WO2022124130A1

WO2022124130A1 - Copper-clad laminated board and printed wiring board

Info

Publication number: WO2022124130A1
Application number: PCT/JP2021/043776
Authority: WO
Inventors: 克哉山本; 恵一長谷部
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2020-12-09
Filing date: 2021-11-30
Publication date: 2022-06-16
Also published as: JPWO2022124130A1; TW202235267A; CN116490555A; KR20230115977A

Abstract

Provided is a copper-clad laminated board obtained by layering a copper foil so that the same is in contact with one or more types of surface selected from the group consisting of a prepreg and a resin sheet. The prepreg contains a substrate and a resin composition impregnated in, or coated on, the substrate. The resin sheet contains a resin composition. The resin composition contains 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 1-30 parts by mass relative to 100 parts by mass of solid resin content. The content of the phosphorus-based flame retardant (C) in the resin composition is 1-30 parts by mass relative to 100 parts by mass of solid resin content. The roughness Rz of a surface of the copper foil, as measured in accordance with JIS B0601: 2013, is 0.2-4.0 µm.

Description

Copper foil-clad laminate and printed wiring board

The present invention relates to a copper foil-clad laminate, a printed wiring board manufactured using the same, and a semiconductor device.

In recent years, information terminal devices such as personal computers and servers, as well as communication devices such as Internet routers and optical communications, are required to process a large amount of information at high speed, and the speed and frequency of electric signals are increasing. There is. Along with this, the laminated boards for printed wiring boards used for these are required to have a low dielectric constant and a low dielectric loss tangent in order to meet the demand for high frequency.

For example, Patent Document 1 describes excellent heat resistance by using a polyphenylene ether resin in which both sides of a 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 having low dielectric properties and various physical properties 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

Laminated boards for printed wiring boards are required to have crack resistance in addition to transmission loss characteristics (low transmission loss) and copper foil peel strength. Here, the crack resistance indicates the insulation reliability when the bending test is performed while passing a current through the substrate on which the circuit is drawn, and means that dielectric breakdown does not occur even if the number of bendings is large. The copper foil-clad laminate disclosed in the above patent document is good in terms of low transmission loss and the like, but still has a problem in terms of crack resistance.

In view of the above circumstances, the present invention uses a copper foil-clad laminate having good copper foil peel strength and transmission loss characteristics (low transmission loss), and also having excellent crack resistance and solder heat resistance. It is an object of the present invention to provide a printed wiring board and a semiconductor device.

As a result of diligent studies, the present inventors have made a copper foil-clad laminate in which copper foil is laminated so as to be in contact with one or more surfaces selected from the group consisting of a prepreg and a resin sheet, and constitutes the prepreg and the resin sheet. By using a copper foil containing a thermosetting compound, a specific amount of a thermoplastic elastomer and a phosphorus-based flame retardant, and having a copper foil surface with a roughness Rz in a specific range, the above-mentioned problems can be solved. We found that it could be solved and completed the present invention.

That is, the present invention is as follows.
[1]
A copper foil-clad laminate in which copper foil is laminated so as to be in contact with one or more surfaces selected from the group consisting of a prepreg and a resin sheet.
The prepreg comprises a substrate and a resin composition impregnated or coated on the substrate.
The resin sheet contains a resin composition and contains
The resin composition contains 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.
A copper foil-clad laminate having a roughness Rz of the copper foil surface measured according to JIS B0601: 2013 of 0.2 to 4.0 μm.
[2]
The copper foil-clad laminate 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 phosphorus-based flame retardant (C) is at least one selected from the group consisting of an aromatic condensed phosphoric acid ester (C-1) and a cyclic phosphazene compound (C-2), according to the above [1] or [2]. ] The copper foil-clad laminate described in.
[4]
The aromatic condensed phosphoric acid 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 copper foil-clad laminate according to any one of the above [1] to [3].

(In equation (2), n represents an integer of 3 to 6.)
[5]
The copper foil-clad laminate according to any one of the above [1] to [4], wherein the thermoplastic elastomer (B) is a styrene-based elastomer.
[6]
The styrene-based elastomer is 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 copper foil-clad laminate according to the above [5], which is one or more selected from the group consisting of.
[7]
The thermosetting compound (A) contains at least one selected from the group consisting of a cyanic acid ester compound, a maleimide compound, a polyphenylene ether compound, an epoxy compound, a phenol compound, and a curable polyimide compound. The copper foil-clad laminate according to any one of [6].
[8]
The copper foil-clad laminate according to any one of the above [1] to [7], wherein the resin composition further contains a filler.
[9]
The copper foil-clad laminate according to the above [8], wherein the filler is one or more selected from the group consisting of silicas, aluminum hydroxide, aluminum nitride, boron nitride, and forsterite.
[10]
The copper foil-clad laminate according to the above [8] or [9], 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]
The copper foil-clad laminate according to any one of the above [1] to [10], wherein the copper foil is an electrolytic copper foil.
[12]
A printed wiring board manufactured by using the copper foil-clad laminate according to any one of the above [1] to [11].
[13]
A semiconductor device manufactured by using the printed wiring board according to the above [12].

INDUSTRIAL APPLICABILITY According to the present invention, a copper foil-clad laminate having good copper foil peel strength and transmission loss characteristics, and also having excellent crack resistance and solder heat resistance, and a printed wiring board and a semiconductor device using the copper foil-clad laminate are provided. Can be done.

The copper foil-clad laminate of the present embodiment is
A copper foil-clad laminate in which copper foil is laminated so as to be in contact with one or more surfaces selected from the group consisting of a prepreg and a resin sheet.
The prepreg comprises a substrate and a resin composition impregnated or coated on the substrate.
The resin sheet contains a resin composition and contains
The resin composition contains 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.
The roughness Rz of the copper foil surface measured according to JIS B0601: 2013 is 0.2 to 4.0 μm.

In the present specification, "resin solid content in the resin composition" means a component of the resin composition excluding the solvent and the filler, and 100 parts by mass of the resin solid content means the resin composition, unless otherwise specified. It means that the total of the components excluding the solvent and the filler in the product is 100 parts by mass.

In the following, first, the resin composition and the components constituting the resin composition used for the copper foil-clad laminate of the present embodiment will be described, and then the prepreg, the resin sheet, and the copper foil-clad laminate obtained by using the resin composition will be described. The board and the like will be described.

[Resin composition]
The resin composition in the present embodiment contains a thermosetting compound (A), a thermoplastic elastomer (B), and a phosphorus-based flame retardant (C).

[Thermosetting compound (A)]
The thermosetting compound (A) is not particularly limited as long as it is a thermosetting compound, and includes, for example, a cyanic acid ester compound, a maleimide compound, a polyphenylene ether compound, an epoxy compound, a phenol compound, and a curable polyimide compound. It is preferable to include one or more selected from the group.

[Cyanic acid 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 (cyanic acid 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 the molecule is more preferable. The lower limit of the number of cyanato groups contained in the cyanate ester compound is preferably 2 or more, and more preferably 3 or more. By setting the number of cyanato groups to the above lower limit or more, the heat resistance tends to be further improved. The upper limit is not particularly specified, but may be, for example, 50 or less.

Examples of the cyanic acid ester compound in the present embodiment include the compound represented by the formula (5).

(In the formula (5), Ar ₁ 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 may independently have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, and a substituent. A good alkoxy group having 1 to 4 carbon atoms, an aralkyl group having a substituent in which an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms are bonded, or an alkyl group having 1 to 6 carbon atoms may be used. It is selected from any one of the alkylaryl groups which may have a substituent in which an aryl group having 6 to 12 carbon atoms is bonded. N ₆ represents the number of cyanato groups bonded to Ar ₁ . N ₇ represents the number of R ₈₁ bonded to Ar _1. 4-n ₆ when Ar ₁ is a phenylene group, 6-n 6 when Ar 1 is a naphthylene group, and 6-n ₆ when Ar 1 is a biphenylene group. 8-n ₆ ; n ₈ represents the average number of iterations and is an integer from 0 to 50. The cyanate ester compound may be a mixture of compounds with different n ₈ ; Z is independent of each other. Single bond, divalent organic group having 1 to 50 carbon atoms (hydrogen atom may be replaced with a hetero atom), divalent organic group having 1 to 10 nitrogen atoms (-N-RN-, etc.) , Carbonyl group (-CO-), carboxy group (-C (= O) O-), carbonyldioxide group (-OC (= O) O-), sulfonyl group (-SO _2- ), and divalent It is selected from either a sulfur atom or a divalent oxygen atom.)

The alkyl group in R ₈₁ of the formula (5) may have a linear structure, a branched chain structure, a cyclic structure (cycloalkyl group or the like). Further, the hydrogen atom in the alkyl group in the alkyl group in R ₈₁ and the aryl group in R ₈₁ of the formula (5) is a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, a cyano group or the like. It may be replaced with.
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 and 2,2-dimethylpropyl group. Examples thereof include a group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a trifluoromethyl group and the like.
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 and a trifluorophenyl. Examples thereof include a group, a methoxyphenyl group, an o-, m- or a p-tolyl group.
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, a tert-butoxy group and the like.
Specific examples of the divalent organic group in Z of the formula (5) include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, a biphenylylmethylene group, and a dimethylmethylene-phenylene. -Examples include a dimethylmethylene group, a fluorinatedyl group, a phthalidodiyl group and the like. 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, a cyano group or the like. Examples of the divalent organic group having a nitrogen number of 1 to 10 in Z of the formula (5) include an imino group and a polyimide group.

Further, examples of Z in the formula (5) include those having a structure represented by the following formula (6) or the following formula (7).

(In the 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 independently hydrogen atoms and have 1 to 1 carbon atoms, respectively. It is selected from any one of 6 alkyl groups, 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. R ₁₁ , R ₁₂ Are independently 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. N ₉ is 0. Although an integer of 5 is shown, the cyanate ester compound may be a mixture of compounds in which n ₉ has a different group.)

(In the 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 independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, and carbon. It is selected from any one of an aryl group having a number of 6 to 12, a benzyl group, an alkoxy group having 1 to 4 carbon atoms, and an aryl group substituted with at least one of a hydroxy group, a trifluoromethyl group and a cyanato group. Although n ₁₀ represents an integer of 0 to 5, the cyanate ester compound may be a mixture of compounds in which n ₁₀ has a different group.)

Further, as Z in the formula (5), a divalent group represented by the following formula can be mentioned.

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

Examples of the cyanic acid ester compound represented by the formula (5) include a phenol novolac type cyanic acid ester compound, a naphthol aralkyl type cyanic acid ester compound, a biphenyl aralkyl type cyanic acid ester compound, and a naphthylene ether type cyanic acid ester compound. Examples thereof include a xylene resin type cyanate ester compound, an adamantan skeleton type cyanate ester compound, a bisphenol A type cyanate ester compound, a diallyl bisphenol A type cyanate ester compound, and a naphthol aralkyl type cyanate ester compound.

Specific examples of the cyanate ester compound represented by the formula (5) include 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-2,5-,1 -Cyanato-2,6-, 1-Cyanato-3,4- or 1-Cyanato-3,5-dimethylbenzene, Cyanatoethylbenzene, Cyanatobutylbenzene, Cyanatooctylbenzene, Cyanatononylbenzene, 2-( 4-Cianaphenyl) -2-phenylpropane (cyanate of 4-α-cumylphenol), 1-cyanato-4-cyclohexylbenzene, 1-cyanato-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-メトキシ－４－アリルベンゼン（オイゲノールのシアネート）、メチル（４－シアナトフェニル）スルフィド、１－シアナト－３－トリフルオロメチルベンゼン、４－シアナトビフェニル、１－シアナト－２－又は１－シアナト－ 4-Acetylbenzene, 4-Cyanatobenzaldehyde, 4-Cyanato benzoic acid methyl ester, 4-Cyanato benzoic acid phenyl ester, 1-Cyanato-4-acetaminobenzene, 4-Cyanatobenzophenone, 1-Cyanato-2,6 -Di-tert-butylbenzene, 1,2-disyanatobenzene, 1,3-disyanatobenzene, 1,4-disyanatobenzene, 1,4-disyanato-2-tert-butylbenzene, 1,4-disianato -2,4-dimethylbenzene, 1,4-disyanato-2,3,4-dimethylbenzene, 1,3-disyanato-2,4,6-trimethylbenzene, 1,3-disyanato-5-methylbenzene, 1 -Cyanato or 2-cyanatonaphthalene, 1-cyanato 4-methoxynaphthalene, 2-cyanato-6-methylnaphthalene, 2-cyanato-7-methoxynaphthalene, 2,2'-disyanat-1,1'-binaphthyl, 1 , 3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-disianatocinaphthalene, 2,2'-or 4 , 4'-Gisiana Tobiphenyl, 4,4'-disyanato octafluorobiphenyl, 2,4'-or 4,4'-disyanatodiphenylmethane, 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-cyanato) Phenyl) 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) 4-Cyanatophenyl) -2,2-dimethylpentane, 4,4-bis (4-cyanatophenyl) -3-methylheptane, 3,3-bis (4-cyanatophenyl) -2-methylheptane, 3,3-bis (4-Cyanatophenyl) -2,2-dimethylhexane, 3,3-bis (4-Cyanatophenyl) -2,4-dimethylhexane, 3,3-bis (4-Cyanato) Phenyl) -2,2,4-trimethylpentane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, bis (4-cyanatophenyl) phenyl Methan, 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-disyanato Benzophenone, 1,3-bis (4-cyanatophenyl) -2-propen-1-one, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) sulfide, bis (4-cyanatophenyl) ) Sulfon, 4-Cyanato benzoic acid-4-Cyanatophenyl ester (4-Cyanatophenyl-4-Cyanatobenzoate), Bis- (4-Cyanatophenyl) carbonate, 1,3-Bis (4-Cyanato) Phenyl) adamantan, 1,3-bis (4-cyanatophenyl) -5,7-dimethyladamantan, 3,3-bis (4-cyanatophenyl) isobenzofuran-1 (3H) -on (phenol phthalein) Cyanate), 3,3-bis (4-cyanato-3-methylphenyl) isobenzofuran-1 (3H) -one (o-cresolphthaline cyanate), 9,9-bis (4-cyanatophenyl) fluorene , 9,9-bis (4-cyanato-3-methylphenyl) fluorene, 9,9-bis (2-cyanato-5-biphenylyl) fluoren, tris (4-cyanatophenyl) methane, 1,1,1 -Tris (4-Cyanatophenyl) Etan, 1,1,3-Tris (4-Cyanatophenyl) Propane, α, α, α'-Tris (4-Cyanatophenyl) -1-ethyl-4-isopropyl Benzene, 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-me) Chill-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'-oxydiphthalimide, bis (N-4-cyanatophenyl) -4,4'-oxydiphthalimide, bis (N-4-cyanato-2-methyl) Phenol) -4,4'-(hexafluoroisopropyridene) diphthalimide, tris (3,5-dimethyl-4-cyanatobenzyl) isocyanurate, 2-phenyl-3,3-bis (4-cyanatophenyl) Phenolimidine, 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 and cresol novolak resin (known) Depending on the method, phenol, alkyl-substituted phenol or halogen-substituted phenol is reacted with a formaldehyde compound such as formarin or paraformaldehyde in an acidic solution), trisphenol novolak resin (hydroxybenzaldehyde and phenol in the presence of an acidic catalyst). ), Fluolenovolac resin (a reaction of a fluorenone compound and 9,9-bis (hydroxyaryl) fluorene 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 represented by Ar _4- (CH ₂ Z') ₂ and a phenol compound reacted with an acidic catalyst or no catalyst, Ar _4- ( Reaction of a bis (alkoxymethyl) compound represented by CH ₂ OR) ₂ or a bis (hydroxymethyl) compound represented by Ar _4- (CH ₂ OH) ₂ with a phenol compound in the presence of an acidic catalyst. , Or aromatic aldehyde compound, aralkyl compound, phenol compound and polycondensation), phenol-modified xyleneformaldehyde resin (by a known method, xyleneformaldehyde resin and phenol compound in the presence of an acidic catalyst) (Reacted with), modified naphthalene formaldehyde resin (reacted with naphthalene formaldehyde resin and hydroxy-substituted aromatic compound in the presence of an acidic catalyst by a known method), phenol-modified dicyclopentadiene resin, polynaphthylene ether. Phenolic resins having a structure (a polyvalent hydroxynaphthalene compound having two or more phenolic hydroxy groups in one molecule, dehydrated and condensed in the presence of a basic catalyst by a known method) are described above. Examples thereof include those which have been acid esterified by the same method as in the above, but the present invention is not particularly limited. These cyanate ester compounds may be used alone or in combination of two or more.

Among them, phenol novolac type cyanate ester compound, naphthol aralkyl type cyanate ester compound, naphthylene ether type cyanate ester compound, bisphenol A type cyanate ester compound, bisphenol M type cyanate ester compound, diallyl bisphenol type cyanate ester Preferred, naphthol aralkyl-type cyanate ester compounds are particularly preferred.

The cured product of the resin composition using these cyanate ester compounds has excellent properties such as heat resistance and low dielectric property (low dielectric constant, low dielectric loss tangent property), and the printed wiring including the cured product. Plates tend to be excellent in copper foil peel strength, mechanical strength, heat resistance, and low transmission loss.

The content of the cyanic acid ester compound in the resin composition according to the present embodiment can be appropriately set according to the desired properties and is not particularly limited. Specifically, the content of the cyanic acid ester compound is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and 10 parts by mass when the resin solid content in the resin composition is 100 parts by mass. It is more preferably parts or more, and may be 15 parts by mass or more. The upper limit of the content is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, further preferably 70 parts by mass or less, further preferably 60 parts by mass or less, and 55 parts by mass. It may be as follows. Within 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 be more excellent in low transmission loss.
Only one type of cyanic acid ester compound may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above 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, for example, N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidephenyl) methane, 4,4'-diphenylmethane bismaleimide, and bis (3,5-dimethyl-4-maleimide). Phenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) methane, phenylmethanemaleimide, o-phenylene bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene biscitraconimide, m- Phenylene biscitraconimide, p-phenylene biscitraconimide, 2,2-bis (4- (4-maleimidephenoxy) -phenyl) propane, 3,3'-diethyl-5,5'-dimethyl-4,4'- Diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulphon Bismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, 1,3-bis (4-maleimidephenoxy) benzene, 4,4'-diphenylmethanebiscitraconimide, 2,2-bis [4- (4- (4- (4- (4- (4-) Citraconimidephenoxy) phenyl] propane, bis (3,5-dimethyl-4-citraconeimidephenyl) methane, bis (3-ethyl-5-methyl-4-citraconeimidephenyl) methane, bis (3,5-diethyl-) Examples thereof include 4-citraconimidephenyl) methane, maleimide compounds represented by the following formulas (2), (3), (4) and (17).
Among these, maleimide compounds represented by the following formulas (2), (3), (4) and (17) are particularly preferable in terms of low thermal expansion and improvement of heat resistance of the cured product of the resin composition. These maleimide compounds may be used alone or in combination of two or more.

(In the above formula (2), R ₄ independently represents a hydrogen atom or a methyl group, and n ₄ represents an integer of 1 or more.)

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

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

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

In the above formula (2), R ₄ independently represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. Further, in the formula (2), n ₄ represents an integer of 1 or more, and the upper limit of n ₄ is usually 10, and from the viewpoint of solubility in an organic solvent, the upper limit of n ₄ is preferably 10. It is 7, more preferably 5. The maleimide compound may contain two or more compounds having different _n4s .

In the above formula (3), R ₅ is an independent hydrogen atom and 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 and an isobutyl group). , T-butyl group, n-pentyl group, etc.), or phenyl group. Among these, from the viewpoint of improving the flame resistance and the copper foil peel strength of the copper foil-clad laminate, the group is preferably selected from the group consisting of a hydrogen atom, a methyl group, and a phenyl group, and the hydrogen atom and methyl are preferable. It is more preferably one of the groups, and even more preferably a hydrogen atom.

In the above formula (3), 1 ≦ n ₅ ≦ 10. From the viewpoint of further excellent solvent solubility, n ₅ is preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less. The maleimide compound may contain two or more compounds having different _n5s .

In the above formula (4), R ₆ independently represents a hydrogen atom, a methyl group or an ethyl group, and R ₇ independently represents a hydrogen atom or a methyl group. From the viewpoint of being more excellent in the low dielectric property 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), R ₈ is preferably a methyl group from the viewpoint of being more excellent in the low dielectric property of the cured product of the resin composition which independently exhibits a hydrogen atom, a methyl group or an ethyl group. Examples of such compounds include 2,2-bis (4- (4-maleimidephenoxy) -phenyl) propane.

As the maleimide compound used in the present embodiment, a commercially available maleimide compound may be used. For example, as the maleimide compound represented by the formula (2), "BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd., represented by the formula (3). The maleimide compound to be used is "MIR-3000" manufactured by Nippon Kayaku Co., Ltd., the maleimide compound represented by the formula (4) is "BMI-70" manufactured by KI Kasei Co., Ltd., and the maleimide represented by the formula (17). As the compound, "BMI-80" manufactured by KI Kasei Co., Ltd. can be preferably used.

The content of the maleimide compound in the resin composition according to the present embodiment can be appropriately set according to the desired properties 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 20 parts by mass or more when the resin solid content in the resin composition is 100 parts by mass. Is even more preferable. The upper limit value is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, further preferably 60 parts by mass or less, and may be 50 parts by mass or less. Within such a range, the cured product of the resin composition tends to more effectively exhibit high heat resistance and low water absorption.
Only one type of maleimide compound may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[Polyphenylene ether compound]
The polyphenylene ether compound according to this embodiment includes the formula (8) :.

(In formula (8), R ₈ , R ₉ , R ₁₀ , and R ₁₁ each independently represent an alkyl group, an aryl group, a halogen atom, or a hydrogen atom having 6 or less carbon atoms.)
It is preferable that the compound contains a polymer of the structural unit represented by.
The polyphenylene ether compound has the formula (9) :.

(In formula (9), R ₁₂ , R ₁₃ , R ₁₄ , R ₁₈ , and R ₁₉ each independently represent an alkyl group or a phenyl group having 6 or less carbon atoms. R ₁₅ , R ₁₆ , and R ₁₇ are respectively. Independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)
Structure represented by and / or formula (10) :.

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 and an alkyl group or phenyl group having 6 or less carbon atoms. -A- may further include a structure represented by a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

Examples of -A- in the formula (10) include a methylene group, an ethylidene group, a 1-methylethylidene group, a 1,1-propyridene group, a 1,4-phenylenebis (1-methylethylidene) group and a 1,3-. Examples thereof include, but are not limited to, a divalent organic group such as a phenylenebis (1-methylethylidene) group, a cyclohexylidene group, a phenylmethylene group, a naphthylmethylene group and a 1-phenylethylidene group.

In the polyphenylene ether compound, a part or all of the terminal was 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 and the like. Modified polyphenylene ether can also be used. These may be used individually by 1 type or in combination of 2 or more types.
Examples of the modified polyphenylene ether having a hydroxyl group at the end include SA90 manufactured by SABIC Innovative Plastics Co., Ltd. Examples of the polyphenylene ether having a methacrylic group at the end include SA9000 manufactured by SABIC Innovative Plastics Co., Ltd.

The method for producing the modified polyphenylene ether is not particularly limited as long as the effect of the present invention can be obtained. For example, it can be produced by the method described in Japanese Patent No. 4591665.

The modified polyphenylene ether preferably contains a modified polyphenylene ether having an ethylenically unsaturated group at the terminal. Examples of the ethylenically unsaturated group include an alkenyl group such as an ethenyl group, an allyl group, an acrylic group, a methacrylic group, a propenyl group, a butenyl group, a hexenyl group and an octenyl group, a cycloalkenyl group such as a cyclopentenyl group and a cyclohexenyl group, and vinyl. Examples thereof include an alkenylaryl group such as a benzyl group and a vinylnaphthyl group, and a vinylbenzyl group is preferable. The terminal ethylenically unsaturated group may be single or plural, may be the same functional group, or may be a different functional group.

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

(In formula (1), X represents an aromatic group,-(YO) _m- represents a polyphenylene ether moiety. R ₁ , R ₂ , and R ₃ are independent hydrogen atoms, alkyl groups, and alkenyl groups, respectively. It represents a group or an alkynyl group, m represents an integer of 1 to 100, n represents an integer of 1 to 6, q represents an integer of 1 to 4, and m is preferably an integer of 1 or more and 50 or less. , More preferably 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. It is preferably an integer of 1 or more and 3 or less, more preferably 1 or 2, and ideally 2.)
The structure represented by is mentioned.

The aromatic group represented by X in the formula (1) is a group obtained by removing q hydrogen atoms from one ring structure selected from a benzene ring structure, a biphenyl ring structure, an indenyl ring structure, and a naphthalene ring structure. (For example, a phenylene group, a biphenylene group, an indenylene group, and a naphthylene group) can be mentioned, and a biphenylene group is preferable.
Here, the aromatic group represented by X is a diphenyl ether group in which an aryl group is bonded with an oxygen atom, a benzophenone group in which a carbonyl group is bonded, a 2,2-diphenylpropane group bonded by an alkylene group, or the like. May include.
Further, the aromatic group may be substituted with a general substituent such as an alkyl group (preferably an alkyl group having 1 to 6 carbon atoms, particularly a methyl group), an alkenyl group, an alkynyl group or a halogen atom. However, since the aromatic group is substituted with the polyphenylene ether moiety via the oxygen atom, the limit of the number of general substituents depends on the number of the polyphenylene ether moiety.

As the polyphenylene ether moiety in the formula (1), the structural unit represented by the above-mentioned formula (8), (9) or (10) can be used, and in particular, the structural unit represented by the formula (8) is included. Is particularly preferred.

The modified polyphenylene ether represented by the formula (1) preferably has a number average molecular weight of 1000 or more and 7000 or less. Further, in the formula (1), one having a minimum melt viscosity of 50,000 Pa · s or less can be used. In particular, in the formula (1), those having a number average molecular weight of 1000 or more and 7000 or less and a minimum melt viscosity of 50,000 Pa · s or less are preferable.
The number average molecular weight is measured using gel permeation chromatography according to a routine method. The number average molecular weight is more preferably 1000 to 3000. By setting the number average molecular weight to 1000 or more and 7000 or less, the effect of achieving both moldability and electrical characteristics is more effectively exhibited.
The minimum melt viscosity is measured using a dynamic viscoelasticity measuring device according to a conventional method. The minimum melt viscosity is more preferably 500 to 50,000 Pa · s. By setting the minimum melt viscosity to 50,000 Pa · s or less, the effect of achieving both moldability and electrical characteristics is more effectively exhibited.

The modified polyphenylene ether is preferably a compound represented by the following formula (11) in the formula (1).

(In the formula (11), X is an aromatic group, − (YO) _m − indicates a polyphenylene ether moiety, and m indicates an integer of 1 to 100. M is preferably 1 or more. It is an integer of 50 or less, and more preferably an integer of 1 or more and 30 or less.)
X, − (YO) _m − and m in the formula (11) are synonymous with those in the formula (1).

X in the formula (1) and the formula (11) is the formula (12), the formula (13), or the formula (14), and − (YO) _m − in the formula (1) and the formula (11) is , Formula (15) or formula (16) may be arranged, or formula (15) and formula (16) may be block or randomly arranged structure.

(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 group having 20 or less carbon atoms. It is a divalent hydrocarbon group.)
As the specific example of -B-, the same as the specific example of -A- in the formula (10) can be mentioned.

(In the formula (14), -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)
As the specific example of -B-, the same as the specific example of -A- in the formula (10) can be mentioned.

The method for producing the modified polyphenylene ether having the structure represented by the formula (11) is not particularly limited, and for example, the bifunctional phenylene ether obtained by oxidatively coupling a bifunctional phenol compound and a monofunctional phenol compound. It can be produced by converting the terminal phenolic hydroxyl group of the oligomer into vinylbenzyl ether.
Further, as such a modified polyphenylene ether, a commercially available product can be used, and for example, OPE-2St1200 and OPE-2st2200 manufactured by Mitsubishi Gas Chemical Company, Inc. 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, preferably 15 parts by mass or more, based on 100 parts by mass of the resin solid content of the resin composition. More preferably, it is 18 parts by mass or more. The upper limit of the content is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, further preferably 50 parts by mass or less, and 40 parts by mass or less or 30 parts by mass. It may be as follows. By setting the content of the polyphenylene ether compound in such a range, the low dielectric property, the copper foil peel strength, and the heat resistance of the cured product of the resin composition tend to be more excellent.
These polyphenylene ether compounds may be used alone or in admixture of two or more. When two or more types are used, it is preferable that the total amount is within the above range.

[Epoxy compound]
As the epoxy compound according to the present embodiment, any known epoxy compound or resin having two or more epoxy groups in one molecule can be appropriately used, and the type thereof 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 novolac type epoxy resin, bisphenol A novolak type epoxy resin, glycidyl ester type epoxy resin, aralkylnovolac Type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, cresol novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, phenol aralkyl Double bond of type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, glycidyl ester, butadiene, etc. Examples thereof include a compound obtained by epoxidizing the above, a compound obtained by reacting a hydroxyl group-containing silicone resin with epichlorohydrin, and the like. Among these epoxy compounds, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, polyfunctional phenol type epoxy resin, and naphthalene type epoxy resin are preferable in terms of flame retardancy and heat resistance. These epoxy compounds may be used alone or in combination of two or more.

The content of the epoxy compound in the resin composition according to the present embodiment can be appropriately set according to the 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 epoxy compound is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and 5 parts by mass or more. It is more preferable to have. The upper limit of the content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less. By setting the content of the epoxy compound in such a range, the copper foil peel 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 hydroxy groups in one molecule, and for example, bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, and the like. Biphenyl S-type phenol resin, phenol novolak resin, Bisphenol A novolak type phenol resin, glycidyl ester type phenol resin, aralkyl novolak phenol resin, biphenyl aralkyl type phenol resin, cresol novolak type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac Resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolak type phenol resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, Examples thereof include a polyol type phenol resin and a phosphorus-containing phenol resin. Among these, at least one selected from the group consisting of biphenyl aralkyl type phenol resin, naphthol aralkyl type phenol resin, and phosphorus-containing phenol resin is preferable from the viewpoint of further improving heat resistance and flame resistance. These phenol compounds may be used alone or in combination of two or more.

The content of the phenol compound in the resin composition according to the present embodiment can be appropriately set according to the 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 5 parts by mass or more. It is more preferable to have. The upper limit of the content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less. By setting the content of the phenol compound in such a range, the copper foil peel 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 bisallyl nadiimide is preferable from the viewpoint of low dielectric property, and it is particularly selected from the group consisting of the following formulas (17) and (18). It is preferably at least one kind.

The content of the curable polyimide compound in the resin composition according to the present embodiment can be appropriately set according to the 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 curable polyimide compound is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and 5 parts by mass. The above is more preferable. The upper limit of the content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further 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 in such a range, the dielectric properties, copper foil peel strength, and heat resistance of the cured product of the resin composition tend to be more excellent.

[Thermoplastic elastomer (B)]

The resin composition according to the present embodiment contains the 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 cured product of the resin composition has crack resistance, low dielectric properties, and transmission loss characteristics. When it is 30 parts by mass or less, the solder heat resistance of the cured product of the resin composition tends to be good.

The content of the thermoplastic elastomer (B) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and 8 parts by mass or more with respect to 100 parts by mass of the resin solid content of the resin composition. It is more preferable to have 10 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 20 parts by mass or less with respect to 100 parts by mass of the resin solid content of the resin composition. May be good. When the content of the thermoplastic elastomer (B) is within the above range, the cured product of the resin composition tends to have more excellent crack resistance, low dielectric property, transmission loss property, and solder heat resistance. In the present embodiment, two or more kinds of thermoplastic elastomers (B) may be contained, and when two or more kinds are contained, it is preferable that the total amount thereof is within the above range.

The thermoplastic elastomer (B) is not particularly limited, and examples thereof include the following "styrene-based elastomers" and "other thermoplastic elastomers", but from the viewpoint of low dielectric properties and reduction of transmission loss, styrene-based elastomers (B) are used. It is preferably an elastomer.

[Styrene-based elastomer]
The "styrene-based elastomer" according to the present embodiment refers to an elastomer which is a block copolymer having a polystyrene block structure, and does not include a random copolymer.

Examples of the styrene-based elastomer used in the resin composition according to the present embodiment include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, and a styrene-hydrogenated butadiene-styrene block copolymer. 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- At least one selected from the group consisting of hydrogenated (isoprene / butadiene) block copolymers can be mentioned. These styrene-based elastomers may be used alone or in combination of two or more. In particular, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-hydrogenated butadiene-styrene block copolymer, and styrene-hydrogenated isoprene-styrene block copolymer are resin compositions. It is preferable because the cured product tends to give better low dielectric styrene.

As the styrene (styrene unit) in the polystyrene block structure in the present embodiment, one having a substituent may be used. 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 styrene-based 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 is preferably less than 99% by mass, more preferably 70% by mass or less, for example. Within such a range, the solvent solubility and the compatibility with other compounds tend to be further improved. Here, the styrene content is (a) / (b) × 100 when the mass of the styrene unit contained in the styrene-based elastomer is (a) g and the mass of the entire styrene-based elastomer is (b) g. It is a value expressed in (unit:%).

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 the styrene-butadiene-styrene block copolymer. Be done. Examples of the styrene-isoprene-styrene block copolymer include SIS5250 (manufactured by JSR Corporation). Examples of the styrene-hydrogenated isoprene-styrene block copolymer include SEPTON2104 (manufactured by Kuraray Co., Ltd.). Further, examples of the styrene-hydrogenated butadiene-styrene block copolymer include H-1043 (manufactured by Asahi Kasei Corporation).

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, preferably 5 parts by mass or more, based on 100 parts by mass of the resin solid content of the resin composition. It is more preferably 8 parts by mass or more, and it may be 10 parts by mass or more. The upper limit of the content of the styrene-based elastomer is preferably 25 parts by mass or less, more preferably 22 parts by mass or less, and 20 parts by mass or less with respect to 100 parts by mass of the resin solid content of the resin composition. It may be. When the content of the styrene-based elastomer is within the above range, the cured product of the resin composition tends to have more excellent crack resistance, low dielectric property, transmission loss property, and solder heat resistance. In the present embodiment, two or more kinds of styrene-based elastomers may be contained, and when two or more kinds are contained, it is preferable that the total amount thereof is within the above range.

[Other thermoplastic elastomers]
"Other thermoplastic elastomers" are distinguished from "styrene-based elastomers". The "styrene-based elastomer" indicates an elastomer having a polystyrene block structure and being a block copolymer, and the "other thermoplastic elastomer" indicates an elastomer other than that. That is, a random copolymer, a block copolymer having no styrene skeleton, or the like is applicable.
The other thermoplastic elastomer is selected from the group consisting of, for example, polyisoprene, polybutadiene, styrene-butadiene random copolymer, butyl rubber, ethylene propylene rubber, fluororubber, silicone rubber, hydrogenated compounds thereof, and alkyl compounds thereof. At least one is mentioned. Among these, at least one selected from the group consisting of polyisoprene, polybutadiene, styrene-butadiene random copolymer, butyl rubber, and ethylene propylene rubber is more preferable from the viewpoint of being more excellent in compatibility with the polyphenylene ether compound. ..

[Phosphorus flame retardant (C)]
The resin composition in the present 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% by mass with respect to 100 parts by mass of the resin solid content. It is a department. 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 property, and transmission loss property of the cured product of the resin composition are improved. When it is 30 parts by mass or less, the copper foil peel strength, crack resistance, and solder heat resistance of the cured product of the resin composition tend to be good.

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, and 8 parts by mass or more with respect to 100 parts by mass of the resin solid content of the resin composition. Is more preferable, and it may be 10 parts by mass or more, or 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 20 parts by mass or less with respect to 100 parts by mass of the resin solid content of the resin composition. May be good. When the content of the phosphorus-based flame retardant (C) is within the above range, the crack resistance, low dielectric property, transmission loss property, copper foil peel strength, and solder heat resistance of the cured product of the resin composition tend to be more excellent. It is in. In the present embodiment, two or more kinds of phosphorus-based flame retardants (C) may be contained, and when two or more kinds are contained, it is preferable that the total amount thereof is within the above range.

Further, the content of the phosphorus-based flame retardant (C) is 15 with respect to 100 parts by mass of the resin solid content of the resin composition from the viewpoint of particularly enhancing the crack resistance and the copper foil peel strength of the cured product of the resin composition. It is preferably 2 parts by mass or more, and particularly preferably 20 parts by mass or more. 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, based on 100 parts by mass of the resin solid content of the resin composition. Yes, it may be 25 parts by mass or less.

Since the total content of the thermoplastic elastomer (B) and the phosphorus-based flame retardant (C) tends to further improve the crack resistance and the copper foil peel strength of the cured product of the resin composition, the resin solid content is 100. It is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, further preferably 20 parts by mass or more, particularly preferably 25 parts by mass or more, and 30 parts by mass with respect to parts by mass. It may be more than a mass part. Further, since the solder heat resistance of the cured product of the resin composition tends to be further improved, the total content of the thermoplastic elastomer (B) and the phosphorus-based flame retardant (C) is 100 parts by mass of the resin solid content. On the other hand, it is preferably 60 parts by mass or less, more preferably 55 parts by mass or less, further preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less.

The phosphorus-based flame retardant (C) is not particularly limited, and is, for example, red phosphorus, tricresyl phosphate, triphenyl phosphate, cresyldiphenyl phosphate, trixylenyl phosphate, trialkyl phosphate, dialkyl phosphate, tris (chloroethyl). Phosphazene, phosphazene, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and the like can be mentioned.

The phosphorus-based flame retardant (C) is a group consisting of an aromatic condensed phosphoric acid ester (C-1) and a cyclic phosphazene compound (C-2) from the viewpoints of low dielectric property, reduction of transmission loss, and improvement of crack resistance. It is preferable to use one or more selected species.

Examples of the aromatic condensed phosphoric acid ester (C-1) include resorcinol bis-diphenyl phosphate, bisphenol A bis-diphenyl phosphate, and a compound represented by the following formula (1). Above all, from the viewpoint of low dielectric property and reduction of transmission loss, the compound represented by the following formula (1) is preferable.

The cyclic phosphazene compound (C-2) is represented by hexaphenoxycyclotriphosphazene, hexafluorocyclotriphosphazene, pentafluoro (phenoxy) cyclotriphosphazene, ethoxy (pentafluoro) cyclotriphosphazene, and the following formula (2). Examples include compounds. Above all, from the viewpoint of solvent solubility, the compound represented by the following formula (2) is preferable.

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

Examples of the compound represented by the above formula (2) include Ravitor FP-300B (manufactured by Fushimi Pharmaceutical Co., Ltd.).

[Filler]
It is desirable that the resin composition according to the present embodiment contains a filler in order to improve low dielectric constant, low dielectric loss tangent property, flame resistance and low thermal expansion. As the filler used in the present embodiment, known fillers can be appropriately used, and the types thereof are not particularly limited, and those generally used in the art can be preferably used. Specifically, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerodil, hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, coagulated boron nitride, silicon nitride. , Aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat-treated product (aluminum hydroxide heat-treated to reduce a part of crystalline water), boehmite, metal hydrates such as magnesium hydroxide, oxidation Molybdenum compounds such as molybdenum and zinc molybdenate, zinc borate, zinc nitrate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C -Glass, L-glass, D-glass, S-glass, M-glass G20, short glass fibers (including fine glass powders such as E glass, T glass, D glass, S glass, and Q glass), hollow. In addition to inorganic fillers such as glass and spherical glass, organic fillers such as styrene type, butadiene type, acrylic type rubber powder, core shell type rubber powder, silicone resin powder, silicone rubber powder, and silicone composite powder, etc. Can be mentioned. These fillers may be used alone or in combination of two or more.
Among these, one 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 and hydroxides are preferable. Aluminum, aluminum nitride, boron nitride, and forsterite are more preferred. By using these fillers, the cured product of the resin composition tends to have improved properties such as thermal expansion characteristics, dimensional stability, and flame retardancy.

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, but when the resin solid content in the resin composition is 100 parts by mass, it is not particularly limited. It is preferably 30 parts by mass or more, and more preferably 50 parts by mass or more. The upper limit is preferably 1600 parts by mass or less, more preferably 500 parts by mass or less, and particularly preferably 300 parts by mass or less. Alternatively, the content of the filler may be 75 to 250 parts by mass or 100 to 200 parts by mass. By setting the content of the filler in this range, the moldability of the resin composition tends to be improved.
The resin composition may contain only one type of filler, or may contain two or more types of filler. When two or more kinds are contained, it is preferable that the total amount is within the above range.

Here, when using the filler, it is preferable to use at least one selected from the group consisting of a silane coupling agent and a wet dispersant in combination.
As the silane coupling agent, those generally used for surface treatment of inorganic substances can be preferably used, and the type thereof is not particularly limited. Specifically, aminosilanes such as γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxylane, γ-glycidoxypropyltrimethoxysilane, β- (3,4). -Epoxycyclohexyl) Epoxysilanes such as ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilanes, vinylsilanes such as vinyl-tri (β-methoxyethoxy) silanes, N-β- (N-vinylbenzylaminoethyl)- Examples thereof include cationicsilane type such as γ-aminopropyltrimethoxysilane hydrochloride and phenylsilane type. The silane coupling agent may be used alone or in combination of two or more.
Further, as the wet dispersant, those generally used for paints can be preferably used, and the type thereof is not particularly limited. Preferably, a copolymer-based wet dispersant is used, and specific examples thereof include DISPERBYK-110, 111, 161 and 180, 2009, 2152, BYK-W996, BYK-W9010 manufactured by Big Chemie Japan Co., Ltd. , BYK-W903, BYK-W940 and the like. The wet dispersant may be used alone or in combination of two or more.

The content of the silane coupling agent is not particularly limited, and may be about 1 part by mass 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 dispersant (particularly the wet dispersant) 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. Examples of other components include oxetane resins, benzoxazine compounds, flame retardants, curing accelerators, organic solvents and the like.

[Oxetane resin]
The oxetane resin is not particularly limited, and is, for example, oxetane, alkyl oxetane (for example, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxatan, etc.), 3-methyl-. 3-methoxymethyl oxetane, 3,3-di (trifluoromethyl) perfluoxetane, 2-chloromethyl oxetane, 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (Toa Synthetic Co., Ltd.) Products), OXT-121 (Products of Toa Synthetic Co., Ltd.) and the like. These oxetane resins may be used alone or in combination of two or more.

[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 for example, bisphenol A type benzoxazine BA-BXZ (product of Konishi Chemical Co., Ltd.), bisphenol F. Examples thereof include type benzoxazine BF-BXZ (product of Konishi Chemical Co., Ltd.) and bisphenol S type benzoxazine BS-BXZ (product of Konishi Chemical Co., Ltd.). These benzoxazine compounds may be used alone or in combination of two or more.

[Flame retardants]
The resin composition according to the present embodiment may contain a flame retardant other than the above-mentioned phosphorus-based flame retardant (C) in order to further improve the flame resistance. Known flame retardants can be used, for example, brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl (meth) acrylate. , Pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, halogenated flame retardants such as chlorinated paraffin, aluminum hydroxide, magnesium hydroxide, Examples thereof include 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 alone or in combination of two or more.

The content of the flame retardant is preferably 1 part by mass or more, and more preferably 5 parts by mass or more, with respect to 100 parts by mass of the resin solid content in the 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.
Only one kind of flame retardant may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount is within the above 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 usually used as a curing accelerator such as maleimide compounds, cyanate esters compounds, and epoxy compounds, and organic metal salts (for example, zinc octylate, zinc naphthenate, cobalt naphthenate, etc.). Copper naphthenate, iron acetylacetone, nickel octylate, manganese octylate, etc.), phenolic compounds (eg, phenol, xylenol, cresol, resorcin, catechol, octylphenol, nonylphenol, etc.), alcohols (eg, 1-butanol, 2-ethyl) Hexanol, etc.), imidazoles (eg, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc.), and derivatives such as carboxylic acids of these imidazoles or adducts of acid anhydrides thereof, amines, etc. (For example, dicyandiamide, benzyldimethylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), phosphorus compounds (eg, phosphine-based compounds, phosphinoxide-based compounds, phosphonium salt-based compounds, diphosphin-based compounds, etc.), epoxys. -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.). The curing accelerator may be used alone or in combination of two or more.

The content of the curing accelerator may be 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 this embodiment may contain an organic solvent. In this case, the resin composition according to the present embodiment is in the form (solution or varnish) in which at least a part, preferably all of the above-mentioned various resin components 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, preferably all of the above-mentioned various resin components, and the polar organic solvent is, for example, a ketone. Classes (eg, 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, acetate, etc.) Examples thereof include isoamyl, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.) amides (eg, dimethoxyacetamide, dimethylformamide, etc.), and examples of the non-polar organic solvent include aromatic hydrocarbons (eg, toluene, xylene). Etc.). These organic solvents may be used alone or in combination of two or more.

The resin composition according to the present embodiment may contain various polymer compounds such as thermosetting resins, thermoplastic resins, and oligomers thereof, and various additives other than the above components. Additives include UV absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, flow modifiers, lubricants, defoaming agents, leveling agents, gloss. Agents, polymerization inhibitors and the like can be mentioned. These additives may be used alone or in combination of two or more.

[Method for preparing resin composition]
The resin composition according to the present embodiment can be prepared according to a conventional method, and contains a thermosetting compound (A), a thermoplastic elastomer (B) and a phosphorus-based flame retardant (C), and other optional components described above. The preparation method is not particularly limited as long as it is a method for obtaining a resin composition uniformly containing. For example, the thermosetting compound (A), the thermoplastic elastomer (B), the phosphorus-based flame retardant (C), and the above-mentioned other optional components are sequentially added to the solvent and sufficiently stirred to relate to the present embodiment. The resin composition can be easily prepared.

[Prepreg]
The prepreg according to the present embodiment includes a base material and a resin composition impregnated or coated on the base material. Here, the resin composition is a resin composition containing the above-mentioned 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 coating the base material with the resin composition according to the present embodiment and then semi-curing it by a method of drying at 120 to 220 ° C. for about 2 to 15 minutes. Be done. In this case, the amount of the resin composition (including the cured product of the resin composition) adhered to the substrate, that is, the amount of the resin composition (including the filler) with respect to the total amount of the prepreg after semi-curing is 20 to 99% by mass. It is preferably in the range.

The base material is not particularly limited as long as it is a base material used for various printed wiring board materials. As the material of the base material, for example, glass fiber (for example, E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass, etc.) Examples thereof include inorganic fibers other than glass (for example, quartz, etc.) and organic fibers (for example, polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.). The form of the base material is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, chopped strand mats, and surfaced mats. These base materials may be used alone or in combination of two or more. Among these base materials, woven fabrics that have undergone super-opening treatment and filling treatment are preferable from the viewpoint of dimensional stability, and silane coupling agents such as epoxy silane treatment and amino silane treatment are preferable from the viewpoint of moisture absorption and heat resistance. A glass woven fabric surface-treated with is preferable. From the viewpoint of electrical characteristics, low dielectric glass cloth made of glass fibers exhibiting low dielectric constant and low dielectric loss tangent properties such as L-glass, NE-glass, and Q-glass is more preferable.

[Resin sheet]
The resin sheet according to this embodiment contains a resin composition. Here, the resin composition is a resin composition containing the above-mentioned 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 from the resin composition according to the present embodiment arranged on the surface of the support. The resin sheet can be used as a build-up film or a dry film solder resist. The method for producing the resin sheet is not particularly limited, but for example, the resin sheet is obtained by applying (coating) a solution prepared by dissolving the resin composition according to the present embodiment in a solvent to a support and drying the resin sheet. The method can be mentioned.

Examples of the support include polyethylene films, polypropylene films, polycarbonate films, polyethylene terephthalate films, ethylene tetrafluoroethylene copolymer films, and release films and polyimide films in which a release agent is applied to the surface of these films. Examples thereof include an organic film base material, a conductor foil such as a copper foil and an aluminum foil, and a plate-like one such as a glass plate, a SUS plate, and an FRP, but the present invention is not particularly limited.

As a coating method (coating method), for example, a method in which a solution obtained by dissolving the resin composition according to the present embodiment in a solvent is coated on a support with a bar coater, a die coater, a doctor blade, a baker applicator, or the like. Can be mentioned. Further, after drying, the support can be peeled off or etched from the resin sheet on which the support and the resin composition are laminated to obtain a single-layer sheet (resin sheet). A support is used by supplying a solution obtained by dissolving the resin composition according to the present embodiment in a solvent into a mold having a sheet-shaped cavity and drying the resin composition to form a sheet. It is also possible to obtain a single-layer sheet (resin sheet) without any need.

In the production of the single-layer sheet or the resin sheet with a support according to the present embodiment, the drying conditions for removing the solvent are not particularly limited, but the solvent in the resin composition can be easily removed and dried. From the viewpoint of suppressing the progress of curing over time, a temperature of 20 ° C. to 200 ° C. for 1 to 90 minutes is preferable. Further, in the single-layer sheet or the resin sheet with a support, the resin composition can be used in an uncured state in which the solvent is simply dried, or if necessary, it is made into a semi-cured state (B stage). It can also be used. Further, the thickness of the resin layer of the single-layer sheet or the resin sheet with a support according to the present embodiment can be adjusted by the concentration of the solution of the resin composition according to the present embodiment and the coating thickness, and is not particularly limited. From the viewpoint of facilitating the removal of the solvent during drying, 0.1 to 500 μm is preferable.

[Copper foil-clad laminate]
The copper foil-clad laminate according to the present embodiment is a copper foil-clad laminate in which copper foil is laminated so as to be in contact with one or more surfaces selected from the group consisting of a prepreg and a resin sheet.
The prepreg comprises a substrate and a resin composition impregnated or coated on the substrate.
The resin sheet contains a resin composition and contains
The resin composition contains a thermoplastic compound (A), a thermoplastic elastomer (B), and a phosphorus-based flame retardant (C), and the content of the thermoplastic elastomer (B) in the resin composition is high. It is 1 to 30 parts by mass with respect to 100 parts by mass of the resin solid content, 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. And
The roughness Rz of the copper foil surface measured according to JIS B0601: 2013 is 0.2 to 4.0 μm.
Here, the roughness Rz of the copper foil surface indicates the roughness of the copper foil surface on the side in contact with one or more types selected from the group consisting of the prepreg and the resin sheet.

When both the prepreg and the resin sheet are used in the copper foil-clad laminate according to the present embodiment, the resin compositions used for them may be the same or different. In the copper foil-clad laminate of the present embodiment, one or more selected from the group consisting of the prepreg and the resin sheet may be in a semi-cured state (B stage) or in a completely cured state (C stage). You may. In the semi-cured state (B stage), each component contained in the resin composition does not actively start a reaction (curing), but the resin composition is heated to a dry state, that is, to the extent that it is not sticky. This refers to a state in which the solvent is volatilized, and includes a state in which the solvent is only volatilized without being cured without heating. In the present embodiment, the minimum melt viscosity in the semi-cured state (B stage) is usually 20,000 Pa · s or less. The lower limit of the minimum melt viscosity is, for example, 10 Pa · s or more. In this embodiment, the minimum melt viscosity is measured by the following method. That is, 1 g of the resin powder collected from the resin composition is used as a sample, and the minimum melt viscosity is measured with a rheometer (ARES-G2 (trade name) manufactured by TA Instruments). Here, a disposable plate having a plate diameter of 25 mm is used, and the resin is used under the conditions of a heating rate of 2 ° C./min, a frequency of 10.0 rad / sec, and a strain of 0.1% in a range of 40 ° C. or higher and 180 ° C. or lower. Measure the minimum melt viscosity of the powder.

In the present embodiment, "a copper foil is laminated so as to be in contact with one or more surfaces selected from the group consisting of a prepreg and a resin sheet" means that an adhesive layer is formed between the prepreg or the resin sheet and the copper foil. It does not include layers such as, and means that the prepreg or resin sheet and the copper foil are in direct contact with each other. As a result, the copper peel strength of the copper foil-clad laminate is increased, and the insulation reliability of the printed wiring board is improved.

It is preferable that the copper foil-clad laminate of the present embodiment has a high copper foil peel 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. The upper limit of the copper foil peel strength is not particularly specified, but is practically 1.4 kN / m or less, for example.

It is preferable that the copper foil-clad laminate of the present embodiment has a small dielectric loss tangent. Specifically, using a sample obtained by removing the copper foil from the copper foil-clad laminate by etching, the measured value of the dielectric tangent at 10 GHz measured by the cavity resonator perturbation method is 0. It is preferably less than 0035, 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.

[Copper foil]
In the copper foil in the present embodiment, the roughness Rz of the copper foil surface measured according to JIS B0601: 2013 is adjusted to 0.2 to 4.0 μm. When the roughness Rz of the copper foil surface is less than 0.2 μm, the roughness of the copper foil surface becomes too small and the copper foil peel strength becomes insufficient. On the other hand, when the roughness Rz of the copper foil surface exceeds 4.0, the roughness of the copper foil surface becomes too large and the transmission loss characteristic deteriorates. The roughness Rz of the copper foil surface is preferably 0.5 to 4 μm, more preferably 0.6 to 3 μm, and further preferably 0.7 to 2 μm from the viewpoint of reducing transmission loss.
Here, the roughness Rz of the copper foil surface can be measured according to the method described in Examples described later.

The copper foil-clad laminate according to the present embodiment is a copper foil arranged so as to directly contact one or more of the prepreg and / or the resin sheet according to the present embodiment and one or both sides of the prepreg and / or the resin sheet. And have. As a method for manufacturing a copper 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 and arranging copper foils on one or both sides thereof for laminating and molding. Can be mentioned.
The copper foil is not particularly limited as long as it is used as a material for printed wiring boards and the roughness Rz of the copper foil surface measured according to JIS B0601: 2013 satisfies the above range, and is not particularly limited. For example, rolled copper foil and electrolytic copper. Examples thereof include copper foil such as foil, and among them, electrolytic copper foil is preferable from the viewpoint of copper foil peel strength and formability of fine wiring. The thickness of the copper foil is not particularly limited and may be about 1.5 to 70 μm. Examples of the forming method include a method usually used for forming a laminated plate for a printed wiring board and a multilayer plate, and more specifically, a multi-stage press machine, a multi-stage vacuum press machine, a continuous forming machine, an autoclave forming machine and the like are used. Then, a method of laminating molding at a temperature of about 180 to 350 ° C., a heating time of about 100 to 300 minutes, and a surface pressure of about 20 to 100 kg / cm ² can be mentioned.

Further, a multilayer board can be obtained by laminating and molding the prepreg and / or the resin sheet according to the present embodiment in combination with the wiring board for the inner layer separately prepared. As a method for manufacturing a multilayer board, for example, copper foils having a thickness of about 35 μm are arranged on both sides of the prepreg and / or the resin sheet according to the present embodiment in which one or more sheets are stacked, and laminated by the above molding method. After the copper foil-clad laminate is formed, an inner layer circuit is formed, and the circuit is blackened to form an inner layer circuit board. After that, the inner layer circuit board and the prepreg and / or resin according to the present embodiment are formed. A multilayer plate can be produced by alternately arranging the sheets one by one, further arranging the copper foil on the outermost layer, and laminating and molding under the above conditions, preferably under vacuum. The copper foil-clad laminate according to the present embodiment can be suitably used as a printed wiring board.

[Printed wiring board]
The printed wiring board according to the present embodiment includes an insulating layer and a conductor layer arranged on the surface of the insulating layer, and the insulating layer includes a layer formed from the resin composition according to the present embodiment. Such a printed wiring board can be manufactured according to a conventional method, and the manufacturing method thereof is not particularly limited, but for example, it can be manufactured by using the above-mentioned copper foil-clad laminate. The following is an example of a method for manufacturing a printed wiring board. First, the above-mentioned copper foil-clad laminate is prepared. Next, the surface of the copper foil-clad laminate is etched to form an inner layer circuit, and an inner layer substrate is produced. The inner layer circuit surface of this inner layer substrate is surface-treated to increase the adhesive strength as necessary, then the required number of the above-mentioned prepregs are laminated on the inner layer circuit surface, and the copper foil for the outer layer circuit is laminated on the outer side thereof. Then, heat and pressurize to integrally mold. In this way, a multi-layer laminated board in which an insulating layer made of a base material and a cured product of a resin composition is formed between an inner layer circuit and a copper foil for an outer layer circuit is manufactured. Next, after drilling holes for through holes and via holes in the multilayer laminated board, a plated metal film for conducting the inner layer circuit and the copper foil for the outer layer circuit is formed on the wall surface of the holes, and further, the outer layer circuit is formed. A printed wiring board is manufactured by forming an outer layer circuit by etching a copper foil for use.

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 is the resin composition according to the present embodiment described above and a cured product thereof. The configuration includes at least one of them. That is, the prepreg according to the above-mentioned embodiment (including at least one of the substrate and the resin composition according to the present embodiment impregnated or coated thereto and the cured product thereof), and the copper foil according to the above-mentioned present embodiment. The layer of the resin composition of the upholstered laminated board (the layer containing at least one of the resin composition of the present invention and the cured product thereof) is an insulating layer containing at least one of the resin composition and the cured product thereof according to the present embodiment. Will be composed of.

[Semiconductor device]
The semiconductor device of this embodiment can be manufactured by mounting a semiconductor chip on a conductive portion of the printed wiring board of this embodiment. Here, the conduction point is a place where an electric signal is transmitted in the multilayer printed wiring board, and the place may be a surface or an embedded place. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method for mounting the semiconductor chip when manufacturing the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and a bump. None Examples thereof include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.
In the following Examples and Comparative Examples, the measurement and evaluation of each physical property were performed according to the following.

(Roughness Rz of copper foil surface)
For the copper foils A, B, and C used in Examples or Comparative Examples, the roughness Rz of the surface in contact with the laminated prepreg was measured according to JIS B0601: 2013.

(Transmission loss)
A microstrip line was formed by etching the copper foil-clad laminate obtained in Examples or Comparative Examples so that the characteristic impedance was 50Ω, and a network analyzer N5227A manufactured by Keysight Technology Co., Ltd. was used. The transmission coefficient was measured to determine the transmission loss at a frequency of 28 GHz.
A, B, C and D in the table were evaluated according to the following criteria. The closer the transmission loss is to 0, the better.
A: -0.39 dB / m or less B: -0.39 dB / m or more, -0.41 dB / m or less C: -0.41 dB / m or more, -0.43 dB / m or less D: -0.43 dB / Over m

(Copper foil peel strength)
For the copper foil-clad laminate obtained in the examples or comparative examples, a test piece (30 mm × 150 mm × 0.8 mm) with a copper foil was prepared, and according to JIS C6481: 1996, the number of tests was 3 for the copper foil. The peel strength was measured, and the average value of the lower limit was used 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 the 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 the copper foil was used according to JIS C5016: 1994. After attaching an insulatingly coated electric wire to the terminal part of the conductor pattern of the sample, fixing the upper end part of the substrate to the plunger, and installing a load of 1 kgf on the lower end part, in the energized state, at an angle of 135 ° and a speed of 175 cpm, both directions. The number of reciprocating bends was measured from the start of bending to the disconnection. A, B, C and D in the table were evaluated according to the following criteria.
A: 90 times or more B: 60 times or more and less than 90 times C: 40 times or more and less than 60 times D: less than 40 times

(Solder heat resistance)
For the copper foil-clad laminate obtained in the examples or comparative examples, a test piece (50 mm × 50 mm × 0.8 mm) with a copper foil was prepared according to JIS C5012: 1992, and the solder heated to 288 ° C. After floating the test piece in the tank for 30 minutes, it was visually confirmed whether there was any abnormality such as delamination in the copper foil-clad laminate. A and B in the table 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 conversion) 1.28 mol) and 194.6 g (1.92 mol) of triethylamine (1.5 mol with respect to 1 mol of hydroxy group) were dissolved in 1800 g of dichloromethane, and this was used as Solution 1.

Cyanogen chloride 125.9 g (2.05 mol) (1.6 mol with respect to 1 mol of hydroxy group), dichloromethane 293.8 g, 36% hydrochloric acid 194.5 g (1.92 mol) (1.5 mol with respect to 1 mol of hydroxy group), Solution 1 was poured over 30 minutes while maintaining a liquid temperature of −2 to −0.5 ° C. with 1205.9 g of water under stirring. After pouring 1 solution, the mixture was stirred at the same temperature for 30 minutes, and then a solution (solution 2) in which 65 g (0.64 mol) of triethylamine (0.5 mol with respect to 1 mol of hydroxy group) was dissolved in 65 g of dichloromethane was used for 10 minutes. I poured it over. After pouring 2 of the solution, the reaction was completed by stirring at the same temperature for 30 minutes.

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

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

(Each component contained in the resin composition)
The following components were used as the components contained in the resin compositions of Examples or Comparative Examples.
Maleimide resin: MIR-3000, Polyphenylene ether resin manufactured by Nippon Kayaku Co., Ltd .: OPE-2St2200, manufactured by Mitsubishi Gas Chemical Company, Inc., number average molecular weight 2200, vinyl group equivalent: 1100 g / eq.
Thermoplastic Elastomer: Hydrogenated Styrene Thermoplastic Elastomer (SEBS), Tuftec H-1043, Phosphorus Flame Retardant 1: 1,3-Phenylenbis (2,6-di-xylenyl phosphate) manufactured by Asahi Kasei Co., Ltd., PX-200, Phosphorus Flame Retardant manufactured by Daihachi Chemical Industry Co., Ltd .2: Cyclic organophosphazen compound, Ravitor FP-300B, Filler manufactured by Fushimi Pharmaceutical Co., Ltd .: Spherical silica, SC2050-MB, Admatex Co., Ltd. Made, average particle diameter 0.5 μm

(Copper foil)
The copper foil used in the examples or comparative examples is shown below. The roughness Rz is the roughness Rz of the surface in contact with the laminated prepreg in the example or comparative example measured by the method described above. In the examples or comparative examples, these roughness surfaces are arranged so as to be in contact with the surface of the laminated prepreg to obtain a copper foil-clad laminate.
Copper foil A: TQ-M5-VSP (manufactured by Mitsui Mining & Smelting Co., Ltd.), electrolytic copper foil, Rz = 0.7 μm, thickness 12 μm
Copper foil B: 3EC-M3-VLP (manufactured by Mitsui Mining & Smelting Co., Ltd.), electrolytic copper foil, Rz = 4.0 μm, thickness 12 μm
Copper foil C: 3EC-III (manufactured by Mitsui Mining & Smelting Co., Ltd.), electrolytic copper foil, Rz = 5.5 μm, thickness 12 μm

(Example 1)
65 parts by mass of maleimide resin MIR-3000, 15 parts by mass of thermoplastic elastomer H-1043 (styrene ratio 67%), 20 parts by mass of phosphorus-based flame retardant PX-200, 100 parts by mass of filler SC2050-MB. , Ethylmethylketone is used to mix and dilute to prepare a varnish, the obtained varnish is impregnated and coated on a glass woven cloth having a thickness of 0.075 mm, and heated and dried at 160 ° C. for 5 minutes to form a resin composition. A prepreg having a content of 60% by mass was obtained. Eight obtained prepregs were stacked and the copper foil A shown above was placed one above the other, and laminated and molded at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, and a copper foil with an insulating layer thickness of 0.8 mm was formed. A stretched laminated board was obtained.

(Example 2)
65 parts by mass of polyphenylene ether resin OPE-2St2200, 15 parts by mass of thermoplastic elastomer H-1043 (styrene ratio 67%), 20 parts by mass of phosphorus-based flame retardant PX-200, 100 parts by mass of filler SC2050-MB, To prepare a varnish by mixing and diluting with ethyl methyl ketone, impregnating the obtained varnish on a glass woven cloth having a thickness of 0.075 mm, and heating and drying at 160 ° C. for 5 minutes to form a resin composition. A prepreg having a substance content of 60% by mass was obtained. Eight obtained prepregs were stacked and the copper foil A shown above was placed one above the other, and laminated and molded at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, and a copper foil with an insulating layer thickness of 0.8 mm was formed. A stretched laminated board was obtained.

(Example 3)
75 parts by mass of polyphenylene ether resin OPE-2St2200, 5 parts by mass of thermoplastic elastomer H-1043 (styrene ratio 67%), 20 parts by mass of phosphorus-based flame retardant PX-200, 100 parts by mass of filler SC2050-MB, To prepare a varnish by mixing and diluting with ethyl methyl ketone, impregnating the obtained varnish on a glass woven cloth having a thickness of 0.075 mm, and heating and drying at 160 ° C. for 5 minutes to form a resin composition. A prepreg having a substance content of 60% by mass was obtained. Eight obtained prepregs were stacked and the copper foil A shown above was placed one above the other, and laminated and molded at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, and a copper foil with an insulating layer thickness of 0.8 mm was formed. A stretched laminated board was obtained.

(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 (styrene ratio 67%), phosphorus-based flame retardant PX- 20 parts by mass of 200 and 100 parts by mass of the filler SC2050-MB are mixed and diluted with ethyl methyl ketone to prepare a varnish, and the obtained varnish is impregnated into a glass woven cloth having a thickness of 0.075 mm. The coating was applied and dried by heating at 160 ° C. for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight obtained prepregs were stacked and the copper foil A shown above was placed one above the other, and laminated and molded at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, and a copper foil with an insulating layer thickness of 0.8 mm was formed. A stretched laminated board was obtained.

(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 (styrene ratio 67%), phosphorus-based flame retardant PX- 20 parts by mass of 200 and 100 parts by mass of the filler SC2050-MB are mixed and diluted with ethyl methyl ketone to prepare a varnish, and the obtained varnish is impregnated into a glass woven cloth having a thickness of 0.075 mm. The coating was applied and dried by heating at 160 ° C. for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight obtained prepregs were stacked and the copper foil B shown above was placed one above the other, and laminated and molded at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, and a copper foil with an insulating layer thickness of 0.8 mm was formed. A stretched laminated board was obtained.

(Example 6)
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 (styrene ratio 67%), phosphorus-based flame retardant Rabbitl FP 20 parts by mass of -300B and 100 parts by mass of the filler SC2050-MB were mixed and diluted with ethylmethylketone to prepare a varnish, and the obtained varnish was put into a glass woven cloth having a thickness of 0.075 mm. It was impregnated and dried by heating at 160 ° C. for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight obtained prepregs were stacked and the copper foil A shown above was placed one above the other, and laminated and molded at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, and a copper foil with an insulating layer thickness of 0.8 mm was formed. A stretched laminated board was obtained.

(Comparative Example 1)
81 parts by mass of maleimide resin MIR-3000, 19 parts by mass of thermoplastic elastomer H-1043 (styrene ratio 67%), 100 parts by mass of filler SC2050-MB, were mixed and diluted with ethyl methyl ketone. A varnish was prepared, and the obtained varnish was impregnated and coated on a glass woven cloth having a thickness of 0.075 mm and dried by heating at 160 ° C. for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight obtained prepregs were stacked and the copper foil A shown above was placed one above the other, and laminated and molded at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, and a copper foil with an insulating layer thickness of 0.8 mm was formed. A stretched laminated board was obtained.

(Comparative Example 2)
81 parts by mass of polyphenylene ether resin OPE-2St2200, 19 parts by mass of thermoplastic elastomer H-1043 (styrene ratio 67%), 100 parts by mass of filler SC2050-MB, were mixed and diluted with ethyl methyl ketone. The obtained varnish was impregnated and coated on a glass woven cloth having a thickness of 0.075 mm and dried by heating at 160 ° C. for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight obtained prepregs were stacked and the copper foil A shown above was placed one above the other, and laminated and molded at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, and a copper foil with an insulating layer thickness of 0.8 mm was formed. A stretched laminated board was obtained.

(Comparative Example 3)
94 parts by mass of polyphenylene ether resin OPE-2St2200, 6 parts by mass of thermoplastic elastomer H-1043 (styrene ratio 67%), 100 parts by mass of filler SC2050-MB, were mixed and diluted with ethyl methyl ketone. The obtained varnish was impregnated and coated on a glass woven cloth having a thickness of 0.075 mm and dried by heating at 160 ° C. for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight obtained prepregs were stacked and the copper foil A shown above was placed one above the other, and laminated and molded at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, and a copper foil with an insulating layer thickness of 0.8 mm was formed. A stretched laminated board was obtained.

(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 (styrene ratio 67%), filler SC2050-MB. 100 parts by mass is mixed and diluted with ethyl methyl ketone to prepare a varnish, and the obtained varnish is impregnated into a 0.075 mm thick glass woven cloth, coated, and dried by heating at 160 ° C. for 5 minutes. A prepreg having a resin composition content of 60% by mass was obtained. Eight obtained prepregs were stacked and the copper foil A shown above was placed one above the other, and laminated and molded at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, and a copper foil with an insulating layer thickness of 0.8 mm was formed. A stretched laminated board was obtained.

(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 (styrene ratio 67%), phosphorus-based flame retardant PX- 40 parts by mass of 200 and 100 parts by mass of the filler SC2050-MB are mixed and diluted with ethylmethylketone to prepare a varnish, and the obtained varnish is impregnated into a 0.075 mm thick glass woven cloth. The coating was applied and dried by heating at 160 ° C. for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight obtained prepregs were stacked and the copper foil A shown above was placed one above the other, and laminated and molded at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, and a copper foil with an insulating layer thickness of 0.8 mm was formed. A stretched laminated board was obtained.

(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 (styrene ratio 67%), phosphorus-based flame retardant Rabbitl FP 40 parts by mass of -300B and 100 parts by mass of the filler SC2050-MB were mixed and diluted with ethylmethylketone to prepare a varnish, and the obtained varnish was put into a glass woven cloth having a thickness of 0.075 mm. It was impregnated and dried by heating at 160 ° C. for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight obtained prepregs were stacked and the copper foil A shown above was placed one above the other, and laminated and molded at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, and a copper foil with an insulating layer thickness of 0.8 mm was formed. A stretched laminated board was obtained.

(Comparative Example 7)
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 (styrene ratio 67%), phosphorus-based flame retardant PX- 20 parts by mass of 200 and 100 parts by mass of the filler SC2050-MB are mixed and diluted with ethyl methyl ketone to prepare a varnish, and the obtained varnish is impregnated into a glass woven cloth having a thickness of 0.075 mm. The coating was applied and dried by heating at 160 ° C. for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight obtained prepregs were stacked and the copper foil C shown above was placed one above the other, and laminated and molded at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, and a copper foil with an insulating layer thickness of 0.8 mm was formed. A stretched laminated board was obtained.

(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-based flame retardant PX-200, 100 parts by mass of filler SC2050-MB. , Ethylmethylketone is used to mix and dilute to prepare a varnish, the obtained varnish is impregnated and coated on a glass woven cloth having a thickness of 0.075 mm, and heated and dried at 160 ° C. for 5 minutes to form a resin composition. A prepreg having a content of 60% by mass was obtained. Eight obtained prepregs were stacked and the copper foil A shown above was placed one above the other, and laminated and molded at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, and a copper foil with an insulating layer thickness of 0.8 mm was formed. A stretched laminated board was obtained.

(Comparative Example 9)
Maleimide resin MIR-3000 by 10 parts by mass, polyphenylene ether resin OPE-2St2200 by 20 parts by mass, SNCN by 10 parts by mass, thermoplastic elastomer H-1043 (styrene ratio 67%) by 40 parts by mass, phosphorus-based flame retardant PX- 20 parts by mass of 200 and 100 parts by mass of the filler SC2050-MB are mixed and diluted with ethyl methyl ketone to prepare a varnish, and the obtained varnish is impregnated into a glass woven cloth having a thickness of 0.075 mm. The coating was applied and dried by heating at 160 ° C. for 5 minutes to obtain a prepreg having a resin composition content of 60% by mass. Eight obtained prepregs were stacked and the copper foil A shown above was placed one above the other, and laminated and molded at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes, and a copper foil with an insulating layer thickness of 0.8 mm was formed. A stretched laminated board was obtained.

Each physical property was evaluated using the copper foil-clad laminates obtained in Examples 1 to 6 and Comparative Examples 1 to 9, and the evaluation results are shown in Table 1.

As shown in Table 1 above, the copper foil-clad laminates of Examples 1 to 6 have good copper foil peel strength and low transmission loss, and are also excellent in crack resistance and solder heat resistance. confirmed.

This application is based on a Japanese patent application (Japanese Patent Application No. 2020-204372) filed with the Japan Patent Office on December 9, 2020, the contents of which are incorporated herein by reference.

The copper foil-clad laminate of the present invention has industrial applicability as a material for constituting a printed wiring board, a semiconductor device, or the like.

Claims

A copper foil-clad laminate in which copper foil is laminated so as to be in contact with one or more surfaces selected from the group consisting of a prepreg and a resin sheet.
The prepreg comprises a substrate and a resin composition impregnated or coated on the substrate.
The resin sheet contains a resin composition and contains
The resin composition contains 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.
A copper foil-clad laminate having a roughness Rz of the copper foil surface measured according to JIS B0601: 2013 of 0.2 to 4.0 μm.
The copper foil-clad laminate according to claim 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.
The invention according to claim 1 or 2, wherein the phosphorus-based flame retardant (C) is at least one selected from the group consisting of an aromatic condensed phosphoric acid ester (C-1) and a cyclic phosphazene compound (C-2). Copper foil-clad laminate.
The aromatic condensed phosphoric acid 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 copper foil-clad laminate according to any one of claims 1 to 3.

(In equation (2), n represents an integer of 3 to 6.)
The copper foil-clad laminate according to any one of claims 1 to 4, wherein the thermoplastic elastomer (B) is a styrene-based elastomer.
The styrene-based elastomer is 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 copper foil-clad laminate according to claim 5, which is one or more selected from the group consisting of.
Claims 1 to 6 include the thermosetting compound (A) at least one selected from the group consisting of a cyanic acid ester compound, a maleimide compound, a polyphenylene ether compound, an epoxy compound, a phenol compound, and a curable polyimide compound. The copper foil-clad laminate according to any one of the above.
The copper foil-clad laminate according to any one of claims 1 to 7, wherein the resin composition further contains a filler.
The copper foil-clad laminate according to claim 8, wherein the filler is at least one selected from the group consisting of silicas, aluminum hydroxide, aluminum nitride, boron nitride, and forsterite.
The copper foil-clad laminate according to claim 8 or 9, 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.
The copper foil-clad laminate according to any one of claims 1 to 10, wherein the copper foil is an electrolytic copper foil.
A printed wiring board manufactured by using the copper foil-clad laminate according to any one of claims 1 to 11.
A semiconductor device manufactured by using the printed wiring board according to claim 12.