KR20230117325A - Resin composition, prepreg, resin sheet, metal foil clad laminate, and printed wiring board - Google Patents

Abstract

A resin composition containing a thermosetting compound (A), a thermoplastic elastomer (B), and a phosphorus-based flame retardant (C), wherein the content of the thermoplastic elastomer (B) in the resin composition is 1 to 30 parts by mass based on 100 parts by mass of the resin solid content part, and the content of the phosphorus-based flame retardant (C) in the resin composition is 1 to 30 parts by mass with respect to 100 parts by mass of the resin solid content.

Description

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

The present invention relates to a resin composition, a prepreg, a resin sheet, and a metal foil-clad laminate, a printed wiring board, and a semiconductor device manufactured using the same.

BACKGROUND OF THE INVENTION [0002] In recent years, information terminal devices such as personal computers and servers and communication devices such as Internet routers and optical communications are required to process large amounts of information at high speed, and electrical signals are being increased in speed and frequency. Correspondingly, laminates for printed wiring boards used for these are required to have low dielectric constant and low dielectric dissipation factor in order to respond to the demand for high frequencies.

For example, in Patent Document 1, excellent heat resistance, low dielectric properties and various physical properties are obtained by using together a polyphenylene ether resin in which both sides of the molecular chain are modified with unsaturated bond substituents and three or more specific crosslinkable curing agents. It has been reported that a thermosetting resin composition provided at the same time, a prepreg using the composition, a laminated sheet, and a printed circuit board can be obtained.

Japanese Unexamined Patent Publication No. 2019-90037

In addition to dielectric loss tangent characteristics (low dielectric loss tangent) and copper foil peel strength, crack resistance is also requested|required of the laminated board for printed wiring boards. Here, the crack resistance indicates the insulation reliability when a bending test is performed while applying an electric current to a substrate on which a circuit is drawn, and indicates that dielectric breakdown does not occur even if the number of times of bending is large. While the copper clad laminate disclosed in the above Patent Document has good dielectric loss tangent characteristics and the like, it still leaves problems with respect to crack resistance.

In view of the above circumstances, the present invention is a resin composition capable of obtaining a metal foil-clad laminate having good copper foil peel strength and dielectric dissipation characteristics (low dielectric loss tangent), and also excellent in crack resistance and solder heat resistance, and this metal foil-clad laminate It aims at providing a printed wiring board and a semiconductor device using the.

As a result of intensive studies, the present inventors have found that the above problems can be solved by setting a resin composition containing a thermosetting compound, a specific amount of a thermoplastic elastomer, and a phosphorus-based flame retardant, and completed the present invention.

That is, this invention is as follows.

[One]

A resin composition comprising a thermosetting compound (A), a thermoplastic elastomer (B), and a phosphorus-based flame retardant (C),

The content of the thermoplastic elastomer (B) in the resin composition is 1 to 30 parts by mass with respect to 100 parts by mass of the resin solid content,

The resin composition in which the content of the phosphorus-based flame retardant (C) in the resin composition is 1 to 30 parts by mass with respect to 100 parts by mass of the resin solid content.

[2]

The resin composition according to the above [1], wherein the content of the phosphorus-based flame retardant (C) in the resin composition is 15 to 30 parts by mass with respect to 100 parts by mass of the resin solid content.

[3]

The resin composition according to [1] or [2] above, wherein the phosphorus-based flame retardant (C) is at least one selected from the group consisting of aromatic condensed phosphate esters (C-1) and cyclic phosphazene compounds (C-2). .

[4]

In the above [3], wherein the aromatic condensed phosphate ester (C-1) is a compound represented by the following formula (1), and the cyclic phosphazene compound (C-2) is a compound represented by the following formula (2) The resin composition described.

[Formula 1]

[Formula 2]

(In Formula (2), n represents an integer of 3 to 6.)

[5]

The resin composition according to any one of [1] to [4], wherein the thermoplastic elastomer (B) is a styrenic elastomer.

[6]

The styrenic elastomer is from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-hydrogenated butadiene-styrene block copolymer, and a styrene-hydrogenated isoprene-styrene block copolymer The resin composition according to the above [5], which is one or more selected species.

[7]

The thermosetting compound (A) is selected from the group consisting of cyanate ester compounds, maleimide compounds, polyphenylene ether compounds, epoxy compounds, phenol compounds, and curable polyimide compounds. ] to the resin composition according to any one of [6].

[8]

The resin composition according to any one of [1] to [7], wherein the resin composition further contains a filler.

[9]

The resin composition according to [8] above, wherein the filler is at least one selected from the group consisting of silicas, aluminum hydroxide, aluminum nitride, boron nitride, and forsterite.

[10]

The resin composition according to [8] or [9] above, wherein the content of the filler in the resin composition is 30 to 300 parts by mass with respect to 100 parts by mass of the resin solid content.

[11]

A prepreg comprising a substrate and the resin composition according to any one of [1] to [10] impregnated or applied to the substrate.

[12]

A resin sheet containing the resin composition according to any one of [1] to [10] above.

[13]

A laminated board comprising at least one selected from the group consisting of the prepreg according to [11] above and the resin sheet according to [12] above.

[14]

A metal foil-clad laminate comprising at least one prepreg according to [11] above and a metal foil laminated on one or both surfaces of the prepreg.

[15]

A metal foil clad laminate comprising at least one resin sheet according to the above [12] and a metal foil laminated on one or both surfaces of the resin sheet.

[16]

A printed wiring board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer,

The printed wiring board in which the said insulating layer contains at least one of the layer formed from the resin composition as described in any one of said [1]-[10], and the layer formed from the prepreg as described in said [11].

[17]

A semiconductor device manufactured using the printed wiring board described in [16] above.

By using the resin composition of the present invention, it is possible to provide a metal foil-clad laminate having good copper foil peeling strength and good dielectric loss tangent characteristics, and also excellent in crack resistance and solder heat resistance, as well as printed wiring boards and semiconductor devices using the same.

The resin composition of the present embodiment,

A resin composition comprising a thermosetting compound (A), a thermoplastic elastomer (B), and a phosphorus-based flame retardant (C),

The content of the thermoplastic elastomer (B) in the resin composition is 1 to 30 parts by mass with respect to 100 parts by mass of the resin solid content,

The content of the phosphorus-based flame retardant (C) in the resin composition is 1 to 30 parts by mass with respect to 100 parts by mass of the resin solid content.

In this specification, "resin solid content in a resin composition" refers to components excluding solvents and fillers in a resin composition unless otherwise specified, and 100 parts by mass of resin solid content refers to components excluding solvents and fillers in a resin composition. It shall mean that the sum total of components is 100 mass parts.

In the following, first, the resin composition of the present embodiment and components constituting the same are described, and then prepregs, resin sheets, metal foil-clad laminates, and the like obtained using the resin composition are described.

[Resin composition]

The resin composition in this embodiment contains a thermosetting compound (A), a thermoplastic elastomer (B), and a phosphorus flame retardant (C).

[Thermosetting compound (A)]

The thermosetting compound (A) is not particularly limited as long as it is a thermosetting compound, and examples thereof include cyanate ester compounds, maleimide compounds, polyphenylene ether compounds, epoxy compounds, phenol compounds, and curable polyimide compounds. It is preferable to include one or more selected types.

[Cyanate ester compound]

The cyanate ester compound according to the present embodiment is not particularly limited as long as it is a resin having an aromatic moiety substituted with at least one cyanato group (cyanate ester group) in the molecule, but is substituted with at least one cyanato group. A cyanate ester compound having two or more aromatic moieties in a molecule is more preferable. It is preferable that it is 2 or more, and, as for the minimum of the number of cyanato groups which a cyanate ester compound has, it is more preferable that it is 3 or more. When the number of cyanato groups is equal to or greater than the lower limit, the heat resistance tends to be further improved. The upper limit is not particularly defined, but may be, for example, 50 or less.

As a cyanate ester compound in this embodiment, the compound represented by Formula (5) is mentioned, for example.

[Formula 3]

(In formula (5), Ar ₁ each independently represents a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a biphenylene group which may have a substituent. R ₈₁ is each independently hydrogen An alkyl group of 1 to 6 carbon atoms which may have an atom or a substituent, an aryl group of 6 to 12 carbon atoms which may have a substituent, an alkoxy group of 1 to 4 carbon atoms which may have a substituent, an alkyl group of 1 to 6 carbon atoms and a carbon atom of 6 to 6 It is selected from any one of an aralkyl group which may have a substituent bonded to a 12 aryl group or an alkylaryl group which may have a substituent bonded to an alkyl group having 1 to 6 carbon atoms and an aryl group having ₆ to 12 carbon _atoms . Represents the number of cyanato groups to be bonded, and is an integer from 1 to 3. n ₇ represents the number of R ₈₁ bonds to Ar ₁ , 4-n ₆ when Ar ₁ is a phenylene group, and 6- when Ar 1 is a naphthylene group. In the case of n ₆ and a biphenylene group, it is 8-n _6. n ₈ represents the average number of repetitions and is an integer of 0 to 50. The cyanate ester compound may be a mixture of compounds having different n _8. Z is each Independently, a single bond, a divalent organic group of 1 to 50 carbon atoms (the hydrogen atom may be substituted with a hetero atom), a divalent organic group of 1 to 10 nitrogen atoms (-NRN-, etc.), a carbonyl group (-CO-), Any one of a carboxyl group (-C(=O)O-), a carbonyl dioxide group (-OC(=O)O-), a sulfonyl group (-SO ₂ -), and a divalent sulfur atom or a divalent oxygen atom are selected from.)

The alkyl group for R ₈₁ in Formula (5) may have a linear structure, a branched chain structure, or a cyclic structure (such as a cycloalkyl group). In addition, the hydrogen atom in the alkyl group in the alkyl group in R ₈₁ of Formula (5) and the aryl group in R ₈₁ is a halogen atom such as a fluorine atom and a chlorine atom, an alkoxy group such as a methoxy group and a phenoxy group, It may be substituted with a cyano group or the like.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 1-ethylpropyl group, 2,2-dimethylpropyl group , cyclopentyl group, hexyl group, cyclohexyl group, trifluoromethyl group, etc. are mentioned.

Specific examples of the aryl group include a phenyl group, a xylyl group, a mesityl group, a naphthyl group, a phenoxyphenyl group, an ethylphenyl group, an o-, m- or p-fluorophenyl group, a dichlorophenyl group, a dicyanophenyl group, a trifluorophenyl group, A methoxyphenyl group, an o-, m-, or p-tolyl group etc. are mentioned.

Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.

Specific examples of the divalent organic group in Z of formula (5) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, a biphenylylmethylene group, A dimethylmethylene-phenylene-dimethylmethylene group, a fluorenediyl group, a phthalidyl group, etc. are mentioned. The hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, or a cyano group. An imino group, a polyimide group, etc. are mentioned as a divalent organic group of 1-10 nitrogen atoms in Z of Formula (5).

Moreover, as Z in formula (5), what is a structure represented by following formula (6) or following formula (7) is mentioned.

[Formula 4]

(In formula (6), Ar ₂ is selected from any one of a phenylene group, a naphthylene group, and a biphenylene group. R ₉ , R ₁₀ , R ₁₃ , and R ₁₄ are each independently a hydrogen atom and 1 to 6 carbon atoms is selected from any one of an alkyl group, an aryl group having 6 _to 12 carbon atoms, and an aryl group substituted _with at least one of a trifluoromethyl group and a phenolic hydroxy group. It is selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, _an alkoxy group having 1 to 4 carbon atoms, and a hydroxy group. The acid ester compound may be a mixture of compounds having groups with different n ₉ .)

[Formula 5]

(In Formula (7), Ar ₃ is selected from any one of a phenylene group, a naphthylene group, or a biphenylene group. R ₁₅ and R ₁₆ are each independently a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, or a carbon number of 6 to 6 12 aryl groups, benzyl groups, alkoxy groups having 1 to 4 carbon atoms, and aryl groups substituted _with at least one of a hydroxyl group, a trifluoromethyl group, and a cyanato group. represents an integer of 0 to 5, but the cyanate ester compound may be a mixture of compounds having groups with different n ₁₀ .)

Moreover, as Z in formula (5), the bivalent group represented by the following formula is mentioned.

[Formula 6]

(In the formula, n ₁₁ represents an integer of 4 to 7. R ₁₇ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

Specific examples of Ar ₂ in formula (6) and Ar ₃ in formula (7) include a 1,4-phenylene group, a 1,3-phenylene group, a 4,4'-biphenylene group, and a 2,4'-biphenylene group. Phenylene group, 2,2'-biphenylene group, 2,3'-biphenylene group, 3,3'-biphenylene group, 3,4'-biphenylene group, 2,6-naphthylene group, 1,5 -Naphthylene group, 1,6-naphthylene group, 1,8-naphthylene group, 1,3-naphthylene group, 1,4-naphthylene group, etc. are mentioned. The alkyl group and aryl group in R ₉ to R ₁₄ in formula (6) and R ₁₅ and R ₁₆ in formula (7) are the same as those described in formula (5).

Examples of the cyanate ester compound represented by formula (5) include a phenol novolak type cyanate ester compound, a naphthol aralkyl type cyanate ester compound, a biphenyl aralkyl type cyanate ester compound, and a naphthylene ether type cyanic acid. Ester compounds, xylene resin type cyanate ester compounds, adamantane skeleton type cyanate ester compounds, bisphenol A type cyanate ester compounds, diallyl bisphenol A type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, etc. can be heard

Moreover, as a specific example of the cyanate ester compound represented by Formula (5), cyanatobenzene, 1-cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methylbenzene, 1 -Cyanato-2-, 1-cyanato-3-, or 1-cyanato-4-methoxybenzene, 1-cyanato-2,3-, 1-cyanato-2,4-, 1-cyanato Nato-2,5-, 1-cyanato-2,6-, 1-cyanato-3,4- or 1-cyanato-3,5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanato Nattooctylbenzene, cyanatononylbenzene, 2-(4-cyanatophenyl)-2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyana Nato-4-vinylbenzene, 1-cyanato-2- or 1-cyanato-3-chlorobenzene, 1-cyanato-2,6-dichlorobenzene, 1-cyanato-2-methyl-3-chlorobenzene , cyanatonitrobenzene, 1-cyanato-4-nitro-2-ethylbenzene, 1-cyanato-2-methoxy-4-allylbenzene (cyanate of eugenol), methyl (4-cyanatophenyl ) Sulfide, 1-cyanato-3-trifluoromethylbenzene, 4-cyanatobiphenyl, 1-cyanato-2- or 1-cyanato-4-acetylbenzene, 4-cyanatobenzaldehyde, 4- Cyanatobenzoic acid methyl ester, 4-cyanatobenzoic acid phenyl ester, 1-cyanato-4-acetaminobenzene, 4-cyanatobenzophenone, 1-cyanato-2,6-di-tert-butylbenzene, 1, 2-dicyanatobenzene, 1,3-dicyanatobenzene,

1,4-dicyanatobenzene, 1,4-dicyanato-2-tert-butylbenzene, 1,4-dicyanato-2,4-dimethylbenzene, 1,4-dicyanato-2,3 ,4-dimethylbenzene, 1,3-dicyanato-2,4,6-trimethylbenzene, 1,3-dicyanato-5-methylbenzene, 1-cyanato or 2-cyanatonaphthalene, 1-cyana Nato-4-methoxynaphthalene, 2-cyanato-6-methylnaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2'-dicyanato-1,1'-binaphthyl, 1,3 -, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanatocinnaphthalene, 2,2'- or 4,4 '-dicyanatobiphenyl, 4,4'-dicyanatooctafluorobiphenyl, 2,4'- or 4,4'-dicyanatodiphenylmethane, bis(4-cyanato-3,5-dimethylphenyl ) Methane, 1,1-bis (4-cyanatophenyl) ethane, 1,1-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (3-allyl-4-cyanatophenyl)propane, 2,2-bis(4-cyanato-3-methylphenyl)propane, 2,2-bis(2-cyanato-5-biphenylyl)propane, 2 2-bis (4-cyanatophenyl) hexafluoropropane, 2,2-bis (4-cyanato-3,5-dimethylphenyl) propane, 1,1-bis (4-cyanatophenyl) butane, 1,1-bis(4-cyanatophenyl)isobutane, 1,1-bis(4-cyanatophenyl)pentane, 1,1-bis(4-cyanatophenyl)-3-methylbutane,

1,1-bis(4-cyanatophenyl)-2-methylbutane, 1,1-bis(4-cyanatophenyl)-2,2-dimethylpropane, 2,2-bis(4-cyanatophenyl) Butane, 2,2-bis (4-cyanatophenyl) pentane, 2,2-bis (4-cyanatophenyl) hexane, 2,2-bis (4-cyanatophenyl) -3-methylbutane, 2, 2-bis(4-cyanatophenyl)-4-methylpentane, 2,2-bis(4-cyanatophenyl)-3,3-dimethylbutane, 3,3-bis(4-cyanatophenyl)hexane, 3,3-bis(4-cyanatophenyl)heptane, 3,3-bis(4-cyanatophenyl)octane, 3,3-bis(4-cyanatophenyl)-2-methylpentane, 3,3- Bis(4-cyanatophenyl)-2-methylhexane, 3,3-bis(4-cyanatophenyl)-2,2-dimethylpentane, 4,4-bis(4-cyanatophenyl)-3-methyl Heptane, 3,3-bis (4-cyanatophenyl) -2-methylheptane, 3,3-bis (4-cyanatophenyl) -2,2-dimethylhexane, 3,3-bis (4-cyanato Phenyl) -2,4-dimethylhexane, 3,3-bis (4-cyanatophenyl) -2,2,4-trimethylpentane, 2,2-bis (4-cyanatophenyl) -1,1,1 ,3,3,3-hexafluoropropane, bis(4-cyanatophenyl)phenylmethane,

1,1-bis(4-cyanatophenyl)-1-phenylethane, bis(4-cyanatophenyl)biphenylmethane, 1,1-bis(4-cyanatophenyl)cyclopentane, 1,1-bis (4-cyanatophenyl)cyclohexane, 2,2-bis(4-cyanato-3-isopropylphenyl)propane, 1,1-bis(3-cyclohexyl-4-cyanatophenyl)cyclohexane, bis (4-cyanatophenyl)diphenylmethane, bis(4-cyanatophenyl)-2,2-dichloroethylene, 1,3-bis[2-(4-cyanatophenyl)-2-propyl]benzene, 1 ,4-bis[2-(4-cyanatophenyl)-2-propyl]benzene, 1,1-bis(4-cyanatophenyl)-3,3,5-trimethylcyclohexane, 4-[bis(4 -Cyanatophenyl)methyl]biphenyl, 4,4-dicyanatobenzophenone, 1,3-bis(4-cyanatophenyl)-2-propen-1-one, bis(4-cyanatophenyl) Ether, bis(4-cyanatophenyl)sulfide, bis(4-cyanatophenyl)sulfone, 4-cyanatobenzoic acid-4-cyanatophenyl ester (4-cyanatophenyl-4-cyanatobenzoate), Bis-(4-cyanatophenyl)carbonate, 1,3-bis(4-cyanatophenyl)adamantane, 1,3-bis(4-cyanatophenyl)-5,7-dimethyladamantane, 3 ,3-bis(4-cyanatophenyl)isobenzofuran-1(3H)-one (cyanate of phenolphthalein), 3,3-bis(4-cyanato-3-methylphenyl)isobenzofuran-1(3H ) -one (cyanate of o-cresolphthalein), 9,9-bis (4-cyanatophenyl) fluorene, 9,9-bis (4-cyanato-3-methylphenyl) fluorene, 9,9 -bis(2-cyanato-5-biphenylyl)fluorene, tris(4-cyanatophenyl)methane,

1,1,1-tris(4-cyanatophenyl)ethane, 1,1,3-tris(4-cyanatophenyl)propane, α,α,α'-tris(4-cyanatophenyl)-1- Ethyl-4-isopropylbenzene, 1,1,2,2-tetrakis(4-cyanatophenyl)ethane, tetrakis(4-cyanatophenyl)methane, 2,4,6-tris(N-methyl- 4-cyanatoanilino)-1,3,5-triazine, 2,4-bis(N-methyl-4-cyanatoanilino)-6-(N-methylanilino)-1,3,5 -triazine, bis(N-4-cyanato-2-methylphenyl)-4,4'-oxydiphthalimide, bis(N-3-cyanato-4-methylphenyl)-4,4'-oxydiff Timide, bis(N-4-cyanatophenyl)-4,4'-oxydiphthalimide, bis(N-4-cyanato-2-methylphenyl)-4,4'-(hexafluoroiso Propylidene) diphthalimide, tris (3,5-dimethyl-4-cyanatobenzyl) isocyanurate, 2-phenyl-3,3-bis (4-cyanatophenyl) phthalimidine, 2-( 4-methylphenyl) -3,3-bis (4-cyanatophenyl) phthalimidine, 2-phenyl-3,3-bis (4-cyanato-3-methylphenyl) phthalimidine, 1-methyl-3, 3-bis(4-cyanatophenyl)indolin-2-one, 2-phenyl-3,3-bis(4-cyanatophenyl)indolin-2-one,

Phenol novolac resin or cresol novolac resin (a product obtained by reacting phenol, alkyl-substituted phenol or halogen-substituted phenol with a formaldehyde compound such as formalin or paraformaldehyde in an acidic solution by a known method), trisphenolo Ballak resin (reacting hydroxybenzaldehyde and phenol in the presence of an acidic catalyst), fluorene novolak resin (reacting a fluorenone compound and 9,9-bis(hydroxyaryl)fluorenes in the presence of an acidic catalyst) ), phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin or biphenyl aralkyl resin (by a known method, a bishalogenomethyl compound as represented by Ar ₄ -(CH ₂ Z') ₂ and a phenolic compound reacted with an acid catalyst or without a catalyst, a bis(alkoxymethyl) compound as represented by Ar ₄ -(CH ₂ OR) ₂ or a bis(hydride) as represented by Ar ₄ -(CH ₂ OH) ₂ oxymethyl) compound and a phenol compound reacted in the presence of an acidic catalyst, or a product obtained by polycondensation of an aromatic aldehyde compound, an aralkyl compound, or a phenol compound), a phenol-modified xylene formaldehyde resin (by a known method, Xylene formaldehyde resin and a phenol compound reacted in the presence of an acidic catalyst), modified naphthalene formaldehyde resin (by a known method, a product obtained by reacting a naphthalene formaldehyde resin and a hydroxy-substituted aromatic compound in the presence of an acidic catalyst) ), phenol-modified dicyclopentadiene resin, phenol resin having a polynaphthylene ether structure (by a known method, a polyhydric hydroxynaphthalene compound having two or more phenolic hydroxyl groups in one molecule is prepared in the presence of a basic catalyst and those obtained by cyanate esterification of phenol resins such as those obtained by dehydration condensation) by the same method as described above, but are not particularly limited. These cyanate ester compounds may be used independently or may use 2 or more types together.

Among these, phenol novolak-type cyanate ester compounds, naphthol aralkyl-type cyanate ester compounds, naphthylene ether-type cyanate ester compounds, bisphenol A-type cyanate ester compounds, bisphenol M-type cyanate ester compounds, diallyl bisphenol-type cyanate Acid esters are preferred, and naphthol aralkyl type cyanate ester compounds are particularly preferred.

A cured product of a resin composition using these cyanate ester compounds has excellent properties such as heat resistance and low dielectric properties (low dielectric constant and low dielectric loss tangibility), and a printed wiring board containing the cured product has a copper foil peel strength, It tends to be excellent in mechanical strength, heat resistance, and low dielectric loss tangent.

The content of the cyanate ester compound in the resin composition according to the present embodiment can be appropriately set according to desired characteristics, and is not particularly limited. Specifically, the content of the cyanate ester compound is preferably 1 part by mass or more, more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, when the resin solid content in the resin composition is 100 parts by mass, 15 parts by mass or more may be sufficient. The upper limit of the content is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, and may be 55 parts by mass or less. By setting it as such a range, the low dielectric property of the cured product of the resin composition becomes more excellent, and the printed wiring board containing the cured product tends to have a better low dielectric loss tangent.

One type of cyanate ester compound may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

[Maleimide compound]

The maleimide compound according to the present embodiment is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule, but is preferably a compound having two or more maleimide groups in the molecule. Specific examples of the maleimide compound include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidephenyl)methane, 4,4'-diphenylmethanebismaleimide, bis( 3,5-dimethyl-4-maleimidephenyl)methane, bis(3,5-diethyl-4-maleimidephenyl)methane, phenylmethanemaleimide, o-phenylenebismaleimide, m-phenylenebismaleimide Mid, p-phenylenebismaleimide, o-phenylenebiscitraconimide, m-phenylenebiscitraconimide, p-phenylenebiscitraconimide, 2,2-bis(4-(4) -maleimidephenoxy)-phenyl)propane, 3,3'-diethyl-5,5'-dimethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaley Mid, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis (3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, 4,4'-diphenylmethanebiscitraconimide, 2,2-bis[4-(4- Citraconimidephenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimidephenyl)methane, bis(3-ethyl-5-methyl-4-citraconimidephenyl)methane, bis (3,5-diethyl-4-citraconimide phenyl)methane, maleimide compounds represented by the following formulas (2), (3), (4) and (17), and the like are exemplified.

Among these, maleimide compounds represented by the following formulas (2), (3), (4) and (17) are particularly preferred from the viewpoint of improving the low thermal expansion property and heat resistance of the cured product of the resin composition. These maleimide compounds may be used independently or may use 2 or more types together.

[Formula 7]

(In the formula (2), each R ₄ independently represents a hydrogen atom or a methyl group, and n ₄ represents an integer greater than or equal to 1.)

[Formula 8]

(In the formula (3), R ₅ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and n ₅ represents an integer of 1 or more and 10 or less.)

[Formula 9]

(In the formula (4), each R ₆ independently represents a hydrogen atom, a methyl group or an ethyl group, and each R ₇ independently represents a hydrogen atom or a methyl group.)

[Formula 10]

(In the formula (17), each R ₈ independently represents a hydrogen atom, a methyl group or an ethyl group.)

In the formula (2), R ₄ each independently represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. In Formula (2), n ₄ represents an integer greater than or equal to 1, the upper limit of n ₄ is usually 10, and the upper limit of n ₄ is preferably 7 from the viewpoint of solubility in organic solvents. Preferably it is 5. The maleimide compound may contain two or more types of compounds having different n ₄ .

In the formula (3), each R ₅ independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, t-butyl group, n-pentyl group, etc.), or a phenyl group. Among these, from the viewpoint of improving the flame resistance and metal foil (copper foil) peeling strength of the metal foil-clad laminate, a group selected from the group consisting of a hydrogen atom, a methyl group, and a phenyl group is preferable, and one of a hydrogen atom and a methyl group is more preferable. , more preferably a hydrogen atom.

In the above formula (3), 1 ≤ n ₅ ≤ 10. n ₅ is preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, from the viewpoint of further excellent solvent solubility. The maleimide compound may contain two or more types of compounds having different n ₅ .

In the formula (4), R ₆ each independently represents a hydrogen atom, a methyl group or an ethyl group, and each R ₇ independently represents a hydrogen atom or a methyl group. From the standpoint of further excellent low dielectric properties of the cured product of the resin composition, R ₆ is preferably a methyl group or an ethyl group. Examples of such compounds include 3,3'-diethyl-5,5'-dimethyl-4,4'-diphenylmethanebismaleimide.

In the formula (17), each R ₈ independently represents a hydrogen atom, a methyl group or an ethyl group, and from the viewpoint of further excellent low dielectric properties of a cured product of the resin composition, R ₈ is preferably a methyl group. An example of such a compound is 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane.

The maleimide compound used in this embodiment may use a commercially available one, for example, "BMI-2300" by Daiwa Chemical Industry Co., Ltd., maleimide represented by formula (3) as a maleimide compound represented by formula (2) "MIR-3000" manufactured by Nippon Kayaku Co., Ltd. as a compound, "BMI-70" manufactured by K-I Chemicals Co., Ltd. as a maleimide compound represented by formula (4), manufactured by K-I Chemical Co., Ltd. as a maleimide compound represented by formula (17) "BMI-80" can be used preferably.

The content of the maleimide compound in the resin composition according to the present embodiment can be appropriately set according to desired characteristics, and is not particularly limited. The content of the maleimide compound is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more, when the resin solid content in the resin composition is 100 parts by mass. The upper limit is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, and may be 50 parts by mass or less. By setting it as such a range, there exists a tendency for the high heat resistance and low water absorption property of the hardened|cured material of a resin composition to be exhibited more effectively.

1 type of maleimide compound may be used, and may use 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.

[Polyphenylene ether compound]

As a polyphenylene ether compound concerning this embodiment, formula (8):

[Formula 11]

(In Formula (8), R ₈ , R ₉ , R ₁₀ , and R ₁₁ each independently represent an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom, or a hydrogen atom.)

It is preferable that it is a compound containing the polymer of the structural unit represented by.

The polyphenylene ether compound is Formula (9):

[Formula 12]

(In formula (9), R ₁₂ , R ₁₃ , R ₁₄ , R ₁₈ , and R ₁₉ each independently represent an alkyl group having 6 or less carbon atoms or a phenyl group. R ₁₅ , R ₁₆ , and R ₁₇ each independently represent hydrogen represents an atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

The structure represented by, and/or Formula (10):

[Formula 13]

(In Formula (10), R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , and R ₂₇ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A - is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms).

As -A- in Formula (10), for example, a methylene group, an ethylidene group, a 1-methylethylidene group, a 1,1-propylidene group, a 1,4-phenylenebis(1-methylethyl divalent organic groups such as den) group, 1,3-phenylenebis(1-methylethylidene) group, cyclohexylidene group, phenylmethylene group, naphthylmethylene group, and 1-phenylethylidene group; , but is not limited thereto.

The polyphenylene ether compound is a modified polyphenyl functionalized with an ethylenically unsaturated group such as a vinylbenzyl group, an epoxy group, an amino group, a hydroxyl group, a mercapto group, a carboxy group, a methacryl group, a silyl group, etc. Renether can also be used. You may use these individually by 1 type or in combination of 2 or more types.

Examples of the modified polyphenylene ether having a terminal hydroxyl group include SA90 manufactured by SABIC Innovative Plastics. Moreover, as a polyphenylene ether whose terminal is a methacryl group, SA9000 by SABIC Innovative Plastics company etc. are mentioned, for example.

The manufacturing method of modified polyphenylene ether is not specifically limited as long as the effect of this invention is acquired. For example, it can be manufactured by the method described in Patent No. 4591665.

It is preferable that modified polyphenylene ether contains the modified polyphenylene ether which has an ethylenically unsaturated group at the terminal. Examples of the ethylenically unsaturated group include alkenyl groups such as ethenyl group, allyl group, acryl group, methacryl group, propenyl group, butenyl group, hexenyl group and octenyl group, cycloalkenyl groups such as cyclopentenyl group and cyclohexenyl group, Alkenylaryl groups, such as a vinylbenzyl group and a vinylnaphthyl group, are mentioned, and a vinylbenzyl group is preferable. The terminal ethylenically unsaturated group may be single or plural, and may be the same functional group or different functional groups.

As modified polyphenylene ether having an ethylenically unsaturated group at the terminal, formula (1):

[Formula 14]

(In Formula (1), X represents an aromatic group, and -(YO) _m - represents a polyphenylene ether moiety. R ₁ , R ₂ , R ₃ are each independently a hydrogen atom, an alkyl group, an alkenyl group or an alky represents a yl group, m represents an integer of 1 to 100, n represents an integer of 1 to 6, and q represents an integer of 1 to 4. m is preferably an integer of 1 to 50, more preferably Preferably, it is an integer of 1 or more and 30 or less, and n is preferably an integer of 1 or more and 4 or less, more preferably 1 or 2, and ideally 1. Also, q is preferably 1. It is an integer greater than or equal to 3, more preferably 1 or 2, and ideally 2.)

The structure represented by can be mentioned.

As an aromatic group represented by X in Formula (1), a group excluding q hydrogen atoms from one type of ring structure selected from a benzene ring structure, a biphenyl ring structure, an indenyl ring structure, and a naphthalene ring structure (eg For example, a phenylene group, a biphenylene group, an indenylene group, and a naphthylene group), and preferably a biphenylene group.

Here, the aromatic group represented by X may include a diphenyl ether group to which an aryl group is bonded with an oxygen atom, a benzophenone group to which a carbonyl group is bonded, and a 2,2-diphenylpropane group bonded to an alkylene group. .

Further, the aromatic group may be substituted with a general substituent such as an alkyl group (preferably an alkyl group of 1 to 6 carbon atoms, particularly a methyl group), an alkenyl group, an alkynyl group, and a halogen atom. However, since the aromatic group is substituted on the polyphenylene ether moiety via an oxygen atom, the general limit on the number of substituents depends on the number of polyphenylene ether moieties.

As the polyphenylene ether moiety in formula (1), structural units represented by formulas (8), (9) or (10) described above can be used, and particularly structural units represented by formula (8) are included. It is particularly desirable to

Moreover, as modified polyphenylene ether represented by Formula (1), it is preferable that the number average molecular weight is 1000 or more and 7000 or less. Moreover, in Formula (1), what has a minimum melt viscosity of 50000 Pa.s or less can be used. In particular, in Formula (1), it is preferable that the number average molecular weight is 1000 or more and 7000 or less, and the minimum melt viscosity is 50000 Pa·s or less.

The number average molecular weight is measured using gel permeation chromatography according to the conventional method. As for the number average molecular weight, it is more preferable that it is 1000-3000. By setting the number average molecular weight to 1000 or more and 7000 or less, the effect of coexistence of moldability and electrical properties is exhibited more effectively.

The lowest melt viscosity is measured using a dynamic viscoelasticity measuring device according to a conventional method. As for minimum melt viscosity, 500-50000 Pa.s is more preferable. By setting the minimum melt viscosity to 50000 Pa·s or less, the effect of coexistence of moldability and electrical properties is exhibited more effectively.

As modified polyphenylene ether, it is preferable that it is a compound represented by following formula (11) also in formula (1).

[Formula 15]

(In formula (11), X is an aromatic group, -(YO) _m - respectively represents a polyphenylene ether moiety, and m represents an integer of 1 to 100. m is preferably 1 or more and 50 It is the following integer, More preferably, it is an integer of 1 or more and 30 or less.)

X, -(YO) _m - and m in formula (11) have the same meaning as those in formula (1).

X in formulas (1) and (11) is formula (12), formula (13) or formula (14), and -(YO) _m - in formulas (1) and formula (11) It may be a structure in which Formula (15) or Formula (16) is arranged, or a structure in which Formula (15) and Formula (16) are arranged in a block or randomly.

[Formula 16]

[Formula 17]

(In Formula (13), R ₂₈ , R ₂₉ , R ₃₀ and R ₃₁ each independently represent a hydrogen atom or a methyl group. -B- is a linear, branched or cyclic 2 of 20 or less carbon atoms; It is a hydrocarbon group of .)

Specific examples of -B- include the same as the specific examples of -A- in formula (10).

[Formula 18]

(In Formula (14), -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

Specific examples of -B- include the same as the specific examples of -A- in formula (10).

[Formula 19]

[Formula 20]

The method for producing the modified polyphenylene ether having a structure represented by formula (11) is not particularly limited, and examples thereof include a bifunctional phenylene ether oligomer obtained by oxidatively coupling a bifunctional phenolic compound and a monofunctional phenolic compound. It can be manufactured by vinylbenzyl etherifying the terminal phenolic hydroxyl group of

Moreover, commercially available products can be used for such modified polyphenylene ether, and for example, Mitsubishi Gas Chemical Co., Ltd. OPE-2St1200 and OPE-2st2200 can be preferably used.

The content of the polyphenylene ether compound in the resin composition according to the present embodiment is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, based on 100 parts by mass of the resin solid content of the resin composition. It is more preferable that it is more than a mass part. The upper limit of the content is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 50 parts by mass or less, and may be 40 parts by mass or less or 30 parts by mass or less. By setting the content of the polyphenylene ether compound within such a range, the low dielectric properties, metal foil peeling strength, and heat resistance of the cured product of the resin composition tend to be more excellent.

These polyphenylene ether compounds can also be used individually by 1 type or in mixture of 2 or more types suitably. When using 2 or more types, it is preferable that a total amount becomes the said range.

[Epoxy compound]

As the epoxy compound according to the present embodiment, a known epoxy compound or resin having two or more epoxy groups in one molecule can be appropriately used, and the type is not particularly limited. Specifically, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, glycidyl ester type epoxy resin , aralkyl novolac type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolak type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton Modified novolak type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, alicyclic epoxy resins, polyol type epoxy resins, phosphorus-containing epoxy resins, Compounds obtained by epoxidizing double bonds such as glycidylamine, glycidyl ester, and butadiene, and compounds obtained by reaction between hydroxyl group-containing silicone resins and epichlorohydrin, and the like are exemplified. Among these epoxy compounds, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferable from the viewpoint of flame retardancy and heat resistance. These epoxy compounds can be used individually by 1 type or in combination of 2 or more types.

The content of the epoxy compound in the resin composition according to the present embodiment can be appropriately set according to desired characteristics, and is not particularly limited. Specifically, when the resin solid content in the resin composition is 100 parts by mass, the content of the epoxy compound is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more. The upper limit of the content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less. By setting the content of the epoxy compound within such a range, the copper foil peeling strength and heat resistance of the cured product of the resin composition tend to be more excellent.

[phenol compound]

The phenol compound is not particularly limited as long as it is a compound or resin having two or more phenolic hydroxyl groups in one molecule, and examples thereof include bisphenol A phenol resin, bisphenol E phenol resin, bisphenol F phenol resin, and bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolak type phenol resin, glycidyl ester type phenol resin, aralkyl novolak type phenol resin, biphenyl aralkyl type phenol resin, cresol novolak type phenol resin, polyfunctional phenol Resins, naphthol resins, naphthol novolak resins, polyfunctional naphthol resins, anthracene type phenol resins, naphthalene skeleton modified novolak type phenol resins, phenol aralkyl type phenol resins, naphthol aralkyl type phenol resins, dicyclopentadiene type phenol resins , biphenyl type phenol resins, alicyclic phenol resins, polyol type phenol resins, phosphorus-containing phenol resins, and the like. Among these, at least one selected from the group consisting of biphenyl aralkyl type phenol resins, naphthol aralkyl type phenol resins, and phosphorus-containing phenol resins is preferable from the viewpoint of further improving heat resistance and flame resistance. These phenol compounds may be used independently or may use 2 or more types together.

The content of the phenolic compound in the resin composition according to the present embodiment can be appropriately set according to desired properties, and is not particularly limited. Specifically, when the resin solid content in the resin composition is 100 parts by mass, the content of the phenol compound is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more. The upper limit of the content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less. By setting the content of the phenolic compound within such a range, the copper foil peeling strength and heat resistance of the cured product of the resin composition tend to be more excellent.

[Curable polyimide compound]

The curable polyimide compound is not particularly limited as long as it is generally known, but from the viewpoint of low dielectric properties, bisallylnadiimide is preferable, and among these, at least one selected from the group consisting of the following formulas (17) and (18) It is preferable that it is 1 type.

[Formula 21]

[Formula 22]

The content of the curable polyimide compound in the resin composition according to the present embodiment can be appropriately set according to desired characteristics, and is not particularly limited. Specifically, when the resin solid content in the resin composition is 100 parts by mass, the content of the curable polyimide compound is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more. The upper limit of the content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less. By setting the content of the curable polyimide compound within such a range, the cured product of the resin composition tends to have better dielectric properties, copper foil peeling strength, and heat resistance.

[Thermoplastic Elastomer (B)]

The resin composition according to the present embodiment contains a thermoplastic elastomer (B), and the content of the thermoplastic elastomer (B) in the resin composition is 1 to 30 parts by mass with respect to 100 parts by mass of the resin solid content. When the content of the thermoplastic elastomer (B) in the resin composition is 1 part by mass or more with respect to 100 parts by mass of the resin solid content, the crack resistance, low dielectric constant, and low dielectric loss tangibility of the cured product of the resin composition are improved, and when it is 30 parts by mass or less , the cured product of the resin composition tends to have good solder heat resistance.

The content of the thermoplastic elastomer (B) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 8 parts by mass or more, and 10 parts by mass or more with respect to 100 parts by mass of the resin solid content of the resin composition. may be continued The upper limit of the content is preferably 25 parts by mass or less, more preferably 22 parts by mass or less, and may be 20 parts by mass or less with respect to 100 parts by mass of the resin solid content of the resin composition. When the content of the thermoplastic elastomer (B) is within the above range, the cured product of the resin composition tends to have better crack resistance, low dielectric constant, low dielectric loss tangent and solder heat resistance. In this embodiment, two or more types of thermoplastic elastomers (B) may be included, and when two or more types are included, it is preferable that their total amount is within the above range.

The thermoplastic elastomer (B) is not particularly limited, and examples thereof include "styrenic elastomers" and "other thermoplastic elastomers" shown below. From the viewpoints of low dielectric constant and low dielectric loss tangent, styrenic elastomers It is desirable to be

[Styrenic Elastomer]

The "styrenic elastomer" according to the present embodiment refers to an elastomer that is a block copolymer having a polystyrene block structure, and does not include random copolymers.

Styrenic elastomers used in the resin composition according to the present embodiment include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-hydrogenated butadiene-styrene block copolymers, and styrene-hydrogenated isoprene. -Styrene block copolymer, styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-hydrogenated butadiene block copolymer, styrene-hydrogenated isoprene block copolymer and styrene-hydrogenated (isoprene/butadiene) block copolymer At least 1 type selected from the group which consists of is mentioned. These styrenic elastomers may be used independently or may use 2 or more types together. In particular, styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-hydrogenated butadiene-styrene block copolymers, and styrene-hydrogenated isoprene-styrene block copolymers have excellent cured products of resin compositions. It is preferable because it tends to impart a low dielectric loss tangent.

As styrene (styrene unit) in the polystyrene block structure in this embodiment, you may use what has a substituent. Specifically, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used.

The styrene content (hereinafter also referred to as "styrene ratio") in the styrenic elastomer is not particularly limited, but is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit of the styrene content is not particularly limited as long as it is less than 100% by mass, but, for example, it is preferably less than 99% by mass, and more preferably 70% by mass or less. By setting it as such a range, there exists a tendency for solvent solubility and compatibility with other compounds to improve more. Here, the styrene content is (a) g for the mass of the styrene unit contained in the styrene-based elastomer and (b) g for the mass of the entire styrenic elastomer, (a) / (b) × 100 (unit: % ) is the value represented by

As the styrene-based elastomer in the present embodiment, a commercially available product may be used, and examples thereof include TR2630 (manufactured by JSR Corporation) and TR2003 (manufactured by JSR Corporation) as a styrene-butadiene-styrene block copolymer. can Moreover, as a styrene-isoprene-styrene block copolymer, SIS5250 (made by JSR Corporation) is mentioned. Examples of the styrene-hydrogenated isoprene-styrene block copolymer include SEPTON2104 (manufactured by Kuraray Co., Ltd.). Moreover, as a styrene-hydrogenated butadiene-styrene block copolymer, H-1043 (made by Asahi Kasei Co., Ltd.) is mentioned.

When the thermoplastic elastomer (B) is a styrene-based elastomer, the content of the styrene-based elastomer is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and 8 parts by mass with respect to 100 parts by mass of the resin solid content of the resin composition. Part or more is more preferable, and 10 parts by mass or more may be sufficient. The upper limit of the content of the styrenic elastomer is preferably 25 parts by mass or less, more preferably 22 parts by mass or less, and may be 20 parts by mass or less with respect to 100 parts by mass of the resin solid content of the resin composition. When the content of the styrenic elastomer is within the above range, the cured product of the resin composition tends to have better crack resistance, low dielectric constant, low dielectric loss tangent and solder heat resistance. In this embodiment, two or more types of styrenic elastomers may be included, and when two or more types are included, it is preferable that their total amount is within the above range.

[Other thermoplastic elastomers]

"Other thermoplastic elastomers" are distinguished from "styrenic elastomers". "Styrene-based elastomer" refers to an elastomer that has a polystyrene block structure and is a block copolymer, and "other thermoplastic elastomer" refers to other elastomers. That is, random copolymers, block copolymers having no styrene backbone, and the like correspond thereto.

Examples of other thermoplastic elastomers include at least one selected from the group consisting of polyisoprene, polybutadiene, styrene-butadiene random copolymers, butyl rubber, ethylene propylene rubber, fluororubber, silicone rubber, hydrogenated compounds thereof, and alkyl compounds thereof. One species can be cited. Among these, from the viewpoint of more excellent compatibility with polyphenylene ether compounds, at least one selected from the group consisting of polyisoprene, polybutadiene, styrene butadiene random copolymer, butyl rubber, and ethylene propylene rubber is more preferred. .

[Phosphorus flame retardant (C)]

The resin composition in this embodiment contains a phosphorus-based flame retardant (C), and the content of the phosphorus-based flame retardant (C) in the resin composition is 1 to 30 parts by mass with respect to 100 parts by mass of the resin solid content. When the content of the phosphorus-based flame retardant in the resin composition is 1 part by mass or more with respect to 100 parts by mass of the resin solid content, the crack resistance, low dielectric constant, and low dielectric loss tangibility of the cured product of the resin composition tend to be improved, and when it is 30 parts by mass or less , The cured product of the resin composition tends to have good copper foil peeling strength, crack resistance, and solder heat resistance.

The content of the phosphorus-based flame retardant (C) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 8 parts by mass or more, and 10 parts by mass or more with respect to 100 parts by mass of the resin solid content of the resin composition. It may be 15 parts by mass or more. The upper limit of the content is preferably 25 parts by mass or less, more preferably 22 parts by mass or less, and may be 20 parts by mass or less with respect to 100 parts by mass of the resin solid content of the resin composition. When the content of the phosphorus-based flame retardant (C) is within the above range, the cured product of the resin composition tends to have better crack resistance, low dielectric constant, low dielectric loss tangent, copper foil peeling strength, and solder heat resistance. In this embodiment, two or more types of phosphorus-based flame retardants (C) may be included, and when two or more types are included, it is preferable that their total amount is within the above range.

In addition, the content of the phosphorus-based flame retardant (C) is preferably 15 parts by mass or more, relative to 100 parts by mass of the resin solid content of the resin composition, from the viewpoint of particularly enhancing the crack resistance and copper foil peeling strength of the cured product of the resin composition, and 20 parts by mass Part or more is particularly preferred. On the other hand, from the same viewpoint, the upper limit of the content of the phosphorus-based flame retardant (C) is preferably 30 parts by mass or less, more preferably 28 parts by mass or less, and 25 parts by mass or less with respect to 100 parts by mass of the resin solid content of the resin composition. may be

The total content of the thermoplastic elastomer (B) and the phosphorus-based flame retardant (C) is 10 parts by mass with respect to 100 parts by mass of the resin solid content from the point where the crack resistance and copper foil peeling strength of the cured product of the resin composition tend to be improved. It is preferably above, more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, particularly preferably 25 parts by mass or more, and may be 30 parts by mass or more. In addition, since the solder heat resistance of the cured product of the resin composition tends to be improved, the total content of the thermoplastic elastomer (B) and the phosphorus-based flame retardant (C) is preferably 60 parts by mass or less with respect to 100 parts by mass of the resin solid content. It is more preferably 55 parts by mass or less, still more preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less.

Examples of the phosphorus flame retardant (C) include, but are not particularly limited to, red phosphorus, tricresyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, trixylenyl phosphate, trialkyl phosphate, dialkyl phosphate, tris(chloroethyl) ) phosphate, phosphazene, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and the like.

The phosphorus-based flame retardant (C) is selected from the group consisting of aromatic condensed phosphate esters (C-1) and cyclic phosphazene compounds (C-2) from the viewpoint of low dielectric constant, low dielectric loss tangent, and improved crack resistance. It is preferable to use 1 or more types.

Examples of the aromatic condensed phosphoric acid ester (C-1) include resorcinol bis-diphenyl phosphate, bisphenol A bis-diphenyl phosphate, and compounds represented by the following formula (1). Especially, it is preferable that it is a compound represented by following formula (1) from a viewpoint of low dielectric constant and low dielectric loss tangent.

[Formula 23]

Examples of the cyclic phosphazene compound (C-2) include hexaphenoxycyclotriphosphazene, hexafluorocyclotriphosphazene, pentafluoro(phenoxy)cyclotriphosphazene, and ethoxy(pentafluoro)cyclotriphos. phazene, a compound represented by the following formula (2), and the like are exemplified. Especially, it is preferable that it is a compound represented by following formula (2) from a solvent solubility viewpoint.

[Formula 24]

(In Formula (2), n represents an integer of 3 to 6.)

As a compound represented by said Formula (2), Labitol FP-300B (made by Fushimi Pharmaceutical Co., Ltd.) is mentioned, for example.

[filling]

The resin composition according to the present embodiment preferably contains a filler in order to improve low dielectric constant, low dielectric loss tangent, flame resistance, and low thermal expansion. As the filler used in the present embodiment, a known filler can be appropriately used, and the type is not particularly limited, and fillers generally used in the art can be preferably used. Specifically, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosol, and hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, and aggregated boron nitride , silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat-treated products (aluminum hydroxide is heated to reduce a part of the water of crystallization), metal hydrates such as boehmite and magnesium hydroxide, molybdenum oxide and zinc molybdate Molybdenum compounds such as zinc borate, zinc tartrate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, Inorganic fillers such as D-glass, S-glass, M-glass G20, short glass fibers (including glass fine powders such as E-glass, T-glass, D-glass, S-glass, and Q-glass), hollow glass, and spherical glass. In addition, organic fillers such as styrene-type, butadiene-type, acryl-type rubber powder, core-shell type rubber powder, silicone resin powder, silicone rubber powder, and silicone composite powder may be mentioned. These fillers may be used independently or may use 2 or more types together.

Among these, one or two or more selected from the group consisting of silicas, aluminum hydroxide, aluminum nitride, boron nitride, and forsterite, boehmite, magnesium oxide, and magnesium hydroxide are preferable, and silicas, aluminum hydroxide, Aluminum nitride, boron nitride, and forsterite are more preferred. By using these fillers, properties such as thermal expansion characteristics, dimensional stability, and flame retardancy of the cured product of the resin composition tend to be improved.

The content of the filler in the resin composition according to the present embodiment can be appropriately set according to the desired characteristics, and is not particularly limited. When the resin solid content in the resin composition is 100 parts by mass, it is preferably 30 parts by mass or more, and It is more preferable that it is more than a mass part. As an upper limit, 1600 parts by mass or less is preferable, 500 parts by mass or less is more preferable, and 300 parts by mass or less is particularly preferable. Alternatively, the content of the filler may be 75 to 250 mass, or 100 to 200 mass. When the content of the filler is within this range, the moldability of the resin composition tends to be improved.

The resin composition may contain only 1 type of filler, or may contain 2 or more types of fillers. When containing 2 or more types, it is preferable that a total amount becomes the said range.

When using a filler here, it is preferable to use together at least 1 sort(s) selected from the group which consists of a silane coupling agent and a wet dispersing agent.

As the silane coupling agent, those generally used for surface treatment of inorganic materials can be preferably used, and the type is not particularly limited. Specifically, aminosilanes such as γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β-( Epoxysilanes such as 3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinylsilanes such as γ-methacryloxypropyltrimethoxysilane and vinyl-tri(β-methoxyethoxy)silane, N- cationic silane systems such as β-(N-vinylbenzylaminoethyl)-γ-aminopropyl trimethoxysilane hydrochloride; and phenylsilane systems. A silane coupling agent may be used independently and may use 2 or more types together.

Moreover, as a wet dispersant, what is generally used for coating materials can be used suitably, and the kind is not specifically limited. Preferably, a copolymer-based wetting and dispersing agent is used, and specific examples thereof include DISPERBYK-110, 111, 161, 180, 2009, 2152, BYK-W996, BYK-W9010, manufactured by Big Chemie Japan Co., Ltd. BYK-W903, BYK-W940, etc. are mentioned. A wet dispersing agent may be used independently and may use 2 or more types together.

The content of the silane coupling agent is not particularly limited, and may be about 1 to 5 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. The content of the dispersing agent (especially the wet dispersing agent) is not particularly limited, and may be, for example, about 0.5 to 5 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

[Other Ingredients]

The resin composition of the present embodiment may contain other components other than those described above. Other components include, for example, oxetane resins, benzoxazine compounds, flame retardants, curing accelerators, and organic solvents.

[Oxetane resin]

The oxetane resin is not particularly limited, and examples thereof include oxetane, alkyloxetane (eg, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3- dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3-di(trifluoromethyl)perfluorooxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl ) Oxetane, biphenyl type oxetane, OXT-101 (manufactured by Toa Chemical Co., Ltd.), OXT-121 (manufactured by Toa Chemical Co., Ltd.), and the like. These oxetane resins may be used independently or may use 2 or more types together.

[benzoxazine compound]

The benzoxazine compound is not particularly limited as long as it is a compound having two or more dihydrobenzoxazine rings in one molecule, and examples thereof include bisphenol A benzoxazine BA-BXZ (manufactured by Cornish Chemical Co., Ltd.); Bisphenol F type benzoxazine BF-BXZ (made by Cornish Chemical Co., Ltd.), bisphenol S type benzoxazine BS-BXZ (made by Cornish Chemical Co., Ltd.), etc. are mentioned. These benzoxazine compounds may be used independently or may use 2 or more types together.

[Flame retardant]

The resin composition according to the present embodiment may contain a flame retardant other than the phosphorus-based flame retardant (C) described above for further improvement in flame resistance. As such a flame retardant, a known flame retardant can be used, and examples thereof include brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromo bisphenol A, and pentabromobenzyl (meth)acrylate. , pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, halogenated flame retardants such as chlorinated polystyrene, chlorinated paraffin, aluminum hydroxide, magnesium hydroxide , inorganic flame retardants such as partial boehmite, boehmite, zinc borate and antimony trioxide, and silicone flame retardants such as silicone rubber and silicone resin. These flame retardants may be used independently or may use 2 or more types together.

It is preferable that it is 1 mass part or more, and, as for content of a flame retardant, it is more preferable that it is 5 mass parts or more with respect to 100 mass parts of resin solid content in a resin composition. The upper limit of the content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and may be 15 parts by mass or less.

A flame retardant may use only 1 type, and may use 2 or more types. When using 2 or more types, it is preferable that a total amount becomes the said range.

[Curing accelerator]

The resin composition according to the present embodiment may contain a curing accelerator for appropriately adjusting the curing rate. Examples of the curing accelerator include those normally used as curing accelerators such as maleimide compounds, cyanate ester compounds, and epoxy compounds, and organometallic salts (eg, zinc octylate, zinc naphthenate, cobalt naphthenate, Copper naphthenate, iron acetylacetone, nickel octylate, manganese octylate, etc.), phenolic compounds (eg, phenol, xylenol, cresol, resorcin, catechol, octylphenol, nonylphenol, etc.), alcohols ( For example, 1-butanol, 2-ethylhexanol, etc.), imidazoles (for example, 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.), derivatives such as carboxylic acids of these imidazoles or adducts of their acid anhydrides, amines (eg, dicyandiamide, benzyldimethylamine, 4 -Methyl-N,N-dimethylbenzylamine, etc.), phosphorus compounds (eg, phosphine-based compounds, phosphine oxide-based compounds, phosphonium salt-based compounds, diphosphine-based compounds, etc.), epoxy-imidazole adduct-based compounds , peroxides (eg, benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropylperoxycarbonate, di-2-ethylhexylperoxycarbonate, etc.), azo compounds (eg For example, azobisisobutyronitrile etc.) are mentioned. A hardening accelerator may be used independently and may use 2 or more types together.

The content of the curing accelerator may be usually about 0.005 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

[organic solvent]

The resin composition according to the present embodiment may contain an organic solvent. In this case, the resin composition according to the present embodiment is in a form (solution or varnish) in which at least a part, preferably all, of the various resin components described above are dissolved or compatible with an organic solvent. The organic solvent is not particularly limited as long as it is a polar organic solvent or a non-polar organic solvent capable of dissolving or compatible with at least a part of, preferably all of, the various resin components described above, and the polar organic solvent includes, for example, ketones (eg For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (eg, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (eg, ethyl lactate, methyl acetate) , ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.) amides (eg, dimethoxyacetamide, dimethylformamides, etc.); Aromatic hydrocarbons (eg, toluene, xylene, etc.) are mentioned as a nonpolar organic solvent. These organic solvents may be used independently or may use 2 or more types together.

The resin composition according to the present embodiment may contain various polymer compounds and various additives such as other thermosetting resins, thermoplastic resins, and oligomers thereof other than the above components. Examples of additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, flow regulators, lubricants, antifoaming agents, leveling agents, brightening agents, and polymerization inhibitors. These additives may be used independently or may use 2 or more types together.

[Preparation method of resin composition]

The resin composition according to the present embodiment can be prepared according to a conventional method, and uniformly contains a thermosetting compound (A), a thermoplastic elastomer (B), a phosphorus-based flame retardant (C), and other optional components described above. The preparation method is not particularly limited as long as the resin composition is obtained. For example, the resin composition according to the present embodiment can be easily prepared by successively blending the thermosetting compound (A), the thermoplastic elastomer (B), the phosphorus-based flame retardant (C), and the other optional components described above in a solvent and sufficiently stirring the mixture. can be prepared

[Prepreg]

The prepreg according to the present embodiment includes a substrate and a resin composition impregnated or applied to the substrate. Here, the resin composition is a resin composition containing the above-described thermosetting compound (A), a specific amount of the thermoplastic elastomer (B), and a phosphorus-based flame retardant (C). The prepreg according to the present embodiment is obtained, for example, by impregnating or applying the resin composition according to the present embodiment to a substrate, followed by semi-curing by a method of drying at 120 to 220°C for about 2 to 15 minutes. In this case, the amount of adhesion of the resin composition (including cured products of the resin composition) to the substrate, that is, the amount of the resin composition (including the filler) relative to the total amount of the prepreg after semi-curing is in the range of 20 to 99% by mass it is desirable

The substrate is not particularly limited as long as it is a substrate used for various printed wiring board materials. As the material of the substrate, for example, glass fiber (e.g., E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass etc.) Inorganic fibers other than glass (eg, quartz), organic fibers (eg, polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.). The form of the substrate is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat. These base materials may be used independently or may use 2 or more types together. Among these substrates, from the viewpoint of dimensional stability, a woven fabric subjected to superopening treatment and clogging treatment is preferable, and from the viewpoint of moisture absorption heat resistance, glass woven fabric surface-treated with a silane coupling agent such as epoxysilane treatment or aminosilane treatment, etc. desirable. From the viewpoint of electrical properties, low-k glass fibers made of glass fibers exhibiting low dielectric constant and low dielectric loss tangent, such as L-glass, NE-glass, and Q-glass, are more preferred.

[Resin sheet]

The resin sheet according to this embodiment contains a resin composition. Here, the resin composition is a resin composition containing the above-described thermosetting compound (A), a specific amount of the thermoplastic elastomer (B), and a phosphorus-based flame retardant (C). The resin sheet may be a resin sheet with a support including a support and a layer formed of the resin composition according to the present embodiment disposed on the surface of the support. A resin sheet can be used as a film for build-up or a dry film solder resist. The method for producing the resin sheet is not particularly limited, but examples include a method of obtaining a resin sheet by applying (coating) a solution obtained by dissolving the resin composition according to the present embodiment described above in a solvent to a support and drying the sheet. there is.

As the support, for example, a polyethylene film, a polypropylene film, a polycarbonate film, a polyethylene terephthalate film, an ethylene tetrafluoroethylene copolymer film, and a release film obtained by applying a release agent on the surface of these films, a polyimide film, etc. Examples include organic film substrates, conductor foils such as copper foil and aluminum foil, glass plates, SUS plates, and plate-shaped ones such as FRP, but are not particularly limited.

Examples of the application method (coating method) include a method of applying a solution obtained by dissolving the resin composition according to the present embodiment in a solvent onto a support with a bar coater, die coater, doctor blade, baker applicator, or the like. . Moreover, it can also be set as a single layer sheet (resin sheet) by peeling or etching a support body from the resin sheet with a support body in which the support body and the resin composition were laminated|stacked after drying. Further, by supplying a solution obtained by dissolving the resin composition according to the present embodiment in a solvent into a mold having a sheet-like cavity, drying it, and molding it into a sheet shape, a single-layer sheet (resin sheet) can be obtained without using a support. may be

Further, in the production of the single-layer sheet or the resin sheet with a support body according to the present embodiment, the drying conditions for removing the solvent are not particularly limited, but the solvent in the resin composition is easily removed, and furthermore, at the time of drying From the viewpoint of suppressing the progress of curing, 1 to 90 minutes is preferable at a temperature of 20°C to 200°C. In addition, in a single-layer sheet or a resin sheet with a support, the resin composition may be used in an uncured state in which the solvent is only dried, or, if necessary, in a semi-cured (B-staged) state. In addition, the thickness of the resin layer of the single-layer sheet or resin sheet with a support body according to the present embodiment can be adjusted according to the concentration of the solution of the resin composition according to the present embodiment and the coating thickness, and is not particularly limited, but is not particularly limited. From the viewpoint of being easily removed, 0.1 to 500 μm is preferable.

[Laminate]

The laminated board of this embodiment contains one or more types selected from the group which consists of the above-mentioned prepreg and resin sheet. When two or more types are laminated with respect to a prepreg and a resin sheet, the resin composition used for each prepreg and resin sheet may be the same or different. Moreover, when using both a prepreg and a resin sheet, the resin composition used for them may be the same or different.

[Metal Foil Clad Laminate]

The metal foil-clad laminate according to the present embodiment includes at least one prepreg described above and metal foil laminated on one side or both sides of the prepreg.

Further, the metal foil-clad laminate according to the present embodiment may include at least one resin sheet described above and metal foil laminated on one or both surfaces of the resin sheet.

Further, the metal foil-clad laminate according to the present embodiment may include the above-described laminate and metal foil laminated on one or both surfaces of the laminate.

In the metal foil-clad laminate according to the present embodiment, the resin composition used for each prepreg and resin sheet may be the same or different, and when using both the prepreg and the resin sheet, the resin composition used for them They may be the same or different.

In the metal foil clad laminate according to the present embodiment, the metal foil is laminated on at least one selected from the group consisting of prepreg and resin sheet, but above all, the surface of at least one selected from the group consisting of prepreg and resin sheet It is preferable that metal foil is laminated so as to be in contact with. "Metal foil is laminated so as to be in contact with the surface of one or more types selected from the group consisting of prepreg and resin sheet" means that a layer such as an adhesive layer is not included between the prepreg or resin sheet and the metal foil, and the prepreg or It means that the resin sheet and metal foil are in direct contact. This tends to increase the metal foil peeling strength of the metal foil clad laminate and improve the insulation reliability of the printed wiring board.

The metal foil-clad laminate according to this embodiment may have one or more overlapping prepregs and/or resin sheets according to this embodiment, and metal foil disposed on one side or both sides of the prepreg and/or resin sheet. As a method for manufacturing the metal foil-clad laminate according to the present embodiment, for example, a method of stacking one or more prepregs and/or resin sheets according to the present embodiment, arranging metal foil on one side or both sides, and laminating molding. can be heard Examples of the molding method include methods commonly used when forming laminated boards and multilayer boards for printed wiring boards, and more specifically, using a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, and the like, at a temperature of 180 to A method of laminating molding at about 350°C, a heating time of about 100 to 300 minutes, and a surface pressure of about 20 to 100 kg/cm 2 is exemplified.

Moreover, it is also possible to set it as a multilayer board by laminating and molding a combination of the prepreg and/or the resin sheet according to the present embodiment and a wiring board for inner layer produced separately. As a method for producing a multi-layer board, for example, copper foil having a thickness of about 35 μm is placed on both sides of the prepreg and/or resin sheet according to the present embodiment in which one or more sheets are overlapped, and the copper foil is laminated and formed by the above-described molding method. After forming the coated laminate, an inner-layer circuit is formed, the circuit is subjected to blackening treatment to form an inner-layer circuit board, and then the inner-layer circuit board and the prepreg and/or resin sheet according to the present embodiment are alternately placed one by one. A multi-layer board can be produced by arranging, further disposing copper foil on the outermost layer, and laminating molding under the above conditions, preferably under vacuum. The metal foil clad laminate according to the present embodiment can be suitably used as a printed wiring board.

It is preferable that the metal foil-clad laminate of this embodiment has a large metal foil peeling strength. Specifically, the measured value obtained according to JIS C6481:1996 is preferably 0.4 kN/m or more, and more preferably 0.5 kN/m or more. About the upper limit of metal foil peeling strength, although it does not set in particular, For example, 1.4 kN/m or less is practical.

The metal foil-clad laminate of the present embodiment preferably has a small dielectric loss tangent. Specifically, it is preferable that the measured value of the dielectric loss tangent at 10 GHz measured by the cavity resonator perturbation method in accordance with JIS C2138: 2007 is less than 0.0035 using a sample in which the metal foil is removed from the metal foil-clad laminate by etching, It is more preferably less than 0.0030, and particularly preferably less than 0.0025. The lower limit of the dielectric loss tangent is not particularly limited, but, for example, 0.0001 or more is practical.

[metal foil]

The metal foil in the present embodiment is not particularly limited, and examples thereof include gold foil, silver foil, copper foil, tin foil, nickel foil, and aluminum foil. Among these, copper foil is preferable. The copper foil is not particularly limited as long as it is generally used for printed wiring board materials, and examples thereof include copper foils such as rolled copper foil and electrolytic copper foil. , electrodeposited copper foil is preferred. The thickness of the copper foil is not particularly limited, and may be about 1.5 to 70 µm.

When using copper foil as metal foil, as for copper foil, it is preferable that the roughness (Rz) of the copper foil surface measured according to JISB0601:2013 is adjusted to 0.2-4.0 micrometer. When the roughness (Rz) of the copper foil surface is less than 0.2 μm, the roughness of the copper foil surface tends to be too small and the copper foil peeling strength becomes insufficient. On the other hand, when the roughness (Rz) of the surface of the copper foil exceeds 4.0, the surface roughness of the copper foil tends to be too large and the dielectric loss tangent characteristic deteriorates. From the viewpoint of reducing the dielectric loss tangent, the surface roughness (Rz) of the copper foil is more preferably 0.5 to 4 μm, still more preferably 0.6 to 3 μm, and particularly preferably 0.7 to 2 μm.

Here, roughness (Rz) of the surface of copper foil can be measured according to the method described in the Example mentioned later.

[printed wiring board]

The printed wiring board according to the present embodiment includes an insulating layer and a conductor layer disposed on a surface of the insulating layer, and the insulating layer includes at least one of a layer formed of the resin composition and a layer formed of prepreg according to the present embodiment. include Such a printed wiring board can be manufactured according to a conventional method, and the manufacturing method thereof is not particularly limited. For example, it can be manufactured using the above-mentioned metal foil clad laminated board. Hereinafter, an example of the manufacturing method of a printed wiring board is shown. First, the above-mentioned metal foil clad laminate is prepared. Next, an etching treatment is applied to the surface of the metal foil-clad laminate to form an inner layer circuit, thereby producing an inner layer substrate. The surface of the inner-layer circuit of this inner-layer substrate is subjected to surface treatment to increase adhesive strength as necessary, and then the prepreg described above is overlaid on the surface of the inner-layer circuit on the required number of sheets, and a metal foil for outer-layer circuit is laminated on the outside thereof. and heat pressurized to integrally mold. In this way, a multi-layered laminate in which an insulating layer made of a cured product of a base material and a resin composition is formed between the inner circuit and the outer circuit copper foil is manufactured. Next, after perforation processing for through holes and via holes was performed on the multilayer laminate, a plated metal film for conducting the inner circuit and the outer circuit metal foil was formed on the wall surface of the hole, and the outer circuit metal foil was etched. A printed wiring board is manufactured by forming an outer layer circuit.

The printed wiring board obtained in the above production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer has a configuration in which the resin composition according to the present embodiment described above and at least any of a cured product thereof are included. do. That is, the prepreg according to the present embodiment described above (including the base material and the resin composition impregnated or applied thereto and at least any of the cured products thereof), and the metal foil-clad laminate according to the present embodiment described above. The resin composition layer (a layer containing at least one of the resin composition of the present invention and a cured product thereof) is composed of an insulating layer containing at least one of the resin composition according to the present embodiment and a cured product thereof.

[Semiconductor device]

The semiconductor device of this embodiment can be manufactured by mounting a semiconductor chip at the conduction point of the printed wiring board of this embodiment. Here, the conduction point is a point where electric signals are transmitted in the multilayer printed wiring board, and the location may be a surface or an embedded point. In addition, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor as a material.

The semiconductor chip mounting method in manufacturing the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip functions effectively, but specifically includes a wire bonding mounting method, a flip chip mounting method, and a bumpless mounting method. A packaging method using a build-up layer (BBUL), a packaging method using an anisotropic conductive film (ACF), a packaging method using a non-conductive film (NCF), and the like are exemplified.

Example

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. The present invention is not limited at all by the following examples.

In the following Examples and Comparative Examples, measurement of each physical property and each evaluation were carried out according to the following.

(roughness of copper foil surface (Rz))

About the copper foil used in the Example or the comparative example, according to JIS B0601:2013, the roughness (Rz) of the surface which contacts the laminated prepreg was measured.

(dielectric tangent)

For the copper foil-clad laminate obtained in Examples or Comparative Examples, a test piece (30 mm × 150 mm × 0.8 mm) with copper foil was prepared, using a sample in which the copper foil was removed by etching, in accordance with JIS C2138: 2007, The dielectric loss tangent at 10 GHz was measured by the cavity resonator perturbation method. The cavity resonator was manufactured by EM Laboratory, and the network analyzer was 8722 ES manufactured by Agilent.

A, B, and C in the table were evaluated according to the following criteria. The closer the dielectric loss tangent is to 0, the better it means.

A: Less than 0.0025

B: 0.0025 or more, less than 0.0030

C: 0.0030 or more, less than 0.0035

(Copper foil peel strength)

For the copper foil-clad laminate obtained in Examples or Comparative Examples, a test piece (30 mm × 150 mm × 0.8 mm) with copper foil was prepared, and according to JIS C6481: 1996, the peel strength of the copper foil was measured with test number 3 , the average value of the lower limit was taken as the measured value.

A, B, and C in the table were evaluated according to the following criteria.

A: 0.5 kN/m or more

B: 0.4 kN/m or more, less than 0.5 kN/m

C: Less than 0.4 kN/m

(crack resistance)

For the copper foil-clad laminate obtained in Examples or Comparative Examples, a test piece (15 mm × 130 mm × 0.1 mm) in which a wiring pattern having a wiring width of 1 mm was formed on copper foil according to JIS C5016: 1994 was used, and the sample conductor After attaching an insulated wire to the terminal part of the pattern, fixing the upper part of the board to the plunger, and applying a load of 1 kgf to the lower part, start bending in both directions at an angle of 135° and a speed of 175 cpm while being energized. and the number of reciprocating bends until disconnection was measured. A, B, C, and D in the table were evaluated according to the following criteria.

A: More than 90 times

B: 60 or more and less than 90

C: 40 or more and less than 60

D: less than 40 times

(solder heat resistance)

For the copper foil-clad laminates obtained in Examples or Comparative Examples, according to JIS C5012: 1992, a test piece (50 mm × 50 mm × 0.8 mm) with copper foil was prepared and placed in a bath containing solder heated to 288 ° C. for 30 minutes. After floating the test piece, it was visually confirmed whether or not there was an abnormality such as delamination in the copper foil-clad laminate. A and B in the table|surface were evaluated according to the following criteria.

A: No delamination for 30 minutes

B: Delamination occurs within 30 minutes

(Synthesis Example 1) Synthesis of 1-naphthol aralkyl type cyanate ester resin (SNCN)

α-naphthol aralkyl resin (SN495V, OH group equivalent: 236 g/eq., manufactured by Nippon Steel Chemical Co., Ltd.) 300 g (OH group equivalent 1.28 mol) and triethylamine 194.6 g (1.92 mol) (hydroxyl group 1.5 mol per 1 mol) was dissolved in 1800 g of dichloromethane, and this was used as solution 1.

125.9 g (2.05 mol) of cyanide chloride (1.6 mol per 1 mol of hydroxyl group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol per 1 mol of hydroxyl group), 1205.9 g of water While stirring, the solution 1 was poured over 30 minutes while maintaining the liquid temperature at -2 to -0.5°C. After 1 drop of the solution was completed, after stirring at the same temperature for 30 minutes, a solution (solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol with respect to 1 mol of hydroxyl group) was dissolved in 65 g of dichloromethane was added to 10 Dropped over minutes. After 2 weeks of running the solution, the reaction was completed by stirring at the same temperature for 30 minutes.

Thereafter, the reaction solution was allowed to stand to separate an organic phase and an aqueous phase. The obtained organic phase was washed 5 times with 1300 g of water, and the electrical conductivity of the wastewater at the 5th washing with water was 5 µS/cm, and it was confirmed that ionic compounds that could be removed by washing with water were sufficiently removed.

The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated to dryness at 90 DEG C for 1 hour to obtain 331 g of the target 1-naphthol aralkyl type cyanate ester compound (SNCN) (orange viscous substance). The mass average molecular weight (Mw) of the obtained SNCN was 600. In addition, the infrared absorption spectrum of SNCN showed absorption at 2250 cm ^-1 (cyanate ester group), and no absorption of hydroxyl groups.

(Each component included in the resin composition)

As each component contained in the resin composition of an Example or a comparative example, the following were used.

Maleimide resin: MIR-3000, manufactured by Nippon Kayaku Co., Ltd.

Polyphenylene ether resin: OPE-2St2200, manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 2200, vinyl group equivalent: 1100 g/eq.

Thermoplastic elastomer: Hydrogenated styrenic thermoplastic elastomer (SEBS), Tuftec H-1043, manufactured by Asahi Kasei Co., Ltd.

Phosphorus flame retardant 1: 1,3-phenylene bis(2,6-di-xylenyl phosphate), PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.

Phosphorus-based flame retardant 2: cyclic organophosphazene compound, Labitol FP-300B, manufactured by Fushimi Pharmaceutical Co., Ltd.

Filler: spherical silica, SC2050-MB, manufactured by Admatex Co., Ltd., average particle size 0.5 ㎛

(copper foil)

Copper foils used in Examples or Comparative Examples are shown below. The roughness (Rz) is the roughness (Rz) of the surface in contact with the laminated prepreg in Examples or Comparative Examples, measured by the method described above. In Examples or Comparative Examples, the measured roughness surface is disposed so as to contact the surface of the laminated prepreg to obtain a copper foil clad laminate.

Copper foil: TQ-M5-VSP (manufactured by Mitsui Metal Mining Co., Ltd.), electrolytic copper foil, Rz = 0.7 μm, thickness 12 μm

(Example 1)

65 parts by mass of maleimide resin MIR-3000, 15 parts by mass of thermoplastic elastomer H-1043 (67% of styrene), 20 parts by mass of phosphorus flame retardant PX-200, 100 parts by mass of filler SC2050-MB, ethyl methyl ketone A varnish was prepared by mixing and diluting the varnish obtained by impregnating and coating a glass cloth having a thickness of 0.075 mm, followed by heating and drying at 160°C for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight sheets of the obtained prepreg were stacked, the copper foils shown above were placed vertically, and laminated molding was performed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper foil clad laminate having an insulating layer thickness of 0.8 mm.

(Example 2)

65 parts by mass of polyphenylene ether resin OPE-2St2200, 15 parts by mass of thermoplastic elastomer H-1043 (67% of styrene), 20 parts by mass of phosphorus flame retardant PX-200, 100 parts by mass of filler SC2050-MB, ethylmethyl It was mixed and diluted using a ketone to prepare a varnish, and the obtained varnish was impregnated and coated on a glass woven fabric having a thickness of 0.075 mm, and heat-dried at 160°C for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight sheets of the obtained prepreg were stacked, the copper foils shown above were placed vertically, and laminated molding was performed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper foil clad laminate having an insulating layer thickness of 0.8 mm.

(Example 3)

75 parts by mass of polyphenylene ether resin OPE-2St2200, 5 parts by mass of thermoplastic elastomer H-1043 (67% of styrene), 20 parts by mass of phosphorus flame retardant PX-200, 100 parts by mass of filler SC2050-MB, ethylmethyl It was mixed and diluted using a ketone to prepare a varnish, and the obtained varnish was impregnated and coated on a glass woven fabric having a thickness of 0.075 mm, and heat-dried at 160°C for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight sheets of the obtained prepreg were stacked, the copper foils shown above were placed vertically, and laminated molding was performed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper foil clad laminate having an insulating layer thickness of 0.8 mm.

(Example 4)

35 parts by mass of maleimide resin MIR-3000, 20 parts by mass of polyphenylene ether resin OPE-2St2200, 10 parts by mass of SNCN, 15 parts by mass of thermoplastic elastomer H-1043 (67% of styrene), phosphorus-based flame retardant PX- 200 by 20 parts by mass and 100 parts by mass of the filler SC2050-MB were mixed and diluted using ethyl methyl ketone to prepare a varnish, and the resulting varnish was impregnated and coated on a glass cloth having a thickness of 0.075 mm, and heated at 160 ° C. for 5 minutes. It was made to dry and the prepreg of 60 mass % of resin composition content was obtained. Eight sheets of the obtained prepreg were stacked, the copper foils shown above were placed vertically, and laminate molding was performed at a pressure of 30 kgf/cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper foil clad laminate having an insulating layer thickness of 0.8 mm.

(Example 5)

35 parts by mass of maleimide resin MIR-3000, 20 parts by mass of polyphenylene ether resin OPE-2St2200, 10 parts by mass of SNCN, 15 parts by mass of thermoplastic elastomer H-1043 (67% of styrene), phosphorus-based flame retardant labitol 20 parts by mass of FP-300B and 100 parts by mass of the filler SC2050-MB were mixed and diluted using ethyl methyl ketone to prepare a varnish, and the obtained varnish was impregnated and coated on a glass cloth having a thickness of 0.075 mm, and 5 parts at 160 ° C. It was made to heat-dry for minutes and obtained the prepreg of 60 mass % of resin composition content. Eight sheets of the obtained prepreg were stacked, the copper foils shown above were placed vertically, and laminated molding was performed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper foil clad laminate having an insulating layer thickness of 0.8 mm.

(Comparative Example 1)

81 parts by mass of maleimide resin MIR-3000, 19 parts by mass of thermoplastic elastomer H-1043 (67% of styrene), and 100 parts by mass of filler SC2050-MB were mixed and diluted using ethyl methyl ketone to prepare a varnish. , The obtained varnish was impregnated and coated on glass cloth having a thickness of 0.075 mm, and heat-dried at 160°C for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight sheets of the obtained prepreg were stacked, the copper foils shown above were placed vertically, and laminated molding was performed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper foil clad laminate having an insulating layer thickness of 0.8 mm.

(Comparative Example 2)

81 parts by mass of polyphenylene ether resin OPE-2St2200, 19 parts by mass of thermoplastic elastomer H-1043 (67% of styrene), and 100 parts by mass of filler SC2050-MB were mixed and diluted using ethyl methyl ketone to prepare a varnish. The varnish obtained by manufacture was impregnated into a 0.075 mm thick glass woven fabric, and heat-dried at 160°C for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight sheets of the obtained prepreg were stacked, the copper foils shown above were placed vertically, and laminated molding was performed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper foil clad laminate having an insulating layer thickness of 0.8 mm.

(Comparative Example 3)

94 parts by mass of polyphenylene ether resin OPE-2St2200, 6 parts by mass of thermoplastic elastomer H-1043 (67% of styrene), and 100 parts by mass of filler SC2050-MB were mixed and diluted using ethyl methyl ketone to prepare a varnish. The varnish obtained by manufacture was impregnated into a 0.075 mm thick glass woven fabric, and heat-dried at 160°C for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight sheets of the obtained prepreg were stacked, the copper foils shown above were placed vertically, and laminated molding was performed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper foil clad laminate having an insulating layer thickness of 0.8 mm.

(Comparative Example 4)

44 parts by mass of maleimide resin MIR-3000, 25 parts by mass of polyphenylene ether resin OPE-2St2200, 13 parts by mass of SNCN, 19 parts by mass of thermoplastic elastomer H-1043 (67% of styrene), filler SC2050-MB 100 parts by mass were mixed and diluted with ethyl methyl ketone to prepare a varnish, and the obtained varnish was impregnated and coated on a glass cloth having a thickness of 0.075 mm, and heated and dried at 160 ° C. for 5 minutes to obtain a resin composition content of 60% by mass. prepreg was obtained. Eight sheets of the obtained prepreg were stacked, the copper foils shown above were placed vertically, and laminated molding was performed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper foil clad laminate having an insulating layer thickness of 0.8 mm.

(Comparative Example 5)

26 parts by mass of maleimide resin MIR-3000, 15 parts by mass of polyphenylene ether resin OPE-2St2200, 8 parts by mass of SNCN, 11 parts by mass of thermoplastic elastomer H-1043 (67% of styrene), phosphorus flame retardant PX- 40 parts by mass of 200 and 100 parts by mass of the filler SC2050-MB were mixed and diluted using ethyl methyl ketone to prepare a varnish, and the obtained varnish was impregnated and coated on a glass cloth having a thickness of 0.075 mm, and heated at 160 ° C. for 5 minutes. It was made to dry and the prepreg of 60 mass % of resin composition content was obtained. Eight sheets of the obtained prepreg were stacked, the copper foils shown above were placed vertically, and laminated molding was performed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper foil clad laminate having an insulating layer thickness of 0.8 mm.

(Comparative Example 6)

26 parts by mass of maleimide resin MIR-3000, 15 parts by mass of polyphenylene ether resin OPE-2St2200, 8 parts by mass of SNCN, 11 parts by mass of thermoplastic elastomer H-1043 (67% of styrene), phosphorus-based flame retardant labitol 40 parts by mass of FP-300B and 100 parts by mass of filler SC2050-MB were mixed and diluted with ethyl methyl ketone to prepare a varnish, and the obtained varnish was impregnated and coated on a glass cloth having a thickness of 0.075 mm, and 5 parts at 160 ° C. It was made to heat-dry for minutes and obtained the prepreg of 60 mass % of resin composition content. Eight sheets of the obtained prepreg were stacked, the copper foils shown above were placed vertically, and laminated molding was performed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper foil clad laminate having an insulating layer thickness of 0.8 mm.

(Comparative Example 7)

10 parts by mass of maleimide resin MIR-3000, 20 parts by mass of polyphenylene ether resin OPE-2St2200, 10 parts by mass of SNCN, 40 parts by mass of thermoplastic elastomer H-1043 (67% of styrene), phosphorus-based flame retardant PX- 200 was mixed and diluted with 20 parts by mass of SC2050-MB and 100 parts by mass of filler SC2050-MB with ethyl methyl ketone to prepare a varnish. It was made to dry and the prepreg of 60 mass % of resin composition content was obtained. Eight sheets of the obtained prepreg were stacked, the copper foils shown above were placed vertically, and laminated molding was performed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper foil clad laminate having an insulating layer thickness of 0.8 mm.

(Comparative Example 8)

50 parts by mass of maleimide resin MIR-3000, 20 parts by mass of polyphenylene ether resin OPE-2St2200, 10 parts by mass of SNCN, 20 parts by mass of phosphorus flame retardant PX-200, 100 parts by mass of filler SC2050-MB, ethyl Mixing and diluting using methyl ketone to prepare a varnish, the obtained varnish was impregnated and coated on a glass woven fabric having a thickness of 0.075 mm, and heated and dried at 160°C for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight sheets of the obtained prepreg were stacked, the copper foils shown above were placed vertically, and laminated molding was performed at a pressure of 30 kgf / cm 2 and a temperature of 220 ° C. for 120 minutes to obtain a copper foil clad laminate having an insulating layer thickness of 0.8 mm.

Each physical property was evaluated using the copper foil clad laminate obtained in Examples 1-5 and Comparative Examples 1-8, and the evaluation result was shown in Table 1 and Table 2.

As shown in Table 1 and Table 2, it was confirmed that the copper foil-clad laminates of Examples 1 to 5 had good copper foil peeling strength and low dielectric loss tangent, and were also excellent in crack resistance and solder heat resistance.

This application is based on the Japanese Patent Application (Japanese Patent Application No. 2020-204474) filed with the Japan Patent Office on December 9, 2020, the contents of which are hereby incorporated by reference.

The copper foil-clad laminate obtained using the resin composition of the present invention has industrial applicability as a material constituting printed wiring boards, semiconductor devices, and the like.

Claims (17)

A resin composition comprising a thermosetting compound (A), a thermoplastic elastomer (B), and a phosphorus-based flame retardant (C),
The content of the thermoplastic elastomer (B) in the resin composition is 1 to 30 parts by mass with respect to 100 parts by mass of the resin solid content,
The resin composition in which the content of the phosphorus-based flame retardant (C) in the resin composition is 1 to 30 parts by mass with respect to 100 parts by mass of the resin solid content. According to claim 1,
The resin composition in which the content of the phosphorus-based flame retardant (C) in the resin composition is 15 to 30 parts by mass with respect to 100 parts by mass of the resin solid content. According to claim 1 or 2,
The resin composition in which the phosphorus-based flame retardant (C) is at least one selected from the group consisting of aromatic condensed phosphate esters (C-1) and cyclic phosphazene compounds (C-2). According to claim 3,
The resin composition in which the said aromatic condensed phosphate ester (C-1) is a compound represented by following formula (1), and the said cyclic phosphazene compound (C-2) is a compound represented by following formula (2).

(In Formula (2), n represents an integer of 3 to 6.) According to any one of claims 1 to 4,
The resin composition wherein the thermoplastic elastomer (B) is a styrenic elastomer. According to claim 5,
The styrenic elastomer is from the group consisting of a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-hydrogenated butadiene-styrene block copolymer, and a styrene-hydrogenated isoprene-styrene block copolymer One or more selected resin compositions. According to any one of claims 1 to 6,
The thermosetting compound (A) contains at least one selected from the group consisting of a cyanate ester compound, a maleimide compound, a polyphenylene ether compound, an epoxy compound, a phenol compound, and a curable polyimide compound. The resin composition. According to any one of claims 1 to 7,
The resin composition in which the said resin composition further contains a filler. According to claim 8,
The resin composition according to claim 1 , wherein the filler is at least one selected from the group consisting of silicas, aluminum hydroxide, aluminum nitride, boron nitride, and forsterite. According to claim 8 or 9,
The resin composition in which content of the said filler in the said resin composition is 30-300 mass parts with respect to 100 mass parts of resin solid content. A prepreg comprising a substrate and the resin composition according to any one of claims 1 to 10 impregnated or applied to the substrate. A resin sheet comprising the resin composition according to any one of claims 1 to 10. A laminated board comprising at least one selected from the group consisting of the prepreg according to claim 11 and the resin sheet according to claim 12. A metal foil clad laminate comprising at least one sheet of the prepreg according to claim 11 and a metal foil laminated on one or both surfaces of the prepreg. A metal foil-clad laminate comprising at least one resin sheet according to claim 12 and metal foil laminated on one or both surfaces of the resin sheet. A printed wiring board comprising an insulating layer and a conductor layer disposed on a surface of the insulating layer,
The printed wiring board in which the said insulating layer contains at least one of the layer formed from the resin composition of any one of Claims 1-10, and the prepreg of Claim 11. A semiconductor device manufactured using the printed wiring board according to claim 16.