TWI882987B - Resin composition, prepreg, metal-clad laminate, resin composite sheet, and printed wiring board - Google Patents

Abstract

The present invention provides a resin composition having low dielectric constant and dielectric loss tangent and high heat resistance, and a prepreg, a metal-clad laminate, a resin composite sheet, and a printed wiring board using the resin composition. A resin composition contains a multifunctional vinyl aromatic polymer (A) and a thermosetting compound (B), and does not contain a free radical polymerization initiator.

Description

Resin composition, prepreg, metal-clad laminate, resin composite sheet, and printed wiring board

The present invention relates to a resin composition, and a prepreg, a metal-clad laminate, a resin composite sheet, and a printed wiring board using the resin composition.

In recent years, the high integration and miniaturization of semiconductor components used in electronic equipment, communication equipment, etc., led by mobile terminals, has been accelerating. Along with this, the search for technology that can perform high-density mounting of semiconductor components is also seeking improvements to printed wiring boards, which occupy an important position among them. On the other hand, the uses of electronic equipment are diversifying and continuing to expand. Under its influence, the various properties required of printed wiring boards, metal-clad laminates, prepregs, etc. used therein are also diversifying and becoming more stringent. Considering such required properties, in order to obtain improved printed wiring boards at the same time, various materials and processing methods have been proposed. As one of them, the improvement and development of the resin material constituting the prepreg can be cited.

For example, Patent Document 1 discloses a resin composition comprising: a terminal vinyl compound (a) of a bifunctional phenylene ether oligomer having a polyphenylene ether skeleton, a specific maleimide compound (b), a naphthol aralkyl type cyanate resin (c), and a novolac type epoxy resin modified with a naphthalene skeleton (d).

Patent document 2 discloses a flame retardant resin composition, which is composed of a resin having a maleimide group at at least one end (an aminobismaleimide resin using N,N'-4,4'-diphenylmethane bismaleimide and a diamine as raw materials), and a copolymer of brominated styrene represented by formula (c1) and divinylbenzene represented by formula (c2). [Chemistry 1] [Prior art literature] [Patent literature]

[Patent document 1] Japanese Patent Publication No. 2010-138364 [Patent document 2] Japanese Patent Publication No. 03-006293

[Identify the problem you want to solve]

Including the above examples, various properties of printed wiring boards have been improved by using their material development, but in view of the progress of technology and the expansion of applications, further improvement of performance is required. In particular, in recent years, materials with high heat resistance, low dielectric constant, and low dielectric loss tangent have been sought. The present invention is to solve this problem and aims to provide a resin composition with low dielectric constant and dielectric loss tangent and high heat resistance, and a prepreg, metal foil laminate, resin composite sheet, and printed wiring board using the resin composition. [Means for solving the problem]

Based on the above-mentioned problems, the inventors of this case studied the composition of resin compositions particularly suitable for printed wiring boards such as prepregs, and found that the resin composition obtained by combining a multifunctional vinyl aromatic polymer with a thermosetting compound exhibits a low dielectric constant, a low dielectric loss tangent, and high heat resistance. However, it was found that these properties would deteriorate if a free radical polymerization initiator was added. The present invention was completed by utilizing these findings, and specifically, the above-mentioned problems were solved by utilizing the following means>1>, preferably>2> to>11>.

>1> A resin composition comprising a polyfunctional vinyl aromatic polymer (A) and a thermosetting compound (B), and does not contain a free radical polymerization initiator. >2> The resin composition of >1>, wherein the polyfunctional vinyl aromatic polymer (A) is a polymer having a constituent unit represented by formula (V). [Chemistry 2] In the formula, Ar represents an aromatic hydrocarbon linking group. * represents a bonding position. >3> A resin composition as described in >1> or >2>, wherein the aforementioned thermosetting compound (B) has one or more functional groups selected from the group consisting of a cyano group, a vinyl group, a maleimide group, and a nadiimide group. >4> A resin composition as described in any one of >1> to >3>, wherein the content of the aforementioned thermosetting compound (B) is 5 to 95 parts by mass relative to 100 parts by mass of the total amount of the resin components in the resin composition. >5> A resin composition as described in any one of >1> to >4>, wherein the content of the aforementioned multifunctional vinyl aromatic polymer (A) is 5 to 95 parts by mass relative to 100 parts by mass of the total amount of the resin components in the resin composition. >6> A resin composition as described in any one of >1> to >5>, further comprising a filler (C). >7> A resin composition as described in >6>, wherein the content of the filler (C) is 10 to 500 parts by mass relative to 100 parts by mass of the total amount of the resin components in the resin composition. >8> A prepreg formed by a substrate and a resin composition as described in any one of >1> to >7>. >9> A metal foil-clad laminate comprising: at least one layer formed by a prepreg as described in >8>; and a metal foil disposed on one or both sides of the layer formed by the prepreg. >10> A resin composite sheet comprising: a support; and a layer formed by a resin composition as described in any one of >1> to >7> disposed on the surface of the support. >11> A printed wiring board comprising: an insulating layer; and a conductive layer disposed on a surface of the insulating layer; the insulating layer comprises at least one of a layer formed of a resin composition as described in any one of >1> to >7> and a layer formed of a prepreg as described in >8>. [Effect of the invention]

According to the present invention, a resin composition having low dielectric constant and dielectric loss tangent and high heat resistance, and a prepreg, a metal-clad laminate, a resin composite sheet, and a printed wiring board using the resin composition can be provided.

In the following, the content of the present invention is described in detail with respect to its preferred embodiment. In addition, in this specification, "to" is used to mean that the numerical values described before and after it are included as the lower limit and the upper limit.

The resin composition of this embodiment is characterized by containing a multifunctional vinyl aromatic polymer (A) and a thermosetting compound (B), and does not contain a free radical polymerization initiator. By such a structure, a resin composition with low dielectric constant and dielectric loss tangent and high heat resistance can be provided. In addition, the peeling strength can also be improved. In addition, various other properties can also be improved. In particular, in recent years, communication and motion signals have a tendency to be high-frequency, and the resin composition of this embodiment can still achieve a low dielectric constant, a low dielectric loss tangent, and improved heat resistance even in the high-frequency region. The reasons are believed to be as follows, but not limited to the following. That is, the resin composition of the present embodiment is a thermosetting resin composition in which the thermosetting groups of the multifunctional vinyl aromatic polymer (A) or the thermosetting compound (B) are cured by heat. It is believed that when such a resin composition does not contain a thermal free radical polymerization initiator, the polymerization start temperature of the multifunctional vinyl aromatic polymer (A) is close to the polymerization start temperature of the thermosetting compound (B), and both the multifunctional vinyl aromatic polymer (A) and the thermosetting compound (B) can be fully cured, resulting in a low dielectric constant, a low dielectric loss tangent, and high heat resistance. In addition, by not containing a photo-radical polymerization initiator, the photocuring of the multifunctional vinyl aromatic polymer (A) and the thermosetting compound (B) can be effectively inhibited even if it is not shielded from light during storage. In addition, the resin composition of the present embodiment is preferably a non-photosensitive thermosetting resin composition that is hardened mainly by heat rather than by light.

>Multifunctional vinyl aromatic polymer (A)> The resin composition of this embodiment contains a multifunctional vinyl aromatic polymer (A). The multifunctional vinyl aromatic polymer (A) is preferably a polymer obtained by polymerizing an aromatic compound having two or more vinyl groups in the molecule. The aromatic compound having two or more vinyl groups in the molecule may be, for example, any of the positional isomers of the vinyl group, or a mixture of such positional isomers. More specifically, when the multifunctional vinyl aromatic polymer (A) is an aromatic compound having two vinyl groups in the molecule, it may be any of the meta-isomer, para-isomer, ortho-isomer, or a mixture of such positional isomers, and is preferably any of the meta-isomer, para-isomer, or a mixture of such positional isomers. As monomers constituting the polyfunctional vinyl aromatic polymer (A), there can be mentioned aromatic compounds having one or more vinyl groups (hereinafter, aromatic compounds having two or more vinyl groups are also referred to as polyfunctional vinyl aromatic compounds), preferably aromatic compounds having one or two vinyl groups. For example, as the polyfunctional vinyl aromatic polymer (A), there can be exemplified a polymer containing a constituent unit (a) derived from an aromatic compound having two vinyl groups (also referred to as a divinyl aromatic compound) and a constituent unit (b) derived from an aromatic compound having one vinyl group.

The divinyl aromatic compound forming the constituent unit (a) is preferably a compound having a hydrocarbon aromatic ring, and examples thereof include divinylbenzene, diallylbenzene, bis(vinyloxy)benzene, bis(1-methylvinyl)benzene, divinylnaphthalene, divinylanthracene, divinylbiphenyl, divinylphenanthrene, bis(4-allyloxyphenyl)fluorene, and the like. Among them, divinylbenzene is particularly preferred. The form of the constituent unit derived from the divinyl aromatic compound in the polymer may be (a-1) a form in which only one vinyl group undergoes polymerization reaction, while the other vinyl group remains unreacted; and (a-2) a form in which both vinyl groups undergo polymerization reaction. In this embodiment, the form (a-1) in which one vinyl group remains unreacted is preferably included. In addition, the polyfunctional vinyl aromatic compound (preferably a divinyl aromatic compound) may also have any substituent Z (for example, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a halogen atom, etc.) within the scope of exerting the effect of the present invention.

The structural unit (a) derived from the polyfunctional vinyl aromatic compound (preferably a divinyl aromatic compound) preferably comprises a structural unit represented by the following formula (V). [Chemistry 3] In formula (V), Ar represents an aromatic hydrocarbon linking group. Specific examples include the following examples of L ^1. In the formula, * represents a bonding position. The aromatic hydrocarbon linking group may be a group consisting only of an aromatic hydrocarbon that may also have a substituent, or a group consisting of a combination of an aromatic hydrocarbon that may also have a substituent and other linking groups. It is preferably a group consisting only of an aromatic hydrocarbon that may also have a substituent. In addition, the substituent that the aromatic hydrocarbon may also have may include the above-mentioned substituent Z. In addition, the above-mentioned aromatic hydrocarbon preferably has no substituent. The aromatic hydrocarbon linking group is usually a divalent linking group.

Specific examples of the aromatic hydrocarbon linking group include phenylene, which may have a substituent, naphthalene diyl, anthracene diyl, phenanthrene diyl, biphenyl diyl, and fluorene diyl, and among them, phenylene, which may have a substituent, is preferred. The substituent may be exemplified by the substituent Z described above, and the phenylene and other groups described above preferably have no substituent.

The constituent unit (a) derived from a polyfunctional vinyl aromatic compound (preferably a divinyl aromatic compound) preferably comprises at least one of a constituent unit represented by the following formula (V1), a constituent unit represented by the following formula (V2), and a constituent unit represented by the following formula (V3). In addition, * in the following formula represents a bonding position.

[Chemistry 4] In formulas (V1) to (V3), ^L1 is an aromatic hydrocarbon linking group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms). Specifically, phenylene groups, naphthalene diyl groups, anthracene diyl groups, phenanthrene diyl groups, biphenyl diyl groups, and fluorene diyl groups, which may have a substituent, are exemplified. Among them, phenylene groups, which may have a substituent, are preferred. Examples of the substituent include the substituent Z described above, and the phenylene groups described above preferably have no substituent.

The multifunctional vinyl aromatic polymer (A) may be a homopolymer of the constituent unit (a) as described above, or a copolymer with the constituent unit (b). When the multifunctional vinyl aromatic polymer (A) is a copolymer, the copolymerization ratio of the constituent unit (a) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more. The upper limit is actually 90 mol% or less.

When the multifunctional vinyl aromatic polymer (A) is a copolymer containing a constituent unit (b) derived from a monovinyl aromatic compound, examples of the monovinyl aromatic compound include vinyl aromatic compounds such as styrene, vinyl naphthalene, and vinyl biphenyl; vinyl aromatic compounds substituted with an alkyl group such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o-, p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, methylvinylbiphenyl, and ethylvinylbiphenyl. The monovinyl aromatic compounds exemplified here may also appropriately have the above-mentioned substituent Z. Moreover, the monovinyl aromatic compounds may be used alone or in combination of two or more.

The constituent unit (b) derived from a monovinyl aromatic compound is preferably a constituent unit represented by the following formula (V4).

[Chemistry 5] In formula (V4), ^L2 is an aromatic hydrocarbon linking group, and preferred specific examples include the above examples of ^L1 . ^RV1 is a hydrogen atom or a alkyl group having 1 to 12 carbon atoms (preferably an alkyl group). When ^RV1 is a alkyl group, the carbon number is preferably 1 to 6, more preferably 1 to 3. ^RV1 and ^L2 may also have the above-mentioned substituent Z.

When the multifunctional vinyl aromatic polymer (A) is a copolymer containing the constituent unit (b), the copolymerization ratio of the constituent unit (b) is preferably 10 mol% or more, preferably 15 mol% or more, and the upper limit is preferably 98 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less.

The multifunctional vinyl aromatic polymer (A) may also have other constituent units. As other constituent units, for example, constituent units (c) derived from cycloolefin compounds can be listed. Cycloolefin compounds can be listed as hydrocarbons having a double bond in the ring structure. Specifically, monocyclic cyclic alkenes such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene can be listed, and compounds having a norbornene ring structure such as norbornene and dicyclopentadiene can also be listed, and cycloolefin compounds obtained by aromatic ring condensation such as indene and vinylnaphthalene can also be listed. Examples of norbornene compounds include those described in paragraphs 0037 to 0043 of Japanese Patent Application Publication No. 2018-39995, and the contents are incorporated into this specification. In addition, the cycloolefin compounds exemplified herein may further have the above-mentioned substituent Z.

When the multifunctional vinyl aromatic polymer (A) is a copolymer containing the constituent unit (c), the copolymerization ratio of the constituent unit (c) is preferably 10 mol% or more, more preferably 20 mol% or more, and particularly preferably 30 mol% or more. The upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, particularly preferably 70 mol% or less, and may be 50 mol% or less, or 30 mol% or less.

The multifunctional vinyl aromatic polymer (A) may further include constituent units (d) from different polymerizable compounds (hereinafter, also referred to as other polymerizable compounds). As other polymerizable compounds (monomers), for example, compounds containing three vinyl groups may be listed. Specifically, 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane may be listed. Alternatively, ethylene glycol diacrylate, butadiene, etc. may be listed. The copolymerization ratio of the constituent units (d) from other polymerizable compounds is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less.

As one embodiment of the multifunctional vinyl aromatic polymer (A), a polymer having the constituent unit (a) as an essential constituent unit and containing at least one of the constituent units (b) to (d) can be exemplified. In addition, a state in which the total of the constituent units (a) to (d) accounts for more than 95 mol% of all the constituent units, and further accounts for more than 98 mol%. As another embodiment of the multifunctional vinyl aromatic polymer (A), it is preferable that the constituent unit (a) is used as an essential constituent unit, and the constituent units containing aromatic rings in all the constituent units excluding the terminal are more than 90 mol%, more preferably more than 95 mol%, and can also be 100 mol%. When calculating the mole % per all constituent units, one constituent unit is derived from one molecule of the monomer constituting the multifunctional vinyl aromatic polymer (A).

The method for producing the multifunctional vinyl aromatic polymer (A) is not particularly limited and may be a conventional method, for example, a method of polymerizing a monomer containing a divinyl aromatic compound (a monovinyl aromatic compound, a cycloolefin compound, etc. may coexist as necessary) in the presence of a Lewis acid catalyst. The Lewis acid catalyst may be a metal fluoride or a complex thereof.

The structure of the chain end of the multifunctional vinyl aromatic polymer (A) is not particularly limited. The group derived from the above divinyl aromatic compound can be exemplified by the structure of the following formula (E1). In addition, ^L1 in formula (E1) is the same as that defined in the above formula (V1). * indicates a bonding position. *-CH=CH- ^L1 -CH= _CH2 (E1)

When the group from the monovinyl aromatic compound is the chain end, the following structure can be adopted. In the formula, ^L2 and R ^V1 have the same meanings as those defined in the above formula (V4). * indicates the bonding position. *-CH=CH- ^L2 -R ^V1 (E2)

The molecular weight of the multifunctional vinyl aromatic polymer (A) is preferably 300 or more, more preferably 500 or more, and particularly preferably 1,000 or more in terms of the number average molecular weight Mn. The upper limit is preferably 100,000 or less, more preferably 10,000 or less, particularly preferably 5,000 or less, and even more preferably 4,000 or less. The monodispersity (Mw/Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is preferably 100 or less, more preferably 50 or less, and particularly preferably 20 or less. The lower limit is actually 1.1 or more. The multifunctional vinyl aromatic polymer (A) is preferably soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.

In this specification, for the multifunctional vinyl aromatic polymer (A), reference may be made to the compounds and their synthesis reaction conditions described in paragraphs 0029 to 0058 of International Publication No. 2017/115813, the compounds and their synthesis reaction conditions described in paragraphs 0013 to 0058 of Japanese Patent Publication No. 2018-039995, and the compounds and their synthesis reaction conditions described in paragraphs 0008 to 0043 of Japanese Patent Publication No. 2018-168347. The compounds and their synthesis reaction conditions, etc. described in paragraphs 0014 to 0042 of Japanese Patent Application Laid-Open No. 2006-070136, the compounds and their synthesis reaction conditions, etc. described in paragraphs 0014 to 0061 of Japanese Patent Application Laid-Open No. 2006-089683, and the compounds and their synthesis reaction conditions, etc. described in paragraphs 0008 to 0036 of Japanese Patent Application Laid-Open No. 2008-248001 are incorporated into the present specification.

As for the content of the multifunctional vinyl aromatic polymer (A), when the total amount of the resin components in the resin composition is 100 parts by mass, it is preferably 5 parts by mass or more, preferably 10 parts by mass or more, particularly preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more. In addition, it can also be 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, and 60 parts by mass or more. By having the content of the multifunctional vinyl aromatic polymer (A) be above the above lower limit, a low dielectric constant can be achieved particularly effectively. On the other hand, as for the upper limit of the content of the multifunctional vinyl aromatic polymer (A), when the total amount of the resin components in the resin composition is 100 parts by mass, it is preferably 95 parts by mass or less, preferably 90 parts by mass or less, particularly preferably 85 parts by mass or less, and even more preferably 80 parts by mass or less. The resin composition may contain only one type of polyfunctional vinyl aromatic polymer (A) or two or more types. When containing two or more types, the total amount is preferably within the above range. In addition, the resin component includes a polyfunctional vinyl aromatic polymer (A) and a thermosetting compound (B) and other resins described below.

>Thermosetting compound (B)> The resin composition of this embodiment contains a thermosetting compound (B). In this specification, the thermosetting compound (B) means a thermosetting compound other than the multifunctional vinyl aromatic polymer (A). The thermosetting compound (B) is preferably a compound having one or more functional groups selected from the group consisting of a cyano group, a vinyl group (but excluding groups that can become multifunctional vinyl aromatic polymers, maleimide groups, and nadicimide groups. Preferably, it is vinylphenyl), maleimide groups, and nadicimide groups. It is more preferably a cyanate compound (B1) having a cyano group, a modified polyphenylene ether compound (B2) having a vinyl group (preferably vinylphenyl), a maleimide compound (B3) having a maleimide group, or a nadicimide compound (B4) having a nadicimide group. It is particularly preferably a cyanate compound (B1) having a cyano group, a modified polyphenylene ether compound (B2) having a vinyl group (preferably vinylphenyl), or a maleimide compound (B3) having a maleimide group.

>>Cyanate compound (B1)>> Cyanate compound is a general term for compounds having a cyano group. The cyanate compound (B1) used in the present invention preferably has one or more cyano groups in one molecule, and preferably has two or more. In addition, the upper limit of the number of cyano groups in one molecule of the cyanate compound (B1) is preferably 12 or less, and preferably 10 or less. In addition, the cyano group of the above-mentioned cyanate compound (B1) is preferably a cyano group directly bonded to an aromatic ring. As for the cyanate compound (B1), for example, at least one selected from the group consisting of naphthol aralkyl type cyanate compounds (naphthol aralkyl type cyanate), naphthyl ether type cyanate compounds, phenol novolac type cyanate compounds, biphenyl aralkyl type cyanate compounds, bisphenol A type cyanate compounds, diallyl bisphenol A type cyanate compounds, bisphenol M type cyanate compounds, xylene resin type cyanate compounds, trisphenol methane type cyanate compounds, and adamantane skeleton type cyanate compounds can be listed. Among them, at least one selected from the group consisting of naphthol aralkyl type cyanate compounds, naphthyl ether type cyanate compounds, and xylene resin type cyanate compounds is preferred, and naphthol aralkyl type cyanate compounds are more preferred. These cyanate compounds can be prepared by known methods, and commercial products can also be used.

The cyanate compound (B1) includes a naphthol aralkyl type cyanate compound represented by the following formula (S1). The naphthol aralkyl type cyanate compound represented by the formula (S1) is obtained by condensing a naphthol aralkyl resin obtained by reacting naphthols such as α-naphthol or β-naphthol with phthalic acid, α,α'-dimethoxy-p-xylene, 1,4-di(2-hydroxy-2-propyl)benzene, etc., and cyanogen halides. The preparation method is not particularly limited, and the compound can be prepared by any existing method for cyanate synthesis. [Chemistry 6] In formula (S1), R ^C1 to R ^C4 each independently represent a hydrogen atom or a methyl group. ^{n C} is a number from 1 to 10. Two or more compounds having different n ^C may be contained. For the cyanate compound (B1), reference may be made to paragraphs 0024 and 0025 of JP-A-2010-138364, the contents of which are incorporated herein.

>>Modified polyphenylene ether compound (B2)>> The thermosetting compound (B) is preferably a modified polyphenylene ether compound (B2) whose terminal is modified with a substituent containing a vinyl group (preferably a vinylphenyl group). The modified polyphenylene ether compound (B2) used in the present invention preferably has one or more vinyl groups in one molecule, and preferably has two or more. In addition, the upper limit of the number of vinyl groups in one molecule of the modified polyphenylene ether compound (B2) is preferably 5 or less, and preferably 3 or less. The modified polyphenylene ether compound (B2) is, for example, a polyphenylene ether in which all or part of the terminal is modified with a vinyl group or a vinylphenyl group. The "polyphenylene ether" referred to in this specification refers to a compound having a polyphenylene ether skeleton represented by the following formula (X1).

[Chemistry 7] In formula (X1), R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ may be the same or different, and represent an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom, or a hydrogen atom. * represents a bonding position.

The modified polyphenylene ether may further contain repeating units represented by formula (X2) or formula (X3). [Chemical 8] In formula (X2), R ²⁸ , R ²⁹ , R ³⁰ , R ³⁴ , and R ³⁵ may be the same or different, and are an alkyl group having 6 or less carbon atoms or a phenyl group. R ³¹ , R ³² , and R ³³ may be the same or different, and are a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. * indicates a bonding position. [Chemistry 9] In formula (X3), R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , and R ⁴³ may be the same or different and are hydrogen atoms, alkyl groups having 6 or less carbon atoms, or phenyl groups. A is a linear, branched, or cyclic divalent hydrocarbon having 1 to 20 carbon atoms. * indicates a bonding position.

The modified polyphenylene ether compound (B2) may be a modified polyphenylene ether partially or entirely functionalized with an ethylenically unsaturated group such as vinylbenzyl, an epoxy group, an amine group, a hydroxyl group, a hydroxyl group, a carboxyl group, a silyl group, or the like. Such a modified polyphenylene ether may be used alone or in combination of two or more. Examples of polyphenylene ethers having a hydroxyl group at the end include SA90 manufactured by SABIC INNOVATIVE PLASTICS.

The method for producing the modified polyphenylene ether compound (B2) is not particularly limited as long as the effect of the present invention can be obtained. For example, those functionalized with vinylbenzyl groups can be produced by dissolving a difunctional phenylene ether oligomer and vinylbenzyl chloride in a solvent, adding a base and reacting them under heating and stirring, and then solidifying the resin. Those functionalized with carboxyl groups can be produced, for example, by melt-kneading and reacting polyphenylene ether with an unsaturated carboxylic acid or its functionalized derivative in the presence or absence of a free radical initiator. Alternatively, polyphenylene ether and an unsaturated carboxylic acid or its functionalized derivative are dissolved in an organic solvent in the presence or absence of a free radical initiator and reacted in the solution.

The modified polyphenylene ether compound (B2) preferably comprises a modified polyphenylene ether having an ethylenically unsaturated group at at least one terminal (preferably both terminals) (hereinafter, sometimes referred to as "modified polyphenylene ether (g)"). Examples of the ethylenically unsaturated group include alkenyl groups such as vinyl, allyl, acryl, methacryl, propenyl, butenyl, hexenyl and octenyl; cycloalkenyl groups such as cyclopentenyl and cyclohexenyl; and alkenylaryl groups such as vinylphenyl, vinylbenzyl and vinylnaphthyl. The two ethylenically unsaturated groups at both terminals may be the same functional group or different functional groups.

The modified polyphenylene ether (g) can be exemplified by the structure represented by formula (1). [Chemical 10] In the formula (1), ^Xa represents an aromatic group, ( ^Ya -O)m represents a polyphenylene ether moiety, ^R1 , ^R2 , and ^R3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group, m represents a number of 1 to 100, n represents a number of 1 to 6, and q represents a number of 1 to 4. ^R1 , ^R2 , and ^R3 are preferably hydrogen atoms. m is preferably a number of 1 to 50, more preferably a number of 1 to 30. n is preferably a number of 1 to 4, more preferably 1 or 2, and more preferably 1. Moreover, q is preferably a number of 1 to 3, more preferably 1 or 2, and more preferably 2. Two or more compounds in which m, n, and q are different from each other may be contained.

The modified polyphenylene ether (g) is preferably represented by formula (2). In formula (2), at least one of a and b is not 0 and represents a number from 0 to 100. a and b are preferably numbers from 1 to 50, more preferably numbers from 1 to 30. Here, -(OXO)- is preferably represented by formula (3) or formula (4). Two or more compounds having different a and b may be contained. [Chemical 12] In formula (3), R ⁴ , R ⁵ , R ⁶ , R ¹⁰ , and R ¹¹ may be the same or different, and are an alkyl group having 6 or less carbon atoms or a phenyl group. R ⁷ , R ⁸ , and R ⁹ may be the same or different, and are a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. * indicates a bonding position. [Chemical 13] In formula (4), ^R12 , ^R13 , ^R14 , ^R15 , ^R16 , ^R17 , ^R18 , and ^R19 may be the same or different and are hydrogen atoms, alkyl groups having 6 or less carbon atoms, or phenyl groups. ^A1 is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms. * indicates a bonding position.

In addition, -(YO)- in formula (2) is preferably represented by formula (5). [Chemical 14] In formula (5), R ²² and R ²³ may be the same or different and are a hydrogen atom, an alkyl group having a carbon number of 6 or less, or a phenyl group. R ²⁰ and R ²¹ may be the same or different and are an alkyl group having a carbon number of 6 or less, or a phenyl group.

As for ^A1 in formula (4), examples thereof include divalent organic groups such as methylene, ethylene, 1-methylethylene, 1,1-propylene, 2,2-propylene, 1,4-phenylenebis(1-methylethylene), 1,3-phenylenebis(1-methylethylene), cyclohexylene, phenylmethylene, naphthylmethylene, and 1-phenylethylene, but are not limited thereto.

In the modified polyphenylene ether, preferably ^R4 , ^{R5, R6, R10, R11, R20 , and R21 are alkyl} groups having 3 or less carbon atoms, ^{and R7} , R8, ^R9 , ^R12 , ^R13 , R14, ^R15 , ^R16 , ^{R17 , R18} , ^R19 , ^R22 , and ^R23 are hydrogen atoms or alkyl groups having 3 or less carbon atoms. In particular, -(OXO)- represented by formula (3) or (4) is a polyphenylene ether of formula (9), formula (10), and/or formula (11), and -(YO)- represented by formula (5) is a polyphenylene ether of formula (12) or formula (13), or a structure obtained by randomly arranging formulas (12) and (13).

[Chemistry 15] In formula (10), R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , and R ⁴⁷ may be the same or different and are hydrogen atoms or methyl groups. A ² is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms. * is a bonding position. Specific examples of A ² in formula (10) and formula (11) are the same as those of A ¹ in formula (4).

The number average molecular weight of the modified polyphenylene ether compound (B2) obtained by GPC in terms of polystyrene is preferably 500 to 3000. When the number average molecular weight is above the lower limit, the adhesion of the resin composition of the present embodiment when it is made into a film tends to be further suppressed. When the number average molecular weight is below the upper limit, the solubility in the solvent tends to be further improved. In addition, the weight average molecular weight of the modified polyphenylene ether compound (B2) obtained by GPC in terms of polystyrene is preferably 800 to 10000, and more preferably 800 to 5000. By being above the aforementioned lower limit, the dielectric constant and dielectric loss tangent of the resin composition tend to become lower, and by being below the aforementioned upper limit, the solubility in the solvent, low viscosity and formability tend to be further improved. In addition, the carbon-carbon unsaturated double bond equivalent at the end of the modified polyphenylene ether compound (B2) is preferably 400 to 5000 g per carbon-carbon unsaturated double bond, and more preferably 400 g to 2500 g. By being above the aforementioned lower limit, the dielectric constant and dielectric loss tangent tend to become lower. By being below the aforementioned upper limit, the solubility in the solvent, low viscosity and formability tend to be further improved.

The method for producing the modified polyphenylene ether compound (B2) is not particularly limited, and it can be produced, for example, by a step of obtaining a difunctional phenylene ether oligomer by oxidative coupling of a difunctional phenol compound and a monofunctional phenol compound (oxidative coupling step), and a step of etherifying the terminal phenolic hydroxyl group of the obtained difunctional phenylene ether oligomer with vinylbenzyl (vinylbenzyl etherification step). As such a modified polyphenylene ether compound (B2), for example, OPE-2St1200 manufactured by Mitsubishi Gas Chemical Co., Ltd. can be used.

>>Maleimide compound (B3)>> Maleimide compound (B3) refers to a compound having one or more maleimide groups in a molecule. The maleimide compound (B3) used in the present invention preferably has one or more maleimide groups in one molecule, and more preferably has two or more maleimide groups. In addition, the upper limit of the number of maleimide groups in one molecule of the maleimide compound (B3) is preferably 15 or less, and more preferably 13 or less. Among them, preferably, it is a bismaleimide compound or polymaleimide compound having two or more maleimide groups in the molecule, and more preferably, it is 4,4'-diphenylmethanemaleimide, 4,4'-diphenylether bismaleimide, metaphenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, or a compound containing a constituent unit represented by any one of the following formulae (31) to (34). [Chemistry 16] In formula (31), R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a phenyl group. In formula (31), R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each independently represent a methyl group, an ethyl group, a phenyl group or a hydrogen atom, and more preferably a hydrogen atom. n1 is a number of 1 to 10, and more preferably a number of 1 to 4. Compounds having two or more different n1s may be contained.

[Chemistry 17] In formula (32), R ⁵⁶ each independently represents a methyl group or an ethyl group, and R ⁵⁷ each independently represents a hydrogen atom or a methyl group. It is preferred that 1 to 3 of the 4 R ⁵⁶ are methyl groups and the remaining 3 to 1 are ethyl groups, and it is more preferred that 2 of the 4 R ⁵⁶ are methyl groups and the remaining 2 are ethyl groups. It is more preferred that the two R ⁵⁶ substituted on the two aromatic rings are methyl groups and ethyl groups.

[Chemistry 18] In formula (33), R ⁵⁸ each independently represents a hydrogen atom, a methyl group or an ethyl group. R ⁵⁸ is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[Chemistry 19] In formula (34), ^R59 each independently represents a hydrogen atom, a methyl group or an ethyl group. ^R59 is preferably a methyl group or an ethyl group, and more preferably a methyl group.

The unsaturated amide group equivalent of the maleimide compound (B3) is preferably 200 g/eq or more and 400 g/eq or less. When two or more maleimide compounds are contained, the equivalent is the weighted average unsaturated amide group equivalent in consideration of the mass of each maleimide compound contained in the resin composition.

>>Nadipic imide compound (B4)>> The nadic imide compound (B4) is a compound having a nadic imide group in the molecule. The nadic imide compound (B4) used in the present invention preferably has one or more nadic imide groups in one molecule, and more preferably has two or more. In addition, the upper limit of the number of nadic imide groups in one molecule of the nadic imide compound (B4) is preferably 5 or less, and more preferably 3 or less. More specifically, the nadic imide compound (B4) preferably has a group represented by the following formula (N1) or (N2). * represents a bonding position. [Chemical 20] In formula (N1) and formula (N2), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The nadic acid imide compound is preferably a compound represented by the following formula (N3). [Chemical 21] In formula (N3), ^R1 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and ^R2 represents an alkylene group having 1 to 6 carbon atoms or a divalent linking group containing an aromatic ring. Examples of the divalent linking group containing an aromatic ring include phenylene, biphenylene, and naphthylene. In addition, the description of the nadic acid imide compound (B4) can be referred to in paragraphs 0026 to 0035 of International Publication No. 2015/105109, and the contents are incorporated into this specification.

The content of the thermosetting compound (B) is preferably 5 parts by mass or more, preferably 10 parts by mass or more, particularly preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more relative to 100 parts by mass of the total resin component in the resin composition of the present embodiment. The upper limit is preferably 95 parts by mass or less, preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less. In addition, relative to 100 parts by mass of the multifunctional vinyl aromatic polymer (A), it is preferably 1 part by mass or more, preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more. The upper limit is preferably 1900 parts by mass or less, preferably 900 parts by mass or less, particularly preferably 400 parts by mass or less, and also 120 parts by mass or less, and may also be 80 parts by mass or less, and may also be 60 parts by mass or less. The resin composition may contain only one thermosetting compound (B) or two or more thereof. When containing two or more thereof, the total amount is preferably within the above range.

When the resin composition of the present embodiment does not contain the filler (C) described later, the resin component preferably accounts for more than 90% by mass of the resin composition, preferably more than 95% by mass, and particularly preferably more than 98% by mass. When the resin composition of the present embodiment contains a filler (C), the resin component preferably accounts for more than 15% by mass of the resin composition, preferably more than 20% by mass, and particularly preferably more than 30% by mass. In addition, as for the upper limit, the resin component preferably accounts for less than 90% by mass of the resin composition, preferably less than 85% by mass, and particularly preferably less than 80% by mass.

>Free radical polymerization initiator> The resin composition of this embodiment does not contain a free radical polymerization initiator. Here, "does not contain" means not actively mixed, and does not include the case where impurities are mixed unintentionally. The case where impurities are mixed unintentionally means, for example, less than 4 ppm on a mass basis, and further less than 1 ppm. In the present invention, it is preferably 0 ppm. The type of free radical polymerization initiator is not particularly limited, and thermal free radical polymerization initiators and photo radical polymerization initiators can be listed. Specifically, as free radical polymerization initiators, peroxides, azo compounds, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanone compounds, ketal compounds, benzophenone compounds, and phosphine oxide compounds can be listed. Peroxides include compounds having a peroxy group (-O-O-) in the molecule, preferably compounds having a tert-butyl peroxy group, compounds having a cumyl peroxy group, and compounds having a benzoyl peroxy group. Specific examples include: benzoyl peroxide (BPO), p-chlorobenzoyl peroxide, dicumyl peroxide (dicup), di-tert-butyl peroxide, diisopropyl peroxycarbonate, 2,5-dimethyl-2,5-di-tert-butyl peroxyhexyne (DYBP), and 2,5-dimethyl-2,5-di-tert-butyl peroxyhexane. Commercially available products include PERBUTYL H, PERBUTYL P, PERBUTYL PV, PERCUMYL H, PERCUMYL P, PERCUMYL D, PEROCTA H, PERHEXA 25B, etc. manufactured by NOF Corporation. Azo compounds refer to compounds having an azo group (-N=N-) in the molecule, and specifically, azobisisobutyronitrile (AIBN) can be cited. Commercially available products include AIBN, V-70, and V-65 manufactured by FUJIFILM Wako Pure Chemical. Also, although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can be cited as a free radical polymerization initiator. Commercially available products include NOFMER BC-90, etc. In addition, free radical polymerization initiators described in paragraph 0042 of International Publication No. 2013/047305 can also be exemplified, and such contents are incorporated into this specification. On the other hand, the resin composition of this embodiment can also be a composition that does not contain a cationic polymerization initiator. In addition, the resin composition of this embodiment may also be a composition without a photopolymerization initiator.

>Filler (C)> In order to improve low dielectric constant, low dielectric loss tangent, flame retardancy and low thermal expansion, the resin composition of this embodiment preferably contains a filler (C), preferably an inorganic filler. The filler (C) used can be a known one, and its type is not particularly limited, and it is ideal to use a filler commonly used in this field. Specifically, they include: natural silica, fused silica, synthetic silica, amorphous silica, aerosol silica (AEROSIL), hollow silica and other silicas; white carbon black, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, condensed boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat-treated product (aluminum hydroxide is heat-treated to remove part of the crystal water), alumina, magnesium hydroxide and other metal hydrates; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc borate, zinc stannate, aluminum oxide, clay and other metal hydrates. , kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass staple (including glass micropowders such as E-glass, T-glass, D-glass, S-glass, Q-glass, etc.), hollow glass, spherical glass and other inorganic fillers; others include styrene type, butadiene type, acrylic type and other rubber powders, core-shell type rubber powders, silicone resin powders, silicone rubber powders, silicone composite powders and other organic fillers. Among them, one or more selected from the group consisting of silica, aluminum hydroxide, alumina, magnesium oxide and magnesium hydroxide is preferred, and silica is more preferred. The silica is preferably spherical silica. The spherical silica may also be hollow silica. By using such fillers, the thermal expansion characteristics, dimensional stability, flame retardancy and other characteristics of the resin composition are improved.

The content of the filler (C) in the resin composition of this embodiment can be appropriately set according to the desired properties, and there is no special limitation. When the total amount of the resin components in the resin composition is 100 parts by mass, it is preferably 10 parts by mass or more, preferably 20 parts by mass or more, preferably 30 parts by mass or more, and can also be 50 parts by mass or more. The upper limit is preferably 500 parts by mass or less, preferably 400 parts by mass or less, preferably 300 parts by mass or less, and even more preferably 250 parts by mass or less, and can also be 200 parts by mass or less. The filler (C) can be one type or two or more types. When two or more types are used, the total amount should be within the above range.

>Other resin components> The resin composition of this embodiment may also contain other resin components other than the above-mentioned multifunctional vinyl aromatic polymer (A) and thermosetting compound (B). Examples of other resin components include one or more selected from the group consisting of epoxy resins, phenolic resins, cyclohexane resins, benzophenone compounds, compounds having polymerizable unsaturated groups, elastomers, and active ester compounds. In the resin composition of the present embodiment, the total content of the multifunctional vinyl aromatic polymer (A) and the thermosetting compound (B) in the resin component is preferably 50 mass % or more, preferably 70 mass % or more, more preferably 80 mass % or more, and even more preferably 90 mass % or more, and may be 95 mass % or more, 97 mass % or more, or 98 mass % or more.

> Hardening accelerator (catalyst)> The resin composition of the present embodiment may further contain a hardening accelerator. The hardening accelerator is not particularly limited, and examples thereof include: organic metal salts (e.g., zinc octanoate, zinc cycloalkanoate, cobalt cycloalkanoate, copper cycloalkanoate, iron acetylacetonate, nickel octanoate, manganese octanoate, etc.), phenol compounds (e.g., phenol, xylenol, cresol, resorcinol, o-catechin, octylphenol, nonylphenol, etc.), alcohols (e.g., 1-butanol, 2-ethylhexanol, etc.), imidazoles (e.g., 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl- 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc.), and derivatives of such imidazoles such as carboxylic acids or their anhydrides, amines (e.g., dicyandiamide, benzyldimethylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), phosphorus compounds (e.g., phosphine compounds, phosphine oxide compounds, phosphonium salt compounds, diphosphine compounds, etc.), epoxy-imidazole adduct compounds. The hardening accelerator is preferably an imidazole and an organic metal salt, preferably an imidazole.

When a hardening accelerator is contained, the lower limit of the content of the hardening accelerator is preferably 0.005 parts by mass or more, preferably 0.01 parts by mass or more, and particularly preferably 0.1 parts by mass or more, relative to 100 parts by mass of the total amount of the resin components in the resin composition. In addition, the upper limit of the content of the aforementioned hardening accelerator is preferably 10 parts by mass or less, preferably 5 parts by mass or less, and particularly preferably 2 parts by mass or less, relative to 100 parts by mass of the total amount of the resin components in the resin composition. One hardening accelerator may be used alone, or two or more may be used in combination. When two or more are used, the total amount is within the above range.

>Solvent> The resin composition of this embodiment may also contain a solvent, preferably an organic solvent. In this case, the resin composition of this embodiment is at least a part of the various resin components mentioned above, preferably in a form that is completely dissolved in the solvent or compatible with the solvent (solution or varnish). The solvent is not particularly limited as long as it is a polar organic solvent or a non-polar organic solvent that can dissolve at least a part of the various resin components mentioned above, preferably all of them, or is compatible with them. Examples of polar organic solvents include ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosols (e.g., propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (e.g., ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), and amides (e.g., dimethoxyacetamide, dimethylformamide, etc.). Examples of non-polar organic solvents include aromatic hydrocarbons (e.g., toluene, xylene, etc.). Solvents can be used alone or in combination of two or more.

>Other ingredients> In addition to the above ingredients, the resin composition of this embodiment may also contain flame retardants, ultraviolet absorbers, antioxidants, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, flow regulators, lubricants, defoamers, dispersants, leveling agents, glossing agents, polymerization inhibitors, silane coupling agents, etc. within the scope that does not hinder the effects of the present invention. These additives can be used alone or in combination of two or more.

> Physical properties of resin composition > The resin composition of this embodiment, when formed into a 1.6 mm thick plate-shaped cured product, can set the dielectric constant (Dk) at 10 GHz to less than 2.6, or less than 2.5. The lower limit of the dielectric constant is preferably 1.0, but is actually greater than 2.1. In addition, the resin composition of this embodiment, when formed into a 1.6 mm thick plate-shaped cured product, can set the dielectric loss tangent (Df) at 10 GHz to less than 0.0030, or less than 0.0025, or less than 0.0020, or less than 0.0015. The lower limit of the dielectric loss tangent is preferably 0, but is actually greater than 0.0001. The dielectric constant and dielectric loss tangent are measured using the method described in the following embodiments.

The resin composition of the preferred embodiment of the present invention can achieve a low coefficient of thermal expansion (CTE). For example, the CTE (ppm/°C) specified in JIS C 6481 5.19 is preferably 75 or less, more preferably 72 or less, and even more preferably 70 or less. The lower limit is not particularly limited, and is actually 50 or more.

When the resin composition of this embodiment is formed into a 1.6 mm thick plate-shaped hardened product, the glass transition temperature can be set to above 230°C, above 235°C, or above 240°C. The upper limit of the glass transition temperature is not particularly specified, but is below 400°C, and is further practically below 350°C. Furthermore, when the resin composition of the present embodiment is formed into a 1.6 mm thick plate-shaped cured product, its glass transition temperature is preferably 8°C or higher, and more preferably 10°C or higher than the glass transition temperature of a 1.6 mm thick plate-shaped cured product formed by a resin composition mixed with a thermal free radical polymerization initiator (e.g., PERBUTYL P (trade name) manufactured by NOF Corporation) in an amount equivalent to 1 mass % of the resin component contained in the resin composition. The upper limit is, for example, 25°C or lower. The glass transition temperature is measured by the method described in the embodiment described below.

>Manufacturing method of resin composition> The resin composition of this embodiment can be manufactured according to the conventional method. For example, a state in which a multifunctional vinyl aromatic polymer (A) and a thermosetting compound (B) are mixed can be cited. The ideal content at this time is as described above. In addition, in the resin composition of this embodiment, fillers (C), other resin components, and other additives can also be appropriately coexisted and kneaded. It is also possible to improve the appearance or make other properties better by blending other resin components. One example of the resin composition of this embodiment is a varnish containing a solvent. Another example of the resin composition of this embodiment is a plate-like cured product or a film. In addition, the resin composition of this embodiment can be ideally used for the purposes described below.

>Application> The resin composition of this embodiment can be used as a cured product. Specifically, the resin composition of this embodiment can be ideally used as an insulating layer of a printed wiring board and a semiconductor packaging material as a low dielectric constant material and/or a low dielectric loss tangent material. The resin composition of this embodiment can be ideally used as a material for constituting a prepreg, a metal foil-clad laminate formed from a prepreg, a resin composite sheet, and a printed wiring board. When the resin composition of this embodiment is used to make a layered molded product, its thickness is preferably 5 μm or more, preferably 10 μm or more. The upper limit is preferably 2 mm or less, preferably 1 mm or less. In addition, the thickness of the layered molded product, for example, when the resin composition of the present embodiment is impregnated in glass cloth, means the thickness including the glass cloth. The molded product such as a film formed by the resin composition of the present embodiment can be used for purposes of exposure and development to form a pattern, and can also be used for purposes without exposure and development. It is particularly suitable for purposes without exposure and development.

>>Prepreg>> The prepreg of the ideal embodiment is formed by a substrate (prepreg substrate) and the resin composition of the present embodiment. The prepreg of the present embodiment can be obtained, for example, by applying (for example, impregnating or coating) the resin composition of the present embodiment to the substrate and then semi-hardening it by heating (for example, drying at 120 to 220°C for 2 to 15 minutes). At this time, the amount of the resin composition attached to the substrate, that is, the amount of the resin composition (including the filler) relative to the total amount of the prepreg after semi-hardening, is preferably in the range of 20 to 99% by mass.

As for the substrate, there is no particular limitation as long as it is a substrate used for various printed wiring board materials. Examples of the material of the substrate include: glass fiber (for example, E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, spherical glass, etc.), inorganic fibers other than glass (for example, quartz, etc.), and organic fibers (for example, polyimide, polyamide, polyester, liquid crystal polyester, etc.). The form of the substrate is not particularly limited, and examples include: substrates composed of layered fibers such as woven fabrics, non-woven fabrics, coarse yarns, chopped strands, and surface felt. In particular, substrates composed of long fibers such as glass cloth are preferred. Here, long fibers refer to, for example, those having a number average fiber length of 6 mm or more. These substrates can be used alone or in combination of two or more. Among these substrates, from the perspective of dimensional stability, it is preferable to use a woven fabric that has been subjected to super fiber opening treatment or pore blocking treatment. From the perspective of moisture absorption and heat resistance, it is preferable to use a glass woven fabric that has been surface treated with a silane coupling agent such as epoxysilane treatment or aminosilane treatment. From the perspective of electrical properties, it is preferable to use a low dielectric glass cloth composed of glass fibers exhibiting low dielectric constant and low dielectric loss tangent such as L-glass, NE-glass, and Q-glass. The thickness of the substrate is not particularly limited, and can be, for example, about 0.01 to 0.19 mm.

>>Metal foil-clad laminated plate>> The metal foil-clad laminated plate of an ideal embodiment includes: at least one layer formed by the prepreg of this embodiment, and metal foil arranged on one or both sides of the layer formed by the prepreg. The metal foil-clad laminated plate of this embodiment can be produced, for example, by a method of arranging at least one sheet (preferably stacking two or more sheets) of the prepreg of this embodiment, arranging metal foil on one or both sides thereof, and performing lamination forming. In more detail, it can be produced by arranging metal foil such as copper and aluminum on one or both sides of the prepreg and performing lamination forming. The number of prepreg sheets is preferably 1 to 10 sheets, more preferably 2 to 10 sheets, and even more preferably 2 to 7 sheets. There is no particular limitation on the metal foil as long as it is used as a material for printed wiring boards. For example, rolled copper foil, electrolytic copper foil and other copper foils can be listed. The thickness of the copper foil is not particularly limited and can be about 1.5 to 70 μm. The forming method can be the method commonly used when forming laminated boards and multi-layer boards for printed wiring boards. More specifically, there can be a method of using a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, etc., at a temperature of about 180 to 350°C, a heating time of about 100 to 300 minutes, and a surface pressure of about 20 to 100 kg/ ^cm2 for laminate forming. Furthermore, a multi-layer board can be produced by combining the prepreg of the present embodiment with a separately produced inner layer wiring board (also referred to as an inner layer circuit board) and laminating them. As for the method for producing the multi-layer board, for example, copper foil of about 35 μm can be arranged on both sides of a sheet of the prepreg of the present embodiment, and after laminating them by the above-mentioned forming method, an inner layer circuit is formed, and the circuit is subjected to blackening treatment to form an inner layer circuit board. Thereafter, the inner layer circuit board and the prepreg of the present embodiment are alternately arranged one by one, and copper foil is further arranged on the outermost layer. Under the above-mentioned conditions, it is preferred to perform laminating and forming under vacuum to produce the multi-layer board. The metal-clad laminate of this embodiment can be preferably used as a printed wiring board.

>>Printed wiring board>> The printed wiring board of an ideal embodiment is a printed wiring board including an insulating layer and a conductive layer arranged on the surface of the insulating layer, wherein the insulating layer contains at least one of a layer formed by the resin composition of the present embodiment and a layer formed by the prepreg of the above-mentioned embodiment. Such a printed wiring board can be manufactured according to the conventional method, and its manufacturing method is not particularly limited. An example of a method for manufacturing a printed wiring board is shown below. First, a metal foil laminate such as the above-mentioned copper foil laminate is prepared. Then, the surface of the metal foil laminate is etched to form an inner layer circuit to produce an inner layer substrate. The inner circuit surface of the inner substrate is subjected to surface treatment to improve the bonding strength as required, and then the required number of prepregs are stacked on the inner circuit surface, and a metal foil for the outer circuit is stacked on the outer side thereof, and the prepreg is heated and pressed to form an integral body. In this way, a multi-layer laminate is manufactured with a base material and an insulating layer composed of a cured product of a thermosetting resin composition formed between the inner circuit and the metal foil for the outer circuit. Then, after the multi-layer laminate is subjected to hole opening processing for through holes and via holes, a plated metal film is formed on the wall surface of the hole to conduct the metal foil for the inner layer circuit and the outer layer circuit. The metal foil for the outer layer circuit is further etched to form the outer layer circuit, thereby manufacturing a printed wiring board.

The printed wiring board obtained in the above manufacturing example has an insulating layer and a conductive layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition of the above embodiment. That is, the prepreg of the above embodiment (for example, a prepreg formed by a substrate and the resin composition of the present embodiment impregnated or coated on the substrate) and the layer formed by the resin composition of the metal foil-clad laminate of the above embodiment are the insulating layer of the present embodiment.

>>Resin composite sheet>> The resin composite sheet of an ideal embodiment includes a support, and a layer formed of the resin composition of the present embodiment disposed on the surface of the aforementioned support. The resin composite sheet can be used as a thin film for build-up or a dry film solder resist. The method for manufacturing the resin composite sheet is not particularly limited, and for example, a method of obtaining the resin composite sheet by applying (coating) a solution obtained by dissolving the resin composition of the present embodiment in a solvent on a support and drying the solution can be cited.

Examples of the support used herein include polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene tetrafluoroethylene copolymer film, and organic film substrates such as release films obtained by coating a release agent on the surface of these films, polyimide films, etc.; conductive foils such as copper foil and aluminum foil, glass plates, SUS plates, FRP and the like, but there are no particular limitations.

As for the coating method (coating method), for example, there can be cited a method of coating a solution obtained by dissolving a resin composition in a solvent on a support using a coating rod, a die coater, a doctor blade coater, a Baker coater, etc. In addition, after drying, the support is peeled off or etched from a resin composite sheet formed by laminating the support and the resin composition, thereby making a single-layer sheet. In addition, by supplying a solution obtained by dissolving the resin composition of the present embodiment in a solvent into a mold having a sheet-shaped mold groove, and drying it to form a sheet, a single-layer sheet without using a support can also be obtained.

When preparing the resin composite sheet of the present embodiment, the drying conditions for removing the solvent are not particularly limited. Considering that the solvent is likely to remain in the resin composition at a low temperature and the resin composition is hardened at a high temperature, it is preferably carried out at a temperature of 20°C to 200°C for 1 to 90 minutes. In addition, in the resin composite sheet, the resin composition can be used in an unhardened state where the solvent has just been dried, or can be used in a semi-hardened (B-stage) state as needed. In addition, the thickness of the resin layer of the resin composite sheet of the present embodiment can be adjusted by the solution concentration of the resin composition of the present embodiment and the coating thickness, and is not particularly limited. Generally speaking, considering that the solvent is likely to remain when drying if the coating thickness becomes thicker, it is preferably 0.1 to 500 μm. [Example]

The following examples are given to further illustrate the present invention. The materials, usage amounts, proportions, processing contents, processing sequence, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the main purpose of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In this example, unless otherwise specified, the measurement is performed at 23°C.

>Example 1> 75 parts by mass of the following synthesized multifunctional vinylbenzene polymer (ap), 25 parts by mass of biphenyl aralkyl maleimide (MIR-3000 (trade name) manufactured by Nippon Kayaku Co., Ltd.), and 0.5 parts by mass of imidazole catalyst (2E4MZ (trade name) manufactured by Shikoku Chemical Co., Ltd.) were dissolved and mixed in methyl ethyl ketone to obtain a varnish.

(Synthesis of multifunctional vinylbenzene polymer (ap)) 2.25 mol (292.9 g) of divinylbenzene, 1.32 mol (172.0 g) of ethylvinylbenzene, 11.43 mol (1190.3 g) of styrene, and 15.0 mol (1532.0 g) of n-propyl acetate were placed in a reactor, and 600 mmol of diethyl ether complex of boron trifluoride was added at 70°C, and the reaction was allowed to proceed for 4 hours. After the polymerization solution was stopped with an aqueous sodium bicarbonate solution, the oil layer was washed three times with pure water, and decompressed and devolatiled at 60°C to recover the multifunctional vinylbenzene polymer (ap). The obtained multifunctional vinylbenzene polymer (ap) was weighed, and 860.8 g of the multifunctional vinylbenzene polymer (ap) was confirmed.

The Mn of the obtained multifunctional vinylbenzene polymer (ap) was 2060, the Mw was 30700, and the Mw/Mn was 14.9. By performing ¹³ C-NMR and ¹ H-NMR analysis, resonance lines derived from each monomer unit were observed in the multifunctional vinylbenzene polymer (ap). Based on the NMR measurement results and the GC analysis results, the ratio of the constituent units of the multifunctional vinylbenzene polymer (ap) was calculated as follows. Constituent units derived from divinylbenzene: 20.9 mol% (24.3 mass%) Constituent units derived from ethylvinylbenzene: 9.1 mol% (10.7 mass%) Constituent units derived from styrene: 70.0 mol% (65.0 mass%) In addition, the constituent units having residual vinyl groups derived from divinylbenzene were 16.7 mol% (18.5 mass%).

>>Production of 1.6mm thick hardened plate test piece>> The solvent was evaporated from the obtained varnish to obtain a mixed resin powder. The mixed resin powder was filled into a mold with a side of 100mm and a thickness of 1.6mm, and 12μm copper foil (3EC-M3-VLP, Mitsui Metals & Mining Co., Ltd.) was placed on both sides. Vacuum pressing was performed for 120 minutes at a pressure of 30kg/ ^cm2 and a temperature of 220℃ to obtain a hardened plate with a side of 100mm and a thickness of 1.6mm.

The physical properties of the obtained 1.6 mm thick hardened plate (dielectric properties (Dk, Df), peel strength, glass transition temperature, coefficient of thermal expansion (CTE)) were evaluated according to the following method.

>Example 2> The same method as in Example 1 was used to obtain a varnish except that 25 parts by mass of biphenyl aralkyl maleimide was changed to 12.5 parts by mass and 12.5 parts by mass of phenyl ether maleimide (BMI-80 (trade name) manufactured by K･I Chemical Co., Ltd.) was added. A 1.6 mm thick cured plate was obtained from the obtained varnish in the same manner as in Example 1. The physical properties of the obtained 1.6 mm thick cured plate were evaluated according to the method described below.

>Example 3> The same procedure as in Example 1 was followed except that 25 parts by mass of BisM maleimide (manufactured by K.I Chemical Co., Ltd., BMI-BisM (trade name)) was used instead of 25 parts by mass of biphenyl aralkyl maleimide to obtain a varnish. A 1.6 mm thick cured plate was obtained from the obtained varnish in the same manner as in Example 1. The physical properties of the obtained 1.6 mm thick cured plate were evaluated according to the method described below.

>Example 4> The same method as in Example 1 was used to obtain a varnish except that 25 parts by mass of terminal-modified polyphenylene ether (OPE-2St 1200 (trade name) manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used instead of 25 parts by mass of biphenyl aralkyl maleimide and no imidazole catalyst was used. A 1.6 mm thick cured plate was obtained from the obtained varnish in the same manner as in Example 1. The physical properties of the obtained 1.6 mm thick cured plate were evaluated according to the method described below.

>Example 5> The same process as in Example 1 was performed except that 25 parts by mass of the following naphthol aralkyl cyanate resin was used to replace 25 parts by mass of biphenyl aralkyl maleimide, and 0.1 parts by mass of an organic metal catalyst (Oct-Mn (trade name) manufactured by Nippon Chemical Industry Co., Ltd.) was used to replace 0.5 parts by mass of an imidazole catalyst. A varnish having a thickness of 1.6 mm was obtained from the obtained varnish in the same manner as in Example 1. The physical properties of the obtained 1.6 mm thick cured plate were evaluated according to the method described below.

(Synthesis of α-naphthol aralkyl type cyanate resin) 0.47 mol (OH group conversion) of α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g/eq., manufactured by Nippon Steel Chemical Co., Ltd.: containing 1 to 5 repeating units of naphthol aralkyl) was dissolved in 500 mL of chloroform, and 0.7 mol of triethylamine was added to the solution to prepare solution 1. While maintaining the temperature at -10°C, solution 1 was added dropwise to 300 g of 0.93 mol of cyanogen chloride chloroform solution already charged in a reactor over 1.5 hours. After the addition was completed, the mixture was stirred for 30 minutes. Thereafter, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was further added dropwise to the reactor, and stirred for 30 minutes to complete the reaction. After filtering the by-product triethylamine hydrochloride from the reaction solution, the obtained filtrate was washed with 500 mL of 0.1N hydrochloric acid, and then washed with 500 mL of water for 4 times. After drying with sodium sulfate, it was evaporated at 75°C and further degassed under reduced pressure at 90°C to obtain a brown solid α-naphthol aralkyl type cyanate compound represented by formula (S1) (wherein R ^C1 to R ^C4 are all hydrogen atoms and n ^c is a mixture of 1 to 5.). The obtained α-naphthol aralkyl type cyanate compound was analyzed by infrared absorption spectroscopy, and the absorption of the cyanate group was confirmed near 2264 cm ^-1 . [Chemistry 22]

>Reference Example 1> Other than adding 1 part by mass of a thermal radical polymerization initiator (PERBUTYL P (trade name) manufactured by NOF Corporation), the same procedure as in Example 1 was followed to obtain a varnish. From the obtained varnish, a 1.6 mm thick cured plate was obtained in the same manner as in Example 1. The physical properties of the obtained 1.6 mm thick cured plate were evaluated according to the method described below.

>Reference Example 2> Other than adding 1 part by mass of a thermal free radical polymerization initiator (PERBUTYL P (trade name) manufactured by NOF Corporation), the same procedure as in Example 4 was followed to obtain a varnish. From the obtained varnish, a 1.6 mm thick cured plate was obtained in the same manner as in Example 4. The physical properties of the obtained 1.6 mm thick cured plate were evaluated according to the method described below.

>Reference Example 3> Other than adding 1 part by mass of a thermal free radical polymerization initiator (PERBUTYL P (trade name) manufactured by NOF Corporation), the same procedure as in Example 5 was followed to obtain a varnish. From the obtained varnish, a 1.6 mm thick cured plate was obtained in the same manner as in Example 5. The physical properties of the obtained 1.6 mm thick cured plate were evaluated according to the method described below.

> Dielectric properties (Dk and Df)> For the test piece obtained by etching away the copper foil of the obtained 1.6mm thick hardened plate, the relative dielectric constant (Dk) and dielectric loss tangent (Df) at 10GHz were measured using a perturbation method cavity resonator. The measurement temperature was 23℃. The perturbation method cavity resonator used was Agilent8722ES, a product of Agilent.

>Peel strength> Using the hardened plate obtained in the above manner, the copper foil peel strength (adhesion) was measured twice according to the provisions of 5.7 "Peel strength" of JIS C6481, and the average value was calculated. The measurement temperature was 23℃.

>Glass transition temperature> The glass transition temperature (Tg) was measured by a dynamic viscoelasticity analyzer using the DMA (Dynamic Mechanical Analysis) bending method in accordance with JIS C6481 5.17.2 for a test piece obtained by removing the copper foil of the obtained hardened plate with a thickness of 1.6 mm by etching. The glass transition temperature was estimated from the obtained tanδ graph. The dynamic viscoelasticity analyzer used was a device manufactured by TA Instruments.

>Coefficient of linear thermal expansion (CTE)> (CTE: Coefficient of linear thermal expansion) For a test piece obtained by removing the copper foil of a 1.6 mm thick hardened plate by etching, the coefficient of thermal expansion of the hardened plate was measured using the TMA method (Thermo-Mechanical Analysis) specified in JIS C 6481 5.19 to obtain its value. Specifically, after removing the copper foil on both sides of the hardened plate obtained above by etching, the temperature was raised from 40°C to 340°C at 10°C per minute using a thermomechanical analyzer (manufactured by TA Instrument) to measure the linear thermal expansion coefficient (ppm/°C). ppm is a volume ratio. Other details are based on the above JIS C 6481 5.19.

[Table 1] (Marks in the table) Dk: Relative dielectric constant at 10 GHz Df: Dielectric loss tangent at 10 GHz Peel strength: Result of copper foil peeling test Glass transition temperature: Glass transition temperature estimated from tanδ measured by DMA method CTE: Coefficient of thermal expansion measured by TMA method

From the results in Table 1 above, it can be seen that the resin composition of the present embodiment, which is a combination of a multifunctional vinyl aromatic polymer (A) (multifunctional vinyl benzene polymer (ap)) and a thermosetting compound (B), has excellent dielectric properties (low dielectric constant, low dielectric loss tangent), and has a high glass transition temperature and a low thermal expansion coefficient. In addition, the peeling strength is also high. On the other hand, if a free radical polymerization initiator is contained, it can be seen from the comparison between Reference Example 1 and Example 1, Reference Example 2 and Example 4, and Reference Example 3 and Example 5 that the dielectric loss tangent becomes higher, the glass transition temperature decreases, and the thermal expansion coefficient also becomes higher. In addition, the peeling strength is also low.

Claims (10)

A resin composition comprising a multifunctional vinyl aromatic polymer (A) and a thermosetting compound (B), and containing no free radical polymerization initiator; the multifunctional vinyl aromatic polymer (A) is a copolymer comprising a constituent unit (a) and a constituent unit (b); the molecular weight of the multifunctional vinyl aromatic polymer (A) is 300 or more in terms of number average molecular weight Mn; the constituent unit (a) comprises a constituent unit represented by the following formula (V); the constituent unit (b) comprises a constituent unit represented by the following formula (V4); and the thermosetting compound (B) has one or more functional groups selected from the group consisting of a cyano group, a vinyl group, a maleimide group, and a nadiimide group;

In formula (V), Ar represents an aromatic hydrocarbon linking group; * represents a bonding position;

In formula (V4), ^L2 is an aromatic hydrocarbon linking group, R ^V1 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and * represents a bonding position. The resin composition of claim 1, wherein the content of the thermosetting compound (B) is 5 to 95 parts by mass relative to 100 parts by mass of the total resin component in the resin composition. The resin composition of claim 1 or 2, wherein the content of the multifunctional vinyl aromatic polymer (A) is 5 to 95 parts by weight relative to 100 parts by weight of the total resin component in the resin composition. The resin composition of claim 1 or 2 further contains a filler (C). The resin composition of claim 4, wherein the content of the filler (C) is 10 to 500 parts by mass relative to 100 parts by mass of the total resin component in the resin composition. The resin composition of claim 1 or 2, wherein the molecular weight of the multifunctional vinyl aromatic polymer (A) is greater than 1000 in terms of number average molecular weight Mn. A prepreg formed by a substrate and a resin composition as described in any one of claims 1 to 6. A metal foil-clad laminate comprising: at least one layer formed by the prepreg as claimed in claim 7; and metal foil disposed on one or both sides of the layer formed by the prepreg. A resin composite sheet comprising: a support; and a layer formed of a resin composition as described in any one of claims 1 to 6 and disposed on the surface of the support. A printed wiring board comprising: an insulating layer; and a conductive layer disposed on a surface of the insulating layer; the insulating layer comprises at least one of a layer formed of a resin composition as in any one of claims 1 to 6 and a layer formed of a prepreg as in claim 7.