Resin composition, curable resin composition, cured product, and article

Abstract

To provide: a resin composition and a curable resin composition which are capable of forming a cured product having low dielectric properties and excellent heat resistance; and a cured product and an article that contain them.SOLUTION: The resin composition comprises: (A) a (meth)acrylate-modified phenolic resin, which is a (meth)acrylic acid ester of a phenolic hydroxyl group- and aromatic ring-containing resin obtained from reaction raw materials (a) that are a fluorene compound (provided that the compound has no substituent at the 9-position), a phenolic hydroxyl group-containing compound and a compound represented by general formula (1); and (B) a resin having a polymerizable unsaturated group.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] 2. Description of the Related Art In recent years, curable resin compositions, such as active energy ray-curable resin compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting resin compositions that can be cured by heat, have been widely used in the fields of inks, paints, coating agents, adhesives, optical members, and the like. In particular, since the above-mentioned coating agent is required to have various properties such as curability, heat resistance, and low dielectric properties depending on the application, it is essential to manufacture the coating agent using appropriate materials that meet the above-mentioned properties. For example, Patent Document 1 describes a curable vinylbenzyl compound obtained by reacting one or more indene compounds having a specific chemical structure with a reaction raw material containing a vinylbenzyl halide in the presence of an alkali. Patent Document 1 also describes that the curable vinylbenzyl compound can become a cured product excellent in low dielectric constant, low dielectric tangent, high heat resistance, and low water absorption. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 3615742 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the number of groups polymerizable or reactive with other resins present in the molecule of the curable vinylbenzyl compound of Patent Document 1 is very small, making it poorly versatile as a coating agent. Therefore, the present disclosure aims to provide a resin composition, a curable resin composition, and a cured product and article thereof that are polymerizable with other resins and capable of forming a cured product having excellent heat resistance and dielectric properties. [Means for solving the problem]

[0005] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems and have found that a resin composition containing a specific (meth)acrylate-modified phenolic resin (A) polymerizable with other resins and a resin (B) having a polymerizable unsaturated group can provide a resin composition capable of forming a cured product exhibiting high heat resistance, low dielectric properties and a low dielectric tangent, a curable resin composition, and a cured product and article thereof, thereby completing the present invention. That is, the present invention is as follows.

[0006] [1] A resin composition comprising: a (meth)acrylate-modified phenolic resin (A) which is a (meth)acrylic acid ester of a phenolic hydroxyl group- and aromatic ring-containing resin, the (meth)acrylate-modified phenolic resin (A) being produced by reacting a fluorene compound (having no substituent at the 9-position), a phenolic hydroxyl group-containing compound, and a compound represented by general formula (1) as reaction raw materials (a); and a resin (B) having a polymerizable unsaturated group. [ka] (In the above general formula (1), Ar represents an aromatic ring group which may have a substituent. R 11 , R 12 , R 22 and R 21 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, X 11 and X 21 are each independently a leaving group.

[0007] [2] The resin composition according to [1], wherein a ratio (Mf / M1) of the number of moles (Mf) of the fluorene compound to the number of moles (M1) of the compound represented by general formula (1) is 0.01 to 0.99.

[0008] [3] The resin composition according to [1] or [2], wherein the (meth)acrylate-modified phenolic resin (A) is represented by the following general formula (5): [ka] "In the above general formula (5), Z 1 each independently represents the following general formula (2A): [ka] (In the above general formula (2A), R 2a and R 2b each independently represents an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom, and each of m1 and m2 independently represents an integer of 0 to 4. * represents a bond to another atom. [ka] (In the above general formula (4A), R b are each independently a hydrogen atom or a methyl group, R 51 are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or when m3 is 2 or more, the two or more R 51 may form a ring together with the carbon atom to which they are bonded, and each m3 is independently an integer of 0 to 4. * represents a bond to another atom. Z′ and Z″ each independently represent a group represented by the general formula (2A-LR): [ka] (In the above general formula (2A-LR), R 2a’ and R 2b’m1 is independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom; ’ and m2 ’ are each independently an integer of 0 to 4. * represents a bond to another atom.) or a structural unit represented by the following general formula (4A-LR): [ka] (In the above general formula (4A-LR), R b’ are each independently a hydrogen atom or a methyl group, R 51’ are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or ’ If is 2 or more, then the 2 or more R 51’ may form a ring together with the carbon atom to which they are attached, m3 ’ are each independently an integer of 0 to 4. * represents a bond to another atom. Ar 1 and Ar 2 each independently represents an aromatic ring group which may have a substituent, R 11 , R 12 , R 21 , R 22 , R 31 , R 32 , R 41 and R 42 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, p 0 is the average value, and is a number greater than 0. However, the (meth)acrylate-modified phenolic resin (A) contains a structural unit represented by general formula (2A) and / or general formula (2A-LR) and a structural unit represented by general formula (4A) and / or general formula (4A-LR).

[0009] [4] The resin composition according to any one of [1] to [3], wherein the (meth)acrylate-modified phenolic resin (A) contains a resin represented by the following general formula (5-1.4): [ka] (In the above general formula (5-1.4), Z 1 , Ar 1 , Ar 2 , R 11 , R 12 , R 21 , R 22 , R 31 , R 32 , R 41 and R 42 , R b’ , R 51’ , and m3 ’ has the same meaning as in claim 3, and p1 represents an integer of 1 or 2.

[0010] [5] A curable resin composition comprising the resin composition according to [1] or [2] and a photopolymerization initiator.

[0011] [6] A cured product of the curable resin composition according to [5].

[0012] [7] An article having a coating film made of the cured product according to [6]. Effect of the Invention

[0013] According to the present invention, it is possible to provide a resin composition capable of forming a cured product exhibiting high heat resistance, low dielectric property and low dielectric tangent, a curable resin composition, and a cured product and article thereof. [Brief description of the drawings]

[0014] [Figure 1] 1 shows the results of GPC measurement of the phenolic hydroxyl group- and aromatic ring-containing resin (a-1) synthesized in Synthesis Example 1. [Diagram 2] 1 shows the results of 13C-NMR measurement of the phenolic hydroxyl group- and aromatic ring-containing resin (a-1) synthesized in Synthesis Example 1. [Diagram 3] 1 shows the results of FD-MS measurement of the phenolic hydroxyl group- and aromatic ring-containing resin (a-1) synthesized in Synthesis Example 1. [Figure 4]1 shows the results of GPC measurement of the methacrylate-modified phenolic resin (A-1) synthesized in Synthesis Example 11. [Diagram 5] 1 shows the results of 13C-NMR measurement of the methacrylate-modified phenolic resin (A-1) synthesized in Synthesis Example 11. [Figure 6] 1 shows the results of FD-MS measurement of the methacrylate-modified phenolic resin (A-1) synthesized in Synthesis Example 11. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Below, an embodiment of the present invention (hereinafter referred to as the "present embodiment") will be described in detail, but the present disclosure is not limited to the description below and can be implemented in various modifications within the scope of its gist. [term] In this specification, "(meth)acrylate" refers to one or more species selected from the group consisting of acrylate and methacrylate. In this specification, the term "reaction raw material" refers to a compound that is used to obtain a target compound by a chemical reaction such as synthesis or decomposition and that partially constitutes the chemical structure of the target compound, excluding catalysts and solvents. In particular, in this specification, the term "reaction raw material" refers to a precursor for obtaining the target (meth)acrylate-modified phenolic resin (A) or resin (B) having a polymerizable unsaturated group by a chemical reaction. The term "structural unit" as used herein refers to a (repeating) unit of a chemical structure formed during a reaction or polymerization; in other words, it refers to a partial structure other than the structure of the chemical bonds involved in the reaction or polymerization in a product compound formed during a reaction or polymerization, i.e., a so-called residue. The "aliphatic hydrocarbon group" in this specification may be any of linear, branched, and cyclic types, and may have an unsaturated bond in the structure. The number of carbon atoms in the aliphatic hydrocarbon group is, for example, 1 to 20. Furthermore, two or more aliphatic hydrocarbon groups may be bonded to each other to form a ring structure. The monovalent aliphatic hydrocarbon group in this specification includes an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group. The "alkyl group" in this specification may be either a straight-chain or branched type, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a 3-pentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, an amyl group, a hexyl group, a heptyl group, an octyl group, a cumyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. The "alkenyl group" in this specification may be either a straight-chain or branched type, and examples thereof include a vinyl group, an allyl group, a butenyl group, a butadienyl group, a pentenyl group, a hexyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group. The "alkynyl group" in this specification may be either a straight-chain or branched type, and examples thereof include an ethynyl group, a propargyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, an undecynyl group, and a dodecynyl group. The "cycloalkyl group" in this specification may be a monocyclic group or a polycyclic group. The number of carbon atoms in the cycloalkyl group is, for example, 3 to 30. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a methylcyclohexyl group, and an ethylcyclohexyl group. The "cycloalkenyl group" in this specification may be a monocyclic group or a polycyclic group. The number of carbon atoms in the cycloalkenyl group is, for example, 3 to 30. Examples of the cycloalkenyl group include a cyclohexenyl group, a methylcyclohexenyl group, and an ethylcyclohexenyl group. The "cycloalkynyl group" in this specification may be a monocyclic group or a polycyclic group. The number of carbon atoms in the cycloalkynyl group is, for example, 4 to 30. Examples of the cycloalkynyl group include a cyclohexynyl group, a methylcyclohexynyl group, and an ethylcyclohexynyl group. In this specification, the "divalent aliphatic hydrocarbon group" includes an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkenylene group, and a cycloalkynylene group. The "alkylene group" in this specification may be either a straight-chain or branched type, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, and a dodecylene group. The "alkenylene group" in this specification may be either a straight-chain or branched type, and examples thereof include a vinylene group, a propenylene group, a butenylene group, a butadienylene group, an octenylene group, a decenylene group, and a dodecenylene group. The "alkynylene group" in this specification may be either a straight-chain or branched type, and examples thereof include an ethynylene group, a propynylene group, a butynylene group, a butadinylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group, a nonynylene group, a decynylene group, an undecynylene group, and a dodecynylene group. In the present specification, an "alkoxy group" has an alkyl-O- structure, and the definition of an alkyl group is applied to the alkyl portion in the structure. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, a tert-butoxy group, and an allyloxy group. The "cycloalkylene group" in this specification may be a monocyclic group or a polycyclic group. The number of carbon atoms in the cycloalkylene group is, for example, 3 to 30. The cycloalkylene group is, for example, a divalent group corresponding to the groups exemplified as the cycloalkyl group. The "cycloalkenylene group" in this specification may be a monocyclic group or a polycyclic group. The number of carbon atoms in the cycloalkenylene group is, for example, 3 to 30. The cycloalkenylene group is, for example, a divalent group corresponding to the groups exemplified as the cycloalkenyl group. The "cycloalkynylene group" in this specification may be a monocyclic group or a polycyclic group. The number of carbon atoms in the cycloalkynylene group is, for example, 4 to 30. The cycloalkynylene group is, for example, a divalent group corresponding to the groups exemplified as the cycloalkynyl group. In the present specification, the term "aromatic ring" refers to a hydrocarbon ring having a single ring, multiple rings (including a ring assembly or a bridged ring) or fused rings, which has aromaticity. The number of carbon atoms in the aromatic ring is, for example, 6 to 20. Examples of the aromatic ring include a benzene ring, a biphenyl ring, a naphthalene ring, an indene ring, an anthracene ring, and an adamantane ring. The aromatic ring group is a residue of an aromatic ring. The aromatic ring group also includes an aryl group and an arylalkyl group described below. In addition, examples of a group having a fused ring (hereinafter, a fused ring group) include a group having a naphthalene ring, an indene ring, an anthracene ring, a phenanthrene ring, or a pyrene ring. In addition, a group having a valence of n (for example, 1 to 5) of the fused ring group may be a group obtained by removing any n hydrogen atoms (for example, 1 to 5) from the fused ring or fused ring group. In this specification, an "aryl group" is a monovalent aromatic hydrocarbon group. The number of carbon atoms in the aryl group is, for example, 6 to 20. Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, and a phenanthryl group. In the present specification, the term "arylalkyl group" refers to an alkyl group in which one or more, preferably one or two, particularly one hydrogen atom of an alkyl group is substituted with an aryl group, and the above description of the aryl group and alkyl group is applied to the aryl group and alkyl group. Examples of the arylalkyl group include a benzyl group and a phenethyl group. As used herein, the term "halogen atom" includes fluorine, chlorine, bromine and iodine. In this specification, the term "alicyclic polybasic acid anhydride" refers to a compound in which an acid anhydride group is bonded to an alicyclic structure, regardless of the presence or absence of aromatic rings in other structural portions. In this specification, the number average molecular weight (Mn) and weight average molecular weight (Mw) are values ​​measured using gel permeation chromatography (hereinafter referred to as "GPC") under the measurement conditions described in the examples described later. In this specification, the hydroxyl equivalent is a value measured by neutralization titration method in accordance with JIS K0070. Unless otherwise specified, the materials, components, compounds, resins, catalysts and solvents described in this specification may be used alone or in combination of two or more. In this specification, unless otherwise specified, numerical ranges are intended to include the upper and lower limits of the range. For example, 100 to 2000 g / equivalent means a range of 100 g / equivalent to 2000 g / equivalent. In this specification, the symbols 1, 2, step (1), step (2), step (3), etc. are used to distinguish certain elements, materials, steps, etc. from other elements, materials, steps, etc., and are not intended to limit the amount of the elements or materials or the order of the steps.

[0016] [Resin composition] The present disclosure relates to a resin composition containing a (meth)acrylate-modified phenolic resin (A) and a resin (B) having a polymerizable unsaturated group. The (meth)acrylate-modified phenolic resin (A) is a (meth)acrylic acid ester of a reaction product of a fluorene compound (not having a substituent at the 9-position), a phenolic hydroxyl group-containing compound, and a compound represented by general formula (1). [ka] (In the above general formula (1), Ar represents an aromatic ring group which may have a substituent. R 11 , R 12 , R 22 and R 21 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, X 11 and X 21 are each independently a leaving group. This results in a resin capable of forming a cured product having excellent photosensitivity, high heat resistance, low dielectric constant and low dielectric tangent. In other words, the (meth)acrylate-modified phenolic resin (A) of the present embodiment may be a resin made of a fluorene compound (not having a substituent at the 9-position), a phenolic hydroxyl group-containing compound, a compound represented by general formula (1), and a (meth)acrylation agent as reaction raw materials (a). In other words, the (meth)acrylate-modified phenolic resin (A) is made of a phenolic hydroxyl group- and aromatic ring-containing resin and a (meth)acrylation agent as reaction raw materials (b). The phenolic hydroxyl group- and aromatic ring-containing resin is made of a fluorene compound (not having a substituent at the 9-position), a phenolic hydroxyl group-containing compound, and a compound represented by general formula (1) as reaction raw materials (c). Therefore, the phenolic hydroxyl group and aromatic ring-containing resin is a reaction product of a fluorene compound (which does not have a substituent at the 9-position), a phenolic hydroxyl group-containing compound, and a compound represented by general formula (1), and can be said to be an intermediate of the (meth)acrylate-modified phenolic resin (A).

[0017] In addition, when the (meth)acrylate-modified phenolic resin (A) of this embodiment is specified by another expression other than the reaction raw materials, the chemical structure of the (meth)acrylate-modified phenolic resin (A) essentially contains a structural unit derived from the phenolic hydroxyl group-containing compound into which a (meth)acryloyl group has been introduced by reacting with some or all of the phenolic hydroxyl groups in the phenolic hydroxyl group-containing compound, and a structural unit derived from the compound represented by general formula (1), and may have a structure in which the structural unit derived from the phenolic hydroxyl group-containing compound into which the (meth)acryloyl group has been introduced and / or a structural unit derived from a fluorene compound (provided that the fluorene compound does not have a substituent at the 9-position) is bonded via the structural unit derived from the compound represented by general formula (1). The resin composition of the present disclosure essentially contains a (meth)acrylate-modified phenolic resin (A) and a resin having a polymerizable unsaturated group (B), and may contain additives as necessary. The components contained in the resin composition of the present embodiment, that is, the (meth)acrylate-modified phenolic resin (A), the resin having a polymerizable unsaturated group (B), and optional additives, will be described in detail below.

[0018] ((Meth)acrylate modified phenolic resin (A)) The (meth)acrylate-modified phenolic resin (A) of the present embodiment may be a resin in which at least a portion of the phenolic hydroxyl groups of the reaction product of a fluorene compound (provided that the fluorene compound does not have a substituent at the 9-position), a phenolic hydroxyl group-containing compound, and a compound represented by general formula (1) and the phenolic hydroxyl groups of the aromatic ring-containing resin are modified into (meth)acrylate groups ((meth)acryloyl groups).

[0019] In the resin composition of this embodiment, the upper limit of the content of the (meth)acrylate modified phenolic resin (A) (solid content) is preferably 90 mass% or less, more preferably 80 mass% or less, even more preferably 70 mass% or less, and even more preferably 60 mass% or less, based on the total amount (100 mass%) of the resin composition. The lower limit of the content of the (meth)acrylate modified phenolic resin (A) (solid content) is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total amount (100 mass%) of the resin composition. The upper and lower limits can be combined arbitrarily.

[0020] The (meth)acrylate-modified phenolic resin (A) of the present embodiment is preferably represented by the following general formula (5). [ka] "In the above general formula (5), Z 1 each independently represents the following general formula (2A): [ka] (In the above general formula (2A), R 2a and R 2beach independently represents an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom, and each of m1 and m2 independently represents an integer of 0 to 4. * represents a bond to another atom. [ka] (In the above general formula (4A), R b are each independently a hydrogen atom or a methyl group, R 51 are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or when m3 is 2 or more, the two or more R 51 may form a ring together with the carbon atom to which they are bonded, and each m3 is independently an integer of 0 to 4. * represents a bond to another atom. Z′ and Z″ each independently represent a group represented by the general formula (2A-LR): [ka] (In the above general formula (2A-LR), R 2a’ and R 2b’ m1 is independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom; ’ and m2 ’ are each independently an integer of 0 to 4. * represents a bond to another atom.) or a structural unit represented by the following general formula (4A-LR): [ka] (In the above general formula (4A-LR), R b’ are each independently a hydrogen atom or a methyl group, R 51’ are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or ’ If is 2 or more, then the 2 or more R 51’ may form a ring together with the carbon atom to which they are attached, m3 ’are each independently an integer of 0 to 4. * represents a bond to another atom. Ar 1 and Ar 2 each independently represents an aromatic ring group which may have a substituent, R 11 , R 12 , R 21 , R 22 , R 31 , R 32 , R 41 and R 42 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, p 0 is the average value, and is a number greater than 0. However, the (meth)acrylate-modified phenolic resin (A) contains a structural unit represented by general formula (2A) and / or a structural unit represented by general formula (2A-LR), and a structural unit represented by general formula (4A) and / or a structural unit represented by general formula (4A-LR).

[0021] In the above general formula (5), the structural units represented by the general formulae (2A) and (2A-LR) correspond to the preferred form of the structural unit derived from a fluorene compound (provided that the 9-position does not have a substituent). The structural units represented by the general formulae (4A) and (4A-LR) correspond to the preferred form of the structural unit derived from the phenolic hydroxyl group-containing compound in which a (meth)acryloyl group is introduced by reacting with a part or all of the phenolic hydroxyl groups in the phenolic hydroxyl group-containing compound. Therefore, for example, the [CH2=CRb'-C(=O)-] portion in the general formula (4A-LR) corresponds to the preferred form of the structural unit derived from the (meth)acrylation agent, and the other partial structures of the general formula (4A-LR) correspond to the phenolic hydroxyl group-containing compound. In addition, "R 11 R 12 C-Ar 1 -CR 21 R 22 " portion and "R 31 R 32 C-Ar 2 -CR 41 R 42" portion corresponds to a preferred form of the structural unit derived from the compound represented by general formula (1).

[0022] In addition, the (meth)acrylate-modified phenolic resin (A) of this embodiment may be a resin alone or a resin mixture. Specifically, the (meth)acrylate-modified phenolic resin (A) may be a fluorene ring-containing (meth)acrylate-modified phenolic resin (A1) alone, which contains a structural unit derived from the phenolic hydroxyl group-containing compound to which a (meth)acryloyl group has been introduced by reacting with a part or all of the phenolic hydroxyl groups in the phenolic hydroxyl group-containing compound, a structural unit derived from the compound represented by general formula (1), and a structural unit derived from a fluorene compound (provided that the 9th position does not have a substituent), and has a structure in which the structural unit derived from the phenolic hydroxyl group-containing compound to which the (meth)acryloyl group has been introduced and the structural unit derived from the fluorene compound (provided that the 9th position does not have a substituent) are bonded via the structural unit derived from the compound represented by general formula (1), or may be a resin mixture containing the fluorene ring-containing (meth)acrylate-modified phenolic resin (A1).

[0023] As will be described in detail later, when the (meth)acrylate-modified phenolic resin (A) of the present embodiment is a resin mixture, the resin mixture preferably essentially contains a fluorene ring-containing (meth)acrylate-modified phenolic resin (A1) having a structure in which a structural unit derived from a phenolic hydroxyl group-containing compound to which a (meth)acryloyl group has been introduced and a structural unit derived from a fluorene compound (provided that the fluorene compound does not have a substituent at the 9-position) are bonded via a structural unit derived from a compound represented by general formula (1).

[0024] More specifically, when the (meth)acrylate-modified phenolic resin (A) is, for example, a resin having a structure represented by the above general formula (5), the fluorene ring-containing (meth)acrylate-modified phenolic resin (A1) preferably has a structure in which the structural unit represented by the general formula (2A) and / or the structural unit represented by the general formula (2A-LR) and the structural unit represented by the general formula (4A) and / or the structural unit represented by the general formula (4A-LR) are essentially contained, and the structural unit represented by the general formula (2A) or the structural unit represented by the general formula (4A) is linked to a structural unit derived from a compound represented by the general formula (1). As a result, since the (meth)acrylate-modified phenolic resin (A) contains a fluorene ring with a high proportion of carbon atoms, a cured product having excellent photosensitivity, high heat resistance, low dielectric constant and low dielectric tangent can be formed.

[0025] As described above, the (meth)acrylate-modified phenolic resin (A) of this embodiment may be a resin made of a fluorene compound (not having a substituent at the 9-position), a phenolic hydroxyl group-containing compound, a compound represented by general formula (1), and a (meth)acrylation agent as reaction raw materials (a). The (meth)acrylate-modified phenolic resin (A) is a resin made of a phenolic hydroxyl group- and aromatic ring-containing resin and a (meth)acrylation agent as reaction raw materials (b). Therefore, the phenolic hydroxyl group- and aromatic ring-containing resin, which is an intermediate of the (meth)acrylate-modified phenolic resin (A), and the (meth)acrylation agent will be described below.

[0026] <Resin containing phenolic hydroxyl groups and aromatic rings> The phenolic hydroxyl group- and aromatic ring-containing resin of this embodiment is a reaction product of a fluorene compound (wherein the fluorene compound does not have a substituent at the 9-position), a phenolic hydroxyl group-containing compound, and a compound represented by general formula (1). In other words, the fluorene compound, the phenolic hydroxyl group-containing compound, and the compound represented by general formula (1) are reaction raw materials (c). <<Fluorene compounds>> The fluorene compound of this embodiment is not particularly limited except that it does not have a substituent at the 9th position of the fluorene. The fluorene compound may be unsubstituted or substituted at a position other than the 9th position.

[0027] In a preferred embodiment, the fluorene compound is unsubstituted fluorene. The fluorene compound of the present embodiment is, for example, a compound represented by the following general formula (2). [ka] (In general formula (2), R 2a and R 2b each independently represents an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom; m1 and m2 each independently represent an integer of 0 to 4.

[0028] In the above general formula (2), R 2a and R 2b Examples of the aliphatic hydrocarbon group include an alkyl group having a carbon number of 1 to 4. The alkyl group is preferably a methyl group, an ethyl group, a propyl group, or a butyl group. In the above general formula (2), R 2a and R 2b Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an indenyl group, and an indanyl group. In the above general formula (2), R 2a and R 2b Examples of the arylalkyl group include a benzyl group, a phenethyl group, and a cumyl group. In the above general formula (2), R 2a and R 2b Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. In the above general formula (2), R 2a and R 2b Examples of the halogen atom include fluorine, chlorine, and bromine. In the above general formula (2), m1 and m2 are integers of 0, 1, 2, 3, or 4, and preferably, are integers of 0, 1, or 2. In a preferred embodiment, in the above general formula (2), m1 and m2 are the same. When m1 and m2 are both 1 or greater, R 2a and R 2b When either m1 or m2 is 2 or more, multiple R 2a may be the same or different. Similarly, multiple R 2b may be the same as each other or may be different. In another preferred embodiment, in the fluorene compound represented by the general formula (2), both m1 and m2 are preferably 0, that is, the fluorene compound is preferably an unsubstituted fluorene.

[0029] <<Phenol-containing hydroxyl group compounds>> The phenolic hydroxyl group-containing compound of this embodiment is a compound having one phenolic hydroxyl group in the molecule. The phenolic hydroxyl group-containing compound includes a compound represented by the general formula (3). [ka] (In the above general formula (3), R 51 are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or when m3 is 2 or more, two or more R 51 may form a ring together with the carbon atom to which they are attached, and m3 is an integer of 0 to 4.

[0030] In the above general formula (3), R 51 Examples of the aliphatic hydrocarbon group include an alkyl group, an alkylene group, or an alkenylene group having 1 to 4 carbon atoms. 51When the aliphatic hydrocarbon group is an alkyl group, it is at least one selected from the group consisting of a methyl group, an ethyl group, a propyl group, and a butyl group. 51 When they form a ring together with the carbon atom to which they are attached, R 51 The aliphatic hydrocarbon group includes an alkylene group or an alkenylene group. In the above general formula (3), R 51 Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. In the above general formula (3), R 51 Examples of the arylalkyl group include a benzyl group, a phenethyl group, and a cumyl group. In the above general formula (3), R 51 Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. In the above general formula (3), R 51 Examples of the halogen atom include fluorine, chlorine, and bromine. In a preferred embodiment, in the above general formula (3), R 51 is one or more groups selected from the group consisting of alkyl groups and aryl groups. In the above general formula (3), when m3 is 2 or more, 2 or more R 51 may form a ring together with the carbon atom to which they are bonded. Examples of the ring include a hydrocarbon ring having 6 to 20 carbon atoms constituting the ring. Examples of the ring include a benzene ring, a naphthalene ring, an anthracene ring, an adamantane ring, an indane ring, and an indene ring. 51 The ring formed by may have a substituent. Examples of the substituent include an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, and a halogen atom. 51 The ring formed by may be a heterocycle containing a heteroatom. In the above general formula (3), m3 is an integer of 0, 1, 2, 3, or 4, and preferably 0, 1, or 2. In a preferred embodiment, when m3 is 2 or more, R51 may be joined to the carbon atom to which they are attached to form a benzene ring or a naphthalene ring.

[0031] In a preferred embodiment, the phenolic hydroxyl group-containing compound is preferably at least one selected from the group consisting of phenol, o-cresol, 2,6-dimethylphenol, 2,3,6-trimethylphenol, 1-naphthol, and 2-naphthol.

[0032] (Compound represented by general formula (1)) The compound represented by the general formula (1) of this embodiment can modify the hydrogen atom at the 9th position of the fluorene structural unit to an aralkyl. In addition, the compound represented by the general formula (1) can also react with a phenolic hydroxyl group-containing compound, and therefore can function as a binder. Therefore, the phenolic hydroxyl group- and aromatic ring-containing resin, which is an intermediate of the (meth)acrylate-modified phenolic resin (A), can have a structure in which a total of two or more structural units derived from a phenolic hydroxyl group-containing compound and / or a fluorene compound (without a substituent at the 9th position) are bonded via a structural unit derived from the compound represented by the general formula (1). [ka] In the above general formula (1), Ar represents an aromatic ring group which may have a substituent, and R 11 , R 12 , R 21 and R 22 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and X 11 and X 21 are each independently a leaving group.

[0033] In the above general formula (1), the aromatic ring group as Ar is not particularly limited as long as it is a divalent group having a ring structure with aromaticity (having a ring structure, being completely conjugated, having a planar structure, and satisfying Huckel's rule), and examples thereof include divalent aromatic ring groups such as arylene groups or aralkylene groups, and specifically, divalent aromatic ring groups such as phenylene groups, biphenylene groups, terphenylene groups, naphthylene groups, and anthracenylene groups. In the case of a phenylene group, it is preferable that there are bonds at the 1st and 4th positions, in the case of a naphthylene group, it is preferable that there are bonds at the 2nd and 6th positions, and in the case of an anthracenylene group, it is preferable that there are bonds at the 9th and 10th positions.

[0034] In the above general formula (1), the aromatic ring group may have hydrogen atoms substituted with one or more substituents. Examples of the substituents in the aromatic ring group include an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, and a halogen atom. Examples of the aliphatic hydrocarbon group as a substituent of the aromatic ring group include an alkyl group having 1 to 4 carbon atoms. In a preferred embodiment, the alkyl group is at least one selected from the group consisting of a methyl group, an ethyl group, a propylene group, and a butylene group. Examples of the aryl group which is a substituent of the aromatic ring group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0035] Examples of the arylalkyl group as a substituent of the aromatic ring group include a benzyl group, a phenethyl group, and a cumyl group. Examples of the alkoxy group as a substituent of the aromatic ring group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the halogen atom as a substituent of the aromatic ring group include fluorine, chlorine, and bromine. In a preferred embodiment, the substituents on the aromatic ring group are one or more selected from the group consisting of alkyl groups and aryl groups.

[0036] In the above general formula (1), R 11 , R12 , R 21 and R 22 is preferably each independently an aliphatic hydrocarbon group, and examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, and a butyl group. In one preferred embodiment, R 11 , R 12 , R 21 and R 22 are each independently one or more selected from the group consisting of a hydrogen atom and methyl. R 11 , R 12 , R 21 and R 22 may be the same or different. 11 , R 12 , R 21 and R 22 It is more preferable that they are all the same. In the above general formula (1), X 11 and X 21 are each independently, for example, a hydroxyl group, a halogen atom, an alkoxy group, etc. Examples of the halogen atom include chlorine, bromine, and iodine. Examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms. In a preferred embodiment, the alkoxy group is one or more types selected from the group consisting of a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. In a preferred embodiment, X 11 and X 21 are each independently one or more selected from the group consisting of chlorine, bromine, iodine, a hydroxyl group, and a methoxy group. X 11 and X 21 may be the same as or different from each other.

[0037] In one embodiment, in general formula (1), Ar, Ar 11 -Y-Ar 11 Or Ar 12 and Ar 11each independently represents an aromatic ring group which may have a substituent, and is preferably a divalent group; Ar 12 is a divalent fused cyclic group, Y is a single bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms (preferably a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms), -P(=O)R a1 - group, an oxygen atom, a sulfur atom or a sulfonyl group, R a1 is an aromatic ring group. In a preferred embodiment, the compound represented by general formula (1) is one or more selected from the group consisting of 1,4-bis(chloromethyl)benzene, 2,6-bis(chloromethyl)naphthalene, and 4,4'-bis(chloromethyl)biphenyl.

[0038] (Method for producing resin containing phenolic hydroxyl group and aromatic ring) An example of a method for producing the phenolic hydroxyl group- and aromatic ring-containing resin of this embodiment will be described. The blending amounts of the fluorene compound, the phenolic hydroxyl group-containing compound, and the compound represented by the general formula (1) are, for example, as follows. From the viewpoint of introducing the phenolic hydroxyl group-containing compound, the amount of the fluorene compound is preferably less than 1 mole per mole of the total of the compounds represented by the general formula (1). The amount of the fluorene compound is, for example, 0.01 moles or more or 0.05 moles or more, and 0.99 moles or less or 0.90 moles or less per mole of the total of the compounds represented by the general formula (1). In one embodiment, the amount of the fluorene compound is 0.01 to 0.99 moles per mole of the total of the compounds represented by the general formula (1).

[0039] In one embodiment, in the phenolic hydroxyl group and aromatic ring-containing resin, the ratio (Mf / M1) of the number of moles of the fluorene compound (Mf) to the total number of moles (M1) of the compound represented by general formula (1) is preferably 0.01 to 0.99. In another embodiment, the lower limit of Mf / M1 is preferably 0.01 or more, 0.10 or more, 0.20 or more, 0.30 or more, 0.40 or more, 0.50 or more, 0.60 or more, 0.70 or more, 0.80 or more, 0.90 or more, or 0.95 or more. In yet another embodiment, the upper limit of Mf / M1 is preferably 0.99 or less, 0.90 or less, 0.80 or less, 0.70 or less, 0.60 or less, 0.50 or less, 0.40 or less, 0.30 or less, 0.20 or less, or 0.10 or less. The upper limit and the lower limit can be arbitrarily combined. In yet another embodiment, Mf / M1 is preferably 0.35 to 0.50. Since the fluorene compound and the compound represented by general formula (1) can react in substantially their entirety, the molar ratio of the fluorene compound to the compound represented by general formula (1) used in the reaction is substantially the same as the molar ratio of the structural units derived from the fluorene compound to the structural units derived from the compound represented by general formula (1) in the resulting phenolic hydroxyl group- and aromatic ring-containing resin.

[0040] In the reaction raw material (c), the amount of the phenolic hydroxyl group-containing compound is, for example, an amount in which the hydroxyl group of the phenolic hydroxyl group-containing compound is 0.01 moles or more or 0.02 moles or more, and 10 moles or less or 9.5 moles or less, per mole of the total of the compounds represented by the general formula (1). In one embodiment, the amount of the phenolic hydroxyl group-containing compound in the reaction raw material (c) is an amount in which the hydroxyl group of the phenolic hydroxyl group-containing compound is 0.01 to 10 moles, per mole of the total of the compounds represented by the general formula (1). Regarding the phenolic hydroxyl group-containing compound, some unreacted phenolic hydroxyl group-containing compound is also generated, but the amount of the reacted phenolic hydroxyl group-containing compound can be calculated from the hydroxyl group equivalent of the phenolic hydroxyl group and the aromatic ring-containing resin.

[0041] The phenolic hydroxyl group- and aromatic ring-containing resin can be produced by using a fluorene compound (not having a substituent at the 9-position), a compound represented by general formula (1), and a phenolic hydroxyl group-containing compound as reaction raw materials (c), for example, through the following steps 1 and 2. That is, the production method of the phenolic hydroxyl group- and aromatic ring-containing resin of this embodiment includes the following steps 1 and 2.

[0042] <Process 1> The above-mentioned step 1 is preferably a step of reacting the total amount of the fluorene compound, the total amount of the compound represented by the general formula (1), and a portion of the phenolic hydroxyl group-containing compound in an organic solvent in the presence of an alkali catalyst at 10 to 100°C. Examples of the organic solvent include toluene, xylene, mesitylene, Solvesso (trade name), dimethyl sulfoxide, dimethylformamide, and dimethylacetamide. In addition, for example, the organic solvent described in JP-A-2023-028337 may be used. In a preferred embodiment, the organic solvent is one or more selected from the group consisting of toluene, xylene, mesitylene, Solvesso, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide. The amount of the organic solvent is not particularly limited, and is, for example, 50 to 500% by mass based on the total mass of the compound represented by general formula (1) and the fluorene compound. Examples of the alkali catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxy, sodium ethoxy, sodium tert-butoxy, potassium methoxy, potassium ethoxy, potassium tert-butoxy, triethylamine, pyridine, and dimethylaminopyridine. In a preferred embodiment, the alkali catalyst is one or more selected from the group consisting of sodium hydroxide and potassium hydroxide. The alkali catalyst may be used, for example, as a 1 to 50 mass % aqueous solution. The amount of the alkali catalyst is, for example, 10 to 1000 mol % based on the number of moles of the compound represented by general formula (1).

[0043] In the above step 1, a phase transfer catalyst may be used as necessary. Examples of the phase transfer catalyst include ammonium-based catalysts such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium, tetrabutylammonium iodide, tetrabutylammonium hydroxide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium iodide, and benzyltriethylammonium hydroxide; phosphonium-based catalysts such as tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, and tetrabutylphosphonium hydroxide; and crown ether-based catalysts such as 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, and tribenzo-18-crown-6-ether. In a preferred embodiment, the phase transfer catalyst is one or more selected from the group consisting of tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium bromide, and benzyltriethylammonium iodide.

[0044] In the above step 1, an additive may be used as necessary. Examples of the additive include halides such as lithium bromide, sodium bromide, potassium bromide, cesium bromide, lithium iodide, sodium iodide, potassium iodide, and cesium iodide. In a preferred embodiment, the additive is one or more selected from the group consisting of sodium iodide and potassium iodide. The reaction temperature in the above step 1 is, for example, 10 to 100° C. In terms of reactivity, the reaction temperature is preferably 20 to 80° C. The reaction time in the above step 1 is, for example, 1 to 72 hours. After the reaction in step 1 is completed, the resulting reaction mixture is separated into an upper layer and a lower layer, and the lower layer, which is an aqueous layer, is removed to obtain the product. At this time, water may be added as necessary to dissolve the salt and remove the lower layer. The aqueous layer may be basic, neutral, or acidic. Examples of neutralizing agents used for neutralization include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, sodium monophosphate, and ammonium chloride; and organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid.

[0045] <Process 2> The above step 2 is preferably a step of adding the remainder of the phenolic hydroxyl group-containing compound to the product obtained in the above step 1, and reacting them at 60 to 250° C. in the presence of an acid catalyst. The phenolic hydroxyl group-containing compound used in step 2 may be the same as the phenolic hydroxyl group-containing compound used in step 1, or a different phenolic hydroxyl group-containing compound may be used. 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, aluminum chloride, and zinc chloride. In a preferred embodiment, the acid catalyst is one or more selected from the group consisting of paratoluenesulfonic acid and methanesulfonic acid. The amount of the acid catalyst is, for example, 0.01 to 10% by mass based on the total mass of the reaction raw materials. The reaction temperature in the above step 2 is, for example, 60 to 250° C. In a preferred embodiment, the reaction temperature is 80 to 240° C. The reaction time in step 2 is, for example, 1 to 72 hours.

[0046] After the reaction in step 2 is completed, neutralization and water washing are carried out as necessary, and unreacted reactant materials, organic solvents, etc. are distilled off under reduced pressure and heating conditions to obtain the intermediate product, a phenolic hydroxyl group- and aromatic ring-containing resin.

[0047] In the method for producing the phenolic hydroxyl group- and aromatic ring-containing resin of the present embodiment, for example, instead of step 1, a fluorene compound and a compound represented by general formula (1) may be reacted in an organic solvent at 10 to 100° C. in the presence of a catalyst, and then a part of the phenolic hydroxyl group-containing compound may be added and reacted at 10 to 100° C., followed by removing the water layer and performing a water washing treatment. At that time, the product of step 1 may have a reactive group at the end. The reactive group may be an ether, a halogen group, or a hydroxyl group depending on the type of compound used. In one aspect of this embodiment, a fluorene compound (provided that it does not have a substituent at the 9-position) can produce a structural unit represented by general formula (2A) or general formula (2A'), a phenolic hydroxyl group-containing compound can produce a structural unit represented by general formula (3A) or general formula (3A'), and a compound represented by general formula (1) can produce a structural unit represented by general formula (1A). [ka] In the above general formulas (2A) and (2A'), m1 and m2, and m1' and m2' are each independently the same as m1 and m2 in general formula (2), R 2a and R 2b And R 2a ' and R 2b ' is R in general formula (2) 2a and R 2b and each * represents a bond.

[0048] In the above general formulas (3A) and (3A'), m3 is an integer of 0 to 3, preferably 0, 1, or 2, and m3' is an integer of 0 to 4, preferably 0, 1, or 2. R 51 and R 51’ are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or when m3 is 2 or more, two or more R 51 and R 51’ may form a ring together with the carbon atom to which they are attached, R51 and R 51’ A preferred embodiment of the formula (3) is R 51 and each * represents a bond. In the general formula (1A), Ar and R 11 , R 12 , R 21 and R 22 represents Ar and R in general formula (1). 11 , R 12 , R 21 and R 22 where * represents a bond.

[0049] The phenolic hydroxyl group- and aromatic ring-containing resin may contain a structure in which the structural unit (1A) is bonded to one or more selected from the group consisting of the structural unit (3A) and the structural unit (3A'). That is, the phenolic hydroxyl group- and aromatic ring-containing resin of the present embodiment may be a single resin or a resin mixture. When the phenolic hydroxyl group- and aromatic ring-containing resin is a resin mixture, it may contain a resin that does not contain one or more structural units selected from the group consisting of the structural unit (2A) and the structural unit (2A'). In a preferred embodiment, at least one of the molecular chain terminals of the phenolic hydroxyl group and the aromatic ring-containing resin is the structural unit (3A'). In another preferred embodiment, the molecular chain terminals of both the phenolic hydroxyl group and the aromatic ring-containing resin are the structural unit (3A'). In a preferred embodiment, the phenolic hydroxyl group and aromatic ring-containing resin is composed of one or more structural units selected from the group consisting of structural units (2A) and (2A'), one or more structural units selected from the group consisting of structural units (3A) and (3A'), and structural unit (1A). A bond of the structural unit (1A) may be bonded to a bond of the structural unit (2A). When the structural unit (2A') is present, the structural unit constitutes a molecular chain terminal.

[0050] In a preferred embodiment, at least one of the molecular chain terminals of the phenolic hydroxyl group and the aromatic ring-containing resin is the structural unit (3A'). In another preferred embodiment, the molecular chain terminals of both the phenolic hydroxyl group and the aromatic ring-containing resin are the structural unit (3A').

[0051] Preferred examples of the structural unit represented by the above general formula (1A) include the following formulae (a) to (d). [ka]

[0052] In one embodiment, the phenolic hydroxyl group and aromatic ring-containing resin is preferably represented by the following general formula (i). [ka] In general formula (i), Ar i1 and Ar i2 each independently represents an aromatic ring group which may have a substituent, similar to Ar defined in formula (1), p 0 is the average value, a number greater than 0 and less than or equal to 10, R 11 , R 12 , R 21 and R 22 are each independently as defined in general formula (1), R 31 , R 32 , R 41 and R 42 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and a preferred embodiment is 11 , R 12 , R 21 and R 22 is the same as Z i1 are each independently a structural unit represented by general formula (2A) or general formula (3A), Z i1 and Z i2are each independently a structural unit represented by general formula (2A') or general formula (3A').

[0053] The phenolic hydroxyl group- and aromatic ring-containing resin of the present embodiment represented by the above general formula (i) preferably contains one or more structural units selected from the group consisting of structural units represented by general formula (2A) and structural units represented by general formula (3A), and one or more structural units selected from the group consisting of structural units represented by general formula (2A') and structural units represented by general formula (3A'), and more preferably contains one or more structural units selected from the group consisting of general formula (2A) and general formula (2A'), and one or more structural units selected from the group consisting of general formula (3A) and general formula (3A').

[0054] The phenolic hydroxyl group and aromatic ring-containing resin of the present embodiment may be a single resin or a resin mixture. In a preferred embodiment, the resin mixture of the phenolic hydroxyl group and aromatic ring-containing resin is a resin mixture of the general formula (i): 0 It is preferable that the resin mixture is a mixture containing a compound in which p in the general formula (i) is a natural number of 1 or more. 0 In addition to compounds in which R is a natural number of 1 or more, the examples of the compounds may include compounds containing, in the molecule, both a structural unit represented by general formula (1A) and one or more structural units selected from the group consisting of structural units (2A), (2A'), (3A), and (3A') (for example, a resin that does not contain one or more structural units selected from the group consisting of structural units (2A) or (2A')), and compounds having, in the molecule, both one or more structural units selected from the group consisting of structural units (2A) and (2A') and one or more structural units selected from the group consisting of structural units (3A) and (3A'). In other words, since the phenolic hydroxyl group and aromatic ring-containing resin of this embodiment essentially has a fluorene ring, the (meth)acrylate-modified phenolic resin (A) obtained from the phenolic hydroxyl group and aromatic ring-containing resin also has a high carbon atom occupancy rate, and a composition with excellent low dielectric properties can be prepared.

[0055] In the phenolic hydroxyl group- and aromatic ring-containing resin, the total amount of one or more structural units selected from the group consisting of the structural unit (2A) and the structural unit (2A') is preferably 0.1 to 10 mol, and more preferably 0.5 to 9.5 mol, per 1 mol of the total of one or more structural units selected from the group consisting of the structural unit (3A) and the structural unit (3A').

[0056] In a preferred embodiment, the phenolic hydroxyl group and aromatic ring-containing resin is represented by the following general formula (i-1): [ka] (In the above general formula (i-1), Z i3 , Ar i1 , Ar i2 , R 11 , R 12 , R 21 , R 22 , R 31 , R 32 , R 41 and R 42 , R 51’ , and m3 ’ has the same meaning as in formula (i), and p1 represents an integer of 1 or 2.

[0057] In another preferred embodiment, the phenolic hydroxyl group and aromatic ring-containing resin is represented by the following general formula (i-1.1): [ka] In general formula (i-1.1), R 2a and R 2b and m1 and m2 are as defined in general formula (2A), R 51 and m3 are as defined in general formula (3A), R 51’ and m3' is as defined in general formula (3A'), Ar i1 , Ar i2 and Ar i3 are each independently represented by the following formulae (a-1) to (d-1 [ka] and s is the mean value and is a number greater than 0, t is the average value, and is a number equal to or greater than 0; The order of the structural units marked with s and the structural units marked with t is not limited. In the above general formula (i-1.1), s is, for example, a number from 1 to 10, or 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. t is, for example, a number from 0 to 10, or 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. The sum of s and t is, for example, 10 or less. The phenolic hydroxyl group- and aromatic ring-containing resin represented by the above general formula (i), general formula (i-1) or general formula (i-1.1) is each p 0 Or p 1 The compound may be a mixture of compounds having a structural unit marked with s or a structural unit marked with s and t, the number of which is a natural number of 1 or more.

[0058] In a preferred embodiment, the phenolic hydroxyl group and aromatic ring-containing resin represented by the above general formula (i) contains at least one compound represented by general formula (i-1.2). [ka] In general formula (i-1.2), Ar i1 , Ar i2 , R 11 , R 12 , R 21 , R 22 , R 31 , R 32 , R 41 and R 42 is as defined in general formula (i), p is 1 or 2; R 51’ and m3' are as defined in general formula (3A'), Z i3 is as defined in general formula (i). In one embodiment, in the compound represented by general formula (i-1.2), p or more Z i3 At least one Z i3 is a structural unit represented by general formula (2A) (or a group represented by general formula (2A)).

[0059] The phenolic hydroxyl resin of this embodiment may be a mixture of phenolic hydroxyl resins of this embodiment, and the mixture may contain a compound represented by the following general formula (ii). [ka] In general formula (ii), Ar and R 11 , R 12 , R 21 and R 22 is as defined in general formula (1), R 51’ and m3' is as defined in general formula (3A').

[0060] The number average molecular weight (Mn) of the phenolic hydroxyl group- and aromatic ring-containing resin of this embodiment may be, for example, in the range of 100 to 10,000, and preferably in the range of 200 to 8,000. In one embodiment, the Mn of the phenolic hydroxyl group- and aromatic ring-containing resin is in the range of 300 to 1,200. The weight average molecular weight (Mw) of the phenolic hydroxyl group- and aromatic ring-containing resin of this embodiment may be, for example, in the range of 100 to 50,000, and is preferably in the range of 300 to 4,000.

[0061] The molecular weight distribution (Mw / Mn) of the phenolic hydroxyl group- and aromatic ring-containing resin of the present embodiment is in the range of 1-5, for example, and preferably 1-4. The phenolic hydroxyl group and the hydroxyl group equivalent of the aromatic ring-containing resin of this embodiment are, for example, in the range of 100 to 2000 g / equivalent, preferably in the range of 200 to 1800 g / equivalent. In one embodiment, the phenolic hydroxyl group and the hydroxyl group equivalent of the aromatic ring-containing resin are in the range of 200 to 400 g / equivalent. The above is a description of the phenolic hydroxyl group- and aromatic ring-containing resin, which is an intermediate of the (meth)acrylate-modified phenolic resin (A). The (meth)acrylate-modified phenolic resin (A) of the present embodiment is prepared by converting the proton of the phenolic hydroxyl group of the intermediate phenolic hydroxyl group- and aromatic ring-containing resin into a (meth)acryloyl group [CHR b =CH-C(=O)-(R b In other words, a resin containing a phenolic hydroxyl group and an aromatic ring and a (meth)acrylation agent are used as reaction raw materials (b). The acrylation agent and a synthesis example using the acrylation agent are described below.

[0062] <(Meth)acrylation agent> The (meth)acrylate-modified phenolic resin (A) of the present embodiment is a (meth)acrylic acid ester of the above-mentioned phenolic hydroxyl group- and aromatic ring-containing resin, which is an intermediate, and is a (meth)acrylic acid-modified phenolic resin in which a (meth)acryloyl group has been introduced into the phenolic hydroxyl group of the phenolic hydroxyl group- and aromatic ring-containing resin. When a (meth)acryloyl group is to be introduced into a phenolic hydroxyl group, it is preferable to use a (meth)acrylation agent. The (meth)acrylation agent of the present embodiment is not particularly limited as long as it is a compound capable of reacting with a phenolic hydroxyl group and a hydroxyl group of an aromatic ring-containing resin to introduce a (meth)acryloyl group. Examples of the (meth)acrylation agent include (meth)acrylic anhydride, (meth)acrylic acid chloride, (meth)acrylic acid, and (meth)acrylic acid esters. Examples of the (meth)acrylic acid esters include alkyl esters of (meth)acrylic acid (e.g., alkyl esters having 1 to 4 carbon atoms). The (meth)acrylic anhydride includes methacrylic anhydride and acrylic anhydride, and the (meth)acrylic chloride includes methacrylic chloride and acrylic chloride. The (meth)acrylic acid includes methacrylic acid and acrylic acid, and the (meth)acrylic acid ester includes methacrylic acid ester and acrylic acid ester. When the (meth)acrylation agent is methacrylic anhydride, methacrylic acid chloride, methacrylic acid, methacrylic acid ester, etc., a methacryloyl group is introduced, and when the (meth)acrylation agent is acrylic anhydride, acrylic acid chloride, acrylic acid, acrylic acid ester, etc., an acryloyl group is introduced. Therefore, the above (meth)acrylation agent is contained as a reaction raw material (c) of the (meth)acrylate-modified phenolic resin (A). In this embodiment, the content of the (meth)acrylation agent in the reaction raw material (c) is preferably 0.3 moles or more and 10 moles or less of the (meth)acrylation agent per mole of the phenolic hydroxyl group and the hydroxyl group contained in the aromatic ring-containing resin as an intermediate.

[0063] The (meth)acrylate-modified phenolic resin (A) of the present embodiment may be a mixture, similar to the intermediate phenolic hydroxyl group- and aromatic ring-containing resin. Specifically, the mixture of (meth)acrylate-modified phenolic resins (A) may be a mixture of resins in which (meth)acryloyl groups are introduced into the phenolic hydroxyl groups contained in the resin mixture of the phenolic hydroxyl group- and aromatic ring-containing resin. In a preferred embodiment, the mixture of (meth)acrylate-modified phenolic resins (A) is a phenolic resin having a general formula (i): 0 is a natural number of 1 or more, and a resin in which a (meth)acryloyl group has been introduced into the phenolic hydroxyl group of the compound.

[0064] <Method for producing (meth)acrylate-modified phenolic resin (A)> The (meth)acrylate-modified phenolic resin (A) of the present embodiment is a (meth)acrylic acid ester of an intermediate phenolic hydroxyl group- and aromatic ring-containing resin. Therefore, when the intermediate phenolic hydroxyl group- and aromatic ring-containing resin is used as a starting material, the (meth)acrylate-modified phenolic resin (A) can be obtained, for example, by reacting the intermediate phenolic hydroxyl group- and aromatic ring-containing resin with the (meth)acrylation agent in the presence of a basic or acidic catalyst. Examples of the basic catalyst include amine-containing catalysts such as trimethylamine, triethylamine, N,N-diisopropylmethylamine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonene, pyridine, and dimethylaminopyridine, alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Examples of the acidic catalyst include sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid. Among them, triethylamine, N,N-diisopropylmethylamine, dimethylaminopyridine, and pyridine are preferred in terms of catalytic activity. The above catalysts may be used alone or in combination of two or more.

[0065] In the above reaction, it is preferable to use 0.3 to 10 moles of a basic or acidic catalyst per mole of hydroxyl groups contained in the intermediate phenolic hydroxyl group and aromatic ring-containing resin. These catalysts may be added all at once or in portions. In addition, it is preferable to carry out the reaction of the intermediate phenolic hydroxyl group and aromatic ring-containing resin with a (meth)acrylation agent with 0.3 moles or more and 10 moles or less of the (meth)acrylation agent per mole of hydroxyl groups contained in the intermediate phenolic hydroxyl group and aromatic ring-containing resin. The reaction temperature in the above reaction can be set to 20 to 150° C. The reaction time can be set to 1 to 72 hours. The reaction is preferably carried out in an organic solvent. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, and Solvesso; alcoholic solvents such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, sec-butanol, and tert-butanol; cellosolve solvents such as methyl cellosolve and ethyl cellosolve; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane; and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, and dimethylacetamide. From the viewpoint of solubility, toluene, xylene, mesitylene, Solvesso, isopropyl alcohol, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide are preferred. These organic solvents can be used alone or in combination of two or more at any ratio. The amount of the organic solvent used is not particularly limited, but is preferably 50 to 700% by mass based on the total amount of the charged intermediates, ie, the phenolic hydroxyl group- and aromatic ring-containing resin and the (meth)acrylation agent. After the reaction is completed, the target product, the (meth)acrylate-modified phenolic resin (A) of the present disclosure, can be obtained by performing reprecipitation, recrystallization, washing with water, distillation, etc.

[0066] (Preferable form of (meth)acrylate modified phenolic resin (A)) The (meth)acrylate-modified phenolic resin of the present embodiment can be, for example, one represented by general formula (5). [ka] "In the above general formula (5), Z 1 each independently represents a structural unit represented by general formula (2A) or a structural unit represented by general formula (4A), Z′ and Z″ each independently represent a structural unit represented by the above general formula (2A-LR) or a structural unit represented by the above general formula (4A-LR), Ar 1 and Ar 2 each independently represents an aromatic ring group which may have a substituent, R 11 , R 12 , R 21 , R 22 , R 31 , R 32 , R 41 and R 42 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, p 0 is the average value, and is a number greater than 0. However, the (meth)acrylate-modified phenolic resin (A) contains a structural unit represented by general formula (2A) and / or general formula (2A-LR) and a structural unit represented by general formula (4A) and / or general formula (4A-LR).

[0067] In the above general formula (5), Ar 1 and Ar 2 are preferably each independently one or more of the following formulae (a-1) to (d-1). [ka] In the above general formula (5), Z 1 each independently represents a structural unit represented by the general formula (2A) or a structural unit represented by the general formula (4A), and Z' and Z'' each independently preferably represent a structural unit represented by the general formula (2A-LR) or a structural unit represented by the general formula (4A-LR). In this case, a preferred embodiment of the above general formulas (2A) and (2A-LR) is the same as the above general formula (2). In addition, in the above general formulas (4A) and (4A-LR), m3 is preferably 0, 1 or 2, and m3' is an integer of 0 to 4, preferably 0, 1 or 2. In addition, R 51 and R 51’are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or when m3 is 2 or more, two or more R 51 may form a ring together with the carbon atom to which they are attached, R 51 and R 51’ A preferred embodiment of the formula (3) is R 51 is the same as:

[0068] In the above general formula (5), R 11 , R 12 , R 21 , R 22 , R 31 , R 32 , R 41 and R 42 The preferred embodiment of is as defined in the general formula (1), and R 11 , R 12 , R 21 and R 22 is the same as: In the above general formula (5), R b and R b’ are each independently a hydrogen atom or a methyl group. In the case of a hydrogen atom, an acryloyl group is introduced into the phenolic hydroxyl group, and in the case of a methyl group, a methacryloyl group is introduced into the phenolic hydroxyl group. The (meth)acrylate-modified phenolic resin (A) represented by the general formula (5) is 0 It may be a mixture of compounds in which p is an integer of 0 or more, but all of the compounds are not compounds of general formula (5) in which p is 0. It is preferable to include a compound containing both a structural unit represented by general formula (2A) and / or general formula (2A') and a structural unit represented by general formula (3A) and / or general formula (3A') in the molecule.

[0069] In the (meth)acrylate-modified phenolic resin (A), the total amount of the structural units of general formula (2A) and the structural units of general formula (2A') is preferably 0.1 to 10 mol, and more preferably 0.5 to 9.5 mol, per 1 mol of the structural units of general formula (3A) and the structural units of general formula (3A'). A preferred example is a (meth)acrylate-modified phenolic resin (A) represented by the following general formula (5-1). [ka] (In the above general formula (5-1), Ar i1 , Ar i2 , R 11 , R 12 , R 21 , R 22 , R 31 , R 32 , R 41 and R 42 , Z i3 , R 51’ , m3', p 0 , and R b’ is the same as in general formula (5). In the above general formula (5-1), Ar i1 , Ar i2 , R 11 , R 12 , R 21 , R 22 , R 31 , R 32 , R 41 and R 42 , Z i3 , R 51’ , m3', p 0 , and R b’’ The illustrative and preferred examples are the same as those of the above general formula (5).

[0070] More preferred examples of the (meth)acrylate-modified phenolic resin (A) of the present embodiment include resins represented by the following general formula (5-1.1). [ka] In general formula (5-1.1), R 2aand R 2b and m1 and m2 are as defined in general formula (2A), R 51 and m3 are as defined in general formula (3A), R 51’ and m3' is as defined in general formula (3A'), R b and R b’ each independently represents a hydrogen atom or a methyl group; Ar i1 , Ar i2 and Ar i3 are each independently represented by the following formulae (a-1) to (d-1 [ka] the law of nature, s is the mean value and is a number greater than 0, t is the average value, and is a number equal to or greater than 0; The order of the structural units marked with s and the structural units marked with t is not limited.

[0071] The (meth)acrylate-modified phenolic resin (A) of the general formula (5) and the (meth)acrylate-modified phenolic resin (A) of the general formula (5-1) each have a molecular weight of p 0 and p is an integer of 0 or more (provided that not all of the compounds are compounds of general formula (5) in which p is 0). In this embodiment, the (meth)acrylate-modified phenolic resin (A) of general formula (5) preferably contains at least one of a compound represented by general formula (5-1.2) and a compound represented by general formula (5-1.3). [ka] (In the above general formulas (5-1.2) and (5-1.3), Ar 1 , Ar 2 , R 11 , R 12 , R 21 , R 22 , R 31 , R 32 , R 41and R 42 , Z 1 , R 51’ , m3', and R b’ is the same as in general formula (5). Z in formula (5-1.2) 1 and at least one Z of the general formula (5-1.3) 1 is a structural unit represented by general formula (2A).

[0072] In this embodiment, the (meth)acrylate-modified phenolic resin (A) preferably contains a compound represented by general formula (5-1.4). [ka] (In the above general formula (5-1.4), Ar 1 , Ar 2 , R 11 , R 12 , R 21 , R 22 , R 31 , R 32 , R 41 and R 42 , Z 1 , R 51’ , m3', and R b’ is the same as in general formula (5), and p1 is 1 or 2.

[0073] The (meth)acrylate-modified phenolic resin (A) of the present embodiment may contain a compound represented by the general formula (5-2) as a part thereof. The compound represented by the general formula (5-2) is a compound represented by the general formula (5) ... 0 This corresponds to a compound where is 0. [ka] (In the above general formula (5-2), Ar i2 , R 31 , R 32 , R 41 and R 42 , R 51’ , m3', and R b’ is the same as general formula (5).

[0074] <Form in which the (meth)acrylate-modified phenolic resin (A) is a mixture> The (meth)acrylate-modified phenolic resin (A) of this embodiment may be a mixture. When the (meth)acrylate-modified phenolic resin (A) is a mixture, that is, the (meth)acrylate-modified phenolic resin (A) mixture preferably contains a fluorene ring-containing (meth)acrylate-modified phenolic resin (A1) having a structure in which a structural unit derived from a phenolic hydroxyl group-containing compound to which a (meth)acryloyl group has been introduced and a structural unit derived from a fluorene compound (without having a substituent at the 9-position) are bonded via a structural unit derived from a compound represented by general formula (1).

[0075] More specifically, the (meth)acrylate-modified phenolic resin (A) mixture is preferably composed of a resin component having a partial structure represented by the following general formula (5-3), and contains a fluorene ring-containing (meth)acrylate-modified phenolic resin (A1) represented by the following general formula (5-4). [ka] (In the above general formula (5-3), Z 11 represents a structural unit represented by general formula (4A), Ar 1 , R 11 , R 12 , R 21 and R 22 is the same as general formula (5). [ka] "In the above general formula (5-4), Z 12 each independently represents the following general formula (2A): [ka] (In the above general formula (2A), R 2a and R 2beach independently represents an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom, and each of m1 and m2 independently represents an integer of 0 to 4. * represents a bond to another atom. [ka] (In the above general formula (4A), R b are each independently a hydrogen atom or a methyl group, R 51 are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or when m3 is 2 or more, the two or more R 51 may form a ring together with the carbon atom to which they are bonded, and each m3 is independently an integer of 0 to 4. * represents a bond to another atom. Z 13 and Z 14 each independently represents a general formula (2A-LR) [ka] (In the above general formula (2A-LR), R 2a’ and R 2b’ m1 is independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom; ’ and m2 ’ are each independently an integer of 0 to 4. * represents a bond to another atom.) or a structural unit represented by the following general formula (4A-LR): [ka] (In the above general formula (4A-LR), R b’ are each independently a hydrogen atom or a methyl group, R 51’ are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or ’ If is 2 or more, then the 2 or more R 51’may form a ring together with the carbon atom to which they are attached, m3 ’ are each independently an integer of 0 to 4. * represents a bond to another atom. Ar 1 and Ar 2 each independently represents an aromatic ring group which may have a substituent, R 11 , R 12 , R 21 , R 22 , R 31 , R 32 , R 41 and R 42 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, p 0 is the average value, and is a number greater than 0. p 0 Z 12 and one Z 13 and one Z 14 The sum of (p 0 +2) groups, at least one of which is a structural unit represented by general formula (2A) or general formula (2A-LR), and 0 Z 12 and one Z 13 and one Z 14 The sum of (p 0 At least one of the +2) groups is a structural unit represented by general formula (4A) or general formula (4A-LR).

[0076] In this embodiment, when the (meth)acrylate-modified phenolic resin (A) is a mixture, the content of the fluorene ring-containing (meth)acrylate-modified phenolic resin (A1) represented by general formula (5-4) is preferably 5 to 95 mass%, more preferably 10 to 90 mass%, and even more preferably 20 to 80 mass%, relative to the total amount of the (meth)acrylate-modified phenolic resin (A) mixture (= the entire resin components having the partial structure represented by general formula (5-3)). The number average molecular weight (Mn) of the (meth)acrylate-modified phenolic resin (A) of this embodiment may be in the range of 100 to 10,000, and preferably in the range of 200 to 8,000. The weight average molecular weight (Mw) of the (meth)acrylate-modified phenolic resin may be in the range of 100 to 50,000, and preferably in the range of 300 to 40,000. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the (meth)acrylate-modified phenolic resin (A) of this embodiment can be in the range of 1-5, and is preferably 1-4. The vinyl equivalent (double bond equivalent (g / equivalent)) of the (meth)acrylate-modified phenolic resin (A) of the present embodiment is preferably in the range of 100 to 10,000, and more preferably 200 to 9,000.

[0077] In this specification, the term "vinyl equivalent (double bond equivalent (g / equivalent))" refers to an index of the amount of double bonds contained in a molecule, and for compounds of the same molecular weight, the smaller the double bond equivalent value, the greater the amount of double bonds introduced. In addition, in this specification, the "double bond equivalent" can be substantially the equivalent of a (meth)acrylate group (CH2=CR-C(=O)-OC≡(R represents a hydrogen atom or a methyl group). The "double bond equivalent" is a calculated value calculated from the amounts of raw materials charged, as described in the Examples section.

[0078] (Resin (B) Having a Polymerizable Unsaturated Group) The resin composition of the present embodiment essentially contains a resin (B) having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group contained in the resin (B) include (meth)acryloyl group, allyl group, isopropenyl group, 1-propenyl group, styryl group, styrylmethyl group, maleimide group, and vinyl ether group. The resin (B) having a polymerizable unsaturated group may not contain an acid group. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The content of the resin (B) having a polymerizable unsaturated group contained in the resin composition of this embodiment is, for example, preferably in the range of 5 to 900 parts by mass, more preferably 10 to 800 parts by mass, and even more preferably 10 to 600 parts by mass, relative to 100 parts by mass of the (meth)acrylate-modified phenolic resin (A) described above. The resin (B) having a polymerizable unsaturated group in this embodiment may have a polymerizable unsaturated group, and other specific structures or molecular weights are not particularly limited, and a wide variety of resins can be used. The resin (B) having a polymerizable unsaturated group may be used alone or in combination of two or more. It is preferable that the resin (B) having a polymerizable unsaturated group has a polymerizable unsaturated group but does not have an acid group.

[0079] Specific examples of the resin (B) having a polymerizable unsaturated group include a (meth)acrylate compound (B-1) and / or a resin (B-2) having a polymerizable unsaturated group. The (meth)acrylate compound (B-1) is not particularly limited as long as it has a (meth)acryloyl group, and examples thereof include aliphatic mono(meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate; cyclohexyl (meth)acrylate. alicyclic mono(meth)acrylate compounds such as isobornyl (meth)acrylate and adamantyl mono(meth)acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxyethoxyethyl (meth)acrylate mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzyl benzyl (meth)acrylate, and phenylphenoxyethyl (meth)acrylate; (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various mono(meth)acrylate monomers mentioned above; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various mono(meth)acrylate compounds mentioned above; aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate;Alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; and compounds having a (poly)oxyethylene group in the molecular structure of the above di(meth)acrylate compounds. polyoxyalkylene-modified di(meth)acrylate compounds having a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain introduced therein; lactone-modified di(meth)acrylate compounds having a (poly)lactone structure introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (Poly)oxyalkylene-modified tri(meth)acrylate compounds having a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain introduced into the structure; lactone-modified tri(meth)acrylate compounds having a (poly)lactone structure introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, aliphatic poly(meth)acrylate compounds having 4 or more functional groups, such as acrylate; (poly)oxyalkylene-modified poly(meth)acrylate compounds having 4 or more functional groups, in which a (poly)oxyalkylene chain, such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain, has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compound; and lactone-modified poly(meth)acrylate compounds having 4 or more functional groups, in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compound;Hydroxyethyl (meth)acrylate, Hydroxypropyl (meth)acrylate, Trimethylolpropane (meth)acrylate, Trimethylolpropane di(meth)acrylate, Pentaerythritol (meth)acrylate, Pentaerythritol di(meth)acrylate, Pentaerythritol tri(meth)acrylate, Dipentaerythritol (meth)acrylate, Dipentaerythritol di(meth)acrylate, Dipentaerythritol tri(meth)acrylate (meth)acrylate compounds having a hydroxyl group, such as dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate; (meth)acrylate compounds having a hydroxyl group, such as (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylolpropane chains, (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxyethylene ... (Poly)oxyalkylene modified products having a (poly)oxyalkylene chain such as a styrene chain introduced therein; lactone modified products having a (poly)lactone structure introduced into the molecular structure of the (meth)acrylate compound having a hydroxyl group; (meth)acrylate compounds having an isocyanate group such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate; (meth)acrylate monomers having a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate, and (meth)acrylate compounds having an epoxy group such as mono(meth)acrylates of diglycidyl ether compounds of hydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. The (meth)acrylate compounds (B-1) may be used alone or in combination of two or more.

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

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

[0082] Examples of the epoxy resin include bisphenol type epoxy resin, hydrogenated bisphenol type epoxy resin, biphenol type epoxy resin, hydrogenated biphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin, etc. These epoxy resins may be used alone or in combination of two or more. Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Examples of the hydrogenated bisphenol type epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol B type epoxy resin, hydrogenated bisphenol E type epoxy resin, hydrogenated bisphenol F type epoxy resin, and hydrogenated bisphenol S type epoxy resin. Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'-biphenol type epoxy resin. Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, hydrogenated tetramethyl-4,4'-biphenol type epoxy resin, and hydrogenated tetramethyl-2,2'-biphenol type epoxy resin.

[0083] Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Esters, acid halides, and acid anhydrides of the unsaturated monobasic acids can also be used. Examples of the unsaturated monobasic acid include those represented by the following general formula (6): [ka] (In the above general formula (6), X 61 represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain; X 61 A hydrogen atom in the structure of Y may be substituted with a halogen atom or an alkoxy group. 61 is a hydrogen atom or a methyl group. Compounds represented by the following formula:

[0084] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain. The (poly)ester chain may be, for example, a compound represented by the following general formula (7): [ka] (In the above general formula (7), R 71 and R 72 represents an alkylene group having 1 to 10 carbon atoms, 71 represents an integer of 1 to 5. Examples of the (poly)ester chain include those represented by the following formula: These unsaturated monobasic acids may be used alone or in combination of two or more.

[0085] Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. In addition, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used.

[0086] The (poly)carbonate chain may be, for example, a chain represented by the following general formula (8): [ka] (In the above general formula (8), R 81 represents an alkylene group having 1 to 10 carbon atoms, 81 represents an integer of 1 to 5. Examples of the (poly)carbonate chain include those represented by the following formula:

[0087] Examples of the polybasic acid anhydride include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides. Examples of the aliphatic polybasic acid anhydride include anhydrides of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, etc. In addition, the aliphatic polybasic acid anhydride may have an aliphatic hydrocarbon group of either a straight-chain type or a branched type, and may have an unsaturated bond in the structure. In the present invention, the alicyclic polybasic acid anhydride is one in which an acid anhydride group is bonded to an alicyclic structure, and the presence or absence of aromatic rings in other structural parts is not important. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydrides. Examples of the aromatic polybasic acid anhydride include anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, and benzophenone tetracarboxylic acid. These polybasic acid anhydrides may be used alone or in combination of two or more. Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, cyclohexane diisocyanate, and cyclohexane diisocyanate; Examples of the polyisocyanate include aromatic diisocyanate compounds such as silylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following general formula (9); and isocyanurate-modified, biuret-modified, and allophanate-modified products thereof. These polyisocyanate compounds may be used alone or in combination of two or more. [ka] (In the above general formula (9), R 92 and R 93 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; R 91 each independently represents an alkyl group having 1 to 4 carbon atoms; k 91 is 0 or an integer of 1 to 3, and n 91 is an integer greater than or equal to 1.)

[0088] Examples of the (meth)acrylate compound having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. In addition, (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds described above, and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds described above, and the like can also be used. The method for producing the epoxy resin (B-2.1) having the polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the epoxy resin (B-2.1) having the polymerizable unsaturated group may be carried out in an organic solvent as necessary, and may also use a basic catalyst as necessary.

[0089] Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, cyclohexanone, and dimethylacetamide; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; carbitol, cellosolve, methanol, ethanol, propanol, isopropanol, butanol, and cyclohexanol. Examples of the organic solvent include alcohol solvents such as propylene glycol monomethyl ether, propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol, and other ether solvents, glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether acetate, and other vegetable oils and fats such as soybean oil, linseed oil, rapeseed oil, and safflower oil, as well as methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents may be used alone or in combination of two or more.

[0090] In addition, as the organic solvent, commercially available products can also be used. Examples of commercially available products include "No. 1 Spindle Oil," "No. 3 Solvent," "No. 4 Solvent," "No. 5 Solvent," "No. 6 Solvent," "Naphthesol H," "Alkene 56NT," "AF Solvent No. 4," "AF Solvent No. 5," "AF Solvent No. 6," and "AF Solvent No. 7" manufactured by ENEOS Corporation; "Diadol 13" and "Dialene 168" manufactured by Mitsubishi Chemical Corporation; "F Oxocol" and "F Oxocol 180" manufactured by Nissan Chemical Industries, Ltd.; "Supersol LA35" and "Supersol LA38" manufactured by Idemitsu Kosan Co., Ltd.; and ExxonMobil Examples include "Exxor D80", "Exxor D110", "Exxor D120", "Exxor D130", "Exxor D160", "Exxor D100K", "Exxor D120K", "Exxor D130K", "Exxor D280", "Exxor D300", and "Exxor D320" manufactured by Exxor Chemical Co., Ltd.

[0091] Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and amine compounds such as tetramethylammonium hydroxide; trioctylmethylammonium chloride, tri quaternary ammonium salts such as octylmethylammonium acetate; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. In addition, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, etc. can also be used. The basic catalysts may be used alone or in combination of two or more.

[0092] <Urethane resin having polymerizable unsaturated group (B-2.2)> Examples of the urethane resin (B-2.2) having a polymerizable unsaturated group in this embodiment (hereinafter also referred to as resin (B-2.2)) include those obtained by reacting a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, and, if necessary, a polyol compound and / or a polybasic acid anhydride. As described above, a polybasic acid anhydride can be used as a reaction raw material for the resin (B-2.2), but it is preferable not to use it. The above resin (B-2.2) preferably has a polymerizable unsaturated group but does not have an acid group. The polyisocyanate compound, the (meth)acrylate compound having a hydroxyl group, and the polybasic acid anhydride are the same as those described above for the resin (B-2.1) and the like. Examples of the polyol compounds include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified compounds in which (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are introduced into the molecular structure of the various polyol compounds; lactone modified compounds in which (poly)lactone structures are introduced into the molecular structure of the various polyol compounds, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The polyol compounds may be used alone or in combination of two or more. The method for producing the urethane resin (B-2.2) having the polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the urethane resin (B-2.2) having the polymerizable unsaturated group may be carried out in an organic solvent if necessary, and may also use a basic catalyst if necessary. In this case, the organic solvent and the basic catalyst are the same as those described above for the resin (B-2.1) and the like.

[0093] <Acrylic resin having polymerizable unsaturated group (B-2.3)> Examples of the acrylic resin (B-2.3) having a polymerizable unsaturated group of this embodiment (hereinafter also referred to as resin (B-2.3)) include a reaction product obtained by further reacting a (meth)acrylate compound (β) having a reactive functional group capable of reacting with a hydroxyl group, carboxyl group, isocyanate group, glycidyl group, or other reactive functional group with an acrylic resin intermediate obtained by polymerizing the (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, carboxyl group, isocyanate group, or glycidyl group as an essential component, to introduce a (meth)acryloyl group, and a reaction product obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product as necessary. As described above, the polybasic acid anhydride can be used as a reaction raw material for the resin (B-2.3), but it is preferable not to use it. The above resin (B-2.3) preferably has a polymerizable unsaturated group but does not have an acid group. The acrylic resin intermediate may be a copolymer of the (meth)acrylate compound (α) and other compounds having polymerizable unsaturated groups as necessary. Examples of the compounds having other polymerizable unsaturated groups include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. The compound having an unsaturated group may be used alone or in combination of two or more kinds.

[0094] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but the following combinations are preferable from the viewpoint of reactivity. That is, when water (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having an isocyanate group as the (meth)acrylate compound (β). When a (meth)acrylate having a carboxyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a glycidyl group as the (meth)acrylate compound (β). When a (meth)acrylate having an isocyanate group is used as the (meth)acrylate compound (α), it is preferable to use water (meth)acrylate as the (meth)acrylate compound (β). When a (meth)acrylate having a glycidyl group is used as the (meth)acrylate compound (α), it is preferable to use a (meth)acrylate having a carboxyl group as the (meth)acrylate compound (β). The (meth)acrylate compound (β) may be used alone or in combination of two or more kinds. The polybasic acid anhydride is the same as that described above with respect to the resin (B-2.1) and the like. The method for producing the acrylic resin (B-2.3) having the polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylic resin (B-2.3) having the polymerizable unsaturated group may be carried out in an organic solvent if necessary, and may also use a basic catalyst if necessary. In this case, the organic solvent and the basic catalyst are the same as those described above for the resin (B-2.1) and the like.

[0095] <Amide-imide resin having polymerizable unsaturated group (B-2.4)> The amide-imide resin (B-2.4) having a polymerizable unsaturated group of this embodiment (hereinafter also referred to as resin (B-2.4)) can be, for example, a resin obtained by reacting an amide-imide resin having an acid group and / or an acid anhydride group with a (meth)acrylate compound having a hydroxyl group and / or a (meth)acrylate compound having an epoxy group, and, if necessary, a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. The compound having the reactive functional group may or may not have a (meth)acryloyl group. It is preferable that the resin (B-2.4) has a polymerizable unsaturated group but does not have an acid group. The amide-imide resin (B-2.4) having a polymerizable unsaturated group may have only an acid group or an acid anhydride group, or may have both. However, from the viewpoint of reactivity with a (meth)acrylate compound having a hydroxyl group or an epoxy compound having a (meth)acryloyl group and reaction control, the amide-imide resin (B-2.4) having a polymerizable unsaturated group is preferably one having an acid anhydride group, and more preferably one having both an acid group and an acid anhydride group. The solid content acid value of the amide-imide resin is preferably in the range of 60 to 350 mg KOH / g under neutral conditions, i.e., under conditions where the acid anhydride group is not ring-opened. On the other hand, it is preferably in the range of 61 to 360 mg KOH / g under conditions where the acid anhydride group is ring-opened, such as in the presence of water. The amide-imide resin (B-2.4) having the above-mentioned polymerizable unsaturated group may be, for example, one obtained by using a polyisocyanate compound and a polybasic acid anhydride as reaction raw materials. In this case, the polyisocyanate compound and the polybasic acid anhydride are the same as those described above with respect to the resin (B-2.1). As mentioned above, the polybasic acid anhydride can be used as a reaction raw material for the resin (B-2.4), but it is preferable not to use it. As reaction raw materials for the amide-imide resin (B-2.4) having a polymerizable unsaturated group, a polybasic acid can be used in combination with the polyisocyanate compound and polybasic acid anhydride, if necessary.

[0096] The polybasic acid may be any compound having two or more carboxyl groups in one molecule. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 -dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, etc. In addition, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in the molecule, can also be used. These polybasic acids may be used alone or in combination of two or more. The (meth)acrylate compound having a hydroxyl group is the same as that described above with respect to the resin (B-2.1) and the like. Examples of the (meth)acrylate compound having an epoxy group include (meth)acrylate monomers having a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and mono(meth)acrylates of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These (meth)acrylate compounds having an epoxy group may be used alone or in combination of two or more. The method for producing the amide-imide resin (B-2.4) having the polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the amide-imide resin (B-2.4) having the polymerizable unsaturated group may be carried out in an organic solvent if necessary, and may also use a basic catalyst if necessary. In this case, the organic solvent and the basic catalyst are the same as those described above for the resin (B-2.1) and the like.

[0097] <Acrylamide resin having polymerizable unsaturated group (B-2.5)> Examples of the acrylamide resin (B-2.5) having a polymerizable unsaturated group of this embodiment (hereinafter also referred to as resin (B-2.5)) include those obtained by reacting a compound having a phenolic hydroxyl group, an alkylene oxide or alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, and, if necessary, a polybasic acid anhydride and an unsaturated monobasic acid. As described above, the polybasic acid anhydride can be used as a reaction raw material for the resin (B-2.5), but it is preferable not to use it. The above resin (B-2.5) preferably has a polymerizable unsaturated group but does not have an acid group. The compound having a phenolic hydroxyl group refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following general formulas (10.1) to (10.5). [ka] (In the above general formulas (10.1) to (10.5), R 101 ~R 104 and R 107 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom; R 105 and R 106 j each independently represents a hydrogen atom or a methyl group; 101 ~j 105 Each independently represents an integer of 0 or 1 or more, preferably 0 or an integer of 1 to 3, and more preferably 0 or 1. 101 ~k 105 Each independently represents an integer of 1 or more, preferably 2 or 3.

[0098] In the above general formulae (10.1) to (10.5), the position of the substituent on the aromatic ring is arbitrary. For example, in the naphthalene ring of the general formula (10.2), the substituent may be substituted with any hydrogen atom on the ring. In the general formula (10.3), the substituent may be substituted with any hydrogen atom on the benzene ring present in one molecule of biphenyl. In the general formula (10.4), the substituent may be substituted with any hydrogen atom on the benzene ring present in one molecule of aralkyl. In the general formula (10.5), the substituent may be substituted with any hydrogen atom on the benzene ring present in one molecule. When the number of the substituents in one molecule is j, 101 ~j 105 and k 101 ~k 105 This shows that. Examples of the compound having a phenolic hydroxyl group include reaction products obtained by using a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any one of the following general formulae (11.1) to (11.5) and / or formaldehyde as essential reaction raw materials. Novolac-type phenolic resins using one or more compounds having at least one phenolic hydroxyl group in the molecule as reaction raw materials can also be used. [ka] (In the above general formulas (11.1) to (11.5), h 111 represents 0 or 1; R 111 ~R 116 each independently represents a monovalent aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group; k 111 ~k 116 each independently represents 0 or an integer of 1 to 4; Z 111 ~Z 116 each independently represents a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group; Y 111 represents an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group; n 111 represents an integer from 1 to 4.)

[0099] Specific examples of the above compounds include phenol, cresol, xylenol; dialkylphenols such as dimethylphenol and diethylphenol; trialkylphenols such as trimethylphenol and triethylphenol; diphenylphenol, triphenylphenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, tetramethylbisphenol A, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and phenol resin having a cyclo ring structure. The above-mentioned compounds having a phenolic hydroxyl group may be used alone or in combination of two or more kinds. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. The alkylene oxide may be used alone or in combination of two or more. Among these, the alkylene oxide is preferably ethylene oxide or propylene oxide. Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. The alkylene carbonate may be used alone or in combination of two or more. Among these, the alkylene carbonate is preferably ethylene carbonate or propylene carbonate. Examples of the N-alkoxyalkyl(meth)acrylamide compound include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide, etc. The N-alkoxyalkyl(meth)acrylamide compound may be used alone or in combination of two or more. The polybasic acid anhydrides and unsaturated monobasic acids are the same as those described above for the resin (B-2.1) and the like. The method for producing the acrylamide resin (B-2.5) having the polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylamide resin (B-2.5) having the polymerizable unsaturated group may be carried out in an organic solvent as necessary, and may also use a basic catalyst and an acid catalyst as necessary. In this case, the organic solvent and the basic catalyst are the same as those described above for the resin (B-2.1) and the like. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. In addition, solid acid catalysts having a strong acid such as a sulfonyl group can also be used. These acid catalysts may be used alone or in combination of two or more.

[0100] <Ester resin having polymerizable unsaturated group (B-2.6)> The ester resin (B-2.6) having a polymerizable unsaturated group of this embodiment (hereinafter also referred to as resin (B-2.6)) can be, for example, a compound having a phenolic hydroxyl group, an alkylene oxide or alkylene carbonate, an unsaturated monobasic acid, and, if necessary, a polybasic acid anhydride, which is obtained by reacting the compound. As described above, the polybasic acid anhydride can be used as a reaction raw material for the resin (B-2.6), but it is preferable not to use the polybasic acid anhydride. The resin (B-2.6) preferably has a polymerizable unsaturated group but does not have an acid group. The compounds having a phenolic hydroxyl group, the alkylene oxides, the alkylene carbonates, the unsaturated monobasic acids, and the polybasic acid anhydrides are the same as those described above for resins (B-2.1) and (B-2.5), etc. The method for producing the ester resin (B-2.6) having the polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the ester resin (B-2.6) having the polymerizable unsaturated group may be carried out in an organic solvent if necessary, and may also use a basic catalyst and an acid catalyst if necessary. In this case, the organic solvent, the basic catalyst, and the acid catalyst are the same as those described above for the resin (B-2.1) and the resin (B-2.5).

[0101] [Curable resin composition] The curable resin composition of the present embodiment contains the resin composition of the present embodiment (the (meth)acrylate-modified phenolic resin (A) and the resin having a polymerizable unsaturated group (B)) and a polymerization initiator. The polymerization initiator is preferably a photopolymerization initiator.

[0102] (Polymerization initiator) The polymerization initiator is preferably one or more selected from the group consisting of thermal polymerization initiators and photopolymerization initiators. The amount of the polymerization initiator added is preferably within a range of, for example, 0.1 to 20% by mass relative to the total amount (100% by mass) of the curable resin composition.

[0103] <Thermal polymerization initiator> Examples of the thermal polymerization initiator include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, azobisisobutyronitrile, and 2,2'-azobisdimethyl Valeronitrile, 2,2'-azobis(2-aminodipropane) dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 4,4'-azobis( Examples of the peroxide include azo compounds such as 4-cyanovaleric acid, organic peroxides such as cumene hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and 2,5-dimethylhexane-2,5-dihydroperoxide, and hydrogen peroxide.

[0104] <Photopolymerization initiator> Examples of the photopolymerization initiator of the present embodiment include photoradical polymerization initiators such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone.

[0105] Commercially available photopolymerization initiators include, for example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", "Omnirad-500", and "Omnirad-81". Examples of commercially available photoradical polymerization initiators include KAYACURE-DETX, KAYACURE-MBP, KAYACURE-DMBI, KAYACURE-EPA, and KAYACURE-OA (manufactured by Nippon Kayaku Co., Ltd.), BICURE-10, BICURE-55 (manufactured by Stouffer Chemical Co., Ltd.), Trigonal P1 (manufactured by Akzo Corporation), Sandray 1000 (manufactured by Sandoz Corporation), Deep (manufactured by Upjohn Corporation), Quantacure-PDO, Quantacure-ITX, and Quantacure-EPD (manufactured by Ward Blenkinsop Co., Ltd.), and Runtecure-1104 (manufactured by Runtec Corporation). These photopolymerization initiators can be used alone or in combination of two or more kinds. The content of the photopolymerization initiator in the curable resin composition is preferably 0.5 to 20 mass%, more preferably 1 to 10 mass%, and even more preferably 2 to 10 mass%, relative to 100 mass% of the total components of the curable resin composition other than the solvent.

[0106] <Additives> The resin composition or curable resin composition of the present embodiment may contain, as necessary, an additive selected from the group consisting of a curing agent, a curing accelerator, an ultraviolet absorber, an organic solvent, an inorganic filler or polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, a storage stabilizer, a polymerization inhibitor, and an antioxidant. The content of the additive is preferably 0.01 to 30 mass % in terms of solid content based on the entire resin composition or curable resin composition.

[0107] Examples of the curing agent include polybasic acids, unsaturated monobasic acids, amine compounds, amide compounds, azo compounds, organic peroxides, polyol compounds, and epoxy resins. The content of the curing agent is preferably 0.1 to 30% by mass, calculated as solid content, based on the entire curable resin composition.

[0108] Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and the like. Examples of the polybasic acid include methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, and anhydrides or halides thereof. In addition, examples of the polybasic acid include copolymers of conjugated diene vinyl monomers and acrylonitrile, which have carboxyl groups in the molecule. These polybasic acids can be used alone or in combination of two or more.

[0109] As the unsaturated monobasic acid, the same unsaturated monobasic acids as those exemplified above can be used, and these unsaturated monobasic acids can be used alone or in combination of two or more kinds.

[0110] Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivatives, etc. These amine compounds can be used alone or in combination of two or more kinds. Examples of the amide compound include dicyandiamide, a polyamide resin synthesized from a dimer of linoleic acid and ethylenediamine, etc. These amide compounds can be used alone or in combination of two or more kinds. The azo compound may, for example, be azobisisobutyronitrile.

[0111] As the organic peroxide, the same organic peroxides as those exemplified above can be used. These organic peroxides can be used alone or in combination of two or more kinds.

[0112] Examples of the polyol compound include polyol monomers such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, glycerin mono(meth)acrylate, trimethylolethane, trimethylolmethane mono(meth)acrylate, trimethylolpropane, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, and pentaerythritol di(meth)acrylate; mixtures of the above polyol monomers with succinic acid, adipic acid, azelaic acid, sebacic acid, and the like. polyester polyols obtained by co-condensation with dicarboxylic acids such as carboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and 1,4-cyclohexanedicarboxylic acid; lactone-type polyester polyols obtained by polycondensation reaction of the above polyol monomers with various lactones such as ε-caprolactone, δ-valerolactone, and 3-methyl-δ-valerolactone; and polyether polyols obtained by ring-opening polymerization of the above polyol monomers with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, and propyl glycidyl ether. These polyol compounds can be used alone or in combination of two or more. As the epoxy resin, the same ones as those exemplified above as the epoxy resin can be used, and these epoxy resins can be used alone or in combination of two or more kinds.

[0113] The curing accelerator accelerates the curing reaction, and examples thereof include phosphorus compounds, amine compounds, imidazole, organic acid metal salts, Lewis acids, amine complex salts, etc. These curing accelerators can be used alone or in combination of two or more kinds. The amount of the curing accelerator added is preferably within a range of 0.01 to 10 mass % in terms of solid content based on the entire curable resin composition.

[0114] Examples of the ultraviolet absorbent include triazine derivatives such as 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbents can be used alone or in combination of two or more.

[0115] As the organic solvent, the same organic solvents as those exemplified above can be used, and these organic solvents can be used alone or in combination of two or more kinds. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.

[0116] As the pigment, known and commonly used inorganic pigments and organic pigments can be used. Examples of the inorganic pigment include white pigments, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, graphite, etc. These inorganic pigments can be used alone or in combination of two or more kinds. Examples of the white pigment include titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, zinc sulfide, and the like. Among the above inorganic pigments, white pigments are preferred, and titanium oxide is more preferred, since a curable resin composition capable of forming a cured product excellent in elongation, elasticity, and heat yellowing resistance can be obtained. The content of the white pigment is preferably 1 to 90 mass %, more preferably 5 to 80 mass %, even more preferably 10 to 70 mass %, and still more preferably 20 to 70 mass %, based on the solid content of the curable resin composition.

[0117] Examples of the organic pigment include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments, etc. These organic pigments can be used alone or in combination of two or more kinds. As the polymerization inhibitor, the same ones as those exemplified above as the polymerization inhibitors can be used, and these polymerization inhibitors can be used alone or in combination of two or more kinds.

[0118] As the antioxidant, the same ones as those exemplified above as the antioxidants can be used, and these antioxidants can be used alone or in combination of two or more kinds. Examples of the flame retardant include inorganic phosphorus compounds such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides; phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxy, and the like. Examples of suitable flame retardants include organic phosphorus compounds such as cyclic organic phosphorus compounds such as 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof reacted with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oils, silicone rubbers, and silicone resins; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. These flame retardants can be used alone or in combination of two or more. When these flame retardants are used, the amount is preferably in the range of 0.1 to 20 mass% in the total resin composition. The method for producing the resin composition or the curable resin composition of the present embodiment is not particularly limited, and may be produced by any method. For example, a method of producing the composition by mixing each compounding component may be mentioned. The mixing method is not particularly limited, and a paint shaker, a disperser, a roll mill, a bead mill, a ball mill, an attritor, a sand mill, a bead mill, etc. may be used.

[0119] [Cured product] The cured product of the present embodiment is characterized in that it is obtained by subjecting a curable resin composition to a curing reaction. The cured product of the present embodiment is a cured product of the above-mentioned curable resin composition. The cured product can be obtained by irradiating the above-mentioned curable resin composition with active energy rays. Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. In addition, when ultraviolet rays are used as active energy rays, irradiation may be performed under an inert gas atmosphere such as nitrogen gas, or under an air atmosphere in order to efficiently carry out a curing reaction by ultraviolet rays. As a source of ultraviolet light, ultraviolet lamps are generally used from the viewpoints of practicality and economy, and specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc. The cumulative amount of 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 the occurrence of uncured portions can be prevented or suppressed. The irradiation of active energy rays may be carried out in one step or in two or more steps. In addition, since the cured product of the present embodiment has excellent elongation, elasticity, and heat yellowing resistance, it can be suitably used, for example, in semiconductor device applications as a resist member (solder resist), an insulating material (interlayer insulating material), a packaging material, an underfill material, a package adhesive layer for circuit elements, and an adhesive layer between integrated circuit elements and circuit boards. It can also be suitably used in thin display applications such as LCD and OELD as a thin film transistor protective film, a liquid crystal color filter protective film, a pigment resist for color filters, a resist for black matrices, a spacer, and the like. Among these, it can be particularly suitably used for solder resist applications.

[0120] [Goods] The article of the present embodiment is characterized by having a coating film made of the above-mentioned cured product. In the article of the present embodiment, the coating film can function as an insulating material having excellent heat resistance and coating appearance. The article of this embodiment is typically a printed wiring board or a substrate for a semiconductor package having a solder resist film (the coating film) formed in appropriate positions on the surface layer.

[0121] [Insulating material] The insulating material of the present embodiment is a cured product of the above-mentioned curable resin composition. Examples of the insulating material of the present embodiment include an interlayer insulating material for a build-up board, an insulating material for a circuit board such as an adhesive film for a build-up board, an insulating material for a circuit board, and an insulating material for a board for incorporating electronic components. For example, a method for producing a build-up board from the curable resin composition includes a method consisting of the following three steps. The first step is a step of applying the curable resin composition, which is appropriately blended with rubber, filler, etc., to a circuit board on which a circuit is formed, using a spray coating method, a curtain coating method, etc., and then curing the composition. The second step is a step of subsequently drilling a predetermined through-hole portion or the like as necessary, treating the surface with a roughening agent, forming unevenness by washing the surface with hot water, and plating a metal such as copper. The third step is a step of alternately building up a resin insulating layer and a conductor layer of a predetermined circuit pattern by repeating such operations as desired. It is preferable to drill a through-hole portion or the like after forming the outermost resin insulating layer. The first step can be performed not only by the above-mentioned solution coating, but also by a method of laminating a build-up film that has been coated and dried to a desired thickness in advance. In addition, in the build-up board of this embodiment, a copper foil with a resin, which is a copper foil on which a curable resin composition is semi-cured, is heated and pressed at 170 to 250°C onto a wiring board on which a circuit is formed, to form a roughened surface, thereby eliminating the plating process and enabling the manufacture of a build-up board.

[0122] [Resist material] The resist member of this embodiment is made of a cured product of the above-mentioned curable resin composition. The resist member of this embodiment can be obtained, for example, by applying the above-mentioned curable resin composition (resin material for solder resist) onto a substrate, evaporating and drying the organic solvent at a temperature range of about 60 to 100°C, exposing the substrate 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 substrate at a temperature range of about 140 to 200°C. Examples of the substrate include metal foils such as copper foil and aluminum foil. The resist member of this embodiment is excellent in low dielectric properties and elongation. EXAMPLES

[0123] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the examples given below.

[0124] [GPC measurement] Using the following measuring equipment and conditions, the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the phenolic hydroxyl group- and aromatic ring-containing resin and the (meth)acrylate-modified phenolic resin (A) obtained in the examples and comparative examples were calculated, and the properties of the obtained resins were evaluated.

[0125] "Measuring device" Tosoh Corporation "HLC-8320 GPC" "Measurement conditions" Column: Tosoh Corporation guard column "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G3000HXL" + Tosoh Corporation "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40℃ Developing solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: In accordance with the measurement manual for the "GPC Workstation EcoSEC-WorkStation," the following monodisperse polystyrene with known molecular weight was used. (Polystyrene used) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation Sample: A tetrahydrofuran solution (1.0% by mass, calculated as resin solid content) of the phenolic hydroxyl group and aromatic ring-containing resin or (meth)acrylate-modified phenolic resin (A) obtained in Synthesis Example was filtered through a microfilter (50 μl).

[0126] [FD-MS measurement] The phenolic hydroxyl group- and aromatic ring-containing resin and the (meth)acrylate-modified phenolic resin (A) obtained in the Synthesis Examples were measured using the following measuring device and under the following measuring conditions, and the properties of the obtained resins were evaluated. Measurement equipment: JMS-T100GC AccuTOF Measurement conditions Measurement range: m / z=4.00~2000.00 Rate of change: 51.2mA / min Final current value: 45mA Cathode voltage: -10kV Recording interval: 0.07 seconds

[0127] [ 13 C-NMR measurement] The chemical structures of the phenolic hydroxyl group and aromatic ring-containing resin and the (meth)acrylate-modified phenolic resin (A) obtained in the synthesis examples are shown below. 13 The results were confirmed by C-NMR and measurement conditions. 13 C-NMR: “JNM-ECZ400S” manufactured by JEOL RESONANCE Resonance frequency: 100MHz Number of times: 4000 Solvent: Chloroform-d Sample concentration: 12% by mass Relaxation agent: Chromium(III) acetylacetonate

[0128] [Heat resistance] The curable resin compositions obtained in the examples and comparative examples described below were applied to copper foil using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. 2 The coating film was irradiated with ultraviolet light of 1000 nm. The coating film was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the copper foil to obtain a cured product of the curable resin composition. A test piece 1 of 6 mm x 35 mm was cut out from this cured product, and the temperature (°C) at which the change in elastic modulus was maximum was evaluated as the glass transition temperature (Tg) using a viscoelasticity measuring device by a tensile method (frequency 1 Hz, heating rate 3°C / min). A higher Tg indicates better heat resistance.

[0129] [Dielectric constant] The curable resin compositions obtained in the examples and comparative examples described below were applied to a glass substrate using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply the curable resin compositions to the glass substrate at a temperature of 10 kJ / m 2 The coating film was irradiated with ultraviolet light of 1000 nm. The coating film was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the glass substrate to obtain a cured product of the curable resin composition. The cured product was then stored for 24 hours in a room at a temperature of 23°C and a humidity of 50%, and used as test piece 2. The relative dielectric constant of test piece 2 at 1 GHz was measured by a cavity resonance method using a network analyzer E8362C manufactured by Agilent Technologies.

[0130] [Dissipation factor] For the test piece 2 obtained in the measurement of the relative dielectric constant, the dielectric loss tangent of the test piece 1 at 1 GHz was measured by the cavity resonance method using the above-mentioned "Network Analyzer E8362C."

[0131] [Method for evaluating hydroxyl equivalent] The hydroxyl equivalent in each synthesis example was measured by a method based on the neutralization titration method specified in JIS K 0070 (1992).

[0132] (Synthesis Example 1: Synthesis of phenolic hydroxyl group and aromatic ring-containing resin (a-1)) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating column, and a stirrer was charged with 100.0 parts by mass of fluorene, 226.6 parts by mass of 4,4'-bis(chloromethyl)biphenyl (hereinafter also referred to as BCMB), 14.6 parts by mass of tetrabutylammonium bromide (hereinafter also referred to as TBAB), 6.76 parts by mass of sodium iodide, and 490.0 parts by mass of xylene, and the mixture was heated to 50°C with stirring. Next, 253.2 parts by mass of a 48% by mass aqueous potassium hydroxide solution was slowly added dropwise while being careful of heat generation, and after completion of the addition, the temperature was raised to 60° C. and reacted for 10 hours. Next, 154.4 parts by mass of 2,6-xylenol was charged and reacted for 15 hours at 80° C. Next, 232.9 parts by mass of water was charged to dissolve the salt, and the lower layer was separated to remove the water layer, and the mixture was washed four times with 407.8 parts by mass of water. Subsequently, 213.2 parts by mass of 2,6-xylenol and 4.08 parts by mass of para-toluenesulfonic acid were charged, and the mixture was heated to 170° C. and reacted at the same temperature for 3 hours. After the reaction was completed, the mixture was cooled and neutralized with 3.19 parts by mass of 49% by mass sodium hydroxide, and the solvent and excess 2,6-xylenol were distilled off by heating under reduced pressure to obtain the desired phenolic hydroxyl group and aromatic ring-containing resin (a-1) (hydroxyl group equivalent: 587 g / equivalent). The Mn of the phenolic hydroxyl group and aromatic ring-containing resin (a-1) was 1032 and the Mw was 1616. 13C-NMR confirmed the quaternary carbon at the 9-position of fluorene, and FD-MS confirmed the target compound at m / z 466.3 and 766.4. As an example of synthesis of a resin containing a phenolic hydroxyl group and an aromatic ring, the GPC chart of the obtained resin containing a phenolic hydroxyl group and an aromatic ring (a-1) is shown in FIG. 13 The C-NMR chart is shown in Figure 2, and the FD-MS chart is shown in Figure 3.

[0133] (Synthesis Example 2: Synthesis of phenolic hydroxyl group and aromatic ring-containing resin (a-2)) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating column, and a stirrer was charged with 130.0 parts by mass of fluorene, 205.4 parts by mass of α,α'-dichloro-p-xylene (hereinafter also referred to as PXDC), 7.56 parts by mass of TBAB, 10.6 parts by mass of sodium iodide, and 670.7 parts by mass of xylene, and the mixture was heated to 50°C with stirring. Next, 329.1 parts by mass of a 48% by mass aqueous potassium hydroxide solution was slowly added dropwise while taking care not to generate heat, and after completion of the addition, the temperature was raised to 60°C and reacted for 10 hours. Next, 173.4 parts by mass of 2,6-xylenol was charged, the temperature was raised to 80°C, and the reaction was carried out at the same temperature for 16 hours, after which 460.8 parts by mass of water was charged to dissolve the salt, the lower layer was separated to remove the aqueous layer, and the mixture was washed four times with 504.5 parts by mass of water. Subsequently, 169.2 parts by mass of 2,6-xylenol and 5.05 parts by mass of para-toluenesulfonic acid were charged, and the mixture was heated to 160° C. and reacted at the same temperature for 3 hours. After the reaction was completed, the mixture was cooled and neutralized with 2.19 parts by mass of 49% by mass sodium hydroxide, and the solvent and excess 2,6-xylenol were distilled off by heating under reduced pressure to obtain the desired phenolic hydroxyl group and aromatic ring-containing resin (a-2) (hydroxyl group equivalent: 527 g / equivalent). The Mn of the phenolic hydroxyl group and aromatic ring-containing resin (a-2) was 1199 and the Mw was 1717. 13 C-NMR confirmed the quaternary carbon at the 9-position of fluorene, and FD-MS confirmed the target compound at m / z 614.4, 882.5, and 1106.6.

[0134] (Synthesis Example 3: Synthesis of phenolic hydroxyl group and aromatic ring-containing resin (a-3)) A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer was charged with 50.0 parts by mass of fluorene, 79.0 parts by mass of PXDC, 37.8 parts by mass of BCMB, 7.76 parts by mass of TBAB, 3.99 parts by mass of potassium iodide, and 333.5 parts by mass of xylene, and the mixture was heated to 50°C with stirring. Next, 154.7 parts by mass of 48% by mass potassium hydroxide aqueous solution was slowly dropped while being careful of heat generation, and after the dropwise addition was completed, the temperature was raised to 60°C and reacted for 6 hours. Next, 91.1 parts by mass of 1-naphthol, 142.3 parts by mass of water, and 64.5 parts by mass of isopropyl alcohol were charged, the temperature was raised to 75°C, and the reaction was carried out at the same temperature for 5 hours, after which the lower layer was removed by liquid separation. 460.8 parts by mass of the obtained water was charged, the salt was dissolved, and the lower layer was separated to remove the water layer, and the mixture was washed six times with 209.6 parts by mass of water. Subsequently, 130.1 parts by mass of 1-naphthol and 4.19 parts by mass of para-toluenesulfonic acid were added, and the mixture was heated to 160° C. and reacted at the same temperature for 3 hours. After the reaction was completed, the mixture was cooled and neutralized with 1.82 parts by mass of 49% by mass sodium hydroxide, and the solvent and excess 1-naphthol were distilled off by heating under reduced pressure to obtain the desired phenolic hydroxyl group and aromatic ring-containing resin (a-3) (hydroxyl group equivalent: 360 g / equivalent). The Mn of the phenolic hydroxyl group and aromatic ring-containing resin (a-3) was 782 and the Mw was 1277. 13 C-NMR confirmed the quaternary carbon at the 9-position of fluorene, and FD-MS confirmed the target compound at m / z 658.4, 734.4, 926.5, and 1002.6.

[0135] (Synthesis Example 4: Synthesis of phenolic hydroxyl group and aromatic ring-containing resin (a-4)) A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer was charged with 100.0 parts by mass of fluorene, 158.0 parts by mass of PXDC, 14.6 parts by mass of TBAB, 6.76 parts by mass of sodium iodide, and 515.9 parts by mass of xylene, and the mixture was heated to 50°C with stirring. Next, 253.2 parts by mass of a 48% by mass aqueous potassium hydroxide solution was slowly added dropwise while being careful not to generate heat, and after completion of the addition, the temperature was raised to 60° C. and reacted for 13.5 hours. Next, 136.6 parts by mass of ortho-cresol was charged, and the reaction was carried out at 60° C. for 30 hours and at 80° C. for a further 5 hours, after which 354.4 parts by mass of water and 31.2 parts by mass of an 85% aqueous phosphoric acid solution were charged while being careful not to generate heat, the salt was dissolved, the lower layer was separated to remove the aqueous layer, and the mixture was washed four times with 326.3 parts by mass of water. Subsequently, 130.1 parts by mass of ortho-cresol and 3.26 parts by mass of para-toluenesulfonic acid were added, and the mixture was heated to 160° C. and reacted at the same temperature for 4 hours. After the reaction was completed, the mixture was cooled and neutralized with 1.42 parts by mass of 49% by mass sodium hydroxide, and the solvent and excess ortho-cresol were distilled off by heating under reduced pressure to obtain the desired phenolic hydroxyl group and aromatic ring-containing resin (a-4) (hydroxyl group equivalent: 452 g / equivalent). The Mn of the phenolic hydroxyl group and aromatic ring-containing resin (a-4) was 867 and the Mw was 1153. 13 C-NMR confirmed the quaternary carbon at the 9-position of fluorene, and FD-MS confirmed the target compound at m / z 586.3 and 854.5.

[0136] (Synthesis Example 5: Synthesis of phenolic hydroxyl group and aromatic ring-containing resin (a-5)) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer was charged with 100.0 parts by mass of fluorene, 273.4 parts by mass of 1,4-bis(chloromethyl)benzene, 147.0 parts by mass of phenol, 520.4 parts by mass of toluene and 520.4 parts by mass of DMSO (dimethyl sulfoxide), and the temperature was raised to 40°C to homogenize. Then, 269.4 parts by mass of 49% by mass of sodium hydroxide aqueous solution was dropped so that the temperature was 60°C or less. After dropping, the temperature was raised to 60°C and reacted for 8 hours, after which 383.9 parts by mass of water was added, the salt was dissolved, and the lower layer was removed by liquid separation. Then, the organic layer was neutralized with 6.88 parts by mass of 89% by mass of phosphoric acid aqueous solution, and then washed three times with 383.9 parts by mass of water. Next, 283.1 parts by mass of phenol and 10.4 parts by mass of p-toluenesulfonic acid monohydrate were added, and the mixture was heated to 160°C while azeotroping the water and the solvent, and reacted for 3 hours. After the reaction was completed, the mixture was cooled, and the organic layer was neutralized with 4.52 parts by mass of a 49% by mass aqueous sodium hydroxide solution, and cooled to 80°C while adding 812.8 parts by mass of MIBK, and washed three times with 575.8 parts by mass of water at 80°C. The obtained organic layer was heated and distilled under reduced pressure to remove all volatile matter, and the desired phenolic hydroxyl group and aromatic ring-containing resin (a-5) was obtained. 13 The C-NMR chart confirmed that the reaction had started from the 9-position of the fluorene. The FD-MS chart showed m / z=558.3, 754.4, and 826.4, confirming that the product was the desired phenolic hydroxyl group- and aromatic ring-containing resin.

[0137] (Synthesis Example 6: Synthesis of phenolic hydroxyl group and aromatic ring-containing resin (a-6)) In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer, 100.0 parts by mass of fluorene, 210.6 parts by mass of 1,4-bis(chloromethyl)benzene, 130.1 parts by mass of o-cresol, 440.7 parts by mass of toluene and 440.7 parts by mass of DMSO were added, and the mixture was heated to 40°C and homogenized. Then, 297.7 parts by mass of 49% by mass of sodium hydroxide aqueous solution were dropped so that the temperature was 60°C or less. After the dropping, the temperature was raised to 60°C and reacted for 8 hours, after which 424.2 parts by mass of water was added, the salt was dissolved, and the lower layer was removed by separation. Then, the organic layer was neutralized with 3.97 parts by mass of 89% by mass of phosphoric acid aqueous solution, and then washed three times with 424.2 parts by mass of water. Next, 325.3 parts by mass of o-cresol and 8.81 parts by mass of p-toluenesulfonic acid monohydrate were added, and the mixture was heated to 160°C while azeotroping the water and the solvent, and reacted for 3 hours. After the reaction was completed, the mixture was cooled, and the organic layer was neutralized with 3.83 parts by mass of a 49% by mass aqueous solution of sodium hydroxide, and cooled to 80°C while adding 661.1 parts by mass of toluene, and washed three times with 424.2 parts by mass of water at 80°C. The obtained organic layer was heated and distilled under reduced pressure to remove all volatile matter, and a phenolic hydroxyl group and aromatic ring-containing resin (a-6) was obtained. 13 The C-NMR chart confirmed that the reaction had started from the 9th position of the fluorene. The FD-MS chart showed m / z=586.4, 796.5, and 1064.7, confirming that the product was the desired phenolic hydroxyl group- and aromatic ring-containing resin.

[0138] (Synthesis Example 7: Synthesis of phenolic hydroxyl group and aromatic ring-containing resin (a-7)) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer was charged with 75.0 parts by mass of fluorene, 158.0 parts by mass of 1,4-bis(chloromethyl)benzene, 110.3 parts by mass of 2,6-dimethylphenol, 343.2 parts by mass of toluene and 343.2 parts by mass of DMSO, and the temperature was raised to 40°C to homogenize. Then, 223.3 parts by mass of 49% by mass of sodium hydroxide aqueous solution was dropped so that the temperature was 60°C or less. After dropping, the temperature was raised to 60°C and reacted for 8 hours, after which 318.2 parts by mass of water was added, the salt was dissolved, and the lower layer was removed by separation. Then, the organic layer was neutralized with 2.98 parts by mass of 89% by mass of phosphoric acid aqueous solution, and then washed three times with 318.2 parts by mass of water. Next, 165.4 parts by mass of 2,6-dimethylphenol and 6.86 parts by mass of p-toluenesulfonic acid monohydrate were added, and the mixture was heated to 160°C while azeotroping the water and the solvent, and reacted for 3 hours. After the reaction was completed, the mixture was cooled, and the organic layer was neutralized with 2.98 parts by mass of a 49% by mass aqueous solution of sodium hydroxide, and cooled to 80°C while adding 343.2 parts by mass of toluene, and washed three times with 318.2 parts by mass of water at 80°C. The obtained organic layer was heated and distilled under reduced pressure to remove all volatile matter, and a phenolic hydroxyl group and aromatic ring-containing resin (a-7) was obtained. 13 The C-NMR chart confirmed that the reaction had started from the 9th position of the fluorene. The FD-MS chart showed m / z=614.4 and 838.5, confirming that the product was the desired resin containing a phenolic hydroxyl group and an aromatic ring.

[0139] (Synthesis Example 8: Synthesis of phenolic hydroxyl group and aromatic ring-containing resin (a-8)) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer was charged with 75.0 parts by mass of fluorene, 158.0 parts by mass of 1,4-bis(chloromethyl)benzene, 130.1 parts by mass of 2-naphthol, 363.1 parts by mass of toluene and 363.1 parts by mass of DMSO, and the temperature was raised to 40°C to homogenize. Then, 223.3 parts by mass of 49% by mass of sodium hydroxide aqueous solution was dropped so that the temperature was 60°C or less. After dropping, the temperature was raised to 60°C and reacted for 8 hours, after which 318.2 parts by mass of water was added, the salt was dissolved, and the lower layer was removed by separation. Then, the organic layer was neutralized with 2.98 parts by mass of 89% by mass of phosphoric acid aqueous solution, and then washed three times with 318.2 parts by mass of water. Next, 195.2 parts by mass of 2-naphthol and 7.26 parts by mass of p-toluenesulfonic acid monohydrate were added, and the mixture was heated to 160°C while azeotroping the water and the solvent, and reacted for 3 hours. After the reaction was completed, the mixture was cooled, and the organic layer was neutralized with 3.15 parts by mass of a 49% by mass aqueous solution of sodium hydroxide, and cooled to 80°C while adding 544.6 parts by mass of toluene, and washed three times with 435.7 parts by mass of isopropyl alcohol and 318.2 parts by mass of water. The obtained organic layer was heated and distilled under reduced pressure to remove all volatile matter, and a phenolic hydroxyl group- and aromatic ring-containing resin (a-8) was obtained. 13 The C-NMR chart confirmed that the reaction had started from the 9-position of the fluorene. The FD-MS chart showed m / z=658.4, 904.5, and 1172.7, confirming that the product was the desired phenolic hydroxyl group- and aromatic ring-containing resin.

[0140] (Synthesis Example 9: Synthesis of phenolic hydroxyl group and aromatic ring-containing resin (a-9)) In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer, 75.0 parts by mass of fluorene, 294.2 parts by mass of 4,4'-bis(chloromethyl)biphenyl, 110.3 parts by mass of phenol, 479.5 parts by mass of toluene and 479.5 parts by mass of DMSO were added, and the mixture was heated to 40°C and homogenized. Then, 202.7 parts by mass of 49% by mass of sodium hydroxide aqueous solution were dropped so that the temperature was 60°C or less. After the dropping, the temperature was raised to 60°C and reacted for 8 hours, after which 413.0 parts by mass of water was added, the salt was dissolved and the mixture was cooled to room temperature. Then, 193.5 parts by mass of 89% by mass of phosphoric acid aqueous solution was dropped to neutralize the mixture, and the lower layer was removed by liquid separation. At that time, it was confirmed that the lower layer was acidic. Next, 212.3 parts by mass of phenol and 9.59 parts by mass of p-toluenesulfonic acid monohydrate were added, and the mixture was heated to 160°C while azeotroping the water and the solvent, and reacted for 3 hours. After the reaction was completed, the mixture was cooled to 80°C while adding 719.2 parts by mass of toluene, and 4.2 parts by mass of a 49% by mass aqueous solution of sodium hydroxide was added, followed by washing four times with 394.0 parts by mass of water (80°C) to neutralize the organic layer. The obtained organic layer was heated and distilled under reduced pressure to remove all volatile matter, thereby obtaining a phenolic hydroxyl group and aromatic ring-containing resin (a-9). 13 The C-NMR chart confirmed that the reaction had started from the 9-position of the fluorene. The FD-MS chart showed m / z=710.4 and 982.4, confirming that the product was the desired phenolic hydroxyl group- and aromatic ring-containing resin.

[0141] (Synthesis Example 10: Synthesis of phenolic hydroxyl group and aromatic ring-containing resin (a-10)) In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer, 50.0 parts by mass of fluorene, 79.0 parts by mass of 1,4-bis(chloromethyl)benzene, 37.8 parts by mass of 4,4'-bis(chloromethyl)biphenyl, 7.76 parts by mass of tetrabutylammonium bromide, 4.0 parts by mass of potassium iodide and 333.5 parts by mass of xylene were added, and the mixture was heated to 60°C and homogenized. Then, 154.7 parts by mass of a 48% by mass aqueous sodium hydroxide solution were added dropwise. After the dropwise addition, the mixture was reacted at 60°C for 6 hours. Then, 91.1 parts by mass of 1-naphthol, 64.5 parts by mass of isopropyl alcohol and 142.3 parts by mass of water were added, and the mixture was heated to 75°C and reacted for 5 hours. Next, the lower layer was removed by separation and washed six times with 209.6 parts by mass of water. Next, 130.1 parts by mass of 1-naphthol and 4.2 parts by mass of p-toluenesulfonic acid were added, and the mixture was heated to 160°C and reacted for 3 hours. After the reaction was completed, the mixture was cooled and neutralized by adding 1.8 parts by mass of a 49% by mass aqueous solution of sodium hydroxide. The mixture was then heated and distilled under reduced pressure to remove the solvent and 1-naphthol, yielding a phenolic hydroxyl group- and aromatic ring-containing resin (a-10). 13 The C-NMR chart confirmed that the reaction had started from the 9th position of the fluorene. The FD-MS chart showed m / z=658.4 and 734.4, confirming that the product was the desired resin containing a phenolic hydroxyl group and an aromatic ring. In order to confirm the properties of the intermediate phenolic hydroxyl group and aromatic ring-containing resin, the Mn, Mw, Mw / Mn, hydroxyl group equivalent, softening point and Mf / M1 of the phenolic hydroxyl group and aromatic ring-containing resins (a-5) to (a-10) were measured as examples of the phenolic hydroxyl group and aromatic ring-containing resin. The results are shown in Table 1.

[0142] [Table 1]

[0143] (Synthesis Example 11: Synthesis of (meth)acrylate-modified phenolic resin (A-1)) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 100.0 parts by mass of a phenolic hydroxyl group and aromatic ring-containing resin (a-1), 334.8 parts by mass of toluene, 1.04 parts by mass of 4-dimethylaminopyridine (DMAP), and 24.1 parts by mass of triethylamine (TEA), and 36.8 parts by mass of methacrylic anhydride was added dropwise. Next, the mixture was heated to 80°C while blowing air into it, and reacted at the same temperature for 24 hours. After the reaction was completed, the organic layer was reprecipitated with methanol and dried to obtain a (meth)acrylate-modified phenolic resin (A-1). The Mn of the obtained (meth)acrylate-modified phenolic resin (A-1) was 1135 and the Mw was 1895. As an example of a synthesis example of the (meth)acrylate-modified phenolic resin (A), the GPC chart of (meth)acrylate-modified phenolic resin (A-1) is shown in FIG. 13 The C-NMR chart is shown in Figure 5, and the FD-MS chart is shown in Figure 6.

[0144] (Synthesis Example 12: Synthesis of (meth)acrylate-modified phenolic resin (A-2)) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 100.0 parts by mass of phenolic hydroxyl group and aromatic ring-containing resin (a-2), 338.7 parts by mass of toluene, 1.16 parts by mass of DMAP, and 26.9 parts by mass of TEA, and 41.0 parts by mass of methacrylic anhydride were dropped and charged. Next, the mixture was heated to 80°C while blowing air into it, and reacted at the same temperature for 24 hours. Next, the mixture was cooled to 40°C, washed 10 times with isopropyl alcohol (IPA) and water, and the organic layer was vacuum heated with a rotary evaporator to remove volatiles, and the phenolic hydroxyl group and aromatic ring-containing resin (a-2) was methacrylated to obtain a (meth)acrylate-modified phenolic resin (A-2). The Mn of the obtained (meth)acrylate-modified phenolic resin (A-2) was 1131, and the Mw was 1683. The structure of the (meth)acrylate modified phenolic resin (A-2) was analyzed as follows: 13 C-NMR and 1 H-NMR was used.

[0145] (Synthesis Example 13: Synthesis of (meth)acrylate-modified phenolic resin (A-3)) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 110.0 parts by mass of phenolic hydroxyl group and aromatic ring-containing resin (a-3), 333.0 parts by mass of toluene, 2.05 parts by mass of DMAP, and 0.13 parts by mass of dibutylhydroxytoluene (BHT), and after dehydration, 43.3 parts by mass of TEA was charged, and 66.0 parts by mass of methacrylic anhydride was dropped and charged. Next, the mixture was heated to 80°C while blowing air, and reacted at the same temperature for 24 hours. Next, the mixture was cooled to 60°C, washed 10 times with IPA and water, and the organic layer was vacuum heated with a rotary evaporator to remove volatiles, and the phenolic hydroxyl group and aromatic ring-containing resin (a-3) was methacrylated to obtain (meth)acrylate-modified phenolic resin (A-3). The resulting (meth)acrylate-modified phenolic resin (A-3) had an Mn of 932 and an Mw of 1533. The structural analysis of the (meth)acrylate-modified phenolic resin (A-3) was as follows: 13 C-NMR and 1 H-NMR was used.

[0146] (Synthesis Example 14: Synthesis of (meth)acrylate-modified phenolic resin (A-4)) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 100.0 parts by mass of the phenolic hydroxyl group and aromatic ring-containing resin (a-4), 344.4 parts by mass of toluene, 1.35 parts by mass of DMAP, and 31.3 parts by mass of TEA, and 47.8 parts by mass of methacrylic anhydride were added dropwise. Next, the mixture was heated to 80°C while blowing air into it, and reacted at the same temperature for 24 hours. Next, the mixture was cooled to 40°C, washed 10 times with IPA and water, and the organic layer was vacuum heated in a rotary evaporator to remove volatiles, and the phenolic hydroxyl group and aromatic ring-containing resin (a-4) was methacrylated to obtain a (meth)acrylate-modified phenolic resin (A-4). The Mn of the obtained (meth)acrylate-modified phenolic resin (A-4) was 974, and the Mw was 1289. The structural analysis of the (meth)acrylate-modified phenolic resin (A-4) was as follows: 13 C-NMR and 1 H-NMR was used.

[0147] (Synthesis Example 15: Synthesis of (meth)acrylate-modified phenolic resin (A-5)) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 225 parts by mass of a phenolic hydroxyl group and aromatic ring-containing resin (a-5), 698 parts by mass of toluene, 2.1 parts by mass of DMAP, and 0.3 parts by mass of BHT, and the moisture was removed with a fractionating tube under heating and refluxing conditions. It was then cooled to 70°C, 141.4 parts by mass of TEA was charged, and 215.6 parts by mass of methacrylic anhydride was added dropwise. It was then heated to 80°C and reacted at the same temperature for 24 hours. It was then cooled to 50°C, washed 10 times with IPA and water, and the organic layer was vacuum heated with a rotary evaporator to remove volatiles, and the desired (meth)acrylate-modified phenolic resin (A-5) was obtained.

[0148] (Synthesis Example 16: Synthesis of (meth)acrylate-modified phenolic resin (A-6)) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 254 parts by mass of a phenolic hydroxyl group and aromatic ring-containing resin (a-6), 769 parts by mass of toluene, 2.4 parts by mass of DMAP, and 0.3 parts by mass of BHT, and the moisture was removed with a fractionating tube under heating and refluxing conditions. It was then cooled to 70°C, 141.4 parts by mass of TEA was charged, and 215.6 parts by mass of methacrylic anhydride was added dropwise. It was then heated to 80°C and reacted at the same temperature for 24 hours. It was then cooled to 50°C, washed 10 times with IPA and water, and the organic layer was vacuum heated with a rotary evaporator to remove volatiles, and the desired (meth)acrylate-modified phenolic resin (A-6) was obtained.

[0149] (Synthesis Example 17: Synthesis of (meth)acrylate-modified phenolic resin (A-7)) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 271 parts by mass of a phenolic hydroxyl group and aromatic ring-containing resin (a-7), 810 parts by mass of toluene, 2.5 parts by mass of DMAP, and 0.3 parts by mass of BHT, and the moisture was removed with a fractionating tube under heating and refluxing conditions. It was then cooled to 70°C, 141.4 parts by mass of TEA was charged, and 215.6 parts by mass of methacrylic anhydride were added dropwise. It was then heated to 80°C and reacted at the same temperature for 24 hours. It was then cooled to 50°C, washed 10 times with IPA and water, and the organic layer was vacuum heated with a rotary evaporator to remove volatiles, and the desired (meth)acrylate-modified phenolic resin (A-7) was obtained.

[0150] (Synthesis Example 18: Synthesis of (meth)acrylate-modified phenolic resin (A-8)) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 337 parts by mass of a phenolic hydroxyl group and aromatic ring-containing resin (a-8), 972 parts by mass of toluene, 3.0 parts by mass of DMAP, and 0.4 parts by mass of BHT, and the moisture was removed with a fractionating tube under heating and refluxing conditions. It was then cooled to 70°C, 141.4 parts by mass of TEA was charged, and 215.6 parts by mass of methacrylic anhydride were added dropwise. It was then heated to 80°C and reacted at the same temperature for 24 hours. It was then cooled to 50°C, washed 10 times with IPA and water, and the organic layer was vacuum heated with a rotary evaporator to remove volatiles, and the desired (meth)acrylate-modified phenolic resin (A-8) was obtained.

[0151] (Synthesis Example 19: Synthesis of (meth)acrylate-modified phenolic resin (A-9)) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 287 parts by mass of a phenolic hydroxyl group and aromatic ring-containing resin (a-9), 850 parts by mass of toluene, 2.6 parts by mass of DMAP, and 0.3 parts by mass of BHT, and the moisture was removed with a fractionating tube under heating and refluxing conditions. It was then cooled to 70°C, 141.4 parts by mass of TEA was charged, and 215.6 parts by mass of methacrylic anhydride was added dropwise. It was then heated to 80°C and reacted at the same temperature for 24 hours. It was then cooled to 50°C, washed 10 times with IPA and water, and the organic layer was vacuum heated with a rotary evaporator to remove volatiles, and the desired (meth)acrylate-modified phenolic resin (A-9) was obtained.

[0152] (Synthesis Example 20: Synthesis of (meth)acrylate-modified phenolic resin (A-10)) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 360 parts by mass of a phenolic hydroxyl group and aromatic ring-containing resin (a-10), 1028 parts by mass of toluene, 3.2 parts by mass of DMAP, and 0.4 parts by mass of BHT, and the moisture was removed with a fractionating tube under heating and refluxing conditions. It was then cooled to 70°C, 141.4 parts by mass of TEA was charged, and 215.6 parts by mass of methacrylic anhydride were added dropwise. It was then heated to 80°C and reacted at the same temperature for 24 hours. It was then cooled to 50°C, washed 10 times with IPA and water, and the organic layer was vacuum heated with a rotary evaporator to remove volatiles, and the desired (meth)acrylate-modified phenolic resin (A-10) was obtained.

[0153] (Synthesis Example 21: Production of Resin (B-1) Having Polymerizable Unsaturated Group) A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 188 parts by mass of bisphenol A type epoxy resin (EPICLON 850-S manufactured by DIC Corporation, epoxy equivalent weight 188 g / equivalent), and 0.3 parts by mass of dibutylhydroxytoluene and 0.1 parts by mass of methoquinone as a thermal polymerization inhibitor were added thereto. Thereafter, 72 parts by mass of acrylic acid and 1.3 parts by mass of triphenylphosphine were added, and the reaction was carried out at 120° C. for 8 hours while blowing in air, to obtain a resin (B-1) having a polymerizable unsaturated group.

[0154] (Example 1: Preparation of resin composition (1)) A resin composition (1) was prepared by kneading 20 parts by mass of the (meth)acrylate-modified phenolic resin (A-1) obtained in Synthesis Example 1 and 80 parts by mass of the resin having a polymerizable unsaturated group (B-1) obtained in Synthesis Example 21.

[0155] (Example 2: Preparation of curable resin composition (1)) 100 parts by mass of the resin composition (1) prepared in Example 1 above, a photopolymerization initiator ("Omnirad 907" manufactured by IGM), and methyl ethyl ketone as an organic solvent were mixed in the parts by mass shown in Table 2 and kneaded to obtain a curable resin composition (1).

[0156] (Examples 3 to 11: Preparation of curable resin compositions (2) to (10)) In the composition ratios shown in Table 2, the (meth)acrylate-modified phenolic resins (A-2) to (A-10) synthesized in the above Synthesis Examples, the resin (B-1) having a polymerizable unsaturated group synthesized above, a photopolymerization initiator (IGM's "Omnirad 907"), and methyl ethyl ketone as an organic solvent were mixed in the parts by mass shown in Table 2 and kneaded to obtain curable resin compositions (2) to (10). The above evaluations were carried out using the curable resin compositions (1) to (10) obtained in the above Examples 2 to 11. The results are shown in Table 2.

[0157] (Comparative Example 1: Preparation of curable resin composition (C1)) The resin (B-1) having a polymerizable unsaturated group prepared in Synthesis Example 21, a photopolymerization initiator (IGM's "Omnirad 907"), and an organic solvent, methyl ethyl ketone, were mixed in the composition ratio shown in Table 1, and a curable resin composition (C1) was obtained in the same manner as in Example 2. Table 2 shows the measurement results of the composition, Tg, dielectric constant and dielectric tangent of the curable resin composition (1) obtained in Example 2 and the curable resin composition (C1) obtained in Comparative Example 1.

[0158] [Table 2] In Table 2, the parts by mass of the (meth)acrylate-modified phenolic resins (A-1) to (A-10) and the resin (B-1) having a polymerizable unsaturated group obtained in Synthesis Example 21 are solid content values. It was confirmed that the cured products of the curable resin compositions of the Examples shown in Table 2 had low dielectric constants and high TG (excellent heat resistance). On the other hand, it was confirmed that the cured product obtained from the curable resin composition of Comparative Example 1 was inferior in dielectric properties and heat resistance compared to the Examples because the curable resin composition used did not contain the (meth)acrylate-modified phenolic resins (A-1) to (A-10) defined in the present invention. Therefore, it is considered that the resin composition of this example is superior in heat resistance and dielectric properties (dielectric constant and dielectric tangent) when cured, compared with the resin composition of the comparative example. [Industrial Applicability]

[0159] The resin composition of the present disclosure can form a cured product having low dielectric properties and excellent heat resistance, and therefore can be suitably used in semiconductor device applications as a resist member (solder resist), an insulating material (interlayer insulating material), a packaging material, an underfill material, a package adhesive layer for circuit elements, and an adhesive layer between integrated circuit elements and circuit boards. In addition, in applications for thin displays such as LCD and OELD, the resin composition can be suitably used as a thin film transistor protective film, a liquid crystal color filter protective film, a pigment resist for color filters, a resist for black matrices, a spacer, and the like. Among these, the resin composition can be particularly suitably used for resist members and insulating material applications.

Claims

1. A (meth)acrylate-modified phenolic resin (A) which is a (meth)acrylic acid ester of a phenolic hydroxyl group- and aromatic ring-containing resin, the (meth)acrylate-modified phenolic resin (A) being obtained by reacting a fluorene compound (not having a substituent at the 9-position), a phenolic hydroxyl group-containing compound, and a compound represented by general formula (1) as reaction raw materials (a); A resin composition comprising: (B) a resin having a polymerizable unsaturated group. 【Chemistry 1】 (In the above general formula (1), Ar represents an aromatic ring group which may have a substituent. R １１ , R １２ , R ２２ and R ２１ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, X １１ and X ２１ are each independently a leaving group.

2. The ratio (Mf / M1) of the number of moles (Mf) of the fluorene compound to the number of moles (M1) of the compound represented by the general formula (1) is 0.01 to 0.

99. The resin composition according to claim 1.

3. The resin composition according to claim 1 or 2, wherein the (meth)acrylate-modified phenolic resin (A) is represented by the following general formula (5): 【Chemistry 2】 "In the above general formula (5), Z １ each independently represents the following general formula (2A): 【Chemistry 3】 (In the above general formula (2A), R ２１ and R ２２ each independently represents an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom, and each of m1 and m2 independently represents an integer of 0 to 4. * represents a bond to another atom. 【Chemistry 4】 (In the above general formula (4A), R ｂ are each independently a hydrogen atom or a methyl group; R ５１ are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or when m3 is 2 or more, the two or more R ５１ may form a ring together with the carbon atom to which they are attached, and each m3 is independently an integer of 0 to 4. * represents a bond to another atom. Z′ and Z″ each independently represent a group represented by the general formula (2A-LR): 【Chemistry 5】 (In the above general formula (2A-LR), R ２１’ and R ２２’ each independently represents an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom; ’ and m2 ’ are each independently an integer of 0 to 4. * represents a bond to another atom. 【Chemistry 6】 (In the above general formula (4A-LR), R ｂ’ are each independently a hydrogen atom or a methyl group; R ５１’ are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or m3 ’ If is 2, the two R ７１’ may form a ring together with the carbon atom to which they are attached, m3 ’ are each independently an integer of 0 to 4. * represents a bond to another atom. Ar １ and Ar ２ each independently represents an aromatic ring group which may have a substituent, R １１ , R １２ , R ２１ , R ２２ , R ３１ , R ３２ , R ４１ and R ４２ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, p ０ is the average value, a number greater than 0, However, the (meth)acrylate-modified phenolic resin (A) contains a structural unit represented by general formula (2A) and / or general formula (2A-LR) and a structural unit represented by general formula (4A) and / or general formula (4A-LR).

4. The resin composition according to claim 3, wherein the (meth)acrylate-modified phenolic resin (A) comprises a resin represented by the following general formula (2-1): 【Chemistry 7】 (In the above general formula (5-1.4), Z １ , Ar １ , Ar ２ , R １１ , R １２ , R ２１ , R ２２ , R ３１ , R ３２ , R ４１ and R ４２ , R ｂ’ , R ５１’ , and m3 ’ has the same meaning as in claim 3, and p1 represents an integer of 1 or 2.

5. A curable resin composition comprising the resin composition according to claim 1 or 2 and a photopolymerization initiator.

6. A cured product of the curable resin composition according to claim 5.

7. An article having a coating film comprising the cured product according to claim 6.

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