Resin having acid group and polymerizable unsaturated group, curable resin composition, cured product, insulation material, solder resist resin material and resist member

Abstract

To provide a resin having excellent alkali developability with high adhesion and a low linear expansion coefficient in a cured product, and also to provide a curable resin composition, a cured product, an insulation material, a solder resist resin material and a resist member using the same.SOLUTION: A resin having an acid group and 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; a (meth)acrylate compound (B) having an epoxide group; and a polybasic acid anhydride (C). 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 body-containing 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 an acid group and a polymerizable unsaturated group, a curable resin composition, a cured product, an insulating material, a resin material for a solder resist, and a resist member. [Background technology]

[0002] When mounting and soldering electronic components on a printed wiring board, solder resist is widely used as a material to prevent solder from adhering to areas other than the mounted area and to form a coating that semi-permanently prevents oxidation and corrosion of the wiring. As a technology for forming such solder resist patterns, the photoresist method, which can accurately form fine patterns, is the mainstream, and in particular, due to environmental considerations, the alkaline development type liquid photoresist method has become the mainstream.

[0003] Furthermore, printed wiring boards are becoming increasingly finer, multi-layered, and single-board in order to achieve higher density, and the mounting method is also shifting to surface mount technology (SMT).As a result, there is an increasing demand for solder resist films that are finer, have a high Tg, high resolution, high precision, and high reliability.

[0004] As a conventional curable composition for a solder resist, it is known to use a curable composition containing a resin (resin component) having an acid group and a polymerizable unsaturated group, which uses a cresol novolac epoxy resin, which is a type of epoxy resin derived from a phenolic resin, as a reaction raw material (e.g., Patent Document 1). However, this composition does not satisfy the increasingly high demand for properties such as excellent alkaline developability, and high adhesion and low linear expansion coefficient in the cured product, and is therefore not sufficient for today's market demands.

[0005] Therefore, there has been a demand for a material that has excellent alkaline developability and is capable of forming a cured product having high adhesion and a low linear expansion coefficient. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 8-259663 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a resin that has excellent alkali developability, and in a cured product thereof has high adhesion and a low linear expansion coefficient, and to provide a curable resin composition, a cured product, an insulating material, a resin material for a solder resist, and a resist member using the same. [Means for solving the problem]

[0008] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a resin having an acid group and a polymerizable unsaturated group, which resin has as essential raw materials a specific calixarene-containing phenolic resin, a (meth)acrylate compound having an epoxy group, and a polybasic acid anhydride, as well as a curable resin composition containing the same, a cured product made from the curable resin composition, an insulating material, and a resist member, and have thereby completed the present invention.

[0009] Suitable embodiments of the present disclosure include the following [1] to

[10] . [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); a (meth)acrylate compound (B) having an epoxy group; a polybasic acid anhydride (C); is an essential reactant (2), A resin having an acid group and a polymerizable unsaturated group, characterized in that the calixarene content in the calixarene-containing phenolic resin (A) is 10% or more in terms of area ratio in gel permeation chromatography (GPC). [2] The resin having an acid group and 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 an acid group and 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 in the range of 0.9 to 1.1 moles of the epoxy group contained in the (meth)acrylate compound (B) having an epoxy group per mole of the phenolic hydroxyl group contained in the phenolic hydroxyl group-containing compound (a1). [4] The resin having an acid group and a polymerizable unsaturated group according to any one of the above [1] to [3], wherein the amount of the polybasic acid anhydride (C) used is in the range of 0.2 to 1.05 mol per 1 mol of the phenolic hydroxyl group-containing compound (a1). [5] The resin having an acid group and a polymerizable unsaturated group according to any one of the above [1] to [4], wherein the phenolic hydroxyl group-containing compound (a1) has an aromatic ring, and the linking compound (a2) has an electrophilic reactive group that exhibits electrophilic substitution reactivity with the aromatic ring. [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 compounds selected from the group consisting of the following (i) and (ii): (i) an organic compound (a2-1) containing two or more ethylenically unsaturated bonds or linking functional groups as the electrophilic reactive groups, which may contain an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom; (ii) an organic compound (a2-2) containing one or more aldehyde groups as the electrophilic reactive groups and optionally containing 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 containing the resin having an acid group and 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 item [5], further comprising a resin (D) having an acid group and a polymerizable unsaturated group other than the resin having an acid group and a polymerizable unsaturated group. [9] A cured product of the curable resin composition described in [7] or [8] above.

[10] An insulating material comprising the curable resin composition according to [7] or [8] above.

[11] A resin material for a solder resist, comprising the curable resin composition according to [7] or [8] above.

[12] A resist member made using the resin material for a solder resist according to

[11] above. [Effects of the Invention]

[0010] The resin having an acid group and a polymerizable unsaturated group of the present invention is an alkali-soluble resin having excellent alkali developability, and the cured product has high adhesion and a low coefficient of linear expansion. 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 in solder resist applications. [Brief explanation of the drawings]

[0011] [Figure 1] An example of a GPC chart of a phenolic resin obtained by a method according to the following synthesis example is shown below. DETAILED DESCRIPTION OF THE INVENTION

[0012] The following describes in detail an embodiment of the present invention (hereinafter referred to as the "present embodiment"); however, the present disclosure is not limited to the following description and can be implemented in various modifications within the scope of its gist.

[0013] -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 act as 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 target resin having an acid group and a polymerizable unsaturated group or its precursor compound (e.g., a calixarene-containing phenolic resin) through a chemical reaction (e.g., a polymerization reaction, an etherification reaction, etc.).

[0014] For the sake of convenience, the present specification distinguishes between the reaction raw material for the resin having an acid group and a polymerizable unsaturated group 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 an acid group and a polymerizable unsaturated group, as reaction raw material (1).

[0015] In this specification, the term "phenolic resin" refers to a resin containing a phenolic hydroxyl group in its structure.

[0016] Examples of the "alkyl group" in this specification include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-)heptyl group, (n-)octyl group, (n-)nonyl group, (n-)decyl group, (n-)undecyl group, (n-)dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclononyl group.

[0017] As used herein, the term "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.

[0018] 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.

[0019] 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, and a nonyloxy group.

[0020] As used herein, the term "aryl group" includes a phenyl group, a naphthyl group (1-naphthyl group or 2-naphthyl group), an anthracenyl group, a phenanthrenyl group, a naphthacenyl group, a chrysenyl group, a triphenylenyl group, a pyrenyl group, and the like.

[0021] 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.

[0022] 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-.

[0023] In this specification, "(meth)acrylate" means acrylate and / or methacrylate. Also, "(meth)acryloyl" means acryloyl and / or methacryloyl. Furthermore, "(meth)acrylic" means acrylic and / or methacrylic.

[0024] (Resin having an acid group and a polymerizable unsaturated group) The present disclosure provides: 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); a (meth)acrylate compound (B) having an epoxy group; a polybasic acid anhydride (C); is an essential reactant (2), The calixarene-containing phenolic resin (A) has a calixarene content of 10% or more in terms of area ratio in gel permeation chromatography (GPC). is.

[0025] <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) as a polymer (or an inclusion compound) having a group containing 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).

[0026] The linking compound (a2) can 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). a1 and a repeating unit U derived from the linking compound (a2). a2 and are alternately linked in a cyclic fashion, 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 those. [ka]

[0027] (In the above general formula (1), U a1 is a repeating unit derived from the phenolic hydroxyl group-containing compound (a1) described below, and U a2 is a repeating unit derived from the linking compound (a2) described below, and n1 is an integer of 2 or more. The structure of the calixarene compound will be described in more detail below.

[0028] The lower limit of the calixarene content in the calixarene-containing phenolic resin (A), measured by area ratio in gel permeation chromatography (GPC), is preferably 5% or more, 10% or more, 13% or more, 15% or more, and 18% or more, in that order. The upper limit of the calixarene content, measured by area ratio in gel permeation chromatography (GPC), is preferably 90% or less, 88% or less, and 78% or less, in that order, in that order, in that order. Because the calixarene molecules are uniform, the resin having acid groups and polymerizable unsaturated groups formed from the calixarene-containing phenolic resin (A) is considered to have excellent alkali developability and a low linear expansion coefficient when cured.

[0029] <<Phenolic hydroxyl group-containing 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. In the 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 selected from the group consisting of substituents (for example, one or more selected from the group consisting of halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, carboxylic acids, and amino groups, and preferably the group having the R 1 )), or a structure in which two or more of the aromatic rings are linked by 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).

[0030] In the above general formula (a1), R 1 is preferably any one of 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.

[0031] 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.

[0032] Preferred examples of the phenolic hydroxyl group-containing compound (a1) of this embodiment include compounds represented by any of the following formulae (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 fused 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 the substituent (R ) is on each of the two benzene rings, 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 number of substituents in one molecule.

[0033] 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. Furthermore, when the number of phenolic hydroxyl groups is more than one, it is preferable that the ortho and para positions relative to each phenolic hydroxyl group coincide (i.e., the phenolic hydroxyl groups are located at the meta positions relative to each other), since this structure makes it easy to produce a calixarene compound.

[0034] 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 diols, polynaphthylene ether diols, and trihydroxynaphthalene. Among these, compounds having one phenolic hydroxyl group (phenol, cresol, xylenol, diethylphenol, trimethylphenol, triethylphenol, diphenylphenol, triphenylphenol, 1-naphthol, 2-naphthol) and compounds having two phenolic hydroxyl groups located at meta positions (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.

[0035] <<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). Furthermore, the linking compound (a2) may contain oxygen atoms, nitrogen atoms, sulfur atoms, and / or halogen atoms in addition to carbon atoms and hydrogen atoms.

[0036] When the linking compound (a2) of this embodiment has an electrophilic reactive group that exhibits electrophilic substitution reactivity or electrophilic addition reactivity, it can be easily reacted with a compound such as a cationoid reagent in an electrophilic substitution reaction (ArS E ), the aromatic ring in the phenolic hydroxyl group-containing compound (a1) can react with the linking compound (a2) to link them (in other words, one or more hydrogen atoms in the aromatic ring are substituted). Furthermore, 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 sequentially, such as in the reaction between phenol and an aldehyde compound such as formaldehyde, as typified by novolac resins or resol resins, 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).

[0037] The electrophilic reactive group is not particularly limited as long as it is a group that forms a cation such as a so-called cationoid, since the aromatic ring in the phenolic hydroxyl group-containing compound (a1) and the linking compound (a2) can react and link the two through an electrophilic substitution reaction or an electrophilic addition reaction. 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).

[0038] The ethylenically unsaturated bond group preferably has a group represented by the following formula (i): Furthermore, the linking functional group preferably has a group represented by the following formula (ii): [ka] (In the above formulas (i) and (ii), * represents a bond to another atom, E represents an electron-withdrawing group, and is preferably a group selected from the group consisting of a halogen atom (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 are no bonds between and C, R ii1 In more detail, when E is —O— (oxygen atom), the following formula (ii-1) [ka] represents.)

[0039] 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 moiety) 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 form a bond.

[0040] 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.

[0041] The haloalkyl group is not particularly limited, and 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 iodinated 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 closest to the end. During the polymerization reaction, a cationoid is easily produced by the halogen atoms in the linking compound (a2), which is thought to link the linking compound (a2) and the phenolic hydroxyl group-containing compound (a1).

[0042] 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 closest to the end. It is believed that the hydroxyl group in the linking compound (a2) easily generates a cationoid, and therefore the linking compound (a2) and the phenolic hydroxyl group-containing compound (a1) are linked together.

[0043] 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 closest to the end. It is believed that the oxygen atom in the linking compound (a2) easily generates a cationoid, which links the linking compound (a2) to the phenolic hydroxyl group-containing compound (a1).

[0044] Hereinafter, the linking compound (a2) of this embodiment will be broadly divided into a case where it has two or more electrophilic reactive groups and a case where multiple electrophilic reactive binding sites undergo successive reactions, and will be explained below.

[0045] That is, the linking compound (a2) of this embodiment is preferably one or more compounds selected from the group consisting of the following (i) and (ii):

[0046] (i) Organic compounds (a2-1) containing two or more ethylenically unsaturated bond groups or linking functional groups as electrophilic reactive groups, which may contain oxygen atoms, nitrogen atoms, sulfur atoms, and / or halogen atoms.

[0047] (ii) an organic compound (a2-2) containing one or more aldehyde groups as electrophilic reactive groups, which may contain an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom; However, the linking functional group is a haloalkyl group, a hydroxyalkyl group, or an alkoxyalkyl group.

[0048] - 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 optionally containing 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.

[0049] When the bond represented by the dashed line in the 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).

[0050] [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 represents a single bond or a divalent group. In the general formula (I-1), the divalent group for D is not particularly limited, and examples thereof include divalent hydrocarbon groups which may contain an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom, 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 an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom" 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 obtained by substituting any of these groups 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, a halogen atom, or a hydroxyl group.

[0051] 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 with a substituent; or a divalent group formed by linking one or more arylene groups having 6 to 30 carbon atoms which may be substituted with a substituent and optionally one or more divalent groups other than the arylene groups; and more preferred are a phenylene group, biphenylene group, or naphthalene group which may be substituted with a substituent; or a divalent group formed by linking one or more phenylene groups which may be substituted with a substituent and optionally one or more other divalent groups (i.e., a divalent group containing a benzene ring).

[0052] 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 i5are each independently a monovalent substituent, and represent, for example, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen atom, or an acid group; i1 is 0 or an integer of 1 to 4; L i1 is a divalent linker, and is, for example, an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, a carbonyl group (-C(=O)-), -SO2-, -NH-, or -N=N-, and i2 and i3 are each independently an integer of 1 to 4. In the above general formula (I-1), Z 1 and Z 2 Preferably, each 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. 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 R13 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 are each independently a single bond or an alkylene group having 1 to 20 carbon atoms, and D is a divalent group as described above.

[0053] (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. When a bond represented by a broken 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 (for example, a haloalkylene group, a hydroxyalkylene group, or an alkoxyalkylene group), D 1represents a central structure, preferably a tetravalent group, and specifically, preferably has an alicyclic group. In the above general formula (I-2), D 1 represents 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 fused ring, bridged ring (e.g., bicyclo ring), or spiro ring formed by combining two or more of these monocyclic cycloalkanes, or a polycyclic structure formed by combining these. Furthermore, the alicyclic group may be substituted with one or more (e.g., 1 to 4) substituents, if necessary. Examples of the substituent 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.

[0054] 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 (e.g., alkenylene groups having 2 to 20 carbon atoms) 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.

[0055] 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; bromide 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.

[0056] 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.

[0057] 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.

[0058] 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 formula (I-2.1) and general formula (I-2.2).

[0059] [ka] (In the above general formula (I-2.1), L 3 , L 4 , L5 and L 6 each 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.

[0060] (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.) Specific examples of the linking compound (a2) of this embodiment include octahydrobiphenylene, octahydroindacene, octahydrofluorene, decahydroanthracene, decahydrophenanthrene, tetradecahydronaphthacene, tetradecahydrochrysene, and compounds represented by the following structural formula:

[0061] [ka] and the like.

[0062] Other specific examples of the linking compound (a2) of the present embodiment include dichlorododecahydrobiphenylene, dichlorododecahydroindacene, dichlorododecahydrofluorene, dichlorotetradecahydroanthracene, dichlorotetradecahydrophenanthrene, dichlorooctadecahydronaphthacene, dichlorooctadecahydrochrysene, difluorotetradecahydroanthracene, dibromotetradecahydroanthracene, and diiodotetradecahydroanthracene.

[0063] Other specific examples of the linking compound (a2) of the present embodiment include dihydroxydodecahydrobiphenylene, dihydroxydodecahydroindacene, dihydroxydodecahydrofluorene, dihydroxytetradecahydroanthracene, dihydroxytetradecahydrophenanthrene, dihydroxyoctadecahydronaphthacene, and dihydroxyoctadecahydrochrysene.

[0064] Other specific examples of the linking compound (a2) of the present embodiment include dimethoxydodecahydrobiphenylene, dimethoxydodecahydroindacene, dimethoxydodecahydrofluorene, dimethoxytetradecahydroanthracene, dimethoxytetradecahydrophenanthrene, dimethoxyoctadecahydronaphthacene, dimethoxyoctadecahydrochrysene, and diethoxytetradecahydroanthracene.

[0065] -A linking compound (a2) (hereinafter also referred to as organic compound (a2-2)) whose electrophilic reactive bonding site reacts successively multiple times- The linking compound (a2) of this 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), and therefore two or more phenolic hydroxyl group-containing compounds (a1) can be linked via the linking compound (a2).

[0066] 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. In the above general formula (II), D 2 are each independently a hydrogen atom or a monovalent substituent. The "monovalent substituent" is not particularly limited, but examples thereof include 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 obtained by substituting any of these 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, a carboxyl group, etc.

[0067] The linking compound (a2) or organic compound (a2-2) of 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. R ii1 and R ii2 are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen atom, or a hydroxyl group, and nii1 is an integer of 0 to 4. nii2 is an integer of 0 to 7.

[0068] 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; and 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.

[0069] <<Preferred embodiment of the linking compound (a2) of this embodiment>> A preferred embodiment of the linking compound (a2) of this embodiment is one or more compounds selected from the group consisting of S8, SCl2, compounds represented by the above formula (I) (including compounds represented by general formulas (I-1.1) and (I-1.2)), and compounds represented by the above formula (II) (including compounds represented by formulas (II-1) to (II-4)).

[0070] <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 that has excellent alkali developability and is capable of forming a cured product having high adhesion and a low linear expansion coefficient can be obtained.

[0071] <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). a1and a repeating unit U derived from the linking compound (a2). a2 and are alternately linked in a cyclic fashion, 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 those. [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.

[0072] <<Repeating unit U derived from phenolic hydroxyl group-containing compound (a1) a1 >> The repeating unit U in the general formula (1) a1 may have a structure 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. In the general formula (a1′), * indicates that the 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 on <<Phenolic Hydroxyl Group-Containing Compound (a1)>>.

[0073] Repeating unit U a1Examples of the structure that can be possessed by include structures represented by the following general formulas (3-1) to (3-5). [ka] In the above general formulas (3-1) to (3-5), * indicates an adjacent repeating unit U a2 represents the linkage site with 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 general formula above 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), one repeating unit U a1 p and q may be substituted on any benzene ring present in one repeating unit U a1 The number of substituents in the group is shown.

[0074] Repeating unit U a1 Specific examples of the repeating unit U are those derived from the specific examples of the phenolic hydroxyl group-containing compound (a1) shown in the section on "phenolic hydroxyl group-containing compound (a1)" (in which two hydrogen atoms bonded to the aromatic rings in these compounds are bonded to adjacent repeating units U a2 (Repeating units having a structure converted into a linking site with the repeating unit).

[0075] <<Repeating unit U derived from linking compound (a2) a2 >> Repeating unit U a2 may have different structures depending on whether they are (i) organic compound (a2-1) or (ii) organic compound (a2-2). Preferred embodiments of (i) organic compound (a2-1) or (ii) organic compound (a2-2) are described below.

[0076] - a repeating unit U derived from the 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.

[0077] 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)

[0078] 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 -] moiety, one or more leaving groups are generated, and [E 2 -CR 24 R 25 -] moiety generates one or more leaving groups. * indicates the adjacent repeating unit U a1 represents the linkage site with 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 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 formulas (I'-2.1) to (I'''-2.1), 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 26 , R27 , 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.

[0079] [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 general formula (I'-2.2) is the same as above [E 3 -CR 30 One or more leaving groups are generated from the [E =] moiety. 4 -CR 31 =] represents the generation of one or more leaving groups.) - a repeating unit U derived from the 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'):

[0080] [ka] (In the above general formulas (II) and (II'), D 2are 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, groups obtained by substituting any of these 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. 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.

[0081] [ka] (In the above formulas (II'-1) to (II'-4), k is an integer of 1 to 20. R ii1 and R ii2 are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen atom, or a hydroxyl group, and nii1 is an integer of 0 to 4. nii2 is an integer of 0 to 7.

[0082] <(Meth)acrylate Compound (B) Having Epoxy Group> The (meth)acrylate compound (B) having an epoxy group of 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 its specific structure as long as it has a (meth)acryloyl group and an epoxy group in its molecular structure, and a wide variety of compounds can be used. Examples include (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); and mono(meth)acrylates of diglycidyl ether compounds, such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. Among these, glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate are preferred, with glycidyl (meth)acrylate being more preferred. These (meth)acrylate compounds having an epoxy group can be used alone or in combination of two or more.

[0083] 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, more preferably 0.95 to 1.1 moles, of epoxy groups in the (meth)acrylate compound (B) having an epoxy group per mole of phenolic hydroxyl groups in the calixarene compound-containing phenolic resin (A), because a curable resin composition having excellent alkali developability and capable of forming a cured product with high adhesion and a low linear expansion coefficient can be obtained.

[0084] <Polybasic acid anhydride (C)> The polybasic acid anhydride (C) of 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.

[0085] Examples of the polybasic acid anhydride (C) include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides, acid halides of aliphatic polybasic acid anhydrides, acid halides of alicyclic polybasic acid anhydrides, and acid halides of aromatic polybasic acid anhydrides.

[0086] Examples of the aliphatic polybasic acid anhydrides include acid 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. Furthermore, the aliphatic hydrocarbon group of the aliphatic polybasic acid anhydride may be either linear or branched, and may have an unsaturated bond in the structure.

[0087] 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 an aromatic ring in other structural positions 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.

[0088] Examples of the aromatic polybasic acid anhydride include acid anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid.

[0089] These polybasic acid anhydrides (C) can be used alone or in combination of two or more. Among these, tetrahydrophthalic anhydride, succinic anhydride, and cyclohexanedicarboxylic anhydride are preferred because they can give a curable resin composition that has excellent alkali developability and can form a cured product having high adhesion and a low linear expansion coefficient.

[0090] The amount of the polybasic acid anhydride (C) used is preferably in the range of 0.2 to 1.05 mol, more preferably 0.3 to 1.0, and even more preferably 0.3 to 0.95 mol per mol of the phenolic hydroxyl group-containing compound (a1), in order to obtain a curable resin composition that has excellent alkali developability and is capable of forming a cured product having high adhesion and a low linear expansion coefficient.

[0091] <Other compounds> The resin having an acid group and a polymerizable unsaturated group of the present invention may, if necessary, use compounds other than the calixarene-containing phenolic resin (A), the (meth)acrylate compound having an epoxy group (B), and the polybasic acid anhydride (C) as raw materials or reaction raw materials.

[0092] Examples of the other compounds include unsaturated monobasic acid anhydrides.

[0093] 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.

[0094] The total mass proportion of the calixarene-containing phenolic resin (A), the epoxy group-containing (meth)acrylate compound (B), and the polybasic acid anhydride (C) in the raw material (solid content) of the resin having an acid group and a polymerizable unsaturated group of the present invention is preferably 70 mass% or more, more preferably 80 mass% or more, because this results in a curable resin composition that can form a cured product having excellent alkali developability, high adhesion, and a low linear expansion coefficient. The upper limit of this total mass proportion can be 100 mass% or less, or 98 mass% or less.

[0095] <Method of producing a resin having an acid group and a polymerizable unsaturated group> The resin having an acid group and a polymerizable unsaturated group of the present invention may be produced by any method without any particular limitation. For example, the resin having an acid group and a polymerizable unsaturated group of the present invention may be produced 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), are reacted all at once with the reaction raw materials (2) containing the epoxy group-containing (meth)acrylate compound (B) and the polybasic acid anhydride (C), 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 materials (2) containing the epoxy group-containing (meth)acrylate compound (B) and the polybasic acid anhydride (C). Among these, a preferred method is one in which the phenolic hydroxyl group-containing compound (a1) is first reacted with the compound (a2-1) and / or (a2-2) in the presence of an acidic catalyst at a temperature of 0 to 200°C to produce a calixarene-containing phenolic resin (A), and then the resulting 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 of 80 to 140°C, and then a polybasic acid anhydride (C) is added and reacted at a temperature of 80 to 140°C to produce a resin having an acid group and a polymerizable unsaturated group of the present invention, because the reaction can be easily controlled.

[0096] When the calixarene-containing phenolic resin (A) and the (meth)acrylate compound (B) having an epoxy group are reacted in the presence of a basic catalyst, a step of neutralizing the basic catalyst may be further carried out, if necessary. The step of neutralizing the basic catalyst is preferably carried out after adding the polybasic acid anhydride (C) to the reaction product of the calixarene-containing phenolic resin (A) and the (meth)acrylate compound (B) having an epoxy group and carrying out the reaction at a temperature in the range of 80 to 140°C.

[0097] 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.

[0098] In the resin having an acid group and a polymerizable unsaturated group of this embodiment, the amount of a basic catalyst (for example, an amine compound, such as triethylamine, is used in the examples) remaining in the resin having an acid group and a polymerizable unsaturated group is preferably 100 μg or less, more preferably 50 μg or less, per 1 g of the solid content of the resin having an acid group and a polymerizable unsaturated group. In the curable resin composition described below, the amount is preferably 100 μg or less, more preferably 50 μg or less, per 1 g of the solid content of the curable resin composition.

[0099] 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 an acid group and 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 an acid group and a polymerizable unsaturated group, it is less likely to cause deterioration in developability than when an amine compound such as triethylamine remains, and therefore the amount of the phosphorus-based basic catalyst remaining does not need to be strictly specified.

[0100] 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; and organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid. These acidic compounds may be used alone or in combination of two or more.

[0101] The synthesis of the calixarene-containing phenolic resin (A) or the synthesis of the resin having an acid group and 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 organic compound (a2-1) and / or the organic compound (a2-2), the (meth)acrylate compound having an epoxy group (B), and the polybasic acid anhydride (C) may also be carried out in an organic solvent, if necessary. A polymerization inhibitor or an antioxidant may also be used, if necessary.

[0102] 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. 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.

[0103] 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, dipropylamine, 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 suitable basic catalysts include organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octoate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octoate and bismuth octoate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. 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 solid form.

[0104] The amount of the basic catalyst used is preferably in the range of 0.01 to 5 parts by mass, more preferably in the range of 0.05 to 2 parts by mass, relative to a total of 100 parts by mass of the calixarene-containing phenolic resin (A), the (meth)acrylate compound having an epoxy group (B), and the polybasic acid anhydride (C), since a curable resin composition having excellent alkali developability and capable of forming a cured product having high adhesion and a low linear expansion coefficient can be obtained.

[0105] 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 suitable organic solvents 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 ethers, dialkylene glycol monoalkyl ethers, and dialkylene glycol monoalkyl ether acetates; vegetable oils 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. Separate organic solvents may be selected and used for the reaction to produce the calixarene-containing phenolic resin (A) and the reaction to produce a resin having acid groups and polymerizable unsaturated groups from the calixarene-containing phenolic resin (A). Alternatively, different organic solvents may be used before and after each reaction.

[0106] In addition, commercially available organic solvents can also be used. Examples of commercially available organic solvents include "No. 1 Spindle Oil," "No. 3 Solvent," "No. 4 Solvent," "No. 5 Solvent," "No. 6 Solvent," "Naphtesol 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.

[0107] 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, as this improves the reaction efficiency.

[0108] The organic solvent may be used in combination with water, and the ratio of water to be used in the mixed solvent is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the mixed solvent.

[0109] 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 -trimethyl-1,2-dihydroquinoline and other phenolic compounds, hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, diphenoquinone and other quinone compounds, melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N-(1,2-dihydroquinoline), and other quinone compounds.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 with 2,4,4-trimethylpentene, and reaction products of diphenylamine with 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-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline ... -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 octadecan-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, phosphite compounds such as tris(2,4-di-tert-butylphenyl) phosphite, bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate Examples of polymerization inhibitors include zinc compounds such as zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, and 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.

[0110] 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.

[0111] Commercially available examples of the polymerization inhibitor and 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.

[0112] <Curable resin composition> The resin having an acid group and 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 an acid group and a polymerizable unsaturated group.

[0113] 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.

[0114] 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. 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.

[0115] <Other Resins Having Acid Groups and Polymerizable Unsaturated Groups (D)> The curable resin composition of the present disclosure may further contain a resin (D) having an acid group and a polymerizable unsaturated group other than the resin having an acid group and a polymerizable unsaturated group of the present embodiment (hereinafter also referred to as "another resin (D) having an acid group and a polymerizable unsaturated group").

[0116] Examples of the acid group contained in the resin (D) include a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. Among these, a carboxyl group is preferred as the acid group because it exhibits better developability.

[0117] Examples of the polymerizable unsaturated group contained in the resin (D) include a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, and a vinyl ether group.

[0118] When the curable resin composition of the present embodiment contains the resin (D) having another acid group and a polymerizable unsaturated group, the amount of the resin (D) having another acid group and a polymerizable unsaturated group added is preferably, for example, in the range of 0.5 to 20 mass % in the curable resin composition.

[0119] In the curable resin composition of the present embodiment, the optional component resin (D) having another acid group and a polymerizable unsaturated group may be any resin other than the above-mentioned acid group- and polymerizable unsaturated group-containing resin, as long as the resin has an acid group and a polymerizable unsaturated group. Examples thereof include epoxy resin (DI) having an acid group and a polymerizable unsaturated group, urethane resin (D-II) having an acid group and a polymerizable unsaturated group, acrylic resin (D-III) having an acid group and a polymerizable unsaturated group, amide-imide resin (D-IV) having an acid group and a polymerizable unsaturated group, acrylamide resin (DV) having an acid group and a polymerizable unsaturated group, and ester resin (D-VI) having an acid group and a polymerizable unsaturated group.

[0120] The other resin (D) having an acid group and a polymerizable unsaturated group has a chemical structure different from that of the resin having an acid group and a polymerizable unsaturated group of the present embodiment, and therefore the resin having an acid group and a polymerizable unsaturated group of the present embodiment is excluded from the other resin (D) having an acid group and a polymerizable unsaturated group.

[0121] Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphate group, etc. Examples of the polymerizable unsaturated group include a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, a vinyl ether group, etc.

[0122] The following will be described in the order of epoxy resin (DI) having an acid group and a polymerizable unsaturated group, urethane resin (D-II) having an acid group and a polymerizable unsaturated group, acrylic resin (D-III) having an acid group and a polymerizable unsaturated group, amide-imide resin (D-IV) having an acid group and a polymerizable unsaturated group, acrylamide resin (DV) having an acid group and a polymerizable unsaturated group, and ester resin (D-VI) having an acid group and a polymerizable unsaturated group. Note that the epoxy resin (DI), urethane resin (D-II), acrylic resin (D-III), amide-imide resin (D-IV), acrylamide resin (DV), and ester resin (D-VI) all have chemical structures different from those of resins having an acid group and a polymerizable unsaturated group.

[0123] <<Epoxy resin (DI) containing acid groups and polymerizable unsaturated groups>> Examples of the epoxy resin (DI) having an acid group and a polymerizable unsaturated group of the present embodiment include an acid group-containing epoxy (meth)acrylate resin having an epoxy resin, an unsaturated monobasic acid, and a polybasic acid anhydride as essential raw materials, and an acid group- and urethane group-containing epoxy (meth)acrylate resin having an epoxy resin, an unsaturated monobasic acid, a polybasic acid anhydride, a polyisocyanate compound, and a hydroxyl group-containing (meth)acrylate compound as reaction raw materials.

[0124] Examples of the epoxy resin include bisphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol novolac-type epoxy resins, naphthol novolac-type epoxy resins, naphthol-phenol co-condensed novolac-type epoxy resins, naphthol-cresol co-condensed novolac-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, dicyclopentadiene-phenol addition reaction-type epoxy resins, biphenyl aralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dihydroxybenzene-type epoxy resins, trihydroxybenzene-type epoxy resins, and oxazolidone-type epoxy resins. These epoxy resins can be used alone or in combination of two or more.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Esters, acid halides, and acid anhydrides of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following general formula (6) can also be used.

[0130] [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. Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

[0131] An example of the (poly)ester chain is a (poly)ester chain represented by the following general formula (7).

[0132] [ka] (In the above general formula (7), R 71 and R 72 represents an alkylene group having 1 to 10 carbon atoms, and n 71 represents an integer from 1 to 5.) An example of the (poly)carbonate chain in the above general formula (6) is a (poly)carbonate chain represented by the following general formula (8).

[0133] [ka] (In the above general formula (8), R 81 represents an alkylene group having 1 to 10 carbon atoms, and n 81 represents an integer from 1 to 5.) The molecular weight of the compound represented by formula (6) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400.

[0134] Examples of the aromatic hydrocarbon chain in the general formula (6) include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. Furthermore, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used.

[0135] As the polybasic acid anhydride, the same as those exemplified above as the polybasic acid anhydride (C) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0136] 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; 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 versions of these compounds. These polyisocyanate compounds can be used alone or in combination of two or more.

[0137] [ka] [In the above general formula (9), R 92 and R 93 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. 91 are each independently either an alkyl group having 1 to 4 carbon atoms or a bonding point connecting the structural portion represented by general formula (9) via a methylene group marked with an *. 1 is 0 or an integer of 1 to 3, and m is an integer of 1 to 15. As the hydroxyl group-containing (meth)acrylate compound, the same compounds as those exemplified above as compounds having a hydroxyl group and a (meth)acryloyl group can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more types.

[0138] The method for producing the epoxy resin (DI) having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the epoxy resin (I) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0139] Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers, and dialkylene glycol monoalkyl ether acetates; 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. The amount of the organic solvent used is preferably about 0.1 to 5 times the total mass of the reaction raw materials, as this improves reaction efficiency.

[0140] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0141] <<Urethane resin having acid groups and polymerizable unsaturated groups (D-II)>> Examples of the urethane resin (D-II) having an acid group and a polymerizable unsaturated group of this embodiment include those obtained by reacting a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, a carboxyl group-containing polyol compound, and, if necessary, a polybasic acid anhydride, with a polyol compound other than the carboxyl group-containing polyol compound; and those obtained by reacting a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, a polybasic acid anhydride, and a polyol compound other than the carboxyl group-containing polyol compound.

[0142] As the polyisocyanate compound, the same compounds as those exemplified above as the polyisocyanate compounds can be used, and the polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0143] As the hydroxyl group-containing (meth)acrylate compound, the same compounds as those exemplified above as compounds having a hydroxyl group and a (meth)acryloyl group can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more types.

[0144] Examples of the carboxyl group-containing polyol compound include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, etc. The carboxyl group-containing polyol compounds can be used alone or in combination of two or more.

[0145] As the polybasic acid anhydride, the same as those exemplified above as the polybasic acid anhydride (C) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0146] Examples of polyol compounds other than the carboxyl group-containing polyol compounds include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified 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 polyol compounds; and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various polyol compounds. The polyol compounds other than the carboxyl group-containing polyol compounds can be used alone or in combination of two or more.

[0147] The method for producing the urethane resin (D-II) having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the urethane resin (D-II) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0148] 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.

[0149] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0150] <<Acrylic resin having acid groups and polymerizable unsaturated groups (D-III)>> Examples of the acrylic resin (D-III) having an acid group and a polymerizable unsaturated group include a reaction product obtained by polymerizing an acrylic resin intermediate, which is obtained by polymerizing, as an essential component, a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group, and then reacting the resulting acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group that can react with the functional group, thereby introducing a (meth)acryloyl group; and a product obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product.

[0151] The acrylic resin intermediate may be copolymerized with the (meth)acrylate compound (α) and, if necessary, other polymerizable unsaturated group-containing compounds. Examples of the other polymerizable unsaturated group-containing compounds include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These compounds may be used alone or in combination of two or more.

[0152] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group possessed by the (meth)acrylate compound (α), but the following combinations are preferred from the viewpoint of reactivity. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferred to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate compound (β). When a carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferred to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When an isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferred to use a hydroxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). The (meth)acrylate compounds (β) can be used alone or in combination of two or more.

[0153] The polybasic acid anhydride can be the same as those exemplified above as the polybasic acid anhydride (C), and the polybasic acid anhydrides can be used alone or in combination of two or more.

[0154] The method for producing the acrylic resin (D-III) having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylic resin (D-III) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0155] 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.

[0156] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0157] <<Amide-imide resin having an acid group and a polymerizable unsaturated group (D-IV)>> Examples of the amide-imide resin having an acid group and a polymerizable unsaturated group include those obtained by reacting an amide-imide resin having an acid group and / or an acid anhydride group with a hydroxyl group-containing (meth)acrylate compound and / or an epoxy group-containing (meth)acrylate compound, and, if necessary, with 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.

[0158] The amide-imide resin may have either an acid group or an acid anhydride group, or both. From the viewpoint of reactivity and reaction control with hydroxyl group-containing (meth)acrylate compounds and (meth)acryloyl group-containing epoxy compounds, it is preferable for it to have an acid anhydride group, and it is more preferable for it to have both an acid group and an acid anhydride group. The acid value of the solid content of the amide-imide resin, measured under neutral conditions, i.e., conditions under which the acid anhydride group is not ring-opened, is preferably in the range of 60 to 350 mg KOH / g. On the other hand, it is preferably in the range of 61 to 360 mg KOH / g, measured under conditions under which the acid anhydride group is ring-opened, such as in the presence of water.

[0159] The amide-imide resin may be, for example, one obtained by reacting a polyisocyanate compound with a polybasic acid anhydride as raw materials.

[0160] As the polyisocyanate compound, the same compounds as those exemplified above as the polyisocyanate compounds can be used, and the polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0161] As the polybasic acid anhydride, the same as those exemplified above as the polybasic acid anhydride (C) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0162] Furthermore, the amide-imide resin may contain, as necessary, a polybasic acid as a reaction raw material in addition to the polyisocyanate compound and polybasic acid anhydride.

[0163] The polybasic acid may be any compound having two or more carboxyl groups in one molecule. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3- Examples of suitable polybasic acids include dicarboxylic acids, 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, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid. Examples of suitable polybasic acids include copolymers of conjugated diene vinyl monomers and acrylonitrile, each having a carboxyl group in its molecule. These polybasic acids can be used alone or in combination.

[0164] As the hydroxyl group-containing (meth)acrylate compound, the same compounds as those exemplified above as compounds having a hydroxyl group and a (meth)acryloyl group can be used, and the hydroxyl group-containing (meth)acrylate compound can be used alone or in combination of two or more types.

[0165] As the epoxy group-containing (meth)acrylate compound, the same compounds as those exemplified above as compounds having an epoxy group and a (meth)acryloyl group can be used, and the epoxy group-containing (meth)acrylate compound can be used alone or in combination of two or more types.

[0166] In the present embodiment, the method for producing the amide-imide resin (D-IV) having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the amide-imide resin (D-IV) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0167] 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.

[0168] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0169] <<Acrylamide resin (DV) containing acid groups and polymerizable unsaturated groups>> Examples of the acrylamide resin (DV) having an acid group and a polymerizable unsaturated group of the present embodiment include those obtained by reacting a phenolic hydroxyl group-containing compound, an alkylene oxide or alkylene carbonate, an N-alkoxyalkyl(meth)acrylamide compound, a polybasic acid anhydride, and, if necessary, an unsaturated monobasic acid.

[0170] The phenolic hydroxyl group-containing compound refers to a compound containing at least one phenolic hydroxyl group in the molecule. Examples of the phenolic hydroxyl group-containing compound include compounds represented by any of the following general formulae (10.1) to (10.5), reaction products in which an aromatic polyhydroxy compound and a compound represented by any of the following general formulae (11.1) to (11.5) are used as essential reaction materials, and novolak-type phenolic resins in which one or more aromatic polyhydroxy compounds or other compounds containing one phenolic hydroxyl group in the molecule are used as reaction materials. Examples of the compound containing at least one phenolic hydroxyl group in the molecule include compounds represented by the following general formulae (10.1) to (10.5).

[0171] [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 each independently represents a hydrogen atom or a methyl group; j 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. The positions of the substituents on the aromatic rings in the general formulae (10.1) to (10.5) are arbitrary. For example, in the naphthalene ring of the general formula (10.2), they may be substituted with any hydrogen atom on the ring. In the general formula (10.3), they may be substituted with any hydrogen atom on the benzene ring present in one molecule of biphenyl. In the general formula (10.4), they may be substituted with any hydrogen atom on the benzene ring present in one molecule of aralkyl. In the general formula (10.5), they may be substituted with any hydrogen atom on the benzene ring present in one molecule. When the number of substituents in one molecule is j, 101 ~j 105 and k 101 ~k 105 This indicates that

[0172] [ka] In the above general formulas (11.1) to (11.5), h 81 represents 0 or 1, R 111 ~R 116 each independently represents a monovalent aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group; k 111 ~k 116 each independently represents 0 or an integer of 1 to 4, and 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, and n 111 represents an integer from 1 to 4.) The compounds represented by the above general formulae (11.1) to (11.5) can be used alone or in combination of two or more kinds.

[0173] Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred because it can provide a curable resin composition capable of forming a cured product having high elongation, photosensitivity, heat yellowing resistance, and adhesion. The alkylene oxides can be used alone or in combination of two or more.

[0174] Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferred because it can provide a curable resin composition capable of forming a cured product having high elongation, photosensitivity, heat yellowing resistance, and excellent adhesion. The alkylene carbonates can be used alone or in combination of two or more.

[0175] 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 compounds can be used alone or in combination of two or more.

[0176] As the polybasic acid anhydride, the same as those exemplified above as the polybasic acid anhydride (C) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0177] As the unsaturated monobasic acid, the same unsaturated monobasic acids as those exemplified above can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0178] The method for producing the acrylamide resin having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylamide resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst or an acidic catalyst, if necessary.

[0179] 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.

[0180] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0181] As the acidic catalyst, the same as those exemplified above as the acidic catalyst can be used, and the acidic catalysts can be used alone or in combination of two or more kinds.

[0182] <<Ester resin containing acid groups and polymerizable unsaturated groups (D-VI)>> Examples of the ester resin (D-VI) having an acid group and a polymerizable unsaturated group of the present embodiment include those obtained by reacting a phenolic hydroxyl group-containing compound with an alkylene oxide or alkylene carbonate, an unsaturated monobasic acid, and a polybasic acid anhydride.

[0183] As the phenolic hydroxyl group-containing compound, the same compounds as those exemplified above as the phenolic hydroxyl group-containing compound can be used, and the phenolic hydroxyl group-containing compound can be used alone or in combination of two or more kinds.

[0184] The alkylene oxide may be the same as those exemplified above. Among these, ethylene oxide or propylene oxide is preferred because it can provide a curable resin composition capable of forming a cured product having high elongation, photosensitivity, heat yellowing resistance, and adhesion. The alkylene oxide may be used alone or in combination of two or more.

[0185] The alkylene carbonate may be the same as those exemplified above. Among these, ethylene carbonate or propylene carbonate is preferred because it can provide a curable resin composition capable of forming a cured product having high elongation, photosensitivity, heat yellowing resistance, and adhesion. The alkylene carbonate may be used alone or in combination of two or more.

[0186] As the unsaturated monobasic acid, the same unsaturated monobasic acids as those exemplified above can be used, and the unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0187] As the polybasic acid anhydride, the same as those exemplified above as the polybasic acid anhydride (C) can be used, and the polybasic acid anhydrides can be used alone or in combination of two or more kinds.

[0188] The method for producing the ester resin (D-VI) having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the ester resin (D-VI) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and a basic catalyst or an acidic catalyst may be used, if necessary.

[0189] 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.

[0190] As the basic catalyst, the same ones as those exemplified above as the basic catalyst can be used, and the basic catalysts can be used alone or in combination of two or more kinds.

[0191] As the acidic catalyst, the same as those exemplified above as the acidic catalyst can be used, and the acidic catalysts can be used alone or in combination of two or more kinds.

[0192] <Compound having a polymerizable unsaturated group> The curable resin composition of the present embodiment may further contain a compound having a polymerizable unsaturated group. Such a compound having a polymerizable unsaturated group is typically a compound having no acid group.

[0193] Examples of the compound having a polymerizable unsaturated group include (meth)acrylate compounds. Specific examples 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; alicyclic mono(meth)acrylate compounds such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate; Mono(meth)acrylate compounds; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzyl benzyl (meth)acrylate, phenyl Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as phenoxyethyl (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 above-mentioned various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; ethylene glycol di( aliphatic 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; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate;Aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the 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 chains such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain have been introduced into the molecular structure of the above-mentioned aliphatic tri(meth)acrylate compounds. ) oxyalkylene-modified tri(meth)acrylate compounds; lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate; tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain is introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds; tetrafunctional or higher lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds;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, and the like, in the molecular structure of the (meth)acrylate compounds having a hydroxyl group. Examples of the (meth)acrylate compound include (poly)oxyalkylene modified compounds having a (poly)oxyalkylene chain such as a ethylene chain introduced therein; lactone modified compounds 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 compound having a polymerizable unsaturated group may be used alone or in combination of two or more. The content of the (meth)acrylate compound in the curable resin composition of this embodiment is preferably 90 mass % or less.

[0194] <Additives> Furthermore, 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 needed.

[0195] The curing accelerator 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 in the range of 0.01 to 10 mass % of the solid content of the curable resin composition.

[0196] Examples of the ultraviolet absorber 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, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, etc. These ultraviolet absorbers can be used alone or in combination of two or more.

[0197] As the polymerization inhibitor, the same ones as those exemplified above as polymerization inhibitors can be used, and the polymerization inhibitors can be used alone or in combination of two or more kinds.

[0198] As the antioxidant, the same antioxidants as those exemplified above can be used, and the antioxidants can be used alone or in combination of two or more kinds.

[0199] 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.

[0200] Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

[0201] As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

[0202] Examples of the inorganic pigment include white pigment, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more.

[0203] 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.

[0204] 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.

[0205] 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 obtained by reacting them 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 oil, silicone rubber, and silicone resin; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting-point glass. These flame retardants can be used alone or in combination of two or more. When these flame retardants are used, their content is preferably in the range of 0.1 to 20 mass% of the total resin composition.

[0206] 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 in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere in order to efficiently carry out the ultraviolet curing reaction.

[0207] As a source of ultraviolet light, ultraviolet lamps are commonly 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, and LEDs.

[0208] The cumulative light 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.

[0209] The irradiation of the active energy rays may be carried out in one step or in two or more steps.

[0210] Furthermore, the cured product of the present invention has excellent alkali developability when formed into a cured product, high adhesion, and a low linear expansion coefficient, and therefore 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, etc., or adhesive layer between integrated circuit elements and circuit boards. It can also be suitably used in thin-film display applications such as LCDs and OELDs as thin-film transistor protective films, liquid crystal color filter protective films, pigment resists for color filters, black matrix resists, spacers, etc. Among these, it is particularly suitable for use as a solder resist.

[0211] The resist member of the present invention can be obtained, for example, by applying the solder resist resin material to a substrate, evaporating and drying the organic solvent at a temperature in the range of about 60 to 100°C, exposing the material to active energy rays through a photomask having a desired pattern formed thereon, developing the unexposed areas with an alkaline aqueous solution, and further heating and curing the material at a temperature in the range of about 140 to 200°C.

[0212] Examples of the substrate include a metal-clad laminate made of copper, aluminum, or the like. [Example]

[0213] 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.

[0214] In the examples, the instruments and conditions used for gel permeation chromatography (GPC) are as follows:

[0215] (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 below is shown in Figure 1. The arrows in the figure indicate the peaks of the calixarene compounds. From the GPC chart, the content of the calixarene compounds in the phenolic resin was calculated as the GPC area ratio of the calixarene compounds to the total phenolic resin.

[0216] Measuring device: 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: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual for the GPC Workstation EcoSEC-WorkStation.

[0217] (Polystyrene used) Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" "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 1.0 mass% tetrahydrofuran solution of the solid content of the diphenyl isophthalate derivative, aromatic ester compound (A), and epoxy resin (B) having a polymerizable unsaturated group obtained in the synthesis examples, examples, etc., filtered through a microfilter (50 μl) was used.

[0218] < 1 1H-NMR Measurement 1 1H-NMR: "JNM-ECA600" manufactured by JEOL RESONANCE Magnetic field strength: 600 MHz Number of integrations: 32 times Solvent: DMSO-d6 Sample concentration: 30 mass% 1 From the results of the 1H-NMR chart, peaks derived from the target product were confirmed, and it was confirmed that the target product was obtained in each reaction.

[0219] < 13 13C-NMR Measurement 13 13C-NMR: "JNM-ECA600" manufactured by JEOL RESONANCE Magnetic field strength: 150 MHz Number of integrations: 320 times Solvent: DMSO-d6 Sample concentration: 30 mass% 13 From the results of the 13C-NMR chart, peaks derived from the target product were confirmed, and it was confirmed that the target product was obtained in each reaction.

[0220] <GC Measurement, GC-MS Measurement The amount of the basic catalyst (amine compound) remaining in the resin or resin composition was confirmed by gas chromatography (hereinafter abbreviated as GC), gas chromatography mass spectrometry (hereinafter abbreviated as GCMS), and nuclear magnetic resonance (hereinafter abbreviated as NMR). Specifically, the amount of the basic catalyst (amine compound) remaining was confirmed by measuring the obtained resin or resin composition by GC and GCMS under the following conditions. [GC measurement conditions] Measurement equipment: Gas chromatograph GC-2010 (Shimadzu Corporation) Detector: FID Column: Capillary column DB-5 (0.25 mm x 30 m, 0.25 μm) Column temperature: 50°C → 300°C (heating rate 10°C / min) → (5 min hold) Carrier gas: Helium [GC-MS measurement conditions] Measurement equipment: Gas chromatograph mass spectrometer GCMS-QP2010Plus (Shimadzu Corporation) Column: Capillary column ZB-5 (0.25 mm x 30 m, 0.25 μm) Column temperature: 50℃ → 300℃ (10℃ / min.) → (5min. Hold) Carrier gas: Helium In the above measurement, biphenyl was used as the internal standard.

[0221] (Synthesis Example 1: Production of phenolic resin (1)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 560 parts by mass of toluene, 110 parts by mass of resorcinol, and 7.2 parts by mass of paratoluenesulfonic acid, and the mixture was heated to 115°C under a nitrogen atmosphere. 130 parts by mass of 1,4-divinylbenzene was added dropwise over 2 hours, and the mixture was maintained 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 phenolic resin (1). The hydroxyl group equivalent of this phenolic resin (1) was 130 g / equivalent. The GPC chart of phenolic resin (1) is shown in Figure 1. The arrow in the figure indicates the peak of the calixarene form. The area % of the calixarene form in the GPC of phenolic resin (1) was 18%.

[0222] (Synthesis Example 2: Production of phenolic resin (2)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 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, and the temperature was raised to 100°C under a nitrogen atmosphere. 106 parts by mass of benzaldehyde was added dropwise over 2 hours, and the mixture was held at 100°C for 24 hours. 375 parts by mass of methyl isobutyl ketone was added, and the mixture was washed with water. After confirming that the pH was neutral, the butanol and methyl isobutyl ketone were removed at 170°C to obtain phenolic resin (2). The hydroxyl group equivalent of this phenolic resin (2) was 257 g / equivalent. The area % of the calixarene body in GPC of phenolic resin (2) was 19%.

[0223] (Synthesis Example 3: Production of phenolic resin (3)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 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, and the mixture was heated to 100°C under a nitrogen atmosphere. 122 parts by mass of salicylaldehyde was added dropwise over 2 hours, and the mixture was held at 100°C for 24 hours. 399 parts by mass of methyl isobutyl ketone was added, and the mixture was washed with water. After confirming that the pH was neutral, the butanol and methyl isobutyl ketone were removed at 170°C to obtain phenolic resin (3). The hydroxyl group equivalent of this phenolic resin (3) was 139 g / equivalent. The area % of the calixarene body in GPC of phenolic resin (3) was 55%.

[0224] (Synthesis Example 4: Production of phenolic resin (4)) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 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, and the mixture was heated to 100°C under a nitrogen atmosphere. 122 parts by mass of salicylaldehyde was added dropwise over 2 hours, and the mixture was held at 100°C for 24 hours. 423 parts by mass of methyl isobutyl ketone was added, washed with water, and after confirming that the pH was neutral, the butanol and methyl isobutyl ketone were removed at 170°C to obtain phenolic resin (4). The hydroxyl group equivalent of this phenolic resin (4) was 101 g / equivalent. The area % of the calixarene body in GPC of phenolic resin (4) was 88%.

[0225] (Synthesis Example 5: Production of Resin (C-1) Having Acid Groups and Polymerizable Unsaturated Groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 123 parts by weight of diethylene glycol monomethyl ether acetate, and 214 parts by weight of orthocresol novolac epoxy resin "EPICLON N-680" (manufactured by DIC Corporation, softening point 86°C, epoxy equivalent: 214 g / eq) (hereinafter referred to as "epoxy resin (1)") was dissolved therein. 0.9 parts by weight of dibutylhydroxytoluene and 0.2 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.4 parts by weight of triphenylphosphine. The mixture was then reacted at 120°C for 10 hours while blowing in air. Next, 72 parts by weight of diethylene glycol monomethyl ether acetate and 76 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (C-1) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (C-1) having an acid group and a polymerizable unsaturated group was 65% by mass, and the acid value of the solid content was 80 mgKOH / g.

[0226] Example 1: Synthesis of Resin (1) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 116.6 parts by weight of diethylene glycol monoethyl ether acetate, and 130 parts by weight of the phenolic resin (1) obtained in Synthesis Example 1 was dissolved therein. 0.7 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone (p-methoxyphenol) were added, followed by 142 parts by weight of glycidyl methacrylate and 1.4 parts by weight of triethylamine. The mixture was reacted at 120°C for 20 hours while blowing air into it. Next, 67.5 parts by weight of diethylene glycol monoethyl ether acetate and 69.9 parts by weight of tetrahydrophthalic anhydride were added, and the mixture was reacted at 110°C for 3 hours. Next, 1.4 parts by weight of phosphoric acid was added, and the mixture was stirred at 80°C for 2 hours to obtain a resin (1) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (1) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 78 mgKOH / g.

[0227] (Example 2): Synthesis of Resin (2) Having Acid Groups and Polymerizable Unsaturated Groups A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 171 parts by weight of diethylene glycol monoethyl ether acetate, and 257 parts by weight of the phenolic resin (2) obtained in Synthesis Example 2 was dissolved therein. 1.0 parts by weight of dibutylhydroxytoluene and 0.2 parts by weight of methoquinone (p-methoxyphenol) were added, followed by 142 parts by weight of glycidyl methacrylate and 2.0 parts by weight of triethylamine. The mixture was reacted at 120°C for 20 hours while blowing air into it. Next, 101.1 parts by weight of diethylene glycol monoethyl ether acetate and 106.4 parts by weight of tetrahydrophthalic anhydride were added, and the mixture was reacted at 110°C for 3 hours. Next, 2.0 parts by weight of phosphoric acid was added, and the mixture was stirred at 80°C for 2 hours to obtain a resin (2) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (2) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g.

[0228] (Example 3): Synthesis of Resin (3) Having Acid Groups and Polymerizable Unsaturated Groups A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 120.4 parts by weight of diethylene glycol monoethyl ether acetate, and 139 parts by weight of the phenolic resin (3) obtained in Synthesis Example 3 was dissolved therein. 0.7 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone (p-methoxyphenol) were added, followed by 142 parts by weight of glycidyl methacrylate and 1.4 parts by weight of triethylamine. The mixture was reacted at 120°C for 20 hours while blowing air into it. Next, 71 parts by weight of diethylene glycol monoethyl ether acetate and 74.5 parts by weight of tetrahydrophthalic anhydride were added, and the mixture was reacted at 110°C for 3 hours. Next, 1.4 parts by weight of phosphoric acid was added, and the mixture was stirred at 80°C for 2 hours to obtain a resin (3) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (3) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g.

[0229] (Example 4): Synthesis of Resin (4) Having Acid Groups and Polymerizable Unsaturated Groups A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 104.1 parts by weight of diethylene glycol monoethyl ether acetate, and 101 parts by weight of the phenolic resin (4) obtained in Synthesis Example 4 was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone (p-methoxyphenol) were added, followed by 142 parts by weight of glycidyl methacrylate and 1.2 parts by weight of triethylamine. The mixture was reacted at 120°C for 20 hours while blowing air into the mixture. Next, 61.1 parts by weight of diethylene glycol monoethyl ether acetate and 63.8 parts by weight of tetrahydrophthalic anhydride were added, and the mixture was reacted at 110°C for 3 hours. Next, 1.2 parts by weight of phosphoric acid was added, and the mixture was stirred at 80°C for 2 hours to obtain a resin (4) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (4) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 79 mgKOH / g.

[0230] (Comparative Example 1): Synthesis of Resin (D-1) Having Acid Groups and Polymerizable Unsaturated Groups A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 103.7 parts by weight of diethylene glycol monoethyl ether acetate, and 100 parts by weight of phenol novolak resin "PHENOLITE TD-2093" (DIC Corporation, phenolic hydroxyl group equivalent: 100 g / equivalent) was dissolved therein. 0.6 parts by weight of dibutylhydroxytoluene and 0.1 parts by weight of methoquinone (p-methoxyphenol) were added, followed by 142 parts by weight of glycidyl methacrylate and 1.2 parts by weight of triethylamine. The mixture was reacted at 120°C for 20 hours while blowing in air. Next, 61 parts by weight of diethylene glycol monoethyl ether acetate and 63.8 parts by weight of tetrahydrophthalic anhydride were added and the mixture was reacted at 110°C for 3 hours to obtain a resin (D-1) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this resin (D-1) having an acid group and a polymerizable unsaturated group was 65% by mass, and the acid value of the solid content was 79 mgKOH / g.

[0231] (Examples 5 to 9, Comparative Example 2): Preparation of curable resin compositions and evaluation of alkaline developability <Preparation of Curable Resin Composition> Curable resin compositions (1) to (5) and (C1) were obtained by mixing the components shown in Table 1. The following tests were carried out on the curable resin compositions. <Evaluation of alkaline developability> The curable resin compositions (1) to (5) and (C1) obtained above were applied to a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80°C for 50, 60, 70, 80, and 90 minutes, respectively, to prepare samples with different drying times. These were developed with a 1% by mass aqueous sodium carbonate solution (alkaline aqueous solution) at 30°C for 180 seconds, and the drying time at 80°C of samples that left no residue on the substrate was evaluated as the drying control width (minutes). The results are shown in Table 1. A longer drying control width (minutes) indicates better developability.

[0232] [Table 1]

[0233] (Examples 10 to 14, Comparative Example 3): Preparation of curable resin compositions and evaluation of linear expansion coefficient and adhesion <Preparation of Curable Resin Composition> Curable resin compositions (6) to (10) and (C3) were obtained by mixing the components shown in Table 2. The following tests were carried out on the curable resin compositions. <Measurement and evaluation of linear expansion coefficient> The curable resin compositions (6) to (10) and (C3) 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. 2 After irradiating the laminate with ultraviolet light, the coating was cured at 160°C for 1 hour to obtain a laminate. The resulting laminate was cut into a size of 20 mm x 5 mm to serve as a test piece. Using a thermomechanical analyzer (TMA: Shimadzu Corporation's "TMA-60"), the test piece was subjected to thermomechanical analysis in tension mode under a nitrogen atmosphere under the following measurement conditions: Measurement conditions Measurement load: 6mN Heating rate: 10°C / min twice Measurement temperature range: 1st time: 0℃ to 220℃, 2nd time: -60℃ to 240℃ Measurements under the above conditions were 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 2. The lower the linear expansion coefficient, the better the properties. <Evaluation of Adhesion> The curable resin compositions (6) to (10) and (C3) 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 curable resin compositions (6) to (10) and (C3) to a copper foil (electrolytic copper foil "F2-WS" 18 μm) to a thickness of 50 μm. 2 After irradiating with ultraviolet light of 1000 kJ / cm, the sample was heated at 160°C for 1 hour to obtain test piece 2. 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 Co., Ltd., peel speed 50 mm / min). The results are shown in Table 2. A higher peel strength (N / cm) indicates better adhesion. The peel strength was measured under the following conditions.

[0234] Measuring equipment: A&D Tensilon manufactured by A&D Co., Ltd. Test piece: width 1cm, length 12cm Peel tester Test speed: 50 mm / min Conditions: Temperature 23℃, humidity 50

[0235] [Table 2]

[0236] The specifications of each component shown in Tables 1 and 2 are as follows: Hardener: DIC Corporation, orthocresol novolac epoxy resin, product name "EPICLON N-680" Organic solvent: Diethylene glycol monoethyl ether acetate Photopolymerization initiator: IGM Resins, product name "Omnirad-907" It can be seen from Tables 1 and 2 that the curable resin compositions of the Examples exhibit higher developability than the Comparative Examples, and the resulting cured products exhibit excellent adhesion and a low coefficient of linear expansion.

[0237] In the curable resin composition of Example 5, the content of the remaining basic catalyst (triethylamine) was 50 μg or less per 1 g of the curable resin composition. Among the resins having an acid group and a polymerizable unsaturated group used in Examples 5 to 9, the resin having the lowest content of the remaining basic catalyst (triethylamine) was used, which may have resulted in the most excellent alkaline developability.

[0238] According to the present invention, it is possible to provide a curable resin composition that exhibits high developability and is capable of giving a cured product that has high adhesion and a low coefficient of linear expansion. Furthermore, according to the present invention, it is possible to provide a cured product, an insulating material, and a resist member that have high adhesion and a low coefficient of linear expansion.

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; A polybasic acid anhydride (C), is used as the essential reactant (2), A resin having an acid group and a polymerizable unsaturated group, characterized in that the calixarene content in the calixarene-containing phenolic resin (A) is 10% or more in terms of area ratio in gel permeation chromatography (GPC).

2. The resin having an acid group and 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 an acid group and 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 an acid group and 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 an acid group and 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 an acid group and 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. The amount of the polybasic acid anhydride (C) used is in the range of 0.2 to 1.05 moles per mole of the phenolic hydroxyl group-containing compound (a1). The resin having an acid group and a polymerizable unsaturated group according to claim 1 or 2.

7. 3. A curable resin composition comprising the resin having an acid group and a polymerizable unsaturated group according to claim 1 or 2, and a photopolymerization initiator.

8. The curable resin composition according to claim 7 , further comprising a resin (D) having an acid group and a polymerizable unsaturated group other than the resin having an acid group and a polymerizable unsaturated group.

9. A cured product of the curable resin composition according to claim 7.

10. An insulating material comprising the curable resin composition according to claim 7.

11. A resin material for a solder resist comprising the curable resin composition according to claim 7.

12. A resist member comprising the solder resist resin material according to claim 11.

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