Curable resin composition

Abstract

To provide a curable resin composition containing terminal-modified polyphenylene ether having a vinylsilyl group at a terminal, and a crosslinking auxiliary which enables production of a uniform cured product and satisfies all of a sufficient Tg, low dielectric characteristics, copper foil adhesion and a low coefficient of liner expansion of the cured product.SOLUTION: A curable resin composition contains (A) modified polyphenylene ether represented by formula (1), and (B) an aliphatic maleimide compound having a molecular weight of 2,000 or less, as a crosslinking auxiliary. In the formula (1), Z is an a-valent partial structure, a represents an integer of 2 to 6, Y are each independently a divalent connection group, n represent a repeated number of Y and are each independently an integer of 0 to 200, at least one n in a pieces of (-Yn-A) is an integer of 1 or more, and A represents a hydrogen atom or a silyl group-containing derivative bondable to a polyphenylene ether structure, excluding the case of all the hydrogen atoms.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 fields of electrical and electronics, automobiles, and various other industrial materials. In recent years, it has been expected that polyphenylene ethers exhibiting an extremely low molecular weight are more effective for electronic material applications such as substrate materials than ordinary high-molecular-weight polyphenylene ethers. For this reason, Patent Document 1 proposes a low-molecular-weight polyphenylene ether that has a 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] On the other hand, when polyphenylene ether is used as a molding material for substrate materials, etc., it is required that it has not only excellent dielectric properties but also excellent heat resistance or moldability. However, conventional polyphenylene ether is thermoplastic, and there are cases where sufficient heat resistance cannot be obtained. For this reason, it has been proposed to use polyphenylene ether to which a thermosetting resin such as an epoxy resin has been added, or to use a modified polyphenylene ether.

[0004] Patent Document 2 describes a modified polyphenylene ether compound having a specific polyphenylene ether moiety in its molecular structure and having at least one p-vinylbenzyl group or m-vinylbenzyl group at the molecular end.

[0005] For example, Patent Documents 3 and 4 describe modified polymers having a polyphenylene ether moiety in the molecular structure and having a methacryl group at the molecular end. In particular, methacryl group modification is becoming more widely used because the methacryl group has a moderately high reactivity as a crosslinking group and can be easily introduced to the hydroxyl group end. Furthermore, there are also reports of introducing a vinylsilyl group as a modifying group to the molecular end in order to improve the dielectric properties (for example, Patent Document 5).

[0006] In addition, as disclosed in Patent Document 2, in order to easily ensure the heat resistance of the terminal-modified thermosetting polyphenylene ether, a method of polymerizing the thermosetting polyphenylene ether with another copolymerizable monomer (crosslinking aid) to increase the crosslink density is effective. As described in Patent Document 2, it is preferable to use trialkenyl isocyanurate as the crosslinking aid from the viewpoint of compatibility, and it is known that triallyl isocyanurate (TAIC) and triallyl cyanurate (TAC) are particularly preferable. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2004-99824 A [Patent Document 2] JP 2004-339328 A [Patent Document 3] Special Publication No. 2004-502849 [Patent Document 4] Special Publication No. 2010-538114 [Patent Document 5] China Patent Application Publication No. 106916293 Summary of the Invention [Problem to be solved by the invention]

[0008] Among the above polymers, methacryl group modification is a method that is currently widely used, but since the modified polyphenylene ether has an ester bond at the end, the dipole moment of the bond becomes large, and as a result, the dielectric constant and dielectric loss tangent tend to become high. Furthermore, if a branched polymer structure is made to the polyphenylene ether in order to reduce the solution viscosity, the number of terminal groups per molecule increases compared to a linear polymer, degrading the dielectric properties, and there are many issues with using it as a next-generation low-dielectric material.

[0009] On the other hand, polymers having vinylbenzyl groups at the terminals have the problem that the reactivity of the vinyl groups is too high, so that the polymers cannot be finished dried after synthesis under normal conditions, and they can only be handled in the form of a polymer solution. Also, polymers having vinylbenzyl groups have a smaller dipole moment at the bond, but at the same time, there is also the problem that the copper foil adhesion is reduced. One method for improving these problems is to introduce vinylsilyl groups, which have low polarity and good metal adhesion, into the polymer (e.g., Patent Document 5). However, it has been confirmed that when a polymer having a vinylsilyl group is used, when a crosslinking aid such as TAIC is used, the compatibility is poor and it is difficult to obtain a uniform cured product.

[0010] As described above, a curable resin composition containing a terminal-modified polyphenylene ether having a vinylsilyl group at the terminal and a crosslinking aid has not yet been obtained, which gives a uniform cured product and satisfies all of the requirements for sufficient Tg, low dielectric properties, copper foil adhesion, and a low linear expansion coefficient of the cured product.

[0011] The present invention aims to provide a curable resin composition that contains a terminal-modified polyphenylene ether having a vinylsilyl group at the terminal and a crosslinking aid, which gives a uniform cured product and satisfies all of the requirements for sufficient Tg, low dielectric properties, copper foil adhesion, and a low linear expansion coefficient of the cured product. [Means for solving the problem]

[0012] As a result of intensive research conducted by the present inventors in order to solve the above problems, it has become possible to obtain a curable resin composition capable of solving all of the above problems by using a silicon-containing functional group as a modifying group in a branched polyphenylene ether skeleton having a specific structure and blending an aromatic vinyl compound having a specific structure as a crosslinking aid, and thus the present invention has been completed. That is, the present invention is as follows. [1] A curable resin composition comprising the following components (A) and (B): (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 are hydrogen atoms; [ka] In formula (2), X is an arbitrary linking group having a valence of a, and a plurality of R 5 each independently represents a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and each k independently represents an integer of 1 to 4: [ka] In formula (3), multiple R 11 each independently represents an optionally substituted alkyl group having 1 to 8 carbon atoms, and 12 each independently represents an optionally substituted alkylene group having 1 to 8 carbon atoms; each b independently represents 0 or 1; R 13represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted phenyl group, [ka] In formula (4), multiple R 21 are each independently 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, and two R 21 is not a hydrogen atom at the same time, but two R 21 is not a combination of a partial structure represented by the above formula (3) on one side and a hydrogen atom, a methyl group, or an ethyl group on the other side, but a combination of multiple R 22 each independently represents 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. (B) an aliphatic maleimide compound having a molecular weight of 2000 or less, which is a crosslinking auxiliary; [2] The component (B) is represented by the following formula (18): [ka] {In formula (18), R 40 , R 41 , R 42 represents a hydrogen atom or a hydrocarbon having 50 or less carbon atoms which may have a maleimide group in the side chain, R 40 , R 41 , R 42 may be bonded to each other to form a cyclic structure. The curable resin composition according to [1], wherein the maleimide compound is an aliphatic maleimide compound having a molecular weight of 2000 or less and represented by the formula: [3] The component (B) is represented by the following formula (19): [ka] {In formula (19), R 43 , R 44 , R 45represent a hydrogen atom or each independently a hydrocarbon having 6 or less carbon atoms.} The curable resin composition according to [2], wherein the maleimide compound is an aliphatic maleimide compound having a molecular weight of 2000 or less and represented by the formula: [4] The curable resin composition according to [1] or [2], wherein the component (B) is an aliphatic maleimide compound having a dimer acid skeleton and a molecular weight of 2000 or less. [5] The curable resin composition according to any one of [1] to [4], further comprising (C) an initiator. [6] 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 having the partial structure represented by the formula (3) on either the 2nd or 6th position is 5 and a hydrogen atom, a methyl group, or an ethyl group is bonded to the other carbon atom at the 2-position or the 6-position. [7] The curable resin composition according to [6], wherein the partial structure represented by the formula (3) is a t-butyl group. [8] The curable resin composition according to any one of [1] to [7], wherein the number of OH terminals contained in the polyphenylene ether is 0 to 3,000 μmol / g. [9] R in the above formula (4) 21 The curable resin composition according to any one of [1] to [8], wherein is a methyl group.

[10] A in the formula (1) is the following formula (5): [ka] In formula (5), multiple R 31 , and R 34 are each independently 1~30 is a divalent hydrocarbon group having a plurality of R 32 , and R 33 are each independently 1~30A is a monovalent hydrocarbon group, aryl group, alkoxy group, aryloxy group, amino group, or hydroxyalkyl group containing an olefinic carbon-carbon double bond, 1~30 a hydrocarbon-based substituent of the formula (1), a part of which may be substituted with a hydrogen atom, a hydroxyl group, 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 t is an integer of 0 to 8. The curable resin composition according to any one of [1] to [9],

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

[10] , wherein the curable resin composition is represented by the following formula:

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

[11] , further comprising (D) a solvent. Effect of the Invention

[0013] By using a curable resin composition containing (A) a modified polyphenylene ether having a vinylsilyl group and (B) a crosslinking aid as defined in the present invention, a uniform cured product can be obtained, and a curable resin composition can be provided which satisfies all of the requirements for sufficient Tg, low dielectric properties, copper foil adhesion, and a low linear expansion coefficient of the cured product. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Hereinafter, an embodiment for carrying out 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 only this embodiment, and the present invention can be carried out by appropriately modifying it within the scope of the gist of the present invention.

[0015] <Curable resin composition> The curable resin composition of the present embodiment is characterized by including the following components (A) and (B). (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 are hydrogen atoms; [ka] In formula (2), X is an arbitrary linking group having a valence of a, and a plurality of R5 each independently represents a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and each k independently represents an integer of 1 to 4: [ka] In formula (3), multiple R 11 each independently represents an optionally substituted alkyl group having 1 to 8 carbon atoms, and 12 each independently represents an optionally substituted alkylene group having 1 to 8 carbon atoms; each b independently represents 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, [ka] In formula (4), multiple R 21 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, and two R 21 is not a hydrogen atom at the same time, but two R 21 is not a combination of a partial structure represented by the above formula (3) on one side and a hydrogen atom, a methyl group, or an ethyl group on the other side, but a combination of multiple R 22 each independently represents 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. (B) an aliphatic maleimide compound having a molecular weight of 2000 or less, which is a crosslinking auxiliary;

[0016] In the present embodiment, by using a curable resin composition containing (A) a modified polyphenylene ether having a vinylsilyl group and (B) an aliphatic maleimide compound having a molecular weight of 2000 or less as a crosslinking auxiliary, a uniform cured product can be obtained, and a curable resin composition can be provided that satisfies all of the requirements for sufficient Tg of the cured product, low dielectric properties, copper foil adhesion, and a low linear expansion coefficient. The components constituting the curable resin composition of the present embodiment will be described in detail below.

[0017] <(A) Modified polyphenylene ether> The modified polyphenylene ether according to this embodiment has a structure represented by the following formula (1). [ka] In formula (1), Z is a partial structure having a central phenol moiety with a valence of a, represented by formula (2) below, where a is an integer of 3 to 6.

[0018] The "central phenol moiety" refers to a central skeleton that is the starting point of the reaction when the polyfunctional polyphenylene ether is polymerized, and the structure of the central phenol moiety can be identified by analyzing the polyfunctional modified polyphenylene ether composition by techniques such as nuclear magnetic resonance (NMR) and mass spectrometry. A specific method for identifying the structure of the central phenol moiety from the polyfunctional modified polyphenylene ether composition includes, for example, a method in which only low molecular weight components are analyzed from the mass spectrometry results of the polyfunctional modified polyphenylene ether composition, and the structure of the central phenol moiety is estimated from the peak of the fragment ion by electric impact or electric ionization (EI). Furthermore, a method in which the NMR measurement of the polyfunctional modified polyphenylene ether composition is performed, and the structure of the central phenol moiety is estimated by comparing it with the NMR measurement results of a known polyfunctional phenol compound can be included. The structure of the central phenol moiety can be more accurately identified by combining the mass spectrometry results and the NMR measurement results.

[0019] 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)) n -A) may be bonded to the structure. [ka] In formula (2), a can be an integer of 2 to 6 similar to that in formula (1), and is preferably the same integer as that in formula (1). In the central phenol moiety of formula (2), each of the a partial structures may be the same structure or different.

[0020] In formula (2), X is any linking group having a valence of a, 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, silicon, etc.; or groups combining these; etc. X may be a linking group other than a single bond.

[0021] X in formula (2) may be a linking group that links the a-valent partial structures to each other.

[0022] In formula (2), X is a single bond or an ester bond or the like, 5 an a-valent alkyl skeleton bonded to a benzene ring to which R 5 an a-valent aryl skeleton bonded to a benzene ring to which R 5 an a-valent heterocyclic skeleton bonded to a benzene ring to which is bonded;

[0023] 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 units are directly bonded to a benzene ring in a partial structure (as long as a benzene ring is bonded to the a units of branched ends, there may be a branched end to which no benzene ring is bonded). In addition, 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 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 5and the like.

[0024] Multiple R in formula (2) 5 each independently represents a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and each k independently represents an integer of 1 to 4.

[0025] 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, Each b is 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 substituent includes, for example, a halogen atom.

[0026] 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 terminal thereof, and more preferably a tert-butyl group.

[0027] 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 is5 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. 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- in formula (2) is bonded. The benzene ring in formula (2) has (Y n -A) may be bonded to the 1-position of the above formula (1) through an oxygen atom. n -A) is bonded to the 4-position, and the central part X is bonded to the 4-position.

[0028] 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-hydroxy-3-ethoxyphenyl)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, 2,6-bis[(4-hydroxy-3-methylphenyl)methyl]-4-ethylphenol, 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,Examples of the phenol include, but are not limited to, 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), and 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane.

[0029] The number of phenolic hydroxyl groups in the polyhydric phenol compound is not particularly limited as long as it is 3 or more, but since an increase in the number of polyphenylene ether ends may result in a large change in molecular weight during polymerization, the number is preferably 3 to 6, and more preferably 3 to 4.

[0030] 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, and 1,1-bis(2-methyl-4-hydroxy-5-t-butylphenyl)butane.

[0031] In the above formula (1), each of the multiple Y's is independently a divalent linking group having a structure represented by the following formula (4) (i.e., a phenol unit having a substituent), n represents the number of repetitions of Y, each of which is independently an integer of 0 to 200, and a number of (-Y n -In A), at least one n is an integer of 1 or more. [ka]

[0032] 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, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Examples of the substituent include a halogen atom.

[0033] In equation (4), two R 21 From the viewpoint of providing the modified polyphenylene ether-containing composition with all of low dielectric properties, appropriate metal peelability, low solution viscosity, sufficient Tg upon curing, etc., it is preferable that both are not hydrogen atoms, and / or that one of them is not a partial structure represented by the above formula (3) and the other is either a hydrogen atom, a methyl group, or an ethyl group.

[0034] 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, 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.

[0035] 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 Examples of such phenols include 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, and 2,6-dimethyl-3-t-butylphenol.

[0036] Among the monohydric phenol compounds, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-diphenylphenol, 2,3,6-trimethylphenol, and 2,5-dimethylphenol are preferred because they are inexpensive and easily available, and 2,6-dimethylphenol and 2,3,6-trimethylphenol are more preferred.

[0037] The above phenol compounds may be used alone or in combination of two or more.

[0038] Examples of the monohydric phenol compound include a method of using 2,6-dimethylphenol and 2,6-diethylphenol in combination, a method of using 2,6-dimethylphenol and 2,6-diphenylphenol in combination, a method of using 2,3,6-trimethylphenol and 2,5-dimethylphenol in combination, a method of using 2,6-dimethylphenol and 2,3,6-trimethylphenol in combination, etc. In this case, the mixing ratio of the phenol compounds to be combined can be selected arbitrarily.

[0039] The phenol compound used may 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.

[0040] Phenol compounds for the a-valent partial structure as represented by the above formula (2) can be industrially advantageously produced by reacting a corresponding monohydric phenol compound with an aldehyde (e.g., formaldehyde, etc.), a ketone (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, etc.) or a dihalogenated aliphatic hydrocarbon, or by reacting the corresponding monohydric phenol compounds with each other.

[0041] In the above formula (1), A represents a hydrogen atom, except when all A's are hydrogen atoms, or a silyl group-containing derivative capable of bonding to a polyphenylene ether structure.

[0042] Here, A in formula (1) is preferably a substituent represented by the following formula (5) from the viewpoint of obtaining low dielectric properties, appropriate metal peelability, low solution viscosity, and sufficient Tg properties upon curing. [ka] In formula (5), R 31 , and R 34 are each independently the carbon number C 1~30 is a divalent hydrocarbon group having a plurality of R 32 , and R 33 are each independently 1~30 In formula (5), B is a monovalent hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydroxyalkyl group containing an olefinic carbon-carbon double bond. 1~30 A portion of the hydrocarbon substituents may be substituted with hydrogen, a hydroxyl group, 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 formula (5), t is an integer of 0 to 8, and preferably an integer of 0 to 5.

[0043] 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 excessively large, Tg or metal peelability decreases, or the carbon-carbon double bond of an olefinic compound decreases. 32 and R 33 The number of carbon atoms is C 1~30 The degree is preferable, C 1~20 The degree is more preferable, C 1~12 A degree is even more preferable.

[0044] 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 n-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 ethyl, 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, 2-phenylethyl, and the like.

[0045] 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-methylhexyl, 6-methylhexyl, 7-methylhexyl, 8-methylhexyl, 9-methylhexyl, 10-methylhexyl, 11-methylhexyl, 12-methylhexyl, 13-methylhexyl, 14-methylhexyl, 15-methylhexyl, 16-methylhexyl, 17-methylhexyl, 18-methylhexyl, 19-methylhexyl, 20-methylhexyl, 21-methylhexyl, 22-methylhexyl, 23-methylhexyl, 24-methylhexyl, 25-methylhexyl, 26-methylhexyl, 27-methylhexyl, 28-methylhexyl, 29-methylhexyl, 30-methylhexyl, 31-methylhexyl, 32-methylhexyl, 33-methylhexyl, 34-methylhexyl, 35-methylhexyl, 36-methylhexyl, 37-methylhexyl, 38-methylhexyl, 39-methylhexyl, 40-methylhexyl, 41-methylhexyl, 42-methylhexyl, 43-methylhexyl, 44-methylhexyl, 45-methylhexyl, 46-methylhexyl, 47-methylhexyl, 48-methylhexyl, 4 n-ethylhexyl, 1-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.

[0046] 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, and 3,4,5-triethylphenyl.

[0047] R 32 and / or R 33The aryl group of 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, and 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 2,4,6-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.

[0048] 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 of the dimethyl-1-butoxy 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.

[0049] 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, 1-octoxy, 2-octoxy, 3-octoxy, 4-octoxy, 2-ethylmethyl-1-propoxy, cyclohexoxy, 1-octoxy, 2-octoxy, 3-octoxy, 4-octoxy, 2-ethylmethyl-1-propoxy, cyclohexoxy, 1-octoxy, 2-ethyl ...oxy, 2-ethyloxy, 2-ethyloxy, 2- 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.

[0050] 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.

[0051] R 32 and / or R 33The aryloxy group in the above 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-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, and more preferably phenoxy, 4-methylphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4-dimethylphenoxy, 2,4,6-trimethylphenoxy, 4-t-butylphenoxy, 2-t-butylphenoxy, 2-methyl-4-t-butylphenoxy, and 2-methyl-6-t-butylphenoxy.

[0052] 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.

[0053] In formula (5), R 31 and R 34From the viewpoint of dielectric properties or solubility in a solvent, and from the viewpoint of increasing the degree of freedom of the terminal functional group and improving reactivity, it is preferable that the hydrocarbon group of R has a large number of carbon atoms. On the other hand, if the number of carbon atoms is excessively large, a decrease in Tg or a decrease in metal peelability or a decrease in the carbon-carbon double bond of an olefinic system occurs. 31 and R 34 The number of carbon atoms is C 1~30 The degree is preferable, C 1~20 The degree is more preferable, C 1~12 A degree is even more preferable.

[0054] 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.

[0055] 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-1,6-hexylene, Examples of dimethyl-1,6-hexylene include 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, and 2,5-dimethyl-1,6-hexylene.

[0056] 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.

[0057] 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 Examples of the alkylene alkyl group include ethyl-1,7-heptylene, 4-methyl-1,7-heptylene, 2-methyl-1,7-heptylene, 5-methyl-1,7-heptylene, 6-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, and dodecylmethylene.

[0058] R 31 and / or R 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.

[0059] 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 -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.

[0060] In the 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, a m-isopropenylphenyl group, a Examples of such alkyl groups 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.

[0061] 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 1~30 is a divalent hydrocarbon group having a plurality of R 32 , and R 33 are each independently 1~30 The monovalent hydrocarbon group is 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).

[0062] In formula (6) and / or formula (7), a plurality of R 35are each independently a hydrogen atom, a hydroxyl group, or C 1~30 Examples of the alkyl groups include hydrocarbon groups, aryl groups, alkoxy groups, aryloxy groups, amino groups, hydroxyalkyl groups, vinyl groups, isopropenyl groups, and halogen groups.

[0063] In formula (7), R 36 is C 1~3 or an amino group, or oxygen, and a part of the hydrocarbon group is preferably 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. 1~5 In addition, R 36 The hydrocarbon group as the alkyl 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.

[0064] 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 excessively large, Tg or metal peelability decreases, or the carbon-carbon double bond of an olefinic compound decreases. 35 The number of carbon atoms is C 1~30 The degree is preferable, C 1~20 The degree is more preferable, C 1~12 A degree is even more preferable.

[0065] 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. , 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, butylpentyl, 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 such alkylcyclohexyl include arylcyclohexyl, 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.

[0066] 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.

[0067] 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 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.

[0068] 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 groups substituted with a propenyl group and 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 of such ethylene 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.

[0069] 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 the modified polyphenylene ether-containing composition with all of low dielectric properties, appropriate metal peelability, low solution viscosity, sufficient Tg upon curing, etc.

[0070] <Modified polyphenylene ether composition> The curable resin composition according to the present embodiment includes, for example, a modified polyphenylene ether composition. The modified polyphenylene ether composition includes a polyphenylene ether having a structure represented by the above formula (1) (wherein, in the formula, each a represents an integer of 2 or 3 to 6, except when all a's are 2), 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 formulae (9) and (11), and a represents 2 or an integer of 3 to 6, except when all a's are 2.

[0071] In formula (8), a (-Y n -A) may be the same or different, where Y is a substituted phenylene monomer unit, Y n represents a polyphenylene ether structure in which n substituted phenylene monomer units are bonded consecutively. Z is based on a polyhydric phenol compound having a phenol structure to which a polyphenylene ether unit structures can be bonded. In addition, 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).

[0072] The modified polyphenylene ether composition comprises a modified polyphenylene ether having a structure represented by the above formula (8), and at least one (-Yn -A) is (-Y n -H) modified or unmodified polyphenylene ether, 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.

[0073] 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 in the structure represented by the above formula (8), all of the (-Y n -A) is (Y n The modified polyphenylene ether may include 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.

[0074] 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 a solid.

[0075] Z in formula (8) may be a structure having a central phenol moiety with a valence of a, as represented by the following formula (9), and a in formula (8) or (9) is preferably an integer of 3 to 6.

[0076] The central phenol moiety is as explained in the above section <Modified polyphenylene ether>.

[0077] 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)) n -A) may be bonded to the structure. [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.

[0078] 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. Also, 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.

[0079] X in the above formula (9) is R 5 an a-valent alkyl skeleton bonded to a benzene ring to which R 5 an a-valent aryl skeleton bonded to a benzene ring to which R 5 an a-valent heterocyclic skeleton bonded to a benzene ring to which is bonded;

[0080] 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 units are directly bonded to a benzene ring in a partial structure (as long as a benzene ring is bonded to the a units of branched ends, there may be a branched end to which no benzene ring is bonded). In addition, 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 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 5 and the like.

[0081] Multiple R in Eq. (9) 5 each independently represents a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and each k independently represents an integer of 1 to 4.

[0082] 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 substituent includes, for example, a halogen atom.

[0083] 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 terminal thereof, and more preferably a tert-butyl group.

[0084] The carbon atom of the benzene ring to which -O- in formula (9) is bonded is the 1st position, and either the 2nd or 6th carbon atom of R has a partial structure represented by formula (10) 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 above formula (9) may have a structure in which a hydrocarbon group or a partial structure represented by the above formula (10) is bonded to the carbon atoms at the 2nd and 6th positions of the benzene ring to which -O- is bonded. The benzene ring in the above formula (9) may have a structure in which (Y n -A) may be bonded to the 1-position via an oxygen atom, n -A) is bonded to the 4-position, and the central part X is bonded to the 4-position.

[0085] When a=2 in formula (8), Z may be, for example, a structure represented by formula (11) below. [ka] Multiple R in formula (11) 5 each independently represents an optional substituent, and each k independently represents 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.

[0086] 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.

[0087] 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 independently an integer of 0 to 200, and at least one n is an integer of 1 or more.

[0088] 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 The R 21 and R 22 It is preferable that the ratio is the same as

[0089] 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).

[0090] Examples of the 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 thereto.

[0091] 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 ends may result in a large change in molecular weight during polymerization, the number is preferably 2 to 6, and more preferably 2 to 4.

[0092] 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).

[0093] 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 the above formula (1) 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.

[0094] The modified polyphenylene ether (composition) of this embodiment is 1 A modified polyphenylene ether having the structure of the above formula (1) as a result of H-NMR measurement, n -A) is (Y n -H) and all (-Y n -A) is (Y n and in the structure of the above formula (1), all of the (-Y n -A) is (Y n The ratio of the integrated value of the peak derived from the peroxide appearing in the above region of 7.6 to 8.3 ppm to the integrated value of the peak derived from the central phenol moiety represented by the above formula (2) contained in the polyphenylene ether (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 is 1 or less to the integrated value of the peak derived from the central phenol moiety means that the modified polyphenylene ether composition does not contain a by-product peroxide adduct and the purity of the target polyfunctional modified polyphenylene ether, etc. 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.

[0095] The number average molecular weight (Mn) of the modified polyphenylene ether (composition) in this embodiment is 500 to 15,000 g / mol, preferably 1,000 to 10,000 g / mol, and more preferably 2,000 to 8,000 g / mol. By having the number average molecular weight (Mn) within the above range, the flowability is improved when dissolved in a solvent for preparing a varnish in the process of applying it to a substrate material, and the 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.

[0096] 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 the number of A substituents excludes the case where A=hydrogen atom (H). Among them, the number of A substituents in the composition is preferably 700 to 3,000 μmol / g, more preferably 700 to 2,000 μmol / g. When the number of A substituents in the composition is 700 μmol / g or more, the crosslink density can be increased during curing, and a cured product having a high glass transition temperature and excellent dielectric properties tends to be obtained. When the number of A substituents in the composition is 3,000 μmol / g or less, the viscosity of a varnish obtained by dissolving the polyphenylene ether composition in a solvent can be reduced, and the processability tends to be good when applied to a substrate material.

[0097] The number of A substituents can be evaluated by known methods such as titration, spectroscopy, and quantitative NMR depending on the type of functional group. For example, in the quantitative NMR method, 1 When H-NMR is used, the measurement is performed in the presence of a standard sample with a known structure and a polyfunctional polyphenylene ether composition. The polyfunctional polyphenylene ether composition and the standard sample with a known weight 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 dissolved in a deuterated solvent, does not react with the polyfunctional polyphenylene ether composition, and 1 There is no particular limitation as long as the peak in H-NMR does not interfere with the peak derived from the polyfunctional polyphenylene ether composition. For a specific method for evaluating the number of A substituents, see the description in the Examples.

[0098] From the viewpoint of having all of low dielectric properties, adequate metal peelability, low solution viscosity, sufficient Tg upon curing, etc., the modified polyphenylene ether-containing composition according to this embodiment preferably contains 0.5 to 95 mass % of a modified polyphenylene ether having a structure represented by the above formula (8).

[0099] <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) (hereinafter also referred to as an unmodified polyfunctional polyphenylene ether (composition)) having a hydroxyl group at the molecular end and represented by the following formula (1)' by a polymerization method, and introducing the A substituent in formula (1) into the end, i.e., modifying it. [ka] In formula (1)', Z, Y, n, and a include the same as those in formula (1) above, and are preferably the same as those defined in formula (1) above.

[0100] (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.

[0101] Here, a good solvent for an unmodified polyfunctional polyphenylene ether composition is a solvent capable of dissolving the polyfunctional polyphenylene ether. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene (including o-, m-, and p-isomers), ethylbenzene, and styrene; halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; and nitro compounds such as nitrobenzene.

[0102] The polymerization catalyst used in this embodiment may be a known catalyst system that can be generally used for the production of polyphenylene ether. A commonly known catalyst system is one that is composed of a transition metal ion having redox ability and an amine compound that can form 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. Since the polymerization reaction proceeds efficiently under slightly alkaline conditions, a small amount of alkali or an additional amine compound may be added thereto.

[0103] The polymerization catalyst preferably used in the present 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, and not all of them are hydrogen atoms at the same time; and R 18 is a linear or methyl-branched alkylene group having 2 to 5 carbon atoms.

[0104] Examples of the copper compound of the catalyst component described herein are listed below. Suitable copper compounds include cuprous compounds, cupric compounds, or mixtures thereof. Examples of cupric compounds include, for example, cupric chloride, cupric bromide, cupric sulfate, and cupric nitrate. Examples of cuprous compounds include, for example, cuprous chloride, cuprous bromide, cuprous sulfate, and cuprous nitrate. Particularly preferred metal compounds among these are cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide. These copper salts may be synthesized at the time of use from oxides (e.g., cuprous oxide), carbonates, hydroxides, and the like and corresponding halogens or acids. A method that is often used is to prepare the copper salt by mixing the cuprous oxide exemplified above with hydrogen halide (or a solution of hydrogen halide).

[0105] 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 an aqueous solution or a solution using a suitable solvent. These halogen compounds can be used alone or in combination of two or more kinds as a component. A preferred halogen compound is an aqueous solution of hydrogen chloride or an aqueous solution of hydrogen bromide.

[0106] 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 amount of copper atoms used is preferably in the range of 0.02 to 0.6 moles per 100 moles of the phenol compound added to the polymerization reaction.

[0107] Next, examples of the diamine compound of the catalyst component are listed below. For example, 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.

[0108] In this embodiment, the polymerization catalyst may contain a primary amine and a secondary monoamine as a component. 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.

[0109] The polymerization catalyst of the present embodiment may also contain a tertiary monoamine compound as a component thereof. The tertiary monoamine compound is an aliphatic tertiary amine including an alicyclic tertiary amine. Examples of the tertiary monoamine compound 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 in the range of 15 moles or less relative to 100 moles of the phenol compound added to the polymerization reaction.

[0110] In this embodiment, there is no limitation on adding a surfactant that is known to have an effect of improving polymerization activity. For example, trioctylmethylammonium chloride, known under the trade name Aliquat 336 or Capriquat, can be used as such a surfactant. The amount of the surfactant used is preferably within a range not exceeding 0.1% by mass based on 100% by mass of the total amount of the polymerization reaction mixture.

[0111] In the polymerization step of this embodiment, the oxygen-containing gas may be pure oxygen, or 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. Normal pressure is sufficient for the pressure in the system during the polymerization reaction, but reduced or increased pressure may be used as necessary.

[0112] 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.

[0113] In the method for producing the unmodified polyfunctional 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 the unmodified polyfunctional 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 the above formula (1)' can be produced with high purity during the production of the unmodified polyfunctional polyphenylene ether (composition), or the proportion of by-products produced by peroxides can be reduced, and the desired polyfunctional modified polyphenylene ether containing the structure of the above formula (1) can be produced with high purity.

[0114] (Copper extraction and by-product removal process) In this embodiment, there is no particular restriction on the post-treatment method after the polymerization reaction is completed. Usually, an acid such as hydrochloric acid or acetic acid, or ethylenediaminetetraacetic acid (EDTA) and its salts, nitrilotriacetic acid and its salts, etc. are added to the reaction liquid to deactivate the catalyst. In addition, a method for removing and treating the dihydric phenol by-product generated by the polymerization of polyphenylene ether can be performed using a conventionally known method. If the metal ions, which are the catalysts described above, are substantially deactivated, the mixture can be decolorized or post-treated simply by heating it. Also, a method of adding a required amount of a known reducing agent to the system is possible. Examples of known reducing agents include hydroquinone and sodium dithionite.

[0115] (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 may be performed into an organic phase and an aqueous phase, and the aqueous phase may be removed to remove the copper catalyst from the organic base. This liquid-liquid separation step is not particularly limited, and may include methods such as static separation and separation using a centrifuge. In order to promote the liquid-liquid separation, a known surfactant or the like may be used.

[0116] (concentration / drying process) In the method for producing the polyfunctional modified polyphenylene ether (composition) of the present embodiment, the organic phase containing the unmodified polyfunctional polyphenylene ether (composition) after the liquid-liquid separation may be concentrated and dried by volatilizing the solvent. Note that this step may be omitted when a modification reaction (for example, a reaction for introducing the substituent A in formula (1) to the terminal of the unmodified polyfunctional polyphenylene ether (composition)) is subsequently performed.

[0117] The method for volatilizing the solvent contained in the organic phase is not particularly limited, but examples thereof 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 the solvent is distilled off to concentrate the organic phase, and a method in which toluene is distilled off using an apparatus such as a rotary evaporator to concentrate the organic phase.

[0118] The temperature of 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 polyfunctional 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.

[0119] In order to obtain the unmodified polyfunctional polyphenylene ether (composition) with high efficiency, a method of increasing the drying temperature, a method of increasing the degree of vacuum in the drying atmosphere, a method of stirring during drying, and the like are effective, but a method of increasing the drying temperature is particularly preferable from the viewpoint of production efficiency. In the drying step, it is preferable to use a dryer equipped with a mixing function. Examples of the mixing function include a stirring type and a rolling type dryer. This allows the processing amount to be increased, and the productivity to be maintained at a high level.

[0120] [Modification reaction step] In this embodiment, the method for introducing the substituent A in formula (1) or (8) (for example, the functional group of the above formula (5)) to the end 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.

[0121] Specific examples of the halogenated silyl compounds 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 of such silane include aryldibromosilane, 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.

[0122] The aminosilyl compounds include methylvinylsilyl-tris(1,2,4-triazole), divinylsilyl bis(1,2,4-triazole), allylmethylsilyl bis(1,2,4-triazole), diallylsilyl bis(1,2,4-triazole), tris(1,2,4-triazolyl)silyl-2-norbornene, 6-methylbis(1,2,4-triazolyl)silyl-2-norbornene, 6-dimethylbis(1,2,4-triazolyl)silyl-2-norbornene, phenylvinylsilyl bis(1,2,4-triazole), 3-methacryloxypropylmethylsilyl bis(1,2,4-triazole), allylphenylsilyl(1,2,4-triazole), and 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, divinylsilyl bisimidazole, allylmethylsilyl bisimidazole, diallylsilyl bisimidazole, trisimidazolylsilyl-2-norbornene, 6-methylbisimidazolylsilyl-2-norbornene, 6-dimethylbisimidazolylsilyl-2-norbornene, phenylvinylsilyl bisimidazole, 3-methacryloxypropylmethylsilyl bisimidazole, allylphenylsilylimidazole, Examples thereof include diphenylvinylsilylimidazole, dimethylvinylsilylimidazole, allyldimethylsilylimidazole, methylphenylvinylsilylimidazole, 5-norbornene-2-yl(ethyl)dimethylsilylimidazole, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, and bis(dimethylamino)methylvinylsilane.

[0123] Examples of the alkoxysilane compound include trimethoxyvinylsilane, methoxydimethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, methacryloxypropyldimethoxymethylsilane, methacryloxypropyltrimethoxysilane, methacryloxypropyldiethoxymethylsilane, methacryloxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminophenoxydimethylvinylsilane, and 4-aminophenoxydimethylvinylsilane.

[0124] The reaction of introducing the above-mentioned compound into the terminal of the unmodified polyphenylene ether is generally a direct reaction with a hydroxyl group, but may also be a reaction with an alkali metal salt of a hydroxyl group. Alternatively, a halogenated silyl compound may be reacted with imidazole, triazole, pyrrolidine, or piperidine to form an amine compound, which may then be reacted with a hydroxyl group. In the direct reaction of a halogenated silyl compound with a hydroxyl group, an acid such as hydrogen halide is generated, so a weak base such as an amine may be allowed to coexist in order to trap the acid.

[0125] In order to prevent side reactions, the amines to be coexisted are preferably tertiary amines.Specific examples of the amines to be coexisted 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.

[0126] 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.

[0127] In addition, moisture not only causes undesirable side reactions during the reaction, but also causes hydrolysis after the reaction, which can reduce the reaction yield, so it is preferable to remove moisture from the reaction solvent, amine, etc. in advance. The preferred moisture content in the reaction system is preferably less than 200 ppm, more preferably less than 100 ppm.

[0128] In order 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 the like. The amount of residual amine before the purification step is less than 10,000 ppm.

[0129] In a preferred embodiment for achieving a high modification rate in the modification reaction step, the amount of the halogenated silyl compound used in the modification reaction is 1.00 times or more and less than 4 times the moles, preferably 1.05 times to 3 times the moles, more preferably 1.1 times to 2.5 times the moles, relative to 1 mole of hydroxyl groups in the polymer. If the amount of the halogenated silyl compound used is less than 1.00 times the moles relative to 1 mole of hydroxyl groups, a sufficient modification rate cannot be obtained, while if it is 4 times or more the moles, undesirable by-products may be generated during purification after the reaction, resulting in a decrease in purification yield. The amount of the amine used to be coexistent for the purpose of trapping the acid during the reaction is preferably 1.00 times or more and less than 6 times the moles, more preferably 1.05 times to 4 times the moles, and even more preferably 1.1 times to 4 times the moles, relative to 1 mole of hydroxyl groups. If the amount of the amine used is less than 1.00 times the moles relative to 1 mole of hydroxyl groups, a sufficient modification rate cannot be obtained, and if it is 6 times or more the effect on the conversion rate remains the same, but it is not preferable because a large amount of amine needs to be removed after the reaction.

[0130] 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 and a solution of the unmodified polyphenylene ether in a good solvent thereof. A combination of a plurality of temperature conditions may also be used.

[0131] After the modification reaction, if there is an excess of the halogenated silyl compound, it may be subjected to a treatment such as deactivation by reacting it with an alcohol such as methanol or ethanol.

[0132] After the modification reaction, the target product may be washed with water, an acidic or alkaline aqueous solution or filtered 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.

[0133] The method for producing the polyfunctional modified polyphenylene ether (composition) of the present embodiment is not limited to the method for producing the polyfunctional modified polyphenylene ether composition of the present embodiment described above, and the order or number of the above-mentioned polymerization step, copper extraction and by-product removal step, liquid-liquid separation step, and concentration and drying step may be appropriately adjusted.

[0134] <(B) Aliphatic maleimide compound with a molecular weight of 2000 or less as a crosslinking aid> The curable resin composition of the present embodiment contains an aliphatic maleimide compound having a molecular weight of not more than 2000. The aliphatic maleimide compound having a molecular weight of not more than 2000 functions as a crosslinking aid in the curable resin composition of the present embodiment.

[0135] In the curable resin composition of this embodiment, the maleimide group exhibits good curing reaction behavior in the presence of the modified polyphenylene ether of component (A), and since its structure is an aliphatic group with low polarity, the cured product exhibits low dielectric tangent (Df). When the maleimide compound contains an aromatic skeleton, the compatibility between the compound and component (A) decreases, and a homogeneous composition does not form, and a homogeneous cured product tends not to be formed.

[0136] The aliphatic maleimide compound of component (B) in this embodiment has a molecular weight of not more than 2000. A larger molecular weight tends to result in a lower Df of the cured product, while a smaller molecular weight is preferred because it tends to result in a lower viscosity of the resin composition. From such a viewpoint, the aliphatic maleimide compound of the component (B) of this embodiment has a molecular weight of 2000 or less, more preferably 1000 or less, and particularly preferably 500 or less.

[0137] In addition, the number of maleimide groups contained in the aliphatic maleimide compound of component (B) of this embodiment is not particularly limited, but the fewer the number of functional groups, the more uniform the crosslinked structure becomes, and the higher the adhesiveness tends to be, which can be evaluated by copper foil adhesive strength, etc. From this viewpoint, the number of functional groups contained in the aliphatic maleimide compound of component (B) is preferably 6 or less, more preferably 4 or less, and particularly preferably 2 or 1.

[0138] <Aliphatic maleimide> A specific example of the aliphatic maleimide compound of component (B) of this embodiment is an aliphatic maleimide compound having a molecular weight of 2000 or less and represented by the following formula (18): [ka] {In formula (18), R 40 , R 41 , R 42 represents a hydrogen atom or a hydrocarbon having 50 or less carbon atoms which may each independently have a total of three or less maleimide groups in the side chain, R 40 , R 41 , R 42 may be bonded to each other to form a cyclic structure. Examples include:

[0139] R 40 , R 41 , R 42 represents a hydrogen atom or a hydrocarbon having 50 or less carbon atoms which may each independently have a total of three or less maleimide groups in the side chain, R 40 , R 41 , R 42 may be bonded to each other to form a cyclic structure. R 40 , R 40 , R 40 If the carbon number of R exceeds 50, the viscosity of the composition tends to increase. 40 , R 40 , R 40If the total number of maleimide groups bonded to the polymer as side chains is 4 or more, a branching reaction may proceed in the early stage of curing, resulting in an increase in viscosity of the composition.

[0140] <Monofunctional aliphatic maleimide> A preferred embodiment of the component (B) represented by formula (18) is a monofunctional aliphatic maleimide having a structure represented by the following formula (19): [ka] {In formula (19), R 43 , R 44 , R 45 represent a hydrogen atom or each independently represents a hydrocarbon having 6 or less carbon atoms.

[0141] R 43 , R 44 , R 45 R each independently represents a hydrogen atom or a hydrocarbon having 6 or less carbon atoms. 43 , R 44 , R 45 When the carbon numbers of each of these independently are 7 or more, the viscosity of the composition may increase, or the concentration of the maleimide group may decrease, resulting in a decrease in the curability of the composition. From this perspective, R 43 , R 44 , R 45 The number of carbon atoms is more preferably 3 or less, further preferably 1 or less, and particularly preferably a hydrogen atom. An example of such component (B) is cyclohexylmaleimide.

[0142] <Bifunctional aliphatic maleimide> Another preferred embodiment of the component (B) is an aliphatic maleimide compound having a dimer acid diamine skeleton and a molecular weight of 2000 or less. Dimer acid diamines are compounds derived from dimer acids, which are dimers of unsaturated fatty acids such as oleic acid (see JP 9-12712 A, etc.), and various known dimer diamines can be used without particular limitation, and non-limiting structural formulas are shown below. In each structural formula, m+n=6-17, p+q=8-19, and the dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds. [ka] [ka] [ka] [ka] [ka] [ka]

[0143] An example of a dimer acid diamine skeleton maleimide compound obtained by maleimidizing such a dimer acid diamine is shown below: In the following structural formula, the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond. [ka]

[0144] <Why crosslinking aids are effective> Since the crosslinking aid of component (B) is a low molecular weight compound, by mixing it with component (A), the viscosity of the resin solution and in the molten state is reduced, fluidity is increased, and good moldability is achieved. Furthermore, since the skeleton is an aliphatic skeleton with low polarity, a cured product with a low dielectric tangent (Df) can be obtained. In addition, aliphatic maleimide compounds with a low functionality of 6 or less have a limited number of maleimide groups that contribute to the crosslinking reaction, and therefore prevent the crosslink density of the cured product from increasing excessively, thereby providing a cured product with excellent uniformity, which in turn results in a cured product with excellent toughness and adhesiveness and 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 low linear expansion coefficient.

[0146] <Composition ratio of component (A) and component (B)> The curable resin composition of the present embodiment is not limited by the composition ratio of the (A) component and the (B) component, but the higher the composition ratio of the (A) component, the higher the Tg of the resin tends to be, and the higher the composition ratio of the (B) component, the lower the viscosity of the composition. From such a viewpoint, the composition ratio of the (A) component to the (B) component is preferably 10:90 to 99:1, more preferably 50:50 to 90:10, and further preferably 60:40 to 80:20.

[0147] <(C) Initiator> The curable resin composition of the present embodiment may contain an initiator. The initiator is not particularly limited, but may be an organic peroxide, and one having a one-minute half-life temperature in the range of 155°C to 180°C is preferred from the viewpoint of stability and reactivity during storage of the composition. For example, t-hexylperoxyisopropylmonocarbonate (one-minute half-life temperature, hereinafter: 155.0°C), t-butylperoxy-3,5,5-trimethylhexanoate (166.0°C), t-butylperoxylaurate (159.4°C), t-butylperoxyisopropylmonocarbonate (158.8°C), t-butylperoxy2-ethylhexylmonocarbonate (161.4°C), t-hexylperoxybenzoate (160.3°C), 2,5-dimethylperoxybenzoate (161.4°C), 2,5-dimethylperoxybenzoate (162.4°C), 2,5-dimethylperoxybenzoate (163.4°C), 2,5-dimethylperoxybenzoate (164.4°C), 2,5-dimethylperoxybenzoate (165.4°C), 2,5-dimethylperoxybenzoate (16 ... n-butyl-2,5-di(benzoylperoxy)hexane (158.2°C), t-butyl peroxyacetate (159.9°C), 2,2-di-(t-butylperoxy)butane (159.9°C), t-butyl peroxybenzoate (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).

[0148] 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.

[0149] The amount of the (C) component is preferably 0.001 to 10 phr based on the total amount of the (A) and (B) components. When the amount of the (C) component is 0.001 phr or more, the effect of the (C) component is fully exhibited, and the curing reaction progress is promoted, which tends to increase the Tg of the cured product. When the amount is 10 phr or less, the amount of the initiator and its decomposition products remaining in the cured product can be reduced, and the dielectric tangent of the cured product tends to be prevented from becoming high. From such a viewpoint, the amount of the (C) component is more preferably 0.1 to 5 phr, and even more preferably 0.5 to 2 phr.

[0150] <Solvent> An organic or inorganic solvent can be added to the curable resin composition of the present embodiment as necessary. By adding an organic solvent, the viscosity of the composition can be reduced, and such a curable resin composition may be able to enhance the impregnation of glass fibers when it is impregnated into glass fibers to prepare a laminate. b Such organic solvents include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), ethyl acetate, etc., of which toluene and methyl ethyl ketone are preferred from the viewpoints of their low boiling points and ease of removal by evaporation from the resin composition.

[0151] <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. EXAMPLES

[0152] 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.

[0153] First, the measurement methods and evaluation criteria for each physical property will be described below.

[0154] (1) Abundance ratio of polyphenylene ether (modified polyphenylene ether having the structure of formula (1), modified polyphenylene ether in which one or more (-Yn-A) is (-Yn-H) and not all (-Yn-A) are (-Yn-H) in the structure of formula (1), and polyphenylene ether in which all (-Yn-A) are (-Yn-H) in the structure of formula (1) (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 subjected to a measurement using tetramethylsilane as an internal standard. 1 H-NMR measurements were performed using a JEOL 500 MHz microscope. (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 phenol unit of formula (14): [ka] {In formula (14), multiple R 21 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 an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, 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, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Examples of the substituent include a halogen atom. In equation (14), the two R 21From the viewpoint of providing the modified polyphenylene ether-containing composition with all of low dielectric properties, appropriate metal peelability, low solution viscosity, sufficient Tg upon curing, etc., it is preferable that both are not hydrogen atoms, and / or that one of them is not a partial structure represented by the above formula (3) and the other is either a hydrogen atom, a methyl group, or an ethyl group. In formula (14), 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, 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. c is any 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 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 an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, 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, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Examples of the substituent include a halogen atom.

[0155] In equation (15), the two R 21From the viewpoint of providing the modified polyphenylene ether-containing composition with all of low dielectric properties, appropriate metal peelability, low solution viscosity, sufficient Tg upon curing, etc., it is preferable that both are not hydrogen atoms, and / or that one of them is not a partial structure represented by the above formula (3) and the other is either a hydrogen atom, a methyl group, or an ethyl group.

[0156] 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, 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.

[0157] d and e are each independently any integer from 1 to 100. The diphenyl units specific to the by-product represented by the formula (15):

number

[0158] In addition, the peak due to the central phenol moiety of the main component polyphenylene ether represented by formula (2) used in the examples and comparative examples and the H of the terminal phenol of the by-product represented by formula (14) 1 , and R 22 The peak due to ', R in the central phenol of the by-product represented by formula (15) 22 The peaks due to " appear in the following regions: 1,1,3-Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane(1H): 2.8-3.2 ppm 1,1-bis(2-methyl-4-hydroxy-5-t-butylphenyl)butane(1H): 4.0-4.3ppm 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane(4H): 6.95-7.0ppm 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): 7.34-7.4 ppm

[0159] (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., the peroxide peak) derived from the peroxide appearing in the region of 7.6 to 8.3 ppm was calculated, and the presence ratio of the peroxide peak was analyzed by substituting this into the following formula (17).

number

[0160] (3) Number average molecular weight (Mn) As a measuring device, a gel permeation chromatography System 21 manufactured by Showa Denko K.K. was used, 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.

[0161] 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.

[0162] The column used was two K-805L columns connected in series manufactured by Showa Denko K.K. The solvent used was chloroform, the solvent flow rate was 1.0 mL / min, and the column temperature was 40°C. The measurement sample used was a 1 g / L chloroform solution of the modified polyphenylene ether composition. The UV wavelength of the detection unit was 254 nm for standard polystyrene and 283 nm for polyphenylene ether.

[0163] The number average molecular weight (Mn) (g / mol) was calculated from the peak area ratio based on the curve showing the molecular weight distribution obtained by GPC based on the above measurement data.

[0164] (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.

[0165] (5) Number of A substituents contained in the composition The modified polyphenylene ether composition and a 1,3,5-trimethoxybenzene standard sample (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight 168.19) as an internal standard sample were taken in specified amounts and dissolved in deuterated chloroform containing trimethylsilane. 1H-NMR measurements were performed using a JEOL 500 MHz microscope.

[0166] 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 gram 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.

[0167] (6) Viscosity of Toluene Solution of Modified Polyphenylene Ether Composition (Liquid Viscosity) 2 g of the modified polyphenylene ether composition and 3 g of toluene were weighed. Using a stirrer and a magnetic stirrer, they were stirred for 1 hour and completely dissolved until the solution became transparent, to prepare a 40 wt% toluene solution. The liquid viscosity of this solution was measured using a B-type viscometer at 25°C and 30 rpm.

[0168] (7) Denaturation rate The modification rate was calculated from the change in the amount of hydroxyl groups before and after the reaction by IR measurement in carbon disulfide according to the method described in JP-A-2004-502849 (Patent Document 3).

[0169] (8) Preparation of the cured product Film-like test pieces with thicknesses of 0.1 to 0.3 mm were prepared by a pressing method under the following conditions. The polymer, crosslinking agent, etc. were added to toluene and uniformly dissolved at room temperature overnight, after which NOF Corp.'s Perbutyl P was added. This was applied to the shine side of copper foil and dried at 120°C for 10 minutes, and the resulting solid resin composition was pulverized in an agate mortar. A 100 μm thick Teflon® sheet was cut into a shape of 60 × 60 mm, the Teflon® sheet was placed on the shiny side of the copper foil, and the solid resin composition was added in an amount about 1.5 times the theoretical value (6 × 6 × 0.01 × 1.5 = 0.54 g assuming a specific gravity of 1) to the cavity. The shiny side of the copper foil was then placed on top and the press was applied with 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 3min 160℃~220℃ 4℃ / min, 220℃ Hold time: 60 minutes

[0170] (9) Tg measurement of cured product The glass transition temperature (Tg) of the cured product was measured by DMA under the following conditions using Hitachi High-Tech Science Corporation (DMS6100). 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: Tensile mode Test start temperature: Room temperature Heating rate: 4℃ / 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.

[0171] (10) Measurement of dielectric tangent of cured product The cured material 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, using a split cylinder resonator). (11) Measurement of linear expansion coefficient The linear expansion coefficient was determined by measuring a sample cut from a dielectric tangent measurement test piece using Hitachi High-Tech Science Corporation's TMA7100 under the following conditions. Measurement mode: Tensile Size: Width 2mm, Length 10mm, Thickness 0.2mm Test start temperature: -50℃ Heating rate: 10℃ / min Maximum test temperature: 250℃ Maximum temperature holding time: 5 minutes

[0172] (12) Measurement of copper foil adhesive strength The adhesive strength with copper foil was measured by a T-peel test. A small amount of glass beads (for spacers) with a particle size of about 40 μm (20 to 40 μm) was added to the varnish prepared at a specified ratio. The 35 μm thick copper foil to be adhered was cut to 50 × 80 mm, and a polyimide tape (width 10 mm, thickness 55 μm) was attached to the outer periphery of the copper foil roughened surface. The prepared varnish was poured into the obtained frame, left overnight, dried at 120 ° C for 10 minutes, and the polyimide tape was peeled off to obtain a test piece. Copper foils of the same size were stacked so that the resin layer was sandwiched between them on the roughened surface, and a Teflon (registered trademark) sheet of about 20 mm was sandwiched at one end to ensure a gripping margin, and molded by vacuum pressing under the same conditions as in (8) Preparation of the cured product. The obtained copper foil was cut to prepare 10 mm x 80 mm. A T-peel test is carried out using a tensile testing machine (Instron 59R5582 model) under the following conditions. Expected test piece: 10mm x 80mm Test n=2 and take the average value. Measurement conditions: Test temperature: Room temperature (approx. 23°C), Test speed: 50mm / min, test length: approximately 30mm.

[0173] 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.

[0174] (Production Example 1) A 1.5-liter jacketed reactor equipped with a sparger for introducing an oxygen-containing gas at the bottom of the reactor, stirring turbine blades and baffles, 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 from the sparger at a rate of 1.05 L / min, and at the same time, the polymerization temperature was adjusted by passing a heat medium through the jacket so as to maintain 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 keeping the temperature at 70°C for 2 hours, catalyst extraction and by-product diphenoquinone removal treatment were performed, and the mixture was transferred to a Sharpless centrifuge and separated into an unmodified polyphenylene ether composition solution (organic phase) and an aqueous phase to which the catalyst metal had been transferred. The obtained unmodified polyphenylene ether composition solution was transferred to a jacketed concentration tank, and concentrated by distilling off toluene until the solid content in 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.

[0175] A stirrer was placed in a 300 ml three-neck flask, a Dimroth condenser with a three-way cock was installed on the main tube, and a rubber stopper with a thermometer was attached to one side tube. 20.0 g of the unmodified polyphenylene ether composition obtained in the above process was added from the other side tube, and a rubber stopper was attached. After the inside of the flask was replaced with nitrogen, the mixture was dissolved in 60.0 g of ultra-dehydrated toluene manufactured by Wako Pure Chemical Industries using a syringe while stirring the inside with a magnetic stirrer. Next, 5.72 g of triethylamine was added to the system. Then, 3.38 g of dimethylvinylchlorosilane was collected in a syringe and dropped into the system through the rubber stopper. After the end of the dropwise addition, stirring was continued at 30° C. for 3 hours, and then 0.86 g of ultra-dehydrated methanol manufactured by Wako Pure Chemical Industries was added to the system to stop the reaction.

[0176] Next, the reaction solution was distilled under reduced pressure together with toluene to remove triethylamine. Then, ultra-dehydrated toluene manufactured by Wako Pure Chemical Industries was added to the reaction solution to adjust the solid concentration to 20 wt%. Then, the polymer solution was dropped into methanol (5 times the weight of the organic layer) while stirring. Next, the precipitate was filtered, and the filtered material was vacuum dried at 110°C for 1 hour to obtain a modified polyphenylene ether composition. The reaction was confirmed to have progressed from the results of NMR measurement. The molecular weight of the obtained modified polyphenylene ether composition (PPE-1) was Mw = 4,810 and Mn = 2,610. The conversion rate of the obtained PPE-1 was 96%. The viscosity of a 40 wt% toluene solution of the obtained polymer was 23 mPa·s.

[0177] (Examples 1-2, Comparative Examples 1-2) A curable resin composition solution was prepared according to the formulation shown in Table 1, and the cured product obtained by the above method was evaluated. The results are shown in Table 1.

[0178] [Table 1]

[0179] The abbreviations in Table 1 are as follows. CHMI: N-cyclohexylmaleimide PMI: N-phenylmaleimide TAIC: Triallyl isocyanurate BMI-689: Designer Molecular, Inc., dimer acid bismaleimide, molecular weight 689 [ka] In the formula, the wavy line represents a carbon-carbon single bond or a carbon-carbon double bond.

[0180] From the above results, in the Examples, a uniform cured product was obtained, and a curable resin composition was obtained that satisfied all of the requirements of the cured product, namely, sufficient Tg, low dielectric properties, copper foil adhesion, and low linear expansion coefficient, whereas in the Comparative Examples, either a uniform cured product was not obtained, or a curable resin composition was not obtained that satisfied all of the requirements of the cured product, namely, sufficient Tg, low dielectric properties, copper foil adhesion, and low linear expansion coefficient. [Industrial Applicability]

[0181] The curable resin composition of the present invention is a curable resin composition useful as a substrate material, which is useful for obtaining a uniform cured product by blending a modified polyphenylene ether having a specific structure with a specific crosslinking aid, and which satisfies all of the requirements of sufficient Tg, low dielectric properties, copper foil adhesion, and a low linear expansion coefficient of the cured product.

Claims

1. A curable resin composition comprising the following components (A) and (B): (A) Modified polyphenylene ether A modified polyphenylene ether represented by the following formula (1): 【Chemistry 1】 In formula (1), Z is an a-valent partial structure represented by the following formula (2), a represents an integer of 3 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; 【Chemistry 2】 In formula (2), X is an arbitrary linking group having a valence of a, and a plurality of R ５ each independently represents a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and each k independently represents an integer of 1 to 4: 【Chemistry 3】 In formula (3), a plurality of R １１ each independently represents an optionally substituted alkyl group having 1 to 8 carbon atoms; １２ each independently represents an optionally substituted alkylene group having 1 to 8 carbon atoms; each b independently represents 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; 【Chemistry 4】 In formula (4), a plurality of R ２１ 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, 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 each independently represents 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. (B) an aliphatic maleimide compound having a molecular weight of 2000 or less, which is a crosslinking aid;

2. The component (B) is represented by the following formula (18): 【Chemistry 5】 {In formula (18), R ４０ , R ４１ , R ４２ represents a hydrogen atom or a hydrocarbon having 50 or less carbon atoms which may each independently have a maleimide group on the side chain, R ４０ , R ４１ , R ４２ may be bonded to each other to form a cyclic structure. The curable resin composition according to claim 1, wherein the maleimide compound is an aliphatic maleimide compound having a molecular weight of 2,000 or less and represented by the following formula:

3. The component (B) is represented by the following formula (19): 【Chemistry 6】 {In formula (19), R ４３ , R ４４ , R ４５ represent a hydrogen atom or each independently a hydrocarbon having 6 or less carbon atoms. The curable resin composition according to claim 2, wherein the maleimide compound is an aliphatic maleimide compound having a molecular weight of 2,000 or less and represented by the following formula:

4. The curable resin composition according to claim 1 or 2, wherein the component (B) is an aliphatic maleimide compound having a dimer acid skeleton and a molecular weight of 2,000 or less.

5. The curable resin composition according to any one of claims 1 to 4, further comprising (C) an initiator.

6. In the formula (2), 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 having the partial structure represented by the formula (3) on either the 2nd or 6th position is ５ and a hydrogen atom, a methyl group, or an ethyl group is bonded to the other carbon atom at the 2-position or the 6-position.

7. The curable resin composition according to claim 6, wherein the partial structure represented by the formula (3) is a t-butyl group.

8. The curable resin composition according to any one of claims 1 to 7, wherein the number of OH terminals contained in the polyphenylene ether is 0 to 3,000 µmol / g.

9. R in the above formula (4) ２１ The curable resin composition according to any one of claims 1 to 8, wherein is a methyl group.

10. A in the formula (1) is the following formula (5): 【Chemistry 7】 In formula (5), a plurality of R ３１ , and R ３４ are each independently １～３０ is a divalent hydrocarbon group represented by the formula: ３２ , and R ３３ are each independently １～３０ A is a monovalent hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydroxyalkyl group having an olefinic carbon-carbon double bond; １～３０ a hydrocarbon-based substituent of the formula (1), a part 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 t is an integer of 0 to 8. The curable resin composition according to any one of claims 1 to 9, wherein the curable resin composition is represented by the formula:

11. A in the formula (1) is represented by the following formula (6) and / or (7): 【Chemistry 8】 【Chemistry 9】 In formula (6) and / or formula (7), a plurality of R ３１ , and R ３４ are each independently １～３０ is a divalent hydrocarbon group represented by the formula: ３２ , and R ３３ are each independently １～３０ R is a monovalent hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydroxyalkyl group; ３５ each independently represents a hydrogen atom, a hydroxyl group, or C １～３０ R is a hydrocarbon 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; ３６ is C １～３ a divalent hydrocarbon group or amino group, or an oxygen atom, a portion of the hydrocarbon group may be substituted with an aryl group, an alkoxy group, an allyloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group, and s, t, and u each independently represent an integer of 0 to 8. The curable resin composition according to any one of claims 1 to 10, wherein the curable resin composition is represented by the formula:

12. The curable resin composition according to any one of claims 1 to 11, further comprising (D) a solvent.

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