Curable resin composition

Abstract

To provide a curable resin composition with good moldability that can give uniform cured products, the cured products being satisfactory in all of Tg, low dielectric properties, and low linear expansion coefficients.SOLUTION: A curable resin composition comprises (A) a modified polyphenylene ether, (B) a styrenic elastomer, and (C) a crosslinking aid as an aromatic vinyl compound represented by a formula (18), with the number of vinyl groups in each molecule being three or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition. [Background technology]

[0002] Polyphenylene ether has excellent high-frequency characteristics, flame retardancy, and heat resistance, and is therefore widely used as a material in the electrical and electronic fields, automotive fields, and various other industrial materials fields. In recent years, it has been expected that polyphenylene ethers with extremely low molecular weights, compared with ordinary high-molecular-weight polyphenylene ethers, will be more effective for electronic material applications such as circuit board materials. For this reason, Patent Document 1 proposes a low-molecular-weight polyphenylene ether that has even lower dielectric constant than ordinary high-molecular-weight polyphenylene ethers, which uses 2,6-dimethylphenol as a raw material, and an efficient method for producing the same.

[0003] Furthermore, Patent Documents 2 and 3 describe modified polymers having a polyphenylene ether moiety in the molecular structure and having a methacryl group at the molecular end. In particular, methacryl group modification is becoming widely used because the methacryl group has a moderately high reactivity as a crosslinking group and can be easily introduced to the hydroxyl group end.

[0004] Furthermore, Patent Documents 4 and 5 report attempts to blend methacrylated polyphenylene ether with a copolymer of styrene and an olefin-based alkene compound, and its hydrogenated product (styrene-based elastomer), in order to improve adhesion to metal foil, etc. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-99824 [Patent Document 2] Special Publication No. 2004-502849 [Patent Document 3] Special Publication No. 2010-538114 [Patent Document 4] JP 2017-82200 A [Patent Document 5] Japanese Patent Publication No. 2020-200432 Summary of the Invention [Problem to be solved by the invention]

[0006] As mentioned above, styrene-based elastomers are added to modified polyphenylene ethers because of various advantages. However, methacrylated polyphenylene ethers have low compatibility with styrene-based elastomers. Therefore, resin compositions containing methacrylated polyphenylene ethers and styrene-based elastomers typically undergo macrophase separation before curing or during the curing process. As a result, the presence of a continuous phase of the styrene-based elastomer in the resulting cured product increases the linear expansion coefficient and decreases the Tg.

[0007] Patent Documents 4 and 5 attempt to incorporate a highly polar, low-molecular-weight crosslinking aid such as triallyl isocyanurate (TAIC) in order to suppress such macrophase separation and at the same time reduce viscosity to improve moldability. However, the cured product formed in this way has the problem of high dielectric properties (dielectric constant, dielectric loss tangent) due to the incorporation of a highly polar crosslinking aid.

[0008] In view of the above problems, an object of the present invention is to provide a curable resin composition with good moldability that gives a uniform cured product and satisfies all of the following requirements of the cured product: a sufficient Tg, low dielectric properties, and a low linear expansion coefficient. [Means for solving the problem]

[0009] In order to solve the above problems, the present inventors have used a vinylsilyl group or the like, which is a crosslinking group with low polarity and good metal adhesion, as a modifying group in a polyphenylene ether skeleton, and have blended it with a styrene-based elastomer and a specific crosslinking aid, thereby obtaining a curable resin composition that can solve all of the above problems, and have completed the present invention. [1] A curable resin composition comprising the following components (A), (B), and (C): (A) Modified polyphenylene ether A modified polyphenylene ether represented by the following formula (1): [ka] In formula (1), Z is an a-valent partial structure represented by the following formula (2), a represents an integer of 2 to 6, each Y is independently a divalent linking group having a structure represented by the following formula (4), n represents the number of repetitions of Y, each n is independently an integer of 0 to 200, and a number of [-Y n At least one n in [-A] is an integer of 1 or more, and A represents a hydrogen atom or a silyl group-containing derivative capable of bonding to a polyphenylene ether structure, except when all A's are hydrogen atoms; [ka] In formula (2), X is an arbitrary linking group having a valence of a, and a plurality of R 5 are each independently a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and each k is independently an integer of 1 to 4: [ka] In formula (3), multiple R 11 are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms, and a plurality of R 12 are each independently an optionally substituted alkylene group having 1 to 8 carbon atoms, each b is independently 0 or 1, and R 13represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted phenyl group; [ka] In formula (4), multiple R 21 are each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or a halogen atom, and two R 21 is not a hydrogen atom at the same time, but two R 21 is not a combination of one of the partial structures represented by the above formula (3) and the other of a hydrogen atom, a methyl group, or an ethyl group, but a combination of multiple R 22 are each independently any of a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, and a halogen atom. (B) Styrene-based elastomer (C) Crosslinking aid A crosslinking aid which is an aromatic vinyl compound represented by the following formula (18) and which has 3 or less vinyl groups in the molecule: [ka] {In formula (18), R 37 , R 38 , R 39 represent a hydrogen atom or a hydrocarbon having 4 or less carbon atoms, and R 40 , R 41 each independently represents hydrogen or a saturated or unsaturated hydrocarbon having 8 or less carbon atoms.} [2] The curable resin composition according to [1], wherein the component (B) is a styrene-based elastomer having a number average molecular weight of 300,000 or less. [3] The curable resin composition according to [1] or [2], wherein the component (B) is a styrene-based elastomer having a double bond content of 90% or less. [4] The curable resin composition according to any one of [1] to [3], wherein the component (B) is a styrene-based elastomer having a styrene content of 80% or less. [5] The curable resin composition according to any one of [1] to [4], wherein the component (B) is a styrene-based elastomer containing any one of styrene-butadiene copolymer (SBR), styrene-butadiene-styrene copolymer (SBS), hydrogenated styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer (SIS), hydrogenated styrene-isoprene-styrene copolymer, and hydrogenated styrene (butadiene / isoprene)-styrene copolymer. [6] The curable resin composition according to any one of [1] to [5], wherein the component (B) is a styrene-based elastomer containing a block A mainly composed of vinyl aromatic compound monomer units and a block B mainly composed of conjugated diene monomer units. [7] The curable resin composition according to any one of [1] to [6], wherein the component (B) is a styrene-based elastomer having a hydrogenation rate of 90% or more of double bonds based on conjugated diene monomer units. [8] In the formula (18), R 37 , R 38 , R 39 The curable resin composition according to any one of [1] to [7], wherein is a hydrogen atom. [9] In the formula (18), R 40 The curable resin composition according to any one of [1] to [8], wherein is a tert-butyl group.

[10] In the formula (18), R 41 The curable resin composition according to any one of [1] to [9], wherein is a vinyl group.

[11] The curable resin composition according to any one of [1] to

[10] , wherein the component (C) is 4-tert-butylstyrene.

[12] The curable resin composition according to any one of [1] to

[10] , wherein the component (C) is divinylbenzene.

[13] The curable resin composition according to any one of [1] to

[12] , further comprising (D) an initiator.

[14] In the formula (2), the R 5 At least one of the R groups is a partial structure represented by the formula (3), and the carbon atom of the benzene ring to which -O- in the formula (2) is bonded is the 1st position, and the R group has the partial structure represented by the formula (3) at either the 2nd or 6th carbon atom. 5 and a hydrogen atom, a methyl group, or an ethyl group is bonded to the other carbon atom at the 2- or 6-position.

[15] The curable resin composition according to any one of [1] to

[14] , wherein the partial structure represented by the formula (3) is a t-butyl group.

[16] The curable resin composition according to any one of [1] to

[15] , wherein the number of OH terminals contained in the polyphenylene ether is 0 to 3,000 μmol / g.

[17] R in the formula (4) 21 The curable resin composition according to any one of [1] to

[16] , wherein is a methyl group.

[18] A in the formula (1) is the following formula (5): [ka] {In formula (5), R 31 , and R 34 are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms, and R 32 , and R 33 are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydroxyalkyl group; B is a hydrocarbon-based substituent having 1 to 30 carbon atoms containing an olefinic carbon-carbon double bond, some of which may be substituted with a hydrogen atom, a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group; and s, t, and u are each independently an integer of 0 to 8. The curable resin composition according to any one of [1] to

[17] , represented by the following formula:

[19] A in the formula (1) is the following formula (6) and / or (7): [ka] [ka] {In formula (6) and / or formula (7), R 31 , and R 34 are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms, and R 32 , and R 33 are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydroxyalkyl group, and R 35 are each independently a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 30 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group, and R 36 is a divalent hydrocarbon group or amino group having 1 to 3 carbon atoms, or an oxygen atom, and a portion of the hydrocarbon group may be substituted with an aryl group, an alkoxy group, an allyloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group, and s, t, and u are each independently an integer of 0 to 8. The curable resin composition according to

[18] ,

[20] The curable resin composition according to any one of [1] to

[19] , further comprising (E) a solvent. [Effects of the Invention]

[0010] By using the curable resin composition containing the modified polyphenylene ether having a vinylsilyl group, a styrene-based elastomer, and a crosslinking aid defined in the present invention, it is possible to provide a curable resin composition which has good moldability and a uniform cured product, and which satisfies all of the requirements of a sufficient Tg, low dielectric properties, adhesiveness, and a low linear expansion coefficient of the cured product. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is an optical microscope photograph of the curable resin composition of Example 2. [Figure 2] 1 is an optical microscope photograph of the curable resin composition of Comparative Example 2. [Figure 3] 1 is an SPM image (concave and convex) of a cured product of the curable resin composition of Example 2. [Figure 4] 1 is an SPM image (concave and convex) of a cured product of the curable resin composition of Example 4. [Figure 5] 1 is an SPM image (concave and convex) of a cured product of the curable resin composition of Example 5. [Figure 6] 1 is an SPM image (concave and convex) of a cured product of the curable resin composition of Example 6. [Figure 7] 1 is an SPM image (concave and convex) of a cured product of the curable resin composition of Example 7. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The present embodiment is an example for explaining the present invention, and the present invention is not limited to this embodiment alone. The present invention can be practiced by appropriately modifying it within the scope of its gist.

[0013] <Curable resin composition> The curable resin composition of the present embodiment is characterized by including the following components (A), (B), and (C). (A) Modified polyphenylene ether A modified polyphenylene ether represented by the following formula (1): [ka] In formula (1), Z is an a-valent partial structure represented by the following formula (2), a represents an integer of 2 to 6, each Y is independently a divalent linking group having a structure represented by the following formula (4), n represents the number of repetitions of Y, each n is independently an integer of 0 to 200, and a number of [-Y n At least one n in [-A] is an integer of 1 or more, and A represents a hydrogen atom or a silyl group-containing derivative capable of bonding to a polyphenylene ether structure, except when all A's are hydrogen atoms; [ka] In formula (2), X is an arbitrary linking group having a valence of a, and a plurality of R 5 are each independently a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and each k is independently an integer of 1 to 4: [ka] In formula (3), multiple R 11 are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms, and a plurality of R 12 are each independently an optionally substituted alkylene group having 1 to 8 carbon atoms, each b is independently 0 or 1, and R 13 represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted phenyl group; [ka] In formula (4), multiple R 21 are each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or a halogen atom, and two R 21 is not a hydrogen atom at the same time, but two R 21 is not a combination of one of the partial structures represented by the above formula (3) and the other of a hydrogen atom, a methyl group, or an ethyl group, but a combination of multiple R 22are each independently any of a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, and a halogen atom. (B) Styrene-based elastomer

[0014] In this embodiment, by using a curable resin composition containing (A) a modified polyphenylene ether and (B) a styrene-based elastomer, a uniform cured product can be obtained, and a curable resin composition can be provided that satisfies all of the requirements of a sufficient Tg of the cured product, low dielectric properties, and a low linear expansion coefficient. The components constituting the curable resin composition of this embodiment will be described in detail below.

[0015] <(A) Modified polyphenylene ether> The modified polyphenylene ether according to this embodiment has a structure represented by the following formula (1). [ka] In formula (1), Z is a partial structure having a central phenol moiety with a valence of a, represented by formula (2) below, where a is an integer of 3 to 6.

[0016] The "central phenol moiety" refers to the central skeleton that serves as the starting point of the reaction when polymerizing the polyfunctional polyphenylene ether, and its structure can be identified by analyzing the polyfunctional modified polyphenylene ether composition using techniques such as nuclear magnetic resonance (NMR) and mass spectrometry.

[0017] A specific method for identifying the structure of the central phenol moiety from a polyfunctionally modified polyphenylene ether composition includes, for example, analyzing only low-molecular-weight components from the mass spectrometry results of the polyfunctionally modified polyphenylene ether composition and estimating the structure of the central phenol moiety from the peak of fragment ions obtained by electric impact or electric ionization (EI). Another method includes performing NMR measurement of the polyfunctionally modified polyphenylene ether composition and comparing the results with the NMR measurement results of known polyfunctional phenol compounds to estimate the structure of the central phenol moiety. Combining the results of mass spectrometry and NMR measurement enables more accurate identification of the structure of the central phenol moiety.

[0018] The modified polyphenylene ether has a number of partial structures (e.g., R 5 and the like) is bonded to the a-valent partial structure (i.e., the central phenol moiety represented by the following formula (2)) and the [-Y n -A] may be bonded. [ka] In formula (2), a can be an integer of 2 to 6, as in formula (1), and is preferably the same integer as in formula (1). In the central phenol moiety of formula (2), the a partial structures may be the same or different.

[0019] In formula (2), X is any a-valent linking group, and is not particularly limited, but examples thereof include hydrocarbon groups such as chain hydrocarbons and cyclic hydrocarbons; hydrocarbon groups containing one or more atoms selected from nitrogen, phosphorus, silicon, and oxygen; atoms such as nitrogen, phosphorus, and silicon; or groups combining these; etc. X may be a linking group other than a single bond.

[0020] X in formula (2) may be a linking group that links the a-valent partial structures to each other.

[0021] In formula (2), X is a group that is connected to R via a single bond or an ester bond.5 an a-valent alkyl skeleton bonded to a benzene ring to which R is bonded; 5 an a-valent aryl skeleton bonded to a benzene ring to which R is bonded; 5 an a-valent heterocyclic skeleton bonded to a benzene ring to which is bonded;

[0022] Here, the alkyl skeleton is not particularly limited, but examples thereof include a skeleton in which the branched ends of a chain hydrocarbon (e.g., a chain saturated hydrocarbon) having 1 to 6 carbon atoms and branched to at least a positions are directly bonded to a benzene ring in a partial structure (as long as a benzene ring is bonded to the a branched ends, there may be a branched end to which no benzene ring is bonded). Furthermore, the aryl skeleton is not particularly limited, but examples thereof include a skeleton in which a benzene ring, a mesitylene group, or a 2-hydroxy-5-methyl-1,3-phenylene group is bonded to R via a single bond or an alkyl chain. 5 Furthermore, the heterocyclic skeleton is not particularly limited, but examples thereof include a skeleton in which a triazine ring is bonded to a benzene ring to which R is bonded via a single bond or an alkyl chain. 5 Examples of such a skeleton include a skeleton bonded to a benzene ring to which

[0023] Multiple R in Eq. (2) 5 are each independently either a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and each k is independently an integer of 1 to 4.

[0024] R in equation (2) 5 Examples of R include linear alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, and an n-propyl group, and groups having a partial structure represented by the following formula (3): 5 At least one of the above may be a partial structure represented by the following formula (3). [ka] In formula (3), Multiple R 11each independently represents an optionally substituted alkyl group having 1 to 8 carbon atoms, Multiple R 12 each independently represents an optionally substituted alkylene group having 1 to 8 carbon atoms, b's are independently 0 or 1, R 13 represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted phenyl group. The substituents include halogen atoms and the like.

[0025] The partial structure represented by formula (3) is preferably a group containing a secondary and / or tertiary carbon, such as an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, a 2-dimethylpropyl group, or a structure having a phenyl group at the end of any of these groups, and more preferably a tert-butyl group.

[0026] In this embodiment, when the carbon atom of the benzene ring to which -O- in formula (2) is bonded is the 1st position, R having a partial structure represented by formula (3) at either the 2nd or 6th carbon atom is 5 is bonded to the carbon atom at the 2nd or 6th position, and a hydrogen atom, a methyl group, or an ethyl group is bonded to the other carbon atom at the 2nd or 6th position. In addition, a hydrocarbon group or a partial structure represented by the above formula (3) may be bonded to the carbon atoms at the 2nd and 6th positions of the benzene ring to which -O- is bonded in formula (2). The benzene ring in formula (2) has [Y n -A] may be bonded to the 1-position via an oxygen atom, and n -A] is preferably bonded to the 4-position of the hydroxyl group, and the central part X is bonded to the 4-position of the hydroxyl group.

[0027] Examples of polyhydric phenol compounds for the partial structure represented by the above formula (2) are listed below. Examples of polyhydric phenol compounds include 4,4'-[(3-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(3-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 4,4'-[(4-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(4-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 4,4'-[(2-hydroxy-3-methoxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[( 4,4'-[(4-hydroxyphenyl)methylene]bis(2,3,6-trimethylethylphenol), 4,4'-[(3,4-dihydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(3,4-dihydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 2,2'-[(4-hydroxyphenyl)methylene]bis(3,5,6-trimethylphenol), 4,4'-[4-(4-hydroxyphenyl)cyclohexylidene]bis(2,6-dimethylphenol), 4,4'-[(2-hydroxy phenyl)methylene]-bis(2,3,6-trimethylphenol), 4,4'-[1-[4-[1-(4-hydroxy-3,5-dimethylphenyl)-1-methylethyl]phenyl]ethylidene]bis(2,6-dimethylphenol), 4,4'-[1-[4-[1-(4-hydroxy-3-fluorophenyl)-1-methylethyl]phenyl]ethylidene]bis(2,6-dimethylphenol), 2,6-bis[(4-hydroxy-3,5-dimethylphenyl)ethyl]-4-methylphenol, 2,6-bis[(4-hydroxy-2,3,6-trimethylphenol) 2,6-bis[(4-hydroxy-3,5,6-trimethylphenyl)methyl]-4-methylphenol, 2,4-bis[(4-hydroxy-3-methylphenyl)methyl]-6-methylphenol, 2,6-bis[(4-hydroxy-3-methylphenyl)methyl]-4-methylphenol, 2,4-bis[(4-hydroxy-3-cyclohexylphenyl)methyl]-6-methylphenol, 2,4-bis[(4-hydroxy-3-methylphenyl)methyl]-6-cyclohexylphenol, 2,4-bis[(2-hydroxy-5-methylphenyl)methyl]-6-cyclohexylphenol, 2,4-bis[(4-hydroxy-2,3,6-trimethylphenyl)methyl]-6-cyclohexylphenol, 3,6-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,2-benzenediol, 4,6-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,3-benzenediol, 2,4,6-tris[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,3-benzenediol , 2,4,6-tris[(2-hydroxy-3,5-dimethylphenyl)methyl]-1,3-benzenediol, 2,2'-methylenebis[6-[(4 / 2-hydroxy-2,5 / 3,6-dimethylphenyl)methyl]-4-methylphenol], 2,2'-methylenebis[6-[(4-hydroxy-3,5-dimethylphenyl)methyl]-4-methylphenol], 2,2'-methylenebis[6-[(4 / 2-hydroxy-2,3,5 / 3,4,6-trimethylphenyl)methyl]-4-methylphenol], 2,2'-methylene Bis[6-[(4-hydroxy-2,3,5-trimethylphenyl)methyl]-4-methylphenol], 4,4'-methylenebis[2-[(2,4-dihydroxyphenyl)methyl]-6-methylphenol], 4,4'-methylenebis[2-[(2,4-dihydroxyphenyl)methyl]-3,6-dimethylphenol], 4,4'-methylenebis[2-[(2,4-dihydroxy-3-methylphenyl)methyl]-3,6-dimethylphenol], 4,4'-methylenebis[2-[(2,3,4-trihydroxyphenyl)methyl] ethyl]-3,6-dimethylphenol], 6,6'-methylenebis[4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,2,3-benzenetriol], 1,1-bis(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 4,4'-cyclohexylidenebis[2-cyclohexyl-6-[(2-hydroxy-5-methylphenyl)methyl]phenol], 4,4'-cyclohexylidenebis[2-cyclohexyl-6-[(4-hydroxy-3,5-dimethylphenyl)methyl]phenol], 4,4'-Cyclohexylidenebis[2-cyclohexyl-6-[(4-hydroxy-2-methyl-5-cyclohexylphenyl)methyl]phenol], 4,4'-cyclohexylidenebis[2-cyclohexyl-6-[(2,3,4-trihydroxyphenyl)methyl]phenol], 4,4',4'',4'''-(1,2-ethanediylidene)tetrakis(2,6-dimethylphenol), 4,4',4'',4'''-(1,4-phenylenedimethylidene)tetrakis(2,6-dimethylphenol), 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane, tetramethylbisphenol A, tetramethylbisphenol F, (1,1'-biphenyl)-4,4'-diol, 3,3'-dimethyl(1,1'-biphenyl)-4,4'-diol 2,2',3,3',5,5'-hexamethyl(1,1'-biphenyl)-4,4-diol, 2,3,3',5,5'-pentamethyl(1,1'-biphenyl)-4,4-diol, 2,3',5,5'-tetramethyl(1,1'-biphenyl)-4,4-diol, 2,2',5,5'-tetramethyl(1,1'-biphenyl)-4,4-diol, Examples of the diol include, but are not limited to, methyl(1,1'-biphenyl)-4,4-diol, 2,2',3,5,5'-pentamethyl(1,1'-biphenyl)-4,4-diol, 5,5'-di-t-butyl-2,2'-dimethyl(1,1'-biphenyl)-4,4-diol, and 3,3'-di-t-butyl-5,5'-dimethyl(1,1'-biphenyl)-4,4-diol.

[0028] The number of phenolic hydroxyl groups in the polyhydric phenol compound is not particularly limited as long as it is 2 or more, but since an increase in the number of polyphenylene ether terminals may result in a large change in molecular weight during polymerization, the number is preferably 2 to 6, and more preferably 2 to 4.

[0029] Particularly preferred polyhydric phenol compounds are 4,4'-[(4-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(3-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(4-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 4,4'-[(3-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 4,4',4'',4'''-(1,4-phenylenedimethylidene)tetrakis(2,6-dimethylphenol), 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,1-bis(2-methyl-4-hydroxy-5-t-butylphenyl)butane, tetramethylbisphenol A, and 3,3',5,5'-tetramethyl(1,1'-biphenyl)-4,4'-diol.

[0030] In the above formula (1), each of the multiple Ys is independently a divalent linking group (i.e., a phenol unit having a substituent) having a structure represented by the following formula (4), n represents the number of repeating Ys, each n being independently an integer of 0 to 200, and a number of [-Y n -A], at least one n is an integer of 1 or more. [ka]

[0031] In formula (4), multiple R 21 R each independently represents at least one selected from the group consisting of a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, and a halogen atom. 21 is preferably a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted, more preferably a methyl group, an ethyl group, an n-propyl group, a vinyl group, an aryl group, an ethynyl group, or a propargyl group, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Examples of the substituent include a halogen atom.

[0032] In equation (4), two R 21 and preferably are not both hydrogen atoms, and / or are not a combination in which one is a partial structure represented by the above formula (3) and the other is either a hydrogen atom, a methyl group, or an ethyl group, from the viewpoint of ensuring that the modified polyphenylene ether-containing composition has all of the following properties: low dielectric properties, adequate metal peelability, low solution viscosity, and sufficient Tg upon curing.

[0033] In formula (4), multiple R 22 are each independently at least one selected from the group consisting of a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, and a halogen atom; and are preferably a hydrogen atom or an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group, and even more preferably a hydrogen atom or a methyl group. Examples of the substituent include a halogen atom.

[0034] Examples of monovalent phenol compounds for the structure represented by the above formula (4) include o-cresol, 2,6-dimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-n-propylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-n-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol, 2-phenylphenol, 2,6-diphenylphenol, 2,6-bis-(4-fluorophenyl)phenol, 2-methyl-6-tolylphenol, 2,6-ditolylphenol, 2,5-dimethylphenol, 2,3,6-trimethylphenol, 2,5-diethylphenol, 2-methyl-5-ethylphenol, 2-ethyl -5-methylphenol, 2-allyl-5-methylphenol, 2,5-diallylphenol, 2,3-diethyl-6-n-propylphenol, 2-methyl-5-chlorophenol, 2-methyl-5-bromophenol, 2-methyl-5-isopropylphenol, 2-methyl-5-n-propylphenol, 2-ethyl-5-bromophenol, 2-methyl-5-n-butylphenol, 2,5-di-n-propylphenol, 2-ethyl-5-chlorophenol, 2-methyl-5-bromophenol, 2,6-dimethyl-5-phenylphenol, 2,5-diphenylphenol, 2,5-bis-(4-fluorophenyl)phenol, 2-methyl-5-tolylphenol, 2,5-ditolylphenol, 2,6-dimethyl-3-allylphenol, 2,3,6-triallylphenol, 2,3,6-tributylphenol, 2,6-di-n-butyl-3-methylphenol, 2,6-dimethyl-3-n-butylphenol, 2,6-dimethyl-3-t-butylphenol, and the like.

[0035] Among the monohydric phenol compounds, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-diphenylphenol, 2,3,6-trimethylphenol, or 2,5-dimethylphenol is preferred because it is inexpensive and easily available, and 2,6-dimethylphenol or 2,3,6-trimethylphenol is more preferred.

[0036] The phenol compounds may be used alone or in combination of two or more.

[0037] Examples of the monohydric phenol compound include a method of using a combination of 2,6-dimethylphenol and 2,6-diethylphenol, a method of using a combination of 2,6-dimethylphenol and 2,6-diphenylphenol, a method of using a combination of 2,3,6-trimethylphenol and 2,5-dimethylphenol, a method of using a combination of 2,6-dimethylphenol and 2,3,6-trimethylphenol, etc. In this case, the mixing ratio of the phenol compounds to be combined can be selected arbitrarily.

[0038] The phenol compound used may also contain small amounts of m-cresol, p-cresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, etc., which may be contained as by-products during production.

[0039] Phenol compounds for the a-valent partial structure represented by the above formula (2) can be industrially advantageously produced by reacting a corresponding monohydric phenol compound with an aldehyde (e.g., formaldehyde), a ketone (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone), or a dihalogenated aliphatic hydrocarbon, or by reacting the corresponding monohydric phenol compounds with each other.

[0040] In the above formula (1), A represents a hydrogen atom, or a silyl group-containing derivative capable of bonding to a polyphenylene ether structure, except when A is entirely hydrogen atoms.

[0041] Here, A in formula (1) is preferably a substituent represented by the following formula (5) from the viewpoint of obtaining low dielectric properties, adequate metal peelability, low solution viscosity, and sufficient Tg properties upon curing. [ka] In formula (5), R 31 , and R 34 are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms, and a plurality of R 32 , and R 33 are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydroxyalkyl group. In formula (5), B is a hydrocarbon-based substituent having 1 to 30 carbon atoms and containing an olefinic carbon-carbon double bond, some of which may be substituted with hydrogen, a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group. In formula (5), s, t, and u are each independently an integer of 0 to 8, and preferably an integer of 0 to 5.

[0042] In formula (5), R 32 , and R 33 From the viewpoint of dielectric properties or solubility in a solvent, the hydrocarbon group of R preferably has a large number of carbon atoms. On the other hand, if the number of carbon atoms is too large, Tg or metal peelability may decrease, or the carbon-carbon double bond of an olefin may decrease. 32 and R 33 The number of carbon atoms is preferably about 1 to 30, more preferably about 1 to 20, and even more preferably about 1 to 12.

[0043] In formula (5), R 32 , and / or R 33Specific examples of the monovalent hydrocarbon group include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentylene, 4-methylpentylene, 1,1-dimethylbutylene, and 2,2-dimethylbutylene. , 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl butyl, 3,4-dimethylpentyl, 2-methyl-3,3-dimethylbutyl, 1-methyl-3,3-dimethylbutyl, 1,2,3-trimethylbutyl, 1,3-dimethyl-2-pentyl, 2-isopropylbutyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1-cyclohexylmethyl, 2-ethylcyclopentyl, 3-ethylcyclopentyl, 2,3-dimethylcyclopentyl, 2,4-dimethylcyclopentyl, 2-methylcyclopentylmethyl, 2-cyclopentylethyl, 1-cyclopentylethyl, n -Octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 1,1-dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-Dimethylhexyl, 2,5-dimethylhexyl, 1,1-ethylmethylpentyl, 2,2-ethylmethylpentyl, 3,3-ethylmethylpentyl, 4,4-ethylmethylpentyl, 1-ethyl-2-methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-ethyl-1-methylpentyl, 3-ethyl-1-methylpentyl, 4-ethyl-1-methylpentyl, 2-ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl-2-methylpentyl, 4-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl, 4-ethyl-3-methylpentyl, 1-(2-methylpropyl)butyl, 1-(2-methylpropyl)-2-methylbutyl, 1,1-(2-methylpropyl)ethyl, 1,1-(2-methylpropyl)ethylpropyl Examples include 1,1-diethylpropyl, 2,2-diethylpropyl, 1,1-ethylmethyl-2,2-dimethylpropyl, 2,2-ethylmethyl-1,1-dimethylpropyl, 2-ethyl-1,1-dimethylbutyl, 2,3-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2-methylcyclohexylmethyl, 3-methylcyclohexylmethyl, 4-methylcyclohexylmethyl, 2-ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl, 2-cyclohexylethyl, 1-cyclohexylethyl, 1-cyclohexyl-2-ethylene, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl, and 2-phenylethyl.

[0044] R 32 and / or R 33The monovalent hydrocarbon group is preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methyl n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, and benzyl, and more preferably methyl, ethyl , n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, and benzyl, and more preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl,undecyl, dodecyl, and benzyl.

[0045] R 32 and / or R 33 Specific examples of the aryl group include phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4-n-propylphenyl, 3-n-propylphenyl, 2-n-propylphenyl, 4-isopropylphenyl, 3-isopropylphenyl, 2-isopropylphenyl, 4-n-butylphenyl, 3-n-butylphenyl, 2-n-butylphenyl, 4-isobutylphenyl, 3-isobutylphenyl, 2-isobutylphenyl, 4-t-butylphenyl, 3-t-butylphenyl, 2-t-butylphenyl, and 2,6-dimethylphenyl. , 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,3-dimethylphenyl, 3,5-dimethylphenyl, 3,4-dimethylphenyl, 2,6-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,3-diethylphenyl, 3,5-diethylphenyl, 3,4-diethylphenyl, 2,4,6-trimethylphenyl, 2,3,4-trimethylphenyl, 2,3,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,4,6-triethylphenyl, 2,3,4-triethylphenyl, 2,3,6-triethylphenyl, 3,4,5-triethylphenyl, and the like.

[0046] R 32 and / or R 33The aryl group is preferably phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4-n-propylphenyl, 3-n-propylphenyl, 2-n-propylphenyl, 4-isopropylphenyl, 3-isopropylphenyl, 2-isopropylphenyl, 4-n-butylphenyl, 3-n-butylphenyl, 2-n-butylphenyl, 4-isobutylphenyl, 3-isobutylphenyl, 2-isobutylphenyl, 4-t-butylphenyl, 3-t-butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,3-dimethylphenyl, 3,5-dimethylphenyl, 3,4-dimethylphenyl, 2,6-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,3-diethylphenyl, 3,5-diethylphenyl, 3,4-diethylphenyl, 2,4,6-trimethylphenyl, 2, 3,4-trimethylphenyl, 2,3,6-trimethylphenyl, 3,4,5-trimethylphenyl, and 2,4,6-triethylphenyl, more preferably phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4-n-propylphenyl, 3-n-propylphenyl, 2-n-propylphenyl, 4-isopropylphenyl, 3-isopropylphenyl, 2-isopropylphenyl, 4-n-butylphenyl, 3-n-butylphenyl, 2-n-butylphenyl, 4-isobutylphenyl, 3-isobutylphenyl, 4-t-butylphenyl, 3-t-butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,3-diethylphenyl, 2,4,6-trimethylphenyl, 2,3,6-trimethylphenyl, and 2,4,and 6-triethylphenyl, and more preferably phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 4-isopropylphenyl, 3-isopropylphenyl, 2-isopropylphenyl, 4-n-butylphenyl, 3-n-butylphenyl, 4-isobutylphenyl, 3-isobutylphenyl, 4-t-butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, and 2,4,6-trimethylphenyl.

[0047] R 32 and / or R 33 Specific examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, 2-butoxy, t-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, 2-ethylpropoxy, 3,3-dimethylpropoxy, 1,1-dimethylpropoxy, cyclopentoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 4-methylpentoxy, 3-methylpentoxy, 2-methylpentoxy, Examples include 1,1-dimethyl-1-butoxy, 2,2-dimethyl-1-butoxy, 3,3-dimethyl-1-butoxy, 4,4-dimethyl-1-butoxy, 1,2-dimethyl-1-butoxy, 1,3-dimethyl-1-butoxy, 2-ethyl-1-butoxy, 3-ethyl-1-butoxy, 3,3-ethylmethyl-1-propoxy, cyclohexoxy, 1-octoxy, 2-octoxy, 3-octoxy, 4-octoxy, 2-ethyl-1-hexoxy, and phenylmethoxy.

[0048] R 32 and / or R 33The alkoxy group is preferably methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, 2-butoxy, t-butoxy, 1-pentoxy, 2,2-dimethylpropoxy, 2-ethylpropoxy, 3,3-dimethylpropoxy, 1,1-dimethylpropoxy, cyclopentoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 4-methylpentoxy, 3-methylpentoxy, 2-methylpentoxy, 1,1-dimethyl-1-butoxy, 2,2-dimethyl-1-butoxy, 3,3-dimethyl-1-butoxy, 2-ethyl-1-butoxy, 3-ethyl-1-butoxy, 3,3-ethylmethyl-1-propoxy, cyclohexoxy, 1-octoxy, 2-octoxy, 3-octoxy, 4-octoxy, 2-ethylmethyl-1-propoxy, cyclohexoxy, and phenylmethoxy, more preferably methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, 2-butoxy, t-butoxy, 2,2-dimethylpropoxy, 3,3-dimethylpropoxy, 1,1-dimethylpropoxy, cyclopentoxy, 1-hexoxy, 2,2-dimethyl-1-butoxy, 3,3-dimethyl-1-butoxy, cyclohexoxy, 2-ethyl-1-hexoxy, and phenylmethoxy, and even more preferably methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, 2-butoxy, t-butoxy, 2,2-dimethylpropoxy, cyclopentoxy, 1-hexoxy, 2-ethyl-1-hexoxy, and phenylmethoxy.

[0049] R 32 and / or R 33Specific examples of the aryloxy group include phenoxy, 4-methylphenoxy, 3-methylphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4-dimethylphenoxy, 2,3-dimethylphenoxy, 2,4,6-trimethylphenoxy, 4-isopropylphenoxy, 2-isopropylphenoxy, 3-isopropylphenoxy, 4-isobutylphenoxy, 2-isobutylphenoxy, 3-isobutylphenoxy, 4-t-butylphenoxy, 2-t-butylphenoxy, 3-t-butylphenoxy, 2,6-di-t-butylphenoxy, 2,4-di-t-butylphenoxy, 2,3-di-t-butylphenoxy, 2-methyl-4-t-butylphenoxy, 2-methyl-6-t-butylphenoxy, and 4-methyl-2-t-butylphenoxy.

[0050] R 32 and / or R 33The aryloxy group in the above formula (I) is preferably phenoxy, 4-methylphenoxy, 3-methylphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4-dimethylphenoxy, 2,4,6-trimethylphenoxy, 4-isopropylphenoxy, 2-isopropylphenoxy, 4-isobutylphenoxy, 2-isobutylphenoxy, 4-t-butylphenoxy, 2-t-butylphenoxy, 3-t-butylphenoxy, 2,4-di-t-butylphenoxy, 2,3-di-t-butylphenoxy, 2-methyl-4-t-butylphenoxy, 2-methyl-6-t-butylphenoxy, or 4-methyl-2-t-butylphenoxy, and more preferably phenoxy, 4-methylphenoxy, 3-methylphenoxy, 2 4-t-butylphenoxy, 2-t-butylphenoxy, 2-methyl-4-t-butylphenoxy, and 2-methyl-6-t-butylphenoxy, and more preferably phenoxy, 4-methylphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4-dimethylphenoxy, 2,4,6-trimethylphenoxy, 4-isopropylphenoxy, 2-isopropylphenoxy, 4-isobutylphenoxy, 2-isobutylphenoxy, 4-t-butylphenoxy, 2-t-butylphenoxy, 2-methyl-4-t-butylphenoxy, and 2-methyl-6-t-butylphenoxy.

[0051] R 32 and / or R 33 Specific examples of the amino group include dimethylamino, ethylmethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-t-butylamino, dicyclohexylamino, and the like.

[0052] In formula (5), R 31 and R 34The hydrocarbon group of R preferably has a large number of carbon atoms from the viewpoint of dielectric properties, solubility in solvents, and furthermore from the viewpoint of increasing the degree of freedom of the terminal functional group and improving reactivity. On the other hand, if the number of carbon atoms is excessively large, a decrease in Tg or metal peelability or a decrease in the olefinic carbon-carbon double bond occurs. 31 and R 34 The number of carbon atoms is preferably about 1 to 30, more preferably about 1 to 20, and even more preferably about 1 to 12.

[0053] In formula (5), R 31 and / or R 34Specific examples of the divalent hydrocarbon group include methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,3-trimethylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,2-cyclopentylene, 1,3-cyclopentylene, 2,2-dimethyl-1,3- Propylene, 1,1-dimethyl-1,3-propylene, 3,3-dimethyl-1,3-propylene, hexamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2-ethyl-1,4-butylene, 3-ethyl-1,4-butylene, 1-methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methylpentylene, 1,1-dimethyl-1,4-butylene , 2,2-dimethyl-1,4-butylene, 3,3-dimethyl-1,4-butylene, 1,2-dimethyl-1,4-butylene, 1,3-dimethyl-1,4-butylene, 2,3-dimethyl-1,4-butylene, heptamethylene, 1-methyl-1,6-hexylene, 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene, 4-methyl-1,6-hexylene, 5-methyl-1,6-hexylene, 1-ethyl-1,5-pentylene, 2-ethyl-1,5-pentylene, 3 -ethyl-1,5-pentylene, 1,1-dimethyl-1,5-pentylene, 2,2-dimethyl-1,5-pentylene, 3,3-dimethyl-1,5-pentylene, 4,4-dimethyl-1,5-pentylene, 1,2-dimethyl-1,5-pentylene, 1,3-dimethyl-1,5-pentylene, 1,4-dimethyl-1,5-pentylene, 2,3-dimethyl-1,5-pentylene, 2,4-dimethyl-1,5-pentylene, and 3,4-dimethyl-1,5-pentylene.

[0054] Also, R 31 and / or R 34Specific examples of the divalent hydrocarbon group include 2-methyl-3,3-dimethyl-1,4-butylene, 1-methyl-3,3-dimethyl-1,4-butylene, 1,2,3-trimethyl-1,4-butylene, 1,3-dimethyl-1,4-pentylene, 2-isopropyl-1,4-butylene, 2-methyl-1,4-cyclohexylene, 3-methyl-1,4-cyclohexylene, 4-methyl-1,4-cyclohexylene, and 1-cyclohexyl. Methylene, 2-ethyl-1,3-cyclopentylene, 3-ethyl-1,3-cyclopentylene, 2,3-dimethyl-1,3-cyclopentylene, 2,4-dimethyl-1,3-cyclopentylene, 2-methyl-1,3-cyclopentylmethylene, 2-cyclopentylethylene, 1-cyclopentylethylene, octamethylene, 1-methyl-1,7-heptylene, 1-ethyl-1,6-hexylene, 1-propyl-1,5-pentylene 2-methyl-1,7-heptylene, 3-methyl-1,7-heptylene, 4-methyl-1,7-heptylene, 5-methyl-1,7-heptylene, 6-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, 1,1-dimethyl-1,6-hexylene, 2,2-dimethyl-1,6-hexylene, 3,3-dimethyl- dimethyl-1,6-hexylene, 4,4-dimethyl-1,6-hexylene, 5,5-dimethyl-1,6-hexylene, 1,2-dimethyl-1,6-hexylene, 1,3-dimethyl-1,6-hexylene, 1,4-dimethyl-1,6-hexylene, 1,5-dimethyl-1,6-hexylene, 2,3-dimethyl-1,6-hexylene, 2,4-dimethyl-1,6-hexylene, 2,5-dimethyl-1,6-hexylene, and the like.

[0055] Also, R 31 and / or R 34Specific examples of the divalent hydrocarbon group include 1,1-ethylmethyl-1,5-pentylene, 2,2-ethylmethyl-1,5-pentylene, 3,3-ethylmethyl-1,5-pentylene, 4,4-ethylmethyl-1,5-pentylene, 1-ethyl-2-methyl-1,5-pentylene, 1-ethyl-3-methyl-1,5-pentylene, 1-ethyl-4-methyl-1,5-pentylene, 2-ethyl-1-methyl-1,5-pentylene, 3-ethyl-1-methyl-1,5-pentylene, 4-ethyl-1-methyl-1,5-pentylene, 2-ethyl-3-methyl-1,5 -pentylene, 2-ethyl-4-methyl-1,5-pentylene, 3-ethyl-2-methyl-1,5-pentylene, 4-ethyl-3-methyl-1,5-pentylene, 3-ethyl-4-methyl-1,5-pentylene, 4-ethyl-3-methyl-1,5-pentylene, 1-(2-methylpropyl)-1,4-butylene, 1-(2-methylpropyl)-2-methyl-1,4-butylene, 1,1-(2-methylpropyl)ethylene, 1,1-(2-methylpropyl)ethyl-1,3-propylene, 1,1-diethyl-1,3-propylene, 2,2-diethyl-1,3- Propylene, 1,1-ethylmethyl-2,2-dimethyl-1,3-propylene, 2,2-ethylmethyl-1,1-dimethyl-1,3-propylene, 2-ethyl-1,1-dimethyl-1,4-butylene, 2,3-dimethyl-1,4-cyclohexylene, 2,3-dimethyl-1,4-cyclohexylene, 2,5-dimethyl-1,4-cyclohexylene, 2,6-dimethyl-1,4-cyclohexylene, 3,5-dimethyl-1,4-cyclohexylene, 2-methyl-1,4-cyclohexyl-1-methylene, 3-methyl-1,4-cyclohexyl-1-methylene, 4-methyl-1,4-cyclohexyl-1-methylene, 2-ethyl-1,4-cyclohexylene, 3-ethyl-1,4-cyclohexylene, 4-ethyl-1,4-cyclohexylene, 2-cyclohexylethylene, 1-cyclohexylethylene, 1-cyclohexylethylene, 1-cyclohexyl-2-ethylene, nonylmethylene, 1-methyl-1,8-octylene, decylmethylene, 1-methyl-1,8-nonylene, undecylmethylene, dodecylmethylene, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, methylene-1,4-phenylene-methylene, methylene-1,Examples include 4-phenylene, ethylene-1,4-phenylene, and ethylene-1,4-phenylene-ethylene.

[0056] R 31 and / or R 34 The divalent hydrocarbon group is preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,3-cyclopentene, ethylene, 1,6-hexamethylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2-ethyl-1,4-butylene, 3-ethyl-1,4-butylene, 1-methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methyl-1,5-pentylene, heptamethylene, 1-methyl-1,6-hexylene, 2-methyl-1,6-hexylene, 3- Methyl-1,6-hexylene, 4-methyl-1,6-hexylene, 5-methyl-1,6-hexylene, 1-ethyl-1,5-pentylene, 2-ethyl-1,5-pentylene, 3-ethyl-1,5-pentylene, 2-methyl-1,4-cyclohexylene, 3-methyl-1,4-cyclohexylene, 4-methyl-1,4-cyclohexylene, octamethylene, 1-methyl-1,7-heptylene, 3-methyl and methyl-1,7-heptylene, 4-methyl-1,7-heptylene, 2-methyl-1,7-heptylene, 5-methyl-1,7-heptylene, 6-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, and dodecylmethylene.

[0057] R 31 and / or R 34The divalent hydrocarbon group is more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, hepta methylene, octamethylene, 1-methyl-1,7-heptylene, 3-methyl-1,7-heptylene, 4-methyl-1,7-heptylene, 2-methyl-1,7-heptylene, 5-methyl-1,7-heptylene, 6-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, and dodecylmethylene.

[0058] R 31 and / or R 34 The divalent hydrocarbon group is more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-dimethylethylene, pentamethylene, 2,2-dimethyl-1,3-propylene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, heptamethylene, octamethylene, 1-methyl-1,7-heptylene, 3 1,7-heptylene, 4-methyl-1,7-heptylene, 2-methyl-1,7-heptylene, 5-methyl-1,7-heptylene, 6-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, and dodecylmethylene.

[0059] In formula (5), specific examples of the substituent containing a carbon-carbon double bond for B include a vinyl group, an allyl group, an isopropenyl group, a 5-norbornen-2-yl group, a 1-butenyl group, a 1-pentenyl group, a 3-cyclopentenyl group, a 4-cyclopentenyl group, a p-vinylphenyl group, a p-isopropenylphenyl group, a m-vinylphenyl group, a m-isopropenylphenyl group, an o-vinylphenyl group, an o-isopropenylphenyl group, a p-vinylbenzyl group, a p-isopropenylbenzyl group, a m-vinylbenzyl group, and a m-isopropenylphenyl group. Examples of the alkyl group include isopropenylbenzyl group, o-vinylbenzyl group, o-isopropenylbenzyl group, p-vinylphenylethenyl group, p-vinylphenylpropenyl group, p-vinylphenylbutenyl group, m-vinylphenylethenyl group, m-vinylphenylpropenyl group, m-vinylphenylbutenyl group, o-vinylphenylethenyl group, o-vinylphenylpropenyl group, o-vinylphenylbutenyl group, methacryl group, acrylic group, 2-ethylacrylic group, and 2-hydroxymethylacrylic group.

[0060] More specific examples of A in formula (1) or the substituent represented by formula (5) include structures represented by the following formulas (6) and / or (7). [ka] [ka] In formula (6) and / or formula (7), a plurality of R 31 , and R 34 are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms, and a plurality of R 32 , and R 33 are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydroxyalkyl group. Specific examples and preferred groups of these groups include the specific examples and preferred groups of the corresponding groups explained in the above formula (5).

[0061] In formula (6) and / or formula (7), a plurality of R 35are each independently a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 30 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group.

[0062] In formula (7), R 36 is a hydrocarbon group having 1 to 30 carbon atoms, an amino group, or oxygen, and it is preferable that a part of the hydrocarbon group is substituted with an aryl group, an alkoxy group, an allyloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group. In addition, a part of the amino group may be substituted with an alkyl group having 1 to 5 carbon atoms. 36 The hydrocarbon group preferably has 1 to 3 carbon atoms. In formula (6) and / or formula (7), s, t, and u each independently represent an integer of 0 to 8.

[0063] In formula (6) and / or formula (7), R 35 From the viewpoint of dielectric properties or solubility in a solvent, the hydrocarbon group of R preferably has a large number of carbon atoms. On the other hand, if the number of carbon atoms is too large, Tg or metal peelability may decrease, or the carbon-carbon double bond of an olefin may decrease. 35 The number of carbon atoms is preferably about 1 to 30, more preferably about 1 to 20, and even more preferably about 1 to 12.

[0064] R 35Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, and 3-methylpentyl. ethylene, 4-methylpentylene, 1,1-dimethylbutylene, 2,2-dimethylbutylene, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylbutyl methylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,4-dimethylpentyl, 2-methyl-3,3-dimethylbutyl, 1-methyl-3,3-dimethylbutyl, 1,2,3-trimethylbutyl, 1,3-dimethyl-2-pentyl, 2-isopropylbutyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methyl Examples of the alkyl ester include cyclohexyl, 1-cyclohexylmethyl, 2-ethylcyclopentyl, 3-ethylcyclopentyl, 2,3-dimethylcyclopentyl, 2,4-dimethylcyclopentyl, 2-methylcyclopentylmethyl, 2-cyclopentylethyl, 1-cyclopentylethyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, and 6-methylheptyl.

[0065] Also, R 35Specific examples of the hydrocarbon group include 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 1,1-dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, and 1,1-ethylmethylpentyl. , 2,2-ethylmethylpentyl, 3,3-ethylmethylpentyl, 4,4-ethylmethylpentyl, 1-ethyl-2-methylpentyl, 1-ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-ethyl-1-methylpentyl, 3-ethyl-1-methylpentyl, 4-ethyl-1-methylpentyl, 2-ethyl-3-methylpentyl, 2-ethyl-4-methylpentyl, 3-ethyl-2-methylpentyl, 4-ethyl-3-methylpentyl, 3-ethyl-4-methylpentyl, 4-ethyl ethyl-3-methylpentyl, 1-(2-methylpropyl)butyl, 1-(2-methylpropyl)-2-methylbutyl, 1,1-(2-methylpropyl)ethyl, 1,1-(2-methylpropyl)ethylpropyl, 1,1-diethylpropyl, 2,2-diethylpropyl, 1,1-ethylmethyl-2,2-dimethylpropyl, 2,2-ethylmethyl-1,1-dimethylpropyl, 2-ethyl-1,1-dimethylbutyl, 2,3-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,5-dimethyl ethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2-methylcyclohexylmethyl, 3-methylcyclohexylmethyl, 4-methylcyclohexylmethyl, 2-ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl, 2-cyclohexylethyl, 1-cyclohexylethyl, 1-cyclohexyl-2-ethylene, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl, 2-phenylethyl, and the like.

[0066] R 35The hydrocarbon group is preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1 2-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, and benzyl, and more preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl and benzyl, and more preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl,and benzyl.

[0067] R 36 Specific examples of the hydrocarbon group include methylene, 1,1-dimethylmethylene, 1,1-diethylmethylene, ethylene, trimethylene, 1,2-propylene, 2-methyl-1,3-trimethylene, 1,1-dimethylethylene, 1-ethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene, 1,1-dimethyl-1,3-propylene, 3,3-dimethyl-1,3-propylene, and the like. In addition, some of these may be aryl groups, alkoxy groups, allyloxy groups, amino groups, hydroxyalkyl groups, vinyl groups, isopropyl groups, etc. Specific examples of the group substituted with a propenyl group or a halogen group include 1-phenylmethylene, 1,1-diphenylmethylene, 1-benzylmethylene, 1,1-dibenzylmethylene, 1-methoxymethylene, 1,1-dimethoxymethylene, 1-ethoxymethylene, 1,1-diethoxymethylene, 1-vinylmethylene, 1,1-divinylmethylene, 1-allylmethylene, 1,1-diallylmethylene, 1-isopropenylmethylene, 1,1-diisopropenylmethylene, 1-chloromethylene, 1,1-dichloromethylene, 1- Bromomethylene, 1,1-dibromomethylene, 1-phenylethylene, 1,1-diphenylethylene, 1,2-diphenylethylene, 1,1,2-triphenylethylene, 1,1,2,2-tetraphenylethylene, 1-benzylethylene, 1,1-dibenzylethylene, 1,2-dibenzylethylene, 1,1,2-tribenzylethylene, 1,1,2,2-tetrabenzylethylene, 1-vinylethylene, 1,1-divinylethylene, 1,2-divinylethylene, 1,1,2-trivinylethylene, 1,1,2, Examples include 2-tetravinylethylene, 1-allylethylene, 1,1-diallylethylene, 1,2-diallylethylene, 1,1,2-triallylethylene, 1,1,2,2-tetraallylethylene, 1-chloroethylene, 1,1-dichloroethylene, 1,2-dichloroethylene, 1,1,2-trichloroethylene, 1,1,2,2-tetrachloroethylene, 1-bromoethylene, 1,1-dibromoethylene, 1,2-dibromoethylene, 1,1,2-tribromoethylene, and 1,1,2,2-tetrabromoethylene.

[0068] The number of OH terminals contained in the polyphenylene ether having the structure represented by the above formula (1) is preferably 0 to 3,000 μmol / g, from the viewpoint of providing a modified polyphenylene ether-containing composition with all of low dielectric properties, adequate metal peelability, low solution viscosity, sufficient Tg upon curing, etc.

[0069] <Modified Polyphenylene Ether Composition> The curable resin composition according to the present embodiment includes, for example, a modified polyphenylene ether composition, which includes a polyphenylene ether having a structure represented by the above formula (1) (wherein a represents an integer of 2 to 6), and more specifically, a modified polyphenylene ether having a structure represented by the following formula (8): [ka] In formula (8), Z is an a-valent partial structure represented by the following formulas (9) and (11), where a represents an integer of 2 to 6.

[0070] In formula (8), a [-Y n -A] may be the same or different, where Y is a substituted phenylene monomer unit, and Y n represents a polyphenylene ether structure in which n consecutive substituted phenylene monomer units are bonded. Furthermore, Z is based on a polyhydric phenol compound having a phenol structure to which a polyphenylene ether unit structures can be bonded. Furthermore, in formula (8), A represents a hydrogen atom or a silyl group-containing derivative capable of bonding to the polyphenylene ether structure, and is preferably a functional group containing a silicon atom (Si) as defined in the above formulas (5), (6), and (7).

[0071] The modified polyphenylene ether composition comprises a modified polyphenylene ether having a structure represented by the formula (8), and at least one [—Y n -A] is [-Y n-H], and 1 In the H-NMR measurement results, the ratio of the integrated value of the peak appearing at 7.6 to 8.3 ppm to the integrated value of the peak derived from the structure represented by the following formula (9) is 1 or less, and the number average molecular weight in terms of polystyrene is 500 to 15,000 g / mol.

[0072] The modified polyphenylene ether composition of the present embodiment may contain one or more modified polyphenylene ethers having the structure represented by the above formula (8). In addition, the modified polyphenylene ether composition of the present embodiment may contain one or more [-Y n -A] is [Y n -H] and all [-Y n -A] is [Y n and the modified polyphenylene ether in which all of the [—Y n -A] is [Y n The modified polyphenylene ether may contain a polyphenylene ether having a structure of [-Y —H]. n -A] and unmodified polyphenylene ether [Y n -H], Y and n are preferably the same.

[0073] The polyfunctional modified polyphenylene ether composition of the present embodiment may further contain additives such as a solvent, a polymerization catalyst, a surfactant, etc. The polyfunctional polyphenylene ether composition of the present embodiment may be solid.

[0074] Z in formula (8) may be a structure having a central phenol moiety with a valence of a, as represented by the following formula (9), and a in formula (8) or (9) is preferably an integer of 3 to 6.

[0075] The central phenol moiety is as explained in the above section <Modified polyphenylene ether>.

[0076] The modified polyphenylene ether has a number of partial structures (e.g., R 5 and the like) is bonded to the a-valent partial structure (i.e., the central phenol moiety represented by formula (9)) and the [-Y n -A] may be bonded. [ka] In formula (9), a can be an integer similar to that in formula (8), and is preferably the same integer as that in formula (8). In the central phenol moiety of formula (9), each of the a partial structures may be the same structure or different structures.

[0077] In formula (9), X is any a-valent linking group, and is not particularly limited, but examples thereof include hydrocarbon groups such as chain hydrocarbons and cyclic hydrocarbons; hydrocarbon groups containing one or more atoms selected from nitrogen, phosphorus, silicon, and oxygen; atoms such as nitrogen, phosphorus, and silicon; or groups combining these; etc. Furthermore, X may be a linking group other than a single bond. Furthermore, X may be a linking group that links a-valent partial structures to each other.

[0078] X in the above formula (9) is R 5 an a-valent alkyl skeleton bonded to a benzene ring to which R is bonded; 5 an a-valent aryl skeleton bonded to a benzene ring to which R is bonded; 5 an a-valent heterocyclic skeleton bonded to a benzene ring to which is bonded;

[0079] Here, the alkyl skeleton is not particularly limited, but examples thereof include a skeleton in which the branched ends of a chain hydrocarbon (e.g., a chain saturated hydrocarbon) having 1 to 6 carbon atoms and branched to at least a positions are directly bonded to a benzene ring in a partial structure (as long as a benzene ring is bonded to the a branched ends, there may be a branched end to which no benzene ring is bonded). Furthermore, the aryl skeleton is not particularly limited, but examples thereof include a skeleton in which a benzene ring, a mesitylene group, or a 2-hydroxy-5-methyl-1,3-phenylene group is bonded to R via a single bond or an alkyl chain. 5 Furthermore, the heterocyclic skeleton is not particularly limited, but examples thereof include a skeleton in which a triazine ring is bonded to a benzene ring to which R is bonded via a single bond or an alkyl chain. 5 Examples of such a skeleton include a skeleton bonded to a benzene ring to which

[0080] Multiple R in Eq. (9) 5 are each independently either a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and each k is independently an integer of 1 to 4.

[0081] R in the above formula (9) 5 Examples of R include linear alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, and an n-propyl group, and groups having a partial structure of the following formula (10). 5 At least one of the above may be a partial structure of the following formula (10). [ka] In formula (10), Multiple R 11 each independently represents an optionally substituted alkyl group having 1 to 8 carbon atoms; Multiple R 12 each independently represents an optionally substituted alkylene group having 1 to 8 carbon atoms; each b independently represents 0 or 1; and R 13 represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a phenyl group. The substituents include halogen atoms and the like.

[0082] The above formula (10) is preferably a group containing a secondary and / or tertiary carbon, such as an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, a 2-dimethylpropyl group, or a structure having a phenyl group at the end of any of these groups, and more preferably a tert-butyl group.

[0083] The carbon atom of the benzene ring to which -O- in formula (9) is bonded is the 1st position, and R having a partial structure represented by formula (10) at either the 2nd or 6th carbon atom 5 is bonded to the carbon atom at the 2nd or 6th position, and a hydrogen atom, a methyl group, or an ethyl group is bonded to the other carbon atom at the 2nd or 6th position. The benzene ring in the formula (9) may have a structure in which a hydrocarbon group or a partial structure represented by the formula (10) is bonded to the carbon atoms at the 2nd and 6th positions. The benzene ring in the formula (9) has [Y n -A] may be bonded to the 1-position via an oxygen atom, and n -A] is preferably bonded to the 4-position, and the central part X is bonded to the 4-position.

[0084] When a=2 in formula (8), Z may have a structure represented by formula (11) below, for example. [ka] Multiple R in Equation (11) 5 are each independently an optional substituent, and each k is independently an integer of 1 to 4. R in the above formula (11) 5 Examples of the alkyl group include linear alkyl groups having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, and an n-propyl group.

[0085] In formula (8), when a≧3, Z may be based on or derived from a polyhydric phenol compound for the structure represented by formula (9) above. Specific polyhydric phenols include the compounds defined for the structure represented by formula (2) above.

[0086] In the above formula (8), each Y is independently a divalent linking group (a phenol unit having a substituent) having a structure derived from a monovalent phenol compound represented by the following formula (12), and n represents the number of repetitions of Y, each n being independently an integer of 0 to 200, with at least one n being an integer of 1 or greater.

[0087] The modified polyphenylene ether and / or modified polyphenylene ether composition can be obtained, for example, by copolymerizing a monovalent phenol compound represented by the following formula (12) with an a-valent phenol compound (central phenol) corresponding to the central part X in the structure represented by the above formula (9), followed by a modification reaction. [ka] In formula (12), R 21 , and R 22 Examples of R are the same as those defined in the above formula (4), and R 21 and R 22 is preferably the same as

[0088] Specific examples of the monohydric phenol compound represented by the above formula (12) include the monohydric phenol compounds defined for the structure represented by the above formula (4).

[0089] Examples of dihydric phenols represented by the above formula (11) are listed below. Examples of dihydric phenols include (1,1'-biphenyl)-4,4'-diol, 3,3'-dimethyl(1,1'-biphenyl)-4,4'-diol, 3,3',5,5'-tetramethyl(1,1'-biphenyl)-4,4'-diol, 2,2',3,3',5,5'-hexamethyl(1,1'-biphenyl)-4,4-diol, 2,3,3',5,5'-pentamethyl(1,1'-biphenyl)-4,4-diol, 2,3',5,5'-tetramethyl( 1,1'-biphenyl)-4,4-diol, 2,2',5,5'-tetramethyl(1,1'-biphenyl)-4,4-diol, 2,2',3,5,5'-pentamethyl(1,1'-biphenyl)-4,4-diol, 5,5'-di-t-butyl-2,2'-dimethyl(1,1'-biphenyl)-4,4-diol, 3,3'-di-t-butyl-5,5'-dimethyl(1,1'-biphenyl)-4,4-diol, and the like, but are not limited to these.

[0090] The number of phenolic hydroxyl groups in the polyhydric phenol compound is not particularly limited as long as it is 2 or more, but since an increase in the number of polyphenylene ether terminals may result in a large change in molecular weight during polymerization, the number is preferably 2 to 6, and more preferably 2 to 4.

[0091] The modified polyphenylene ether composition of the present embodiment may contain a monofunctional polyphenylene ether represented by the following formula (13) and / or a modified product of the monofunctional polyphenylene ether represented by the following formula (13). [ka] In formula (13), c is an integer of 1 to 100, and R 21 and R 22 Examples of the group include the same groups as those explained for the above formula (12).

[0092] In the modified polyphenylene ether and / or modified polyphenylene ether composition (hereinafter referred to as modified polyphenylene ether (composition)) of this embodiment, the polyfunctional polyphenylene ether serving as a raw material for the polyfunctional modified polyphenylene ether having the structure of formula (1) above may be produced by a redistribution reaction in which a monofunctional polyphenylene ether is equilibrated with a polyhydric phenol in the presence of an oxidizing agent. The redistribution reaction is known in the art and is described, for example, in U.S. Pat. No. 3,496,236 to Cooper et al. and U.S. Pat. No. 5,880,221 to Liska et al.

[0093] The modified polyphenylene ether (composition) of this embodiment is 1 In the results of H-NMR measurement, the modified polyphenylene ether has the structure of the above formula (1), and in the structure of the above formula (1), one or more [-Y n -A] is [Y n -H] and all [-Y n -A] is [Y n and the modified polyphenylene ether in the structure of the above formula (1) is not [—Y n -A] is [Y n The ratio of the integrated value of the peak derived from the peroxide appearing in the 7.6 to 8.3 ppm region to the integrated value of the peak derived from the central phenol moiety represented by formula (2) contained in the polyphenylene ether having a molecular weight of [—H] is 1 or less, preferably 0.8 or less, and more preferably 0.5 or less. The fact that the integrated value of the peak derived from the peroxide relative to the integrated value of the peak derived from the central phenol moiety is 1 or less means that the modified polyphenylene ether composition does not contain peroxide adducts as by-products, and that the purity of the target polyfunctional modified polyphenylene ether or the like is high. As a result, the glass transition temperature (Tg) of the modified polyphenylene ether composition can be increased. The above ratio can be measured by the method described in the Examples below.

[0094] The modified polyphenylene ether (composition) in this embodiment has a number average molecular weight (Mn) of 500 to 15,000 g / mol, preferably 1,000 to 10,000 g / mol, and more preferably 2,000 to 8,000 g / mol. When the number average molecular weight (Mn) is within the above range, the fluidity is improved when the modified polyphenylene ether is dissolved in a solvent for preparing a varnish in the process of applying the modified polyphenylene ether to a substrate material, and processability when applied to the substrate material can be ensured. The number average molecular weight can be measured by the method described in the Examples below.

[0095] The number of A substituents (referring to A defined in formula (1), hereinafter the same) contained in the polyfunctional modified polyphenylene ether (composition) in this embodiment is not particularly limited, but excludes cases where A = hydrogen atom (H). Among these, the composition preferably contains 700 to 3,000 μmol / g of A substituents, more preferably 700 to 2,000 μmol / g. Having the number of A substituents in the composition at 700 μmol / g or more tends to increase the crosslink density during curing, leading to a tendency to obtain a cured product with a high glass transition temperature and excellent dielectric properties. Having the number of A substituents in the composition at 3,000 μmol / g or less tends to decrease the viscosity of a varnish obtained by dissolving the polyphenylene ether composition in a solvent, leading to a tendency to improve processability when applied to substrate materials.

[0096] The number of A substituents can be evaluated by known methods such as titration, spectroscopy, quantitative NMR, etc., depending on the type of functional group. 1 When H-NMR is used, the measurement is performed in the presence of a standard sample of known structure and a polyfunctional polyphenylene ether composition. The polyfunctional polyphenylene ether composition of known weight and the standard sample are dissolved in a deuterated solvent. 1The number of A substituents can be calculated from the ratio of the integral value of the peak derived from the A substituent to the peak of the standard sample, the weight of the polyfunctional polyphenylene ether composition, the weight of the standard sample, and the molecular weight of the standard sample by measuring H-NMR. The standard sample is soluble in a deuterated solvent, does not react with the polyfunctional polyphenylene ether composition, and 1 There are no particular limitations as long as the peaks in H-NMR do not interfere with the peaks derived from the polyfunctional polyphenylene ether composition. For a specific method for evaluating the number of A substituents, see the description in the Examples.

[0097] The modified polyphenylene ether-containing composition according to the present embodiment preferably contains 0.5 to 95 mass % of a modified polyphenylene ether having a structure represented by the above formula (8), from the viewpoint of having all of low dielectric properties, adequate metal peelability, low solution viscosity, sufficient Tg upon curing, and the like.

[0098] <Method for producing polyfunctional modified polyphenylene ether (composition)> The polyfunctional modified polyphenylene ether (composition) of the present embodiment can be produced, for example, by synthesizing a polyfunctional modified polyphenylene ether (composition) represented by the following formula (1)' (hereinafter also referred to as an unmodified polyfunctional polyphenylene ether (composition)) having hydroxyl groups at the molecular terminals by a polymerization method, and then introducing the A substituent in formula (1) into the terminals, i.e., modifying the polyfunctional modified polyphenylene ether. [ka] In formula (1)', Z, Y, n, and a are the same as those in formula (1) above, and are preferably the same as those defined in formula (1) above.

[0099] (Polymerization process) Here, in the method for producing the unmodified polyfunctional polyphenylene ether (composition), it is preferable to use an aromatic solvent, which is a good solvent for the unmodified polyfunctional polyphenylene ether (composition), as the polymerization solvent in the polymerization step.

[0100] Here, a good solvent for an unmodified polyfunctional polyphenylene ether composition is a solvent that can dissolve the polyfunctional polyphenylene ether, and examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene (including o-, m-, and p-isomers), ethylbenzene, and styrene, and halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; and nitro compounds such as nitrobenzene.

[0101] The polymerization catalyst used in this embodiment may be a known catalyst system that can generally be used for producing polyphenylene ether. Commonly known catalyst systems include those composed of a transition metal ion having oxidation-reduction ability and an amine compound capable of forming a complex with the transition metal ion, such as a catalyst system composed of a copper compound and an amine compound, a catalyst system composed of a manganese compound and an amine compound, or a catalyst system composed of a cobalt compound and an amine compound. Because the polymerization reaction proceeds efficiently under slightly alkaline conditions, a small amount of alkali or an additional amine compound may be added.

[0102] The polymerization catalyst preferably used in this embodiment is a catalyst containing a copper compound, a halogen compound, and an amine compound as catalyst components, and more preferably a catalyst containing a diamine compound represented by general formula (DA1) as the amine compound. [ka] In formula (DA1), R 14 , R 15 , R 16 , and R 17 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, but are not all hydrogen atoms at the same time, and R 18 is a linear or methyl-branched alkylene group having 2 to 5 carbon atoms.

[0103] Examples of copper compounds for the catalyst components described herein are listed below. Suitable copper compounds include cuprous compounds, cupric compounds, and mixtures thereof. Examples of cupric compounds include cupric chloride, cupric bromide, cupric sulfate, and cupric nitrate. Examples of cuprous compounds include cuprous chloride, cuprous bromide, cuprous sulfate, and cuprous nitrate. Among these, particularly preferred metal compounds are cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide. These copper salts may also be synthesized immediately upon use from an oxide (e.g., cuprous oxide), carbonate, hydroxide, or the like and the corresponding halogen or acid. A frequently used method is to mix the cuprous oxide exemplified above with a hydrogen halide (or a solution of a hydrogen halide).

[0104] Examples of halogen compounds include hydrogen chloride, hydrogen bromide, hydrogen iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, and tetraethylammonium iodide. These compounds can be used as aqueous solutions or solutions using appropriate solvents. These halogen compounds can be used alone or in combination of two or more. A preferred halogen compound is an aqueous solution of hydrogen chloride or hydrogen bromide.

[0105] The amount of these compounds used is not particularly limited, but is preferably 2 to 20 times the molar amount of halogen atoms relative to the molar amount of copper atoms, and the preferred amount of copper atoms used is in the range of 0.02 to 0.6 moles per 100 moles of the phenol compound added to the polymerization reaction.

[0106] Examples of diamine compounds for the catalyst component are listed below: N,N,N',N'-tetramethylethylenediamine, N,N,N'-trimethylethylenediamine, N,N'-dimethylethylenediamine, N,N-dimethylethylenediamine, N-methylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N'-triethylethylenediamine, N,N'-diethylethylenediamine, N,N-diethylethylenediamine, N-ethylethylenediamine, N,N-dimethyl-N'-ethylethylenediamine, N,N'-dimethyl-N-ethylethylenediamine, Nn-propylethylenediamine, N,N'-n-propylethylenediamine, Ni-propylethylenediamine, N,N'-i-propylethylenediamine, Nn-butylethylenediamine, amine, N,N'-n-butylethylenediamine, Ni-butylethylenediamine, N,N'-i-butylethylenediamine, Nt-butylethylenediamine, N,N'-t-butylethylenediamine, N,N,N',N'-tetramethyl-1,3-diaminopropane, N,N,N'-trimethyl-1,3-diaminopropane, N,N'-dimethyl-1,3-diaminopropane, N-methyl-1,3-diaminopropane, N,N,N',N'-tetramethyl-1,3-diamino-1-methylpropane, N,N,N',N'-tetramethyl-1,3-diamino-2-methylpropane, N,N,N',N'-tetramethyl-1,4-diaminobutane, and N,N,N',N'-tetramethyl-1,5-diaminopentane. A preferred diamine compound for this embodiment is one in which the number of carbon atoms in the alkylene group connecting the two nitrogen atoms is 2 or 3. The amount of these diamine compounds used is not particularly limited, but is preferably in the range of 0.01 mol to 10 mol per 100 mol of the phenol compound added to the polymerization reaction.

[0107] In this embodiment, the polymerization catalyst may contain a primary amine and a secondary monoamine as components thereof. Examples of the secondary monoamine include, but are not limited to, dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-t-butylamine, dipentylamines, dihexylamines, dioctylamines, didecylamines, dibenzylamines, methylethylamine, methylpropylamine, methylbutylamine, cyclohexylamine, N-phenylmethanolamine, N-phenylethanolamine, N-phenylpropanolamine, N-(m-methylphenyl)ethanolamine, N-(p-methylphenyl)ethanolamine, N-(2',6'-dimethylphenyl)ethanolamine, N-(p-chlorophenyl)ethanolamine, N-ethylaniline, N-butylaniline, N-methyl-2-methylaniline, N-methyl-2,6-dimethylaniline, and diphenylamine.

[0108] A tertiary monoamine compound may also be included as a constituent of the polymerization catalyst in this embodiment. The tertiary monoamine compound is an aliphatic tertiary amine, including an alicyclic tertiary amine. Examples include trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, dimethylethylamine, dimethylpropylamine, allyldiethylamine, dimethyl-n-butylamine, diethylisopropylamine, and N-methylcyclohexylamine. These tertiary monoamines may be used alone or in combination of two or more. The amount of these compounds used is not particularly limited, but is preferably 15 moles or less per 100 moles of the phenol compound added to the polymerization reaction.

[0109] In this embodiment, there is no limitation on adding a surfactant that has been known to have an effect of improving polymerization activity. Examples of such surfactants include trioctylmethylammonium chloride, known under the trade names Aliquat 336 or Capriquat. The amount of surfactant used is preferably within a range not exceeding 0.1% by mass relative to the total amount (100% by mass) of the polymerization reaction mixture.

[0110] As the oxygen-containing gas in the polymerization step of this embodiment, in addition to pure oxygen, a mixture of oxygen and an inert gas such as nitrogen in any ratio, air, or a mixture of air and an inert gas such as nitrogen in any ratio can be used. Normal pressure is sufficient for the pressure in the system during the polymerization reaction, but reduced or increased pressure can also be used as necessary.

[0111] The polymerization temperature is not particularly limited, but if it is too low, the reaction will not proceed easily, and if it is too high, there is a risk of a decrease in reaction selectivity or the production of high molecular weight components. Therefore, the temperature is preferably in the range of 0°C to 60°C, more preferably 10°C to 50°C.

[0112] In the method for producing an unmodified multifunctional polyphenylene ether (composition) of this embodiment, it is preferable to polymerize the polyphenylene ether in a solution state (also referred to as "solution polymerization" in this specification). By producing an unmodified multifunctional polyphenylene ether (composition) by solution polymerization, even when a central phenol having a bulky structure is used, a polyphenylene ether component not containing the structure of formula (1)' can be produced with high purity during the production of the unmodified multifunctional polyphenylene ether (composition), or the proportion of by-products produced by peroxides can be reduced, and the target multifunctional modified polyphenylene ether containing the structure of formula (1) can be produced with high purity.

[0113] (Copper extraction and by-product removal process) In this embodiment, there are no particular limitations on the post-treatment method after the polymerization reaction. Typically, an acid such as hydrochloric acid or acetic acid, or ethylenediaminetetraacetic acid (EDTA) and its salts, nitrilotriacetic acid and its salts, or the like is added to the reaction solution to deactivate the catalyst. Furthermore, a conventionally known method can be used to remove the dihydric phenol by-products generated by the polymerization of polyphenylene ether. If the metal ions serving as the catalyst described above are substantially deactivated, the mixture can be decolorized or post-treated simply by heating. Alternatively, a method in which a required amount of a known reducing agent is added to the system is also possible. Examples of known reducing agents include hydroquinone and sodium dithionite.

[0114] (liquid-liquid separation process) In the method for producing the unmodified polyfunctional polyphenylene ether (composition) of this embodiment, water may be added to extract the compound that has deactivated the copper catalyst, and then liquid-liquid separation into an organic phase and an aqueous phase may be performed. The aqueous phase may then be removed to remove the copper catalyst from the organic base. This liquid-liquid separation step is not particularly limited, but examples include static separation and separation using a centrifuge. To promote the liquid-liquid separation, a known surfactant or the like may be used.

[0115] (concentration / drying process) In the method for producing the polyfunctional modified polyphenylene ether (composition) of this embodiment, the organic phase containing the unmodified polyfunctional polyphenylene ether (composition) after liquid-liquid separation may be concentrated and dried by volatilizing the solvent. Note that this step may be omitted if a modification reaction (e.g., a reaction to introduce the substituent A in formula (1) into the terminal of the unmodified polyfunctional polyphenylene ether (composition)) is subsequently performed.

[0116] The method for volatilizing the solvent contained in the organic phase is not particularly limited, but examples include a method in which the organic phase is transferred to a concentration tank at a high temperature (for example, a drying temperature described below) and concentrated by distilling off the solvent, and a method in which toluene is distilled off using equipment such as a rotary evaporator and concentrated.

[0117] The temperature for the drying treatment in the drying step is preferably at least 60° C. or higher, more preferably 80° C. or higher, even more preferably 120° C. or higher, and most preferably 140° C. or higher. When the multifunctional polyphenylene ether composition is dried at a temperature of 60° C. or higher, the content of high-boiling-point volatile components in the polyphenylene ether powder can be efficiently reduced.

[0118] In order to obtain an unmodified polyfunctional polyphenylene ether (composition) with high efficiency, methods such as increasing the drying temperature, increasing the degree of vacuum in the drying atmosphere, and stirring during drying are effective, but a method of increasing the drying temperature is particularly preferred from the viewpoint of production efficiency. In the drying step, it is preferable to use a dryer with a mixing function. Examples of mixing functions include a stirring type and a tumbling type dryer. This allows the processing volume to be increased, and productivity to be maintained at a high level.

[0119] [Modification reaction step] In this embodiment, the method for introducing the substituent A in formula (1) or (8) (for example, the functional group of formula (5) above) into the terminal of the obtained unmodified polyphenylene ether can be a coupling method with a functional group such as a hydroxyl group using a halogenated silyl compound, an aminosilyl compound, or an alkoxysilyl compound. As the halogenated silyl compound, chlorides, bromides, etc. are generally used, but other halogens may also be used.

[0120] Specific examples of the silyl halide compound include methylvinyldichlorosilane, divinyldichlorosilane, allylmethyldichlorosilane, diallyldichlorosilane, trichlorosilyl-2-norbornene, 6-methyldichlorosilyl-2-norbornene, 6-dimethyldichlorosilyl-2-norbornene, phenylvinyldichlorosilane, 3-methacryloxypropyldichloromethylsilane, 3-chloropropylmethyldivinylsilane, allylphenyldichlorosilane, diphenylvinylchlorosilane, dimethylvinylchlorosilane, chloromethyldimethylvinylsilane, allyldimethylchlorosilane, methylphenylvinylchlorosilane, 5-norbornene-2-yl(ethyl)chlorodimethylsilane, methylvinyl Examples thereof include phenyldibromosilane, divinyldibromosilane, allylmethyldibromosilane, diallyldibromosilane, tribromosilyl-2-norbornene, 6-methyldibromosilyl-2-norbornene, 6-dimethyldibromosilyl-2-norbornene, phenylvinyldibromosilane, 3-methacryloxypropyldibromomethylsilane, 3-bromopropylmethyldivinylsilane, allylphenyldibromosilane, diphenylvinylbromosilane, dimethylvinylchlorosilane, bromomethyldimethylvinylsilane, allyldimethylbromosilane, methylphenylvinylbromosilane, 5-norbornen-2-yl(ethyl)bromodimethylsilane, and 5-norbornen-2-ylchlorodibromosilane.

[0121] The aminosilyl compounds include methylvinylsilyl-tris(1,2,4-triazole), divinylsilylbis(1,2,4-triazole), allylmethylsilylbis(1,2,4-triazole), diallylsilylbis(1,2,4-triazole), tris(1,2,4-triazolyl)silyl-2-norbornene, 6-methylbis(1,2,4-triazolyl)silyl-2-norbornene, and 6-dimethylbis(1,2,4-triazolyl)silyl. 2-Norbornene, phenylvinylsilylbis(1,2,4-triazole), 3-methacryloxypropylmethylsilylbis(1,2,4-triazole), allylphenylsilyl(1,2,4-triazole), diphenylvinylsilyl(1,2,4-triazole), dimethylvinylsilyl(1,2,4-triazole), allyldimethylsilyl(1,2,4-triazole), methylphenylvinylsilyl(1,2,4-triazole), 5- Norbornen-2-yl(ethyl)dimethylsilyl (1,2,4-triazole), methylvinylsilyl-trisimidazole, divinylsilylbisimidazole, allylmethylsilylbisimidazole, diallylsilylbisimidazole, trisimidazolylsilyl-2-norbornene, 6-methylbisimidazolylsilyl-2-norbornene, 6-dimethylbisimidazolylsilyl-2-norbornene, phenylvinylsilylbisimidazole, 3- Examples include methacryloxypropylmethylsilylbisimidazole, allylphenylsilylimidazole, diphenylvinylsilylimidazole, dimethylvinylsilylimidazole, allyldimethylsilylimidazole, methylphenylvinylsilylimidazole, 5-norbornene-2-yl(ethyl)dimethylsilylimidazole, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, and bis(dimethylamino)methylvinylsilane.

[0122] Examples of the alkoxysilane compound include trimethoxyvinylsilane, methoxydimethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, methacryloxypropyldimethoxymethylsilane, methacryloxypropyltrimethoxysilane, methacryloxypropyldiethoxymethylsilane, methacryloxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminophenoxydimethylvinylsilane, and 4-aminophenoxydimethylvinylsilane.

[0123] The reaction for introducing the above-mentioned compound into the terminal of the unmodified polyphenylene ether is generally a direct reaction with a hydroxyl group, but a reaction with an alkali metal salt of a hydroxyl group is also acceptable. Alternatively, a halogenated silyl compound may be reacted with imidazole, triazole, pyrrolidine, or piperidine to form an amine compound, which is then reacted with a hydroxyl group. Since a direct reaction between a halogenated silyl compound and a hydroxyl group generates an acid such as hydrogen halide, a weak base such as an amine may be present to trap the acid.

[0124] In order to prevent side reactions, the amines to be used in the presence of the amine compound are preferably tertiary amines. Specific examples of the amines to be used in the presence of the amine compound include trimethylamine, diethylmethylamine, triethylamine, diethylamine, di-n-propylamine, tri-n-propylamine, triisopropylamine, di-n-butylamine, di-n-butylmethylamine, di-n-butylethylamine, di-n-propylmethylamine, diisopropylmethylamine, di-n-propylethylamine, diisopropylethylamine, tri-n-butylamine, tri-t-butylamine, triisobutylamine, di-t-butylamine, diisobutylamine, tetramethylethylenediamine, tetraethylethylenediamine, tetramethylmethylenediamine, tetraethylmethylenediamine, pyridine, dimethylaniline, and dimethylaminopyridine.

[0125] The amines to be allowed to coexist are preferably trimethylamine, diethylmethylamine, triethylamine, tri-n-propylamine, triisopropylamine, di-n-butylmethylamine, di-n-butylethylamine, di-n-propylmethylamine, di-n-propylethylamine, diisopropylethylamine, tri-n-butylamine, tri-t-butylamine, triisobutylamine, tetramethylethylenediamine, tetraethylethylenediamine, tetramethylmethylenediamine, tetraethylmethylenediamine, pyridine, dimethylaniline, and dimethylaminopyridine, and more preferably triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-t-butylamine, triisobutylamine, tetramethylethylenediamine, tetramethylmethylenediamine, tetraethylmethylenediamine, pyridine, dimethylaniline, and dimethylaminopyridine.

[0126] Furthermore, since water not only causes undesirable side reactions during the reaction but also causes hydrolysis reactions after the reaction, which reduces the reaction yield, it is preferable to remove water from the reaction solvent, amine, etc. in advance. The preferred water content in the reaction system is preferably less than 200 ppm, more preferably less than 100 ppm.

[0127] To prevent side reactions or the formation of by-products during purification, excess amines may be removed from the system after the reaction. In the case of amines with low boiling points, they can be removed from the reaction system by distillation or other methods. The amount of residual amine before the purification step is less than 10,000 ppm.

[0128] In a preferred embodiment for achieving a high modification rate in the modification reaction step, the amount of the halide silyl compound used in the modification reaction is 1.00 to less than 4 moles, preferably 1.05 to 3 moles, and more preferably 1.1 to 2.5 moles, per mole of hydroxyl groups in the polymer. If the amount of the halide silyl compound used is less than 1.00 moles per mole of hydroxyl groups, a sufficient modification rate cannot be obtained. On the other hand, if the amount is 4 moles or more, undesirable by-products may be generated during purification after the reaction, resulting in a decrease in the purification yield. The amount of the amine used to trap the acid during the reaction is preferably 1.00 to less than 6 moles, more preferably 1.05 to 4 moles, and even more preferably 1.1 to 4 moles, per mole of hydroxyl groups. If the amount of the amine used is less than 1.00 moles per mole of hydroxyl groups, a sufficient modification rate cannot be obtained. If the amount is 6 moles or more, the effect on the conversion rate remains the same, but a large amount of amine must be removed after the reaction, which is not preferred.

[0129] The modification reaction temperature is not particularly limited, but is preferably a temperature condition under which the unmodified polyphenylene ether does not precipitate from the unmodified polyphenylene ether solution containing the unmodified polyphenylene ether and a good solvent for the unmodified polyphenylene ether. A combination of multiple temperature conditions may also be used.

[0130] After the modification reaction, if there is an excess of the silyl halide compound, it may be deactivated by reacting it with an alcohol such as methanol or ethanol.

[0131] After the modification reaction, the target product may be filtered or washed with water or an acidic or alkaline aqueous solution to remove by-products such as amine salts, or the target product may be recovered by dropping the polymer solution into a poor solvent such as an alcohol and reprecipitation. After washing the polymer solution, the solvent may be distilled off under reduced pressure to recover the desired polymer.

[0132] The method for producing the polyfunctionally modified polyphenylene ether (composition) of the present embodiment is not limited to the method for producing the polyfunctionally modified polyphenylene ether composition of the present embodiment described above, and the order or number of the above-described polymerization step, copper extraction and by-product removal step, liquid-liquid separation step, and concentration and drying step may be appropriately adjusted.

[0133] <(B) Styrene-based elastomer> The resin composition of this embodiment contains (B) a styrene-based elastomer as an essential component. In this embodiment, the styrene-based elastomer refers to a copolymer of a hydrocarbon having 1 to 4 carbon atoms, a chlorine-substituted styrene, or an unsubstituted styrene with an olefin-based alkene compound, or a hydrogenated product thereof, and may be a block copolymer or a random copolymer.

[0134] Specific examples include styrene-based elastomers such as styrene-butadiene copolymer (SBR), styrene-butadiene-styrene copolymer (SBS), hydrogenated styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer (SIS), hydrogenated styrene-isoprene-styrene copolymer, hydrogenated styrene (butadiene / isoprene)-styrene copolymer, etc. These styrene-based elastomers may be used alone or in combination of two or more. Among these, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene copolymer (SBS), and hydrogenated styrene-butadiene-styrene copolymer are preferred.

[0135] <Block copolymer / random copolymer> The (B) styrene-based elastomer of this embodiment can be synthesized by polymerizing a vinyl aromatic compound and a conjugated diene compound as monomers. Examples of the synthesized styrene-based elastomer include a "block copolymer styrene-based elastomer" consisting of a block (block (A)) mainly composed of a vinyl aromatic compound and a block (block (B)) mainly composed of a conjugated diene, a "random copolymer styrene-based elastomer" consisting of a structure in which a vinyl aromatic compound and a conjugated diene compound are randomly copolymerized, and a "hybrid styrene-based elastomer" consisting of both a block copolymer structure and a random copolymer structure. Specific examples of such styrene-based elastomers include commercially available hydrogenated styrene-butadiene block copolymers manufactured by Asahi Kasei Corporation, such as Tuftec H1221, H1062, H1041, H1051, and H1043; commercially available hydrogenated styrene-butadiene copolymers, such as S1605 and S1606; commercially available styrene-butadiene block copolymers manufactured by Asahi Kasei Corporation, such as Tufprene A, Tufprene 125, Tufprene 126S, and Asaprene T-411 and T-432; and commercially available styrene-butadiene copolymers, such as Asaflex 800S, 805, and 810.

[0136] <Number average molecular weight of styrene elastomer> The preferred range of the number average molecular weight of the styrene-based elastomer (B) of this embodiment varies depending on the double bond content.

[0137] When the double bond content of the styrene-based elastomer is less than 20%, a larger number average molecular weight has the advantage that the elastic modulus of the cured product obtained by curing the resin composition tends to be higher, but a larger number average molecular weight may take longer to dissolve the resin composition in a solvent.Furthermore, a smaller number average molecular weight has the advantage that the fluidity of the resin composition is increased, but the elastic modulus of the cured product obtained by curing the resin composition may be lower.

[0138] From this viewpoint, the number average molecular weight of the styrene-based elastomer having a double bond content of less than 20% is preferably 500 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, more preferably 10,000 or more and 100,000 or less, even more preferably 30,000 or more and 60,000 or less, and particularly preferably 40,000 or more and 50,000 or less.

[0139] Furthermore, when the double bond content of the styrene-based elastomer is 20% or more, the double bonds in the elastomer significantly contribute to the crosslinking reaction during the curing reaction, so that as the number average molecular weight increases, the elastic modulus of the cured product increases, but the viscosity of the resin composition increases more quickly, which can reduce moldability.Furthermore, as the number average molecular weight decreases, the fluidity of the resin composition increases, but the cured product can become more brittle.

[0140] From this viewpoint, the number average molecular weight of a styrene-based elastomer having a double bond content of 20% or more is preferably 500 or more and 300,000 or less, more preferably 1,000 or more and less than 10,000, even more preferably 2,000 or more and 8,000 or less, and particularly preferably 3,000 or more and 5,000 or less.

[0141] The number average molecular weight of the randomly polymerized styrene elastomer is preferably 500 or more and 300,000 or less, more preferably 1,000 or more and less than 10,000, even more preferably 2,000 or more and 8,000 or less, and particularly preferably 3,000 or more and 5,000 or less.

[0142] On the other hand, the number average molecular weight of the block copolymer type styrene elastomer is preferably 500 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, even more preferably 10,000 or more and 100,000 or less, particularly preferably 30,000 or more and 60,000 or less, and most preferably 50,000 or more and 40,000 or more.

[0143] <Double bond content of styrene elastomer> The preferred range of the double bond content of the (B) styrene-based elastomer of this embodiment varies depending on the number average molecular weight.

[0144] If the number average molecular weight of the styrene-based thermal elastomer is less than 10,000, the fluidity of the resin composition increases as the double bond content of the styrene-based elastomer increases, but a brittle cured product may be formed upon curing.

[0145] From this viewpoint, in the case of a styrene-based elastomer having a number average molecular weight of less than 10,000, the double bond content is preferably 10% or more and 90% or less, more preferably 20% or more and 80% or less, and even more preferably 50% or more and 70% or less.

[0146] When the number average molecular weight of the styrene-based elastomer is 10,000 or more, the elastic modulus of the cured resin increases as the double bond content of the styrene-based elastomer increases, but it may take a long time to dissolve the resin composition in a solvent.

[0147] From this viewpoint, in the case of a styrene-based elastomer having a number average molecular weight of 10,000 or more, the double bond content is preferably 90% or less, more preferably 50% or less, even more preferably 10% or less, and particularly preferably 1% or less.

[0148] <Styrene content of styrene-based elastomer> The styrene content of the styrene-based elastomer, component (B), is not particularly limited, but the higher the styrene content, the better the compatibility with the terminally modified polyphenylene ether, component (A), at the resin composition stage, and the more uniform the resin composition tends to be, while the lower the styrene content, the lower the dielectric loss tangent of the cured product obtained by curing.

[0149] From this viewpoint, in the case of a styrene-based elastomer having a number average molecular weight of less than 10,000, the styrene content is preferably 1% or more and 80% or less, more preferably 10% or more and 70% or less, even more preferably 15% or more and 60% or less, particularly preferably 20% or more and 50% or less, and most preferably 25% or more and 40% or less.

[0150] In addition, in the case of a styrene-based elastomer having a number average molecular weight of 10,000 or more, the styrene content is preferably 1% or more and 80% or less, more preferably 10% or more and 70% or less, even more preferably 20% or more and 50% or less, and particularly preferably 30% or more and 40% or less.

[0151] <Hydrogenation rate of double bonds of styrene elastomer> In the styrene-based elastomer that is component (B), the hydrogenation rate of double bonds based on conjugated diene monomer units is not particularly limited, but from the viewpoint of preventing deterioration, it is preferably 90% or more, and more preferably 98% or more.

[0152] <(C) Crosslinking Coagent> The crosslinking aid of the component (B) according to this embodiment is an aromatic vinyl compound having a structure represented by the following formula (18) in which the number of vinyl groups in the molecule is 3 or less. [ka] {In formula (18), R 37 , R 38 , R 39 represent a hydrogen atom or a hydrocarbon having 4 or less carbon atoms, and R 40 , R 41 each independently represents hydrogen or a saturated or unsaturated hydrocarbon having 8 or less carbon atoms.} Contains as an essential component. R 37 , R 38 , R 39 are hydrogen atoms or hydrocarbons each independently having 4 or less carbon atoms. The fewer the carbon atoms, the higher the reactivity tends to be, while the greater the carbon atoms, the lower the vapor pressure tends to be, and the less evaporation of component (C) tends to occur when the resin composition is heated. From this perspective, R 37 , R 38 , R 39 The fewer the number of carbon atoms, the more preferable, and a hydrogen atom is most preferable.

[0153] R40 , R 41 are each independently hydrogen or a saturated or unsaturated hydrocarbon having 8 or less carbon atoms. The viscosity of the resin composition tends to decrease as the number of carbon atoms decreases, and the vapor pressure tends to decrease as the number of carbon atoms increases, resulting in a decrease in the amount of evaporation of component (C) when the resin composition is heated.

[0154] From this perspective, the more preferable R 40 , R 41 The combination of the above is preferably a combination of one hydrogen atom and the other hydrocarbon having 1 to 6 carbon atoms, more preferably a combination of hydrocarbon having 2 to 4 carbon atoms. Also, R 40 , R 41 When R is a saturated hydrocarbon, the toughness of the cured product formed by curing the curable resin composition tends to be high, and when R is an unsaturated hydrocarbon, the glass transition temperature of the cured product tends to be high. 40 and R 41 More preferably, the total number of unsaturated groups contained in is one or zero. R 40 is preferably a tert-butyl group, and R 41 is preferably a vinyl group.

[0155] From the above viewpoints, particularly preferred structures of the crosslinking aid of component (C) include 4-tert-butylstyrene, 3-tert-butylstyrene, 2-tert-butylstyrene, 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene.

[0156] <Reason for the effectiveness of cross-linking aids> The crosslinking aid (C), a low-molecular-weight compound containing aromatic groups, is highly compatible with the modified polyphenylene ether (A) and the styrene-based elastomer (B). Blending this crosslinking aid with these compounds not only produces a uniform resin composition or varnish, but also reduces the viscosity of the molten state or resin solution, improving fluidity and providing excellent moldability. Furthermore, because it exhibits good reactivity with the crosslinking aid's silyl groups, it is possible to form a matrix with a reaction-induced spinodal decomposition structure consisting of a discontinuous phase primarily composed of the styrene elastomer and a continuous phase primarily composed of the polyphenylene ether.

[0157] Furthermore, if the crosslink density becomes too high, the uniformity of the cured product decreases, resulting in a lower dielectric tangent and a brittle cured product. However, component (C) has no more than three vinyl groups per molecule, which prevents the crosslink density of the cured product from becoming too high. In particular, tert-butylstyrene is monofunctional, so it gives a cured product that is highly uniform, therefore highly tough, and forms a cured product with a low dielectric tangent.

[0158] As a result, the curable resin composition of the present embodiment gives a uniform cured product, which satisfies all of the requirements of sufficient Tg, low dielectric properties, copper foil adhesion, and a low linear expansion coefficient.

[0159] <Mixing ratio of component (A) and component (B)> In the curable resin composition of this embodiment, the components (A) and (B) are highly compatible with each other both in a solution state containing a solvent before curing and in a resin mixed state containing no solution, and tend to form a homogeneous composition. However, as the curing reaction progresses in the curing reaction stage, the components (A) and (B) undergo phase separation (reaction-induced spinodal decomposition), and the phase mainly composed of the component (A) which has a high Tg and a low linear expansion coefficient forms a continuous phase, while the phase mainly composed of the component (B) which has a low Df forms a discontinuous phase. As a result, a cured product with a high Tg and a low linear expansion coefficient and Df tends to be formed in the end.

[0160] Therefore, in this embodiment, the higher the ratio of component (A), the higher the heat resistance indicated by Tg and the lower the linear expansion coefficient tend to be, and the higher the blending ratio of component (B), the lower the dielectric loss tangent (Df) tends to be.

[0161] This embodiment is not limited by the ratio of component (A) to component (B), but from the viewpoint of achieving a good balance between heat resistance and dielectric loss tangent, the ratio of component (A) to component (B) is preferably in the range of 99:1 to 10:90, more preferably in the range of 98:2 to 60:40, even more preferably in the range of 95:5 to 80:20, and particularly preferably in the range of 90:10 to 85:15.

[0162] <Composition ratio of component (C)> Although the present embodiment is not limited by the blending ratio of component (C), a lower ratio of component (C) to the total amount of components (A) and (B) tends to result in higher heat resistance, while a higher ratio of component (C) tends to result in lower viscosity and better moldability. From this perspective, the effects of the present invention tend to be better exhibited when the blending ratio of components (A), (B), and (C) in the present invention is such that the ratio of component (C) to the total amount of components (A) and (B) is in the range of 99:1 to 20:80. A more preferred range is 95:5 to 30:70, even more preferred is 90:10 to 50:50, even more preferred is 80:20 to 60:40, and particularly preferred is 70:30 to 65:35.

[0163] <(D) Initiator> The curable resin composition of the present embodiment may contain an initiator. The initiator is not particularly limited, but examples thereof include organic peroxides, and those having a one-minute half-life temperature in the range of 155°C to 180°C are preferred from the viewpoint of the stability and reactivity of the composition during storage. Examples of such initiators include t-hexylperoxyisopropyl monocarbonate (one-minute half-life temperature, hereinafter: 155.0°C), t-butylperoxy-3,5,5-trimethylhexanoate (166.0°C), t-butylperoxylaurate (159.4°C), t-butylperoxyisopropyl monocarbonate (158.8°C), t-butylperoxy-2-ethylhexyl monocarbonate (161.4°C), t-hexylperoxybenzoate (160.3°C), 2,5-dimethylhexanoate (161.4°C), and 2,5-dimethylhexanoate (162.4°C). t-butylperoxybenzoate (166.8°C), n-butyl 4,4-di-(t-butylperoxy)valerate (172.5°C), di(2-t-butylperoxyisopropyl)benzene (175.4°C), dicumyl peroxide (175.2°C), di-t-hexyl peroxide (176.7°C), 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (179.8°C), and t-butylcumyl peroxide (173.3°C).

[0164] Among these, the organic peroxide is preferably at least one selected from the group consisting of t-butyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxybenzoate, di(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and t-butylcumyl peroxide.

[0165] The blending amount of component (D) is preferably 0.001 to 10 phr based on the total amount of components (A) and (C). When the blending amount of component (D) is 0.001 phr or more, the effects of component (D) are fully exerted, and the Tg of the cured product tends to be higher by accelerating the progress of the curing reaction. Furthermore, when the blending amount is 10 phr or less, the amount of initiator and its decomposition products remaining in the cured product tends to be reduced, and the dielectric loss tangent of the cured product tends to be prevented from becoming high. From this perspective, the blending amount of component (D) is more preferably 0.1 to 5 phr, and even more preferably 0.5 to 2 phr.

[0166] <(E) Solvent> An organic or inorganic solvent can be added to the curable resin composition of the present embodiment as needed. The addition of an organic solvent can reduce the viscosity of the composition, and such a curable resin composition can improve the impregnation of glass fibers when impregnating glass fibers to produce a laminate.

[0167] Examples of such organic solvents include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), and ethyl acetate. Toluene and methyl ethyl ketone are particularly preferred because they have low boiling points and can be easily removed by evaporation from the resin composition.

[0168] <Other ingredients> The curable resin composition of the present embodiment may contain additives such as a flame retardant, an elastomer, and a filler, as long as the purpose of the composition is not impaired. [Example]

[0169] Hereinafter, the present embodiment will be described in more detail based on Production Examples and Examples, but the present embodiment is not limited to the following Production Examples and Examples.

[0170] First, the measurement methods and evaluation criteria for each physical property will be described below.

[0171] (1) Presence ratio of polyphenylene ether Here, the proportion of polyphenylene ether present is determined based on the ratio of the modified polyphenylene ether having the structure of formula (1) to the ratio of the polyphenylene ether having one or more [-Y n -A] is [-Y n -H] and all [-Y n -A] is not [-Yn-H], and in the structure of formula (1), all of [-Y n -A] is [-Y n -H] (main component polyphenylene ether). (1-1) The modified polyphenylene ether compositions obtained in the Examples and Comparative Examples and the polyhydric phenols used as raw materials were dissolved in deuterated chloroform, and the resulting mixture was analyzed using tetramethylsilane as an internal standard. 1 H-NMR measurements were carried out (JEOL, 500 MHz). (1-2) The peaks of polyhydric phenols contained in the product were identified from the peak positions due to the central phenol moiety. (1-3) A central phenol unit of the main component polyphenylene ether represented by formula (2), and a polyphenylene ether represented by formula (14): [ka] {In formula (14), multiple R 21 , R 21 Each ' independently represents at least one selected from the group consisting of a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, and a halogen atom; an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms is preferred, more preferably a methyl group, ethyl group, n-propyl group, vinyl group, aryl group, ethynyl group, or propargyl group, even more preferably a methyl group or ethyl group, and particularly preferably a methyl group. Examples of the substituent include a halogen atom. In equation (14), two R 21and preferably are not simultaneously a hydrogen atom, and / or are not a combination in which one is a partial structure represented by the above formula (3) and the other is a hydrogen atom, a methyl group, or an ethyl group, from the viewpoint of ensuring that the modified polyphenylene ether-containing composition has all of the following properties: low dielectric properties, adequate metal peelability, low solution viscosity, and sufficient Tg upon curing. In formula (14), multiple R 22 , R 22 Each ' independently represents at least one selected from the group consisting of a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, and a halogen atom; a hydrogen atom or an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms is preferred, a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group is more preferred, and a hydrogen atom or a methyl group is even more preferred. Examples of the substituent include a halogen atom. c is an integer between 1 and 100. and a terminal phenoxy unit specific to the by-product represented by formula (15): [ka] {In formula (15), multiple R 21 , R 21 " each independently represents at least one selected from the group consisting of a hydrogen atom; an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms; and a halogen atom; and is preferably an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, more preferably a methyl group, ethyl group, n-propyl group, vinyl group, aryl group, ethynyl group, or propargyl group, still more preferably a methyl group or ethyl group, and particularly preferably a methyl group. Examples of the substituent include a halogen atom. In equation (15), two R 21and preferably are not simultaneously a hydrogen atom, and / or are not a combination in which one is a partial structure represented by the above formula (3) and the other is a hydrogen atom, a methyl group, or an ethyl group, from the viewpoint of ensuring that the modified polyphenylene ether-containing composition has all of the following properties: low dielectric properties, adequate metal peelability, low solution viscosity, and sufficient Tg upon curing. Multiple R 22 , R 22 " each independently represents at least one selected from the group consisting of a hydrogen atom; an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms; and a halogen atom; and is preferably a hydrogen atom or an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group, and even more preferably a hydrogen atom or a methyl group. Examples of the substituent include a halogen atom. d and e each independently represent any integer from 1 to 100.} The diphenyl units specific to the by-products represented by the formula (16) were assigned to the peaks in the obtained NMR spectrum, and the abundance ratios of various polyphenylene ethers were calculated by the formula (16):

number

[0172] In the examples and comparative examples, the peaks due to the central phenol moiety of the main component polyphenylene ether represented by formula (2) and the H of the terminal phenol of the by-product represented by formula (14) are 1 , and R 22 The peak due to ', R in the central phenol of the by-product represented by Eq. (15) 22 The peaks due to " appear in the following region: 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane(1H): 2.8 to 3.2 ppm 1,1-bis(2-methyl-4-hydroxy-5-t-butylphenyl)butane(1H): 4.0-4.3 ppm 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane(4H): 6.95-7.0 ppm Terminal phenoxy unit (3H) of the by-product represented by formula (14): 7.05 to 7.1 ppm Diphenyl (4H) by-product represented by formula (15): 7.34 to 7.4 ppm

[0173] (2) The ratio of the integrated value of the peak appearing at 7.6 to 8.3 ppm to the integrated value of the peak originating from the structure of formula (2) (the ratio of the peroxide peaks present) the above 1 In the H-NMR measurement, the integrated value E of the peak area due to the central phenol moiety of the main component polyphenylene ether represented by formula (2) was used, and the integrated value G of the area of ​​the impurity peak (i.e., peroxide peak) derived from peroxide appearing in the region of 7.6 to 8.3 ppm was calculated. The abundance ratio of the peroxide peak was analyzed by substituting this into the following formula (17).

number

[0174] (3) Number average molecular weight (Mn) A gel permeation chromatography System 21 manufactured by Showa Denko K.K. was used as the measuring device, and a calibration curve was prepared using standard polystyrene and ethylbenzene. Using this calibration curve, the number average molecular weight (Mn) of the resulting modified polyphenylene ether composition was measured.

[0175] The standard polystyrenes used were those with molecular weights of 3,650,000, 2,170,000, 1,090,000, 681,000, 204,000, 52,000, 30,200, 13,800, 3,360, 1,300, and 550.

[0176] Two Showa Denko K-805L columns connected in series were used. Chloroform was used as the solvent, and measurements were performed at a solvent flow rate of 1.0 mL / min and a column temperature of 40°C. A 1 g / L chloroform solution of the modified polyphenylene ether composition was prepared and used as the measurement sample. The UV wavelength of the detection unit was 254 nm for standard polystyrene and 283 nm for polyphenylene ether.

[0177] The number average molecular weight (Mn) (g / mol) was calculated from the ratio of peak areas based on the curve showing the molecular weight distribution obtained by GPC based on the above measurement data.

[0178] (4) Glass transition temperature (Tg) The glass transition temperature of the modified polyphenylene ether composition was measured using a differential scanning calorimeter (DSC) (PerkinElmer - Pyrisl). In a nitrogen atmosphere, the composition was heated from room temperature to 200°C at a heating rate of 20°C per minute, then cooled to 50°C at a heating rate of 20°C per minute, and the glass transition temperature was then measured at a heating rate of 20°C per minute.

[0179] (5) The number of A substituents contained in the composition A specified amount of the modified polyphenylene ether composition and a 1,3,5-trimethoxybenzene standard (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight 168.19) as an internal standard sample were taken and dissolved in deuterated chloroform containing trimethylsilane. 1H-NMR measurements were carried out (JEOL, 500 MHz).

[0180] Next, the integral value of the peak (3.7 to 3.8 ppm: 9H) of the proton derived from the methoxy group of 1,3,5-trimethoxybenzene and the integral value of the peak (5.5 to 5.9 ppm: 1H) appearing on the high magnetic field side among the protons at the C=C bond terminal of the methacryl group were determined, and the number of methacryl groups per 1 g of the modified polyphenylene ether composition (unit: μmol / g) was calculated from these integral values ​​and the weights of the polyphenylene ether composition and 1,3,5-trimethoxybenzene used in the measurement.

[0181] (6) Viscosity of Toluene Solution of Modified Polyphenylene Ether Composition (Liquid Viscosity) 2 g of the modified polyphenylene ether composition and 3 g of toluene were weighed. Using a stirring bar and a magnetic stirrer, these were stirred for 1 hour until the solution became transparent and completely dissolved, thereby preparing a 40 wt% toluene solution. The liquid viscosity of this solution was measured using a Brookfield viscometer at 25°C and 30 rpm.

[0182] (7) Denaturation rate The modification rate was calculated from the change in the amount of hydroxyl groups before and after the reaction as determined by IR measurement in carbon disulfide, according to the method described in JP-A-2004-502849 (Patent Document 2).

[0183] (8) Preparation of cured product Film-like test pieces with a thickness of 0.1 to 0.3 mm were prepared by a pressing method under the following conditions. The polymer, styrene elastomer, etc. were added to toluene so that the solid content concentration was 34%, and the mixture was allowed to dissolve uniformly at room temperature overnight, after which NOF Perbutyl P was added to form a varnish. This was applied to the shine side of copper foil and dried at 120°C for 10 minutes, and the resulting solid resin composition was pulverized in an agate mortar. A 100 μm thick Teflon® sheet was cut into a 60 × 60 mm shape, the Teflon® sheet was placed on the shiny side of the copper foil, and the solid resin composition was added to the cavity in an amount approximately 1.5 times the theoretical value (6 × 6 × 0.01 × 1.5 = 0.54 g assuming a specific gravity of 1). The shiny side of the copper foil was then placed on top, and the press was performed under a pressure of 40 (kg / cm). 2 ) and vacuum press cured under constant vacuum conditions at the following temperature conditions. Room temperature to 50℃, 4℃ / min, 50℃ hold for 1 min 50℃~160℃ 4℃ / min, 160℃ hold 3 min 160℃~220℃ 4℃ / min, 220℃ Hold time: 60 min

[0184] (9) Tg measurement of the cured product The glass transition temperature (Tg) of the cured product was measured by DMA using Hitachi High-Tech Science (DMS6100) under the following conditions. Test pieces were cut out to a size that allowed appropriate measurements over the entire temperature range of the DMA device, and dynamic viscoelasticity tests were performed. Test piece: Strip, Measurement mode: Tension mode Test start temperature: Room temperature Heating rate: 4°C / min Maximum test temperature: 300℃ Maximum temperature holding time: 5 minutes Measurement frequency: 1Hz Analysis: The tan δ peak was taken as Tg. Furthermore, the storage modulus at a temperature 30°C higher than the tan δ peak was read and used to calculate the crosslink density.

[0185] (10) Measurement of dielectric tangent of cured product The cured product having a thickness of 0.1 to 0.3 mm was cut into a shape of 50 x 50 mm, and the dielectric loss tangent at 10 GHz was measured using a network analyzer (KEYSIGHT TECHNOLOGIES PNA N5227B, cavity resonator method, split cylinder resonator used).

[0186] (11) Measurement of linear expansion coefficient The linear expansion coefficient was determined by measuring a sample cut from a dielectric loss tangent measurement specimen using Hitachi High-Tech Science Corporation's TMA7100 under the following conditions. Measurement mode: Tensile Size: Width 2mm, Length 10mm, Thickness 0.2mm Test start temperature: -50℃ Heating rate: 10°C / min Maximum test temperature: 250℃ Maximum temperature holding time: 5 minutes

[0187] (12) Number average molecular weight of styrene elastomer Measurement was carried out by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight was determined from a PS (polystyrene) equivalent calibration curve at the obtained peak. Measuring device: GPC HLC-8220 (TOSOH Corporation, trade name) Columns: TAKgel GMHXL SuperH5000: 1, SuperH4000: 2 (TOSOH Corporation, product name) Solvent: tetrahydrofuran Temperature: 40℃ Samples for calibration curve: Commercially available standard samples (manufactured by TOSOH), 10 points measured

[0188] (13) Styrene content of styrene-based elastomer The content of vinyl aromatic compound monomer units (styrene content) was determined by nuclear magnetic resonance spectroscopy (NMR) under the following conditions. Measuring equipment: JNM-LA400 (JEOL) Solvent: deuterated chloroform Sample concentration: 50mg / mL Observation frequency: 400MHz Chemical shift standard: TMS (tetramethylsilane) Pulse delay: 2.904 seconds Number of scans: 64 Pulse width: 45° Measurement temperature: 26℃

[0189] (14) Double bond content of styrene-based elastomer The double bond content of the styrene elastomer was determined by measuring it by nuclear magnetic resonance spectroscopy (NMR) under the same conditions as those for the styrene content of the styrene elastomer. The weight ratio of the conjugated diene monomer was calculated based on the amount of vinyl bonds in the conjugated diene monomer unit.

[0190] (15) Evaluation of uniformity of resin composition A resin composition solution was separately prepared by removing only the initiator from the curable resin composition solution. 2 μl of the resin composition solution was dropped onto a glass slide placed on a hot plate at 160 °C, allowed to stand for 2 minutes, and then the pressure was reduced to 100 mmHg for 30 seconds to remove the toluene, yielding a resin composition. The resulting resin composition, while still on the glass slide and maintained at 160 °C, was transferred onto a hot stage of a microscope set at 160 °C, and observed through a 10x eyepiece in the transmission mode of an optical microscope, followed by photographs. The case where no texture was observed and the sample was uniformly transparent was rated as ◯, the case where texture was observed was x, and the case where no texture was observed but fluctuations were observed was rated as △.

[0191] (16) Measurement of copper foil adhesive strength The adhesive strength with copper foil was measured by a T-peel test. A small amount of glass beads (for spacers) with a particle size of approximately 40 μm (20-40 μm) was added to a varnish prepared at a specified ratio. 35 μm-thick copper foil was cut into a 50 × 80 mm piece, and polyimide tape (10 mm wide, 55 μm thick) was attached to the outer periphery of the roughened copper foil surface. The prepared varnish was poured into the resulting frame, left overnight, dried at 120°C for 10 minutes, and the polyimide tape was peeled off to obtain a test specimen. Copper foils of the same size were stacked on top of each other with the resin layer sandwiched between the roughened surfaces. A Teflon® sheet of approximately 20 mm was placed at one end to ensure a gripping margin, and the specimen was vacuum-pressed and cured under the same temperature conditions as in the "Preparation of the Cured Product" section (8) above. The resulting copper foil was cut into a 10 mm × 80 mm measurement sample. Using the measurement sample, a T-peel test was carried out under the following conditions using a tensile tester (Instron 59R5582 model) to measure the copper foil adhesive strength. Test piece: 10mm x 80mm. Tested twice and the average value was taken. Measurement conditions: Test temperature: Room temperature (approximately 23°C), Test speed: 50mm / min, test length: approximately 30mm.

[0192] (17) Laminate impregnation properties The varnish prepared by the method described in the above item (8) "Preparation of cured product" was impregnated into a glass cloth cut into a shape of 30 x 60 mm, dried at 120°C for 10 minutes, and four sheets of the obtained prepreg were stacked and pressed under a pressure of 40 (kg / cm). 2 ) and press-cured under constant vacuum conditions at the following temperature conditions. Room temperature to 50℃, 4℃ / min, 50℃ hold for 1 min 50℃~160℃ 4℃ / min, 160℃ hold 3 min 160℃~220℃ 4℃ / min, 220℃ Hold time: 60 min A transparent laminate was evaluated as ◯, a laminate that was entirely cloudy or had significant blurring was evaluated as X, and a laminate that had partially cloudy areas was evaluated as △.

[0193] Hereinafter, the methods for producing the unmodified polyphenylene ether compositions of each Production Example and Production Comparative Example, and the methods for producing the modified polyphenylene ether compositions of each Example and Comparative Example will be described.

[0194] (Production Example 1) A 1.5-liter jacketed reactor equipped with a sparger at the bottom for introducing an oxygen-containing gas, a stirring turbine blade and a baffle, and a reflux condenser on the vent gas line at the top of the reactor was charged with a previously prepared mixture of 0.1026 g of cuprous oxide and 0.7712 g of 47% hydrogen bromide, 0.2471 g of N,N'-di-t-butylethylenediamine, 3.6407 g of dimethyl-n-butylamine, 1.1962 g of di-n-butylamine, 894.04 g of toluene, 73.72 g of 2,6-dimethylphenol, and 26.28 g of 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane (ADEKA: AO-30). Next, while vigorously stirring these components, air was introduced into the reactor via the sparger at a rate of 1.05 L / min. At the same time, a heat transfer medium was passed through the jacket to maintain the polymerization temperature at 40°C. 160 minutes after the start of air introduction, the air flow was stopped, and 1.1021 g of ethylenediaminetetraacetic acid tetrasodium salt tetrahydrate (a reagent manufactured by Dojindo Laboratories) was added to the polymerization mixture as a 100 g aqueous solution, and the mixture was heated to 70°C. After maintaining the temperature at 70°C for 2 hours, the catalyst was extracted and the by-product diphenoquinone was removed. The mixture was then transferred to a Sharpless centrifuge and separated into an unmodified polyphenylene ether composition solution (organic phase) and an aqueous phase containing the catalyst metal. The resulting unmodified polyphenylene ether composition solution was transferred to a jacketed concentration tank and concentrated by distilling off toluene until the solids content of the unmodified polyphenylene ether composition solution reached 55% by mass. Next, toluene was further distilled off from the concentrate using an oil bath and a rotary evaporator set at 230°C, and the solid content was dried to obtain an unmodified polyphenylene ether composition.

[0195] A stirrer was placed in a 300 ml three-neck flask, and a Dimroth condenser with a three-way stopcock was attached to the main tube. A rubber stopper with a thermometer inserted was attached to one side tube. 20.0 g of the unmodified polyphenylene ether composition obtained in the above process was added to the other side tube, and a rubber stopper was attached. After replacing the atmosphere inside the flask with nitrogen, the mixture was dissolved in 60.0 g of ultra-dehydrated toluene (Wako Pure Chemical Industries, Ltd.) using a syringe while stirring the contents with a magnetic stirrer. Next, 5.72 g of triethylamine was added to the system. 3.38 g of dimethylvinylchlorosilane was then collected in a syringe and added dropwise to the system through the rubber stopper. After the dropwise addition, stirring was continued at 30°C for 3 hours, and then 0.86 g of ultra-dehydrated methanol (Wako Pure Chemical Industries, Ltd.) was added to the system to stop the reaction.

[0196] Next, the reaction solution was distilled under reduced pressure to remove triethylamine together with toluene. Ultra-dehydrated toluene (Wako Pure Chemical Industries, Ltd.) was then added to the reaction solution to adjust the solids concentration to 20 wt%. The polymer solution was then added dropwise to methanol (5 times the weight of the organic layer) with stirring. The precipitate was then filtered, and the residue was dried in vacuo at 110°C for 1 hour to obtain a modified polyphenylene ether composition. NMR analysis confirmed the progress of the reaction. The molecular weight of the resulting modified polyphenylene ether composition (PPE-1) was Mw = 4,810 and Mn = 2,610. The conversion rate of the resulting PPE-1 was 96%. The viscosity of a 40 wt% toluene solution of the resulting polymer was 23 mPa·s.

[0197] (Examples 1-8, Comparative Examples 1 and 2) Curable resin composition solutions were prepared using the styrene-based elastomers shown in Table 1 and in the formulations shown in Tables 2 and 3, and the cured products obtained by the above methods were evaluated and the results are shown in Tables 2 and 3. The blend amounts are in parts by mass.

[0198] Optical photographs (transmission mode) of the resin compositions prepared in Example 2 and Comparative Example 2 at 160° C. are shown in FIG. 1 and FIG. 2, respectively. The resin composition of Example 2 is uniform, whereas the resin composition of Comparative Example 2 exhibits a distinct texture and is non-uniform. SPM images of the cured products obtained in Examples 2, 4, 5, 6, and 7 are shown in Figures 3 to 7, respectively. The bright areas in the images represent the PPE phase, and the dark areas represent the elastomer phase. It was confirmed that the PPE phase formed a continuous phase in the cured products obtained in the present invention. In particular, in Example 2 (FIG. 3) and Example 5 (FIG. 5), the elastomer phase with low polarity forms large domains. In Example 2, the low styrene concentration of the blended Elastomer 1 contributed to the formation of a cured product with a low Df. In Example 5, it is shown that the large number average molecular weight of the blended elastomer 4 contributed to the formation of a cured product with a low Df.

[0199] [Table 1]

[0200] [Table 2]

[0201] [Table 3]

[0202] The abbreviations in Tables 2 and 3 are as follows: TAIC: Triallyl isocyanurate SA9000: SABIC methacrylic modified PPE (molecular weight 2500) Perbutyl P: manufactured by NOF Corporation tBS: 4-tert-Bu-styrene DVB: Divinylbenzene (reagent manufactured by Tokyo Chemical Industry Co., Ltd., purity 57%)

[0203] As is clear from Tables 2 and 3, in the examples, uniform cured products were obtained, and curable resin compositions with good moldability were obtained that satisfied all of the requirements of sufficient Tg, low dielectric properties, and a low linear expansion coefficient of the cured products. In contrast, Comparative Example 1, which did not contain a styrene-based elastomer, did not achieve sufficient Tg, low dielectric properties, copper foil adhesive strength, or laminate impregnation. Furthermore, Comparative Example 2, which used TAIC as a cross-linking aid, did not achieve a uniform resin composition. Furthermore, the low dielectric properties and copper foil adhesive strength were also insufficient. [Industrial Applicability]

[0204] The curable resin composition of the present invention is a curable resin composition useful as a substrate material, which can obtain a uniform cured product by blending a terminal-modified polyphenylene ether having a specific structure, a specific styrene-based elastomer, and a crosslinking aid having a specific structure, and which satisfies all of the requirements of sufficient Tg, low dielectric properties, adhesion, low linear expansion coefficient, and moldability of the cured product.

Claims

1. A curable resin composition comprising the following components (A), (B), and (C): (A) Modified polyphenylene ether A modified polyphenylene ether represented by the following formula (1): 【Chemical 1】 In formula (1), Z is an a-valent partial structure represented by the following formula (2), a represents an integer of 2 to 6, each Y is independently a divalent linking group having a structure represented by the following formula (4), n represents the number of repetitions of Y, each n is independently an integer of 0 to 200, and a number of [-Y ｎ At least one n in the formula (A) is an integer of 1 or more, and A represents a silyl group-containing derivative represented by the following formula (5): 【Chemistry 2】 In formula (2), X is an arbitrary linking group having a valence of a, and a plurality of R ５ are each independently a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and each k is independently an integer of 1 to 4: 【Chemistry 3】 In formula (3), a plurality of R １１ are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms, and a plurality of R １２ are each independently an optionally substituted alkylene group having 1 to 8 carbon atoms, each b is independently 0 or 1, and R １３ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted phenyl group; 【Chemistry 4】 In formula (4), a plurality of R ２１ are each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or a halogen atom; ２１ is not a hydrogen atom at the same time, but two R ２１ is not a combination of one of the partial structures represented by the above formula (3) and the other of a hydrogen atom, a methyl group, or an ethyl group, but a combination of multiple R ２２ are each independently any one of a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, and a halogen atom. 【Chemistry 5】 In formula (5), R 31 and R 34 are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms, R 32 and R 33 are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydroxyalkyl group, B is a hydrocarbon-based substituent having 1 to 30 carbon atoms containing an olefinic carbon-carbon double bond, some of which may be substituted with a hydrogen atom, a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group, and s, t, and u are each independently an integer of 0 to 8. (B) Styrene-based elastomer A styrene-based elastomer comprising a block A mainly composed of vinyl aromatic compound monomer units and a block B mainly composed of conjugated diene monomer units: (C) Crosslinking aid A crosslinking aid which is an aromatic vinyl compound represented by the following formula (18) and which has 3 or less vinyl groups in the molecule: 【Chemistry 6】 {In formula (18), R ３７ , R ３８ , R ３９ represent a hydrogen atom or a hydrocarbon having 4 or less carbon atoms, and R ４０ , R ４１ each independently represents hydrogen or a saturated or unsaturated hydrocarbon having 8 or less carbon atoms.

2. 2. The curable resin composition according to claim 1, wherein the component (B) is a styrene-based elastomer having a number average molecular weight of 300,000 or less.

3. 3. The curable resin composition according to claim 1, wherein the component (B) is a styrene-based elastomer having a double bond content of 90% or less.

4. The curable resin composition according to any one of claims 1 to 3, wherein the component (B) is a styrene-based elastomer having a styrene content of 80% or less.

5. The curable resin composition according to any one of claims 1 to 4, wherein the component (B) is a styrene-based elastomer having a hydrogenation rate of double bonds based on conjugated diene monomer units of 90% or more.

6. In the formula (18), R ３７ , R ３８ , R ３９ The curable resin composition according to any one of claims 1 to 5, wherein is a hydrogen atom.

7. In the formula (18), R ４０ The curable resin composition according to any one of claims 1 to 6, wherein is a tert-butyl group.

8. In the formula (18), R ４１ The curable resin composition according to any one of claims 1 to 7, wherein is a vinyl group.

9. The curable resin composition according to any one of claims 1 to 8, wherein the component (C) is 4-tertbutylstyrene.

10. The curable resin composition according to any one of claims 1 to 9, wherein the component (C) is divinylbenzene.

11. The curable resin composition according to any one of claims 1 to 10, further comprising (D) an initiator.

12. In the formula (2), the R ５ At least one of the carbon atoms in the benzene ring to which —O— in the formula (2) is bonded is the 1st position, and R ５ and a hydrogen atom, a methyl group, or an ethyl group is bonded to the other carbon atom at the 2- or 6-position.

13. The curable resin composition according to any one of claims 1 to 12, wherein the partial structure represented by the formula (3) is a t-butyl group.

14. The curable resin composition according to any one of claims 1 to 13, wherein the number of OH terminals contained in the polyphenylene ether is 0 to 3,000 µmol / g.

15. R in the formula (4) ２１ The curable resin composition according to any one of claims 1 to 14, wherein is a methyl group.

16. A in the formula (1) is the following formula (6) or (7): 【Chemistry 7】 【Chemistry 8】 {In formula (6) or formula (7), R ３１ , and R ３４ are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms, and R ３２ , and R ３３ are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydroxyalkyl group, and R ３５ are each independently a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 30 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group; R ３６ represents a divalent hydrocarbon group or amino group having 1 to 3 carbon atoms, or an oxygen atom, and a portion of the hydrocarbon group may be substituted with an aryl group, an alkoxy group, an allyloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group, and s, t, and u each independently represent an integer of 0 to 8. The curable resin composition according to claim 15, wherein

17. The curable resin composition according to any one of claims 1 to 16, further comprising (E) a solvent.

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