CN108603003B

CN108603003B - Resin composition, prepreg, metal foil-clad laminate, resin sheet, printed wiring board, and semiconductor device

Info

Publication number: CN108603003B
Application number: CN201780009567.7A
Authority: CN
Inventors: 铃木卓也; 浦滨成弘; 若林润
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2016-02-02
Filing date: 2017-01-27
Publication date: 2021-07-20
Anticipated expiration: 2037-01-27
Also published as: JPWO2017135168A1; CN108603003A; JP6880510B2; WO2017135168A1; KR20180104290A; TW201739820A; TWI781918B

Abstract

Provided are a resin composition having excellent dielectric constant, dielectric loss tangent, fine wiring embeddability, heat resistance, and developability, and having physical properties suitable for a protective film and an interlayer insulating layer of a printed wiring board, and a prepreg, a metal foil-clad laminate, a resin sheet, a printed wiring board, and a semiconductor device using the same. A resin composition comprising fluororesin particles (A) having silica particles adhered to the surface thereof and a resin component (B).

Description

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

Technical Field

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

Background

In recent years, high integration and miniaturization of semiconductors widely used in electronic devices, communicators, personal computers, and the like have been accelerated, and data communication used for information communication has been accelerated and increased in capacity. In order to reduce the transmission delay and transmission loss of signals, printed circuit boards are required to have a low dielectric constant (low Dk) and a low dielectric loss tangent (low Df). In order to meet these demands, studies have been made on the use of resin compositions having excellent electrical characteristics (low dielectric constant and low dielectric loss tangent).

Further, as printed wiring boards are reduced in size and increased in density, multilayer layers used in multilayer printed wiring boards are increased in number, and miniaturization and high density of wiring are required. Therefore, the resin composition used for the multilayer is required to have high fluidity during molding and high heat resistance after embedding fine wiring in order to embed fine wiring. In such a resin composition, a fluororesin filler has been studied and used for improving electrical characteristics. For example, patent document 1 discloses a resin composition having excellent electrical characteristics by using a polyphenylene ether resin together with a fluororesin filler. Patent document 2 discloses a resin composition in which a norbornene resin is used together with a fluororesin filler, so that a cured product thereof is excellent in electrical characteristics and adhesion and has good wire embeddability.

Documents of the prior art

Patent document

Patent document 1: japanese Kokai publication No. 2006-516297

Patent document 2: japanese patent laid-open publication No. 2007-177073

Disclosure of Invention

Problems to be solved by the invention

However, the present inventors have found that various problems are present in a cured product using a conventional fluororesin filler.

For example, in patent document 1, the heat resistance of the resulting cured product is insufficient.

In patent document 2, the moisture absorption and heat resistance after the wiring is embedded are insufficient.

The present invention has been made in view of the above problems, and provides a resin composition having excellent dielectric constant, dielectric loss tangent, fine wiring embeddability, heat resistance, and developability when used in a multilayer printed wiring board, and a prepreg, a metal foil-clad laminate, a resin sheet, a printed wiring board, and a semiconductor device using the same.

Means for solving the problems

The present inventors have found that the above problems can be solved by using a resin composition containing silica-coated fluororesin particles (a) and a resin component (B), and have completed the present invention.

That is, the present invention includes the following.

[ 1] A resin composition comprising fluororesin particles (A) covered with silica and a resin component (B).

The resin composition according to [ 1], wherein the silica-coated fluororesin particles (A) have a volume average particle diameter of primary particles of 5 μm or less.

[ 3] the resin composition according to [ 1] or [ 2], wherein the content of the silica-coated fluororesin particles (A) in the resin composition is 3 to 400 parts by mass per 100 parts by mass of the resin solid content in the resin composition.

The resin composition according to any one of [ 1] to [ 3], wherein the resin component (B) contains at least one selected from the group consisting of a maleimide compound, a cyanate ester compound, an epoxy resin, a phenol resin, an oxetane resin, a benzoxazine compound and a compound having an ethylenically unsaturated group.

[ 5 ] the resin composition according to any one of [ 1] to [4 ], further comprising a filler (C) other than the silica-coated fluororesin particles (A).

The resin composition according to any one of [ 1] to [ 5 ], which further comprises a flame retardant (D).

The resin composition according to any one of [ 1] to [ 6 ], further comprising a photo-curing initiator (E).

〔8〕

The resin composition according to item 4, wherein the compound having an ethylenically unsaturated group contains at least one member selected from the group consisting of a 2-functional phenylene ether oligomer having a vinyl group and an oligomer of α -methylstyrene.

〔9〕

The resin composition according to item [4 ], wherein the compound having an ethylenically unsaturated group contains at least one selected from the group consisting of acid-modified bisphenol F type epoxy (meth) acrylate, a compound represented by the following general formula (1), and dipentaerythritol hexa (meth) acrylate.

(in the formula (1), a plurality of R₁Each independently represents a hydrogen atom or a methyl group, a plurality of R₂Each independently represents a hydrogen atom or a methyl group, a plurality of R₃Each independently represents a substituent represented by the following formula (2), a substituent represented by the following formula (3), or a hydroxyl group. ).

(in the formula (3), R₄Represents a hydrogen atom or a methyl group. ).

〔10〕

The resin composition according to [ 9 ], wherein the compound having an ethylenically unsaturated group comprises at least a compound represented by the general formula (1).

[ 11 ] A prepreg comprising a base material and the resin composition according to any one of [ 1] to [ 10 ] impregnated or coated on the base material.

A metal foil-clad laminate comprising at least 1 or more sheets of the prepreg according to [ 11 ] and a metal foil disposed on one or both surfaces of the prepreg.

[ 13 ] A resin sheet comprising a support and the resin composition according to any one of [ 1] to [ 10 ] disposed on a surface of the support.

[ 14 ] A printed wiring board having the resin composition according to any one of [ 1] to [ 10 ].

A semiconductor device having the resin composition according to any one of [ 1] to [ 10 ].

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a resin composition having excellent dielectric constant, dielectric loss tangent, fine wiring embeddability, heat resistance, and developability, and having physical properties suitable for a protective film and an interlayer insulating layer of a printed wiring board, and a prepreg, a metal foil-clad laminate, a resin sheet, a printed wiring board, and a semiconductor device using the resin composition.

Detailed Description

Hereinafter, a mode for carrying out the present invention (hereinafter, referred to as "the present embodiment") will be described in detail. The following embodiments are illustrative of the present invention, and are not intended to limit the present invention to the following. The present invention can be suitably modified within the scope of the gist of the present invention.

In the present specification, "(meth) acryloyl group" means both "acryloyl group" and its corresponding "methacryloyl group", "(meth) acrylate" means both "acrylate" and its corresponding "methacrylate", and "(meth) acrylic acid" means both "acrylic acid" and its corresponding "methacrylic acid". In the present embodiment, the term "resin solid component" or "resin solid component in the resin composition" means components other than the solvent and the filler in the resin composition unless otherwise specified, and the term "100 parts by mass of the resin solid component" means 100 parts by mass in total of the components other than the solvent and the filler in the resin composition.

The resin composition of the present embodiment is characterized by containing silica-coated fluororesin particles (a) and a resin component (B). Hereinafter, each component will be described.

< silica-coated fluororesin pellets (A) >

The silica-coated fluororesin pellets (a) used in the present embodiment are fluororesin pellets having silica adhered to the surface thereof, and include fluororesin pellets and silica pellets adhered to the surface of the fluororesin. The method for adhering the silica particles to the surface of the fluororesin particles is not particularly limited, and may be carried out by simply mixing or by applying vibration after mixing. The adhesion of the silica particles to the surface of the fluororesin particles may be carried out in a dry state. The mixing ratio of the fluororesin particles and the silica particles is not particularly limited. Even in a small amount, if silica particles are present on the surface of the fluororesin particles, the flow property improving effect of the silica particles is exhibited, and the wiring embeddability of the resin composition of the present embodiment and the moisture absorption heat resistance after the wiring embedding can be improved.

The fluororesin particles used in the silica-coated fluororesin particles (a) in the present embodiment are not particularly limited, and examples thereof include Polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-chlorotrifluoroethylene copolymer (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), and polyvinylidene fluoride (PVDF). Among them, PTFE is preferable from the viewpoint of excellent electrical characteristics. These may be used singly or in admixture of 2 or more kinds as appropriate.

The fluororesin particles preferably have a volume average particle diameter of 5 μm or less, more preferably 4 μm or less, and still more preferably 3 μm or less, from the viewpoint of improving the embeddability of fine wiring. From the viewpoint of improving the electrical characteristics, the volume average particle diameter of the primary particles is preferably 0.005 μm or more, more preferably 0.01 μm or more, and still more preferably 0.02 μm or more.

The "volume average particle diameter" in the present specification means an arithmetic average diameter of a volume-based particle diameter distribution. The volume average particle diameter can be measured by, for example, a wet laser diffraction scattering method.

The content of the silica particles in the silica-coated fluororesin pellet (a) is not particularly limited, and is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, and further preferably 0.01 mass% or more with respect to the mass of the fluororesin pellet from the viewpoint of improving the flowability. From the viewpoint of exhibiting the electrical characteristics of the fluororesin pellets, the content is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less.

The silica particles are not particularly limited as long as the volume average particle diameter of the primary particles is smaller than the volume average particle diameter of the fluororesin particles. Among these, the volume average particle diameter of the primary particles is preferably 200nm or less, preferably 100nm or less, more preferably 70nm or less, and still more preferably 50nm or less, from the viewpoint of expressing the electrical characteristics of the fluororesin. From the viewpoint of improving the fluidity, the volume average particle diameter of the primary particles is preferably 0.3nm or more, more preferably 0.5nm or more, and still more preferably 1nm or more.

The silica-coated fluororesin particles (a) preferably have a volume average particle diameter of primary particles of 5 μm or less, more preferably 4 μm or less, and still more preferably 3 μm or less, from the viewpoint of improving the embeddability of fine wiring, the dielectric constant, and the dielectric loss tangent, and still more preferably 2 μm or less. From the viewpoint of improving the electrical characteristics, the volume average particle diameter of the primary particles is preferably 0.005 μm or more, more preferably 0.01 μm or more, and still more preferably 0.02 μm or more.

The silica-coated fluororesin particles may be commercially available ones, and examples thereof include 0.5. mu.mPTE-YA (trade name) and PTFE-YA4 (3.0. mu.m, trade name) (see above, manufactured by Admatechs Company Limited).

The content of the silica-coated fluororesin particles (a) in the resin composition of the present embodiment is not particularly limited, and is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and further preferably 30 parts by mass or more, per 100 parts by mass of the resin solid content in the resin composition, from the viewpoint of improving the electrical characteristics of the resin composition. From the viewpoint of improving heat resistance, it is preferably 400 parts by mass or less, more preferably 300 parts by mass or less, still more preferably 200 parts by mass or less, and still more preferably 100 parts by mass or less, per 100 parts by mass of the resin solid content in the resin composition.

< resin component (B) >

The resin component (B) used in the present embodiment can be used in various forms depending on the electrical properties and the like obtained by covering the fluororesin particles (a) with silica, and the properties such as flame retardancy, heat resistance, thermal expansion properties and the like of a cured product obtained by curing required in the field using the resin composition. For example, when adhesiveness is required, an epoxy resin is exemplified, when heat resistance is required, a maleimide compound, a cyanate ester compound, and a benzoxazine compound are exemplified, when thermosetting or photocuring is required, a compound having an ethylenically unsaturated group is exemplified, and further, a phenol resin, an oxetane resin, and the like can be used.

One or more than 2 kinds of them may be used, or may be suitably mixed and used.

The details of the resin component (B) will be described below.

< Maleimide Compound >

The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2-bis {4- (4-maleimidophenoxy) -phenyl } propane, 4-diphenylmethane bismaleimide, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, phenylmethaneimide, o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, o-phenylenebdicitraquinimide, m-phenylenebdicitraquinacridimide, m-phenylenebisconimide, p-phenylenebisconiumimide, p-phenylenebisconiumoniumimide, m-phenylenebisconiumoniumimide, p-oniumoniumoniumimide, p-aryloniumoniumoniumimide, p-phenylenebisconiumoniumoniumoniumoniumoniumoniumoniumoniumimides, and, P-phenylenebdicitraconimide, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane, 3-dimethyl-5, 5-diethyl-4, 4-diphenylmethane bismaleimide, 4-methyl-1, 3-phenylenebismaleimide, 1, 6-bismaleimide- (2,2, 4-trimethyl) hexane, 4-diphenyl ether bismaleimide, 4-diphenylsulfone bismaleimide, 1, 3-bis (3-maleimidophenoxy) benzene, 1, 3-bis (4-maleimidophenoxy) benzene, 4-diphenylmethane biscitraconimide, 2-bis [4- (4-citraconimidophenoxy) phenyl ] propane, Bis (3, 5-dimethyl-4-citraconimidophenyl) methane, bis (3-ethyl-5-methyl-4-citraconimidophenyl) methane, bis (3, 5-diethyl-4-citraconimidophenyl) methane, polyphenylmethane maleimide, novolak-type maleimide compounds, diphenylaralkyl-type maleimide compounds, maleimide compounds represented by the following formula (4), maleimide compounds represented by the following formula (5), prepolymers of these maleimide compounds, prepolymers of maleimide compounds and amine compounds, and the like.

(in the formula (4), a plurality of R₅Each independently represents a hydrogen atom or a methyl group. n is₁Represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5. ).

(in the formula (5), a plurality of R₆Each independently represents a hydrogen atom or a methyl group. n is₂Represents an integer of 1 or more, preferably an integer of 1 to 5. ).

These maleimide compounds can also be used alone in 1 or suitable mixed use of 2 or more. Among them, the maleimide compound represented by the formula (4) and the compound represented by the formula (5) are preferable, and the maleimide compound represented by the formula (4) is more preferable, from the viewpoint of excellent heat resistance. As the maleimide compound represented by the above formula (4), commercially available products can be used, and for example, BMI-2300 (manufactured by Katsuka chemical industry Co., Ltd.) can be mentioned. As the maleimide compound represented by the above formula (5), commercially available compounds can be used, and for example, MIR-3000 (manufactured by Nippon chemical Co., Ltd.) can be used.

The content of the maleimide compound in the resin composition of the present embodiment is not particularly limited, but is preferably 0.01 to 50 parts by mass, more preferably 0.02 to 45 parts by mass, even more preferably 0.03 to 20 parts by mass, even more preferably 0.1 to 10 parts by mass, and even more preferably 1 to 7 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition. When the content of the maleimide compound is in the above range, the heat resistance of the cured product tends to be further improved.

< cyanate ester Compound >

The cyanate ester compound is not particularly limited as long as it is a resin having an aromatic moiety substituted with at least 1 cyanate group (cyanato group) in the molecule.

Examples of the compound include compounds represented by the general formula (6).

(here, in the formula, Ar₁Represents a benzene ring, a naphthalene ring or a compound in which 2 benzene rings are singly bonded. In the case of a plurality of them, they may be the same as or different from each other. Ra independently represents 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, or a group in which an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms are bonded. The aromatic ring in Ra may haveHaving substituent groups, Ar₁And the substituents in Ra may be optionally substituted. p represents and Ar₁The number of bonded cyanate groups is independently an integer of 1 to 3. q represents and Ar₁Number of bonded Ra, Ar₁4-p in the case of a benzene ring, 6-p in the case of a naphthalene ring, and 8-p in the case of 2 benzene rings bonded by a single bond. t represents an average repetition number and is an integer of 0 to 50, and the cyanate ester compound may be a mixture of compounds having different t. When X is plural, each independently represents a single bond, a 2-valent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom), a 2-valent organic group having 1 to 10 nitrogen atoms (for example, -N-R-N- (where R represents an organic group)), a carbonyl group (-CO-), a carboxyl group (-C (═ O) O-), a carbonyl group (-OC (═ O) O-), a sulfonyl group (-SO-)₂-), a 2-valent sulfur atom, or a 2-valent oxygen atom. ).

The alkyl group in Ra of the general formula (6) may have any of a linear or branched structure and a cyclic structure (for example, cycloalkyl).

The hydrogen atom in the alkyl group in the general formula (6) and the aryl group in Ra 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.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, a 1-ethylpropyl group, a2, 2-dimethylpropyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and a trifluoromethyl group.

Specific examples of the aryl group include a phenyl group, a xylyl group, a xylylene group, a naphthyl group, a phenoxyphenyl group, an ethylphenyl group, an o-, m-or p-fluorophenyl group, a dichlorophenyl group, a dicyanophenyl group, a trifluorophenyl group, a methoxyphenyl group, an o-, m-or p-tolyl group, and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.

Specific examples of the 2-valent organic group having 1 to 50 carbon atoms in X of the general formula (6) include 2-valent organic groups having an aromatic ring, such as an alkylene group such as a methylene group, an ethylene group, a trimethylene group, or a propylene group, a cycloalkylene group such as a cyclopentylene group, a cyclohexylene group, or a trimethylcyclohexylene group, a biphenylmethylene group, a dimethylmethylene-phenylene-dimethylmethylene group, a fluorenediyl group, or a phthalenediyl group. The hydrogen atom in the 2-valent 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 2-valent organic group having 1 to 10 nitrogen atoms in X of the general formula (6) include a group represented by-N-R-N- (R is an organic group), an imino group, and a polyimide group.

Examples of the organic group of X in the general formula (6) include structures represented by the following general formula (7) and the following general formula (8).

Here, in the formula, Ar₂Represents a phenyltetrayl group, a naphthyltetrayl group or a biphenyltetrayl group, and when u is 2 or more, they may be the same or different from each other. Rb, Rc, Rf and Rg each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group or an aryl group having at least 1 phenolic hydroxyl group. Rd and Re are independently selected from any one of hydrogen atom, alkyl group with 1-6 carbon atoms, aryl group with 6-12 carbon atoms, alkoxy group with 1-4 carbon atoms or hydroxyl group. u represents an integer of 0 to 5.

Here, in the formula, Ar₃Represents a phenyltetrayl group, a naphthyltetrayl group or a biphenyltetrayl group, and when v is 2 or more, they may be the same or different from each other. Ri and Rj each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a trifluoromethyl group, or an aryl group substituted with at least 1 cyanate group. v represents an integer of 0 to 5, and may be a mixture of compounds having different v.

Further, X in the general formula (6) may be a 2-valent group represented by the following formula.

In the formula, z represents an integer of 4 to 7. Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Ar as general formula (7)₂And Ar of the general formula (8)₃Specific examples of the (c) include a phenyltetrayl group having 2 carbon atoms represented by the general formula (7), or 2 oxygen atoms bonded to the 1, 4-or 1, 3-positions represented by the general formula (8), a biphenyltetrayl group having the 2 carbon atoms or 2 oxygen atoms bonded to the 4,4 ' -position, 2 ' -position, 2,3 ' -position, 3 ' -position, or 3,4 ' -position, and a naphthalenetetrayl group having the 2 carbon atoms or 2 oxygen atoms bonded to the 2, 6-position, 1, 5-position, 1, 6-position, 1, 8-position, 1, 3-position, 1, 4-position, or 2, 7-position.

The alkyl group and aryl group in Rb, Rc, Rd, Re, Rf and Rg of the general formula (7) and Ri and Rj of the general formula (8) are the same as those in the above general formula (6).

Specific examples of the cyanate-group-substituted aromatic compound represented by the above general formula (6) include cyanate ester benzene, 1-cyanate ester-2-methylbenzene, 1-cyanate ester-3-methylbenzene, or 1-cyanate ester-4-methylbenzene, 1-cyanate ester-2-methoxybenzene, 1-cyanate ester-3-methoxybenzene, or 1-cyanate ester-4-methoxybenzene, 1-cyanate ester-2, 3-dimethylbenzene, 1-cyanate ester-2, 4-dimethylbenzene, 1-cyanate ester-2, 5-dimethylbenzene, 1-cyanate ester-2, 6-dimethylbenzene, 1-cyanate ester group-3, 4-dimethylbenzene or 1-cyanate-3, 5-dimethylbenzene, cyanatoethylbenzene, cyanatobutylbenzene, cyanatooctylbenzene, cyanatonononylphenene, 2- (4-cyanatophenyl) -2-phenylpropane (cyanate ester of 4-alpha-cumylphenol), 1-cyanate-4-cyclohexylbenzene, 1-cyanate-4-vinylbenzene, 1-cyanate-2-chlorobenzene or 1-cyanate-3-chlorobenzene, 1-cyanate-2, 6-dichlorobenzene, 1-cyanate-2-methyl-3-chlorobenzene, cyanatonitrobenzone, 1-cyanate-4-nitro-2-ethylbenzene, cyanatobenzene, cyanatobutylphenylene, cyanatobenzene, cyanato-2-4-2-4-6-4-methyl-2-4-methyl-4-methyl-ethyl-4-2-chlorobenzene, and benzene, 1-cyanate-2-methoxy-4-allylbenzene (cyanate ester of eugenol), methyl (4-cyanatophenyl) sulfide, 1-cyanate-3-trifluoromethylbenzene, 4-cyanate-biphenyl, 1-cyanate-2-acetylbenzene or 1-cyanate-4-acetylbenzene, 4-cyanate benzaldehyde, 4-cyanate-methyl benzoate, 4-cyanate-phenyl benzoate, 1-cyanate-4-acetylaminobenzene, 4-cyanate-benzophenone, 1-cyanate-2, 6-di-tert-butylbenzene, 1, 2-dicyanobenzene, 1, 3-dicyanobenzene, 1, 4-dicyanobenzene, 1, 4-dicyanate-2-tert-butylbenzene, 1, 4-dicyanate-2, 4-dimethylbenzene, 1, 4-dicyanate-2, 3, 4-trimethylbenzene, 1, 3-dicyanate-2, 4, 6-trimethylbenzene, 1, 3-dicyanate-5-methylbenzene, 1-cyanate ester naphthalene or 2-cyanate ester naphthalene, 1-cyanate ester-4-methoxynaphthalene, 2-cyanate ester-6-methylnaphthalene, 2-cyanate ester-7-methoxynaphthalene, 2 '-dicyanate ester-1, 1' -binaphthyl, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2, 6-or 2, 7-dicyanate dinaphthalene, 2 ' -or 4,4 ' -dicyanate diphenyl, 4 ' -dicyanate octafluorodiphenyl, 2,4 ' -or 4,4 ' -dicyanate diphenylmethane, bis (4-cyanato-3, 5-dimethylphenyl) methane, 1-bis (4-cyanatophenyl) ethane, 1-bis (4-cyanatophenyl) propane, 2-bis (4-cyanato-3-methylphenyl) propane, 2-bis (2-cyanato-5-biphenyl) propane, 2-bis (4-cyanatophenyl) hexafluoropropane, 2, 2-bis (4-cyanate-3, 5-dimethylphenyl) propane, 1-bis (4-cyanatophenyl) butane, 1-bis (4-cyanatophenyl) isobutane, 1-bis (4-cyanatophenyl) pentane, 1-bis (4-cyanatophenyl) -3-methylbutane, 1-bis (4-cyanatophenyl) -2, 2-dimethylpropane, 2-bis (4-cyanatophenyl) butane, 2-bis (4-cyanatophenyl) pentane, 2-bis (4-cyanatophenyl) hexane, 2, 2-bis (4-cyanatophenyl) -3-methylbutane, 2-bis (4-cyanatophenyl) -4-methylpentane, 2-bis (4-cyanatophenyl) -3, 3-dimethylbutane, 3-bis (4-cyanatophenyl) hexane, 3-bis (4-cyanatophenyl) heptane, 3-bis (4-cyanatophenyl) octane, 3-bis (4-cyanatophenyl) -2-methylpentane, 3-bis (4-cyanatophenyl) -2-methylhexane, 3-bis (4-cyanatophenyl) -2, 2-dimethylpentane, 2-bis (4-cyanatophenyl) hexane, 4, 4-bis (4-cyanatophenyl) -3-methylheptane, 3, 3-bis (4-cyanatophenyl) -2, 2-dimethylhexane, 3, 3-bis (4-cyanatophenyl) -2, 4-dimethylhexane, 3, 3-bis (4-cyanatophenyl) -2,2, 4-trimethylpentane, 2-bis (4-cyanatophenyl) -1,1,1,3,3, 3-hexafluoropropane, bis (4-cyanatophenyl) phenylmethane, 1, 1-bis (4-cyanatophenyl) -1-phenylethane, bis (4-cyanatophenyl) phenylmethane, 1, 1-bis (4-cyanatophenyl) cyclopentane, 1-bis (4-cyanatophenyl) cyclohexane, 2-bis (4-cyanato-3-isopropylphenyl) propane, 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-bis (4-cyanatophenyl) -3,3, 5-trimethylcyclohexane, 4- [ bis (4-cyanatophenyl) methyl ] biphenyl, 4-dicyanato benzophenone, 1, 3-bis (4-cyanatophenyl) -2-propen-1-one, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) sulfide, bis (4-cyanatophenyl) sulfone, 4-cyanatobenzoic acid-4-cyanatophenyl ester (4-cyanatophenyl-4-cyanatobenzoate), bis- (4-cyanatophenyl) carbonate, 1, 3-bis (4-cyanatophenyl) adamantane, 1, 3-bis (4-cyanatophenyl) -5, 7-dimethyladamantane, 1, 3-bis (3-methyl-4-cyanatophenyl) -5, 7-dimethyladamantane, 3-bis (4-cyanatophenyl) isobenzofuran-1 (3H) -one (cyanate ester of phenolphthalein), 3-bis (4-cyanato-3-methylphenyl) isobenzofuran-1 (3H) -one (cyanate ester of o-cresolphthalein), 9' -bis (4-cyanatophenyl) fluorene, 9-bis (4-cyanato-3-methylphenyl) fluorene, 9-bis (2-cyanato-5-biphenyl) fluorene, tris (4-cyanatophenyl) methane, 1,1, 1-tris (4-cyanatophenyl) ethane, mixtures thereof, and mixtures thereof, 1,1, 3-tris (4-cyanatophenyl) propane, α, α, α '-tris (4-cyanatophenyl) -1-ethyl-4-isopropylbenzene, 1,2, 2-tetrakis (4-cyanatophenyl) ethane, tetrakis (4-cyanatophenyl) methane, 2,4, 6-tris (N-methyl-4-cyanatoanilino) -1,3, 5-triazine, 2, 4-bis (N-methyl-4-cyanatoanilino) -6- (N-methylanilino) -1,3, 5-triazine, bis (N-4-cyanate-2-methylphenyl) -4, 4' -oxybisphthalimide, and mixtures thereof, Bis (N-3-cyanato-4-methylphenyl) -4,4 ' -oxybisphthalimide, bis (N-4-cyanatophenyl) -4,4 ' -oxybisphthalimide, bis (N-4-cyanato-2-methylphenyl) -4,4 ' - (hexafluoroisopropylidene) bisphthalimide, tris (3, 5-dimethyl-4-cyanatobenzyl) isocyanurate, 2-phenyl-3, 3-bis (4-cyanatophenyl) benzyllactam, 2- (4-methylphenyl) -3, 3-bis (4-cyanatophenyl) benzyllactam, 2-phenyl-3, 3-bis (4-cyanato-3-methylphenyl) benzyllactam, 1-methyl-3, 3-bis (4-cyanatophenyl) indolin-2-one, and 2-phenyl-3, 3-bis (4-cyanatophenyl) indolin-2-one, and prepolymers thereof.

Among them, prepolymers of 2, 2-bis (4-cyanatophenyl) propane are preferable from the viewpoint of excellent heat resistance, dielectric constant and dielectric loss tangent.

These cyanate ester compounds may be used alone in 1 kind or in combination of 2 or more kinds.

Further, as other specific examples of the compound represented by the above general formula (6), there may be mentioned phenol novolac resins and cresol novolac resins (obtained by reacting phenol, alkyl-substituted phenol or halogen-substituted phenol with a formaldehyde compound such as formalin or paraformaldehyde in an acidic solution by a known method), trisphenol novolac resins (obtained by reacting hydroxybenzaldehyde with phenol in the presence of an acidic catalyst), fluorene novolac resins (obtained by reacting a fluorenone compound with 9, 9-bis (hydroxyaryl) fluorenes in the presence of an acidic catalyst), phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, and biphenyl aralkyl resins (obtained by reacting Ar with a known method₂-(CH₂Y)₂(Ar₂Represents a phenyl group, and Y represents a halogen atom. The same applies to this item. ) A bishalomethyl compound as shown above and a phenol compound are reacted with each other in the presence or absence of an acid catalyst, Ar₂-(CH₂OR)₂Bis (A) as shownAn alkoxymethyl) compound and a phenolic compound in the presence of an acidic catalyst, or Ar₂-(CH₂OH)₂A phenol resin such as a bis (hydroxymethyl) compound shown above which is obtained by reacting a phenol compound in the presence of an acid catalyst or by polycondensing an aromatic aldehyde compound, an aralkyl compound and a phenol compound), a phenol-modified xylene-formaldehyde resin (obtained by reacting a xylene-formaldehyde resin with a phenol compound in the presence of an acid catalyst by a known method), a modified naphthalene-formaldehyde resin (obtained by reacting a naphthalene-formaldehyde resin with a hydroxy-substituted aromatic compound in the presence of an acid catalyst by a known method), a phenol-modified dicyclopentadiene resin, a phenol resin having a polynaphthylene ether structure (obtained by dehydrating and condensing a polyhydroxynaphthalene compound having 2 or more phenolic hydroxyl groups in 1 molecule in the presence of a basic catalyst by a known method), a cyanate ester obtained by the same method as described above, and the like, And prepolymers thereof, and the like. And is not limited to these. These cyanate ester compounds may be used alone in 1 kind or in combination of 2 or more kinds. In addition, from the viewpoint of excellent heat resistance, dielectric constant and dielectric loss tangent, it is preferable to use these cyanate ester compounds together with the cyanate ester compound represented by the above general formula (6).

Among them, phenol novolac type cyanate ester compounds, naphthol aralkyl type cyanate ester compounds, biphenyl aralkyl type cyanate ester compounds, naphthylene ether type cyanate ester compounds, xylene resin type cyanate ester compounds, and adamantane skeleton type cyanate ester compounds are preferable, and naphthol aralkyl type cyanate ester compounds are particularly preferable from the viewpoint of heat resistance.

The method for producing these cyanate ester compounds is not particularly limited, and known methods can be used. Examples of the above-mentioned production method include a method in which a hydroxyl group-containing compound having a desired skeleton is obtained or synthesized, and the hydroxyl group is modified by a known method to be cyanated. Examples of the method for cyanating a hydroxyl group include the methods described in Ian Hamilton, "Chemistry and Technology of Cyanate esters Resins," Black Academic & Professional ".

A resin cured product using these cyanate ester compounds has excellent characteristics such as a glass transition temperature, low thermal expansion properties, and plating adhesion.

In the resin composition of the present embodiment, the content of the cyanate ester compound is not particularly limited, and is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 40 parts by mass, further preferably 0.3 to 20 parts by mass, further preferably 0.5 to 10 parts by mass, and further more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition, from the viewpoint of excellent heat resistance, dielectric constant, and dielectric loss tangent.

< epoxy resin >

As the epoxy resin, any known compound can be suitably used as long as it has 2 or more epoxy groups in 1 molecule, and the kind thereof is not particularly limited. Specific examples thereof include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, xylene novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene skeleton-modified novolac type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, 3 functional phenol type epoxy resin, 4 functional phenol type epoxy resin, triglycidyl isocyanurate, glycidyl ester type epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenol novolac type epoxy resin, phenol aralkyl novolac type epoxy resin, Naphthol aralkyl novolak type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyhydric alcohol type epoxy resin, phosphorus-containing epoxy resin, a compound obtained by epoxidizing a double bond of glycidyl amine, butadiene or the like, a compound obtained by a reaction of a hydroxyl group-containing silicone resin and epichlorohydrin, and halides thereof.

Among them, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, naphthalene type epoxy resins, and brominated bisphenol a type epoxy resins are preferable in terms of flame retardancy and heat resistance.

These epoxy resins may be used alone in 1 kind, or may be suitably mixed and used in 2 or more kinds.

The content of the epoxy resin is not particularly limited, and is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 45 parts by mass, more preferably 5 to 40 parts by mass, even more preferably 10 to 25 parts by mass, even more preferably 15 to 25 parts by mass, and most preferably 12 to 20 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition. When the content of the epoxy resin is within the above range, flame retardancy and heat resistance tend to be further improved.

< phenol resin >

As the phenol resin, a conventionally known phenol resin can be used as long as it has 2 or more hydroxyl groups in 1 molecule. Examples thereof include bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, multifunctional phenol resin, naphthol resin, the resin composition is not particularly limited, and may include, but is not limited to, naphthol novolac resins, polyfunctional naphthol resins, anthracene-type phenol resins, naphthalene skeleton-modified novolac-type phenol resins, phenol aralkyl-type phenol resins, naphthol aralkyl-type phenol resins, dicyclopentadiene-type phenol resins, biphenyl-type phenol resins, alicyclic phenol resins, polyhydric alcohol-type phenol resins, phosphorus-containing phenol resins, phenol resins containing a polymerizable unsaturated hydrocarbon group, hydroxyl group-containing silicone resins, and the like. Among these phenol resins, biphenyl aralkyl type phenol resins, naphthol aralkyl type phenol resins, phosphorus-containing phenol resins, and hydroxyl group-containing silicone resins are preferable in terms of flame retardancy. These phenol resin can be used alone in 1, or can also be appropriately mixed with 2 or more.

The content of the phenolic resin is not particularly limited, and is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 45 parts by mass, and still more preferably 0.3 to 40 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition. When the content of the phenol resin is within the above range, the heat resistance tends to be further improved.

< Oxetane resin >

As the oxetane resin, a generally known oxetane resin can be used. Examples thereof include, but are not particularly limited to, an alkyloxetane such as oxetane, 2-methyloxetane, 2-dimethyloxetane, 3-methyloxetane or 3, 3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3-bis (trifluoromethyl) perfluorooxetane, 2-chloromethyloxetane, 3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (product name, manufactured by Toyo Seisaku Kogyo Co., Ltd.), OXT-121 (product name, manufactured by Toyo Seisaku Kogyo Co., Ltd.), and the like. These may be used alone in 1 kind or mixed with 2 or more kinds as appropriate.

The content of the oxetane resin is not particularly limited, and is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 45 parts by mass, and further preferably 0.3 to 40 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition. When the content of the oxetane resin is in the above range, the heat resistance tends to be further improved.

< benzoxazine Compound >

As the benzoxazine compound, a generally known compound can be used as long as it has 2 or more dihydrobenzoxazine rings in 1 molecule. Examples thereof include bisphenol A type benzoxazine BA-BXZ (trade name, product of Michelia Kogyo Co., Ltd.), bisphenol F type benzoxazine BF-BXZ (trade name, product of Michelia Kogyo Co., Ltd.), bisphenol S type benzoxazine BS-BXZ (product of Michelia Kogyo Co., Ltd.), phenolphthalein type benzoxazine, and the like, without any particular limitation. These may be used singly or in admixture of 2 or more kinds as appropriate.

The content of the benzoxazine compound is not particularly limited, and is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 45 parts by mass, and further preferably 0.3 to 40 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition. When the content of the benzoxazine compound is in the above range, the heat resistance tends to be further improved.

< Compound having ethylenically unsaturated group >

In the resin composition of the present embodiment, a compound having an ethylenically unsaturated group may be used in combination in order to improve thermosetting properties and curing properties by active energy rays (for example, photocuring properties by ultraviolet rays). The compound having an ethylenically unsaturated group used in the present embodiment is not particularly limited as long as it has 1 or more ethylenically unsaturated groups in 1 molecule, and examples thereof include compounds having a (meth) acryloyl group, a vinyl group, and the like. These may be used singly or in admixture of 2 or more kinds as appropriate.

Examples of the compound having a (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, ethylene glycol (glycol) di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, and the like, Polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogenated bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, epsilon-caprolactone-modified hydroxypivalic acid neopentyl glycol di (meth) acrylate, epsilon-caprolactone-modified dipentaerythritol hexa (meth) acrylate, epsilon-caprolactone-modified dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) acrylate, and ethylene oxide adducts thereof, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, hydrogenated bisphenol ethylene oxide (meth) acrylate, and hydrogenated bisphenol ethylene oxide (meth) acrylate, And ethylene oxide adducts thereof, and the like.

Further, urethane (meth) acrylates having both a (meth) acryloyl group and a urethane bond in the same molecule, polyester (meth) acrylates having both a (meth) acryloyl group and an ester bond in the same molecule, epoxy (meth) acrylates derived from an epoxy resin and having a (meth) acryloyl group, and reactive oligomers obtained by complexing these bonds may also be mentioned.

The urethane (meth) acrylates are reactants of a hydroxyl group-containing (meth) acrylate, a polyisocyanate, and other alcohols used as needed. For example, a mixture of toluene diisocyanate and hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like, glycerol (meth) acrylates such as glycerol mono (meth) acrylate, glycerol di (meth) acrylate and the like, sugar alcohol (meth) acrylates such as pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like, polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexylmethylene diisocyanate, and isocyanurates and biuret reactants thereof are reacted to form urethane (meth) acrylates.

The epoxy (meth) acrylates are carboxylic acid ester compounds of a compound having an epoxy group and (meth) acrylic acid. Examples of the epoxy (meth) acrylate include phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, trishydroxyphenylmethane type epoxy (meth) acrylate, dicyclopentadiene phenol type epoxy (meth) acrylate, bisphenol a type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, bisphenol a novolac type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, glyoxal type epoxy (meth) acrylate, heterocyclic epoxy (meth) acrylate, acid anhydride-modified epoxy (meth) acrylate thereof, and compounds represented by the general formula (1).

In the above general formula (1), a plurality of R₁Each independently represents a hydrogen atom or a methyl group. Among these, from the viewpoint of improving the reactivity of the photocuring reaction, hydrogen atoms are preferable, and R is more preferable₁All are hydrogen atoms.

Plural R₂Each independently represents a hydrogen atom or a methyl group. Among these, from the viewpoint of improving the heat resistance of the cured product, it is preferable to contain a methyl group, and more preferably R₂All are methyl groups.

Plural R₃Each independently represents a substituent represented by the formula (2), a substituent represented by the formula (3), or a hydroxyl group. Among them, hydroxyl groups are preferably contained from the viewpoint of improving heat resistance. In addition, in the present embodiment, a plurality of R's are used₃The compound containing the substituent represented by the above formula (2) is also preferable from the viewpoint of improving developability. In this embodiment, a plurality of R's are used₃The compound containing a substituent represented by the above formula (3) is also preferable from the viewpoint of improving heat resistance. In the above formula (3), R₄Represents a hydrogen atom or a methyl group. Among them, from the viewpoint of improving the reactivity of the photocuring reaction, a hydrogen atom is preferable.

For a plurality of R₃From the viewpoint of improving developability, it is preferable that all R be used₃Wherein the ratio of the substituent represented by the formula (2) is 20% to 85%, and the ratio of the substituent represented by the formula (3) is 5% to 70% and a hydroxyl group ratio of 10% to 75%.

When the compound represented by the general formula (1) includes any one or more of the following compounds (a1) to (a5), it is preferable to include at least the compound (a1), more preferably 2 or more of the compounds (a1) to (a5), and still more preferably 1 or more of the compounds (a1) and the compounds (a2) to (a5), because reactivity of a photocuring reaction, and heat resistance and developability of a cured product can be improved. The compound (a) also preferably contains at least the compounds (a2) and (A3).

The acid value of the compound represented by the general formula (1) is 30mgKOH/g or more from the viewpoint of improving the developability, and is preferably 50mgKOH/g or more from the viewpoint of further improving the developability. The acid value of the compound represented by the general formula (1) is 120mgKOH/g or less from the viewpoint of preventing dissolution by a developer after curing with an active energy ray, and is preferably 110mgKOH/g or less from the viewpoint of further preventing dissolution. The "acid value" in the present embodiment is represented by a value obtained by a method based on JIS K0070: 1992.

Examples of the acid anhydride-modified epoxy acrylate include acid-modified bisphenol F-type epoxy acrylates.

As the compound represented by the general formula (1), there can be used commercially available ones, and examples thereof include KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD (registered trademark) ZCR-6006H, KAYARAD (registered trademark) ZCR-6007H, KAYARAD (registered trademark) ZCA-601H (trade name, above) manufactured by Nippon Kabushiki Kaisha. Further, as the acid-modified bisphenol F type epoxy acrylate, KAYARAD (registered trademark) ZFR-1553H (trade name) available from Nippon Kagaku K.K.

Examples of the compound having a vinyl group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and a 2-functional phenylene ether oligomer having a vinyl group. Examples of the styrene include styrene, methylstyrene, ethylstyrene, divinylbenzene, α -methylstyrene, and oligomers thereof. Examples of the other vinyl compounds include triallyl isocyanurate, trimethallyl isocyanurate, bisallylnadiimide (bisallylnadiimide), and the like.

Among these, at least one or more selected from the group consisting of a 2-functional phenylene ether oligomer having a vinyl group, an oligomer of α -methylstyrene, an acid-modified bisphenol F-type epoxy (meth) acrylate, a compound represented by the general formula (1), pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, cresol novolac-type epoxy (meth) acrylate, bisphenol a-type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, and diallyl nadiimide are preferable. More preferably, the resin composition is one or more selected from the group consisting of a 2-functional phenylene ether oligomer having a vinyl group, an oligomer of α -methylstyrene, an acid-modified bisphenol F-type epoxy (meth) acrylate, a compound represented by the general formula (1) and dipentaerythritol hexa (meth) acrylate, from the viewpoint of obtaining good heat resistance, dielectric constant and dielectric loss tangent.

When thermosetting is required, a 2-functional phenylene ether oligomer having a vinyl group and/or an oligomer of α -methylstyrene are preferable from the viewpoint of satisfactory thermosetting, satisfactory embeddability of fine wiring, and excellent solder heat resistance, dielectric constant, and dielectric loss tangent. When photocurability is required, the inclusion of at least one or more selected from the group consisting of acid-modified bisphenol F-type epoxy (meth) acrylate, the compound represented by the general formula (1), and dipentaerythritol hexa (meth) acrylate is preferable because good embeddability of fine wiring, solder heat resistance, dielectric constant, dielectric loss tangent, and developability are also excellent, and therefore when the compound represented by the general formula (1) is used, further excellent heat resistance is more preferable. By including such a compound having an ethylenically unsaturated group, the heat resistance of the resulting cured product tends to be further improved.

These compounds having an ethylenically unsaturated group may be used singly or may be used in a mixture of 2 or more as appropriate. These compounds having an ethylenically unsaturated group may include structural isomers, stereoisomers and other isomers, and 2 or more compounds having different structures may be used in combination as appropriate.

The content of the compound having an ethylenically unsaturated group is not particularly limited, and is preferably 0.1 to 90 parts by mass, more preferably 0.2 to 85 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition. When the compound having an ethylenically unsaturated group is in the above range, solder heat resistance tends to be further improved. In particular, when thermosetting is required, the content of the compound having an ethylenically unsaturated group is preferably 5 to 90 parts by mass, more preferably 7 to 85 parts by mass, and still more preferably 10 to 83 parts by mass, based on 100 parts by mass of the resin solid component in the resin composition, from the viewpoints of satisfactory thermosetting property and obtaining favorable embeddability of fine wiring, solder heat resistance, dielectric constant, and dielectric loss tangent. When photocurability is required, the content of the compound having an ethylenically unsaturated group is preferably 5 to 90 parts by mass, more preferably 7 to 85 parts by mass, even more preferably 10 to 80 parts by mass, and even more preferably 10 to 73 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition, from the viewpoints of obtaining good embeddability and solder heat resistance of fine wiring, and obtaining a dielectric constant, a dielectric loss tangent, and developability.

< Filler (C) other than the silica-coated fluororesin particles (A) >

The resin composition of the present embodiment may further contain a filler (C) other than the silica-coated fluororesin particles (a) (hereinafter, referred to as another filler (C)) within a range not to impair the characteristics of the present embodiment. By using the other filler (C) in combination, desired properties such as flame retardancy, heat resistance and thermal expansion properties of the cured product can be improved.

The other filler (C) is not particularly limited as long as it has an insulating property, and examples thereof include natural silica, fused silica, synthetic silica, amorphous silica, fumed silica, hollow silica and other silicas, white carbon (white carbon), titanium white, zinc oxide, magnesium oxide, zirconium oxide and other oxides, boron nitride, aggregated boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide heat-treated product (heat-treated aluminum hydroxide to reduce a part of crystal water), boehmite, magnesium hydroxide and other metal hydrates, molybdenum oxide, zinc molybdate and other molybdenum compounds, zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, and the like, Examples of the filler include inorganic fillers such as NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass short fibers (including glass fine powders such as E glass, T glass, D glass, S glass, and Q glass), hollow glass, spherical glass, and the like, and organic fillers such as styrene-type, butadiene-type, and acrylic-type rubber powders, core-shell-type rubber powders, and silicone resin powders, silicone rubber powders, and silicone composite powders. Among them, one or more selected from the group consisting of silicon oxide, aluminum hydroxide, boehmite, magnesium oxide, magnesium hydroxide, and barium sulfate is preferable. These may be used singly or in admixture of 2 or more kinds as appropriate.

These other fillers (C) may be surface-treated with a silane coupling agent or the like described later.

In particular, silica is preferable, and fused silica is particularly preferable, from the viewpoint of improving the heat resistance of the cured product. Specific examples of the silica include SFP-130MC manufactured by Denka Company Limited, SC2050-MB, SC2050-MNU, SC1050-MLE, YA010C-MFN, YA050C-MJA manufactured by Admatech Company Limited, and the like.

The average particle diameter of the other filler (C) is not particularly limited, and is preferably 15 μm or less in terms of the median particle diameter from the viewpoint of improving the dispersibility of the other filler (C) in the resin composition. The median particle diameter is preferably 0.005 μm or more from the viewpoint of improving the dispersibility of the other filler (C) in the resin composition.

In the present specification, the term "median particle diameter" refers to a particle diameter such that when the particle size distribution of a powder is divided into 2 parts based on a certain particle diameter, the number or mass of particles on the larger particle diameter side and the number or mass of particles on the smaller particle diameter side occupy 50% of the total powder. The median diameter can be measured by a wet laser diffraction scattering method.

The content of the other filler (C) in the resin composition of the present embodiment is not particularly limited, and is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more per 100 parts by mass of the resin composition, from the viewpoint of improving the heat resistance of the cured product. From the viewpoint of improving the developability of the resin composition and the embeddability of fine wiring, the amount is preferably 400 parts by mass or less, more preferably 350 parts by mass or less, still more preferably 300 parts by mass or less, and still more preferably 100 parts by mass or less, per 100 parts by mass of the resin composition.

< silane coupling agent and wetting dispersant >

The resin composition of the present embodiment may further contain a silane coupling agent and/or a wetting dispersant within a range not to impair the characteristics of the present embodiment. By using a silane coupling agent and/or a wetting dispersant in combination, desired properties such as dispersibility of the filler and adhesive strength between the resin and the filler can be improved.

The silane coupling agent is not particularly limited as long as it is a silane coupling agent used for surface treatment of a general filler. Specific examples thereof include vinylsilane-based silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, aminosilane-based silanes such as γ -aminopropyltriethoxysilane and N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane; epoxy silane systems such as gamma-glycidoxypropyltrimethoxysilane; acrylic silanes such as gamma-acryloxypropyltrimethoxysilane; cationic silanes such as N-beta- (N-vinylbenzylaminoethyl) -gamma-aminopropyltrimethoxysilane hydrochloride and N- (vinylbenzene) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; and phenyl silane-based silane coupling agents. These silane coupling agents may also be used alone in 1 kind or appropriate combination of 2 or more.

The content of the silane coupling agent in the resin composition of the present embodiment is not particularly limited, and is usually 0.1 to 10 parts by mass per 100 parts by mass of the resin composition.

The wetting dispersant is not particularly limited as long as it is a dispersion stabilizer for coating materials. Specific examples thereof include wetting dispersants such as DISPERBYK (registered trademark) -110, 111, 118, 180, 161, BYK (registered trademark) -W996, W9010, and W903 manufactured by BYK Japan KK. These wetting and dispersing agents may be used alone in 1 kind, or may be suitably mixed and used in 2 or more kinds.

The content of the wetting dispersant in the resin composition of the present embodiment is not particularly limited, and is usually 0.1 to 10 parts by mass per 100 parts by mass of the resin composition.

< flame retardant (D) >

The resin composition of the present embodiment may further contain a flame retardant (D) within a range not to impair the characteristics of the present embodiment. By using the flame retardant (D) in combination, desired properties such as flame retardancy, heat resistance and thermal expansion properties of the cured product can be improved.

As the flame retardant (D), any conventionally known flame retardant can be used as long as it has flame retardancy. Examples thereof include brominated organic compounds such as brominated polycarbonate, decabromodiphenylethane, 4-dibromobiphenyl, ethylenebistetrabromophthalimide, etc., and are not particularly limited. These may be used alone in 1 kind, or may be suitably mixed and used in 2 or more kinds.

The content of the flame retardant (D) in the resin composition of the present embodiment is not particularly limited, and is usually 0.1 to 10 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the resin composition in the resin composition.

< photo-curing initiator (E) >

When a resin component (B) that can be photo-cured by ultraviolet light or the like (a maleimide compound, an epoxy resin, a compound having an ethylenically unsaturated group, a phenol resin, an oxetane resin, or the like) is used in the resin composition of the present embodiment, a photo-curing initiator (E) may be contained within a range that does not impair the characteristics of the present embodiment in order to improve the photo-curability thereof.

The photo-curing initiator (E) is not particularly limited, and a photo-curing initiator known in the art generally used for photo-curable resin compositions can be used.

Examples thereof include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide and di-tert-butyl diperoxyphthalate, acetophenone, 2-diethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, acetophenones such as 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-propan-1-one, acetophenones such as benzoin, benzoyl peroxide, lauroyl peroxide, and the like, Free radical type photo-curing initiators such as anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone, ketals such as 2, 4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone, ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal, benzophenones such as benzophenone, 4-benzoyl-4 '-methylbenzene sulfide and 4, 4' -bismethylaminobenzophenone, phosphine oxides such as 2,4, 6-trimethylbenzoyl diphenylphosphine oxide and bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, oxime esters such as 1- [4- (phenylthio) -1, 2-octanedione 2- (O-benzoyloxime) ], and the like, Cationic photopolymerization initiators such as p-methoxyphenyldiazofluorophosphonate, N-diethylaminophenyldiazohexafluoro phosphonate and other Lewis acids diazonium salts, diphenyliodonium hexafluoro phosphonate, diphenyliodonium hexafluoroantimonate and other Lewis acid iodonium salts, triphenylsulfonium hexafluoro phosphonate, triphenylsulfonium hexafluoroantimonate and other Lewis acid sulfonium salts, triphenylphosphonium hexafluoroantimonate and other Lewis acid phosphonium salts, other halides, triazine initiators, borate initiators, and other photoacid generators.

Among them, a radical type photo-curing initiator of acetophenone type such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by BASF Japan ltd., Irgacure (registered trademark) 369) is preferable from the viewpoints of reactivity suitable for use in multilayer printed wiring boards and high reliability for metal conductors.

These photo-curing initiators (E) may be used alone in 1 kind or may be used in a mixture of 2 or more kinds as appropriate, and both of radical type and cationic type initiators may be used in combination.

The content of the photo-curing initiator (E) in the resin composition of the present embodiment is not particularly limited, and is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, further preferably 0.3 part by mass or more, and further preferably 1 part by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition, from the viewpoint of sufficiently curing the resin composition by active energy rays and improving heat resistance. From the viewpoint of inhibiting thermal curing after photocuring and reducing heat resistance, the amount is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, further preferably 20 parts by mass or less, and still further preferably 10 parts by mass or less, based on 100 parts by mass of the resin solid content in the resin composition.

< Heat curing Accelerator >

In the resin composition of the present embodiment, a thermosetting accelerator may be used in combination within a range not to impair the characteristics of the present embodiment. The thermosetting accelerator is not particularly limited, and examples thereof include organic peroxides exemplified by benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, di-tert-butyl diperoxyphthalate, and the like; azo compounds such as azobisnitrile; tertiary amines such as N, N-dimethylbenzylamine, N-dimethylaniline, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-N-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, and N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, catechol, and the like; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetonate; a substance obtained by dissolving these organic metal salts in a hydroxyl group-containing compound such as phenol or bisphenol; inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; organic tin compounds such as dioctyltin oxide, other alkyltin, and alkyltin oxide; imidazole compounds such as 1, 2-dimethylimidazole, 1-benzyl-2-phenylimidazole, and 2,4, 5-triphenylimidazole.

These thermal curing accelerators may be used alone in 1 kind, or may be used in combination of 2 or more kinds as appropriate.

The content of the thermosetting accelerator in the resin composition of the present embodiment is not particularly limited, and is usually 0.1 to 10 parts by mass per 100 parts by mass of the resin composition in the resin composition.

< organic solvent >

The resin composition of the present embodiment may contain a solvent as needed. For example, if an organic solvent is used, the viscosity of the resin composition at the time of production can be adjusted. The type of the solvent is not particularly limited as long as it can dissolve a part or all of the resin in the resin composition. Specific examples thereof are not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether and its acetate.

These organic solvents may be used alone in 1 kind, or may be suitably mixed and used in 2 or more kinds.

< other ingredients >

Various polymer compounds such as thermosetting resins, thermoplastic resins and oligomers thereof, and elastomers not listed up to now may be used in combination in the resin composition of the present embodiment as long as the properties of the present embodiment are not impaired; flame-retardant compounds not listed so far; additives, and the like. These are not particularly limited as long as they are generally used. Examples of the flame-retardant compound include nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, phosphate compounds of phosphorus compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters. Examples of the additives include ultraviolet absorbers, antioxidants, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, surface conditioners, gloss agents, and polymerization inhibitors. These components can be used alone in 1 kind, or can also be appropriately mixed and used 2 or more.

The content of other components in the resin composition of the present embodiment is not particularly limited, and is usually 0.1 to 10 parts by mass per 100 parts by mass of the resin composition.

The resin composition of the present embodiment is prepared by appropriately mixing the silica-coated fluororesin particles (a), the resin component (B), and the above-mentioned other optional components used as desired. The resin composition of the present embodiment can be suitably used in the form of varnish when producing a prepreg and a resin sheet of the present embodiment described later.

< method for producing resin composition >

The method for producing the resin composition of the present embodiment is not particularly limited, and examples thereof include a method in which the above components are sequentially mixed in a solvent and sufficiently stirred.

In the production of the resin composition, known treatments (stirring, mixing, kneading, etc.) for uniformly dissolving or dispersing the respective components may be performed as necessary. Specifically, the dispersibility of the silica-coated fluororesin particles (a) in the resin composition can be improved by performing the agitation dispersion treatment using an agitation tank equipped with an agitator having an appropriate agitation capability. The stirring, mixing and kneading treatment can be suitably carried out by using a known apparatus such as a stirring apparatus for dispersion purpose, e.g., an ultrasonic homogenizer, an apparatus for mixing purpose, e.g., a three-roll mill, a ball mill, a bead mill or a sand mill, or a revolution or rotation type mixing apparatus. In addition, in the preparation of the resin composition of the present embodiment, an organic solvent may be used as necessary. The type of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition, and specific examples thereof are as described above.

< use >

The resin composition of the present embodiment can be used for applications requiring an insulating resin composition, and is not particularly limited, and can be used for applications such as a photosensitive film, a photosensitive film with a support, an insulating resin sheet such as a prepreg, a circuit board (for laminate board applications, multilayer printed circuit board applications, and the like), a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a via filling resin, and a component embedding resin. Among them, the resin composition can be preferably used as a resin composition for an insulating layer of a multilayer printed wiring board or a solder resist.

< prepreg >

The prepreg of the present embodiment is obtained by impregnating or applying the resin composition of the present embodiment to a substrate. The method for producing a prepreg is not particularly limited as long as it is a method for producing a prepreg by combining the resin composition of the present embodiment and a substrate. Specifically, the prepreg of the present embodiment can be produced by a method of impregnating or applying the resin composition of the present embodiment to a substrate, and then semi-curing the resin composition at 120 to 220 ℃ for about 2 to 15 minutes. In this case, the amount of the resin composition attached to the base material, that is, the amount of the resin composition (including the filler) is preferably in the range of 20 to 99 mass% with respect to the total amount of the prepreg after semi-curing.

As the base material used for producing the prepreg of the present embodiment, known base materials used for various printed circuit board materials can be used. Examples thereof include, but are not limited to, glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, and spherical glass, inorganic fibers other than glass such as quartz, organic fibers such as polyimide, polyamide, and polyester, and woven fabrics such as liquid crystal polyester. As the shape of the base material, woven fabric, nonwoven fabric, roving, chopped glass mat, surfacing mat, and the like are known, and any of them is acceptable. The base material can be used alone 1 or a combination of 2 or more. The thickness of the base material is not particularly limited, but is preferably in the range of 0.01 to 0.2mm in the case of laminate applications, and woven fabrics subjected to the super-open treatment and the eyelet blocking treatment are particularly suitable from the viewpoint of dimensional stability. Further, a glass woven fabric subjected to surface treatment such as epoxysilane treatment or aminosilane treatment with a silane coupling agent is preferable from the viewpoint of moisture absorption and heat resistance. In addition, the liquid crystal polyester woven fabric is preferable in view of electrical characteristics.

< Metal foil clad laminate >

The metal foil-clad laminate of the present embodiment is formed by laminating at least 1 or more sheets of the prepreg, and disposing metal foils on one or both surfaces thereof. Specifically, one or more prepregs are stacked, and a metal foil of copper, aluminum, or the like is disposed on one or both surfaces of the stacked prepregs, followed by lamination molding. The metal foil used here is not particularly limited as long as it is a metal foil used for a printed wiring board material, and a copper foil such as a rolled copper foil or an electrolytic copper foil is preferable. The thickness of the metal foil is not particularly limited, but is preferably 2 to 70 μm, more preferably 3 to 35 μm. As the molding conditions, a usual method of laminating a printed wiring board or a multilayer board can be applied. For example, the sheet can be heated at a temperature of 180 to 350 ℃ for 100 to 300 minutes and a surface pressure of 20 to 100kg/cm by using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, or the like²The metal foil-clad laminate of the present invention is produced by lamination molding. The prepreg may be combined with a separately prepared wiring board for an inner layer and laminated to form a multilayer board. The multilayer board can be produced, for example, as follows: arranging 35 μm copper foils on both surfaces of 1 sheet of the prepreg, laminating and molding under the above conditions, forming an inner layer circuit, blackening the circuit to form an inner layer circuit board, and then alternately arranging the inner layer circuit board and the prepreg 1 sheet by 1 sheet, and further arranging the prepreg 1 sheet by 1 sheetThe copper foil is disposed on the outermost layer, and the multilayer board is produced by laminating and molding under the above conditions, preferably under vacuum.

< resin sheet >

On the other hand, the resin sheet of the present embodiment can be obtained by applying a solution obtained by dissolving the resin composition of the present embodiment in a solvent to a support and drying the solution. Examples of the support used herein include, but are not particularly limited to, polyethylene films, polypropylene films, polycarbonate films, polyethylene terephthalate films, ethylene tetrafluoroethylene copolymer films, release films obtained by applying a release agent to the surfaces of these films, organic film substrates such as polyimide films, conductive foils such as copper foils and aluminum foils, glass plates, SUS plates, and FRPs.

Further, in the resin sheet of the present embodiment, the resin composition layer may be protected by a protective film.

By protecting the resin composition layer side with the protective film, adhesion and damage of dust and the like to the surface of the resin composition layer can be prevented. As the protective film, a film made of the same material as the resin film can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 50 μm, and more preferably in the range of 5 μm to 40 μm. When the thickness is less than 1 μm, the handling property of the protective film tends to be lowered, and when it exceeds 50 μm, the cost tends to be low. In the protective film, the adhesion between the resin composition layer and the protective film is preferably smaller than the adhesion between the resin composition layer and the support.

Examples of the coating method include the following methods: a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied to a support by a bar coater, a die coater, a doctor blade, a Baker applicator, or the like, thereby producing a laminated sheet in which the support and the resin sheet are integrated. After drying, the support may be peeled off from the laminate sheet or etched to form a single-layer sheet of a resin sheet alone. The resin composition of the present embodiment may be dissolved in a solvent to prepare a solution, which is supplied into a mold having a sheet-shaped cavity and dried to form a sheet, thereby obtaining a single-layer sheet without using a support.

In the production of the resin sheet (single-layer or laminated sheet) according to the present embodiment, the drying conditions for removing the solvent are not particularly limited, and the solvent is likely to remain in the resin composition at a low temperature, and the resin composition is cured at a high temperature, and therefore, the temperature is preferably from 20 ℃ to 200 ℃ for 1 to 90 minutes. The thickness of the resin layer of the resin sheet (single layer or laminate sheet) of the present embodiment can be adjusted by the concentration of the solution of the resin composition of the present embodiment and the coating thickness, and is not particularly limited, and is preferably 0.1 to 500 μm, since the solvent tends to remain during drying when the coating thickness is generally increased.

< printed Circuit Board >

The metal foil-clad laminate and the resin sheet according to the present embodiment can be suitably used as a printed wiring board. The printed wiring board can be manufactured by a conventional method, and the manufacturing method thereof is not particularly limited. An example of a method for manufacturing a printed wiring board using a metal foil-clad laminate is described below. First, a metal foil-clad laminate such as the copper-clad laminate is prepared. Next, the surface of the metal foil-clad laminate was subjected to etching treatment to form an inner layer circuit, thereby producing an inner layer substrate. The surface of the inner layer circuit of the inner layer substrate is subjected to surface treatment for improving the adhesive strength as required, and then a required number of prepregs are stacked on the surface of the inner layer circuit, and further a metal foil for an outer layer circuit is stacked on the outer side of the prepregs, and the prepregs are heated and pressed to be integrally molded. In this way, a multilayer laminated board in which the insulating layer composed of the base material and the cured product of the thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit is manufactured. Next, the multilayer laminated board is subjected to drilling for via holes and via holes, and then a metal plating film for conducting the metal foil for the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of the hole, and further the metal foil for the outer layer circuit is subjected to etching treatment to form the outer layer circuit, thereby manufacturing a printed wiring board.

The printed wiring board obtained in the above-described manufacturing example includes an insulating layer and a conductor layer formed on a surface of the insulating layer, and the insulating layer is configured to include the resin composition of the present embodiment. That is, the prepreg of the present embodiment (the base material and the resin composition of the present embodiment impregnated or applied to the base material) and the layer of the resin composition of the metal foil-clad laminate of the present embodiment (the layer formed of the resin composition of the present invention) are each composed of an insulating layer containing the resin composition of the present embodiment.

An example of a method for manufacturing a printed circuit board using a resin sheet is described below. The resin sheet of the present embodiment can be suitably used as an interlayer insulating layer of a printed wiring board, and can be obtained by stacking and curing 1 or more of the resin sheets. Specifically, the present invention can be produced by the following method.

The resin composition layer side of the resin sheet of the present embodiment is molded on one surface or both surfaces of the circuit board. The molding conditions may be those for usual laminate sheets or multilayer sheets for printed wiring boards, or may be those for vacuum lamination. Examples of the circuit board include a glass epoxy substrate, a metal substrate, a ceramic substrate, a silicon substrate, a semiconductor sealing resin substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Here, the circuit board refers to a board in which a conductor layer (circuit) formed by patterning is formed on one surface or both surfaces of the above-described board. In a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, a substrate serving as a conductor layer (circuit) patterned on one or both surfaces of the outermost layer of the multilayer printed wiring board is also included in the circuit substrate described herein. The surface of the conductor layer may be roughened in advance by blackening treatment, copper etching, or the like. In the molding step, when the resin sheet has a protective film, the protective film is peeled off and removed, and then the resin sheet and the circuit board are preheated as necessary, and the resin composition layer is pressed and heated while being pressed against the circuit board. In the resin sheet of the present embodiment, a method of laminating the resin sheet on a circuit board under reduced pressure by a vacuum lamination method can be suitably used.

The conditions for the laminating step are not particularly limited, and for example, it is preferable that the pressure bonding temperature (laminating temperature) is 50 to 140 ℃ and the pressure bonding pressure is 1kgf/cm²～15kgf/cm²The lamination is preferably performed under reduced pressure with a pressure bonding time of 5 to 300 seconds and an air pressure of 20mmHg or less. The laminating step may be a batch type or a continuous type using a roll. The vacuum lamination method can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a 2-stage lamination laminator manufactured by ltd, Nikko-Materials co.

The hole processing is performed to form a via hole, a through hole, or the like. The hole-machining treatment is performed by using 1 kind of known method such as an NC drill, a carbon dioxide laser, a UV laser, a YAG laser, or a plasma, or by combining 2 or more kinds as necessary. When the resin sheet is a photocurable resin composition, a hole-processing treatment may be performed by exposure and development.

Before or after the hole-forming treatment, a post-baking step is performed as necessary to form an insulating layer (cured product). Examples of the post-baking step include an ultraviolet irradiation step using a high-pressure mercury lamp and a heating step using a clean oven. When ultraviolet rays are irradiated, the dose of the ultraviolet rays can be adjusted as needed, and the dose can be set to 0.05J/cm, for example²～10J/cm²The irradiation is performed with right and left irradiation amounts. The heating conditions may be appropriately selected depending on the kind, content, and the like of the resin component in the resin composition, and are preferably selected in the range of 20 minutes to 180 minutes at 150 ℃ to 220 ℃, and more preferably in the range of 30 minutes to 150 minutes at 160 ℃ to 200 ℃.

When the insulating layer has a conductor layer on its surface, a metal plating film for electrically connecting the metal foil for the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of the hole, and the metal foil for the outer layer circuit is etched to form the outer layer circuit, thereby manufacturing a printed wiring board.

When there is no conductor layer on the surface of the insulating layer, a conductor layer is formed on the surface of the insulating layer by dry plating or wet plating. As the dry plating, a known method such as a vapor deposition method, a sputtering method, an ion plating method, or the like can be used. In the vapor deposition method (vacuum vapor deposition method), for example, a metal film can be formed on the insulating layer by placing the support in a vacuum chamber and heating and evaporating the metal. In the sputtering method, for example, a support may be placed in a vacuum chamber, an inert gas such as argon gas may be introduced, a direct current voltage may be applied to the inert gas, the inert gas thus ionized may be caused to collide with a target metal, and a metal film may be formed on an insulating layer by the metal thus collided.

In the case of wet plating, the surface of the insulating layer to be formed is roughened by sequentially performing a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing solution on the surface of the insulating layer. The swelling treatment with the swelling solution is performed by immersing the insulating layer in the swelling solution at 50 to 80 ℃ for 1 to 20 minutes. Examples of the swelling solution include an alkali solution, and examples of the alkali solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling solutions include APPDES (registered trademark) MDS-37, manufactured by Shanghai Kabushiki Kaisha.

The roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ℃ for 5 to 30 minutes. Examples of the oxidizing agent include an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide/sulfuric acid, and nitric acid. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10 mass%. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as APPDES (registered trademark) MDE-40 and APPDES (registered trademark) ELC-SH, manufactured by Shanmura industries, Ltd. The neutralization treatment with the neutralization solution is carried out by immersing the substrate in the neutralization solution at 30 to 50 ℃ for 1 to 10 minutes. As the neutralizing solution, an acidic aqueous solution is preferred, and as a commercially available product, APPDES (registered trademark) MDN-62 available from Tomura industries, Ltd.

Then, electroless plating and electroplating are combined to form a conductor layer. Alternatively, a plating resist layer opposite to the conductor layer pattern may be formed, and the conductor layer may be formed by electroless plating alone. As a method of forming a pattern thereafter, for example, a subtractive method, a semi-additive method, or the like can be used.

< semiconductor device >

The semiconductor device of the present embodiment includes an interlayer insulating layer containing the resin composition of the present embodiment, and can be manufactured specifically by the following method. A semiconductor device can be manufactured by mounting a semiconductor chip on a conductive portion of the multilayer printed circuit board of this embodiment mode. Here, the conductive portion refers to a portion of the multilayer printed circuit board that transmits an electrical signal, and the position thereof may be a surface or an embedded portion. The semiconductor chip is not particularly limited as long as it is a circuit element made of a semiconductor.

The method of mounting the semiconductor chip in the manufacture of the semiconductor device of the present embodiment is not particularly limited as long as the semiconductor chip can effectively function, and specifically, a wire bonding mounting method, a flip chip mounting method, a mounting method using a bump-less build-up layer (BBUL), a mounting method using an Anisotropic Conductive Film (ACF), a mounting method using a non-conductive film (NCF), and the like can be cited.

Further, a semiconductor device can also be manufactured by laminating the resin sheet of this embodiment to a semiconductor chip. After lamination, the multilayer printed wiring board can be manufactured by the same method as that described above.

Examples

The present invention will be described more specifically with reference to synthesis examples and examples, but the present invention is not limited to these examples at all.

[ Synthesis example 1]

(Synthesis of cyanate ester Compound)

300g (1.28 mol in terms of OH groups) of 1-naphthol aralkyl resin (available from Nippon iron Co., Ltd.) and 194.6g (1.92mol) of triethylamine (1.5 mol based on 1mol of hydroxyl group) were dissolved in 1800g of dichloromethane to prepare solution 1.

Cyanogen chloride 125.9g (2.05mol) (1.6 mol based on 1mol of hydroxyl group), methylene chloride 293.8g, 36% hydrochloric acid 194.5g (1.92mol) (1.5 mol based on 1mol of hydroxyl group), and water 1205.9g were poured into solution 1 over 30 minutes while maintaining the liquid temperature at-2 ℃ to-0.5 ℃ with stirring. After completion of the injection of solution 1, the mixture was stirred at the same temperature for 30 minutes, and then a solution (solution 2) prepared by dissolving 65g (0.64mol) of triethylamine (0.5 mol based on 1mol of hydroxyl groups) in 65g of methylene chloride was injected over 10 minutes. After the end of the injection of solution 2, the reaction was terminated by stirring at the same temperature for 30 minutes.

Thereafter, the reaction solution was allowed to stand, and the organic phase and the aqueous phase were separated. The organic phase obtained was washed 5 times with 1300g of water. The conductivity of the wastewater of the 5 th water washing was 5. mu.S/cm, and it was confirmed that: by washing with water, ionic compounds to be removed are sufficiently removed.

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

[ Synthesis example 2]

(Synthesis of 2-functional phenylene ether oligomer having vinyl group)

23.88g (17.4mmol) of CuBr, 0.75g (4.4mmol) of N, N '-di-t-butylethylenediamine, 28.04g (277.6mmol) of N-butyldimethylamine and 2600g of toluene were put into a 12L longitudinal reactor equipped with a stirrer, a thermometer, an air inlet tube and a baffle, and stirred at a reaction temperature of 40 ℃ while bubbling a mixed gas having an oxygen concentration of 8% prepared by mixing nitrogen and air at a flow rate of 5.2L/min, 129.3g (0.48mol) of 2, 2', 3,3 ', 5, 5' -hexamethyl- (1,1 '-biphenol) -4, 4' -diol dissolved in 2300g of methanol in advance, 2, 6-dimethylphenol 233.7g (1.92mol), 2,3, 6-trimethylphenol 64.9g (0.48mol), N '-di-t-butylethylenediamine 0.51g (2.9mmol), N' -di-t-butylethylenediamine, A mixed solution of 10.90g (108.0mmol) of n-butyldimethylamine was stirred. After the completion of the dropwise addition, 1500g of water in which 19.89g (52.3mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with 1N hydrochloric acid aqueous solution, followed by washing with pure water. The resulting solution was concentrated to 50% by weight with an evaporator to obtain 836.5g of a toluene solution of a 2-functional phenylene ether oligomer. The 2-functional phenylene ether oligomer had a number average molecular weight of 986, a weight average molecular weight of 1530 and a hydroxyl group equivalent of 471.

(Synthesis of vinyl Compound)

836.5g of a toluene solution of a 2-functional phenylene ether oligomer, 162.6g of chloromethylstyrene (trade name CMS-P, AGC SEIMI CHEMICAL CO., LTD., manufactured by LTD.), 1600g of methylene chloride, 12.95g of benzyldimethylamine, 420g of pure water, and 178.0g of a 30.5 wt% aqueous NaOH solution were put into a reactor equipped with a stirrer, a thermometer, and a reflux tube, and stirred at a reaction temperature of 40 ℃. After stirring for 24 hours, the organic layer was washed with 1N hydrochloric acid aqueous solution, followed by washing with pure water. The obtained solution was concentrated by an evaporator, and was solid-solidified by dropping it into methanol, and the solid was recovered by filtration and dried under vacuum to obtain 503.5g of a vinyl compound. The vinyl compound had a number average molecular weight of 1187, a weight average molecular weight of 1675, and a vinyl equivalent of 590 g/vinyl.

[ example 1]

(preparation of resin composition and prepreg)

Methyl ethyl ketone (hereinafter, sometimes abbreviated as MEK) slurry (0.5 μm tfe-YA (trade name), volume average particle diameter of primary particles of 0.5 μm, nonvolatile content of 20 mass%, manufactured by adatech Company Limited) 250 parts by mass (50 parts by mass in terms of nonvolatile content), SNCN 2.1 parts by mass obtained in synthesis example 1 as a cyanate ester compound, prepolymer of 2, 2-bis (4-cyanatophenyl) propane (CA210 (trade name), equivalent 139, manufactured by mitsubishi gas chemical corporation) 6.6 parts by mass, brominated bisphenol a epoxy resin (E153 (trade name), epoxy equivalent 400, secondary hydroxyl content of 0.3meq/g, manufactured by DIC corporation) as an epoxy resin, vinyl compound (number average molecular weight of 7 1187) obtained in synthesis example 2 as a compound having an ethylenically unsaturated group, Vinyl equivalent 590 g/vinyl) 77.5 parts by mass, α -methylstyrene oligomer (KA3085 (trade name), mass average molecular weight: 664. U.S. Eastman Chemical Company) 3.2 parts by mass, and MEK slurry of vinylsilane-treated silica (SC2050MNU (trade name), median diameter 0.5 μm, nonvolatile matter 70% by mass, Admatech Company Limited) 71.4 parts by mass (50 parts by mass in terms of nonvolatile matter) as another filler (C) were mixed to obtain a varnish (solution of resin composition). The varnish was diluted with methyl ethyl ketone, impregnated with an E glass woven cloth having a thickness of 0.1mm, and dried by heating at 160 ℃ for 5 minutes to obtain a prepreg having a resin content of 50 mass%.

(production of inner layer Circuit Board)

Both surfaces of a glass cloth base BT resin double-sided copper-clad laminate (copper foil 12 μm thick, 0.2mm thick, CCL (registered trademark) -HL832NS (trade name) manufactured by mitsubishi gas chemical) on which an inner layer circuit having a minimum wiring pitch of 10 μm was formed were subjected to roughening treatment of copper surface by CZ8100 manufactured by MEC COMPANY ltd to obtain an inner layer circuit board.

(production of Metal-clad laminate)

The prepreg was placed on the upper and lower sides of an inner layer circuit board, and electrolytic copper foils (3EC-M3-VLP (trade name), manufactured by Mitsui Metal Co., Ltd.) having a thickness of 12 μ M were placed on the upper and lower sides under a pressure of 30kgf/cm²And a metal-clad laminate obtained by laminating the inner layer circuit board, the resin composition layer and the copper foil by laminating molding at 220 ℃ for 120 minutes.

(preparation of cured product for evaluation)

4 sheets of the prepreg were stacked, and a 12 μ M-thick electrolytic copper foil (3EC-M3-VLP (trade name), manufactured by Mitsui Metal Co., Ltd.) was placed on top of each other under a pressure of 30kgf/cm²And then, the laminate was laminated at 220 ℃ for 120 minutes to obtain a metal foil-clad laminate having an insulating layer thickness of 0.4 mm. The entire metal foil of the metal foil-clad laminate thus obtained was removed by etching to obtain a cured product for evaluation.

[ example 2]

A varnish was prepared in the same manner as in example 1 except that 125 parts by mass (50 parts by mass in terms of nonvolatile content) of MEK slurry (PTFE-YA4 (trade name), 3.0 μm in volume average particle size of primary particles, 40% by mass in nonvolatile content, manufactured by admatech Company Limited) of a PTFE filler was coated with silica having a volume average particle size of 3.0 μm as primary particles of silica-coated fluororesin particles (a), and a prepreg, a metal foil-clad laminate, and a cured product for evaluation were obtained.

[ example 3]

An MEK slurry (0.5. mu. m TFE-YA (trade name), a volume average particle diameter of primary particles of 0.5. mu.m, a nonvolatile matter of 20% by mass, manufactured by Admatech Company Limited) of a silica-coated PTFE filler as the silica-coated fluororesin particles (A) was mixed in an amount of 250 parts by mass (50 parts by mass in terms of nonvolatile matter), 2.0 parts by mass of SNCN obtained in Synthesis example 1 as a cyanate ester compound, 10.0 parts by mass of a prepolymer of 2, 2-bis (4-cyanatophenyl) propane (CA210 (trade name), cyanate ester equivalent 139, manufactured by Mitsubishi gas chemical Co., Ltd.), a brominated bisphenol A type epoxy resin (E153 (trade name), epoxy equivalent 400, secondary hydroxyl group amount of 0.3meq/g, manufactured by Mitsubishi corporation) as an epoxy resin, a vinyl compound obtained in Synthesis example 2 as a compound having an ethylenically unsaturated group (number average molecular weight of 1187, DIC, Vinyl equivalent 590 g/vinyl) 72.8 parts by mass, an α -methylstyrene oligomer (KA3085 (trade name), mass average molecular weight: 664. U.S. Eastman chemical Company) 3.0 parts by mass, MEK slurry of vinylsilane-treated silica (SC2050MNU (trade name), median diameter 0.5 μm, nonvolatile matter 70% by mass, Admatech Company Limited) 71.4 parts by mass (50 parts by mass in terms of nonvolatile matter), and brominated polycarbonate (FG8500 (trade name), Kitikon corporation, bromine content 58% by weight) as a flame retardant (D) were mixed together to obtain a varnish. Thereafter, a prepreg, a metal foil-clad laminate, and a cured product for evaluation were obtained in the same manner as in example 1.

[ example 4 ]

(preparation of resin composition and resin sheet)

An MEK slurry (0.5. mu. m TFE-YA (trade name), a volume average particle diameter of primary particles of 0.5. mu.m, a nonvolatile matter of 20% by mass, manufactured by Admatech Company Limited) of a silica-coated PTFE filler as the silica-coated fluororesin particles (A) was mixed in an amount of 250 parts by mass (50 parts by mass in terms of nonvolatile matter), 2.1 parts by mass of SNCN obtained in Synthesis example 1 as a cyanate ester compound, 10.6 parts by mass of a prepolymer of 2, 2-bis (4-cyanatophenyl) propane (CA210 (trade name), cyanate ester equivalent 139, manufactured by Mitsubishi gas chemical Co., Ltd.), a brominated bisphenol A type epoxy resin (E153 (trade name), epoxy equivalent 400, secondary hydroxyl group amount of 0.3meq/g, manufactured by Co., Ltd.), and a vinyl compound obtained in Synthesis example 2 as a compound having an ethylenically unsaturated group (number average molecular weight: 1187, DIC 7, and the like, Vinyl equivalent 590 g/vinyl) 77.5 parts by mass, α -methylstyrene oligomer (KA3085 (trade name), mass average molecular weight: 664. U.S. Eastman chemical Company) 3.2 parts by mass, and MEK slurry of vinylsilane-treated silica (SC2050MNU (trade name), median diameter 0.5 μm, nonvolatile matter 70% by mass, Admatech Company Limited) 71.4 parts by mass (50 parts by mass in terms of nonvolatile matter) as another filler (C) were mixed to obtain a varnish. These varnishes were applied to an electrolytic copper foil (3EC-M2S-VLP (trade name), manufactured by Mitsui Metal Co., Ltd.) having a thickness of 12 μ M, and heat-dried at 120 ℃ for 5 minutes to obtain a resin sheet having a copper foil as a support and a resin composition layer having a thickness of 40 μ M.

(production of Metal-clad laminate)

The resin surface of the resin sheet using the copper foil as a support was placed on the inner layer circuit board used in example 1, and the pressure was set to 30kgf/cm²And a metal-clad laminate obtained by laminating the inner layer circuit board, the resin composition layer and the copper foil by laminating molding at 220 ℃ for 120 minutes.

(preparation of cured product for evaluation)

The entire metal foil of the metal foil-clad laminate thus obtained was removed by etching to obtain a cured product for evaluation.

[ comparative example 1]

A varnish was prepared in the same manner as in example 3 except that 125 parts by mass (50 parts by mass in terms of nonvolatile matter) of a PTFE dispersion (exp. fd-030 (trade name), median particle diameter 0.5 μm, nonvolatile matter 40%, manufactured by DIC corporation) was used instead of the silica-coated fluororesin particles (a), and a prepreg, a metal foil-clad laminate, and a cured product for evaluation were obtained.

[ comparative example 2]

A varnish was prepared in the same manner as in example 1 except that the fluororesin pellets (a) were not covered with silica, and as the other filler (C), 142.9 parts by mass (100 parts by mass in terms of nonvolatile matter) of MEK slurry of vinylsilane-treated silica (SC2050MNU (trade name), median particle diameter of 0.5 μm, nonvolatile matter of 70%, manufactured by admatech Company Limited) was used, and a prepreg, a metal foil-clad laminate, and a cured product for evaluation were obtained.

[ example 5 ]

An MEK slurry (0.5. mu. m TFE-YA (trade name), a volume average particle diameter of primary particles of 0.5. mu.m, a nonvolatile matter of 20 mass%, manufactured by Admatech Company Limited) of 250 parts by mass (50 parts by mass in terms of nonvolatile matter), a maleimide compound (BMI-2300 (trade name), manufactured by Kazakh Kagaku Kogyo Co., Ltd.), 3.5 parts by mass of a benzidine-based epoxy resin (NC3000H (trade name), manufactured by Nippon Kayaku Kogyo Co., Ltd.) as an epoxy resin, a propylene glycol monomethyl ether acetate (hereinafter, abbreviated as PMA) as an acid-modified bisphenol F-type epoxy acrylate compound having an ethylenically unsaturated group, a solution (KAYARAD (registered trade name) ZFR-1553H (trade name) Nonvolatile fraction 68 mass%, acid value: 70mgKOH/g, manufactured by Nippon chemical Co., Ltd.) (77.6 parts by mass (52.8 parts by mass in terms of nonvolatile matter), dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA (trade name), manufactured by Nippon chemical Co., Ltd.) 18.9 parts by mass, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure (registered trademark) 369 (trade name), manufactured by BASF Japan Ltd.) as a photo-curing initiator (E) were mixed, and stirred by an ultrasonic homogenizer to obtain a varnish (a solution of the resin composition). These varnishes were applied to a 38 μm thick PET film (trade name, manufactured by Unipell (registered trademark) TR1-38, Unitika Ltd.) and dried by heating at 80 ℃ for 7 minutes to obtain a resin sheet having a thickness of 40 μm in which the PET film was used as a support and the resin composition layer was formed.

(preparation of laminate for evaluation)

The resin surface of the resin sheet using the PET film as a support was placed on the inner layer circuit board used in example 1, and vacuum was applied for 30 seconds (5.0MPa or less) using a vacuum laminator (manufactured by Nikko-Materials co., ltd.), and then the pressure was 10kgf/cm²And laminated molding was carried out at a temperature of 70 ℃ for 30 seconds. Further, the pressure was 10kgf/cm²And laminated at 70 ℃ for 60 seconds to obtain a laminate in which the inner layer circuit board, the resin composition layer and the support are laminated. The laminate thus obtained was irradiated at 200mJ/cm²The ultraviolet exposure step of (3) was performed, and the support was peeled off and developed with a1 mass% sodium carbonate aqueous solution to prepare a laminate for evaluation.

(preparation of cured product for evaluation)

Irradiating the resin sheet with 200mJ/cm²Further subjected to a post-baking step of heating at 180 ℃ for 120 minutes, and then the support was peeled off to prepare a cured product for evaluation.

[ example 6 ]

An MEK slurry (0.5. mu. m TFE-YA (trade name), a volume average particle diameter of primary particles of 0.5. mu.m, a nonvolatile matter of 20 mass%, manufactured by Admatech Company Limited) of a silica-coated PTFE filler as silica-coated fluororesin particles (A) was mixed in 100 parts by mass (20 parts by mass in terms of nonvolatile matter), a maleimide compound (BMI-2300 (trade name), manufactured by Dahua Kazai Kagaku (registered trademark)) of 3.5 parts by mass, a biphenylaralkyl type epoxy resin as an epoxy resin (KAYARAD (registered trademark) NC3000H (trade name), manufactured by Nippon Kayaku Co., Ltd.) of 19.8 parts by mass, a PMA solution (KARADAR (registered trademark) of an acid-modified bisphenol F type epoxy acrylate compound as a compound having an ethylenically unsaturated group (PMA) (KARADR (registered trademark) of 1553H (trade name), a nonvolatile matter of 68% by mass, an acid value of 70: 70, g/g, and a PTFE filler, 77.6 parts by mass (52.8 parts by mass in terms of nonvolatile matter) of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA (trade name), manufactured by Japan chemical corporation) 18.9 parts by mass, MEK slurry of epoxy silane-treated silica (SC2050MB (trade name), median diameter 0.5 μm, nonvolatile matter 70% by mass, manufactured by Admatechs Company Limited) 42.9 parts by mass (36930 parts by mass in terms of nonvolatile matter) as another filler (C), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure (registered trademark)) as a photo-curing initiator (E), and 5 parts by mass of BASF Japan ltd. were mixed and stirred with an ultrasonic homogenizer to obtain a varnish. Thereafter, a resin sheet, a laminate for evaluation, and a cured product for evaluation were obtained in the same manner as in example 5.

[ example 7 ]

A varnish was prepared in the same manner as in example 5 except that 125 parts by mass (50 parts by mass in terms of nonvolatile content) of MEK slurry (PTFE-YA4 (trade name), 3.0 μm in volume average particle size of primary particles, 40% by mass in nonvolatile content, manufactured by admatech Company Limited) of a PTFE filler was coated with silica having a volume average particle size of primary particles of 3.0 μm as the silica-coated fluororesin particles (a), and a resin sheet, a laminate for evaluation, and a cured product for evaluation were obtained.

[ example 8 ]

A varnish was prepared in the same manner as in example 5 except that, instead of the PMA solution of the acid-modified bisphenol F type epoxy acrylate compound (KAYARAD (registered trademark) ZFR-1553H (trade name), nonvolatile content 68 mass%, acid value 70mgKOH/g, manufactured by Nippon Kabushiki Kaisha), 81.2 parts by mass (52.8 parts by mass in terms of nonvolatile content) of the PMA solution of the trisP-PA epoxy acrylate compound represented by formula (4) (KAYARAD (registered trademark) ZCR-6007H (trade name), nonvolatile content 65 mass%, acid value 70mgKOH/g, manufactured by Nippon Kabushiki Kaisha) was used as the compound having an ethylenically unsaturated group, and a resin sheet, a laminate for evaluation, and a cured product for evaluation were obtained.

The KAYARAD (registered trademark) ZCR-6007H is a mixture containing the compound (a1) and at least one of the compounds (a2) to (a 5).

[ comparative example 3]

A varnish was prepared in the same manner as in example 5 except that 125 parts by mass (50 parts by mass in terms of nonvolatile matter) of a PTFE dispersion (exp. fd-030 (trade name), median particle diameter 0.5 μm, nonvolatile matter 40%, manufactured by DIC corporation) was used instead of the silica-coated fluororesin particles (a), and a resin sheet, a laminate for evaluation, and a cured product for evaluation were obtained.

[ comparative example 4 ]

A varnish was prepared in the same manner as in example 5 except that the fluororesin pellets (a) were not covered with silica, and an MEK paste (SC2050MB (trade name), a median particle diameter of 0.5 μm, 70% by mass of nonvolatile matter, manufactured by admatech Company Limited) of epoxy silane-treated silica (50 parts by mass in terms of nonvolatile matter) was used as the other filler (C), to obtain a resin sheet, a laminate for evaluation, and a cured product for evaluation.

[ evaluation of physical Properties measurement ]

The metal-clad laminate, the laminate for evaluation, and the cured product for evaluation were measured and evaluated by the following methods. The results are shown in tables 1 to 3.

< wire embeddability >

A test piece obtained by etching and removing a whole or more than half of a copper foil of a metal foil-clad laminate 50mm × 50mm sample on one surface or a test piece of a laminate 50mm × 50mm for evaluation was treated with a pressure cooker tester (PC-3 type, manufactured by Hill Ltd.) at 121 ℃ under 2 atmospheres for 5 hours, immersed in solder at 260 ℃ for 60 seconds, and then visually observed for change in appearance, and evaluated according to the following criteria.

Very good: in 5 test pieces, no swelling was observed.

O: out of 5 test pieces, swelling was observed in 1.

X: in 5 test pieces, swelling was observed in 2 or more.

< solder Heat resistance >

A test piece of 50 mm. times.50 mm in thickness of the metal-clad laminate or a test piece of 50 mm. times.50 mm in thickness of the laminate for evaluation was floated for 30 minutes in a solder at 280 ℃ and evaluated according to the following criteria with visual observation for the presence or absence of appearance abnormality.

O: in 5 test pieces, no swelling was observed.

X: in 5 test pieces, swelling was observed in 1 or more.

< dielectric constant, dielectric loss tangent >

A dielectric constant and a dielectric loss tangent at 10GHz were measured on a test piece of the cured product for evaluation by a cavity resonator perturbation method (Agilent (registered trademark) 8722ES, manufactured by Agilent Technologies, Inc.).

< developability >

After visually observing the development surface of the laminate for evaluation, the laminate was observed with an SEM (magnification 1000 times), and the presence or absence of residue was evaluated according to the following criteria.

O: the developing residue was not present in the region of 30mm square, and the developability was excellent.

X: the developer residue was found in a range of 30mm square, and the developability was poor.

< Heat resistance (glass transition temperature) >

The temperature of the cured product for evaluation was increased at 10 ℃ per minute using a DMA apparatus (DMAQ 800 (trade name) as a dynamic viscoelasticity measuring apparatus manufactured by TA INSTRUMENTS Co., Ltd.) and the peak position of loss modulus (LossModulus) was defined as the glass transition temperature (Tg).

[ Table 1]

Item

Example 1

Example 2

Example 3

Example 4

Comparative example 1

Comparative example 2

Embeddability of wiring

◎

○

◎

×

◎

Solder heat resistance

○

×

○

Dielectric constant (10GHz)

3.1

3.2

2.6

3.2

3.3

Dielectric materialLoss tangent (10GHz)

0.003

[ Table 2]

Item	Example 5	Example 6	Example 7	Comparative example 3	Comparative example 4
						Embeddability of wiring	◎	◎	○	×	◎
Solder heat resistance	○	○	○	×	○
						Dielectric constant (10GHz)	2.7	2.8	2.7	2.7	2.9
Dielectric loss tangent (10GHz)	0.016	0.016	0.016	0.016	0.016
						Developability	○	○	○	○	○

[ Table 3]

Item	Example 8	Example 5
			Embeddability of wiring	◎	◎
Solder heat resistance	○	○
			Dielectric constant (10GHz)	2.7	2.7
Dielectric loss tangent (10GHz)	0.016	0.016
			Developability	○	○
Heat resistance (Tg (. degree. C.))	162	133

As is clear from tables 1,2 and 3, the wiring embedding property and heat resistance of examples 1 to 8 were excellent, and the dielectric constant and dielectric loss tangent were good. Among them, examples 1,4 and 5 are excellent in embeddability of wiring and dielectric constant. Further, example 8 was excellent in heat resistance (Tg). On the other hand, any of the wiring embeddability, heat resistance and dielectric constant of comparative examples 1 to 4 was insufficient. Therefore, according to the present invention, a resin composition excellent in dielectric constant, dielectric loss tangent, fine wiring embeddability, heat resistance, and developability, and a prepreg, a metal foil-clad laminate, a resin sheet, a printed wiring board, and a semiconductor device using the same can be obtained.

Claims

1. A resin composition comprising silica-coated fluororesin particles (A) and a resin component (B),

the silica-coated fluororesin particles (A) having a volume average particle diameter of primary particles of 2 μm or less,

the resin component (B) contains a compound having an ethylenically unsaturated group,

the compound having an ethylenically unsaturated group contains at least one or more selected from the group consisting of a 2-functional phenylene ether oligomer having a vinyl group, an oligomer of alpha-methylstyrene, an acid-modified bisphenol F-type epoxy (meth) acrylate, a compound represented by the following general formula (1), and dipentaerythritol hexa (meth) acrylate,

in the formula (1), a plurality of R₁Each independently represents a hydrogen atom or a methyl group, a plurality of R₂Each independently represents a hydrogen atom or a methyl group, a plurality of R₃Each independently represents a substituent represented by the following formula (2), a substituent represented by the following formula (3), or a hydroxyl group,

in the formula (3), R₄Represents a hydrogen atom or a methyl group.

2. The resin composition according to claim 1, wherein the content of the silica-coated fluororesin particles (a) in the resin composition is 3 to 400 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition.

3. The resin composition according to claim 1, wherein the resin component (B) further contains any one or more selected from the group consisting of a maleimide compound, a cyanate ester compound, an epoxy resin, a phenol resin, an oxetane resin, and a benzoxazine compound.

4. The resin composition according to claim 1, further comprising a filler (C) other than the silica-coated fluororesin particles (A).

5. The resin composition according to claim 1, further comprising a flame retardant (D).

6. The resin composition according to claim 1, further comprising a photo-curing initiator (E).

7. The resin composition according to claim 1, wherein the compound having an ethylenically unsaturated group contains at least the compound represented by the general formula (1).

8. A prepreg comprising a substrate and the resin composition according to any one of claims 1 to 7 impregnated or coated on the substrate.

9. A metal foil-clad laminate comprising at least 1 sheet of the prepreg according to claim 8 and a metal foil disposed on one or both surfaces of the prepreg.

10. A resin sheet comprising a support and the resin composition according to any one of claims 1 to 7 disposed on the surface of the support.

11. A printed circuit board having the resin composition as set forth in any one of claims 1 to 7.

12. A semiconductor device having the resin composition according to any one of claims 1 to 7.