JP2023141184A - Curable resin composition, prepreg, laminate, printed wiring board, and composite material - Google Patents

Abstract

To provide a curable resin composition which enables production of a uniform cured product, satisfies all of a sufficient glass transition temperature (Tg) of the cured product, low dielectric characteristics, and a low linear expansion coefficient, and has good moldability.SOLUTION: A curable resin composition contains (A) modified polyphenylene ether having a silyl group-containing group, (B) a styrenic elastomer, (C) a crosslinking auxiliary which is represented by the following formula (18) and is an aromatic vinyl compound having the number of vinyl groups in the molecule of 3 or less, (D) a liquid elastomer, and (E) a vinyl group-containing silane-based compound represented by the following formula (19). In the formula (18), R37 to R42, and n are defined in the specifications.SELECTED DRAWING: None

Description

The present invention relates to curable resin compositions, prepregs, laminates, printed wiring boards, and composite materials.

Polyphenylene ether has excellent high frequency properties, flame retardancy, and heat resistance, and is therefore widely used as a material in the electrical and electronic fields, the automobile field, and various other industrial material fields. In recent years, polyphenylene ethers having an extremely lower molecular weight than ordinary high molecular weight polyphenylene ethers are expected to be effective for electronic material applications such as substrate materials. For this reason, Patent Document 1 proposes a low-molecular-weight polyphenylene ether with a dielectricity lower than that of general high-molecular-weight polyphenylene ether using 2,6-dimethylphenol as a raw material, and an efficient method for producing the same.

Further, Patent Documents 2 and 3 describe modified polymers having a polyphenylene ether moiety in the molecular structure and a methacrylic group at the end of the molecule. In particular, methacrylic group modification is becoming a widely used method because the reactivity of the methacrylic group as a crosslinking group is moderately high and the method for introducing the hydroxyl group into the terminal is easy.

Furthermore, in Patent Documents 4 and 5, a copolymer of styrene and an olefin-based alkene compound and its hydrogenated product (styrene-based elastomer) are added to methacrylated polyphenylene ether in order to improve adhesion with metal foil. Attempts to mix them have been reported.

Japanese Patent Application Publication No. 2004-99824 Special Publication No. 2004-502849 Special Publication No. 2010-538114 JP2017-82200A JP2020-200432A

As mentioned above, styrenic elastomers have been added to modified polyphenylene ethers due to various advantages, but methacrylated polyphenylene ethers have low compatibility with styrene elastomers. Therefore, a resin composition containing a methacrylated polyphenylene ether and a styrene elastomer usually undergoes macrophase separation at the stage of the resin composition before curing or during the curing process. As a result, the presence of a continuous phase of styrene-based elastomer in the formed cured product increases the coefficient of linear expansion and lowers the glass transition temperature (Tg).

In Patent Documents 4 and 5, a highly polar and low molecular weight crosslinking agent such as triallyl isocyanurate (TAIC) is used for the purpose of suppressing such macrophase separation and simultaneously lowering viscosity to improve moldability. Attempts have been made to incorporate However, the cured product thus formed has a problem in that it has high dielectric properties (permittivity, dielectric loss tangent) because it contains a highly polar crosslinking auxiliary agent.

In addition, when preparing a composite of the curable resin composition and glass cloth (prepreg) by coating and drying a solution (varnish) of the curable resin composition on glass cloth, the concentration of the varnish solution of the resin composition It is necessary to have a high concentration of 50% by mass or more in order to increase the content of the resin composition in the composite, but such a high concentration varnish increases the solution viscosity and impairs coating properties. there were.

In view of the above problems, the present invention provides a uniform cured product that has a sufficient glass transition temperature (Tg), low dielectric properties, low coefficient of linear expansion, and appropriate solution viscosity for a high concentration varnish. The object of the present invention is to provide a curable resin composition with satisfactory moldability.

In order to solve the above problems, the present inventors used a polyphenylene ether skeleton as a modified group such as a vinylsilyl group, which is a crosslinking group with low polarity and good metal adhesion, and used a styrene elastomer, a specific crosslinking aid, and a liquid By blending an elastomer, a curable resin composition that can solve all of the above problems can be obtained, leading to the completion of the present invention. Some aspects of the invention are listed below.
<1>
A curable resin composition containing the following components (A), (B), (C), (D) and (E):
(A) Modified polyphenylene ether Modified polyphenylene ether represented by the following formula (1):
{In formula (1), Z is an a-valent partial structure represented by the following formula (2), a represents an integer of 2 to 6, and Y is each independently represented by the following formula (4). A divalent linking group having the structure shown, n represents the number of repeats of Y, each independently an integer of 0 to 200, and at least one of a [-Y _n -A] n is an integer of 1 or more, A represents a hydrogen atom or a silyl group-containing derivative capable of bonding to a polyphenylene ether structure, except in the case of all hydrogen atoms,
In formula (2), X is an a-valent arbitrary linking group, and each of the plurality of R ⁵ is independently represented by a linear alkyl group having 1 to 8 carbon atoms and the following formula (3) any of the substructures, and k is each independently an integer from 1 to 4,
In formula (3), a plurality of R ¹¹ 's are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms, and a plurality of R ¹² 's are each independently an optionally substituted carbon alkyl group. is an alkylene group of number 1 to 8, b is each independently 0 or 1, and R ¹³ is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a substituted represents any of the phenyl groups,
In formula (4), a plurality of R ²¹ 's each independently represent 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 ^21s are not hydrogen atoms at the same time, and one of the two R ^21s is a partial structure represented by the above formula (3), and the other is a hydrogen atom, a methyl group, or Rather than a combination of ethyl groups, the plurality of R ²² 's each independently represent a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, and an optionally substituted hydrocarbon group having 6 to 6 carbon atoms. 12 aryl groups and halogen atoms}
(B) Styrenic elastomer (C) Crosslinking aid A crosslinking aid which is an aromatic vinyl compound represented by the following formula (18) and having 3 or less vinyl groups in the molecule:
{In formula (18), R ³⁷ , R ³⁸ , and R ³⁹ each independently represent a hydrogen atom or a hydrocarbon group having 4 or less carbon atoms, and R ⁴⁰ and R ⁴¹ each independently represent a hydrogen atom or represents a saturated or unsaturated hydrocarbon group having 8 or less carbon atoms}
(D) Liquid elastomer
(E) Vinyl group-containing silane compound represented by the following formula (19):
{In formula (19), R ⁴² represents a hydrogen atom or a hydrocarbon having 4 or less carbon atoms, and n represents an integer from 2 to 6}.
<2>
The curable resin composition according to item 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 item 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 items 1 to 3, wherein the component (B) is a styrenic elastomer having a styrene content of 80% or less.
<5>
The component (B) is 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, the styrenic elastomer according to any one of items 1 to 4, Curable resin composition.
<6>
Any of items 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. The curable resin composition according to item 1.
<7>
The curable resin composition according to any one of items 1 to 6, wherein the component (B) is a styrenic elastomer in which the hydrogenation rate of double bonds based on conjugated diene monomer units is 90% or more. thing.
<8>
The curable resin composition according to any one of items 1 to 7, wherein in the formula (18), R ³⁷ , R ³⁸ , and R ³⁹ are hydrogen atoms.
<9>
The curable resin composition according to any one of items 1 to 8, wherein in the formula (18), R ⁴⁰ is a tert-butyl group.
<10>
The curable resin composition according to any one of items 1 to 9, wherein in the formula (18), R ⁴¹ is a vinyl group.
<11>
The curable resin composition according to any one of items 1 to 10, wherein the component (C) is 4-tertbutylstyrene.
<12>
The curable resin composition according to any one of items 1 to 10, wherein the component (C) is divinylbenzene.
<13>
The curable resin composition according to any one of items 1 to 12, wherein the component (D) is a styrene-butadiene copolymer.
<14>
Any one of items 1 to 12, wherein the component (D) is either 2,4,6,8-tetramethyl-tetravinylcyclotetrasiloxane or 2,4,6-trimethyl-trivinylcyclotrisiloxane. The curable resin composition described in 2.
<15>
(F) The curable resin composition according to any one of items 1 to 14, further comprising an initiator.
<16>
In the formula (2), at least one of R ⁵ is a partial structure represented by the formula (3), in which one carbon atom of the benzene ring to which -O- in the formula (2) is bonded is ^R5 having a partial structure represented by the formula (3) above is bonded to one carbon atom at the 2nd or 6th position, and the other carbon atom at the 2nd or 6th position is a hydrogen atom, a methyl group, or The curable resin composition according to any one of items 1 to 15, to which an ethyl group is bonded.
<17>
The curable resin composition according to any one of items 1 to 16, wherein the partial structure represented by formula (3) is a t-butyl group.
<18>
The curable resin composition according to any one of items 1 to 17, wherein the number of OH terminals contained in the polyphenylene ether is 0 to 3,000 μmol/g.
<19>
The curable resin composition according to any one of items 1 to 18, wherein R ²¹ in the formula (4) is a methyl group.
<20>
A in the above formula (1) is the following formula (5):
{In formula (5), R ³¹ and R ³⁴ are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms, and R ³² and R ³³ are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms. 30 monovalent hydrocarbon group, aryl group, alkoxy group, allyloxy group, amino group, or hydroxyalkyl group, and B is a hydrocarbon having 1 to 30 carbon atoms containing an olefinic carbon-carbon double bond. A system substituent, some of which may be substituted with a hydrogen atom, hydroxyl group, aryl group, alkoxy group, allyloxy group, amino group, hydroxyalkyl group, vinyl group, isopropenyl group, or halogen group, s, t, and u are each independently integers from 0 to 8}
The curable resin composition according to any one of items 1 to 19, represented by:
<21>
A in the formula (1) is the following formula (6) and/or (7):

{In formula (6) and/or formula (7), R ³¹ and R ³⁴ are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms, and R ³² and R ³³ are each is 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, and each R ³⁵ is independently a hydrogen atom, a hydroxyl group, or a carbon 1 to 30 hydrocarbon groups, aryl groups, alkoxy groups, allyloxy groups, amino groups, hydroxyalkyl groups, vinyl groups, isopropenyl groups, or halogen groups, and R ³⁶ is a divalent group having 1 to 3 carbon atoms. is a hydrocarbon group or an amino group, or an oxygen atom, and a part of the hydrocarbon group is substituted with an aryl group, an alkoxy group, an allyloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group. and s, t, and u are each independently an integer from 0 to 8}
The curable resin composition according to item 20, which is represented by:
<22>
(G) The curable resin composition according to any one of items 1 to 21, further comprising a solvent.
<23>
A prepreg comprising the curable resin composition according to any one of items 1 to 22.
<24>
A laminate comprising a cured product of the curable resin composition according to any one of items 1 to 22.
<25>
A printed wiring board comprising a cured product of the curable resin composition according to any one of items 1 to 22.
<26>
A composite material comprising a cured product of the curable resin composition according to any one of items 1 to 22.
<27>
The composite material according to item 26, which is a carbon fiber reinforced composite material.

By using a curable resin composition containing a modified polyphenylene ether having a vinylsilyl group, a styrene elastomer, a liquid elastomer, and a crosslinking aid as specified in the present invention, a uniform cured product with good moldability can be obtained, It is possible to provide a curable resin composition that satisfies all of the requirements of a cured product: sufficient Tg, low dielectric properties, adhesiveness, low coefficient of linear expansion, and appropriate solution viscosity for a high concentration varnish.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. This embodiment is an illustration for explaining the present invention, and the present invention is not limited only to this embodiment, and the present invention can be implemented with appropriate modifications within the scope of the gist.

<Curable resin composition>
The curable resin composition of this embodiment is characterized by containing the following components (A), (B), (C), (D) and (E):
(A) Modified polyphenylene ether Modified polyphenylene ether represented by the following formula (1):
{In formula (1), Z is an a-valent partial structure represented by the following formula (2), a represents an integer of 2 to 6, and Y is each independently represented by the following formula (4). A divalent linking group having the structure shown, n represents the number of repeats of Y, each independently an integer of 0 to 200, and at least one of a [-Y _n -A] n is an integer of 1 or more, A represents a hydrogen atom or a silyl group-containing derivative capable of bonding to a polyphenylene ether structure, except in the case of all hydrogen atoms,
In formula (2), X is an a-valent arbitrary linking group, and each of the plurality of R ⁵ is independently represented by a linear alkyl group having 1 to 8 carbon atoms and the following formula (3) any of the substructures, and k is each independently an integer from 1 to 4,
In formula (3), a plurality of R ¹¹ 's are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms, and a plurality of R ¹² 's are each independently an optionally substituted carbon alkyl group. is an alkylene group of number 1 to 8, b is each independently 0 or 1, and R ¹³ is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a substituted represents any of the phenyl groups,
In formula (4), a plurality of R ²¹ 's each independently represent 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 ^21s are not hydrogen atoms at the same time, and one of the two R ^21s is a partial structure represented by the above formula (3), and the other is a hydrogen atom, a methyl group, or Rather than a combination of ethyl groups, the plurality of R ²² 's each independently represent a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, and an optionally substituted hydrocarbon group having 6 to 6 carbon atoms. 12 aryl groups and halogen atoms},
(B) Styrenic elastomer,
(C) crosslinking aid,
(D) a liquid elastomer, and (E) a vinyl group-containing silane compound.

In this embodiment, a curable resin composition includes (A) modified polyphenylene ether, (B) styrene elastomer, (C) crosslinking aid, (D) liquid elastomer, and (E) vinyl group-containing silane compound. By using a curable resin composition, a uniform cured product can be obtained, and a curable resin composition that satisfies all of the following requirements: sufficient Tg, low dielectric properties, low coefficient of linear expansion, and appropriate solution viscosity for a high concentration varnish. can be provided.
Hereinafter, the components constituting the curable resin composition of this embodiment will be explained in detail.

<(A) Modified polyphenylene ether>
The modified polyphenylene ether according to this embodiment has a structure represented by the following formula (1).
In formula (1), Z is a partial structure having an a-valent central phenol moiety represented by the following formula (2), and a is an integer of 2 to 6, preferably an integer of 3 to 6. .

The above-mentioned "central phenolic moiety" refers to the central skeleton that becomes the starting point of the reaction when polyfunctional polyphenylene ether is polymerized, and the polyfunctional modified polyphenylene ether composition is analyzed by methods such as nuclear magnetic resonance (NMR) and mass spectrometry. The structure can be identified by analysis.

As a specific method for identifying the structure of the central phenol moiety 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 electrical shock or electrical ionization is performed. (EI) to estimate the structure of the central phenol site from the fragment ion peak. Furthermore, a method of estimating the structure of the central phenol moiety 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 moiety.

The modified polyphenylene ether has a number of partial structures (for example, a phenol which may be substituted with ^R5 , etc.) bonded to the a-valent center X, and the a-valent partial structure (i.e., the following formula (2) It may be a structure in which [-Y _n -A] of formula (1) is bonded to the central phenol moiety represented by the formula (1).
In formula (2), a may be an integer from 2 to 6 similar to that in formula (1), and preferably the same integer as in formula (1). In the central phenol moiety of formula (2), each of the a partial structures may have the same structure or may have different structures.

In formula (2), X is any a-valent linking group, including, but not limited to, hydrocarbon groups such as chain hydrocarbons and cyclic hydrocarbons; selected from nitrogen, phosphorus, silicon, and oxygen. A hydrocarbon group containing one or more atoms; atoms such as nitrogen, phosphorus, silicon; or a combination thereof; and the like. X may be a linking group other than a single bond.

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

In formula (2), X is an a-valent alkyl skeleton bonded to the benzene ring to ^which R ⁵ is bonded via a single bond or an ester bond; An a-valent aryl skeleton that is bonded to the benzene ring to which R 5 is bonded; an a-valent heterocyclic skeleton that is bonded to the benzene ring to which R ⁵ is bonded via a single bond or an ester bond;

Here, the alkyl skeleton is not particularly limited, but for example, the branch end of a chain hydrocarbon having at least a branched carbon atoms (for example, a chain saturated hydrocarbon) has a benzene ring as a partial structure. Directly bonded skeletons (benzene rings need only be bonded to a number of branched terminals, and there may be branched terminals to which no benzene rings are bonded), and the like. Further, the aryl skeleton is not particularly limited, but for example, a benzene ring, mesitylene group, or 2-hydroxy-5-methyl-1,3-phenylene group is bonded to R ⁵ through a single bond or an alkyl chain. Examples include skeletons bonded to the benzene ring. Further, the heterocyclic skeleton is not particularly limited, but includes, for example, a skeleton in which a triazine ring is bonded to a benzene ring to which R ⁵ is bonded via a single bond or an alkyl chain.

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

R ⁵ in formula (2) is a linear alkyl group having 1 to 8 carbon atoms such as a methyl group, ethyl group, or n-propyl group, a group 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).
In formula (3),
A plurality of R ^11s are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms,
A plurality of R ^12s are each independently an optionally substituted alkylene group having 1 to 8 carbon atoms,
b is each independently 0 or 1,
R ¹³ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted phenyl group.
Examples of the above-mentioned substituents include halogen atoms and the like.

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

In this embodiment, when the carbon atom of the benzene ring to which -O- in formula (2) is bonded is set to the 1st position, a partial structure represented by the formula (3) is attached to one of the carbon atoms at the 2nd or 6th position. It is preferable that R ⁵ having the above bond be bonded, and a hydrogen atom, methyl group, or ethyl group is bonded to the other carbon atom at the 2-position or the 6-position. Furthermore, a hydrocarbon group or a partial structure represented by the above formula (3) may be bonded to the carbon atoms at the 2- and 6-positions of the benzene ring to which -O- in formula (2) is bonded. . In the benzene ring in the above formula (2), [Y _n -A] in the above formula (1) is bonded to a carbon atom other than the 2-position and the 6-position through the central X and the oxygen atom. Preferably, [Y _n -A] of the above formula (1) is bonded to the 1st position via an oxygen atom, and the central portion X is bonded to the 4th position.

Examples of polyhydric phenol compounds for the partial structure represented by the above formula (2) are listed below.
Examples of polyhydric phenol compounds include 4,4'-[(3-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(3-hydroxyphenyl)methylene]bis(2 , 3,6-trimethylphenol), 4,4'-[(4-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(4-hydroxyphenyl)methylene]bis(2 , 3,6-trimethylphenol), 4,4'-[(2-hydroxy-3-methoxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(4-hydroxy-3- ethoxyphenyl)methylene]bis(2,3,6-trimethylethylphenol), 4,4'-[(3,4-dihydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[ (3,4-dihydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 2,2'-[(4-hydroxyphenyl)methylene]bis(3,5,6-trimethylphenol), 4, 4'-[4-(4-hydroxyphenyl)cyclohexylidene]bis(2,6-dimethylphenol), 4,4'-[(2-hydroxyphenyl)methylene]-bis(2,3,6-trimethyl phenol), 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'-cyclohexylidene Bis[2-cyclohexyl-6-[(4-hydroxy-3,5-dimethylphenyl)methyl]phenol], 4,4'-cyclohexylidene bis[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'- Examples include, but are not limited to, dimethyl(1,1'-biphenyl)-4,4-diol.

The number of phenolic hydroxyl groups in the polyhydric phenol compound is not particularly limited as long as it is 2 or more, but if the number of polyphenylene ether terminals increases, the molecular weight change during polymerization may increase, so it is preferably 2 to 6. , more preferably 2 to 4.

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

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

In formula (4), a plurality of R ²¹ 's each independently represent 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, ethyl group, n-propyl group, vinyl group, aryl group, or ethynyl group. , or a propargyl group, more preferably a methyl group or an ethyl group, particularly preferably a methyl group. Examples of the above-mentioned substituents include halogen atoms and the like.

In formula (4), the two R ^21s are hydrogen at the same time, from the viewpoint that the modified polyphenylene ether-containing composition has all of the following: low dielectric properties, appropriate metal releasability, low solution viscosity, and sufficient Tg during curing. It is preferable that it is not an atom, and/or it is preferable that it is not a combination in which one is a partial structure represented by the above formula (3) and the other is a hydrogen atom, a methyl group, or an ethyl group. .

In formula (4), each of the plurality of R ²² 's independently represents a hydrogen atom; an optionally substituted hydrocarbon group having 1 to 6 carbon atoms; an optionally substituted aryl group having 6 to 12 carbon atoms; and a halogen atom; preferably a hydrogen atom or an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrogen atom , methyl group, ethyl group, or n-propyl group, and more preferably a hydrogen atom or a methyl group. Examples of the above-mentioned substituents include halogen atoms and the like.

Examples of monovalent phenol compounds for the structure represented by the above formula (4) include o-cresol, 2,6-dimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2, 6-diethylphenol, 2-n-propylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-n-propyl Phenol, 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-trialylphenol, 2,3,6-tributylphenol, 2,6-di-n-butyl-3-methylphenol, 2,6-dimethyl-3-n-butylphenol, 2,6-dimethyl- Examples include 3-t-butylphenol.

Among the above-mentioned monovalent phenol compounds, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-diphenylphenol, 2,3,6-trimethylphenol are particularly preferred because they are inexpensive and easily available. , or 2,5-dimethylphenol is preferred, and 2,6-dimethylphenol or 2,3,6-trimethylphenol is more preferred.

In addition, the said phenol compound may be used individually by 1 type, or may be used in combination of 2 or more types.

As the monovalent phenol compound, for example, 2,6-dimethylphenol and 2,6-diethylphenol are used in combination, 2,6-dimethylphenol and 2,6-diphenylphenol are used in combination. A method of using 2,3,6-trimethylphenol and 2,5-dimethylphenol in combination, a method of using 2,6-dimethylphenol and 2,3,6-trimethylphenol in combination, etc. Can be mentioned. At this time, the mixing ratio of the phenol compounds to be combined can be arbitrarily selected.

In addition, the phenol compound used contains small amounts of m-cresol, p-cresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, etc., which may be included as by-products during manufacturing. Good too.

The phenol compound for the a-valent partial structure as represented by the above formula (2) includes a corresponding monovalent phenol compound, aldehydes (e.g., formaldehyde, etc.), ketones (e.g., acetone, methyl ethyl ketone, etc.), It can be advantageously produced industrially by reaction with dihalogenated aliphatic hydrocarbons (methyl isobutyl ketone, acetophenone, cyclohexanone, etc.), or reactions between corresponding monovalent phenol compounds.

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 hydrogen atoms are present.

Here, A in formula (1) is expressed by the following formula (5) from the viewpoint of obtaining low dielectric properties, appropriate metal releasability, low solution viscosity, and sufficient Tg properties during curing. Substituents are preferred.
In formula (5), R ³¹ and R ³⁴ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms, and a plurality of R ³² and R ³³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms. ~30 monovalent hydrocarbon groups, aryl groups, alkoxy groups, allyloxy groups, amino groups, or hydroxyalkyl groups. In formula (5), B is a hydrocarbon substituent having 1 to 30 carbon atoms containing an olefinic carbon-carbon double bond, some of which are hydrogen, hydroxyl group, aryl group, alkoxy group, or allyloxy group. , an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group. In formula (5), s, t, and u are each independently an integer of 0 to 8, preferably an integer of 0 to 5.

In formula (5), it is more preferable that the hydrocarbon groups of R ³² and R ³³ have a large 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 releasability ^, or a decrease in olefinic carbon-carbon double bonds will occur. It is preferably about 1 to 20, more preferably about 1 to 12.

In formula (5), specific examples of the monovalent hydrocarbon group for R ³² and/or R ³³ include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-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-methylpentylene, 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-methyl Pentyl, 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-diethyl Propyl, 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- Examples include phenylethyl.

The monovalent hydrocarbon group for R ³² and/or R ³³ is preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-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. Yes, more preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-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, more preferably, Methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-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.

Specific examples of the aryl group for R ³² and/or R ³³ include phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 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-tert-butylphenyl, 3-tert-butylphenyl, 2-tert-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-trimethyl Examples include phenyl, 3,4,5-trimethylphenyl, 2,4,6-triethylphenyl, 2,3,4-triethylphenyl, 2,3,6-triethylphenyl, 3,4,5-triethylphenyl, etc. .

The aryl group for R ³² and/or R ³³ is preferably phenyl, 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, 4- n-propylphenyl, 3-n-propylphenyl, 2-n-propylphenyl, 4-isopropylphenyl, 3-isopropylphenyl, 2-isopropylphenyl, 4-n-butylphenyl, 3-n-butylphenyl, 2- n-butylphenyl, 4-isobutylphenyl, 3-isobutylphenyl, 2-isobutylphenyl, 4-tert-butylphenyl, 3-tert-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-ethyl Phenyl, 4-n-propylphenyl, 3-n-propylphenyl, 2-n-propylphenyl, 4-isopropylphenyl, 3-isopropylphenyl, 2-isopropylphenyl, 4-n-butylphenyl, 3-n-butyl Phenyl, 2-n-butylphenyl, 4-isobutylphenyl, 3-isobutylphenyl, 4-tert-butylphenyl, 3-tert-butylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 2,5 -dimethylphenyl, 2,6-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,3-diethylphenyl, 2,4,6-trimethylphenyl, 2,3,6-trimethylphenyl, and 2,4,6-triethylphenyl, 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-tert-butylphenyl, 2,6-dimethylphenyl, 2,4- They are dimethylphenyl, 2,5-dimethylphenyl, and 2,4,6-trimethylphenyl.

Specific examples of the alkoxy group for R ³² and/or R ³³ 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-methylpen Toxy, 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, Examples include cyclohexoxy, 1-octoxy, 2-octoxy, 3-octoxy, 4-octoxy, 2-ethyl-1-hexoxy, phenylmethoxy and the like.

The alkoxy group for R ³² and/or R ³³ 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-to xoxy, 2,2-dimethyl-1-butoxy, 3,3-dimethyl-1-butoxy, cyclohexoxy, 2-ethyl-1-hexoxy, and phenylmethoxy, more preferably methoxy, ethoxy, propoxy, iso These are propoxy, n-butoxy, isobutoxy, 2-butoxy, t-butoxy, 2,2-dimethylpropoxy, cyclopentoxy, 1-hexoxy, 2-ethyl-1-hexoxy, and phenylmethoxy.

Specific examples of the allyloxy group for R ³² and/or R ³³ 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-tert-butylphenoxy, 2-tert-butylphenoxy, 3-tert-butylphenoxy, 2,6-di-tert-butylphenoxy, 2,4-di-tert-butylphenoxy, 2,3-di-tert-butylphenoxy, 2-methyl -4-tert-butylphenoxy, 2-methyl-6-tert-butylphenoxy, 4-methyl-2-tert-butylphenoxy and the like.

The allyloxy group for R ³² and/or R ³³ is preferably phenoxy, 4-methylphenoxy, 3-methylphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4-dimethylphenoxy, 2,4 , 6-trimethylphenoxy, 4-isopropylphenoxy, 2-isopropylphenoxy, 4-isobutylphenoxy, 2-isobutylphenoxy, 4-tert-butylphenoxy, 2-tert-butylphenoxy, 3-tert-butylphenoxy, 2,4 -di-tert-butylphenoxy, 2,3-di-tert-butylphenoxy, 2-methyl-4-tert-butylphenoxy, 2-methyl-6-tert-butylphenoxy, and 4-methyl-2-tert- 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-tert-butylphenoxy, 2-tert-butylphenoxy, 2-methyl-4-tert-butylphenoxy, and 2-methyl-6 -tert-butylphenoxy, more preferably phenoxy, 4-methylphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4-dimethylphenoxy, 2,4,6-trimethylphenoxy, 4-tert -butylphenoxy, 2-tert-butylphenoxy, 2-methyl-4-tert-butylphenoxy, and 2-methyl-6-tert-butylphenoxy.

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

In formula (5), the hydrocarbon groups R ³¹ and R ³⁴ are carbon A larger number is more preferable. On the other hand, if the number of carbon atoms is excessively large, a decrease in Tg, a decrease in metal releasability ^, or a decrease in olefinic carbon-carbon double bonds will occur ^. It is preferably about 30, more preferably about 1 to 20, even more preferably about 1 to 12.

In formula (5), specific examples of the divalent hydrocarbon group for R ³¹ and/or R ³⁴ 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.

Further, specific examples of the divalent hydrocarbon group for R ³¹ and/or R ³⁴ 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 Ren, 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.

Further, specific examples of the divalent hydrocarbon group for R ³¹ and/or R ³⁴ 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-cyclohexyl Silene, 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-1,4-phenylene, ethylene-1,4-phenylene, ethylene-1,4-phenylene-ethylene and the like.

The divalent hydrocarbon group of R ³¹ and/or R ³⁴ 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.

The divalent hydrocarbon group of R ³¹ and/or R ³⁴ is more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-dimethyl Ethylene, 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. .

The divalent hydrocarbon group of R ³¹ and/or R ³⁴ is more preferably methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,2-propylene, 1,1-dimethyl Ethylene, 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.

In formula (5), specific examples of the substituent containing a carbon-carbon double bond in B include vinyl group, allyl group, isopropenyl group, 5-norbornen-2yl, 1-butenyl group, 1-pentenyl group. 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, methacrylic group, acrylic group, 2-ethyl acrylic group, 2-hydroxymethyl acrylic group, and the like.

A more specific example of A in formula (1) or a more specific example of the substituent represented by formula (5) is a structure represented by the following formula (6) and/or (7). can be mentioned.
In formula (6) and/or formula (7), a plurality of R ³¹ and R ³⁴ are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms, and a plurality of R ³² and R ³³ are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, an aryl group, an alkoxy group, an allyloxy group, an amino group, or a hydroxyalkyl group. Specific examples and preferred groups of these groups include specific examples and preferred groups of the corresponding groups explained in formula (5) above.

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

In formula (7), R ³⁶ is a hydrocarbon group having 1 to 30 carbon atoms, an amino group, or oxygen, and a part of the hydrocarbon group is an aryl group, an alkoxy group, an allyloxy group, an amino group, or a hydroxy group. Preferably, it is substituted with an alkyl group, a vinyl group, an isopropenyl group, or a halogen group. Further, part of the amino group may be substituted with an alkyl group having 1 to 5 carbon atoms. Further, R ³⁶ may be divalent, and the hydrocarbon group as R ³⁶ preferably has 1 to 3 carbon atoms.

In formula (6) and/or formula (7), s, t, and u are each independently an integer of 0 to 8.

In formula (6) and/or formula (7), it is more preferable that the hydrocarbon group for R ³⁵ has a large 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 releasability, or a decrease in olefinic carbon-carbon double bonds will occur, so the number of carbon atoms in R ³⁵ is preferably about 1 to 30. , more preferably about 1 to 20, and even more preferably about 1 to 12.

Specific examples of the hydrocarbon group for ^R35 include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-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-methyl Pentyl, 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-methyl Examples include heptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl and the like.

Further, specific examples of the hydrocarbon group for ^R35 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, to 1,4-dimethyl xyl, 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-methyl Pentyl, 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- Examples include cyclohexylethyl, 1-cyclohexyl-2-ethylene, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, benzyl, 2-phenylethyl and the like.

The hydrocarbon group of R ³⁵ is preferably methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-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-methyl Heptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, and benzyl, more preferably methyl and ethyl. , n-propyl, 2-propyl, n-butyl, isobutyl, tert-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-ethyl xyl, 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, tert-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.

Specific examples of the hydrocarbon group for ^R36 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 Specific examples of groups partially substituted with aryl groups, alkoxy groups, allyloxy groups, amino groups, hydroxyalkyl groups, vinyl groups, isopropenyl groups, and halogen groups 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-tetra Phenylethylene, 1-benzylethylene, 1,1-dibenzylethylene, 1,2-dibenzylethylene, 1,1,2-tribenzylethylene, 1,1,2,2-tetrabenzylethylene, 1-vinylethylene , 1,1-divinylethylene, 1,2-divinylethylene, 1,1,2-trivinylethylene, 1,1,2,2-tetravinylethylene, 1-allylethylene, 1,1-diallylethylene, 1 ,2-diallylethylene, 1,1,2-triallylethylene, 1,1,2,2-tetraallylethylene, 1-chloroethylene, 1,1-dichloroethylene, 1,2-dichloroethylene, 1,1,2 -Trichlorethylene, 1,1,2,2-tetrachlorethylene, 1-bromoethylene, 1,1-dibromoethylene, 1,2-dibromoethylene, 1,1,2-tribromoethylene, 1,1,2,2- Examples include tetrabromoethylene.

The number of OH terminals contained in the polyphenylene ether having the structure represented by the above formula (1) is such that the modified polyphenylene ether-containing composition has low dielectric properties, appropriate metal releasability, low solution viscosity, and sufficient Tg during curing. From the viewpoint of having all of the above, it is preferably 0 to 3,000 μmol/g.

<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 has a structure represented by the above formula (1) (wherein a is from 2 to (which represents an integer of 6), and more specifically includes a modified polyphenylene ether having a structure represented by the following formula (8).
In formula (8), Z is an a-valent partial structure represented by the following formulas (9) and (11), and a represents an integer of 2 to 6.

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

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

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 type or multiple types. Furthermore, in the modified polyphenylene ether composition of the present embodiment, in the structure of formula (8), one or more [-Y _n -A] is [Y _n -H], and all [-Y _n - [A] is not [Y _n -H], and a polyphenylene ether in which all [-Y _n -A] are [Y _n -H] in the structure represented by the above formula (8). You can stay there. Here, Y and n are preferably the same in [-Y _n -A] of the modified polyphenylene ether and [Y _n -H] of the unmodified polyphenylene ether.

The polyfunctional modified polyphenylene ether composition of this embodiment may further contain additives such as a solvent, a polymerization catalyst, and a surfactant. The polyfunctional polyphenylene ether composition of this embodiment may be solid.

Z in formula (8) may have a structure having an a-valent central phenol moiety represented by formula (9) below, and a in formula (8) or (9) is an integer of 3 to 6. It is preferable that there be.

The central phenol moiety is as explained in the above item <Modified polyphenylene ether>.

The modified polyphenylene ether has a number of partial structures (for example, phenol which may be substituted with R ⁵ etc.) bonded to the a-valent center X, and the a-valent partial structure (i.e., the formula (9) It may be a structure in which [-Y _n -A] of formula (8) is bonded to the central phenol moiety (as shown).
In formula (9), a may be the same integer as in formula (8), and preferably the same integer as in formula (8). In the central phenol moiety of formula (9), each of the a partial structures may have the same structure or may be different.

In formula (9), X is any a-valent linking group, including, but not limited to, hydrocarbon groups such as chain hydrocarbons and cyclic hydrocarbons; selected from nitrogen, phosphorus, silicon, and oxygen. A hydrocarbon group containing one or more atoms; atoms such as nitrogen, phosphorus, silicon; or a combination thereof; and the like. Moreover, X may be a linking group other than a single bond. Furthermore, X may be a linking group that connects the a-valent partial structures to each other.

X in the above formula (9) is an a-valent alkyl skeleton bonded to the benzene ring to which R ⁵ is bonded via a single bond or an ester bond; An a-valent aryl skeleton that is bonded to the benzene ring to which ^{R 5} is bonded; an a-valent heterocyclic skeleton that is bonded to the benzene ring to which R ⁵ is bonded via a single bond or an ester bond; etc. .

Here, the alkyl skeleton is not particularly limited, but for example, the branch end of a chain hydrocarbon having at least a branched carbon atoms (for example, a chain saturated hydrocarbon) has a benzene ring as a partial structure. Directly bonded skeletons (benzene rings need only be bonded to a number of branched terminals, and there may be branched terminals to which no benzene rings are bonded), and the like. Further, the aryl skeleton is not particularly limited, but for example, a benzene ring, mesitylene group, or 2-hydroxy-5-methyl-1,3-phenylene group is bonded to R ⁵ through a single bond or an alkyl chain. Examples include skeletons bonded to the benzene ring. Further, the heterocyclic skeleton is not particularly limited, but includes, for example, a skeleton in which a triazine ring is bonded to a benzene ring to which R ⁵ is bonded via a single bond or an alkyl chain.

A plurality of R ⁵ 's in formula (9) are each independently a linear alkyl group having 1 to 8 carbon atoms or a partial structure represented by the following formula (3), and each k is They are independently integers from 1 to 4.

As R ⁵ in the above formula (9), a linear alkyl group having 1 to 8 carbon atoms such as a methyl group, ethyl group, n-propyl group, a group having a partial structure of the following formula (10), etc. Can be mentioned. At least one of R ⁵ may be a partial structure of the following formula (10).
In formula (10),
The plurality of R ^11s are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms;
The plurality of R ^12s 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 a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a phenyl group.
Examples of the above-mentioned substituents include halogen atoms and the like.

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

The carbon atom of the benzene ring to which -O- of formula (9) is bonded is the 1st position, and R ⁵ having a partial structure represented by the formula (10) is bonded to one of the carbon atoms at the 2nd or 6th position, 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. It may be a structure in which a hydrocarbon group or a partial structure represented by the above formula (10) is bonded to the carbon atoms at the 2- and 6-positions of the benzene ring to which -O- in formula (9) is bonded. In the benzene ring in the above formula (9), [Y _n -A] in the above formula (1) or (8) is bonded to a carbon atom other than the 2-position and the 6-position via the center X and the oxygen atom. It is preferable that [Y _n -A] of the above formula (8) is bonded to the 1st position via an oxygen atom, and the central portion X is bonded to the 4th position.

When a=2 in formula (8), Z may have a structure represented by the following formula (11), for example.
A plurality of R ⁵ 's in formula (11) are each independently an arbitrary substituent, and k is each independently an integer of 1 to 4.
Examples of R ⁵ in the above formula (11) include linear alkyl groups having 1 to 8 carbon atoms such as a methyl group, an ethyl group, and an n-propyl group.

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

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

The above-mentioned modified polyphenylene ether and/or modified polyphenylene ether composition corresponds to, for example, a monovalent phenol compound represented by the following formula (12) and a central portion X in the structure represented by the above formula (9). It is obtained by copolymerizing with an a-valent phenol compound (center phenol) and carrying out a modification reaction.
In formula (12), R ²¹ and R ²² include the same groups as defined in formula (4) above, and are the same as R ²¹ and R ²² defined in formula (4) above. It is preferable that there be.

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

Examples of dihydric phenols represented by the above formula (11) are listed below.
Examples of dihydric phenols include (1,1'-biphenyl)-4,4'-diol, 3,3'-dimethyl(1,1'-biphenyl)-4,4'-diol, and 3,3'-diol. ',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-tert-butyl-2,2'-dimethyl(1,1'-biphenyl)-4,4-diol, 3, Examples include, but are not limited to, 3'-di-tert-butyl-5,5'-dimethyl(1,1'-biphenyl)-4,4-diol.

The number of phenolic hydroxyl groups in the polyhydric phenol compound is not particularly limited as long as it is 2 or more, but if the number of polyphenylene ether terminals increases, the molecular weight change during polymerization may increase, so it is preferably 2 to 6. , more preferably 2 to 4.

The modified polyphenylene ether composition of the present embodiment may contain a monofunctional polyphenylene ether represented by the following formula (13) and/or a modified product of the monofunctional polyphenylene ether represented by the following formula (13). do not have.
In formula (13), c is any integer from 1 to 100, and R ²¹ and R ²² include the same groups as explained for formula (12) above.

In the modified polyphenylene ether and/or modified polyphenylene ether composition (hereinafter referred to as modified polyphenylene ether (composition)) of the present embodiment, the polyfunctional Polyphenylene ethers may be produced by a redistribution reaction in which monofunctional polyphenylene ethers are equilibrated with polyhydric phenols in the presence of an oxidizing agent. Redistribution reactions are known in the art and are described, for example, in Cooper et al., US Pat. No. 3,496,236, and Liska et al., US Pat. No. 5,880,221.

The modified polyphenylene ether (composition) of the present embodiment is a modified polyphenylene ether having the structure of the above formula (1) in the ¹ H-NMR measurement results, and one or more [-Y _n - A] is [Y _n -H] and all [-Y _n -A] are not [Y _n -H], and in the structure of the above formula (1), all [-Y _n -A] is [Y _n -H] Appears in the region of 7.6 to 8.3 ppm with respect to the integrated value of the peak derived from the central phenol moiety represented by the above formula (2), which is contained in the polyphenylene ether where [Y n -H] The ratio of the integrated value of peaks derived from peroxide is 1 or less, preferably 0.8 or less, and more preferably 0.5 or less. The fact that the integrated value of the peak derived from peroxide is 1 or less with respect to the integrated value of the peak derived from the central phenol site indicates that the modified polyphenylene ether composition contains a peroxide adduct as a by-product. First, it means that the target product, such as polyfunctional modified polyphenylene ether, has high purity. 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 Examples below.

The number average molecular weight (Mn) of the modified polyphenylene ether (composition) in this embodiment is 500 to 15,000 g/mol, preferably 1,000 to 10,000 g/mol, and more preferably 2,000 g/mol. ~8,000g/mol. By having a number average molecular weight (Mn) within the above range, fluidity is further improved when dissolved in a solvent for producing a varnish in the process of applying it to a substrate material, and workability is ensured when applying it to a substrate material. be able to.
The number average molecular weight can be measured by the method described in Examples below.

The number of A substituents (referring to A defined in formula (1), hereinafter the same shall apply) contained in the polyfunctional modified polyphenylene ether (composition) in this embodiment is not particularly limited, but A The case where A=hydrogen atom (H) is excluded from the number of substituents. Among these, it is preferable that the composition contains 700 to 3,000 μmol/g of A substituents, 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 can be obtained. It is in. When the number of A substituents in the composition is 3,000 μmol/g or less, the viscosity of the varnish prepared by dissolving the polyphenylene ether composition in a solvent can be lowered, and processability tends to be good when applied to a substrate material.

As a method for evaluating the number of A substituents, known methods such as titration, spectroscopy, quantitative NMR, etc. can be used depending on the type of functional group. For example, in a quantitative NMR method, when ¹ H-NMR is used, a standard sample with a known structure and a polyfunctional polyphenylene ether composition are coexisting for measurement. A polyfunctional polyphenylene ether composition of known weight and a standard sample are dissolved in a deuterated solvent and ¹ H-NMR is measured, and the ratio of the integral value of the peak derived from the A substituent to the peak of the standard sample, The number of A substituents can be determined by calculation from the weight of the composition, the weight of the standard sample, and the molecular weight of the standard sample. The standard sample is not particularly limited as long as it is dissolved in a deuterated solvent, does not react with the polyfunctional polyphenylene ether composition, and has a peak in ¹ H-NMR that does not interfere with the peak derived from the polyfunctional polyphenylene ether composition. For a specific evaluation method of the number of A substituents, the description in Examples can be referred to.

The modified polyphenylene ether-containing composition according to the present embodiment is expressed by the above formula (8) from the viewpoint of having all of low dielectric properties, appropriate metal releasability, low solution viscosity, and sufficient Tg during curing. It is preferable that the modified polyphenylene ether contains 0.5 to 95% by mass of a modified polyphenylene ether having a structure.

<Production method of polyfunctional modified polyphenylene ether (composition)>
The method for producing the polyfunctional modified polyphenylene ether (composition) of the present embodiment includes, for example, a polyfunctional modified polyphenylene ether (composition) whose molecular terminal is a hydroxyl group, which is represented by the following formula (1)' by a polymerization method. It can be produced by synthesizing an unmodified polyfunctional polyphenylene ether (hereinafter also referred to as a composition) and introducing the A substituent in formula (1) to its terminal, that is, modifying it.
In formula (1)', Z, Y, n, and a are the same as those in formula (1) above, and are preferably the same as defined in formula (1) above.

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

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

As the polymerization catalyst used in this embodiment, a known catalyst system that can generally be used in the production of polyphenylene ether can be used. A generally known catalyst system is one consisting of a transition metal ion having redox ability and an amine compound capable of forming a complex with the transition metal ion. For example, a catalyst system consisting of a copper compound and an amine compound is known. A catalyst system, a catalyst system consisting of a manganese compound and an amine compound, a catalyst system consisting of a cobalt compound and an amine compound, etc. Since the polymerization reaction proceeds efficiently under slightly alkaline conditions, some alkali or an additional amine compound may be added here.

The polymerization catalyst suitably used in this embodiment is a catalyst comprising a copper compound, a halogen compound, and an amine compound as constituent components of the catalyst, and more preferably a diamine compound represented by the general formula (DA1) as the amine compound. It is a catalyst containing.
In formula (DA1), R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, and all of them are hydrogen atoms at the same time. and R ¹⁸ is a linear or methyl branched alkylene group having 2 to 5 carbon atoms.

Examples of the copper compounds of the catalyst components mentioned here are listed below. As suitable copper compounds it is possible to use cuprous compounds, cupric compounds or mixtures thereof. Examples of the cupric compound include cupric chloride, cupric bromide, cupric sulfate, cupric nitrate, and the like. Further, examples of the cuprous compound include cuprous chloride, cuprous bromide, cuprous sulfate, cuprous nitrate, and the like. Among these, particularly preferred metal compounds are cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide. These copper salts may also be synthesized at the time of use from oxides (eg cuprous oxide), carbonates, hydroxides, etc. and the corresponding halogens or acids. A frequently used method is to mix cuprous oxide and hydrogen halide (or a solution of hydrogen halide) as exemplified above.

Examples of halogen compounds include hydrogen chloride, hydrogen bromide, hydrogen iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, tetramethylammonium chloride, and tetramethylammonium bromide. , tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and the like. Moreover, these can be used as an aqueous solution or a solution using a suitable solvent. These halogen compounds may be used alone or in combination of two or more. A preferred halogen compound is an aqueous solution of hydrogen chloride or an aqueous solution of hydrogen bromide.

The amount of these compounds used is not particularly limited, but it is preferably 2 times or more and 20 times or less as a halogen atom with respect to the molar amount of copper atoms, and the use of copper atoms is preferable with respect to 100 moles of the phenol compound added to the polymerization reaction. The amount ranges from 0.02 mol to 0.6 mol.

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-tert-butylethylenediamine, N,N'-tert-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, etc. . A preferred diamine compound for this embodiment is one in which the alkylene group connecting two nitrogen atoms has 2 or 3 carbon atoms. The amount of these diamine compounds to be used is not particularly limited, but is preferably in the range of 0.01 mol to 10 mol per 100 mol of the phenol compound added to the polymerization reaction.

In this embodiment, primary amines and secondary monoamines can be included as constituent components of the polymerization catalyst. Examples of secondary monoamines include, but are not limited to, dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, Di-tert-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.

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

In this embodiment, there is no restriction at all regarding the addition of a surfactant that is conventionally known to have an effect of improving polymerization activity. Such surfactants include, for example, trioctylmethylammonium chloride, known under the trade name Aliquat 336 or Capriquat. The amount used is preferably in a range not exceeding 0.1% by mass based on 100% by mass of the total amount of the polymerization reaction mixture.

In addition to pure oxygen, the oxygen-containing gas used in the polymerization process of this embodiment may include a mixture of oxygen and an inert gas such as nitrogen in any ratio, air, or even air and an inert gas such as nitrogen. Mixtures in any ratio can be used. Normal pressure is sufficient for the system internal pressure during the polymerization reaction, but reduced pressure or increased pressure can be used if necessary.

The polymerization temperature is not particularly limited, but if it is too low, the reaction will be difficult to proceed, and if it is too high, there is a risk of reducing reaction selectivity or producing high molecular weight components, so it is preferably 0°C to 60°C, more preferably is in the range of 10°C to 50°C.

In the method for producing an unmodified polyfunctional polyphenylene ether (composition) of the present embodiment, during polyphenylene ether polymerization, it is preferable to polymerize in a solution state (herein also referred to as "solution polymerization"). By producing an unmodified polyfunctional polyphenylene ether (composition) by solution polymerization, even when a central phenol having a bulky structure is used, the above-mentioned conditions can be achieved during production of the unmodified polyfunctional polyphenylene ether (composition). A polyphenylene ether component that does not contain the structure of formula (1)' can be produced with high purity, or the proportion of by-products produced by peroxide can be reduced, and the polyphenylene ether component that does not contain the structure of formula (1) of the target product can be produced. Polyfunctional modified polyphenylene ether etc. can be produced with high purity.

(Copper extraction and by-product removal process)
In this embodiment, there is no particular restriction on the post-treatment method after the polymerization reaction is completed. Usually, an acid such as hydrochloric acid or acetic acid, ethylenediaminetetraacetic acid (EDTA) and its salts, nitrilotriacetic acid and its salts, etc. are added to the reaction solution to deactivate the catalyst. Further, a method for removing by-products of dihydric phenol produced by polymerization of polyphenylene ether can also be carried out using conventionally known methods. If the metal ions as the catalyst described above are substantially deactivated, the mixture can be decolorized or post-treated simply by heating. It is also possible to add a required amount of a known reducing agent into the system. Known reducing agents include hydroquinone, sodium dithionite, and the like.

(liquid-liquid separation process)
In the method for producing an unmodified polyfunctional polyphenylene ether (composition) of the present embodiment, water is added to extract the compound that has deactivated the copper catalyst, and liquid-liquid separation is performed between the organic phase and the aqueous phase. Thereafter, the copper catalyst may be removed from the solid base by removing the aqueous phase. This liquid-liquid separation step is not particularly limited, but includes methods such as static separation and separation using a centrifuge. In order to promote the liquid-liquid separation, a known surfactant or the like may be used.

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

The method for volatilizing the solvent contained in the organic phase is not particularly limited, but the organic phase may be transferred to a concentration tank at a high temperature (for example, the drying temperature described below may be used), and the solvent may be distilled off and concentrated. method, or a method in which toluene is distilled off and concentrated using equipment such as a rotary evaporator.

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

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

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

Specific examples of halogenated silyl compounds include methylvinyldichlorosilane, divinyldichlorosilane, allylmethyldichlorosilane, diallyldichlorosilane, trichlorosilyl-2-norbornene, 6-methyldichlorosilyl-2-norbornene, 6-dimethyldichlorosilyl -2-Norbornene, phenylvinyldichlorosilane, 3-methacryloxypropyldichloromethylsilane, 3-chloropropylmethyldivinylsilane, allyl phenyldichlorosilane, diphenylvinylchlorosilane, dimethylvinylchlorosilane, chloromethyldimethylvinylsilane, allyldimethylchlorosilane, methyl Phenylvinylchlorosilane, 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, allyl phenyldibromosilane, diphenylvinylbromosilane, dimethylvinylchlorosilane, Examples include bromomethyldimethylvinylsilane, allyldimethylbromosilane, methylphenylvinylbromosilane, 5-norbornen-2-yl(ethyl)bromodimethylsilane, 5-norbornen-2-ylchlorodibromosilane, and the like.

Examples of aminosilyl compounds include methylvinylsilyl-tris(1,2,4-triazole), divinylsilylbis(1,2,4-triazole), allylmethylsilylbis(1,2,4-triazole), diallylsilylbis (1,2,4-triazole), tris(1,2,4-triazolyl)silyl-2-norbornene, 6-methylbis(1,2,4-triazolyl)silyl-2-norbornene, 6-dimethylbis(1 ,2,4-triazolyl)silyl-2-norbornene, phenylvinylsilylbis(1,2,4-triazole), 3-methacryloxypropylmethylsilylbis(1,2,4-triazole), allyl phenylsilyl(1 , 2,4-triazole), diphenylvinylsilyl (1,2,4-triazole), dimethylvinylsilyl (1,2,4-triazole), allyldimethylsilyl (1,2,4-triazole), methylphenylvinyl Silyl (1,2,4-triazole), 5-norbornen-2-yl(ethyl)dimethylsilyl (1,2,4-triazole), methylvinylsilyl-trisimidazole, divinylsilylbisimidazole, allylmethylsilylbisimidazole , diallylsilylbisimidazole, trisimidazolylsilyl-2-norbornene, 6-methylbisimidazolylsilyl-2-norbornene, 6-dimethylbisimidazolylsilyl-2-norbornene, phenylvinylsilylbisimidazole, 3-methacryloxypropylmethylsilylbis Imidazole, allyl phenylsilylimidazole, diphenylvinylsilylimidazole, dimethylvinylsilylimidazole, allyldimethylsilylimidazole, methylphenylvinylsilylimidazole, 5-norbornen-2-yl(ethyl)dimethylsilylimidazole, 1,3-divinyl-1, Examples include 1,3,3-tetramethyldisilazane, bis(dimethylamino)methylvinylsilane, and the like.

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

The reaction for introducing the above compound into the terminal of unmodified polyphenylene ether is generally a direct reaction with a hydroxyl group, but a reaction with an alkali metal salt of a hydroxyl group may also be used. Alternatively, the halogenated silyl compound may be reacted with imidazole, triazole, pyrrolidine, or piperidine to form an amine compound, and then reacted with a hydroxyl group. In the direct reaction between a halogenated silyl compound and a hydroxyl group, acids such as hydrogen halides are generated, so a weak base such as an amine may be present in order to trap the acids.

In order to prevent side reactions, the amines that are allowed to coexist are preferably tertiary amines. Specific examples of amines to coexist include trimethylamine, diethylmethylamine, triethylamine, diethylamine, di-n-propylamine, tri-n-propylamine, triisopropylamine, di-n-butylamine, di-n-butylmethyl. Amine, di-n-butylethylamine, di-n-propylmethylamine, diisopropylmethylamine, di-n-propylethylamine, diisopropylethylamine, tri-n-butylamine, tri-tert-butylamine, triisobutylamine, di-tert -butylamine, diisobutylamine, tetramethylethylenediamine, tetraethylethylenediamine, tetramethylmethylenediamine, tetraethylmethylenediamine, pyridine, dimethylaniline, dimethylaminopyridine and the like.

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

In addition, water can cause not only undesirable side reactions during the reaction, but also hydrolysis reactions after the reaction, reducing the reaction yield. Therefore, remove water from the reaction solvent and amine in advance. It is preferable to leave it there. The preferred amount of water in the reaction system is preferably less than 200 ppm, more preferably less than 100 ppm.

In order to prevent side reactions or generation of by-products during purification, excess amines may be removed from the system after the reaction. In the case of low-boiling amines, amines can be removed from the reaction system by distillation or the like. The amount of amine remaining before the purification step is less than 10,000 ppm.

In a preferred embodiment to achieve a high modification rate in the modification reaction step, the amount of the halogenated silyl compound used in the modification reaction is 1.00 times or more in mole per 1 mole of hydroxyl group in the polymer. and less than 4 times the mole, preferably 1.05 times the mole to 3 times the mole, more preferably 1.1 times the mole to 2.5 times the mole. If the amount of the halogenated silyl compound used is less than 1.00 times the mole of hydroxyl group, a sufficient modification rate will not be obtained, while if it is more than 4 times the mole, undesirable by-products will be produced during purification after the reaction. may occur, resulting in a decrease in purification yield. The amount of the amine used to coexist for the purpose of trapping 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, and more preferably 1.05 times mole to 4 times mole, and more preferably 1.00 times mole or more and less than 6 times mole per mole of hydroxyl group. Preferably it is 1.1 to 4 times the mole. If the amount of amine used is less than 1.00 times the mole of hydroxyl group, sufficient modification rate will not be obtained, and if it is more than 6 times the mole, the effect on the conversion rate will not change, but a large amount of amine will be used after the reaction. This is not desirable as it requires removal.

The modification reaction temperature is not particularly limited, but it is preferably a temperature condition at which unmodified polyphenylene ether does not precipitate from an unmodified polyphenylene ether solution consisting of unmodified polyphenylene ether and a good solvent thereof. Further, a combination of a plurality of temperature conditions may be used.

After the modification reaction, if there is an excess of the halogenated silyl compound, it may be reacted with an alcohol such as methanol or ethanol to perform a treatment such as deactivation.

In addition, after the modification reaction, in order to remove by-products such as amine salts, the target product may be filtered or washed with water, acidic, or alkaline aqueous solutions, or the polymer solution may be washed with a poor solvent such as alcohol. The target product may be recovered by dropping it into the solution and re-precipitating it. Alternatively, after washing the polymer solution, the solvent may be distilled off under reduced pressure to recover the desired polymer.

The method for producing the polyfunctionally modified polyphenylene ether (composition) of the present embodiment is not limited to the method for producing the polyfunctionally modified polyphenylene ether composition of the present embodiment described above, but includes the polymerization step, copper extraction and The order or number of by-product removal steps, liquid-liquid separation steps, concentration/drying steps, etc. may be adjusted as appropriate.

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

Specifically, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene copolymer (SBS), hydrogenated styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer (SIS), Examples include styrenic elastomers such as hydrogenated styrene-isoprene-styrene copolymer and hydrogenated styrene (butadiene/isoprene) styrene copolymer. These styrene elastomers may be used alone or in combination of two or more.
Among these, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene copolymer (SBS), and hydrogenated styrene-butadiene-styrene copolymer are preferred. Note that SBR may be in a rubbery or solid form.

<Block copolymer/random copolymer>
The styrene elastomer (B) 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 is a "block copolymerized styrenic elastomer" consisting of a block mainly composed of a vinyl aromatic compound (block (A)) and a block mainly composed of a conjugated diene (block (B)). "Random copolymerization type styrenic elastomer" which has a structure in which a vinyl aromatic compound and a conjugated diene compound are randomly copolymerized, and "hybrid type elastomer" which has a structure in which both a block copolymerization structure and a random copolymerization structure Examples include styrene elastomers.
Specific examples of such styrene-based elastomers include Tuftec H1221, H1062, H1041, H1051, and H1043, which are commercially available hydrogenated styrene-butadiene block copolymers manufactured by Asahi Kasei Corporation. Commercially available copolymers include S1605 and S1606, and commercially available styrene-butadiene block copolymers manufactured by Asahi Kasei Corporation include Tufprene A, Tufprene 125, Tufprene 126S, Asaprene T-411, T-432, and Styrene- Commercially available butadiene copolymers include Asaflex 800S, 805, and 810.

<Number average molecular weight of styrene elastomer>
The preferable range of the number average molecular weight of the styrene elastomer (B) of this embodiment differs depending on the double bond content.

When the double bond content of the styrenic elastomer is less than 20%, there is an advantage that the larger the number average molecular weight, the higher the elastic modulus of the cured product obtained by curing the resin composition. When the number average molecular weight becomes large, it may take time to dissolve the resin composition in a solvent. Furthermore, while a smaller number average molecular weight has the advantage of increasing the fluidity of the resin composition, the modulus of elasticity of a cured product obtained by curing the resin composition may decrease.

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 5000 or more and 200,000 or less, and even more preferably 1 It is 10,000 or more and 100,000 or less, more preferably 30,000 or more and 60,000 or less, particularly preferably 40,000 or more and 50,000 or less.

In addition, when the double bond content of the styrene elastomer is 20% or more, the double bonds in the elastomer greatly contribute to the crosslinking reaction during the curing reaction, so as the number average molecular weight increases, the elastic modulus of the cured product decreases. However, the viscosity of the resin composition may increase quickly and the moldability may deteriorate. Further, as the number average molecular weight decreases, the fluidity of the resin composition increases, but the cured product may become brittle.

From such a viewpoint, the number average molecular weight of the styrenic elastomer having a double bond content of 20% or more is preferably 500 or more and 300,000 or less, more preferably 1000 or more and less than 10000, and even more preferably 2000 or more. It is 8,000 or less, particularly preferably 3,000 or more and 5,000 or less.

The number average molecular weight of the random polymerization type styrene elastomer is preferably 500 or more and 300,000 or less, more preferably 1000 or more and less than 10,000, still more preferably 2000 or more and 8000 or less, and particularly preferably 3000 or more. 5000 or less.

On the other hand, the number average molecular weight of the block copolymerizable styrene elastomer is preferably from 500 to 300,000, more preferably from 5,000 to 200,000, even more preferably from 10,000 to 100,000, Particularly preferably 30,000 to 60,000, most preferably 50,000 to 40,000.

<Double bond content of styrenic elastomer>
The preferred range of the double bond content of the styrene elastomer (B) of this embodiment differs depending on the number average molecular weight.

When the number average molecular weight of the styrenic thermal elastomer is less than 10,000, the fluidity of the resin composition increases as the double bond content of the styrene elastomer increases, but a brittle cured product may be formed when cured. be.

From such a viewpoint, in the case of a styrenic elastomer with 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, Even more preferably, it is 50 or more and 70% or less.

When the number average molecular weight of the styrene elastomer is 10,000 or more, the higher the double bond content of the styrene elastomer, the higher the elastic modulus of the cured product, but it takes a long time to dissolve the resin composition in a solvent. Sometimes.

From such a viewpoint, in the case of a styrenic 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, and still more preferably 10% or less. It is particularly preferably 1% or less.

<Styrene content of styrenic elastomer>
The styrene content of the styrene elastomer that is the component (B) is not particularly limited, but the higher the styrene content, the better the compatibility with the terminally modified polyphenylene ether that is the component (A) at the resin composition stage, and The uniformity of the product tends to increase, and the lower the styrene content, the lower the dielectric loss tangent of the cured product.

From such a viewpoint, in the case of a styrene 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, and even more preferably is 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.

In the case of a styrene 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, and still more preferably 20% or more. It is 50% or less, particularly preferably 30% or more and 40% or less.

<Hydrogenation rate of double bonds in styrenic elastomer>
In the styrenic elastomer that is component (B), the hydrogenation rate of double bonds based on conjugated diene monomer units is not particularly limited, but from the viewpoint of suppressing deterioration, it is preferably 90% or more. , more preferably 98% or more.

<(C) Crosslinking aid>
The crosslinking aid as component (B) according to the present embodiment is an aromatic vinyl compound having a structure represented by the following formula (18) and having a structure in which the number of vinyl groups in the molecule is 3 or less.
{In formula (18), R ³⁷ , R ³⁸ , and R ³⁹ each independently represent a hydrogen atom or a hydrocarbon group having 4 or less carbon atoms, and R ⁴⁰ and R ⁴¹ each independently represent hydrogen or a carbon Represents a saturated or unsaturated hydrocarbon group of number 8 or less. }
Contains as an essential ingredient.
R ³⁷ , R ³⁸ , and R ³⁹ are each independently a hydrogen atom or a hydrocarbon group having 4 or less carbon atoms. The smaller the number of carbon atoms, the higher the reactivity. On the other hand, the larger the number of carbon atoms, the lower the vapor pressure, and the less the amount of component (C) evaporated during heating of the resin composition. From such a viewpoint, it is preferable that the number of carbon atoms in R ³⁷ , R ³⁸ and R ³⁹ is as small as possible, and a hydrogen atom is most preferable.

R ⁴⁰ and R ⁴¹ are each independently hydrogen or a saturated or unsaturated hydrocarbon group having 8 or less carbon atoms. The smaller the number of carbon atoms, the lower the viscosity of the resin composition, and the larger the number of carbon atoms, the lower the vapor pressure, and the less the amount of evaporation of component (C) during heating of the resin composition.

From such a viewpoint, a more preferable combination of R ⁴⁰ and R ⁴¹ is one in which one is a hydrogen atom and the other is a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a hydrocarbon group having 2 to 4 carbon atoms. It's a combination.
Furthermore, when R ⁴⁰ and R ⁴¹ are saturated hydrocarbon groups, the toughness of the cured product formed by curing the curable resin composition tends to be high, whereas when they are unsaturated hydrocarbon groups, the toughness of the cured product formed by curing the curable resin composition tends to be high. The glass transition temperature of the cured product tends to be high. From such a viewpoint, it is more preferable that the number of unsaturated groups contained in R ⁴⁰ and R ⁴¹ is one or zero in total.
From the same viewpoint as above, R ⁴⁰ is preferably a tert-butyl group, and R ⁴¹ is preferably a vinyl group.

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

<Reason for the effect of crosslinking aid>
Since the crosslinking aid of the component (C) is a low molecular weight containing aromatics, it is highly compatible with the modified polyphenylene ether of the component (A) and the styrene elastomer of the component (B). By incorporating a crosslinking aid, not only a uniform resin composition or varnish can be obtained, but also the viscosity of the molten state or resin solution is lowered, fluidity is increased, and good moldability is exhibited. Furthermore, since it exhibits good reactivity with the silyl group of the crosslinking aid, it is possible to form a matrix with a reaction-induced spinodal decomposition structure consisting of a discontinuous phase mainly composed of styrene elastomer and a continuous phase mainly composed of polyphenylene ether. .

Additionally, if the crosslinking density increases excessively, the uniformity of the cured product will decrease, resulting in a decrease in dielectric loss tangent and a brittle cured product, but component (C) has three vinyl groups in one molecule. Since the crosslinking density of the cured product is limited to the following, it is suppressed from increasing excessively, and since tert-butylstyrene is monofunctional, the cured product can provide a cured product with high uniformity. Therefore, it forms a cured product with high toughness and low dielectric loss tangent.

As a result, the curable resin composition of this embodiment provides a uniform cured product, and satisfies all of the requirements of sufficient Tg, low dielectric properties, copper foil adhesion, and low coefficient of linear expansion of the cured product. Become.

<(D) Liquid elastomer>
The resin composition of this embodiment contains (D) a liquid elastomer as an essential component. In this embodiment, the liquid elastomer refers to a relatively low molecular weight elastomer that is liquid at 40° C. or lower. By incorporating a liquid elastomer, the viscosity is suppressed even in highly concentrated varnishes, improving the applicability to glass cloth.

Monomers constituting the liquid elastomer are not particularly specified, but include isoprene, butadiene, styrene, and the like. Further, the elastomer may be a homopolymer or a copolymer, and in the case of a copolymer, it may be a block copolymer or a random copolymer. Among them, liquid elastomers containing styrene units are preferred, styrene-butadiene copolymers are more preferred, and styrene-butadiene random copolymers are even more preferred. The liquid copolymer as component (D) may be different from the copolymer such as SBR as component (B) in that it is liquid at 40° C. or lower and/or that it is preferably random.

Further, the molecular weight is not particularly limited as long as it is liquid at 40° C. or less, but the number average molecular weight is preferably 10,000 or less, more preferably 5,000 or less. By using a liquid elastomer having a molecular weight in such a range, the viscosity can be suppressed even in a highly concentrated varnish, and the effect of improving the coatability on glass cloth can be more clearly exhibited.

<Blending ratio of component (A) and component (B)>
In the curable resin composition of this embodiment, the components (A) and (B) have good compatibility and uniformity in both the solution state containing a solvent before curing and the resin mixed state without a solution. On the other hand, as the curing reaction progresses during the curing reaction stage, components (A) and (B) phase separate (reaction-induced spinodal decomposition), and the Tg is high. The phase mainly composed of the (A) component with a low linear expansion coefficient forms a continuous phase, and the phase mainly composed of the (B) component with a low Df forms a discontinuous phase, so the final result is a high Tg and linear expansion. A cured product with a low coefficient and Df tends to be formed.

Therefore, in this embodiment, the higher the ratio of component (A), the higher the heat resistance using Tg as an index, and the lower the linear expansion coefficient. Df) tends to be low.

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

<Blending ratio of component (C)>
This embodiment is not limited by the blending ratio of component (C), but the smaller the ratio of component (C) to the total amount of components (A) and (B), the higher the heat resistance tends to be. The higher the ratio of the components, the lower the dielectric loss tangent tends to be. From such a point of view, the blending ratio of components (A), (B), and (C) of the present invention is such that the ratio of the total amount of components (A) and (B) to the ratio of component (C) is 99:1 to 99:1. When the ratio is in the range of 20:80, the effects of the present invention tend to be exhibited well. More preferably the range is 95:5 to 30:70, still more preferably the range is 90:10 to 50:50, even more preferably the range is 80:20 to 60:40, particularly preferably 70 :30 to 65:35.

<Blending ratio of component (D)>
This embodiment is not limited by the blending ratio of component (D), but the smaller the ratio of component (D) to the total amount of components (A) and (B), the higher the heat resistance tends to be. The higher the ratio of the components, the better the coating properties on glass cloth tend to be. The effects of the present invention are well expressed when the blending ratio of component (D) is in the range of 99:1 to 20:80 to the total amount of component (A) and (B). There is a tendency to More preferably the range is 95:5 to 30:70, still more preferably the range is 90:10 to 50:50, even more preferably the range is 80:20 to 60:40, particularly preferably 70 :30 to 65:35.

<(E) component>
The resin composition of this embodiment contains (E) a vinyl group-containing silane compound represented by the following formula (19) as an essential component.
{In formula (19), R ⁴² represents a hydrogen atom or a hydrocarbon having 4 or less carbon atoms, and n represents an integer of 2 to 6. }

R ⁴² in formula (19) is a hydrogen atom or a hydrocarbon having 4 or less carbon atoms. When the number of carbon atoms in R ⁴² is 5 or more, the viscosity of the simple substance becomes high and the dilution effect is not sufficiently exhibited.
On the other hand, the smaller the number of carbon atoms in ^R42 , the lower the boiling point, and the more likely it is to evaporate when the solvent is distilled off (dryed) after adding a solvent to the curable resin composition of the present invention and making it homogeneous. .

From such a viewpoint, R ⁴² is preferably a hydrogen atom or has a carbon number of 3 or less, more preferably a hydrogen atom or a carbon number of 2 or less, and particularly preferably has a carbon number of 1.

n in formula (19) represents an integer of 2 to 6. When n is larger than 7, the viscosity of the element becomes high and the dilution effect is not sufficiently exerted.
On the other hand, the smaller n is, the lower the boiling point is, and the solvent tends to evaporate more easily when the solvent is distilled off (dryed) after being added to the curable resin composition of the present invention to make it homogeneous.
From this point of view, n is preferably 2 to 5, more preferably 3 to 4, particularly preferably 4.

When component (E) is blended into a curable resin composition, the melt viscosity of the curable resin composition tends to decrease, and furthermore, since the curing speed is moderately slow, the minimum melt viscosity described later tends to decrease. Excellent formability during the curing stage. Furthermore, in applications in which the present curable resin composition is impregnated into glass cloth or the like to produce composite materials, the resulting composite material is Tg, soldering heat resistance, appearance, moisture resistance, water resistance, etc. are increased, and Df is decreased.

２，４，６－トリメチル－トリビニルシクロトリシロキサン：

などが好ましい。 The vinyl group-containing silane compounds of the group represented by formula (19) include:
2,4,6,8-tetramethyl-tetravinylcyclotetrasiloxane:

2,4,6-trimethyl-trivinylcyclotrisiloxane:

etc. are preferable.

The curable resin composition of the present invention is not particularly limited in the amount of component (E), but the higher the ratio of component (B), the higher the Df of the cured product obtained by curing the curable resin composition of the present invention. Also, the higher the ratio of component (E), the more the curing reaction tends to be suppressed, so when a composite material such as a laminate is produced, it has an excellent appearance and tends to have a low Df. From such a point of view, the ratio of component (B) to component (E) is preferably in the range of 99.9:0.1 to 10:90, more preferably in the range of 99:1 to 20:80. The ratio is more preferably 97:3 to 30:70, particularly preferably 95:5 to 40:60, particularly preferably 90:10 to 50:50.

<(F) Initiator>
If desired, the curable resin composition of this embodiment may contain (F) an initiator. The initiator is not particularly limited, but includes organic peroxides, and those with a 1-minute half-life temperature within the range of 155°C to 180°C are preferred from the viewpoint of stability and reactivity during storage of the composition. Preferably, for example, t-hexylperoxyisopropyl monocarbonate (1 minute half-life temperature, hereinafter the same: 155.0°C), t-butylperoxy-3,5,5-trimethylhexanoate (166.0°C) , t-butylperoxylaurate (159.4°C), t-butylperoxyisopropyl monocarbonate (158.8°C), t-butylperoxy2-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-butylperoxybenzoate (166.8°C), n-butyl 4,4-di-(t-butylperoxy)valerate (172.5°C) ), di(2-t-butylperoxyisopropyl)benzene (175.4°C), dicumyl peroxide (175.2°C), di-t-hexyl peroxide (176.7°C), 2,5 -dimethyl-2,5-di(t-butylperoxy)hexane (179.8°C) and t-butylcumyl peroxide (173.3°C).

Among these, organic peroxides include t-butylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxybenzoate, di(2-t-butyl At least one selected from the group consisting of peroxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and t-butylcumyl peroxide is preferred.

The blending amount of component (F) is preferably 0.001 to 10 phr based on the total amount of components (A) and (C). When the amount of component (F) is 0.001 phr or more, the effect of component (F) is sufficiently exhibited, and the Tg of the cured product tends to be higher by promoting the progress of the curing reaction. Further, by setting the amount to 10 phr or less, it is possible to reduce the amount of the initiator and its decomposed products remaining in the cured product, which tends to prevent the dielectric loss tangent of the cured product from increasing. From this point of view, a more preferable amount of component (F) is 0.1 to 5 phr, and even more preferably 0.5 to 2 phr.

<(G) Solvent>
An organic or inorganic solvent can be added to the curable resin composition of this embodiment as component (G), if necessary. The viscosity of the composition can be lowered by adding an organic solvent, and such a curable resin composition can be used to impregnate glass fibers when making a laminate. There are things you can do to improve your sexuality.

Examples of such organic solvents include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), and ethyl acetate, which have a low boiling point and do not evaporate from the resin composition. From the viewpoint of easy removal, toluene and methyl ethyl ketone are particularly preferred.

<Other ingredients>
The curable resin composition of the present embodiment may contain additives such as flame retardants, elastomers, fillers, etc. within a range that does not impair its purpose.

<Minimum melt viscosity>
The curable resin composition of this embodiment can be used industrially by adding an initiator as necessary. One example of its industrial embodiment is a laminate. The laminate is produced by impregnating glass fibers with an organic solvent solution obtained by dissolving the curable resin composition of the present embodiment in an organic solvent such as toluene, and then drying it by hanging it in a hot air dryer. A prepreg is produced by evaporating the organic solvent, and the prepreg can be produced singly or by laminating a plurality of prepregs. In the above process, when pressing and curing the prepreg, the lower the minimum melt viscosity, the more the glass cloth tends to be impregnated into the finer details, and the higher the minimum melt viscosity, the resin of the produced laminate. The content tends to increase, but if it is too high, the resin content tends to decrease.

From such a viewpoint, the curable resin composition of the present embodiment preferably has a minimum melt viscosity of 1 [Pa·s] to 20,000 [Pa·s] in a state substantially free of solvent.

When the minimum melt viscosity is 1 [Pa・s] or more, more of the resin composition is retained in the glass cloth during the curing process, and a laminate with a high resin content tends to be obtained. When it is 20,000 [Pa·s] or less, the resin composition can penetrate into the fine details of the glass cloth, and it tends to be possible to prevent scratches and voids in the laminate.

From such a viewpoint, the curable resin composition of the present embodiment preferably has a minimum melt viscosity of 10 [Pa·s] or more and 10,000 [Pa·s] or less, more preferably 50 [Pa·s]. ] or more and 5000 [Pa・s] or less, more preferably 100 [Pa・s] or more and 1000 [Pa・s] or less, particularly preferably 150 [Pa・s] or more and 500 [Pa・s] or less, especially Preferably, the viscosity is 180 [Pa·s] or more and 300 [Pa·s] or less.

The method for measuring the minimum melt viscosity of the present embodiment is to measure the curable resin composition containing an initiator using a cone-plate rotational viscometer (thermal The minimum melt viscosity can be determined by measuring in vibration mode using a HAAKE MARS III (manufactured by Fisher Scientific Co., Ltd.).

On the other hand, when the curable resin composition of this embodiment contains an initiator and a solvent, the solvent is evaporated from the curable resin composition of this embodiment using an evaporator, a hot air dryer, etc., and the solvent is substantially removed. The minimum melt viscosity can be determined by making a solid curable resin composition containing no .

<Prepreg>
The prepreg of this embodiment includes the curable resin composition of this embodiment.
The curable resin composition of this embodiment is obtained by impregnating a woven fabric or non-woven fabric such as glass fiber or carbon fiber with a curable resin composition solution obtained by adding an organic or inorganic solvent as necessary. A prepreg can be produced by evaporating the solvent using a hot air dryer or the like.

<Varnish concentration during prepreg production>
Although this embodiment is not limited to the concentration of the curable resin composition solution prepared when producing the prepreg, the lower the concentration of the curable resin composition solution, the lower the viscosity, and the lower the concentration of the curable resin composition solution, the lower the viscosity. The higher the concentration of the curable resin composition solution, the higher the resin content of the laminate obtained by curing the prepreg, and the higher the insulation reliability.

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

<Drying temperature, time>
When producing a prepreg by evaporating the solvent from a curable resin composition solution, the prepreg may be efficiently produced by drying by applying hot air while heating with a hot air dryer or the like, if necessary.
At that time, the lower the drying temperature to be set with respect to the exothermic start temperature (T ₁ ) of the DSC chart obtained by DSC measurement of the prepreg, the more likely it is to suppress the curing reaction from proceeding during drying. The higher the drying temperature relative to ₁ , the more completely the solvent tends to be removed by evaporation. From such a point of view, the temperature range is desirably from (T ₁ -80)°C to (T ₁ +80)°C, preferably from (T ₁ -60)°C to (T 1 +30)°C, and more preferably from (T 1 -60)°C to (T ₁ +30)°C. Preferably, a temperature range of (T ₁ -40) °C to (T ₁ +10) °C, more preferably a temperature range of (T ₁ -30) °C to T ₁ tends to yield a prepreg with suitable curability. be.

Although this embodiment is not specific to the drying time for producing prepreg, the shorter the drying time, the more likely it is to suppress the progress of the curing reaction during drying, and the longer the drying time, the more completely the curing reaction can be suppressed. The solvent tends to be removed by evaporation. From this point of view, it is desirable that the drying time is usually 30 seconds to 60 minutes, preferably 1 minute to 30 minutes, more preferably 1.5 minutes to 20 minutes, even more preferably 2 minutes to 15 minutes, especially Preferably it is 3 minutes to 10 minutes.

<Resin content of prepreg>
An example of an embodiment of the curable resin composition of the present embodiment is an industrial use method in which a fiber base material is impregnated with the curable resin composition to produce a prepreg, and the prepreg is laminated and cured. It will be done. In such prepregs, the higher the resin content, the higher the electrical insulation properties of the laminate obtained by laminating and curing the prepregs, and the lower the resin content, the lower the coefficient of linear expansion. There is a tendency. From such a viewpoint, the resin content of the prepreg is preferably 10% or more and 90% or less on a mass basis, more preferably 20% or more and 80% or less, and even more preferably 30% or more and 75% or less, Particularly preferably, it is 40% or more and 70% or less, particularly preferably 50% or more and 65% or less.

<Laminated board>
The laminate of this embodiment includes a cured product of the curable resin composition of this embodiment.
An example of a method for manufacturing the laminate of the present embodiment is an industrial usage method in which a fiber base material is impregnated with the curable resin composition to produce a prepreg, and the prepreg is laminated and cured. In such prepregs, the higher the resin content, the higher the electrical insulation properties of the laminate obtained by laminating and curing the prepregs, and the lower the resin content, the lower the coefficient of linear expansion. There is a tendency. From such a viewpoint, the resin content of the prepreg is preferably 10% or more and 90% or less on a mass basis, more preferably 20% or more and 80% or less, and even more preferably 30% or more and 70% or less, Particularly preferably, it is 40% or more and 60% or less, particularly preferably 45% or more and 55% or less.

<Press temperature and pressure of laminate>
An example of a method for manufacturing the laminate of this embodiment is to laminate prepregs and produce a laminate by, for example, press molding. The higher the curing temperature when producing a laminate, the shorter the curing time and the higher the productivity of the laminate.The lower the curing temperature, the more suppressed thermal deterioration during the curing stage, and the higher the Tg and toughness. There is a tendency for laminated plates to be produced. From such a point of view, the curing temperature is desirably 20°C to 350°C, more preferably 80°C to 300°C, more preferably 100°C to 250°C, even more preferably 150°C to 230°C. The temperature is particularly preferably 180°C to 220°C.

Furthermore, if the curing temperature is increased during curing, a laminate with better toughness tends to be obtained, and the heating rate is preferably 0.5°C/min to 20°C/min, preferably 1°C/min. min to 10°C/min, more preferably 1.5°C/min to 10°C/min, even more preferably 2°C/min to 5°C/min.

Furthermore, a laminate can be produced by press-molding the prepreg during the curing stage. The higher the press pressure at that time, the more likely it is that a laminate with fewer voids can be produced, and the lower the press pressure, the less resin will flow out, resulting in a laminate with a high resin content, excellent insulation reliability, and low dielectric loss tangent. tends to be obtained.
From such a point of view, the press pressure is desirably 2 kgf/cm ² or more and 100 kgf/cm ² or less as a surface pressure applied to the prepreg, preferably 5 kgf/cm ² or more and 50 kgf/cm ² or less, and more preferably 10 kgf/cm 2 or less. /cm ² or more and 50 kgf/cm ² or less, more preferably 20 kgf/cm ² or more and 40 kgf/cm ² or less.

<Printed wiring board>
The printed wiring board of this embodiment includes a cured product of the curable resin composition of this embodiment.
As an example of an embodiment of the curable resin composition of the present embodiment, when preparing a laminate by laminating prepregs, a method such as sandwiching the prepreg between metal foils such as copper foil, etc. Examples include metal-clad laminates with foil bonded to them. Furthermore, the metal layer of the metal-clad laminate may be patterned by etching or the like to form a printed wiring board.

<Composite materials>
The composite material of this embodiment includes a cured product of the curable resin composition of this embodiment.
As an example of an embodiment of the curable resin composition of the present embodiment, a carbon fiber reinforced composite material is obtained by impregnating carbon fiber or a woven or nonwoven fabric of carbon fiber with the curable resin composition of the present embodiment and then curing the composition. (CFRP) is used.

Hereinafter, this embodiment will be described in more detail based on manufacturing examples and examples, but this embodiment is not limited to the following manufacturing examples and examples.

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

(1) Existence ratio of polyphenylene ether Here, the abundance ratio of polyphenylene ether is defined as modified polyphenylene ether having the structure of formula (1), one or more [-Y _n -A] in the structure of formula (1), -Y _n -H] and all [-Y _n -A] are not [-Y _n -H], and all [-Y _n -A] in the structure of formula (1) is the proportion of polyphenylene ether (main component polyphenylene ether) in which is [-Y _n -H].
(1-1)
The modified polyphenylene ether compositions obtained in Examples and Comparative Examples and the polyhydric phenol used as a raw material were dissolved in deuterated chloroform, and ¹ H-NMR measurement (manufactured by JEOL, 500 MHz) was performed using tetramethylsilane as an internal standard. Ta.
(1-2)
The peak of polyhydric phenol contained in the product was identified from the peak position resulting from the central phenol site.
(1-3)
The central phenol unit of the main component polyphenylene ether represented by formula (2) and formula (14):
{In formula (14), a plurality of R ²¹ and R ²¹ ' are each independently a hydrogen atom; an optionally substituted hydrocarbon group having 1 to 6 carbon atoms; an optionally substituted hydrocarbon group having 6 to 6 carbon atoms; 12 aryl groups; and a halogen atom; an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms; more preferably methyl group, ethyl group, n-propyl group, vinyl group, aryl group, ethynyl group, or propargyl group, more preferably methyl group or ethyl group, particularly preferably methyl group. Examples of the above-mentioned substituents include halogen atoms and the like.
In formula (14), the two R ^21s are hydrogen at the same time, from the viewpoint that the modified polyphenylene ether-containing composition has all of the following: low dielectric properties, appropriate metal releasability, low solution viscosity, and sufficient Tg during curing. It is preferable that they are not atoms, and/or that they are not a combination in which one is a partial structure represented by the above formula (3) and the other is a hydrogen atom, a methyl group, or an ethyl group.
In formula (14), a plurality of R ²² and R ²² ' each independently represent a hydrogen atom; an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, and an optionally substituted hydrocarbon group having 6 to 12 carbon atoms; represents at least one selected from the group consisting of an aryl group; and a halogen atom, and is preferably a hydrogen atom or an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, more preferably is a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group, more preferably a hydrogen atom or a methyl group. Examples of the above-mentioned substituents include halogen atoms and the like.
c is any integer from 1 to 100. }
A terminal phenoxy unit specific to the by-product represented by and formula (15):
{In formula (15), a plurality of R ²¹ and R ²¹ '' each independently represent a hydrogen atom; an optionally substituted hydrocarbon group having 1 to 6 carbon atoms; an optionally substituted hydrocarbon group having 6 to 6 carbon atoms; 12 aryl groups; and a halogen atom; an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms; more preferably methyl group, ethyl group, n-propyl group, vinyl group, aryl group, ethynyl group, or propargyl group, more preferably methyl group or ethyl group, particularly preferably methyl group.The above substituents include Examples include a halogen atom.
In formula (15), two R ²¹ are hydrogen at the same time, from the viewpoint that the modified polyphenylene ether-containing composition has all of the following: low dielectric properties, appropriate metal releasability, low solution viscosity, and sufficient Tg during curing. It is preferable that they are not atoms, and/or that they are not a combination in which one is a partial structure represented by the above formula (3) and the other is a hydrogen atom, a methyl group, or an ethyl group.
A plurality of R ²² and R ²² '' each independently represent 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 represents at least one selected from the group consisting of a hydrogen atom or an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a methyl group, ethyl group, or n-propyl group, and more preferably a hydrogen atom or a methyl group. Examples of the above-mentioned substituent include a halogen atom and the like.
d and e are each independently any integer from 1 to 100. }
The diphenyl unit specific to the by-product represented by is assigned to each peak in the obtained NMR spectrum, and the abundance ratio of various polyphenylene ethers is determined by the following formula (16):
{During the ceremony,
C: integrated value of the peak area due to H ¹ and R ²² ' of the terminal phenoxy unit specific to the byproduct represented by formula (14);
D: integrated value of peak area due to ^R22 '' inside the central phenol of the diphenyl unit, which is specific to the byproduct represented by formula (15);
E: integrated value of the peak area resulting from the central phenol moiety of the main component polyphenylene ether represented by formula (2); and F: central phenol represented by formula (2) corresponding to the peak for which integral value C was determined Number of protons derived from the site;
It is. }
It was quantified according to the following.

In addition, the peak resulting from the central phenol moiety of the main component polyphenylene ether represented by formula (2) used in Examples and Comparative Examples, the H ¹ of the terminal phenol of the by-product represented by formula (14), and The peak due to R ²² ′ and the peak due to R ²² ″ inside 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): 6.95-7.0ppm
Terminal phenoxy unit (3H) of the by-product represented by formula (14): 7.05 to 7.1 ppm
By-product diphenyl (4H) represented by formula (15): 7.34 to 7.4 ppm

(2) 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 of formula (2) (existence ratio of peroxide peak)
In the above ^1H -NMR measurement, the integrated value of the peak area resulting from the central phenol moiety of the main component polyphenylene ether represented by formula (2) is defined as E, and the peroxide that appears in the region of 7.6 to 8.3 ppm The abundance ratio of the peroxide peak was analyzed by calculating the integrated value G of the area of the impurity peak (namely, peroxide peak) derived from G and substituting it into the following equation (17).

(3) Number average molecular weight (Mn)
Using Gel Permeation Chromatography System 21 manufactured by Showa Denko Co., Ltd. as a measuring device, a calibration curve was created using standard polystyrene and ethylbenzene, and using this calibration curve, the number average molecular weight (Mn ) were measured.

Standard polystyrene has a molecular weight 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.

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

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

(4) Glass transition temperature (Tg)
The glass transition temperature of the modified polyphenylene ether composition was measured using a differential scanning calorimeter DSC (manufactured by PerkinElmer - Pyrisl). After heating from room temperature to 200°C at a temperature increase rate of 20°C per minute in a nitrogen atmosphere, the temperature was lowered to 50°C at a rate of 20°C per minute, and then the glass transition temperature was measured at a temperature increase rate of 20°C per minute.

(5) Number of A substituents contained in the composition A modified polyphenylene ether composition and a standard 1,3,5-trimethoxybenzene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., molecular weight 168.19) were used as an internal standard sample. A specified amount was taken, dissolved in deuterated chloroform containing trimethylsilane, and ¹ H-NMR measurement (manufactured by JEOL, 500 MHz) was performed.

Next, the integrated value of the proton peak (3.7 to 3.8 ppm: 9H) derived from the methoxy group of 1,3,5-trimethoxybenzene, and the proton at the C=C bond terminal of the methacrylic group on the high magnetic field side. Calculate the integral value of the peak (5.5 to 5.9 ppm: 1H) that appears in The number of methacrylic groups (unit: μmol/g) per 1 g of the composition was calculated.

(6) Viscosity of toluene solution of modified polyphenylene ether composition (liquid viscosity)
2 g of the modified polyphenylene ether composition and 3 g of toluene were weighed. Using a stirrer and a magnetic stirrer, these were stirred for 1 hour and completely dissolved until the solution became transparent, thereby preparing a 40 wt % toluene solution. The liquid viscosity of this solution was measured using a B-type viscometer at 25° C. and 30 rpm.

(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 Application Publication No. 2004-502849 (Patent Document 2).

(8) Preparation of cured product A film-like test piece with a thickness of 0.1 to 0.3 mm was prepared by a pressing method under the following conditions.
Polymers, styrene elastomers, etc. were added to toluene so that the component concentration was 34% and uniformly dissolved at room temperature overnight, and then Perbutyl P manufactured by NOF Corporation was added to prepare a varnish. This was applied to the shine side of copper foil, dried at 120°C for 10 minutes, and the resulting solid resin composition was ground in an agate mortar.
Cut out a 100 μm thick Teflon (registered trademark) sheet into a shape of 60 x 60 mm, place the Teflon (registered trademark) sheet on the shine side of the copper foil, and fill the cavity with an amount of about 1.5 times the theoretical value (specific gravity). 6 x 6 x 0.01 x 1.5 = 0.54 g) of the above solid resin composition was added, covered with the shine side of copper foil, and pressed under a press pressure of 40 (kg/cm ² ) and under constant vacuum conditions. , vacuum press hardening was performed under the following temperature conditions.
Room temperature to 50℃, 4℃/min, 50℃ Hold 1 minute 50℃ to 160℃ 4℃/min, 160℃ Hold 3 minutes 160℃ to 220℃ 4℃/min, 220℃ Hold time: 60 minutes

(9) Tg measurement of cured product The glass transition temperature (Tg) of the cured product was measured by DMA using Hitachi High-Tech Science Co., Ltd. (DMS6100) under the following conditions.
A test piece was cut to a size that allowed adequate measurement in the entire temperature range of the DMA device, and a dynamic viscoelasticity test was conducted.
Test piece: strip, measurement mode: tensile mode Test starting temperature: room temperature Heating rate: 4°C/min Maximum test temperature: 300°C
Maximum temperature holding time: 5 minutes Measurement frequency: 1Hz
Analysis: The tan δ peak was defined as Tg.
Furthermore, the storage modulus at a temperature 30° C. higher than the tan δ peak was read and used for calculating the crosslink density.

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

(11) Measurement of linear expansion coefficient of cured product The linear expansion coefficient was determined by measuring under the following conditions using a sample cut from a test piece for dielectric loss tangent measurement using Hitachi High-Tech Science Co., Ltd. TMA7100.
Measurement mode: Tensile Size: Width 2mm, length 10mm, thickness 0.2mm
Test starting temperature: -50℃
Heating rate: 10℃/min Maximum test temperature: 250℃
Maximum temperature holding time: 5 minutes

(12) Number average molecular weight of styrene elastomer Measurement was performed by gel permeation chromatography (GPC) under the following conditions, and the weight average molecular weight was determined from a PS (polystyrene) conversion calibration curve at the obtained peak.
Measuring device: GPC HLC-8220 (manufactured by TOSOH, product name)
Column: TAKgelGMHXL SuperH5000: 1 column, SuperH4000: 2 columns (manufactured by TOSOH, product name)
Solvent: Tetrahydrofuran Temperature: 40°C
Sample for calibration curve: Commercially available (manufactured by TOSOH) standard sample, 10 points measurement

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

(14) Double bond content of styrenic elastomer The double bond content of the styrene elastomer was determined by measuring by nuclear magnetic resonance spectroscopy (NMR) under the same conditions as the styrene content of the styrene elastomer.
It was calculated by converting it into a conjugated diene monomer weight ratio based on the vinyl bond amount of the conjugated diene monomer unit.

(15) Uniformity evaluation of resin composition A resin composition solution was separately prepared by removing only the initiator from the curable resin composition solution. 2 μl of the resin composition solution was dropped onto a slide glass placed on a hot plate at 160° C., and after being allowed to stand for 2 minutes, the pressure was reduced to 100 mmHg for 30 seconds to remove toluene to obtain a resin composition. While maintaining the temperature of the obtained resin composition as a slide glass at 160 °C, it was transferred to a hot stage set at 160 °C of a microscope, and observed with a 10x eyepiece in transmission mode of an optical microscope. We took a photo shoot.
When no texture was observed and the film was uniformly transparent, it was marked as ○, when texture was observed, it was marked as ×, and when no texture was observed but fluctuations were observed, it was marked as △.

(16) Measurement of copper foil adhesive strength of cured product The adhesive strength with copper foil was measured by a T-peel test. A small amount (about 50 ppm based on the total amount of varnish) of glass beads (for spacers) with a particle size of about 40 μm (20 to 40 μm) was added to a varnish that is a toluene solution prepared at a predetermined ratio and a concentration of ingredients of 34%. A 35 μm thick copper foil as an adherend was cut into a size of 50×80 mm, and a polyimide tape (width: 10 mm, thickness: 55 μm) was attached to the roughened surface of the copper foil. The prepared varnish was poured into the obtained frame, left overnight, dried at 120° C. for 10 minutes, and the polyimide tape was peeled off to obtain a test piece. Copper foils of the same size are stacked on top of each other with the roughened surfaces sandwiching the resin layer, and a Teflon (registered trademark) sheet of approximately 20 mm is sandwiched between one end to ensure gripping margin. Vacuum press hardening was carried out under the same temperature conditions as in "Preparation". The obtained copper foil was cut to prepare a measurement sample of 10 mm x 80 mm.
Using the measurement sample, a T-peel test was conducted under the following conditions using a tensile tester (Instron 59R5582 model) to measure copper foil adhesive strength.
Assumed test piece: 10mm*80mm Tested with n=2 and took the average value.
Measurement conditions: test temperature room temperature (approximately 23°C),
Test speed: 50 mm/min, test length: approximately 30 mm.

(17) Measurement of varnish solution viscosity The solution viscosity of a varnish with a blended component concentration of 62% (ie, 62 wt%) prepared in the following <Prepreg Preparation Method> was measured under the following conditions.
Equipment: TVE-22H manufactured by Toki Sangyo Co., Ltd. (cone plate type)
Measurement temperature: 25.0℃ (set temperature of thermostat)
Cone rotor type: "1°34' x R24" (when solution viscosity is less than 6.4 mPa・s), "3° x R14" (when solution viscosity is 6.4 mPa・s or more)
Sample amount: 1.1ml (when using "1°34' x R24"), 0.4ml (when using "3° x R14")
Measurement conditions: rotation speed 1.0 rpm, and the value 3 minutes after the start of rotation was taken as the measured value.

(18) Minimum melt viscosity of curable resin composition PPE, crosslinking aid, styrene elastomer, initiator, etc. were added to toluene at a concentration of 34% and uniformly dissolved at room temperature overnight, then, Perbutyl P manufactured by NOF Corporation was added to prepare a varnish. This was applied to the shine side of copper foil, dried at 120°C for 10 minutes, and the resulting solid resin composition was ground in an agate mortar.
The obtained solid resin composition was measured using a cone-plate rotational viscometer (HAAKE MARS III manufactured by Thermo Fisher Scientific Co., Ltd., aluminum parallel plate with a diameter of 20 mm) in vibration mode (frequency: 1 Hz, set strain: 0.001, gap). 1 mm) under a nitrogen atmosphere (100°C to 250°C, heating rate 4°C/min). The lowest viscosity in the temperature range of 100°C to 250°C was defined as the lowest melt viscosity.

<Method for producing prepreg>
Glass cloth is impregnated with a varnish for preparing prepreg, which is obtained by dissolving predetermined ingredients in toluene to obtain a toluene solution with a concentration of 62% (i.e., 62 wt%) of the ingredients, and dried in a hot air dryer at 120°C for 10 minutes to produce prepreg. I got it.

(19) DSC reaction behavior measurement The curable resin composition and prepreg were heated at 10°C/min from -50°C to 280°C under a nitrogen stream using a differential scanning calorimeter DSC (7000X manufactured by Hitachi High-Tech Science). After reaching the temperature, the temperature was maintained for 10 minutes and measured, and the reaction start temperature, reaction end temperature, and calorific value were determined. The calorific value of the prepreg was converted into the calorific value per unit mass of resin based on the resin content.

<Method for manufacturing laminate>
Six sheets of prepreg were laminated, sandwiched between copper foils and heated at a rate of 2°C/ ^min from room temperature to 220°C while applying a surface pressure of 40 kgf/cm2, and then heated under pressure at 220°C for 1 hour. A laminate was obtained.
When preparing a test piece for measuring copper foil peel strength, the copper foil was bonded to a prepreg with the roughened surface facing inside to prepare a copper clad laminate and the copper foil peel strength was measured. In other cases, the copper foil was peeled off after the laminate was prepared with the shine side facing inside, and various properties were evaluated.

(20) Measurement of resin content of laminate and prepreg The resin content of prepreg and laminate was measured by TG-DTA. The resin content was determined from the weight loss rate at the time when the temperature was raised from room temperature to 600°C at a rate of 20°C/min under a stream of air and further held at 600°C for 5 hours.

(21) Impregnating property of laminate A glass cloth cut into a shape of 30 x 60 mm was impregnated with the varnish prepared by the method described in <Method for Prepreg Preparation> above (that is, a varnish with a blended component concentration of 62 wt%) at 120°C. and dried for 10 minutes. Four sheets of the obtained prepreg were stacked and press-cured under the following temperature conditions at a press pressure of 40 (kg/cm ² ) and a constant vacuum condition.
Room temperature to 50°C, 4°C/min, 50°C Hold 1 minute 50°C to 160°C 4°C/min, 160°C Hold 3 minutes 160°C to 220°C 4°C/min, 220°C Hold time: 60 minutes Transparent ○ indicates that a certain laminate was obtained; × indicates that the obtained laminate was completely cloudy or had significant fading; The case was marked as △.

(22) Coefficient of linear expansion of the laminate The coefficient of linear expansion (CTE) of the laminate is determined by measuring the sample cut from the test piece for dielectric loss tangent measurement using Hitachi's TMASS6100 under the following conditions. Ta.
Measurement mode: Compression Test start temperature: -50℃
Heating rate: 10℃/min Maximum test temperature: 250℃
Maximum temperature holding time: 5 minutes

(23) Copper foil adhesion strength of the laminate The copper foil adhesion strength between the laminate and the roughened surface of the copper foil was measured using an Instron universal material testing machine (Model 59R5582) using the laminate produced by the above method. was measured under the following conditions.
Test temperature: 23°C, test speed: 50mm/min, peeling width: 10mm

(24) Tg of laminate
The Tg of the laminate was measured using DMA850 manufactured by TA under the following conditions. Test piece: Strip, Measurement mode: Tensile mode Test start temperature: -80℃
Heating rate: 2℃/min Maximum test temperature: 300℃
Maximum temperature holding time: 5 minutes Measurement frequency: 10Hz
Analysis: The tan δ peak was defined as Tg.

(25) Solder heat resistance test The obtained cured product, prepreg, or laminate was subjected to a solder heat resistance test under general conditions, and the condition was observed. If the condition observation passes, mark "OK".

Hereinafter, the manufacturing method of the unmodified polyphenylene ether composition of each manufacturing example and manufacturing comparative example, and the manufacturing method of the modified polyphenylene ether composition of each example and comparative example will be explained.

(Manufacturing example 1)
A 1.5 liter jacketed reactor equipped with a sparger for introducing oxygen-containing gas at the bottom of the reactor, stirring turbine blades and baffles, and a reflux condenser in the vent gas line at the top of the reactor was filled with 0.1026 g of the pre-prepared amount. 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; -n-butylamine, 894.04 g toluene, 73.72 g 2,6-dimethylphenol, 26.28 g 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane (ADEKA: AO-30) was added. Next, while stirring these components vigorously, air began to be introduced into the reactor through a sparger at a rate of 1.05 L/min, and at the same time a heating medium was passed through the jacket to control the polymerization temperature to be maintained at 40°C. 160 minutes after the introduction of air, the air ventilation was stopped, and 1.1021 g of ethylenediaminetetraacetic acid tetrasodium salt tetrahydrate (reagent manufactured by Dojindo Laboratories) was added to the polymerization mixture as a 100 g aqueous solution. Warmed to 70°C. After keeping the temperature at 70°C for 2 hours to perform catalyst extraction and by-produced diphenoquinone removal treatment, the mixed solution was transferred to a Sharpless centrifuge, and the unmodified polyphenylene ether composition solution (organic phase) and catalyst were transferred to a Sharpless centrifuge. The metal was separated into an aqueous phase. The obtained unmodified polyphenylene ether composition solution was transferred to a jacketed concentration tank, and toluene was distilled off and concentrated until the solid content in the unmodified polyphenylene ether composition solution became 55% by mass. Next, toluene was further distilled off from the concentrate using an oil bath set at 230°C and a rotary evaporator, and the solid content was dried to obtain an unmodified polyphenylene ether composition.

A stirring bar was placed in a 300 ml three-necked flask, a Dimroth condenser with a three-way stopcock was installed in the main tube, and a rubber stopper with a thermometer inserted was attached to one side tube. 20.0 g of the unmodified polyphenylene ether composition obtained in the above step was charged from the other side tube, and a rubber stopper was attached. After purging the inside of the flask with nitrogen, the mixture was dissolved in 60.0 g of super-dehydrated toluene manufactured by Wako Pure Chemical Industries, Ltd. using a syringe while stirring the inside with a magnetic stirrer. Then, 5.72 g of triethylamine was added to the system. Thereafter, 3.38 g of dimethylvinylchlorosilane was collected into a syringe and dripped into the system through a rubber stopper. After continuing stirring at 30° C. for 3 hours after the completion of the dropwise addition, 0.86 g of ultra-dehydrated methanol manufactured by Wako Pure Chemical Industries, Ltd. was added to the system to stop the reaction.

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

(Example 1-4, Comparative Example 1-3)
Using the styrene elastomer shown in Table 1 and the liquid elastomer shown in Table 2, a curable resin composition solution was prepared with the formulation shown in Table 3, and the results of evaluating the cured product obtained by the above method are shown in Table 3. It was shown to. In addition, the blending amount indicates parts by mass.

Abbreviations in Table 3 are as follows.
Perbutyl P: α,α-di(t-butylperoxy)diisopropylbenzene (manufactured by NOF Corporation)
tBS: 4-tert-Bu-styrene DVB: divinylbenzene (reagent manufactured by Tokyo Chemical Industry Co., Ltd., purity 57%)
D4V: 2,4,6,8-tetramethyl-tetravinylcyclotetrasiloxane SA9000: PPE modified with a terminal methacrylic group "Product name SA9000" (manufactured by Sabic Innovative Plastics, Mn: 2756, Mw: 4350, Mw/Mn: 1.6, average number of terminal functional groups per molecule: 1.96, number of residual hydroxyl groups per molecule: 0.01)

As is clear from Table 3, in the Examples, a uniform cured product was obtained, and the cured product had sufficient Tg, low dielectric properties, low coefficient of linear expansion, and moldability that satisfied all of the requirements for coating with high concentration varnish. A curable resin composition with good properties was obtained.
On the other hand, in Comparative Examples 1 and 2 which did not contain D4V, the viscosity of the high concentration varnish was high, resulting in poor coatability in the high concentration varnish. Furthermore, in Comparative Example 3 in which PPE modified with a terminal methacrylic group was used instead of vinylsilyl modified PPE, the dielectric properties of the laminate could not be measured due to poor impregnation.

In the curable resin composition of the present invention, a uniform cured product can be obtained by blending a terminal-modified polyphenylene ether with a specific structure, a specific styrene elastomer, a crosslinking aid with a specific structure, and a liquid elastomer. , provides a curable resin composition useful as a substrate material that satisfies all of the requirements of a cured product: sufficient Tg, low dielectric properties, adhesion, low coefficient of linear expansion, moldability, and appropriate solution viscosity for a high concentration varnish. You can.

Claims (27)

A curable resin composition containing the following components (A), (B), (C), (D) and (E):
(A) Modified polyphenylene ether Modified polyphenylene ether represented by the following formula (1):
{In formula (1), Z is an a-valent partial structure represented by the following formula (2), a represents an integer of 2 to 6, and Y is each independently represented by the following formula (4). A divalent linking group having the structure shown, n represents the number of repeats of Y, each independently an integer of 0 to 200, and at least one of a [-Y _n -A] n is an integer of 1 or more, A represents a hydrogen atom or a silyl group-containing derivative capable of bonding to a polyphenylene ether structure, except in the case of all hydrogen atoms,
In formula (2), X is an a-valent arbitrary linking group, and each of the plurality of R ⁵ is independently represented by a linear alkyl group having 1 to 8 carbon atoms and the following formula (3) any of the substructures, and k is each independently an integer from 1 to 4,
In formula (3), a plurality of R ¹¹ 's are each independently an optionally substituted alkyl group having 1 to 8 carbon atoms, and a plurality of R ¹² 's are each independently an optionally substituted carbon alkyl group. is an alkylene group of number 1 to 8, b is each independently 0 or 1, and R ¹³ is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a substituted represents any of the phenyl groups,
In formula (4), a plurality of R ²¹ 's each independently represent 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 ^21s are not hydrogen atoms at the same time, and one of the two R ^21s is a partial structure represented by the above formula (3), and the other is a hydrogen atom, a methyl group, or Rather than a combination of ethyl groups, the plurality of R ²² 's each independently represent a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, and an optionally substituted hydrocarbon group having 6 to 6 carbon atoms. 12 aryl groups and halogen atoms}
(B) Styrenic elastomer (C) Crosslinking aid A crosslinking aid which is an aromatic vinyl compound represented by the following formula (18) and having 3 or less vinyl groups in the molecule:
{In formula (18), R ³⁷ , R ³⁸ , and R ³⁹ each independently represent a hydrogen atom or a hydrocarbon group having 4 or less carbon atoms, and R ⁴⁰ and R ⁴¹ each independently represent a hydrogen atom or represents a saturated or unsaturated hydrocarbon group having 8 or less carbon atoms}
(D) Liquid elastomer
(E) Vinyl group-containing silane compound represented by the following formula (19):
{In formula (19), R ⁴² represents a hydrogen atom or a hydrocarbon having 4 or less carbon atoms, and n represents an integer of 2 to 6}. The curable resin composition according to claim 1, wherein the component (B) is a styrene elastomer having a number average molecular weight of 300,000 or less. The curable resin composition according to claim 1 or 2, wherein the component (B) is a styrene elastomer having a double bond content of 90% or less. 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. The component (B) is a styrene-butadiene copolymer (SBR), a styrene-butadiene-styrene copolymer (SBS), a hydrogenated styrene-butadiene-styrene copolymer, a styrene-isoprene-styrene copolymer (SIS ), hydrogenated styrene-isoprene-styrene copolymer, and hydrogenated styrene (butadiene/isoprene) styrene copolymer, according to any one of claims 1 to 4. curable resin composition. 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. The curable resin composition according to any one of the items. The curable resin according to any one of claims 1 to 6, wherein the component (B) is a styrenic elastomer in which the hydrogenation rate of double bonds based on conjugated diene monomer units is 90% or more. Composition. The curable resin composition according to any one of claims 1 to 7, wherein in the formula (18), R ³⁷ , R ³⁸ , and R ³⁹ are hydrogen atoms. The curable resin composition according to any one of claims 1 to 8, wherein in the formula (18), R ⁴⁰ is a tert-butyl group. The curable resin composition according to any one of claims 1 to 9, wherein in the formula (18), R ⁴¹ is a vinyl group. The curable resin composition according to any one of claims 1 to 10, wherein the component (C) is 4-tertbutylstyrene. The curable resin composition according to any one of claims 1 to 10, wherein the component (C) is divinylbenzene. The curable resin composition according to any one of claims 1 to 12, wherein the component (D) is a styrene-butadiene copolymer. Any one of claims 1 to 12, wherein the component (E) is either 2,4,6,8-tetramethyl-tetravinylcyclotetrasiloxane or 2,4,6-trimethyl-trivinylcyclotrisiloxane. Curable resin composition according to item 1. (F) The curable resin composition according to any one of claims 1 to 14, further comprising an initiator. In the formula (2), at least one of R ⁵ is a partial structure represented by the formula (3), in which one carbon atom of the benzene ring to which -O- in the formula (2) is bonded is ^R5 having a partial structure represented by the formula (3) above is bonded to one carbon atom at the 2nd or 6th position, and the other carbon atom at the 2nd or 6th position is a hydrogen atom, a methyl group, or The curable resin composition according to any one of claims 1 to 15, wherein an ethyl group is bonded. The curable resin composition according to any one of claims 1 to 16, wherein the partial structure represented by formula (3) is a t-butyl group. The curable resin composition according to any one of claims 1 to 17, wherein the number of OH terminals contained in the polyphenylene ether is 0 to 3,000 μmol/g. The curable resin composition according to any one of claims 1 to 18, wherein R ²¹ in the formula (4) is a methyl group. A in the above formula (1) is the following formula (5):
{In formula (5), R ³¹ and R ³⁴ are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms, and R ³² and R ³³ are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms. 30 monovalent hydrocarbon group, aryl group, alkoxy group, allyloxy group, amino group, or hydroxyalkyl group, and B is a hydrocarbon having 1 to 30 carbon atoms containing an olefinic carbon-carbon double bond. A system substituent, some of which may be substituted with a hydrogen atom, hydroxyl group, aryl group, alkoxy group, allyloxy group, amino group, hydroxyalkyl group, vinyl group, isopropenyl group, or halogen group, s, t, and u are each independently integers from 0 to 8}
The curable resin composition according to any one of claims 1 to 19, which is represented by: A in the formula (1) is the following formula (6) and/or (7):

{In formula (6) and/or formula (7), R ³¹ and R ³⁴ are each independently a divalent hydrocarbon group having 1 to 30 carbon atoms, and R ³² and R ³³ are each is 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, and each R ³⁵ is independently a hydrogen atom, a hydroxyl group, or a carbon 1 to 30 hydrocarbon groups, aryl groups, alkoxy groups, allyloxy groups, amino groups, hydroxyalkyl groups, vinyl groups, isopropenyl groups, or halogen groups, and R ³⁶ is a divalent group having 1 to 3 carbon atoms. is a hydrocarbon group or an amino group, or an oxygen atom, and a part of the hydrocarbon group is substituted with an aryl group, an alkoxy group, an allyloxy group, an amino group, a hydroxyalkyl group, a vinyl group, an isopropenyl group, or a halogen group. and s, t, and u are each independently an integer from 0 to 8}
The curable resin composition according to claim 20, which is represented by: (G) The curable resin composition according to any one of claims 1 to 21, further comprising a solvent. A prepreg comprising the curable resin composition according to any one of claims 1 to 22. A laminate comprising a cured product of the curable resin composition according to any one of claims 1 to 22. A printed wiring board comprising a cured product of the curable resin composition according to any one of claims 1 to 22. A composite material comprising a cured product of the curable resin composition according to any one of claims 1 to 22. 27. The composite material according to claim 26, which is a carbon fiber reinforced composite material.