the linking compound (a2) is one or more compounds selected from the group consisting of the following (i) and (ii): (i) An organic compound (a2-1) which contains two or more ethylenically unsaturated bonds or linking functional groups as the electrophilic reactive groups and which may contain an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom. (ii) an organic compound (a2-2) which contains one or more aldehyde groups as the electrophilic reactive group and which may contain an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom; The resin having a polymerizable unsaturated group according to claim 2 , wherein the linking functional group is a haloalkyl group, a hydroxyalkyl group, or an alkoxyalkyl group.

4. The resin having a polymerizable unsaturated group according to claim 1, wherein the ratio of the phenolic hydroxyl group-containing compound (a1) to the linking compound (a2) is such that the number of moles of the linking compound (a2) is in the range of 0.9 to 1.2 per mole of the phenolic hydroxyl group-containing compound (a1).

5. 3. The resin having a polymerizable unsaturated group according to claim 1 or 2, wherein the amount of the (meth)acrylate compound (B) having an epoxy group used is in a range such that the number of moles of the epoxy group in the (meth)acrylate compound (B) having an epoxy group is 0.9 to 1.1 moles per mole of the phenolic hydroxyl group in the phenolic hydroxyl group-containing compound (a1).

6. A curable resin composition comprising the resin having a polymerizable unsaturated group according to claim 1 or 2 and a photopolymerization initiator.

7. The curable resin composition according to claim 4, further comprising another resin component.

8. A cured product of the curable resin composition according to claim 6.

9. An article having a coating film comprising the cured product according to claim 8.

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