Hardening resin composition

Abstract

To provide a curable resin composition which enables production of a uniform cured product, and satisfies all of a sufficient Tg, low dielectric characteristics and a low coefficient linear expansion of the cured product.SOLUTION: A curable resin composition contains (A) modified polyphenylene ether represented by the following formula (1), and a styrenic elastomer. In formula (1), Z is an a-valent partial structure, a represents an integer of 2 to 6, Y is each independently a divalent connection group having a structure represented by the following formula (4), n represents a repeated number of Y and is each independently an integer of 0-200, 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 Art

[0002] Polyphenylene ether has excellent high-frequency characteristics, flame retardancy, and heat resistance, and thus is widely used as a material in the fields of electric and electronic, automotive, and other various industrial materials. In recent years, polyphenylene ether having an extremely low molecular weight is expected to be effective for electronic material applications such as substrate materials, compared with ordinary high molecular weight polyphenylene ether. For this reason, a low molecular weight polyphenylene ether having a lower dielectric constant than a general high molecular weight polyphenylene ether using 2,6-dimethylphenol as a raw material and an efficient production method thereof have been proposed in Patent Document 1.

[0003] In addition, Patent Documents 2 and 3 describe a modified polymer having a polyphenylene ether moiety in its molecular structure and a methacryl group at this molecular terminal. In particular, methacryl group modification has become a widely used technique because the reactivity of the methacryl group as a crosslinking group is moderately high and the method of introducing it to the hydroxyl group terminal is easy. Furthermore, in Patent Documents 4 and 5, attempts have been reported to blend a copolymer of styrene and an olefinic alkene compound and its hydrogenated product (styrene-based elastomer) with a methacrylated polyphenylene ether in order to improve the adhesion to a metal foil and the like.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

[0005] As described above, due to various merits, adding a styrenic elastomer to a modified polyphenylene ether has been carried out. However, the methacrylated polyphenylene ether has low compatibility with the styrenic elastomer. Therefore, a resin composition containing a methacrylated polyphenylene ether and a styrenic elastomer usually undergoes macro phase separation at the stage of the resin composition before curing or during the curing process. As a result, since a continuous phase of the styrenic elastomer exists in the formed cured product, the linear expansion coefficient increases or the Tg decreases.

[0006] In Patent Documents 4 and 5, attempts have been made to blend a highly polar crosslinking aid such as triallyl isocyanurate (TAIC) as a compatibilizer for the purpose of suppressing such macro phase separation. However, the cured product thus formed has a problem that the dielectric properties (dielectric constant, dielectric loss tangent) become high because a highly polar crosslinking aid is blended.

[0007] In view of the above problems, an object of the present invention is to provide a curable resin composition that can obtain a uniform cured product and satisfies all of a sufficient Tg, low dielectric properties, and a low linear expansion coefficient of the cured product. [Means for Solving the Problems]

[0008] In order to solve the above problems, the present inventors used a vinylsilyl group or the like, which has a low polarity and good metal adhesiveness, as a crosslinking group in the polyphenylene ether skeleton as a modifying group, and blended a styrenic elastomer, thereby obtaining a curable resin composition capable of solving all the above problems, and completing the present invention. That is, the present invention is as follows. [1] A curable resin composition containing the following component (A) and component (B). (A) Modified polyphenylene ether A modified polyphenylene ether represented by the following formula (1): [Chemical formula] {In formula (1), Z is an a-valent partial structure represented by the following formula (2), a represents an integer of 2 to 6, Y is each independently a divalent linking group having a structure represented by the following formula (4), n represents the number of repetitions of Y, and each independently is an integer of 0 to 200. At least one of the n in a [-Y n -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 are hydrogen atoms. [Chemical formula] In formula (2), X is an arbitrary a-valent linking group, and a plurality of R 5 are each independently either a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and k is each independently an integer of 1 to 4. [Chemical formula] In formula (3), a plurality of R 11 are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms, a plurality of R 12 are each independently an optionally substituted alkylene group having 1 to 8 carbon atoms, b is each independently 0 or 1, and R 13 represents either a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted phenyl group. [Chemical formula] In formula (4), a plurality of R 21is 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 Rs 21 are not hydrogen atoms at the same time, and two Rs 21 is not a combination in which one is a partial structure represented by the above formula (3) and the other is any one of a hydrogen atom, a methyl group, or an ethyl group, and a plurality of Rs 22 are each independently any one of a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, and a halogen atom.} (B) Styrenic elastomer [2] The curable resin composition according to [1], wherein the component (B) is a styrenic elastomer having a number average molecular weight of 300,000 or less. [3] The curable resin composition according to [1] or [2], wherein the component (B) is a styrenic elastomer having a double bond content of 90% or less. [4] The curable resin composition according to any one of [1] to [3], wherein the component (B) is a styrenic elastomer having a styrene content of 80% or less. [5] The curable resin composition according to any one of [1] to [4], wherein the component (B) is a styrenic elastomer containing any one of styrene-butadiene copolymer (SBR), styrene-butadiene-styrene copolymer (SBS), hydrogenated styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer (SIS), hydrogenated styrene-isoprene-styrene copolymer, and hydrogenated styrene (butadiene / isoprene) styrene copolymer. [6] The curable resin composition according to any one of [1] to [5], wherein the component (B) is a styrenic elastomer containing a block A mainly composed of vinyl aromatic compound monomer units and a block B mainly composed of conjugated diene monomer units. [7] The curable resin composition according to any one of [1] to [6], wherein the component (B) is a styrene-based elastomer having a hydrogenation rate of 90% or more of the double bond based on the conjugated diene monomer unit. [8] The curable resin composition according to any one of [1] to [7], wherein the component (B) is a styrene-based elastomer having a number average molecular weight of 300,000 or less. [9] The curable resin composition according to any one of [1] to [8], further comprising (C) an initiator.

[10] Among the said Rs 5 at least one is a partial structure represented by the said formula (3). Taking the carbon atom of the benzene ring to which -O- in the said formula (2) binds as the 1-position, the partial structure represented by the said formula (3) is bonded to one of the carbon atoms at the 2-position or 6-position, and a hydrogen atom, a methyl group or an ethyl group is bonded to the other carbon atom at the 2-position or 6-position. The curable resin composition according to any one of [1] to [9]. 5

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

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

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

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

[13] Among the Rs of the said formula (4) 21 is a methyl group. The curable resin composition according to any one of [1] to

[12] .

[14] A in the said formula (1) is the following formula (5): [Chemical formula] {In formula (5), R 31 , and R 34 are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms, R 32 , and R 33 ​is, independently of each other, a monovalent hydrocarbon group having 1 to 30 carbon atoms, an aryl group, an alkoxy group, an allyloxy group, an amino group, or a hydroxyalkyl group, B is a hydrocarbon-based substituent having 1 to 30 carbon atoms containing an olefinic carbon-carbon double bond, and a part thereof 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 s, t, and u are each independently an integer of 0 to 8.} The curable resin composition according to any one of [1] to

[13] , represented by

[15] A in the formula (1) is the following formula (6) and / or (7):

Chemical formula

Chemical formula

[14] , represented by

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

[15] , further containing a solvent.

Advantages of the Invention

[0009] By using the curable resin composition containing a modified polyphenylene ether having a vinylsilyl group and a styrene-based elastomer defined in the present invention, a uniform cured product can be obtained, and a curable resin composition can be provided that satisfies all of a sufficient Tg, low dielectric properties, and a low linear expansion coefficient of the cured product.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0011] Hereinafter, modes for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The present embodiment is an exemplification for explaining the present invention, and the present invention is not limited to only this embodiment, and the present invention can be appropriately modified and implemented within the scope of its gist.

[0012] <Curable Resin Composition> The curable resin composition of the present embodiment is characterized by containing the following component (A) and component (B). (A) Modified polyphenylene ether The modified polyphenylene ether represented by the following formula (1):

Chemical Formula

[0013] In this embodiment, by using a curable resin composition containing (A) a modified polyphenylene ether and (B) a styrene-based elastomer, a uniform cured product can be obtained, and a curable resin composition that satisfies all of the sufficient Tg, low dielectric properties, and low linear expansion coefficient of the cured product can be provided. Hereinafter, the components constituting the curable resin composition of this embodiment will be described in detail.

[0014] <(A) Modified polyphenylene ether> The modified polyphenylene ether according to this embodiment has a structure represented by the following formula (1).

Chemical formula

[0015] The above-mentioned "central phenol site" means a central skeleton that serves as a starting point of the reaction when polymerizing a polyfunctional polyphenylene ether, and its structure can be identified by analyzing a polyfunctional modified polyphenylene ether composition by methods such as nuclear magnetic resonance (NMR) and mass spectrometry. As a specific method for identifying the structure of the central phenol site from a polyfunctional modified polyphenylene ether composition, for example, 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 site is estimated from the peak of fragment ions by electron impact or electroionization (EI). Further, a method of estimating the structure of the central phenol site by performing NMR measurement of the polyfunctional modified polyphenylene ether composition and comparing it with the NMR measurement results of known polyfunctional phenol compounds can be mentioned. By combining the mass spectrometry results and the NMR measurement results, it becomes possible to more accurately identify the structure of the central phenol site.

[0016] The above-mentioned modified polyphenylene ether has a a number of partial structures (for example, R) at the a-valent central part X 5a phenol which may be replaced with others) is bonded, and a [-Y in formula (1) is bonded to an a-valent partial structure (i.e., the central phenol site represented by the following formula (2)) n -A) may be bonded. [Chemical formula] In formula (2), examples of a include integers from 2 to 6 similar to formula (1), and preferably the same integer as in formula (1). In the central phenol site of formula (2), the a partial structures may have the same structure or different structures.

[0017] In formula (2), X is an a-valent arbitrary linking group and is not particularly limited. Examples include hydrocarbon groups such as chain hydrocarbons and cyclic hydrocarbons; hydrocarbon groups containing one or more atoms selected from nitrogen, phosphorus, silicon, and oxygen; atoms such as nitrogen, phosphorus, and silicon; or groups combining these; etc. X may be a linking group excluding a single bond.

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

[0019] In formula (2), examples of X include an a-valent alkyl skeleton bonded to the benzene ring to which R is bonded via a single bond or an ester bond, etc.; an a-valent aryl skeleton bonded to the benzene ring to which R is bonded via a single bond or an ester bond, etc.; an a-valent heterocyclic skeleton bonded to the benzene ring to which R is bonded via a single bond or an ester bond, etc.; etc. 5 is bonded; an a-valent aryl skeleton bonded to the benzene ring to which R 5 is bonded; an a-valent heterocyclic skeleton bonded to the benzene ring to which R 5 is bonded; etc.

[0020] Here, the alkyl skeleton is not particularly limited. For example, it includes a skeleton in which the branched ends of a chain hydrocarbon having at least a carbon number of 1 to 6 (e.g., a chain saturated hydrocarbon) are directly bonded to the benzene ring of the partial structure (it is sufficient that the benzene ring is bonded to a branched ends, and there may be branched ends to which the benzene ring is not bonded).), etc. Further, the aryl skeleton is not particularly limited. For example, a benzene ring, a mesitylene group, or a 2-hydroxy-5-methyl-1,3-phenylene group is bonded to the benzene ring to which R 5 is bonded through a single bond or an alkyl chain, and the like. Further, the heterocyclic skeleton is not particularly limited. For example, a skeleton in which a triazine ring is bonded to the benzene ring to which R 5 is bonded through a single bond or an alkyl chain, and the like.

[0021] A plurality of R 5 in formula (2) are each independently either a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and k is each independently an integer of 1 to 4.

[0022] As R 5 in formula (2), examples include linear alkyl groups having 1 to 8 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and groups having a partial structure represented by the following formula (3), etc. At least one of R 5 may be a partial structure represented by the following formula (3).

Chemical formula

[0023] The partial structure represented by the formula (3) is preferably a group containing a secondary and / or tertiary carbon, and examples thereof include 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.

[0024] In the present embodiment, when the carbon atom of the benzene ring to which -O- in the formula (2) is bonded is defined as the 1-position, R having the partial structure represented by the formula (3) is bonded to one of the carbon atoms at the 2-position or the 6-position, and it is preferable that 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. Further, a hydrocarbon group or the partial structure represented by the above formula (3) may be bonded to the carbon atoms at the 2-position and the 6-position of the benzene ring in the formula (2). The benzene ring in the above formula (2) may have [Y in the above formula (1) bonded to the carbon atoms other than the 2-position and the 6-position via the central portion X and an oxygen atom. 5 -A] bonded thereto, and it is preferable that [Y in the above formula (1) is bonded to the 1-position via an oxygen atom and the central portion X is bonded to the 4-position. n -A] bonded thereto, and it is preferable that [Y in the above formula (1) is bonded to the 1-position via an oxygen atom and the central portion X is bonded to the 4-position. n -A] bonded thereto, and it is preferable that [Y in the above formula (1) is bonded to the 1-position via an oxygen atom and the central portion X is bonded to the 4-position.

[0025] Examples of the polyhydric phenol compound 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-hydroxyphenyl)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-trimethylphenyl)methyl]-4-methylphenol, 2,6-bis[(4-hydroxy-3,5,6-trimethylphenyl)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'-methylenebis[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]-3,6-dimethylphenol], 6,6'-methylenebis[4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,2,3-benzenetriol], 1,1-bis(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 4,4'-cyclohexylidenebis[2-cyclohexyl-6-[(2-hydroxy-5-methylphenyl)methyl]phenol], 4,4'-cyclohexylidenebis[2-cyclohexyl-6-[(4-hydroxy-3,5-dimethylphenyl)methyl]phenol], 4,4’-Cyclohexylidenebis[2-cyclohexyl-6-[(4-hydroxy-2-methyl-5-cyclohexylphenyl)methyl]phenol], 4,4’-cyclohexylidenebis[2-cyclohexyl-6-[(2,3,4-trihydroxyphenyl)methyl]phenol], 4,4’,4’’,4’’’-(1,2-ethanediylidene)tetrakis(2,6-dimethylphenol), 4,4’,4’’,4’’’-(1,4-phenylenedimethylidene)tetrakis(2,6-dimethylphenol), 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane, tetramethylbisphenol A, tetramethylbisphenol F, (1,1’-biphenyl)-4,4’-diol, 3,3’-dimethyl(1,1’-biphenyl)-4,4’-diol, 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, etc. are exemplified, but not limited thereto.,

[0026] The number of phenolic hydroxyl groups in the polyhydric phenol compound is not particularly limited as long as it is 2 or more. However, when the number of polyphenylene ether terminals increases, the change in molecular weight during polymerization may become large. Therefore, it is preferably 2 to 6, more preferably 2 to 4.,

[0027] Particularly preferred polyhydric phenol compounds are 4,4'-[(4-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(3-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(4-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 4,4'-[(3-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 4,4',4'',4'''-(1,4-phenylenedimethylene)tetrakis(2,6-dimethylphenol), 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,1-bis(2-methyl-4-hydroxy-5-t-butylphenyl)butane, tetramethyl bisphenol A, 3,3',5,5'-tetramethyl(1,1'-biphenyl)-4,4'-diol.

[0028] In the above formula (1), a plurality of Y are each independently a divalent linking group having a structure represented by the following formula (4) (that is, a phenol unit having a substituent), n represents the number of repetitions of Y, and each is independently an integer from 0 to 200, and among a number of [-Y n -A], at least one n is an integer of 1 or more. [Chemical formula]

[0029] In formula (4), a plurality of R 21 each independently represents at least one selected from the group consisting of a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, and a halogen atom; R 21 is 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, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Examples of the above substituents include a halogen atom and the like.

[0030] In formula (4), two Rs 21 are preferably not hydrogen atoms simultaneously, and / or not a combination where one is the partial structure represented by the above formula (3) and the other is any of a hydrogen atom, a methyl group, or an ethyl group, from the viewpoint of having all of low dielectric properties, appropriate metal peelability, low solution viscosity, sufficient Tg during curing, etc. for the modified polyphenylene ether-containing composition.

[0031] In formula (4), a plurality of Rs 22 each independently represent at least one selected from the group consisting of a hydrogen atom; an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms; and a halogen atom; a hydrogen atom, or an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms is preferable, 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 above substituent include a halogen atom and the like.

[0032] Examples of the monohydric phenol compound for the structure represented by the above formula (4) include o-cresol, 2,6-dimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-n-propylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-n-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol, 2-phenylphenol, 2,6-diphenylphenol, 2,6-bis-(4-fluorophenyl)phenol, 2-methyl-6-tolylphenol, 2,6-ditolylphenol, 2,5-dimethylphenol, 2,3,6-trimethylphenol, 2,5-diethylphenol, 2-methyl-5-ethylphenol, 2-ethyl-5-methylphenol, 2-allyl-5-methylphenol, 2,5-diallylphenol, 2,3-diethyl-6-n-propylphenol, 2-methyl-5-chlorophenol, 2-methyl-5-bromophenol, 2-methyl-5-isopropylphenol, 2-methyl-5-n-propylphenol, 2-ethyl-5-bromophenol, 2-methyl-5-n-butylphenol, 2,5-di-n-propylphenol, 2-ethyl-5-chlorophenol, 2-methyl-5-phenylphenol, 2,5-diphenylphenol, 2,5-bis-(4-fluorophenyl)phenol, 2-methyl-5-tolylphenol, 2,5-ditolylphenol, 2,6-dimethyl-3-allylphenol, 2,3,6-triallylphenol, 2,3,6-tributylphenol, 2,6-di-n-butyl-3-methylphenol, 2,6-dimethyl-3-n-butylphenol, 2,6-dimethyl-3-t-butylphenol, etc.

[0033] Among the above monohydric phenol compounds, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-diphenylphenol, 2,3,6-trimethylphenol, or 2,5-dimethylphenol is particularly preferred because it is inexpensive and easily available, and 2,6-dimethylphenol or 2,3,6-trimethylphenol is more preferred.

[0034] In addition, the above phenol compound may be used alone or in combination of two or more.

[0035] Examples of the above monohydric phenol compounds include methods of using a combination of 2,6-dimethylphenol and 2,6-diethylphenol, methods of using a combination of 2,6-dimethylphenol and 2,6-diphenylphenol, methods of using a combination of 2,3,6-trimethylphenol and 2,5-dimethylphenol, methods of using a combination of 2,6-dimethylphenol and 2,3,6-trimethylphenol, etc. At this time, the mixing ratio of the phenol compounds to be combined can be arbitrarily selected.

[0036] In addition, the phenol compound to be used may contain a small amount of m-cresol, p-cresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, etc., which may be contained as by-products during production.

[0037] The phenol compound for the a-valent partial structure represented by the above formula (2) can be industrially advantageously produced by reacting the corresponding monohydric phenol compound with aldehydes (e.g., formaldehyde, etc.), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, etc.), or dihalogenated aliphatic hydrocarbons, or by reacting the corresponding monohydric phenol compounds with each other.

[0038] In the above formula (1), A represents a hydrogen atom or a silyl group-containing derivative capable of bonding to a polyphenylene ether structure, except when all are hydrogen atoms.

[0039] Here, as A in formula (1), from the viewpoint of obtaining characteristics of low dielectric properties, appropriate metal peelability, low solution viscosity, and sufficient Tg during curing, a substituent represented by the following formula (5) is preferable.

Chemical formula

[0040] In formula (5), the hydrocarbon groups of R 32 , and R 33 are more preferably those having a larger number of carbon atoms from the viewpoints of dielectric properties or solubility in a solvent. On the other hand, if the number of carbon atoms is excessively large, a decrease in Tg, a decrease in metal peelability, or a decrease in the olefinic carbon-carbon double bond occurs. Therefore, the number of carbon atoms of R 32 and R 33 is preferably about 1 to 30, more preferably about 1 to 20, and even more preferably about 1 to 12.

[0041] In formula (5), R 32 , and / or R 33Specific examples of the monovalent hydrocarbon group include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentylene, 4-methylpentylene, 1,1-dimethylbutylene, 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, 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, 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, etc. may be mentioned.,

[0042] R 32 and / or R 33Examples of the monovalent hydrocarbon group include 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; 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; still 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,They are undecyl, dodecyl, and benzyl.

[0043] R 32 and / or R 33 Specific examples of the aryl group of R and / or R 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, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,3-dimethylphenyl, 3,5-dimethylphenyl, 3,4-dimethylphenyl, 2,6-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,3-diethylphenyl, 3,5-diethylphenyl, 3,4-diethylphenyl, 2,4,6-trimethylphenyl, 2,3,4-trimethylphenyl, 2,3,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,4,6-triethylphenyl, 2,3,4-triethylphenyl, 2,3,6-triethylphenyl, 3,4,5-triethylphenyl, and the like.

[0044] R 32 and / or R 33As the aryl group, preferably, phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4-n-propylphenyl, 3-n-propylphenyl, 2-n-propylphenyl, 4-isopropylphenyl, 3-isopropylphenyl, 2-isopropylphenyl, 4-n-butylphenyl, 3-n-butylphenyl, 2-n-butylphenyl, 4-isobutylphenyl, 3-isobutylphenyl, 2-isobutylphenyl, 4-t-butylphenyl, 3-t-butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,3-dimethylphenyl, 3,5-dimethylphenyl, 3,4-dimethylphenyl, 2,6-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,3-diethylphenyl, 3,5-diethylphenyl, 3,4-diethylphenyl, 2,4,6-trimethylphenyl, 2,3,4-trimethylphenyl, 2,3,6-trimethylphenyl, 3,4,5-trimethylphenyl, and 2,4,6-triethylphenyl, more preferably, phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4-n-propylphenyl, 3-n-propylphenyl, 2-n-propylphenyl, 4-isopropylphenyl, 3-isopropylphenyl, 2-isopropylphenyl, 4-n-butylphenyl, 3-n-butylphenyl, 2-n-butylphenyl, 4-isobutylphenyl, 3-isobutylphenyl, 4-t-butylphenyl, 3-t-butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,3-diethylphenyl, 2,4,6-trimethylphenyl, 2,3,6-trimethylphenyl, and 2,4,It is 6-triethylphenyl, and more preferably phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 4-isopropylphenyl, 3-isopropylphenyl, 2-isopropylphenyl, 4-n-butylphenyl, 3-n-butylphenyl, 4-isobutylphenyl, 3-isobutylphenyl, 4-t-butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, and 2,4,6-trimethylphenyl.,

[0045] R 32 and / or R 33 Specific examples of the alkoxy group of and / or R 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, 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, phenylmethoxy, and the like.,

[0046] R 32 and / or R 33The alkoxy group is preferably methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, 2-butoxy, t-butoxy, 1-pentoxy, 2,2-dimethylpropoxy, 2-ethylpropoxy, 3,3-dimethylpropoxy, 1,1-dimethylpropoxy, cyclopentoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 4-methylpentoxy, 3-methylpentoxy, 2-methylpentoxy, 1,1-dimethyl-1-butoxy, 2,2-dimethyl-1-butoxy, 3,3-dimethyl-1-butoxy, 2-ethyl-1-butoxy, 3-ethyl-1-butoxy, 3,3-ethylmethyl-1-propoxy, cyclohexoxy, 1-octoxy, 2-octoxy, 3-octoxy, 4-octoxy, 2-ethyl-1-hexoxy, 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; still more preferably methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, 2-butoxy, t-butoxy, 2,2-dimethylpropoxy, cyclopentoxy, 1-hexoxy, 2-ethyl-1-hexoxy, and phenylmethoxy.

[0047] R 32 and / or R 33Specific examples of the aryloxy group include phenoxy, 4-methylphenoxy, 3-methylphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4-dimethylphenoxy, 2,3-dimethylphenoxy, 2,4,6-trimethylphenoxy, 4-isopropylphenoxy, 2-isopropylphenoxy, 3-isopropylphenoxy, 4-isobutylphenoxy, 2-isobutylphenoxy, 3-isobutylphenoxy, 4-t-butylphenoxy, 2-t-butylphenoxy, 3-t-butylphenoxy, 2,6-di-t-butylphenoxy, 2,4-di-t-butylphenoxy, 2,3-di-t-butylphenoxy, 2-methyl-4-t-butylphenoxy, 2-methyl-6-t-butylphenoxy, 4-methyl-2-t-butylphenoxy, and the like.

[0048] R 32 and / or R 33As the aryloxy group, 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, and 4-methyl-2-t-butylphenoxy, more 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, 2-methyl-4-t-butylphenoxy, and 2-methyl-6-t-butylphenoxy, still 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.

[0049] R 32 and / or R 33 Specific examples of the amino group of and / or R include dimethylamino, ethylmethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-t-butylamino, dicyclohexylamino, and the like.

[0050] In formula (5), R 31 and R 34The hydrocarbon group preferably has a larger number of carbon atoms from the viewpoints of dielectric properties, solubility in a solvent, and further increasing the degree of freedom of the terminal functional group to improve reactivity. On the other hand, if the number of carbon atoms is excessively large, a decrease in Tg, a decrease in metal peelability, or a decrease in olefinic carbon-carbon double bonds will occur. Therefore, R 31 and R 34 preferably have about 1 to 30 carbon atoms, more preferably about 1 to 20 carbon atoms, and even more preferably about 1 to 12 carbon atoms.

[0051] In formula (5), R 31 and / or R 34Specific examples of the divalent hydrocarbon group include methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,3-trimethylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,2-cyclopentylene, 1,3-cyclopentylene, 2,2-dimethyl-1,3-propylene, 1,1-dimethyl-1,3-propylene, 3,3-dimethyl-1,3-propylene, hexamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2-ethyl-1,4-butylene, 3-ethyl-1,4-butylene, 1-methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methylpentylene, 1,1-dimethyl-1,4-butylene, 2,2-dimethyl-1,4-butylene, 3,3-dimethyl-1,4-butylene, 1,2-dimethyl-1,4-butylene, 1,3-dimethyl-1,4-butylene, 2,3-dimethyl-1,4-butylene, heptamethylene, 1-methyl-1,6-hexylene, 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene, 4-methyl-1,6-hexylene, 5-methyl-1,6-hexylene, 1-ethyl-1,5-pentylene, 2-ethyl-1,5-pentylene, 3-ethyl-1,5-pentylene, 1,1-dimethyl-1,5-pentylene, 2,2-dimethyl-1,5-pentylene, 3,3-dimethyl-1,5-pentylene, 4,4-dimethyl-1,5-pentylene, 1,2-dimethyl-1,5-pentylene, 1,3-dimethyl-1,5-pentylene, 1,4-dimethyl-1,5-pentylene, 2,3-dimethyl-1,5-pentylene, 2,4-dimethyl-1,5-pentylene, 3,4-dimethyl-1,5-pentylene, and the like.

[0052] Also, R 31 and / or R 34Specific examples of the divalent hydrocarbon group include 2-methyl-3,3-dimethyl-1,4-butylene, 1-methyl-3,3-dimethyl-1,4-butylene, 1,2,3-trimethyl-1,4-butylene, 1,3-dimethyl-1,4-pentylene, 2-isopropyl-1,4-butylene, 2-methyl-1,4-cyclohexylene, 3-methyl-1,4-cyclohexylene, 4-methyl-1,4-cyclohexylene, 1-cyclohexylmethylene, 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, 4,4-dimethyl-1,6-hexylene, 5,5-dimethyl-1,6-hexylene, 1,2-dimethyl-1,6-hexylene, 1,3-dimethyl-1,6-hexylene, 1,4-dimethyl-1,6-hexylene, 1,5-dimethyl-1,6-hexylene, 2,3-dimethyl-1,6-hexylene, 2,4-dimethyl-1,6-hexylene, 2,5-dimethyl-1,6-hexylene, and the like.

[0053] Also, R 31 and / or R 34Specific examples of the divalent hydrocarbon group include 1,1-ethylmethyl-1,5-pentylene, 2,2-ethylmethyl-1,5-pentylene, 3,3-ethylmethyl-1,5-pentylene, 4,4-ethylmethyl-1,5-pentylene, 1-ethyl-2-methyl-1,5-pentylene, 1-ethyl-3-methyl-1,5-pentylene, 1-ethyl-4-methyl-1,5-pentylene, 2-ethyl-1-methyl-1,5-pentylene, 3-ethyl-1-methyl-1,5-pentylene, 4-ethyl-1-methyl-1,5-pentylene, 2-ethyl-3-methyl-1,5-pentylene, 2-ethyl-4-methyl-1,5-pentylene, 3-ethyl-2-methyl-1,5-pentylene, 4-ethyl-3-methyl-1,5-pentylene, 3-ethyl-4-methyl-1,5-pentylene, 4-ethyl-3-methyl-1,5-pentylene, 1-(2-methylpropyl)-1,4-butylene, 1-(2-methylpropyl)-2-methyl-1,4-butylene, 1,1-(2-methylpropyl)ethylene, 1,1-(2-methylpropyl)ethyl-1,3-propylene, 1,1-diethyl-1,3-propylene, 2,2-diethyl-1,3-propylene, 1,1-ethylmethyl-2,2-dimethyl-1,3-propylene, 2,2-ethylmethyl-1,1-dimethyl-1,3-propylene, 2-ethyl-1,1-dimethyl-1,4-butylene, 2,3-dimethyl-1,4-cyclohexylene, 2,3-dimethyl-1,4-cyclohexylene, 2,5-dimethyl-1,4-cyclohexylene, 2,6-dimethyl-1,4-cyclohexylene, 3,5-dimethyl-1,4-cyclohexylene, 2-methyl-1,4-cyclohexyl-1-methylene, 3-methyl-1,4-cyclohexyl-1-methylene, 4-methyl-1,4-cyclohexyl-1-methylene, 2-ethyl-1,4-cyclohexylene, 3-ethyl-1,4-cyclohexylene, 4-ethyl-1,4-cyclohexylene, 2-cyclohexylethylene, 1-cyclohexylethylene, 1-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, ethylene-1,4-phenylene-ethylene, etc.

[0054] R 31 and / or R 34 The divalent hydrocarbon group of R and / or R 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-cyclopentylene, 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-1,7-heptylene, 4-methyl-1,7-heptylene, 2-methyl-1,7-heptylene, 5-methyl-1,7-heptylene, 6-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, nonylmethylene, decylmethylene, undecylmethylene, and dodecylmethylene.

[0055] R 31 and / or R 34The divalent hydrocarbon group is more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,3-cyclopentylene, 1,6-hexamethylene, 1,4-cyclohexylene, 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.

[0056] R 31 and / or R 34 The divalent hydrocarbon group is even 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.

[0057] In formula (5), specific examples of the substituent containing a carbon-carbon double bond of B include vinyl group, allyl group, isopropenyl group, 5-norbornen-2-yl, 1-butenyl group, 1-pentenyl group, 3-cyclopentenyl, 4-cyclopentenyl, p-vinylphenyl group, p-isopropenylphenyl group, m-vinylphenyl group, m-isopropenylphenyl group, o-vinylphenyl group, o-isopropenylphenyl group, p-vinylbenzyl group, p-isopropenylbenzyl group, m-vinylbenzyl group, m-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, 2-hydroxymethylacrylic group and the like.

[0058] More specific examples of A in formula (1), or more specific examples of the substituent represented by formula (5) include structures represented by the following formula (6) and / or (7).

Chemical formula

Chemical formula

[0059] In formula (6) and / or formula (7), a plurality of R 35is, independently, a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 30 carbon atoms, 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.

[0060] In formula (7), R 36 is a hydrocarbon group having 1 to 30 carbon atoms, 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. Also, a part of the amino group may be substituted with an alkyl group having 1 to 5 carbon atoms. Also, R 36 The hydrocarbon group as preferably has 1 to 3 carbon atoms. In formula (6) and / or formula (7), s, t, and u are each independently an integer from 0 to 8.

[0061] In formula (6) and / or formula (7), the hydrocarbon group of R 35 is more preferably a larger number of carbon atoms from the viewpoint of dielectric properties or solubility in a solvent. On the other hand, if the number of carbon atoms is excessively large, a decrease in Tg, a decrease in metal peelability, or a decrease in olefinic carbon-carbon double bonds will occur. Therefore, the number of carbon atoms of R 35 is preferably about 1 to 30, more preferably about 1 to 20, and even more preferably about 1 to 12.

[0062] R 35Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentylene, 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-dimethylpentyl, 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-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, and the like.

[0063] Also, R 35Specific examples of the hydrocarbon group include 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 1,1-dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 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, 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.

[0064] R 35The hydrocarbon group is preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-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, 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, still more preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, amyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl,and benzyl.

[0065] R 36 Specific examples of the hydrocarbon group of R 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, etc. Further, specific examples of the group in which a part of these is substituted with an aryl group, an alkoxy group, an allyloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group 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-vinyletethylene, 1,1-divinyletethylene, 1,2-divinyletethylene, 1,1,2-trivinyletethylene, 1,1,2,2-tetravinyletethylene, 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, 1,1,2,2-tetrabromoethylene.

[0066] The number of OH terminals contained in the polyphenylene ether having the structure represented by the above formula (1) is preferably 0 to 3,000 μmol / g from the viewpoint of having all of low dielectric characteristics, appropriate metal peelability, low solution viscosity, sufficient Tg during curing, etc. for the modified polyphenylene ether-containing composition.

[0067] <Modified polyphenylene ether composition> The curable resin composition according to the present embodiment includes, for example, a modified polyphenylene ether composition, and the modified polyphenylene ether composition includes a polyphenylene ether having the structure represented by the above formula (1) (wherein a represents an integer of 2 to 6), and more specifically, includes a modified polyphenylene ether having the structure represented by the following formula (8).

Chemical formula

[0068] In formula (8), the a [-Y n -A] may be the same or different from each other. Here, Y is a substituted phenylene monomer unit, and Y n represents a polyphenylene ether structure in which n substituted phenylene monomer units are continuously bonded. Further, Z is based on a polyhydric phenol compound having a phenol structure to which a polyphenylene ether unit structure can be bonded. Also, in formula (8), A represents a hydrogen atom or a silyl group-containing derivative capable of bonding to a polyphenylene ether structure, and is preferably a functional group containing a silicon atom (Si) defined by the above formulas (5), (6), and (7).

[0069] The above modified polyphenylene ether composition includes a modified polyphenylene ether having the structure represented by the above formula (8), and at least one [-Y n -A] in the structure represented by the above formula (8) is [-Y nIt contains 60 mol% or more of modified or unmodified polyphenylene ether which is -H], 1 In the H-NMR measurement results, the ratio of the integrated value of the peak appearing at 7.6 to 8.3 ppm to the integrated value of the peak derived from the structure represented by the following formula (9) is 1 or less, and the number average molecular weight in terms of polystyrene is 500 to 15,000 g / mol.

[0070] The modified polyphenylene ether having the structure represented by the above formula (8) contained in the modified polyphenylene ether composition of the present embodiment may be one kind or a plurality of kinds. Further, in the structure of the above formula (8) of the modified polyphenylene ether composition of the present embodiment, one or more [-Y n -A] is [Y n -H], and all [-Y n -A] is not [Y n -H] modified polyphenylene ether, and all [-Y n -A] is [Y n -H] polyphenylene ether may be included. Here, in [-Y n -A] of the modified polyphenylene ether and [Y n -H] of the unmodified polyphenylene ether, it is preferable that Y and n are the same.

[0071] The multi-functional modified polyphenylene ether composition of the present embodiment may further contain additives such as a solvent, a polymerization catalyst, and a surfactant. The multi-functional polyphenylene ether composition of the present embodiment may be solid.

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

[0073] The above central phenol site is as described in the above item <modified polyphenylene ether>.

[0074] The above-mentioned modified polyphenylene ether has a parts structure (for example, phenol which may be substituted with R 5 etc.) bonded to the a-valent central part X by a number of a, and a [-Y n -A] of Formula (8) may be bonded to the a-valent parts structure (that is, the central phenol site represented by Formula (9)). [Chemical Formula] In Formula (9), examples of a include the same integers as in Formula (8), and preferably the same integer as in Formula (8). In the central phenol site of Formula (9), the a parts structures may be the same or different from each other.

[0075] In Formula (9), X is an arbitrary linking group of a valence and is not particularly limited. For example, it includes 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. Further, X may be a linking group excluding a single bond. Furthermore, X may be a linking group that links the a-valent parts structures to each other.

[0076] Examples of X in the above Formula (9) include an a-valent alkyl skeleton bonded to the benzene ring to which R 5 is bonded via a single bond or an ester bond, etc.; an a-valent aryl skeleton bonded to the benzene ring to which R 5 is bonded via a single bond or an ester bond, etc.; an a-valent heterocyclic skeleton bonded to the benzene ring to which R 5 is bonded via a single bond or an ester bond, etc.; etc.

[0077] Here, the alkyl skeleton is not particularly limited. For example, it includes a skeleton in which the branched ends of a chain hydrocarbon having at least a carbon number of 1 to 6 (e.g., a chain saturated hydrocarbon) are directly bonded to the benzene ring of the partial structure (it is sufficient that the benzene ring is bonded to a branched ends, and there may be branched ends to which the benzene ring is not bonded).), etc. Further, the aryl skeleton is not particularly limited. For example, a benzene ring, a mesitylene group, or a 2-hydroxy-5-methyl-1,3-phenylene group is bonded to the benzene ring to which R 5 is bonded via a single bond or an alkyl chain. Examples include skeletons and the like. Furthermore, the heterocyclic skeleton is not particularly limited. For example, a skeleton in which a triazine ring is bonded to the benzene ring to which R 5 is bonded via a single bond or an alkyl chain, etc. are included.

[0078] The plurality of R 5 in formula (9) are each independently either a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and k is each independently an integer from 1 to 4.

[0079] As R 5 in the above formula (9), examples include linear alkyl groups having 1 to 8 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and a group having the partial structure of the following formula (10), etc. At least one of R 5 may be the partial structure of the following formula (10).

Chemical formula

[0080] The above formula (10) is preferably a group containing secondary and / or tertiary carbon, such as an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, a 2-dimethylpropyl group, or a structure having a phenyl group at the end thereof, etc. More preferably, it is a tert-butyl group.

[0081] Taking the carbon atom of the benzene ring to which -O- of formula (9) is bonded as the 1-position, R having a partial structure represented by formula (10) is bonded to one of the carbon atoms at the 2-position or 6-position, and a hydrogen atom, a methyl group or an ethyl group is bonded to the other carbon atom at the 2-position or 6-position. A hydrocarbon group or a partial structure represented by the above formula (10) may be bonded to the carbon atoms at the 2-position and 6-position of the benzene ring to which -O- of formula (9) is bonded. In the benzene ring in the above formula (9), [Y of the above formula (1) or (8) may be bonded to the carbon atoms other than the 2-position and 6-position via the central portion X and an oxygen atom. 5 -A] may be bonded, and it is preferable that [Y of the above formula (8) is bonded to the 1-position via an oxygen atom. n -A] is bonded and the central portion X is bonded to the 4-position. n When a = 2 in formula (8), Z may be, for example, a structure represented by the following formula (11).

[0082]

Chemical formula

[0083] ​In formula (8), when a ≥ 3, Z may be based on or derived from a polyhydric phenol compound having the structure represented by the above formula (9). Specific polyhydric phenols include the compounds defined for the structure represented by the above formula (2).

[0084] In the above formula (8), each Y is independently a divalent linking group (a phenolic unit having a substituent) having a structure derived from a monohydric phenol compound represented by the following formula (12), n represents the number of repetitions of Y, and each is independently an integer of 0 to 200, and at least one n is an integer of 1 or more.

[0085] The above modified polyphenylene ether and / or modified polyphenylene ether composition can be obtained, for example, by copolymerizing a monohydric phenol compound represented by the following formula (12) and an a-valent phenol compound (central phenol) corresponding to the central part X in the structure represented by the above formula (9) and performing a modification reaction.

Chemical formula

[0086] Specific examples of the monohydric phenol compound represented by the above formula (12) include the monohydric phenol compounds defined for the structure represented by the above formula (4).

[0087] Examples of the dihydric phenols represented by the above formula (11) are listed below. Examples of the dihydric phenols include, but are not limited to, (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, etc.

[0088] The number of phenolic hydroxyl groups in the polyhydric phenol compound is not particularly limited as long as it is 2 or more. However, when the number of polyphenylene ether terminals increases, the change in molecular weight during polymerization may become large. Therefore, it is preferably 2 to 6, more preferably 2 to 4.

[0089] The modified polyphenylene ether composition of this 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).

Chemical formula

[0090] In the modified polyphenylene ether and / or modified polyphenylene ether composition of this embodiment (hereinafter referred to as modified polyphenylene ether (composition)), 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. Patent No. 3,496,236 to Cooper et al. and U.S. Patent No. 5,880,221 to Liska et al.

[0091] The modified polyphenylene ether (composition) of this embodiment is 1 In the H-NMR measurement result, the modified polyphenylene ether having the structure of the above formula (1), one or more [-Y n -A] in the structure of the above formula (1) is [Y n -H], and all [-Y n -A] is not [Y n -H], and all [-Y n -A] in the structure of the above formula (1) is [Y n -H], the ratio of the integrated value of the peak derived from the peroxide appearing in the region of 7.6 to 8.3 ppm to the integrated value of the peak derived from the central phenol site represented by the above formula (2) contained in the polyphenylene ether is 1 or less, preferably 0.8 or less, and more preferably 0.5 or less. That the integrated value of the peak derived from the peroxide is 1 or less with respect to the integrated value of the peak derived from the central phenol site means that the modified polyphenylene ether composition does not contain a peroxide adduct as a by-product and that the purity of the target polyfunctional modified polyphenylene ether and the like is high. As a result, the glass transition temperature (Tg) of the modified polyphenylene ether composition can be increased. The above ratio can be measured by the method described in the examples below.

[0092] The number average molecular weight (Mn) of the modified polyphenylene ether (composition) in the present 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. When the number average molecular weight (Mn) is within the above range, the fluidity when dissolved in a solvent for preparing a varnish in the process of applying to a substrate material is further improved, and the workability during substrate material application can be ensured. The number average molecular weight can be measured by the method described in the examples below.

[0093] The number of A substituents (referring to A defined in formula (1), the same shall apply hereinafter) contained in the polyfunctional modified polyphenylene ether (composition) in the present embodiment is not particularly limited, but the case where A = hydrogen atom (H) is excluded from the number of A substituents. Among them, it is preferable that the composition contains 700 to 3,000 μmol / g of the number of A substituents, and more preferably 700 to 2,000 μmol / g. When the number of A substituents in the composition is 700 μmol / g or more, the crosslinking 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 the varnish obtained by dissolving the polyphenylene ether composition in a solvent can be lowered, and the workability tends to be good during substrate material application.

[0094] As the evaluation method for the number of A substituents, known methods such as titration method, spectroscopic method, quantitative NMR method, etc. can be used according to the type of functional group. For example, in the quantitative NMR method, 1 When using 1H-NMR, a standard sample with a known structure and a polyfunctional polyphenylene ether composition are coexisted and measured. A polyfunctional polyphenylene ether composition with a known weight and a standard sample are dissolved in a deuterated solvent and 1The H-NMR is measured, and the number of A substituents can be determined by calculation from the ratio of the integral values of the peaks derived from the A substituent and 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. The standard sample is dissolved in a deuterated solvent, does not react with the polyfunctional polyphenylene ether composition, and 1 is not particularly limited as long as the peak in the H-NMR does not interfere with the peak derived from the polyfunctional polyphenylene ether composition. For the specific evaluation method of the number of A substituents, reference can be made to the description in the examples.

[0095] From the viewpoint of having all of low dielectric properties, appropriate metal peelability, low solution viscosity, sufficient Tg during curing, etc., the modified polyphenylene ether-containing composition according to this embodiment preferably contains 0.5 to 95% by mass of the modified polyphenylene ether having the structure represented by the above formula (8).

[0096] <Method for Producing Polyfunctional Modified Polyphenylene Ether (Composition)> The method for producing the polyfunctional modified polyphenylene ether (composition) of this embodiment can be produced, for example, by synthesizing a polyfunctional modified polyphenylene ether (composition) represented by the following formula (1)' having a hydroxyl group at the molecular terminal (hereinafter also referred to as an unmodified polyfunctional polyphenylene ether (composition)) by a polymerization method, and introducing an A substituent in the formula (1) to its terminal, that is, by modification.

Chemical Formula

[0097] (Polymerization Step) Here, in the method for producing an unmodified polyfunctional polyphenylene ether (composition), in the polymerization step, it is preferable to use an aromatic solvent that is a good solvent for the unmodified polyfunctional polyphenylene ether (composition) as the polymerization solvent.

[0098] Here, a good solvent for the 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, styrene, etc., or halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, etc.; nitro compounds such as nitrobenzene; and the like.

[0099] As the polymerization catalyst used in this embodiment, generally known catalyst systems that can be used for the production of polyphenylene ether can be employed. As generally known catalyst systems, those composed of a transition metal ion having redox ability and an amine compound capable of forming a complex with the transition metal ion are known. For example, a catalyst system composed of a copper compound and an amine compound, a catalyst system composed of a manganese compound and an amine compound, a catalyst system composed of a cobalt compound and an amine compound, and the like. Since the polymerization reaction proceeds efficiently under slightly alkaline conditions, a slight amount of alkali or a further amine compound may be added here.

[0100] The polymerization catalyst preferably used in this embodiment is a catalyst composed of a copper compound, a halogen compound, and an amine compound as the constituent components of the catalyst, and more preferably, a catalyst containing a diamine compound represented by the general formula (DA1) as the amine compound.

Chemical formula

[0101] Examples of the copper compounds of the catalyst components described herein are listed. As suitable copper compounds, cuprous compounds, cupric compounds, or mixtures thereof can be used. Examples of cupric compounds include, for example, cupric chloride, cupric bromide, cupric sulfate, cupric nitrate, etc. Examples of cuprous compounds include, for example, cuprous chloride, cuprous bromide, cuprous sulfate, cuprous nitrate, etc. Particularly preferred metal compounds among these are cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide. Also, these copper salts may be synthesized from the corresponding halogen or acid with oxides (e.g., cuprous oxide), carbonates, hydroxides, etc. at the time of use. A frequently used method is the method of mixing cuprous oxide exemplified above with hydrogen halide (or a solution of hydrogen halide).

[0102] Examples of halogen compounds include, for example, 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, tetraethylammonium iodide, etc. Also, these can be used as an aqueous solution or a solution using a suitable solvent. These halogen compounds can be used alone as a component or in combination of two or more. Preferred halogen compounds are an aqueous solution of hydrogen chloride or an aqueous solution of hydrogen bromide.

[0103] The usage amounts of these compounds are not particularly limited, but it is preferably 2 times or more and 20 times or less as halogen atoms relative to the molar amount of copper atoms, and the preferred usage amount of copper atoms is in the range of 0.02 mol to 0.6 mol relative to 100 mol of the phenol compound added to the polymerization reaction.

[0104] Next, examples of diamine compounds as catalyst components are listed. 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, N-n-propylethylenediamine, N,N’-n-propylethylenediamine, N-i-propylethylenediamine, N,N’-i-propylethylenediamine, N-n-butylethylenediamine, N,N’-n-butylethylenediamine, N-i-butylethylenediamine, N,N’-i-butylethylenediamine, N-t-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, N,N,N’,N’-tetramethyl-1,5-diaminopentane, and the like can be mentioned. The diamine compound preferred 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 a range of 0.01 mol to 10 mol is preferred with respect to 100 mol of the phenol compound added to the polymerization reaction.

[0105] In this embodiment, as a constituent component of the polymerization catalyst, a primary amine and a secondary monoamine can be included. 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, diphenylamine, and the like.

[0106] As a constituent component of the polymerization catalyst in this embodiment, a tertiary monoamine compound can also be included. The tertiary monoamine compound is an aliphatic tertiary amine including an alicyclic tertiary amine. For example, trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, dimethylethylamine, dimethylpropylamine, allyldiethylamine, dimethyl-n-butylamine, diethylisopropylamine, N-methylcyclohexylamine, and the like can be mentioned. These tertiary monoamines can be used alone or in combination of two or more. Although their usage amounts are not particularly limited, a range of 15 moles or less with respect to 100 moles of the phenol compound added to the polymerization reaction is preferable.

[0107] In this embodiment, there is no limitation whatsoever on adding a surfactant which has conventionally been known to have an effect of improving polymerization activity. Examples of such a surfactant include trioctylmethylammonium chloride known under the trade name of Aliquat 336 or Capriquat. The amount of its use is preferably in a range not exceeding 0.1% by mass with respect to 100% by mass of the total amount of the polymerization reaction mixture.

[0108] As the oxygen-containing gas in the polymerization step of this embodiment, in addition to pure oxygen, those obtained by mixing oxygen and an inert gas such as nitrogen at an arbitrary ratio, air, and further those obtained by mixing air and an inert gas such as nitrogen at an arbitrary ratio can be used. The pressure inside the system during the polymerization reaction is sufficient at normal pressure, but reduced pressure or increased pressure can also be used as necessary.

[0109] The temperature of the polymerization is not particularly limited, but if it is too low, the reaction hardly proceeds, and if it is too high, there is a risk of a decrease in reaction selectivity or generation of high molecular weight components. Therefore, it is preferably in the range of 0°C to 60°C, more preferably 10°C to 50°C.

[0110] In the method for producing the unmodified polyfunctional polyphenylene ether (composition) of this embodiment, it is preferable to polymerize in a solution state (also referred to as "solution polymerization" in this specification) during the polymerization of the polyphenylene ether. By producing the unmodified polyfunctional polyphenylene ether (composition) by solution polymerization, even when using a central phenol having a bulky structure, 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 ratio of by-products generated by peroxides can be reduced, and a polyfunctional modified polyphenylene ether containing the structure of the above formula (1) of the target product can be produced with high purity.

[0111] (Copper extraction and by-product removal step) In this embodiment, there is no particular limitation on the post-treatment method after the polymerization reaction. 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 solution to deactivate the catalyst. In addition, a method for removing by-products of dihydric phenol formed by the polymerization of polyphenylene ether can also be carried out 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 is also possible to add a necessary amount of a known reducing agent to the system. Examples of known reducing agents include hydroquinone and sodium dithionite.

[0112] (Liquid-liquid separation step) In the method for producing the unmodified polyfunctional polyphenylene ether (composition) of this embodiment, water may be added to extract the compound that deactivates the copper catalyst, and after performing liquid-liquid separation into an organic phase and an aqueous phase, the aqueous phase is removed to remove the copper catalyst from the base. This liquid-liquid separation step is not particularly limited, and examples include methods such as static separation and separation using a centrifuge. In order to promote the above liquid-liquid separation, a known surfactant or the like may be used.

[0113] (Concentration and drying step) Subsequently, in the method for producing the polyfunctional modified polyphenylene ether (composition) of this embodiment, the organic phase containing the above unmodified polyfunctional polyphenylene ether (composition) after liquid-liquid separation may be concentrated and dried by volatilizing the solvent. 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, this step may be omitted.

[0114] The method for volatilizing the solvent contained in the above organic phase is not particularly limited. For example, the organic phase can be transferred to a concentration tank at a high temperature (such as the drying temperature described later), and the solvent can be distilled off for concentration, or a device such as a rotary evaporator can be used to distill off toluene for concentration.

[0115] As the temperature of the drying treatment in the drying process, at least 60 °C or higher is preferable, 80 °C or higher is more preferable, 120 °C or higher is further preferable, and 140 °C or higher is most preferable. When drying the polyfunctional polyphenylene ether composition at a temperature of 60 °C or higher, the content of high-boiling volatile components in the polyphenylene ether powder can be efficiently reduced.

[0116] In order to obtain an unmodified polyfunctional polyphenylene ether (composition) with high efficiency, methods such as increasing the drying temperature, increasing the degree of vacuum in the drying atmosphere, and performing stirring during drying are effective. In particular, the method of increasing the drying temperature is preferable from the viewpoint of production efficiency. In the drying process, it is preferable to use a dryer equipped with a mixing function. Examples of the mixing function include stirrer-type and rolling-type dryers. This can increase the throughput and maintain high productivity.

[0117] 〔Modification reaction step〕 In the present embodiment, the method of introducing the substituent of A in formula (1) or (8) (for example, the functional group in formula (5) above) to the terminal of the obtained unmodified polyphenylene ether can be by a coupling method with a functional group such as a hydroxyl group using a halogenated silyl compound, an aminosilyl compound, or an alkoxysilyl compound. As the halogenated silyl compound, chlorides, bromides, etc. are generally used, but other halogens may also be used.

[0118] Specific examples of the halogenated silyl compound include methylvinyldichlorosilane, divinyldichlorosilane, allylmethyldichlorosilane, diallyldichlorosilane, trichlorosilyl-2-norbornene, 6-methyldichlorosilyl-2-norbornene, 6-dimethyldichlorosilyl-2-norbornene, phenylvinyldichlorosilane, 3-methacryloxypropyldichloromethylsilane, 3-chloropropylmethyldivinylsilane, allylphenyldichlorosilane, diphenylvinylchlorosilane, dimethylvinylchlorosilane, chloromethyldimethylvinylsilane, allyldimethylchlorosilane, methylphenylvinylchlorosilane, 5-norbornen-2-yl(ethyl)chlorodimethylsilane, methylvinyldibromosilane, 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 5-norbornen-2-ylchlorodibromosilane, and the like.

[0119] Examples of the aminosilyl compound 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), diphenylvinylsilyl(1,2,4-triazole), dimethylvinylsilyl(1,2,4-triazole), allyldimethylsilyl(1,2,4-triazole), methylphenylvinylsilyl(1,2,4-triazole), 5-norbornene-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, allylphenylsilyl imidazole, diphenylvinylsilyl imidazole, dimethylvinylsilyl imidazole, allyldimethylsilyl imidazole, methylphenylvinylsilyl imidazole, 5-norbornene-2-yl(ethyl)dimethylsilyl imidazole, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, bis(dimethylamino)methylvinylsilane, and the like.

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

[0121] The reaction for introducing the above compound to the end of the unmodified polyphenylene ether is generally a direct reaction with a hydroxyl group, but a reaction with an alkali metal salt of the hydroxyl group is also acceptable. Also, after reacting the silyl halide compound with imidazole, triazole, pyrrolidine, piperidines to form an amine compound, it may be reacted with a hydroxyl group. In the direct reaction between the silyl halide compound and the hydroxyl group, an acid such as hydrogen halide is generated, so a weak base such as an amine may coexist for the purpose of trapping the acid.

[0122] In order to prevent side reactions, the amines to coexist are preferably tertiary amines. Specific examples of the amines to coexist 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, dimethylaminopyridine, and the like.

[0123] The amines to be coexisted are preferably trimethylamine, diethylmethylamine, triethylamine, tri-n-propylamine, triisopropylamine, di-n-butylmethylamine, di-n-butylethylamine, di-n-propylmethylamine, di-n-propylethylamine, diisopropylethylamine, tri-n-butylamine, tri-t-butylamine, triisobutylamine, tetramethylethylenediamine, tetraethylethylenediamine, tetramethylmethylenediamine, tetraethylmethylenediamine, pyridine, dimethylaniline, and dimethylaminopyridine, and more preferably triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-t-butylamine, triisobutylamine, tetramethylethylenediamine, tetramethylmethylenediamine, tetraethylmethylenediamine, pyridine, dimethylaniline, and dimethylaminopyridine.

[0124] In addition, water not only causes unfavorable side reactions during the reaction but also causes hydrolysis reactions after the reaction, leading to a decrease in the reaction yield. Therefore, it is preferable to remove the water in the reaction solvent and amines in advance. The preferable amount of water in the reaction system is preferably less than 200 ppm, more preferably less than 100 ppm.

[0125] To prevent side reactions or the generation of by-products during purification, the excess amines may be removed from the system after the reaction. For low-boiling amines, the amines can be removed by distillation or the like. The residual amine amount before the purification step is less than 10,000 ppm.

[0126] As a preferred embodiment for achieving a high modification rate in the modification reaction step, the amount of the silyl halide compound used in the modification reaction is 1.00 times mole or more and less than 4 times mole, preferably 1.05 times mole to 3 times mole, more preferably 1.1 times mole to 2.5 times mole, based on 1 mole of the hydroxyl group in the polymer. If the amount of the silyl halide compound used is less than 1.00 times mole based on 1 mole of the hydroxyl group, a sufficient modification rate cannot be obtained. On the other hand, if it is 4 times mole or more, undesirable by-products may be generated during purification after the reaction, and a decrease in the purification yield may be observed. The amount of the amine coexisted for the purpose of trapping an acid during the reaction is preferably 1.00 times mole or more and less than 6 times mole, more preferably 1.05 times mole to 4 times mole, still more preferably 1.1 times mole to 4 times mole, based on 1 mole of the hydroxyl group. If the amount of the amine used is less than 1.00 times mole based on 1 mole of the hydroxyl group, a sufficient modification rate cannot be obtained. And if it is 6 times mole or more, the effect on the conversion rate does not change, while a large amount of amine removal is required after the reaction, which is not preferable.

[0127] The modification reaction temperature is not particularly limited, but it is preferably a temperature condition under which the unmodified polyphenylene ether does not precipitate from the unmodified polyphenylene ether solution composed of the unmodified polyphenylene ether and its good solvent. Also, conditions combining a plurality of temperature conditions may be used.

[0128] After the modification reaction, if there is an excess of the silyl halide compound, it may be reacted with alcohols such as methanol or ethanol, and treatments such as deactivation may be performed.

[0129] Also, after the modification reaction, in order to remove by-products such as amine salts, etc., filtration, washing the target product with water, acidic, or alkaline aqueous solutions may be performed, or the polymer solution may be dropped into a poor solvent such as alcohols, and the target product may be recovered by reprecipitation. Also, after washing the polymer solution, the solvent may be distilled off under reduced pressure to recover the predetermined polymer.

[0130] The manufacturing method of the multifunctional modified polyphenylene ether (composition) of the present embodiment is not limited to the manufacturing method of the multifunctional modified polyphenylene ether composition of the present embodiment described above, and the order or number of times of the polymerization step, copper extraction and by-product removal step, liquid-liquid separation step, concentration / drying step, etc. described above may be appropriately adjusted.

[0131] <(B) Styrenic elastomer> The resin composition of the present embodiment contains (B) a styrenic elastomer as an essential component. In the present embodiment, the styrenic elastomer refers to a copolymer of styrene substituted with a hydrocarbon or chlorine atom having 1 to 4 carbon atoms or unsubstituted styrene and an olefinic alkene compound, and its hydrogenated product, and may be a block copolymer or a random copolymer.

[0132] Specifically, styrenic elastomers such as styrene-butadiene copolymer (SBR), styrene-butadiene-styrene copolymer (SBS), hydrogenated styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer (SIS), hydrogenated styrene-isoprene-styrene copolymer, and hydrogenated styrene (butadiene / isoprene) styrene copolymer can be mentioned. These styrenic elastomers may be used alone or in combination of two or more. Among these, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene copolymer (SBS), and hydrogenated styrene-butadiene-styrene copolymer are preferable.

[0133] <Block copolymer / Random copolymer> The (B) styrenic elastomer of the present embodiment can be synthesized, for example, by polymerizing a vinyl aromatic compound and a conjugated diene compound as monomers. The synthesized styrenic elastomer includes a "block copolymer type styrenic elastomer" composed of a block mainly composed of a vinyl aromatic compound (block (A)) and a block mainly composed of a conjugated diene (block (B)), a "random copolymer type styrenic elastomer" having a structure in which a vinyl aromatic compound and a conjugated diene compound are randomly copolymerized, and a "hybrid type styrenic elastomer" composed of both a block copolymer structure and a random copolymer structure, etc.

[0134] <Number average molecular weight of styrenic elastomer> The preferred range of the number average molecular weight of the (B) styrenic elastomer of the present embodiment varies depending on the double bond content.

[0135] When the double bond content of the styrenic elastomer is less than 20%, on the one hand, there is an advantage that the higher the number average molecular weight, the higher the elastic modulus of the cured product obtained by curing the resin composition tends to be. On the other hand, when the number average molecular weight increases, it may take a long time to dissolve the resin composition in a solvent. Also, while there is an advantage that the lower the number average molecular weight, the higher the fluidity of the resin composition, the elastic modulus of the cured product obtained by curing the resin composition may be low.

[0136] From such a viewpoint, the number average molecular weight of the styrenic elastomer having a double bond content of less than 20% is preferably 500 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, still more preferably 10,000 or more and 100,000 or less, even more preferably 30,000 or more and 60,000 or less, and particularly preferably 40,000 or more and 50,000 or less.

[0137] In addition, when the double bond content of the styrene-based elastomer is 20% or more, since the double bonds in the elastomer greatly contribute to the crosslinking reaction during the curing reaction, as the number average molecular weight increases, the elastic modulus of the cured product increases. On the other hand, the viscosity of the resin composition may increase rapidly and the moldability may decrease. As the number average molecular weight decreases, the fluidity of the resin composition increases, but the cured product may become brittle.

[0138] From such a viewpoint, the number average molecular weight of the styrene-based elastomer having a double bond content of 20% or more is preferably 500 or more and 300,000 or less, more preferably 1,000 or more and less than 10,000, still more preferably 2,000 or more and 8,000 or less, and particularly preferably 3,000 or more and 5,000 or less.

[0139] In addition, the number average molecular weight of the random polymerization type styrene-based elastomer is preferably 500 or more and 300,000 or less, more preferably 1,000 or more and less than 10,000, still more preferably 2,000 or more and 8,000 or less, and particularly preferably 3,000 or more and 5,000 or less.

[0140] On the other hand, the number average molecular weight of the block copolymer type styrene-based elastomer is preferably 500 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, still more preferably 10,000 or more and 100,000 or less, particularly preferably 30,000 or more and 60,000 or less, and most preferably 40,000 or more and 50,000 or less.

[0141] <Double bond content of styrene-based elastomer> The preferred range of the double bond content of the (B) styrene-based elastomer of the present embodiment differs depending on the number average molecular weight.

[0142] When the number average molecular weight of the styrene-based thermoelastic elastomer is less than 10,000, as the double bond content rate of the styrene-based elastomer increases, the fluidity of the resin composition increases, but a brittle cured product may be formed when cured.

[0143] From such a perspective, in the case of a styrene-based elastomer having a number average molecular weight of less than 10,000, the double bond content is preferably 10% or more and 90% or less, more preferably 20% or more and 80% or less, and even more preferably 50% or more and 70% or less.

[0144] When the number average molecular weight of the styrene-based elastomer is 10,000 or more, as the double bond content of the styrene-based elastomer increases, the elastic modulus of the cured resin increases, while it may take a long time to dissolve the resin composition in a solvent.

[0145] From such a perspective, in the case of a styrene-based elastomer having a number average molecular weight of 10,000 or more, the double bond content is preferably 90% or less, more preferably 50% or less, further preferably 10% or less, and particularly preferably 1% or less.

[0146] <Styrene content of the styrene-based elastomer> (B) The styrene content of the styrene-based elastomer is not particularly limited. However, the higher the styrene content, the better the compatibility with the terminal-modified polyphenylene ether of component (A) in the resin composition, and the tendency for the uniformity of the resin composition to increase. The lower the styrene content, the tendency for the dielectric tangent of the cured product obtained by curing to decrease.

[0147] From such a perspective, in the case of a styrene-based elastomer having a number average molecular weight of less than 10,000, the styrene content is preferably 1% or more and 80% or less, more preferably 10% or more and 70% or less, further preferably 15% or more and 60% or less, particularly preferably 20% or more and 50% or less, and most preferably 25% or more and 40% or less.

[0148] Also, in the case of a styrene-based elastomer having a number average molecular weight of 10,000 or more, the styrene content is preferably 1% or more and 80% or less, more preferably 10% or more and 70% or less, further preferably 20% or more and 50% or less, and particularly preferably 30% or more and 40% or less.

[0149] <Mixing ratio of component (A) and component (B)> In the curable resin composition of the present embodiment, component (A) and component (B) have good compatibility and tend to form a uniform composition at any stage of the solution state containing the solvent before curing and the resin mixing state not containing the solution. On the other hand, during the curing reaction stage, as the curing reaction progresses, component (A) and component (B) undergo phase separation (reaction-induced spinodal decomposition), and a phase mainly composed of component (A) with a high Tg and a low linear expansion coefficient forms a continuous phase, while a phase mainly composed of component (B) with a low Df forms a discontinuous phase. Therefore, finally, a cured product with a high Tg, a low linear expansion coefficient, and a low Df tends to be formed.

[0150] Therefore, in the present invention, the higher the ratio of component (A), the higher the heat resistance indicated by Tg and the lower the linear expansion coefficient tend to be, and the higher the mixing ratio of component (B), the lower the dielectric loss tangent (Df) tends to be.

[0151] The present invention is not limited by the ratio of component (A) and component (B), but from the viewpoint of achieving a good balance between heat resistance and dielectric loss tangent, the ratio of component (A) and component (B) is preferably in the range of 99:1 to 10:90, more preferably in the range of 98:2 to 60:40, still more preferably in the range of 95:5 to 80:20, and particularly preferably in the range of 90:10 to 85:15.

[0152] <(C) Initiator> The curable resin composition of this embodiment may contain an initiator. The initiator is not particularly limited, but examples include organic peroxides. Those having a one-minute half-life temperature in the range of 155°C to 180°C are preferred from the viewpoints of the stability and reactivity of the composition during storage. For example, t-hexyl peroxyisopropyl monocarbonate (one-minute half-life temperature, hereinafter the same: 155.0°C), t-butyl peroxy-3,5,5-trimethylhexanoate (166.0°C), t-butyl peroxy laurate (159.4°C), t-butyl peroxyisopropyl monocarbonate (158.8°C), t-butyl peroxy 2-ethylhexyl monocarbonate (161.4°C), t-hexyl peroxybenzoate (160.3°C), 2,5-dimethyl-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-butyl cumyl peroxide (173.3°C) etc. can be mentioned.

[0153] Among these, as the organic peroxide, 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-butyl cumyl peroxide is preferred.

[0154] The blending amount of component (C) is preferably 0.001 to 10 phr based on the total amount of components (A) and (B). When the blending amount of component (C) is 0.001 phr or more, the effect of component (C) can be fully exerted, and by promoting the progress of the curing reaction, the Tg of the cured product tends to be higher. Also, when it is 10 phr or less, the residue of the initiator and its decomposition products in the cured product can be reduced, and the tendency to prevent the dielectric tangent of the cured product from increasing can be achieved. From such a viewpoint, the more preferable blending amount of component (C) is 0.1 to 5 phr, and even more preferably 0.5 to 2 phr.

[0155] <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 property to glass fibers when impregnating glass fibers to produce a laminate.

[0156] Examples of such organic solvents include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), ethyl acetate, etc. From the viewpoint of having a low boiling point and being easily removed by evaporation from the resin composition, toluene and methyl ethyl ketone are particularly preferable.

[0157] <Crosslinking aid> In the curable resin composition of the present embodiment, a crosslinking aid having a low molecular weight and capable of forming a crosslinked structure with at least one of a modified polyphenylene ether and a styrene-based elastomer can be blended within a range that does not impair the purpose. By adding the crosslinking aid, the solution viscosity and melt viscosity of the curable resin composition tend to be reduced.

[0158] <Other components> Additives such as a flame retardant, an elastomer, and a filler can be blended in the curable resin composition of the present embodiment within a range that does not impair the purpose.

Examples

[0159] 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.

[0160] First, the measurement methods and evaluation criteria for each physical property and evaluation will be described below.

[0161] (1) Proportion of polyphenylene ether present Here, the proportion of polyphenylene ether present is that of a modified polyphenylene ether having the structure of formula (1), a modified polyphenylene ether in which one or more [-Y n -A] is [-Y n -H], and not all [-Y n -A] is [-Yn-H], and the proportion of polyphenylene ether (main component polyphenylene ether) in which all [-Y n -A] is [-Y n -H] in the structure of formula (1). (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 tetramethylsilane was used as an internal standard. 1 1H-NMR measurement (JEOL 500 MHz) was performed. (1-2) From the peak position due to the central phenol site, the peaks of the polyhydric phenols contained in the product were identified. (1-3) The central phenol unit of the main component polyphenylene ether represented by formula (2), and formula (14):

Chemical formula

Chemical formula

Number

[0162] Note that the peak resulting from the central phenol site of the main component polyphenylene ether represented by formula (2) and the H of the terminal phenol of the by-product represented by formula (14) used in the examples and comparative examples 1 , and R 22 ', the peak resulting from R 22 ", and the peak resulting from the R within the central phenol of the by-product represented by formula (15) appear in the following regions. 1,1,3-Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane (1H): 2.8 to 3.2 ppm 1,1-Bis(2-methyl-4-hydroxy-5-t-butylphenyl)butane (1H): 4.0 to 4.3 ppm 2,2-Bis(3,5-dimethyl-4-hydroxyphenyl)propane (4H): 6.95 to 7.0 ppm Terminal phenoxy unit (3H) of the by-product represented by formula (14): 7.05 to 7.1 ppm Diphenyl (4H) of the by-product represented by formula (15): 7.34 to 7.4 ppm

[0163] (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 resulting from the structure of formula (2) (the presence ratio of the peroxide peak) The above 1In the \(^1H-NMR\) measurement, the integrated value of the peak area attributed to the central phenol site of the main component polyphenylene ether represented by formula (2) was defined as \(E\), the integrated value \(G\) of the impurity peak (i.e., peroxide peak) area derived from peroxide appearing in the region of 7.6 to 8.3 ppm was calculated, and the proportion of the peroxide peak was analyzed by substituting it into the following mathematical formula (17).

Number

[0164] (3) Number-average molecular weight (\(M_n\)) As the measuring device, Gel Permeation Chromatography System 21 manufactured by Showa Denko K.K. was used. A calibration curve was prepared using standard polystyrene and ethylbenzene, and using this calibration curve, the number-average molecular weight (\(M_n\)) of the obtained modified polyphenylene ether composition was measured.

[0165] As the standard polystyrene, 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 were used.

[0166] As the column, two K-805L columns manufactured by Showa Denko K.K. connected in series were used. As the solvent, chloroform was used, the flow rate of the solvent was 1.0 mL / min, and the measurement was carried out at a column temperature of 40°C. As the measurement sample, a 1 g / L chloroform solution of the modified polyphenylene ether composition was prepared and used. The wavelength of UV at the detection part was 254 nm for standard polystyrene and 283 nm for polyphenylene ether.

[0167] Based on the above measurement data, the number-average molecular weight (\(M_n\)) (g / mol) was calculated from the ratio of the peak areas based on the curve showing the molecular weight distribution obtained by GPC.

[0168] (4) Glass transition temperature (\(T_g\)) The glass transition temperature of the modified polyphenylene ether composition was measured using a differential scanning calorimeter DSC (Pyris 1 manufactured by PerkinElmer). After heating from room temperature to 200°C at a heating rate of 20°C per minute in a nitrogen atmosphere, the temperature was decreased to 50°C at 20°C per minute, and then the glass transition temperature was measured at a heating rate of 20°C per minute.

[0169] (5) The number of A substituents contained in the composition A specified amount of the modified polyphenylene ether composition and 1,3,5-trimethoxybenzene standard (manufactured by FUJIFILM Wako Pure Chemical Corporation, molecular weight 168.19) as an internal standard sample were taken, dissolved in deuterated chloroform containing trimethylsilane, 1 and 1H-NMR measurement (500 MHz, manufactured by JEOL) was performed.

[0170] Next, the integration value of the peak of the protons derived from the methoxy group of 1,3,5-trimethoxybenzene (3.7 - 3.8 ppm: 9H) and the integration value of the peak that appears on the high magnetic field side among the protons at the C=C bond terminal of the methacryl group (5.5 - 5.9 ppm: 1H) were determined. From these integration values and the weights of the polyphenylene ether composition and 1,3,5-trimethoxybenzene used in the measurement, the number of methacryl groups per gram of the modified polyphenylene ether composition (unit: μmol / g) was calculated.

[0171] (6) Viscosity of the toluene solution of the modified polyphenylene ether composition (liquid viscosity) 2 g of the modified polyphenylene ether composition and 3 g of toluene were weighed. Using a stir bar and a magnetic stirrer, these were stirred for 1 hour and completely dissolved until the solution became transparent to prepare a 40 wt% toluene solution. For this solution, the liquid viscosity was measured using a B-type viscometer under the conditions of 25°C and 30 rpm.

[0172] (7) Modification 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 Japanese Patent Publication No. 2004 - 502849 (Patent Document 3).

[0173] (8) Preparation of the cured product Under the following conditions, a film-shaped test piece with a thickness of 0.1 to 0.3 mm was produced by the pressing method. Polymers, styrene-based elastomers, etc. were added to toluene and uniformly dissolved at room temperature overnight, and then Nippon Oil's Perbutyl P was added. This was applied to the shiny surface of the copper foil and dried at 120 °C for 10 minutes, and the obtained solid resin composition was pulverized in an agate mortar. A 100-μm-thick Teflon (registered trademark) sheet was cut into a 60 × 60 mm shape, the above Teflon (registered trademark) sheet was placed on the shiny surface of the copper foil, and about 1.5 times the theoretical value (specific gravity 1, 6 × 6 × 0.01 × 1.5 = 0.54 g) of the above solid resin composition was added to the cavity part, covered with the shiny surface of the copper foil, and pressed and cured under a pressing pressure of 40 (kg / cm 2 ) under constant vacuum conditions under the following temperature conditions. Room temperature to 50 °C, 4 °C / min, 50 °C Hold for 1 minute 50 °C to 160 °C, 4 °C / min, 160 °C Hold for 3 minutes 160 °C to 220 °C, 4 °C / min, 220 °C Hold time: 60 minutes

[0174] (9) Tg measurement of the cured product Using Hitachi High-Technologies Corporation (DMS6100), the glass transition temperature (Tg) of the cured product was measured by DMA under the following conditions. A test piece was cut out to a size that allows qualified measurement in the entire temperature range of the DMA apparatus, and a dynamic viscoelasticity test was performed. Test piece: strip, measurement mode: tensile mode Test start temperature: room temperature Temperature increase rate: 4 °C / min Test maximum temperature: 300 °C Maximum temperature holding time: 5 minutes Measurement frequency: 1 Hz Analysis: The tanδ peak was taken as Tg. Furthermore, the storage elastic modulus at a temperature 30 °C higher than the tanδ peak was read and used for the calculation of the crosslink density.

[0175] (10) Dielectric tangent measurement of the cured product The cured product with a thickness of 0.1 to 0.3 mm was cut into a shape of 50×50 mm, and the dielectric loss tangent at 10 GHz was measured using a network analyzer (PNA N5227B, Keysight Technologies, cavity resonator method, split cylinder resonator).

[0176] (11) Measurement of coefficient of linear expansion The coefficient of linear expansion was measured and determined under the following conditions using a sample cut from the test piece for dielectric loss tangent measurement with TMA7100 of Hitachi High-Technologies Corporation. Measurement mode: Tensile Size: Width 2 mm, length 10 mm, thickness 0.2 mm Test start temperature: -50°C Heating rate: 10°C / min Test maximum temperature: 250°C Holding time at maximum temperature: 5 minutes

[0177] (12) Number average molecular weight of styrene-based elastomer Under the following conditions, it was measured by gel permeation chromatography (GPC), and the weight average molecular weight was determined from the calibration curve in terms of PS (polystyrene) at the obtained peak. Measuring device: GPC HLC-8220 (manufactured by Tosoh Corporation, product name) Column: TAKgel GMHXL SuperH5000: 1 piece, SuperH4000: 2 pieces (manufactured by Tosoh Corporation, product name) Solvent: Tetrahydrofuran Temperature: 40°C Calibration curve sample: Commercially available (manufactured by Tosoh Corporation) standard sample, 10-point measurement

[0178] (13) Styrene content of styrene-based elastomer The content of vinyl aromatic compound monomer units (styrene content) was measured and determined under the following conditions by nuclear magnetic resonance spectrum analysis (NMR). Measuring instrument: JNM-LA400 (manufactured by JEOL) Solvent: Deuterated chloroform Sample concentration: 50 mg / mL Observation frequency: 400 MHz Chemical shift reference: TMS (tetramethylsilane) Pulse delay: 2.904 seconds Number of scans: 64 times Pulse width: 45° Measurement temperature: 26 °C

[0179] (14) Double bond content of styrenic elastomer The double bond content of the styrenic elastomer was measured and determined by nuclear magnetic resonance spectrum analysis (NMR) under the same conditions as the styrene content of the styrenic elastomer. Based on the vinyl bond amount of the conjugated diene monomer unit, it was calculated by converting it into the weight ratio of the conjugated diene monomer.

[0180] (15) Evaluation of the uniformity of the resin composition A resin composition solution was separately prepared by formulating the curable resin composition solution with only the initiator removed. 2 μl of the resin composition solution was dropped onto a slide glass placed on a hot plate at 160 °C, allowed to stand for 2 minutes, and then the pressure was reduced to 100 mmHg for 30 seconds to remove toluene, obtaining a resin composition. With the obtained resin composition still on the slide glass and maintaining the temperature at 160 °C, it was transferred to a hot stage set at 160 °C of a microscope and observed with a 10x eyepiece in the transmission mode of the optical microscope, and photography was performed.

[0181] Hereinafter, the production methods of the unmodified polyphenylene ether compositions of each production example and production comparative example, and the production methods of the modified polyphenylene ether compositions of each example and comparative example will be described.

[0182] (Production Example 1) A 1.5-liter jacketed reactor equipped with a sparger for introducing an oxygen-containing gas, a stirring turbine blade and a baffle at the bottom of the reactor, and a reflux condenser in the vent gas line at the upper part 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 (AO-30 manufactured by ADEKA). Then, while vigorously stirring these components, air was introduced from the sparger into the reactor 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 ventilation was stopped, and 1.1021 g of tetrasodium ethylenediaminetetraacetate tetrahydrate (reagent manufactured by Dojindo Laboratories) was added to this polymerization mixture as a 100 g aqueous solution and warmed to 70°C. After holding at 70°C for 2 hours and performing catalyst extraction and treatment for removing by-produced diphenoquinone, the mixture was transferred to a centrifuge manufactured by Sharpless and separated into an undenatured polyphenylene ether composition solution (organic phase) and an aqueous phase containing the catalytic metal. The obtained undenatured polyphenylene ether composition solution was transferred to a jacketed concentrator, and toluene was distilled off and concentrated until the solid content in the undenatured polyphenylene ether composition solution reached 55% by mass. Then, using an oil bath set at 230°C and a rotary evaporator, toluene was further distilled off from the concentrate, and the solid content was dried to obtain an undenatured polyphenylene ether composition.

[0183] A stir bar was placed in a 300 ml three-necked flask, and a Dimroth condenser with a three-way cock attached to the main tube was installed. A rubber stopper with a thermometer inserted into one side tube was attached. 20.0 g of the unmodified polyphenylene ether composition obtained in the above step was introduced from the other side tube, and a rubber stopper was attached. After purging the inside of the flask with nitrogen, while stirring the inside with a magnetic stirrer, it was dissolved with 60.0 g of Wako Pure Chemical Industries, Ltd. ultra-dehydrated toluene using a syringe. 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 completion of the dropping, stirring was continued at 30 °C for 3 hours, and then 0.86 g of Wako Pure Chemical Industries, Ltd. ultra-dehydrated methanol was added to the system to stop the reaction.

[0184] Next, the reaction solution was distilled under reduced pressure to remove triethylamine together with toluene. Then, Wako Pure Chemical Industries, Ltd. ultra-dehydrated toluene was added to the reaction solution to adjust the solid content concentration to 20% by weight. Then, the polymer solution was dropped into methanol (5 times the weight of the organic layer) with stirring. Next, the precipitate was filtered, and the filtrate was vacuum-dried at 110 °C for 1 hour to obtain a modified polyphenylene ether composition. It was confirmed from the measurement results of NMR that the reaction was proceeding. The molecular weight of the obtained modified polyphenylene ether composition (PPE-1) was Mw = 4,810 and Mn = 2,610. Also, 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.

[0185] (Example 1-7, Comparative Example 1) Using the styrene-based elastomers shown in Table 1, a curable resin composition solution was prepared with the formulation shown in Table 2, and the results of evaluating the cured product obtained by the above method are shown in Table 1.

[0186] Also, the results of the uniformity evaluation test of the resin compositions of Example 1 and Comparative Example 1 are shown in FIGS. 1 and 2. In FIG. 1 (Example 1), it was a uniform resin composition, while in FIG. 2 (Comparative Example 1), a distinct texture was observed, and it was confirmed that it was a non-uniform resin composition.

[0187] In addition, the SPM image of the cured product obtained in Example 1 is shown in Fig. 3. In the figure, the white portion indicates the PPE phase, and the black portion indicates the elastomer phase. It was confirmed that the PPE phase forms a continuous phase.

[0188]

Table 1

[0189]

Table 2

Industrial Applicability

[0190] By blending a terminal-modified polyphenylene ether having a specific structure and a specific styrene-based elastomer, the curable resin composition of the present invention can obtain a uniform cured product, satisfying all of the sufficient Tg, low dielectric properties, and low coefficient of linear expansion of the cured product, and can provide a curable resin composition useful as a substrate material.

Claims

1. A curable resin composition comprising the following component (A) and component (B). (A) Modified polyphenylene ether Modified polyphenylene ether represented by the following formula (1): 【Chemical Formula 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, Y is each independently a divalent linking group having a structure represented by the following formula (4), n represents the number of repetitions of Y, and each independently represents an integer of 0 to 200. At least one n in a [-Y ｎ -A] is an integer of 1 or more, A is represented by the following formula (6), 【Chemical Formula 2】 In formula (2), X is an arbitrary a-valent linking group, and a plurality of R ５ are each independently either a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and k is each independently an integer of 1 to 4, 【Chemical Formula 3】 In formula (3), a plurality of R １１ are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms, a plurality of R １２ are each independently an optionally substituted alkylene group having 1 to 8 carbon atoms, b is each independently 0 or 1, and R １３ represents any one of a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted phenyl group, 【Chemical Formula 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. Two R ２１ are not hydrogen atoms at the same time, and two R ２１ are not a combination where one is a partial structure represented by the above formula (3) and the other is any one of a hydrogen atom, a methyl group, or an ethyl group. A plurality of R ２２Each is 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, 【Chemical Formula 5】 In formula (6), R31 and R34 are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms, R32 and R33 are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, an aryl group, an alkoxy group, an allyloxy group, an amino group, or a hydroxyalkyl group, R35 is each independently a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 30 carbon atoms, 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, R36 is a divalent hydrocarbon group or an amino group having 1 to 3 carbon atoms, or an oxygen atom, and a part 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 is an integer from 0 to 8, and t and u are each 0.} (B) Styrenic elastomer

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

3. The curable resin composition according to claim 1 or 2, wherein the component (B) is a styrenic elastomer having a double bond content of 90% or less.

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

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

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

7. The curable resin composition according to any one of claims 1 to 6, wherein the component (B) is a styrenic elastomer having a hydrogenation rate of double bonds based on conjugated diene monomer units of 90% or more.

8. The curable resin composition according to any one of claims 1 to 7, wherein the component (B) is a styrenic elastomer having a number average molecular weight of 300,000 or less.

9. The curable resin composition according to any one of claims 1 to 8, further comprising (C) an initiator.

10. Among the Rs ５ at least one is a partial structure represented by the formula (3). Taking the carbon atom of the benzene ring to which -O- in the formula (2) is bonded as the 1-position, the partial structure represented by the formula (3) is bonded to one of the carbon atoms at the 2-position or 6-position, and a hydrogen atom, a methyl group, or an ethyl group is bonded to the other carbon atom at the 2-position or 6-position. The curable resin composition according to any one of claims 1 to 9. ５ The curable resin composition according to any one of claims 1 to 9, wherein the partial structure represented by the formula (3) is a t-butyl group.

11. The curable resin composition according to any one of claims 1 to 10, wherein the partial structure represented by the formula (3) is a t-butyl group.

12. The curable resin composition according to any one of claims 1 to 11, wherein the number of OH terminals contained in the polyphenylene ether is 0 to 3,000 μmol / g.

13. R in the formula (4) ２１ The curable resin composition according to any one of claims 1 to 12, wherein is a methyl group.

14. The curable resin composition according to any one of claims 1 to 13, further comprising (D) a solvent.

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