Curable resin composition

Abstract

To provide a curable resin composition that impregnates a base material easily in preparing a substrate and satisfies all of sufficient low dielectric characteristics, a low linear expansion coefficient, and high copper foil adhesive strength of a cured product.SOLUTION: A curable resin composition contains (A) modified polyphenylene ether, (B) styrene-based elastomer, and (C) a cross-linking auxiliary represented by formula (18), which is an aromatic vinyl compound having three or less vinyl groups in the molecule. The curable resin composition has a solution viscosity of a toluene solution of 62% solid concentration of 1-7,000 [mPa s] as measured with a cone plate type rotary viscometer.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 methacrylic group at the molecular end. In particular, methacrylic group modification is becoming widely used because the reactivity of the methacrylic group as a crosslinking group is moderately high and it is easy to introduce it to the hydroxyl group end. Meanwhile, Patent Document 4 reports an example in which a vinylsilyl group is introduced as a modifying group at the molecular end in order to improve dielectric properties, heat resistance, etc.

[0004] Furthermore, Patent Document 5 reports an attempt to improve adhesion to metal foil, etc., by blending methacrylated polyphenylene ether with a block copolymer of a vinyl aromatic compound and an olefin-based alkene compound, and / or its hydrogenated product (styrene-based elastomer), and dissolving the mixture in a solvent to produce a varnish. [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] Chinese Patent Application Publication No. 106916293 [Patent Document 5] Japanese Patent Publication No. 2020-200432 Summary of the Invention [Problem to be solved by the invention]

[0006] As described above, styrene-based elastomers are added to modified polyphenylene ether because of various advantages. However, it has been confirmed that when a varnish is prepared by blending a styrene-based elastomer with polyphenylene ether modified with vinylsilyl groups as disclosed in Patent Document 4, it becomes difficult to impregnate the substrate during substrate preparation, and the dielectric properties, linear expansion coefficient, and copper foil adhesive strength of the formed cured product may deteriorate.

[0007] In view of the above problems, an object of the present invention is to provide a curable resin composition that can be easily impregnated into a substrate when preparing a board, and that satisfies all of the following requirements of a cured product: sufficiently low dielectric properties, a low coefficient of linear expansion, and high copper foil adhesive strength. [Means for solving the problem]

[0008] In order to solve the above problems, the present inventors have obtained a curable resin composition that can solve all of the above problems by comprising a modified polyphenylene ether using a vinylsilyl group or the like as a modifying group, which is a crosslinking group with low polarity and good metal adhesion, a styrene-based elastomer, and a specific crosslinking aid, and further having a viscosity when dissolved in a specific solvent, and have thereby completed the present invention. That is, the present invention is as follows. [1] A curable resin composition comprising the following components (A), (B), and (C), wherein the solution viscosity of a toluene solution having a solids concentration of 62% is 1 mPa s or more and 7000 mPa s or less, as measured at 25°C and 1 rpm using a cone-plate type rotational viscometer: (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 21are 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) has a styrene content of 33% or more. [3] The curable resin composition according to [1] or [2], wherein the component (B) has a number average molecular weight of 300,000 or less. [4] The curable resin composition according to any one of [1] to [3], wherein the component (B) includes 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. [5] The curable resin composition according to any one of [1] to [4], wherein the component (B) comprises a block A mainly composed of vinyl aromatic compound monomer units and a block B containing conjugated diene monomer units. [6] The curable resin composition according to any one of [1] to [5], 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. [7] The curable resin composition according to any one of [1] to [6], further comprising (D) an initiator. [8] The curable resin composition according to [7], having a minimum melt viscosity of 1 [Pa·s] or more and 20,000 [Pa·s] or less. [9] The curable resin composition according to any one of [1] to [8], further comprising (E) a solvent.

[10] In the formula (18), R 37 , R 38 , R 39 The curable resin composition according to any one of [1] to [9], wherein is a hydrogen atom.

[11] In the formula (18), R 40 The curable resin composition according to any one of [1] to

[10] , wherein is a tert-butyl group.

[12] In the formula (18), R 41 The curable resin composition according to any one of [1] to

[11] , wherein is a vinyl group.

[13] The curable resin composition according to

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

[14] The curable resin composition according to

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

[15] 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.

[16] The curable resin composition according to

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

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

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

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

[17] , wherein is a methyl group.

[19] 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

[18] , represented by the following formula:

[20] 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

[19] , [twenty one] A prepreg comprising the curable resin composition according to any one of [1] to

[20] . [twenty two] A laminate comprising a cured product of the curable resin composition according to any one of [1] to

[20] . [twenty three] A printed wiring board comprising a cured product of the curable resin composition according to any one of [1] to

[20] . [twenty four] A composite material comprising a cured product of the curable resin composition according to any one of [1] to

[20] . [twenty five]

[24] The composite material according to

[24] , which is a carbon fiber reinforced composite material. [Effects of the Invention]

[0009] By using the curable resin composition defined in the present invention, it is possible to provide a curable resin composition that can easily impregnate a substrate when preparing a substrate, and that satisfies all of the requirements of a cured product having sufficiently low dielectric properties, a low coefficient of linear expansion, and high copper foil adhesive strength. DETAILED DESCRIPTION OF THE INVENTION

[0010] 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.

[0011] <Curable resin composition> The curable resin composition of the present embodiment is characterized by containing the following (A) modified polyphenylene ether, (B) styrene-based elastomer, and (C) crosslinking aid. (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 12are 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 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.}

[0012] In this embodiment, by using a curable resin composition containing (A) a modified polyphenylene ether, (B) a styrene-based elastomer, and (C) a cross-linking aid, 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 the present embodiment will be described in detail below.

[0013] <(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 represented by formula (2) below, where a is an integer of 3 to 6.

[0014] 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.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] X in formula (2) may be a linking group that links the a-valent partial structures to each other.

[0019] 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;

[0020] 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

[0021] 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.

[0022] 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 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, 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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]

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] The phenol compounds may be used alone or in combination of two or more.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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).

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] <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.

[0068] 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).

[0069] 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.

[0070] 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.

[0071] 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.

[0072] Z in formula (8) may be a structure having a central phenol moiety with a valence represented by the following formula (9), and a in formula (8) or (9) is preferably an integer of 3 to 6.

[0073] The central phenol moiety is as explained in the above section <Modified polyphenylene ether>.

[0074] 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.

[0075] 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.

[0076] 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;

[0077] 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

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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

[0086] 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).

[0087] 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.

[0088] 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.

[0089] 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).

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] <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.

[0097] (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.

[0098] 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.

[0099] 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.

[0100] The polymerization catalyst preferably used in this embodiment is a catalyst comprising 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.

[0101] 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).

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] (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.

[0112] (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.

[0113] (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.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] [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.

[0118] 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.

[0119] 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.

[0120] Examples of the alkoxysilane compound include trimethoxyvinylsilane, methoxydimethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, methacryloxypropyldimethoxymethylsilane, methacryloxypropyltrimethoxysilane, methacryloxypropyldiethoxymethylsilane, methacryloxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminophenoxydimethylvinylsilane, and 4-aminophenoxydimethylvinylsilane.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] <(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, or chlorine-substituted styrene, or unsubstituted styrene (a vinyl aromatic compound), with an olefin-based alkene compound, or a hydrogenated product thereof, and may be a block copolymer or a random copolymer.

[0132] 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.

[0133] <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 H1051, H1043, H1517, P5051, and P2000; 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.

[0134] <Number average molecular weight of styrene elastomer> Although the present embodiment is not limited to the number-average molecular weight of the styrene-based elastomer (B), when the curable resin composition of the present embodiment is applied to a laminate, a smaller number-average molecular weight of the styrene-based elastomer (B) tends to improve moldability and result in a uniform, highly insulating laminate, while a larger number-average molecular weight tends to result in a cured product with a lower dielectric loss tangent (Df). From these perspectives, the present embodiment tends to achieve the object of the present embodiment more effectively when the number-average molecular weight of the styrene-based elastomer (B) is preferably from 1,000 to 300,000, more preferably from 5,000 to 200,000, even more preferably from 10,000 to 150,000, still more preferably from 20,000 to 100,000, particularly preferably from 30,000 to 80,000, and especially preferably from 40,000 to 60,000.

[0135] <Double bond content of styrene elastomer> The (B) styrene-based elastomer of the present embodiment is not limited by the double bond content of the styrene-based elastomer, but a lower double bond content tends to result in a cured product in which deterioration of the insulation reliability, copper foil peel strength, and the like of the cured product obtained by curing is suppressed.

[0136] From this perspective, the double bond content of the styrene elastomer of component (B) is preferably 90% or less, more preferably 50% or less, even more preferably 10% or less, and particularly preferably 1% or less.

[0137] <Styrene content of styrene-based elastomer> The styrene content (content of vinyl aromatic compound units) of the styrene-based elastomer serving as component (B) is not particularly limited. However, the higher the styrene content, the higher the compatibility of the composition tends to be. As a result, when the curable resin composition of the present embodiment is cured, the cured product tends to have excellent properties such as copper foil adhesive strength and insulation reliability. On the other hand, the lower the styrene content of the styrene-based elastomer, the lower the modulus of elasticity of the elastomer, and therefore the toughness of the cured product obtained by curing the curable resin composition of this embodiment tends to be increased. As an example of this embodiment, there is a method in which an organic or inorganic solvent is added to the curable resin composition of this embodiment to obtain a homogeneous composition, which is then used industrially. The higher the styrene content of the styrene-based elastomer of component (B), the better the compatibility, and therefore the viscosity of the solution tends to decrease. When the curable resin composition solution is then impregnated into a woven or nonwoven fabric such as glass or carbon fiber, the solution tends to penetrate into the fine details of the fibers, and a composite material exhibiting excellent properties tends to be obtained. Furthermore, the higher the styrene content of the styrene-based elastomer (B), the more uniform the curable resin composition in a solvent-free state tends to be, and as a result, the melt viscosity of the curable resin composition tends to be lower. On the other hand, the lower the styrene content of the styrene-based elastomer (B), the more the toughness of the cured product obtained by curing the curable resin composition of this embodiment tends to be higher, and the higher the copper foil peel strength tends to be. From such a viewpoint, the styrene content of the styrene-based elastomer of component (B) is preferably 33% or more and 99% or less, and can also be 38% or more and 95% or less, 40% or more and 90% or less, 45% or more and 80% or less, 50% or more and 75% or less, or 60% or more and 70% or less, and can be selected depending on the desired process characteristics of the curable resin composition and the properties of the cured product.

[0138] <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.

[0139] <(C) Crosslinking Coagent> The crosslinking aid of the component (C) 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.

[0140] R 40 , 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.

[0141] 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 41More preferably, the number of unsaturated groups contained in is one or zero in total. R 40 is preferably a tert-butyl group, and R 41 is preferably a vinyl group.

[0142] 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.

[0143] <Reason for the effectiveness of crosslinking 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.

[0144] 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.

[0145] 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.

[0146] <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.

[0147] 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.

[0148] 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.

[0149] <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 this embodiment tend to be better exhibited when the blending ratio of components (A), (B), and (C) in this embodiment 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.

[0150] <(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).

[0151] 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.

[0152] 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.

[0153] <(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.

[0154] 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.

[0155] <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.

[0156] <Solution Viscosity of Curable Resin Composition> The curable resin composition of this embodiment is specified by the viscosity at 25°C of a toluene solution obtained by adjusting the solid content concentration to 62% being 1 [mPa·s] or more and 7000 [mPa·s] or less. The solution viscosity of the curable resin composition can be determined by measuring with a cone-plate type rotational viscometer such as the TVE-22H viscometer manufactured by Toki Sangyo Co., Ltd. under the measurement condition of 1 rpm.

[0157] For example, in an industrial embodiment of this embodiment, in the application of impregnating glass fibers with the toluene solution and drying the solution to prepare a prepreg, the lower the viscosity of the toluene solution, the easier it is for the toluene solution to impregnate the glass fibers, and the more likely it is that a good laminate with fewer voids and smears will be obtained.Furthermore, the higher the viscosity of the toluene solution, the more likely it is that a laminate with excellent insulation properties will be obtained. From this viewpoint, the curable resin composition of the present embodiment is specified by the fact that a toluene solution obtained by preparing the curable resin composition to a concentration of 62% has a viscosity of 1 mPa·s or more and 7000 mPa·s or less, as measured at 25°C and 1 rpm using a cone-plate type rotational viscometer.

[0158] When a curable resin composition having a toluene solution viscosity of less than 1 mPa s is used, for example, to dissolve the curable resin composition in an organic solvent such as toluene, impregnate the resulting organic solvent solution into glass fibers or the like, and then hang the fibers in a hot air dryer to dry and evaporate the organic solvent such as toluene to produce a prepreg, a large amount of the resin composition solution and / or resin composition will drip from the glass cloth due to the low viscosity, resulting in a prepreg with a low resin content, and a laminate produced by laminating and pressing such prepregs will have an extremely low resin content.

[0159] On the other hand, when a curable resin composition having a viscosity of more than 7000 mPa·s in a toluene solution is dissolved in an organic solvent such as toluene, the resulting organic solvent solution does not sufficiently penetrate into a glass cloth and does not sufficiently adhere to (wet) the surface of the glass fiber during the process of impregnating the curable resin composition into a glass cloth or the like. Laminates made by pressing the prepregs thus obtained have many voids and scratches, fail to exhibit sufficient insulating properties, and are difficult to use industrially.

[0160] From this viewpoint, the viscosity of the toluene solution is preferably 10 mPa·s or more and 5000 mPa·s or less, more preferably 50 mPa·s or more and 2000 mPa·s or less, even more preferably 80 mPa·s or more and 1500 mPa·s or less, particularly preferably 100 mPa·s or more and 500 mPa·s or less, and especially preferably 150 mPa·s or more and 300 mPa·s or less.

[0161] The method for adjusting the viscosity of the toluene solution is not particularly limited, but examples thereof include (A) a method for adjusting the amount of A substituents contained in the modified polyphenylene ether, (A) a method for adjusting the number average molecular weight of the modified polyphenylene ether, (B) a method for adjusting the styrene content of the styrene-based elastomer, (B) a method for adjusting the content of the styrene-based elastomer, and (C) a method for adjusting the content of the cross-linking coagent. Specifically, the viscosity tends to be lowered by reducing the amount of A substituents contained in the (A) modified polyphenylene ether. The viscosity also tends to be lowered by reducing the number-average molecular weight of the (A) modified polyphenylene ether. The viscosity also tends to be lowered by increasing the styrene content of the (B) styrene-based elastomer, by reducing the content of the (B) styrene-based elastomer, and by increasing the content of the (C) cross-linking coagent.

[0162] <Minimum melt viscosity> The curable resin composition of this embodiment can be used industrially by blending an initiator as needed. One example of an industrial embodiment is a laminate. The laminate can be produced by impregnating glass fibers or the like with an organic solvent solution obtained by dissolving the curable resin composition of this embodiment in an organic solvent such as toluene, then hanging the resulting solution in a hot air dryer to dry, evaporating the organic solvent such as toluene, and laminating one or more prepregs. During the above process, when the prepreg is pressed and cured, the lower the minimum melt viscosity, the more likely it is that the glass cloth will be impregnated with the resin. The higher the minimum melt viscosity, the higher the resin content of the resulting laminate. However, if the minimum melt viscosity is too high, the resin content tends to be low.

[0163] From this viewpoint, the curable resin composition of the present embodiment preferably has a minimum melt viscosity of 1 [Pa·s] or more and 20,000 [Pa·s] or less in a state where it does not substantially contain a solvent.

[0164] If the minimum melt viscosity is lower than 1 [Pa·s], a large amount of the resin composition will leak out of the glass cloth during the curing process, resulting in a laminate with a low resin content. If the minimum melt viscosity is higher than 20,000 [Pa·s], the resin composition will not be able to penetrate into the fine details of the glass cloth, resulting in a laminate with many smudges and voids.

[0165] From such a viewpoint, the curable resin composition of the present embodiment preferably has a minimum melt viscosity of 10 [Pa·s] or more and 10,000 [Pa·s] or less, more preferably 50 [Pa·s] or more and 5,000 [Pa·s] or less, even more preferably 100 [Pa·s] or more and 1,000 [Pa·s] or less, particularly preferably 150 [Pa·s] or more and 500 [Pa·s] or less, and especially preferably 180 [Pa·s] or more and 300 [Pa·s] or less.

[0166] In the method for measuring the minimum melt viscosity of the present embodiment, when the curable resin composition contains an initiator and does not contain a solvent, the minimum melt viscosity can be determined by measuring the curable resin composition containing the initiator in vibration mode using a cone-plate type rotational viscometer (such as HAAKE MARSIII manufactured by Thermo Fisher Scientific K.K.).

[0167] On the other hand, when the curable resin composition of the present embodiment contains an initiator and a solvent, the solvent is evaporated from the curable resin composition of the present embodiment using an evaporator, a hot air dryer, or the like to obtain a solid curable resin composition that is substantially free of solvent, and then the minimum melt viscosity can be determined by measuring the viscosity using a cone-plate rotational viscometer in vibration mode.

[0168] <Prepreg> The prepreg of the present embodiment contains the curable resin composition of the present embodiment. The curable resin composition of the present embodiment can be used to prepare a prepreg by impregnating a woven or nonwoven fabric such as glass fiber or carbon fiber with a solution of the curable resin composition, optionally with an organic or inorganic solvent, and then evaporating the solvent using a hot air dryer or the like.

[0169] <Concentration of varnish when creating prepreg> This embodiment is not limited to the concentration of the curable resin composition solution prepared when producing the prepreg, but the lower the concentration of the curable resin composition solution, the lower the viscosity and the higher the impregnation ability into reinforcing materials such as glass cloth tends to be, and the higher the concentration of the curable resin composition solution, the higher the resin content of the laminate obtained by curing the prepreg and the higher the tendency for insulation reliability and the like to be excellent.

[0170] From such a viewpoint, the concentration of the curable resin composition solution is preferably 10% to 90%, more preferably 30% to 80%, still more preferably 40% to 75%, particularly preferably 40% to 70%, and especially preferably 50% to 65%.

[0171] <Drying temperature, time> When preparing a prepreg by evaporating the solvent from the curable resin composition solution, the prepreg may be prepared efficiently by drying the solution by applying hot air while heating it using a hot air dryer or the like, as needed. In this case, the lower the drying temperature set relative to the heat generation onset temperature (T1) in the DSC chart obtained by DSC measurement of the prepreg, the more likely it is that the progress of the curing reaction during drying will be suppressed, and the higher the drying temperature relative to T1, the more likely it is that the solvent will evaporate and be removed more completely. From this perspective, a temperature range of (T1 - 80) ° C to (T1 + 80) ° C is desirable, preferably a temperature range of (T1 - 60) ° C to (T1 + 30) ° C, more preferably a temperature range of (T1 - 40) ° C to (T1 + 10) ° C, and even more preferably a temperature range of (T1 - 30) ° C to T1, tends to produce a prepreg with favorable curability.

[0172] Although the present embodiment is not limited to a drying time for producing a prepreg, a shorter drying time tends to suppress the progress of the curing reaction during drying, and a longer drying time tends to allow the solvent to be evaporated and removed more completely. From this perspective, the drying time is generally desirably 30 seconds to 60 minutes, preferably 1 minute to 30 minutes, more preferably 1.5 minutes to 20 minutes, even more preferably 2 minutes to 15 minutes, and particularly preferably 3 minutes to 10 minutes.

[0173] <Prepreg resin> One example of an embodiment of the curable resin composition of this embodiment is an industrial application method in which the curable resin composition is impregnated into a fiber substrate to produce a prepreg, and the prepreg is then laminated and cured. The higher the resin content of such a prepreg, the higher the electrical insulation of the laminate obtained by laminating and curing the prepreg tends to be. The lower the resin content, the lower the linear expansion coefficient tends to be. From this perspective, the resin content of the prepreg is preferably 10% to 90% by mass, more preferably 20% to 80%, even more preferably 30% to 75%, particularly preferably 40% to 70%, and especially preferably 50% to 65%.

[0174] <Laminate> The laminate of the present embodiment includes a cured product of the curable resin composition of the present embodiment. An example of a method for producing a laminate according to this embodiment is an industrial application method in which a fiber substrate is impregnated with the curable resin composition to produce a prepreg, which is then laminated and cured. The higher the resin content of such a prepreg, the higher the electrical insulation of the laminate obtained by laminating and curing the prepreg. The lower the resin content, the lower the linear expansion coefficient. From this perspective, the resin content of the prepreg is preferably 10% to 90% by mass, more preferably 20% to 80%, even more preferably 30% to 70%, particularly preferably 40% to 60%, and even more preferably 45% to 55%.

[0175] <Laminate pressing temperature and pressure> One example of a method for producing a laminate according to this embodiment involves laminating prepregs and, for example, press-molding them to produce a laminate. The higher the curing temperature used to produce the laminate, the shorter the curing time and the higher the productivity of the laminate. Curing at a lower temperature tends to suppress thermal degradation during the curing stage, resulting in a laminate with a high Tg and toughness. From this perspective, the curing temperature is preferably 20°C to 350°C, more preferably 80°C to 300°C, more preferably 100°C to 250°C, even more preferably 150°C to 230°C, and particularly preferably 180°C to 220°C.

[0176] Furthermore, increasing the curing temperature during curing tends to result in a laminate with better toughness, and the temperature increase rate is desirably 0.5°C / min to 20°C / min, preferably 1°C / min to 10°C / min, more preferably 1.5°C / min to 10°C / min, and even more preferably 2°C / min to 5°C / min.

[0177] Furthermore, laminates can be produced by press-molding the prepreg during the curing stage. Higher press pressures tend to produce laminates with fewer voids, while lower press pressures tend to reduce resin outflow, resulting in laminates with higher resin content, superior insulation reliability, and a low dielectric loss tangent. From this point of view, the pressing pressure applied to the prepreg is 2 kgf / cm 2 More than 100kgf / cm 2 It is desirable that the pressure is equal to or less than 5 kgf / cm 2 More than 50kgf / cm 2 Less than 10 kgf / cm, more preferably 10 kgf / cm 2 More than 50kgf / cm 2 More preferably 20 kgf / cm or less 2 More than 40kgf / cm 2 Click below.

[0178] <Printed wiring board> The printed wiring board of the present embodiment includes a cured product of the curable resin composition of the present embodiment. An example of an embodiment of the curable resin composition of the present embodiment is a metal-clad laminate in which metal foil such as copper foil is bonded to both sides of a prepreg by sandwiching the prepreg between metal foils such as copper foil when laminating the prepreg to prepare a laminate. Further, an example of use is a printed wiring board in which the metal layer of the metal-clad laminate is patterned by etching or the like.

[0179] <Carbon fiber reinforced composite materials> One example of an embodiment of the curable resin composition of the present embodiment is a use in which carbon fiber or a woven or nonwoven fabric of carbon fiber is impregnated with the curable resin composition of the present embodiment and then cured to produce a carbon fiber reinforced composite material (CFRP). [Example]

[0180] 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.

[0181] First, the measurement methods and evaluation criteria for each physical property will be described below.

[0182] (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 [-Y n -H], and in the structure of formula (1), all [-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, and it is preferable that they are not both hydrogen atoms, and / or that they 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. 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; 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 it is preferable that they are not both hydrogen atoms, and / or that they 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. Multiple R22 , 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; 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

[0183] 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

[0184] (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

[0185] (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 obtained modified polyphenylene ether composition was measured.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] (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.

[0190] (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. 1 H-NMR measurements were carried out (JEOL, 500 MHz).

[0191] 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.

[0192] (6) Viscosity of Toluene Solution of Modified Polyphenylene Ether Composition (Solution 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 solution viscosity was measured using a Brookfield viscometer at 25°C and 30 rpm.

[0193] (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).

[0194] (8) 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

[0195] (9) Double bond content of styrene 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.

[0196] (10) 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℃

[0197] (11) Resin composition solution viscosity The curable resin composition was dissolved in toluene at a ratio such that the solid content concentration was 62%, and the obtained 62% toluene solution of the curable resin composition was measured using a cone-plate type rotational viscometer (viscometer TVE-22H manufactured by Toki Sangyo Co., Ltd.) at a temperature condition of 25°C and a rotation speed of 1 rpm.

[0198] <Preparation of cured resin> The cured resin material not containing reinforcing fibers such as lath fibers was pressed under the following conditions to produce film-like test pieces with a thickness of 0.1 to 0.3 mm. The polymer, styrene-based elastomer, etc. were added to toluene to a solids concentration of 34%, and the mixture was left to dissolve uniformly at room temperature overnight. NOF Perbutyl P was then added to form a varnish. This was applied to the shine side of copper foil and dried at 120°C for 10 minutes. The resulting solid resin composition was then 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

[0199] (12) Tg measurement of cured resin 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.

[0200] (13) Measurement of the coefficient of linear expansion (CTE) of cured resin The linear expansion coefficient of a cured resin containing no reinforcing material such as glass cloth was determined using a Hitachi High-Tech Science TMA7100 under the following conditions using a sample cut from a test piece for measuring dielectric loss tangent. 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

[0201] (14) Measurement of dielectric loss tangent (Df) of cured resin and laminate 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).

[0202] (15) Minimum melt viscosity of the curable resin composition PPE, cross-linking aid, styrene elastomer, initiator, etc. were added to toluene to a solids concentration of 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. The solid resin composition obtained was measured (100°C to 250°C, heating rate 4°C / min) in a nitrogen atmosphere using a cone-plate type rotational viscometer (HAAKE MARSIII manufactured by Thermo Fisher Scientific, 20 mm diameter aluminum parallel plate) in vibration mode (frequency 1 Hz, set strain 0.001, gap 1 mm). The lowest viscosity in the temperature range from 100°C to 250°C was taken as the minimum melt viscosity.

[0203] (16) Measurement of copper foil adhesive strength of cured resin The adhesive strength to 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 predetermined 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, and then dried at 120 °C for 10 minutes. The polyimide tape was then 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 (registered trademark) 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, n=2 were tested and the average value was taken. Measurement conditions: Test temperature: Room temperature (approx. 23°C) Test speed: 50 mm / min, Test length: approx. 30 mm

[0204] <Prepreg manufacturing method> The curable resin composition was dissolved in toluene in an arbitrary ratio, and glass cloth was impregnated with the obtained varnish for prepreg production, followed by drying in a hot air dryer at 120° C. for 10 minutes to obtain a prepreg.

[0205] (17) DSC reaction behavior measurement The curable resin composition and prepreg were measured using a differential scanning calorimeter (DSC, manufactured by Hitachi High-Tech Science Corporation, 7000X) under a nitrogen stream, raising the temperature from -50°C to 280°C at a rate of 10°C / min and holding for 10 minutes after reaching 280°C, to determine the reaction initiation temperature, reaction termination temperature, and calorific value. The calorific value of the prepreg was converted to the calorific value per unit mass of resin based on the resin content.

[0206] <How to manufacture laminates> Six prepreg sheets are laminated and sandwiched between copper foils under a surface pressure of 40 kgf / cm 2 The temperature was raised from room temperature to 220°C at a rate of 2°C / min while applying a voltage, and then further heated at 220°C for 1 hour under pressure to obtain a laminate. When preparing test pieces for measuring copper foil peel strength, the copper foil was bonded to the prepreg with the roughened side facing inward to prepare a copper-clad laminate, and the copper foil peel strength was measured. In other cases, the shiny side was placed facing inward, and the copper foil was peeled off after preparing the laminate to evaluate various properties.

[0207] (18) Measurement of resin content in laminates and prepregs The resin content of the prepreg and laminate was measured by TG-DTA. The temperature was raised from room temperature to 600°C at a rate of 20°C / min in an air stream, and then the resin content was calculated from the weight loss rate after holding at 600°C for 5 hours.

[0208] (19) Laminate impregnability The varnish prepared by the method described in the above section (8) "Preparation of cured resin" was impregnated into a glass cloth cut into a shape of 30 x 60 mm, and dried at 120°C for 10 minutes. 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 △.

[0209] (20) Linear expansion coefficient of laminate The coefficient of linear expansion (CTE) of the laminate was determined by measuring a sample cut from a test piece for measuring dielectric tangent using Hitachi's TMASS6100 under the following conditions. Measurement mode: Compression Test start temperature: -50℃ Heating rate: 10°C / min Maximum test temperature: 250℃ Maximum temperature holding time: 5 minutes

[0210] (21) Copper foil peel strength of laminate Using the laminate produced by the above method, the copper foil peel strength between the laminate and the roughened surface of the copper foil was measured under the following conditions using an Instron universal testing machine (Model 59R5582). Test temperature: 23°C, Test speed: 50mm / min, Peel width: 10mm

[0211] 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.

[0212] (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.

[0213] A stirrer was placed in a 300 ml three-neck flask, a Dimroth condenser with a three-way stopcock attached to the main tube, and a rubber stopper with a thermometer 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.

[0214] 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.

[0215] (Examples 1-4, Comparative Examples 1-3) Using the styrene-based elastomer shown in Table 1, a curable resin composition solution was prepared according to the formulation shown in Table 2, and the cured resin obtained by the method described above was evaluated, with the results shown in Table 2. Also, a varnish for producing a prepreg was prepared according to the formulation shown in Table 2, and prepregs and laminates were produced by the method described above, with the evaluation results shown in Table 2. The blend amounts are in parts by mass.

[0216] [Table 1]

[0217] [Table 2]

[0218] The abbreviations in Tables 2 and 3 are as follows: SA9000: SABIC methacrylic modified PPE (molecular weight 2500) tBS: 4-tert-butylstyrene TAIC: Triallyl isocyanurate Perbutyl P: α,α-di(tert-butylperoxy)diisopropylbenzene manufactured by NOF Corporation

[0219] As is clear from Table 2, 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 product. In contrast, in Comparative Examples 1 and 2, where the solution viscosity did not satisfy the requirements of this embodiment, the laminate impregnation was poor, the copper foil peel was low, and a satisfactory Df value was not achieved. Furthermore, in Comparative Example 3, where a methacrylic-modified polyphenylene ether was used and TAIC was used as the crosslinking aid, a varnish with low viscosity when dissolved in a solvent was obtained, but the Df value was high. [Industrial Applicability]

[0220] The curable resin composition of the present invention comprises a terminally modified polyphenylene ether having a specific structure, a styrene-based elastomer, and a crosslinking aid having a specific structure, and further has a specific viscosity when dissolved in a solvent, thereby enabling a uniform cured product to be obtained, and the cured product satisfies all of the requirements of sufficient Tg, low dielectric properties, adhesion, a low coefficient of linear expansion, and moldability, making it possible to provide a curable resin composition that is useful as a substrate material.

Claims

1. A curable resin composition comprising the following components (A), (B), and (C), wherein the solution viscosity of a toluene solution having a solids concentration of 62% is 1 mPa s or more and 7,000 mPa s or less, as measured at 25°C and 1 rpm using a cone-plate type rotational viscometer: (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 -A], at least one n is an integer of 1 or more, and A is represented by the following formula (6): 【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 (6), 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; 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 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 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 (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. The curable resin composition according to claim 1, wherein the component (B) has a styrene content of 33% or more.

3. The curable resin composition according to claim 1 or 2, wherein the number average molecular weight of the component (B) is 300,000 or less.

4. The curable resin composition according to any one of claims 1 to 3, wherein the component (B) comprises any one of a styrene-butadiene copolymer (SBR), a styrene-butadiene-styrene copolymer (SBS), a hydrogenated styrene-butadiene-styrene copolymer, a styrene-isoprene-styrene copolymer (SIS), a hydrogenated styrene-isoprene-styrene copolymer, and a hydrogenated styrene (butadiene / isoprene)-styrene copolymer.

5. The curable resin composition according to any one of claims 1 to 4, wherein the component (B) comprises a block A mainly composed of vinyl aromatic compound monomer units and a block B containing conjugated diene monomer units.

6. 6. The curable resin composition according to claim 5, 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.

7. The curable resin composition according to any one of claims 1 to 6, further comprising (D) an initiator.

8. The curable resin composition according to claim 7, wherein the minimum melt viscosity is 1 [Pa·s] or more and 20,000 [Pa·s] or less.

9. The curable resin composition according to any one of claims 1 to 8, further comprising (E) a solvent.

10. In the formula (18), R ３７ , R ３８ , R ３９ The curable resin composition according to any one of claims 1 to 9, wherein is a hydrogen atom.

11. In the formula (18), R ４０ The curable resin composition according to any one of claims 1 to 10, wherein is a tert-butyl group.

12. In the formula (18), R ４１ The curable resin composition according to any one of claims 1 to 11, wherein is a vinyl group.

13. The curable resin composition according to claim 11, wherein the component (C) is 4-tertbutylstyrene.

14. The curable resin composition according to claim 12, wherein the component (C) is divinylbenzene.

15. 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.

16. The curable resin composition according to claim 15, wherein the partial structure represented by the formula (3) is a t-butyl group.

17. The curable resin composition according to any one of claims 1 to 16, wherein the number of OH terminals contained in the polyphenylene ether is 0 to 3,000 µmol / g.

18. R in the formula (4) ２１ The curable resin composition according to any one of claims 1 to 17, wherein is a methyl group.

19. A prepreg comprising the curable resin composition according to any one of claims 1 to 18.

20. A laminate comprising a cured product of the curable resin composition according to any one of claims 1 to 18.

21. A printed wiring board comprising a cured product of the curable resin composition according to any one of claims 1 to 18.

22. A composite material comprising a cured product of the curable resin composition according to any one of claims 1 to 18.

23. 23. The composite material of claim 22 which is a carbon fiber reinforced composite material.

Images