Resin composition

Abstract

The present invention provides a resin composition which can provide a cured product having excellent stain removability. The present invention is a resin composition comprising (A) hollow organic polymer particles, (B) an epoxy resin, and (C) a curing agent.

Description

TECHNICAL FIELD

[0001] The present application relates to a resin composition containing an epoxy resin. Further, it relates to a cured product, a sheet-shaped laminated material, a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition. BACKGROUND

[0002] As a manufacturing technique of a printed wiring board, a manufacturing method based on a buildup method of alternately laminating an insulating layer and a conductor layer is known. In the manufacturing method based on the buildup method, generally, the insulating layer is formed by curing a resin composition.

[0003] In manufacturing a multilayer printed wiring board, it is required to sufficiently remove contamination (resin residue) in a via hole generated at the time of hole processing on an insulating layer in a roughening process.

[0004] It has been known that, by using core-shell type organic polymer particles as a component of a resin composition, cracks or warping due to deformation of an insulating layer accompanying temperature changes at the time of manufacturing a printed wiring board can be reduced (Patent Literature 1). In addition, various kinds of hollow organic polymer particles are known (Patent Literatures 2 to 5).

[0005] PRIOR ART DOCUMENTS

[0006] PATENT LITERATURE

[0007] Patent Literature 1: Japanese Patent Application Publication No. 2014-005464

[0008] Patent Literature 2: Japanese Patent Application Publication No. 2016-119230

[0009] Patent Literature 3: Japanese Patent Application Publication No. 2017-119823

[0010] Patent Literature 4: Japanese Patent Application Publication No. 2017-154087

[0011] Patent Literature 5: International Publication No. 2018 / 051794 SUMMARY

[0012] PROBLEMS TO BE SOLVED BY THE INVENTION

[0013] The present application relates to a resin composition containing an epoxy resin. Further, it relates to a cured product, a sheet-shaped laminated material, a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition.

[0014] MEANS FOR SOLVING THE PROBLEMS

[0015] As a result of intensive studies to achieve the object of the present application, the present inventors have found that the stain removal property can be unexpectedly improved by using hollow organic polymer particles as a component of the resin composition, thus completing the present application.

[0016] That is, the present application includes the following,

[0017] [1] A resin composition comprising (A) hollow organic polymer particles, (B) an epoxy resin, and (C) a curing agent;

[0018] [2] The resin composition according to the above [1], wherein the content of the (A) component is 3 mass% or more and 40 mass% or less, based on 100 mass% of the non-volatile components in the resin composition;

[0019] [3] The resin composition according to the above [1] or [2], wherein the organic polymer contained in the (A) component is an organic polymer composed of a monomer containing an olefinically unsaturated monomer;

[0020] [4] The resin composition according to the above [3], wherein the organic polymer contained in the (A) component is an organic polymer composed of a monomer containing styrene, or an organic polymer composed of a monomer containing a (meth)acrylic ester;

[0021] [5] The resin composition according to any one of the above [1] to [4], wherein the (A) component is a single-hollow particle;

[0022] [6] The resin composition according to any one of the above [1] to [5], wherein the (A) component has a porosity of 20 vol% or more;

[0023] [7] The resin composition according to any one of the above [1] to [6], wherein the (A) component has an average particle diameter of 0.2 μm or more and 20 μm or less;

[0024] [8] The resin composition according to any one of the above [1] to [7], further comprising (D) an inorganic filler material;

[0025] [9] The resin composition according to any one of the above [1] to [8], further comprising (E) a flame retardant;

[0026]

[10] The resin composition according to the above [9], wherein the (E) component contains a phosphorus-based flame retardant;

[0027]

[11] The resin composition according to the above

[10] , wherein the (E) component contains a phosphorus-based flame retardant containing a phenolic hydroxyl group;

[0028]

[12] The resin composition according to any one of [1] to

[11] above further comprises (F) an elastomer;

[0029]

[13] According to the resin composition described in

[12] above, wherein component (F) is a resin having one or more structures selected from polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure and polycarbonate structure.

[0030]

[14] The resin composition according to

[13] above, wherein component (F) comprises: a resin having a polybutadiene structure;

[0031]

[15] The resin composition according to

[14] above, wherein component (F) comprises: a polybutadiene resin containing phenolic hydroxyl groups;

[0032]

[16] A cured product, which is a cured product of the resin composition described in any one of [1] to

[15] above;

[0033]

[17] A sheet-like laminated material comprising the resin composition described in any one of [1] to

[15] above;

[0034]

[18] A resin sheet having: a support body and a resin composition layer formed of any one of the resin compositions described in [1] to

[15] disposed on the support body;

[0035]

[19] A printed wiring board having an insulating layer formed from a cured product of the resin composition described in any one of [1] to

[15] above;

[0036]

[20] A semiconductor device comprising the printed wiring board described above

[19] .

[0037] The effects of the invention

[0038] Using the resin composition of the present invention, a cured product with excellent stain removal properties can be obtained. Attached Figure Description

[0039] Figure 1 This is a cross-sectional image of a cured resin composition of the present invention according to one embodiment. Detailed Implementation

[0040] The present invention will now be described in detail according to preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any modifications without departing from the scope of the claims and their equivalents.

[0041] <Resin Composition>

[0042] The resin composition of the present application contains (A) hollow organic polymer particles, (B) an epoxy resin, and (C) a curing agent. By using such a resin composition, a cured product having excellent stain removability can be obtained.

[0043] For the resin composition of the present application, in addition to containing (A) hollow organic polymer particles, (B) an epoxy resin, and (C) a curing agent, any component can be further contained. As the any component, for example, (A') non-hollow organic polymer particles, (D) inorganic filler, (E) flame retardant, (F) elastomer, (G) thermoplastic resin, (H) other additive, and (I) organic solvent can be cited. Hereinafter, each component contained in the resin composition is described in detail.

[0044] (A) Hollow Organic Polymer Particles

[0045] The resin composition of the present application contains (A) hollow organic polymer particles. (A) Hollow organic polymer particles are particles containing an organic polymer having a pore (void) inside the particle. (A) Hollow organic polymer particles exist in the resin composition in the form of particles.

[0046] As the formation mode of the pore of (A) Hollow organic polymer particles, there is no particular limitation, and can be the mode of single-hollow particles having one pore inside the particle, or the mode of multi-hollow particles (particles containing hollow porous particles in a porous form inside the particle) having a plurality of pores inside the particle, and the mode of single-hollow particles is preferred.

[0047] (A) Hollow organic polymer particles can be spherical particles, or non-spherical particles, and spherical particles are preferred. (A) Hollow organic polymer particles preferably have a shell formed of at least one layer or more. The layer constituting the shell can be formed of one layer, or a plurality of layers of two or more. (A) Hollow organic polymer particles can be in the form in which the pore is covered with the shell.

[0048] The organic polymer contained in (A) Hollow organic polymer particles is preferably an organic polymer composed of a monomer containing an ethylenic unsaturated monomer. The ethylenic unsaturated monomer has at least one or more ethylenic unsaturated groups. As for the ethylenic unsaturated group, there is no particular limitation as long as it can be subjected to radical polymerization, and can be an ethylenic unsaturated group having a carbon-carbon double bond at the terminal or inside, and specifically, can be an unsaturated aliphatic group such as an allyl group, a 3-cyclohexenyl group, or the like; an aromatic group containing an unsaturated aliphatic group such as a p-vinylphenyl group, an m-vinylphenyl group, a styryl group, or the like; an α,β-unsaturated carbonyl group such as an acryloyl group, a methacryloyl group, a maleoyl group, a fumaryl group, or the like.

[0049] As the olefinically unsaturated monomer, for example, monofunctional olefinically unsaturated monomers, polyfunctional olefinically unsaturated monomers, silyl group-containing olefinically unsaturated monomers, epoxy group-containing olefinically unsaturated monomers, and the like can be given.

[0050] The monofunctional olefinically unsaturated monomer is a compound having one olefinically unsaturated group. As the monofunctional olefinically unsaturated monomer, there is no particular limitation, and for example, monofunctional aromatic vinyl compounds such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, and the like; monofunctional aromatic allyl compounds such as allylbenzene, 1-allyl-4-methylbenzene, and the like; monofunctional olefinic ester compounds such as vinyl acetate, vinyl propionate, allyl acetate, allyl propionate, vinyl butyrate, vinyl benzoate, and the like; monofunctional olefinic ether compounds such as allyl ethyl ether, and the like; aliphatic (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and the like; aromatic (meth)acrylates such as phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and the like; (meth)acrylates containing a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and the like; (meth)acrylates containing a halogen such as 2,2,2-trifluoroethyl (meth)acrylate, and the like; (meth)acrylates containing a cyano group such as methyl cyano(meth)acrylate, ethyl cyano(meth)acrylate, propyl cyano(meth)acrylate, isopropyl cyano(meth)acrylate, and the like; monofunctional olefinically unsaturated carboxylic acid esters; monofunctional olefinically unsaturated carboxylic acid amides such as (meth)acrylamide, maleimide, N-methylmaleimide, N-phenylmaleimide, and the like; monofunctional olefinically unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, and the like; monofunctional olefinically unsaturated nitrile compounds such as (meth)acrylonitrile, and the like can be given. The "(meth)acrylate" includes acrylate and methacrylate. The same applies to "(meth)acrylamide", "(meth)acrylonitrile", and the like. The monofunctional olefinically unsaturated monomer can be used alone or in combination of two or more.

[0051] The polyfunctional olefinically unsaturated monomer is a compound having multiple olefinically unsaturated groups. As the polyfunctional olefinically unsaturated monomer, there is no particular limitation, and examples that can be given include: conjugated dienes such as butadiene, isoprene, etc.; polyfunctional aromatic vinyl compounds such as p-divinylbenzene, m-divinylbenzene, etc.; polyfunctional aromatic olefin compounds; polyfunctional olefin ester compounds such as diallyl phthalate, triallyl isocyanurate, triallyl cyanurate, diallyl maleate, divinyl adipate, divinyl glutarate, etc.; polyfunctional olefin ether compounds such as tetraallyloxyethane, diallyl ether, etc.; polyfunctional olefinically unsaturated carboxylic acid esters such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.; polyfunctional olefinically unsaturated carboxylic acid amides such as N,N'-ethylenebis(meth)acrylamide, etc. One kind of polyfunctional olefinically unsaturated monomer can be used alone, or two or more kinds can be used in combination.

[0052] The silyl group-containing olefinically unsaturated monomer is a compound having at least one or more olefinically unsaturated groups and a silyl group (e.g., trialkoxysilyl group, alkyldialkoxysilyl group, etc.). As the silyl group-containing olefinically unsaturated monomer, there is no particular limitation, and examples that can be given include: vinyl silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, etc.; aromatic olefin silane compounds such as p-vinylphenyltrimethoxysilane, etc.; olefinically unsaturated carboxylic acid ester silane compounds such as 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 8-methacryloyloxyoctyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, etc. One kind of silyl group-containing olefinically unsaturated monomer can be used alone, or two or more kinds can be used in combination.

[0053] The epoxy group-containing olefinically unsaturated monomer is a compound having at least one or more olefinically unsaturated groups and an epoxy group. As the epoxy group-containing olefinically unsaturated monomer, there is no particular limitation, and examples that can be given include: epoxy group-containing aromatic olefin compounds such as styrene-4-glycidyl ether, 4-glycidylstyrene, etc.; epoxy group-containing olefin ether compounds such as allyl glycidyl ether, etc.; epoxy group-containing olefinically unsaturated carboxylic acid esters such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate, etc. One kind of epoxy group-containing olefinically unsaturated monomer can be used alone, or two or more kinds can be used in combination.

[0054] When the monomer constituting the polymer included in the organic polymer forming the (A) hollow organic polymer particles contains an ethylenically unsaturated monomer containing an epoxy group, it is preferable to further contain a crosslinkable monomer. As the crosslinkable monomer, there can be mentioned, for example, aliphatic polyamines such as ethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,6-hexanediamine, N-(2-aminoethyl)piperazine, 1,4-bis(3-aminopropyl)piperazine, 2,4,4-trimethyl-1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, bis(hexamethylene)triamine, poly(propylene glycol)diamine, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 3-amino-1-(cyclohexylamino)propane, 4,4'-diaminodicyclohexylmethane, isophorone diamine, 1,3-bis(aminomethyl)cyclohexane, bis(aminomethyl)norbornane, and the like; aromatic amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone, m-phenylenediamine, p-phenylenediamine, 2,3-toluenediamine, 2,4-toluenediamine, 2,5-toluenediamine, and the like. The crosslinkable monomer can be used singly or in combination of two or more.

[0055] In one embodiment, the organic polymer contained in the (A) hollow organic polymer particles is more preferably an organic polymer constituted by monomers containing one or more monomers selected from the group consisting of aromatic olefin compounds (e.g., monofunctional aromatic olefin compounds, polyfunctional aromatic olefin compounds, aromatic olefin silane-based compounds, aromatic olefin compounds containing an epoxy group, and the like) and ethylenically unsaturated carboxylic acid esters (e.g., monofunctional ethylenically unsaturated carboxylic acid esters, polyfunctional ethylenically unsaturated carboxylic acid esters, ethylenically unsaturated carboxylic acid ester silane-based compounds, ethylenically unsaturated carboxylic acid esters containing an epoxy group, and the like). The organic polymer contained in the (A) hollow organic polymer particles is further preferably an organic polymer constituted by monomers containing one or more monomers selected from the group consisting of aromatic olefin compounds, or an organic polymer constituted by monomers containing one or more monomers selected from the group consisting of ethylenically unsaturated carboxylic acid esters. The organic polymer contained in the (A) hollow organic polymer particles is further preferably an organic polymer constituted by monomers containing styrene, or an organic polymer constituted by monomers containing (meth)acrylic acid esters.

[0056] In one embodiment, the organic polymer contained in the (A) hollow organic polymer particles is more preferably an organic polymer constituted by monomers containing one or more monomers selected from the group consisting of silyl group-containing ethylenically unsaturated monomers and epoxy group-containing ethylenically unsaturated monomers.

[0057] The hollow organic polymer particles (A) can be treated with a surface treatment agent. As the surface treatment agent for the hollow organic polymer particles (A), there can be mentioned, for example, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and the like; carboxylic acids such as acetic acid, propionic acid, butyric acid, acrylic acid, and the like; sulfonic acids such as p-toluenesulfonic acid, ethanesulfonic acid, dodecylbenzenesulfonic acid, and the like; phosphoric acids such as polyoxyethylene alkyl ether phosphates and the like; phosphonic acids, phosphinic acids, and the like; silane coupling agents such as tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, and the like; isocyanate-based compounds such as ethyl isocyanate, and the like.

[0058] The porosity of the hollow organic polymer particles (A) is not particularly limited, and is preferably 1% by volume or more, more preferably 5% by volume or more, further preferably 10% by volume or more, further more preferably 15% by volume or more, further more preferably 20% by volume or more, particularly preferably 25% by volume or more. The upper limit of the porosity of the hollow organic polymer particles (A) is not particularly limited, and can be, for example, 99% by volume or less, 95% by volume or less, 90% by volume or less, 80% by volume or less, 70% by volume or less, 60% by volume or less, or the like. The porosity refers to the proportion of the volume of the pores inside the particles in the total volume of the particles.

[0059] The average particle diameter of the hollow organic polymer particles (A) is not particularly limited, and is preferably 100 μm or less, more preferably 50 μm or less, further preferably 30 μm or less, further more preferably 20 μm or less, particularly preferably 10 μm or less. The lower limit of the average particle diameter of the hollow organic polymer particles (A) is not particularly limited, and is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, further more preferably 0.2 μm or more, particularly preferably 0.3 μm or more. The average particle diameter of the hollow organic polymer particles (A) is a number average value.

[0060] As a commercially available product of the hollow organic polymer particles (A), there can be mentioned, for example, "XX-5598Z" manufactured by Sekisui Plastics Co., Ltd., and the like. In addition, the hollow organic polymer particles (A) can be produced using a publicly known method. As the publicly known method, there can be mentioned, for example, the methods described in WO2018 / 051794, Japanese Patent Application Publication No. 2017-119843, Japanese Patent Application Publication No. 2017-119843, Japanese Patent Application Publication No. 2016-119230, Japanese Patent No. 4-68324, Japanese Patent Application Publication No. 63-135409, Japanese Patent Application Publication No. 2002-241448, and the like.

[0061] The content of the (A) hollow organic polymer particles in the resin composition is not particularly limited, and is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, further more preferably 3% by mass or more, particularly preferably 4% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass. The upper limit of the content of the (A) hollow organic polymer particles in the resin composition is not particularly limited, and is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass.

[0062] <(A') Non-Hollow Organic Polymer Particles>

[0063] For the resin composition of the present application, in addition to containing the (A) hollow organic polymer particles, (A') non-hollow organic polymer particles can be further contained as an arbitrary non-volatile component. The (A') non-hollow organic polymer particles are particles containing an organic polymer that do not have pores inside the particles.

[0064] The (A') non-hollow organic polymer particles exist in the resin composition in the form of particles. As the (A') non-hollow organic polymer particles, for example, non-hollow rubber particles, non-hollow polyamide particles, non-hollow silicone particles, and the like can be given, of which non-hollow rubber particles are preferred.

[0065] As the rubber component contained in the non-hollow rubber particles, for example, the following can be given: polybutadiene, polyisoprene, polychloroprene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, ethylene-propylene-butene terpolymer, and the like olefin-based thermoplastic elastomers; poly(propyl (meth)acrylate), poly(butyl (meth)acrylate), poly(cyclohexyl (meth)acrylate), poly(octyl (meth)acrylate), and the like acrylic-based thermoplastic elastomers; and the like thermoplastic elastomers.

[0066] From the viewpoint of obtaining the desired effects of the present application more remarkably, the (A') non-hollow organic polymer particles are preferably core-shell rubber particles. The so-called core-shell rubber particles are particles of rubber formed of "core particles containing the rubber component as listed above" and "1 or more shell portions covering the same". The core-shell rubber particles do not necessarily mean only particles in which the core particles and the shell portions can be clearly distinguished, but also include particles in which the boundary between the core particles and the shell portions is not clear, and the core particles can also be not completely covered with the shell portions. As the monomer component forming the shell portion of the core-shell rubber particles, the same monomer components as the olefinically unsaturated monomers described in the (A) hollow organic polymer particles can be cited.

[0067] The average particle diameter (average primary particle diameter) of the (A') non-hollow organic polymer particles is not particularly limited, and is preferably 20 nm or more, more preferably 50 nm or more, further preferably 80 nm or more, and particularly preferably 100 nm or more. The upper limit of the average particle diameter (average primary particle diameter) of the (A') non-hollow organic polymer particles is not particularly limited, and is preferably 5,000 nm or less, more preferably 2,000 nm or less, further preferably 1,000 nm or less, and particularly preferably 500 nm or less. The average particle diameter (average primary particle diameter) of the (A') non-hollow organic polymer particles can be measured using a Zeta potential particle size distribution measuring device or the like.

[0068] As commercially available products of the core-shell type rubber particles, for example, "IM401-4-14" manufactured by AICA Industrial Co., Ltd.; "CHT" manufactured by Cheil Industries Co., Ltd.; "B602" manufactured by UMG ABS Co., Ltd.; "PARALOID EXL-2602", "PARALOID EXL-2603", "PARALOID EXL-2655", "PARALOID EXL-2311", "PARALOID-EXL 2313", "PARALOID EXL-2315", "PARALOID KM-330", "PARALOID KM-336P", "PARALOID KCZ-201" manufactured by Dow Chemical Japan Co., Ltd.; "METABLEN C-223A", "METABLEN E-901", "METABLEN S-2001", "METABLEN W-450A", "METABLEN SRK-200" manufactured by Mitsubishi Rayon Co., Ltd.; "Kane Ace M-511", "Kane Ace M-600", "Kane Ace M-400", "Kane Ace M-580", "Kane Ace MR-01" manufactured by Kaneka Co., Ltd., and the like can be given. They can be used alone as one kind or in combination of two or more kinds.

[0069] The content of the (A') non-hollow organic polymer particles in the resin composition is not particularly limited, and when the non-volatile component in the resin composition is taken as 100% by mass, it is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, further more preferably 10% by mass or less, and particularly preferably 7% by mass or less. The lower limit of the content of the (A') non-hollow organic polymer particles in the resin composition is not particularly limited, and when the non-volatile component in the resin composition is taken as 100% by mass, it can be, for example, 0% by mass or more, 0.1% by mass or more, 1% by mass or more, 3% by mass or more, 5% by mass or more, and the like in one embodiment.

[0070] The mass ratio of the (A') non-hollow organic polymer particles to the (A) hollow organic polymer particles ((A') non-hollow organic polymer particles / (A) hollow organic polymer particles) in the resin composition is not particularly limited, and it is preferably 10 or less, more preferably 2 or less, further preferably 1.5 or less, and particularly preferably 1.2 or less.

[0071] (B) Epoxy Resin

[0072] The resin composition of the present application contains a (B) epoxy resin. The (B) epoxy resin refers to a curable resin having an epoxy group.

[0073] Examples of epoxy resins (B) include: bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, and naphthol phenolic varnish. Novolac type epoxy resin, phenolnovolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresolnovolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spirocyclic ring, cyclohexane type epoxy resin, cyclohexanediol type epoxy resin, naphthyl ether type epoxy resin, tris(hydroxymethyl) type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenol benzopyrrolidone type epoxy resin, phenolphthalein type epoxy resin, etc. (B) One type of epoxy resin can be used alone, or two or more types can be used in combination.

[0074] For the resin composition, as epoxy resin (B), it is preferable to include epoxy resin having two or more epoxy groups in one molecule. The proportion of epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of the non-volatile component of epoxy resin (B).

[0075] The epoxy resin includes an epoxy resin that is liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resin"). For the resin composition of the present invention, the epoxy resin may consist only of liquid epoxy resin, or only of solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin. The epoxy resin in the resin composition of the present invention is preferably a solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin, and more preferably a solid epoxy resin.

[0076] As a liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0077] As the liquid epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, and an epoxy resin having a butadiene structure are preferable.

[0078] As the liquid epoxy resin, "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", "EPIKOTE 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidyl amine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycirol type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L", "EP-3980S" (glycidyl amine type epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Corporation; "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Corporation; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600" manufactured by Daicel Corporation, "JP-100", "JP-200" (epoxy resin having a butadiene structure) manufactured by Japan Cabot Corporation; "ZX1658", "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and the like can be given as specific examples. One of them can be used alone, or two or more of them can be used in combination.

[0079] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and a solid epoxy resin of aromatic series having three or more epoxy groups in one molecule is more preferable.

[0080] As the solid epoxy resin, a bisphenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a naphthol novolak type epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthalene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, a phenol aralkyl type epoxy resin, a tetraphenyl ethane type epoxy resin, a phenol benzopyrrolone type epoxy resin, a phenolphthalein type epoxy resin are preferred.

[0081] As specific examples of the solid epoxy resin, "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthalene ether type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (triphenol type epoxy resin) manufactured by Japan Epoxy Resin Co., Ltd.; "NC7000L" (naphthol novolak type epoxy resin) manufactured by Japan Epoxy Resin Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Japan Epoxy Resin Co., Ltd.; "ESN475V" (naphthalene type epoxy resin) manufactured by NIPPON STEEL Chemical & Material Co., Ltd.; "ESN485" (naphthol type epoxy resin) manufactured by NIPPON STEEL Chemical & Material Co., Ltd.; "ESN375" (dihydroxy naphthalene type epoxy resin) manufactured by NIPPON STEEL Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (dixylylphenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" (phenol benzopyrrolone type epoxy resin) manufactured by Japan Epoxy Resin Co., Ltd., and the like can be given. One of them can be used alone, or two or more of them can be used in combination.

[0082] As the (B) component, in the case of using a liquid epoxy resin and a solid epoxy resin in combination, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin / solid epoxy resin) is not particularly limited, and is preferably 10 or less, more preferably 5 or less, further preferably 3 or less, further more preferably 1 or less, and particularly preferably 0.8 or less.

[0083] The epoxy equivalent weight of the (B) epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., further preferably 70 g / eq. to 1,000 g / eq., and further more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent weight is the mass of the resin per 1 equivalent of epoxy groups. The epoxy equivalent weight can be measured in accordance with JIS K 7236.

[0084] The weight average molecular weight (Mw) of the (B) epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and further preferably 400 to 1,500. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a value in terms of polystyrene.

[0085] The content of the (B) epoxy resin in the resin composition is not particularly limited, and is preferably 70 mass% or less, more preferably 60 mass% or less, further preferably 50 mass% or less, further more preferably 40 mass% or less, and particularly preferably 35 mass% or less, based on 100 mass% of the non-volatile components in the resin composition. The lower limit of the content of the (B) epoxy resin in the resin composition is not particularly limited, and is preferably 0.1 mass% or more, more preferably 1 mass% or more, further preferably 5 mass% or more, further more preferably 10 mass% or more, and particularly preferably 15 mass% or more, based on 100 mass% of the non-volatile components in the resin composition.

[0086] (C) Curing Agent

[0087] The resin composition of the present application contains a (C) curing agent. The (C) curing agent can be classified into a (C-1) epoxy curing agent having a function of curing the (B) epoxy resin, and a (C-2) curing accelerator having a function of accelerating the curing of the (B) epoxy resin. For the resin composition of the present application, it is preferable to contain at least one of the (C-1) epoxy curing agent and the (C-2) curing accelerator as the (C) curing agent. Note that the (C) curing agent described herein is a component that does not belong to the (E) flame retardant or the (F) elastomer.

[0088] The content of the (C) curing agent in the resin composition is not particularly limited, and is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, further more preferably 30% by mass or less, particularly preferably 25% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of the (C) curing agent in the resin composition is not particularly limited, and can be, for example, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.2% by mass or more, or the like, based on 100% by mass of the nonvolatile components in the resin composition.

[0089] <(C-1) epoxy curing agent>

[0090] The (C-1) epoxy curing agent is not particularly limited, and examples that can be given include phenol-based curing agents, naphthol-based curing agents, acid anhydride-based curing agents, amine-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents. The (C-1) epoxy curing agent can be used alone or in combination with two or more kinds.

[0091] The phenol-based curing agent and the naphthol-based curing agent preferably have a novolac structure from the viewpoint of heat resistance and water resistance. In addition, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable from the viewpoint of adhesion to the adherend, and a phenol-based curing agent containing a triazine skeleton or a naphthol-based curing agent containing a triazine skeleton is more preferable. Among these, a phenol-based curing agent containing a triazine skeleton is preferable from the viewpoint of satisfying heat resistance, water resistance, and adhesion. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851", "MEH-8000" manufactured by Meiwa Chemical Co., Ltd., "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495V", "SN-375", "SN-395" manufactured by Nippon Steel Chemical Co., Ltd., "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "LA-1356", "TD-2090-60M", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165" manufactured by DIC Corporation, "GDP-6115L", "GDP-6115H" manufactured by Gunze Chemical Co., Ltd., and the like.

[0092] As the acid anhydride-based curing agent, a curing agent having one or more acid anhydride groups in one molecule, preferably a curing agent having two or more acid anhydride groups in one molecule can be given. As specific examples of the acid anhydride-based curing agent, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetra carboxylic dianhydride, biphenyl tetra carboxylic dianhydride, naphthalene tetra carboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetra carboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride ester), a styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid, and the like polymer type acid anhydride can be given. As commercially available products of the acid anhydride-based curing agent, "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nippon Rikagaku Co., Ltd., "YH-306", "YH-307" manufactured by Mitsubishi Chemical Corporation, "HN-2200", "HN-5500" manufactured by Hitachi Chemical Co., Ltd., and the like can be given.

[0093] As amine-based curing agents, examples include curing agents having one or more, preferably two or more, amino groups within one molecule. Examples include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. From the viewpoint of achieving the desired effect of the present invention, aromatic amines are preferred. The amine-based curing agent is preferably a primary or secondary amine, more preferably a primary amine. Specific examples of amine-based curing agents include: 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybiphenylamine, 2,2-bis(3-amino-4-hydroxy) 2,2-bis(4-aminophenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Amine-based curing agents can be commercially available, such as SEIKA's "SEIKACURE-S", Nippon Kayaku Co.'s "KAYABONDC-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS", and Mitsubishi Chemical's "EpicureW".

[0094] As the active ester-based curing agent, there is no particular limitation, and generally, a compound having two or more ester groups with high reactivity in one molecule, such as a phenol ester, a thiol ester, an N-hydroxy amide ester, an ester of a heterocyclic hydroxyl compound, etc. can be preferably used. The active ester-based curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl compound and / or a mercaptan compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. As the carboxylic acid compound, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. can be exemplified. As the phenol compound or the naphthol compound, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, a-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, a dicyclopentadiene-type phenol compound, a phenol novolak resin, etc. can be exemplified. Here, the "dicyclopentadiene-type phenol compound" refers to a phenol compound obtained by condensing two molecules of phenol on one molecule of dicyclopentadiene.

[0095] Specifically, an active ester-based curing agent including a dicyclopentadiene-type phenol structure, an active ester-based curing agent including a naphthalene structure, an active ester-based curing agent including an acetylated product of a phenol novolak resin, an active ester-based curing agent including a benzoylated product of a phenol novolak resin are preferable, and more preferably, an active ester-based curing agent including a naphthalene structure, an active ester-based curing agent including a dicyclopentadiene-type phenol structure. The "dicyclopentadiene-type phenol structure" refers to a divalent structure formed by phenylene-dicyclopentylene-phenylene.

[0096] As commercially available products of the active ester-based curing agent, there are, for example, "EXB9451", "EXB9460", "EXB9460S", "EXB9460S-65T", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM" (manufactured by DIC Corporation) as active ester-based curing agents containing dicyclopentadiene type diphenol structure, "EXB-9416-70BK", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T" (manufactured by DIC Corporation) as active ester compounds containing naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent which is an acetylated product of a phenol novolak resin, "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester-based curing agents which are benzoylated products of a phenol novolak resin, and the like.

[0097] As specific examples of the benzoxazine-based curing agent, there are, for example, "JBZ-OP100D", "ODA-BOZ" (manufactured by JFE Chemical Corporation), "HFB2006M" (manufactured by Showa Highpolymer Co., Ltd.), "P-d", "F-a" (manufactured by Shikoku Chemicals Corporation), and the like.

[0098] As the cyanate ester-based curing agent, there are, for example, difunctional cyanate ester resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidenebisphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanato)phenylpropane, 1,1-bis(4-cyanatophenyl)methane, bis(4-cyanato-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methyl ethylene))benzene, bis(4-cyanatophenyl) sulfide, and bis(4-cyanatophenyl) ether, polyfunctional cyanate ester resins derived from phenol novolak resins, cresol novolak resins, and the like, and prepolymers obtained by partially triazine-izing these cyanate ester resins. As specific examples of the cyanate ester-based curing agent, there are, for example, "PT30" and "PT60" (both are phenol novolak type polyfunctional cyanate ester resins), "BA230", "BA230S75" (prepolymers obtained by triazine-izing a part or all of bisphenol A dicyanate to form a trimer) (manufactured by Lonza Japan Corporation), and the like.

[0099] As specific examples of the carbodiimide-based curing agent, "V-03", "V-07", etc. manufactured by Nippon Shokubai Co., Ltd. can be given.

[0100] The active group equivalent weight of the (C-1) epoxy curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., further preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The active group equivalent weight is the mass of the (C-1) epoxy curing agent per 1 equivalent of the active group. Here, the active group of the (C) curing agent differs depending on the type of the curing agent, and for example, if the curing agent is a phenol-based curing agent and a naphthol-based curing agent, the active group is a phenolic hydroxyl group, and if the curing agent is an active ester-based curing agent, the active group is an active ester group.

[0101] The content of the (C-1) epoxy curing agent in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, further more preferably 30% by mass or less, and particularly preferably 25% by mass or less. The lower limit of the content of the (C-1) epoxy curing agent in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100% by mass, it can be, for example, 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, 5% by mass or more, or 10% by mass or more.

[0102] As the (E) flame retardant or the (F) elastomer, in the case where a component having an active group such as a phenolic hydroxyl group is used, since the component has the same function as the (C-1) epoxy curing agent, the (C-1) epoxy curing agent can not be used.

[0103] <(C-2) Curing Accelerator>

[0104] As the (C-2) curing accelerator, there is no particular limitation, and examples include phosphorus-based curing accelerators, urea-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. The (C-2) curing accelerator can be used alone as one kind, or two or more kinds can be used in combination.

[0105] As the phosphorus-based curing accelerator, there are mentioned, for example, aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrogenhexahydrophtalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, di-tert-butylmethylphosphonium tetraphenylborate and the like; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane and the like; aromatic phosphine-quinone adducts such as triphenylphosphine-p-benzoquinone adduct and the like; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine and the like; aromatic phosphines such as dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino) diphenyl ether and the like.

[0106] As the urea-based curing accelerator, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea, and the like aliphatic dimethylureas; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) (toluene bisdimethylurea), and the like aromatic dimethylureas, and the like can be mentioned.

[0107] As the guanidine-based curing accelerator, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, and the like can be mentioned.

[0108] As the imidazole-based curing accelerator, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and the like imidazole compounds, and adducts of the imidazole compounds with epoxy resins.

[0109] As the imidazole-based curing accelerator, commercially available products can be used, and for example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Chemicals Corporation, "P200-H50" manufactured by Mitsubishi Chemical Corporation and the like can be mentioned.

[0110] As the metal-based curing accelerator, for example, organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, tin and the like can be mentioned. As specific examples of the organic metal complexes, for example, organic cobalt complexes such as acetylacetone cobalt (II), acetylacetone cobalt (III), organic copper complexes such as acetylacetone copper (II), organic zinc complexes such as acetylacetone zinc (II), organic iron complexes such as acetylacetone iron (III), organic nickel complexes such as acetylacetone nickel (II), organic manganese complexes such as acetylacetone manganese (II) and the like can be mentioned. As the organic metal salts, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like can be mentioned.

[0111] As the amine-based curing accelerator, for example, trialkyl amines such as triethylamine, tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene and the like can be mentioned.

[0112] As the amine-based curing accelerator, commercially available products can be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc., and the like.

[0113] The content of the (C-2) curing accelerator in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100% by mass, it is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, further more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. The lower limit of the content of the (C-2) curing accelerator in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100% by mass, it can be, for example, 0% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.2% by mass or more, or the like.

[0114] (D) Inorganic Filler

[0115] The resin composition of the present application sometimes contains a (D) inorganic filler as an arbitrary component. The (D) inorganic filler is contained in the resin composition in the state of particles.

[0116] As the material of the (D) inorganic filler, an inorganic compound is used. As the material of the (D) inorganic filler, examples thereof include silicon dioxide, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconium titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphotungstate, and the like. Among these, silicon dioxide is particularly preferable. As the silicon dioxide, examples thereof include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, and the like. In addition, as the silicon dioxide, spherical silicon dioxide is preferable. The (D) inorganic filler can be used alone as one kind, or two or more kinds can be used in combination at an arbitrary ratio.

[0117] As a commercially available product of the (D) inorganic filler, for example, "UFP-30" manufactured by Kureha Chemical Industry Co., Ltd.; "SP60-05", "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by Denka Co., Ltd.; "Silfil (シルフィル) NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama Co., Ltd.; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs Co., Ltd.; "DAW-03", "FB-105FD" manufactured by Denka Co., Ltd., and the like can be given.

[0118] The average particle diameter of the (D) inorganic filler is not particularly limited, and is preferably 10 μm or less, more preferably 5 μm or less, further preferably 2 μm or less, further more preferably 1 μm or less, particularly preferably 0.7 μm or less. The lower limit of the average particle diameter of the (D) inorganic filler is not particularly limited, and is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, particularly preferably 0.2 μm or more. The average particle diameter of the (D) inorganic filler can be measured by a laser diffraction scattering method based on Mie scattering theory. Specifically, it can be measured by using a laser diffraction scattering type particle size distribution measuring device to make a particle size distribution of the inorganic filler on a volume basis, and taking the median particle diameter as the average particle diameter. The measurement sample can use a sample obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial, and dispersing by ultrasonic waves for 10 minutes. With respect to the measurement sample, a laser diffraction type particle size distribution measuring device is used, the wavelength of the light source is set to blue and red, the particle size distribution of the inorganic filler on a volume basis is measured in a flow cell manner, and the average particle diameter is calculated from the obtained particle size distribution as the median particle diameter. As the laser diffraction type particle size distribution measuring device, for example, "LA-960" manufactured by Horiba Ltd., and the like can be given.

[0119] The specific surface area of the (D) inorganic filler is not particularly limited, and is preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, further preferably 1 m 2 / g or more, particularly preferably 3 m 2 / g or more. The upper limit of the specific surface area of the (D) inorganic filler is not particularly limited, and is preferably 100 m 2 / g or less, more preferably 70 m 2below, further preferably 50 m 2 below, particularly preferably 40 m 2 below. The specific surface area of the inorganic filler can be obtained by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) to adsorb nitrogen gas to the surface of a sample using the BET method, and calculating the specific surface area using the BET multipoint method.

[0120] (D) The inorganic filler material is preferably surface-treated with a suitable surface treatment agent. By surface-treating, the moisture resistance and dispersibility of the inorganic filler material (D) can be improved. As the surface treatment agent, there can be mentioned, for example, vinyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane; epoxy silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; styryl silane coupling agents such as p-styryltrimethoxysilane; methacrylic silane coupling agents such as 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane; acrylic silane coupling agents such as 3-acryloyloxypropyltrimethoxysilane; amino silane coupling agents such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(l,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate silane coupling agents such as tris(trimethoxysilylpropyl)isocyanurate; ureido silane coupling agents such as 3-ureidopropyltrialkoxysilane; mercapto silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane; isocyanate silane coupling agents such as 3-isocyanatopropyltriethoxysilane; anhydride silane coupling agents such as 3-trimethoxysilylpropyl succinic anhydride; and the like. In addition, the surface treatment agent can be used singly or in combination of two or more at an arbitrary ratio.

[0121] As commercially available products of the surface treatment agent, there are, for example, "KBM-1003", "KBE-1003" (vinyl-based silane coupling agent) ; "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy-based silane coupling agent) ; "KBM-1403" (styryl-based silane coupling agent) ; "KBM-502", "KBM-503", "KBE-502", "KBE-503" (methacrylic acid-based silane coupling agent) ; "KBM-5103" (acrylic acid-based silane coupling agent) ; "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amino-based silane coupling agent) ; "KBM-9659" (isocyanurate-based silane coupling agent) ; "KBE-585" (ureido-based silane coupling agent) ; "KBM-802", "KBM-803" (mercapto-based silane coupling agent) ; "KBE-9007N" (isocyanate-based silane coupling agent) ; "X-12-967C" (anhydride-based silane coupling agent) ; "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (non-silane coupling-alkoxysilane compound), and the like.

[0122] From the viewpoint of improving the dispersibility of the inorganic filler material, it is preferable to limit the degree of surface treatment based on the surface treatment agent to a prescribed range. Specifically, for 100 mass% of the inorganic filler material, it is preferable to perform surface treatment with 0.2 mass% to 5 mass% of the surface treatment agent, more preferable to perform surface treatment with 0.2 mass% to 3 mass%, and further preferable to perform surface treatment with 0.3 mass% to 2 mass%.

[0123] The degree of surface treatment based on the surface treatment agent can be evaluated by the carbon amount per unit surface area of the inorganic filler material. From the viewpoint of improving the dispersibility of the inorganic filler material, it is preferable for the carbon amount per unit surface area of the inorganic filler material to be 0.02 mg / m 2 More preferably, it is 0.1 mg / m 2 Further preferably, it is 0.2 mg / m 2 Above. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition, the melt viscosity in the sheet form, it is preferable to be 1.0 mg / m 2The following, more preferably 0.8 mg / m 2 The following, further preferably 0.5 mg / m 2 The following.

[0124] (D) The amount of carbon per unit surface area of the inorganic filler can be measured after washing the inorganic filler subjected to surface treatment with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler subjected to surface treatment with a surface treatment agent, and ultrasonic washing is performed at 25°C for 5 minutes. The supernatant is removed, and the solid component is dried, and then the amount of carbon per unit surface area of the inorganic filler is measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd., or the like can be used.

[0125] The content of (D) the inorganic filler in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100% by mass, it is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, further more preferably 60% by mass or less, and particularly preferably 55% by mass or less. The lower limit of the content of (D) the inorganic filler in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100% by mass, it can be, for example, 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, 10% by mass or more, or the like.

[0126] (E) Flame Retardant

[0127] The resin composition of the present application sometimes contains (E) a flame retardant as an arbitrary component.

[0128] As (E) the flame retardant, for example, phosphorus-based flame retardants such as phosphazene compounds, phosphates, phosphoric acid esters, polyphosphates, phosphinates, phosphinite esters, phosphonates, phosphonic acid esters, and the like; nitrogen-based flame retardants such as aliphatic amine compounds, aromatic amine compounds, nitrogen-containing heterocyclic compounds, urea compounds, and the like; inorganic-based flame retardants such as magnesium hydroxide, aluminum hydroxide, antimony compounds such as antimony trioxide, antimony pentoxide, sodium antimonate, and the like; halogen-based flame retardants such as hexabromobenzene, chlorinated paraffin, brominated polycarbonate resin, brominated epoxy resin, brominated phenoxy resin, brominated polyphenyl ether resin, brominated polystyrene resin, poly(bromobenzyl acrylate) resin, and the like; and the like can be given, of which phosphorus-based flame retardants are preferred. (E) The flame retardant can be used alone as one kind, or two or more kinds can be used in combination.

[0129] As the phosphazene compound, there are, for example, phenoxy cyclotriphosphazene, tris(4-hydroxyphenoxy) triphenoxy cyclotriphosphazene, hexa(4-hydroxyphenoxy) cyclotriphosphazene, tris(4-methylphenoxy) triphenoxy cyclotriphosphazene, tris(4-cyanophenoxy) triphenoxy cyclotriphosphazene, hexa(4-aminophenoxy) cyclotriphosphazene, tris[4-(2-glycidyloxyethyl)phenoxy] triphenoxy cyclotriphosphazene, octaphenoxy cyclotetraphosphazene, and the like.

[0130] As the phosphoric acid salt, there are, for example, ammonium phosphate, melamine phosphate, piperazine phosphate, and the like.

[0131] As the phosphoric acid ester, there are, for example, non-halogen aliphatic phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, and the like; non-halogen aromatic phosphoric acid esters such as triphenyl phosphate, cresyl diphenyl phosphate, xylenyl phenyl phosphate, mesityl phosphate, tri(2,6-dimethylphenyl) phosphate, tri(4-isopropylphenyl) phosphate, tri(4-tert-butylphenyl) phosphate, bis(4-tert-butylphenyl) phenyl phosphate, hydroxyphenyl diphenyl phosphate, octyldiphenyl phosphate, 2-ethylhexyl diphenyl phosphate, and the like; halogen aliphatic phosphoric acid esters such as tri(l-chloro-2-propyl) phosphate, tri(l,3-dichloro-2-propyl) phosphate, tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate, and the like.

[0132] As the polyphosphoric acid salt, there are, for example, ammonium polyphosphate, melamine polyphosphate, and the like.

[0133] As the phosphinic acid salt, there are, for example, dialkyl phosphinic acid salts such as aluminum tris(diethyl phosphinate), zinc bis(diethyl phosphinate), aluminum tris(methylethyl phosphinate), zinc bis(methylethyl phosphinate), titanium tetrakis(diethyl phosphinate), and the like; diaryl phosphinic acid salts such as zinc bis(diphenyl phosphinate), titanium tetrakis(diphenyl phosphinate), and the like.

[0134] As the phosphinic acid ester, for example, dialkyl phosphinic acid esters such as methyl methylphosphinate, ethyl methylphosphinate, ethyl ethylphosphinate, ethylene ethylphosphinate, phenyl ethylphosphinate, and the like; acyclic diaryl phosphinic acid esters such as phenyl phenylphosphinate, methyl phenylphosphinate, ethyl phenylphosphinate, and the like; cyclic diaryl phosphinic acid esters such as 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dihydroxy-2-naphthyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxydiphenyl-4-yl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-[2,4-bis(glycidyloxy)phenyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like; cyclic monoaryl phosphinic acid esters such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like; cyclic arylalkyl phosphinic acid esters such as 9,10-dihydro-10-benzyl-9-oxa-10-phosphaphenanthrene-10-oxide, 10-[2,3-bis(2-hydroxyethoxycarbonyl)propyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a polyether condensate thereof, 10-(2-cyanoethyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-[2-(3,4-epoxycyclohexyl)ethyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3-glycidyloxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like, can be given.

[0135] As the phosphinic acid salt, for example, zinc methanephosphonate, zinc ethylphosphonate, zinc butylphosphonate, zinc phenylphosphonate, and the like, can be given.

[0136] As the phosphinic acid ester, for example, dialkyl phosphinic acid esters such as methyl methylphosphinate, ethyl methylphosphinate, ethyl ethylphosphinate, ethylene ethylphosphinate, phenyl ethylphosphinate, and the like; acyclic diaryl phosphinic acid esters such as phenyl phenylphosphinate, methyl phenylphosphinate, ethyl phenylphosphinate, and the like; cyclic diaryl phosphinic acid esters such as 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dihydroxy-2-naphthyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxydiphenyl-4-yl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-[2,4-bis(glycidyloxy)phenyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like; cyclic monoaryl phosphinic acid esters such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like; cyclic arylalkyl phosphinic acid esters such as 9,10-dihydro-10-benzyl-9-oxa-10-phosphaphenanthrene-10-oxide, 10-[2,3-bis(2-hydroxyethoxycarbonyl)propyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a polyether condensate thereof, 10-(2-cyanoethyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-[2-(3,4-epoxycyclohexyl)ethyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3-glycidyloxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like, can be given.

[0137] (E) The flame retardant preferably comprises a phosphorus-based flame retardant, more preferably a phosphorus-based flame retardant containing phenolic hydroxyl groups, and particularly preferably a phosphonate containing phenolic hydroxyl groups. The phenolic hydroxyl equivalent of the phosphorus-based flame retardant containing phenolic hydroxyl groups is not particularly limited, but is preferably 80 g / eq. to 1,000 g / eq., more preferably 100 g / eq. to 500 g / eq., further preferably 110 g / eq. to 300 g / eq., even more preferably 120 g / eq. to 200 g / eq., and preferably 130 g / eq. to 180 g / eq. The phenolic hydroxyl equivalent is the mass of one equivalent of the phosphorus-based flame retardant containing phenolic hydroxyl groups. Like the epoxy curing agent (C-1), the phosphorus-based flame retardant containing phenolic hydroxyl groups has the function of curing the epoxy resin (B).

[0138] Commercially available flame retardants (E) include, for example: "SPH-100", "SPS-100", "SPB-100", and "SPE-100" (phosphazene compounds) manufactured by Otsuka Chemical Co., Ltd.; "FP-100", "FP-110", "FP-300", and "FP-400" (phosphazene compounds) manufactured by Fushimi Pharmaceutical Co., Ltd.; "HCA-NQ", "HCA-HQ", and "HCA-HQ-HST" (phosphines (containing phenolic hydroxyl groups)) manufactured by Sanko Co., Ltd.; and "PX-200", "PX-201", "PX-202", "CR-733S", "CR-741", and "CR-747" (phosphate esters) manufactured by Daihachi Chemical Co., Ltd.

[0139] The content of (E) flame retardant in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less. The lower limit of the content of (E) flame retardant in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it can be, for example, 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more.

[0140] <(F) Elastomer>

[0141] The resin compositions of the present invention sometimes contain (F) elastomers as optional components. By using (F) elastomers, the softness of the cured resin composition can be improved, and the elastic modulus can be reduced.

[0142] In the present application, the (F) elastomer refers to a resin having flexibility, which is an amorphous resin component that is soluble in an organic solvent, and is preferably a resin having rubber elasticity or a resin that exhibits rubber elasticity by polymerization with other components. As rubber elasticity, for example, a resin that exhibits an elastic modulus of 1 GPa or less at a temperature of 25°C and a humidity of 40% RH when a tensile test is performed in accordance with Japanese Industrial Standards (JIS K7161) can be cited.

[0143] In one embodiment, the (F) component is preferably a resin having one or more structures selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule, more preferably a resin having one or more structures selected from the group consisting of a polybutadiene structure and a polycarbonate structure from the viewpoint of obtaining a material having flexibility, and particularly preferably a resin having a polybutadiene structure. Note that the term "(meth)acrylate" refers to both methacrylate and acrylate.

[0144] In another embodiment, the (F) component is preferably one or more selected from the group consisting of a resin having a glass transition temperature (Tg) of 25°C or lower and a resin that is liquid at 25°C. The glass transition temperature of the resin having a glass transition temperature (Tg) of 25°C or lower is preferably 20°C or lower, and more preferably 15°C or lower. There is no particular limitation on the lower limit of the glass transition temperature, and it can generally be -15°C or higher. In addition, as the resin that is liquid at 25°C, a resin that is liquid at 20°C or lower is preferable, and a resin that is liquid at 15°C or lower is more preferable.

[0145] As a more preferable embodiment, the (F) component is preferably one or more selected from the group consisting of a resin having a glass transition temperature of 25°C or lower and a resin that is liquid at 25°C, and is a resin having one or more structures selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule.

[0146] The polybutadiene structure includes not only a structure formed by polymerization of butadiene, but also a structure formed by hydrogenation of the structure. In addition, the butadiene structure can be hydrogenated only in part thereof, or can be hydrogenated in its entirety. Furthermore, the polybutadiene structure can be included in the main chain or in the side chain in the (F) component.

[0147] As a preferable example of the polybutadiene resin, there can be mentioned a resin containing a hydrogenated polybutadiene skeleton, a polybutadiene resin containing a hydroxyl group, a polybutadiene resin containing a phenolic hydroxyl group, a polybutadiene resin containing a carboxyl group, a polybutadiene resin containing an anhydride group, a polybutadiene resin containing an epoxy group, a polybutadiene resin containing an isocyanate group, a polybutadiene resin containing a urethane group, and the like. Among them, a polybutadiene resin containing a phenolic hydroxyl group is further preferable. Here, the "resin containing a hydrogenated polybutadiene skeleton" means a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and it is not necessary that the polybutadiene skeleton is completely hydrogenated. As the resin containing a hydrogenated polybutadiene skeleton, there can be mentioned, for example, an epoxy resin containing a hydrogenated polybutadiene skeleton, and the like. In addition, the "polybutadiene resin containing a phenolic hydroxyl group" is a resin having a polybutadiene structure and having a phenolic hydroxyl group. The component (F) preferably contains a polybutadiene resin containing a phenolic hydroxyl group.

[0148] As a specific example of the polybutadiene resin which is a resin having a polybutadiene structure in the molecule, there can be mentioned "Ricon 657" (polybutadiene containing an epoxy group), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (polybutadiene containing an anhydride group), "GQ-1000" (polybutadiene into which a hydroxyl group and a carboxyl group are introduced), "G-1000", "G-2000", "G-3000" (both terminal hydroxyl polybutadiene), "GI-1000", "GI-2000", "GI-3000" (both terminal hydroxyl hydrogenated polybutadiene), "PB3600", "PB4700" (polybutadiene skeleton epoxy compound), "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (styrene-butadiene-styrene block copolymer epoxy compound), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy compound), "R-45EPT" (polybutadiene skeleton epoxy compound), and the like manufactured by Cray Valley Co., Ltd., and the like.

[0149] In addition, as examples of the preferred polybutadiene resin, linear polyimides (polyimides described in Japanese Patent Application Publication No. 2006-37083, International Publication No. 2008 / 153208) using a hydroxyl-terminated polybutadiene, a diisocyanate compound, and a polybasic acid or an acid anhydride thereof as raw materials can also be given. The content of the polybutadiene structure of the polyimide resin is preferably 60 to 95 mass%, and more preferably 75 to 85 mass%. Details of the polyimide resin can be found in Japanese Patent Application Publication No. 2006-37083, International Publication No. 2008 / 153208, the contents of which are incorporated herein.

[0150] The number average molecular weight of the hydroxyl-terminated polybutadiene is preferably 500 to 5,000, and more preferably 1,000 to 4,000. The hydroxyl equivalent of the hydroxyl-terminated polybutadiene is preferably 250 to 1,250 g / eq.

[0151] As the diisocyanate compound, for example, aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene diisocyanate, and diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; and alicyclic diisocyanates such as isophorone diisocyanate can be given. Among these, aromatic diisocyanates are preferred, and toluene-2,4-diisocyanate is more preferred.

[0152] As the polybasic acid or the acid anhydride thereof, for example, tetraacids such as ethylene glycol bistrimellitate (anhydride), pyromellitic acid, benzophenonetetracarboxylic acid, diphenyltetracarboxylic acid, naphthalenetetracarboxylic acid, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-cyclohexene-1,2-dicarboxylic acid, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid, and acid anhydrides thereof; triacids such as trimellitic acid, cyclohexanetricarboxylic acid, and acid anhydrides thereof; and 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho(1,2-C)furan-1,3-dione can be given.

[0153] In addition, the resin having a polybutadiene structure can contain a polystyrene structure having a structure obtained by polymerizing styrene.

[0154] As specific examples of the polystyrene resin as a resin having a polystyrene structure in a molecule, there are mentioned a styrene-butadiene-styrene block copolymer (SBS), a styrene-isoprene-styrene block copolymer (SIS), a styrene-ethylene-butylene-styrene block copolymer (SEBS), a styrene-ethylene-propylene-styrene block copolymer (SEPS), a styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), a styrene-butadiene-butylene-styrene block copolymer (SBBS), a styrene-butadiene diblock copolymer, a hydrogenated styrene-butadiene block copolymer, a hydrogenated styrene-isoprene block copolymer, a hydrogenated styrene-butadiene random copolymer, and the like.

[0155] As the polystyrene resin, commercially available products can be used, and there are mentioned, for example, hydrogenated styrene thermoplastic elastomers "H1041", "Tuftec H1043", "Tuftec P2000", "Tuftec MP10" (manufactured by Asahi / Kasei Corporation); epoxidized styrene-butadiene thermoplastic elastomers "Epofriend AT501", "CT310" (manufactured by Daicel Corporation); modified styrene elastomers having a hydroxyl group "SEPTON HG252" (manufactured by Kuraray Corporation); modified styrene elastomers having a carboxyl group "Tuftec N503M", modified styrene elastomers having an amino group "Tuftec N501", modified styrene elastomers having an anhydride group "Tuftec M1913" (manufactured by Asahi / Kasei Chemicals Corporation); unmodified styrene elastomers "SEPTON S8104" (manufactured by Kuraray Corporation); and the like. They can be used alone or in combination of two or more.

[0156] The polysiloxane structure is a structure including a siloxane bond, for example, included in silicone rubber. The polysiloxane structure can be included in a main chain or a side chain in the component (F).

[0157] As specific examples of the polysiloxane resin as a resin having a polysiloxane structure in a molecule, there are mentioned "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., an amine-terminated polysiloxane, a linear polyimide using a tetraacid anhydride as a raw material (International Publication No. 2010 / 053185), and the like.

[0158] The poly(meth)acrylate structure is a structure formed by polymerization of acrylic acid or an acrylate ester, and also includes a structure formed by polymerization of methacrylic acid or a methacrylate ester. The poly(meth)acrylate structure can be included in a main chain or a side chain in the component (F).

[0159] As the poly(meth)acrylate resin having a poly(meth)acrylate structure in the molecule, there are exemplified a poly(meth)acrylate resin having a hydroxyl group, a poly(meth)acrylate resin having a phenolic hydroxyl group, a poly(meth)acrylate resin having a carboxyl group, a poly(meth)acrylate resin having an anhydride group, a poly(meth)acrylate resin having an epoxy group, a poly(meth)acrylate resin having an isocyanate group, a poly(meth)acrylate resin having a urethane group, and the like.

[0160] As the poly(meth)acrylate resin, there are exemplified TEISAN RESIN "SG-70L", "SG-70 8-6", "WS-023", "SG-700AS", "SG-280TEA" (acrylate copolymer resin having a carboxyl group, acid value: 5 to 34 mgKOH / g, weight average molecular weight: 400 to 900 thousands, Tg: -30°C to 5°C), "SG-80H", "SG-80H-3", "SG-P3" (acrylate copolymer resin having an epoxy group, epoxy equivalent: 4761 to 14285 g / eq, weight average molecular weight: 350 to 850 thousands, Tg: 11°C to 12°C), "SG-600TEA", "SG-790" (acrylate copolymer resin having a hydroxyl group, hydroxyl value: 20 to 40 mgKOH / g, weight average molecular weight: 500 to 1200 thousands, Tg: -37°C to -32°C) manufactured by Nagase Chemtex Corporation, "ME-2000", "W-116.3" (acrylate copolymer resin having a carboxyl group), "W-197C" (acrylate copolymer resin having a hydroxyl group), "KG-25", "KG-3000" (acrylate copolymer resin having an epoxy group) manufactured by Kowa Company, Ltd., and the like.

[0161] The polyalkylene structure preferably has a prescribed number of carbon atoms. The number of carbon atoms of the polyalkylene structure is preferably 2 or more, more preferably 3 or more, particularly preferably 5 or more, and is preferably 15 or less, more preferably 10 or less, particularly preferably 6 or less. The polyalkylene structure can be included in the main chain or in the side chain in the component (F).

[0162] The polyalkyleneoxy structure preferably has a prescribed number of carbon atoms. The number of carbon atoms of the polyalkyleneoxy structure is preferably 2 or more, preferably 3 or more, more preferably 5 or more, and is preferably 15 or less, more preferably 10 or less, particularly preferably 6 or less. The polyalkyleneoxy structure can be included in the main chain or in the side chain in the component (F).

[0163] As specific examples of the polyalkylene resin as a resin having a polyalkylene structure in the molecule and the polyalkyleneoxy resin as a resin having a polyalkyleneoxy structure in the molecule, there are "PTXG-1000", "PTXG-1800" manufactured by Asahi Fiber Co., Ltd., "YX-7180" (a resin containing an alkylene structure having an ether bond) manufactured by Mitsubishi Chemical Corporation, "EXA-4850-150", "EXA-4816", "EXA-4822" manufactured by DIC Corporation, "EP-4000", "EP-4003", "EP-4010", "EP-4011" manufactured by ADEKA Corporation, "BEO-60E", "BPO-20E" manufactured by Shin Nippon Rika Co., Ltd., "YL7175", "YL7410" manufactured by Mitsubishi Chemical Corporation, and the like.

[0164] The polyisoprene structure can be contained in the main chain or in the side chain in the component (F). As a specific example of the polyisoprene resin as a resin having a polyisoprene structure in the molecule, there are "KL-610", "KL-613" manufactured by Kuraray Co., Ltd., and the like.

[0165] The polyisobutylene structure can be contained in the main chain or in the side chain in the component (F). As a specific example of the polyisobutylene resin as a resin having a polyisobutylene structure in the molecule, there are "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer), "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by KANEKA Corporation, and the like.

[0166] The polycarbonate structure can be contained in the main chain or in the side chain in the component (F).

[0167] As a preferable example of the polycarbonate resin as a resin having a polycarbonate structure in the molecule, there are a polycarbonate resin containing a hydroxyl group, a polycarbonate resin containing a phenolic hydroxyl group, a polycarbonate resin containing a carboxyl group, a polycarbonate resin containing an anhydride group, a polycarbonate resin containing an epoxy group, a polycarbonate resin containing an isocyanate group, a polycarbonate resin containing a urethane group, and the like.

[0168] As specific examples of the polycarbonate resin, there are "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Corporation, "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd., and the like.

[0169] Further, as examples of the preferred polycarbonate resin, a linear polyimide using a hydroxyl-terminated polycarbonate, a diisocyanate compound, and a polybasic acid or an acid anhydride thereof as raw materials can also be given. This linear polyimide has a urethane structure and a polycarbonate structure. The content ratio of the polycarbonate structure of this polyimide resin is preferably 60 to 95% by mass, and more preferably 75 to 85% by mass. Details of this polyimide resin can be found in International Publication No. 2016 / 129541, the contents of which are incorporated herein.

[0170] Further, as examples of the other preferred polycarbonate resin, a polycarbonate urethane (meth)acrylate using a hydroxyl-terminated polycarbonate, a diisocyanate compound, and a (meth)acrylate containing a hydroxyl group as raw materials can also be given. The polycarbonate urethane (meth)acrylate has not only a urethane structure and a polycarbonate structure, but also two or more (meth)acryloyl groups. As specific examples of the polycarbonate urethane (meth)acrylate, "ART RESIN UN-5500" manufactured by Nippon Shokubai Co., Ltd., and the like can be given.

[0171] As the (meth)acrylate containing a hydroxyl group, there is no particular limitation, and examples that can be given include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, and the like.

[0172] The number average molecular weight of the hydroxyl-terminated polycarbonate is preferably 500 to 50,000, and more preferably 1,000 to 35,000. The weight average molecular weight of the hydroxyl-terminated polycarbonate is preferably 500 to 50,000, and more preferably 1,000 to 35,000. The hydroxyl equivalent of the hydroxyl-terminated polycarbonate is preferably 250 to 1,250 g / eq.

[0173] The (F) component preferably also has an imide structure. By having an imide structure, the heat resistance of the (F) component can be improved, and the crack resistance can be effectively improved.

[0174] The (F) component can have any of a linear structure, a branched structure, and a cyclic structure, but is preferably linear.

[0175] The (F) component preferably contains an elastomer having a reactive group that can react with the (B) epoxy resin. The reactive group also includes a reactive group that appears by heating. By having the (F) component have a functional group, the mechanical strength of the cured product of the resin composition can be improved.

[0176] As the reactive group, a carboxyl group, a hydroxyl group (preferably a phenolic hydroxyl group), an anhydride group, an epoxy group, an isocyanate group, and a carbamate group, etc. can be given. Among these, from the viewpoint of obtaining the effects of the present application, as the reactive group, it is preferable to have one or more reactive groups selected from a hydroxyl group (preferably a phenolic hydroxyl group), an anhydride group, an epoxy group, an isocyanate group, and a carbamate group, and it is particularly preferable to have a phenolic hydroxyl group. An elastomer having a phenolic hydroxyl group or the like, like the (C-l) epoxy curing agent, has a function of curing the (B) epoxy resin.

[0177] The (F) component preferably contains an elastomer having a phenolic hydroxyl group, and it is particularly preferable to contain a polybutadiene resin having a phenolic hydroxyl group.

[0178] The (F) component can be used alone or in combination with two or more.

[0179] From the viewpoint of imparting flexibility, the (F) component is preferably high in molecular weight.

[0180] The (F) component preferably has a number average molecular weight (Mn) of 4,000 or more, more preferably 4,500 or more, further preferably 5,000 or more, particularly preferably 5,500 or more, and preferably 100,000 or less, more preferably 95,000 or less, particularly preferably 90,000 or less. The number average molecular weight Mn of the (F) component is a number average molecular weight converted to polystyrene, measured using GPC (gel permeation chromatography).

[0181] In addition, from the viewpoint of obtaining flexibility, the (F) component preferably has a weight average molecular weight (Mw) of 5,500 to 100,000, more preferably 10,000 to 90,000, further preferably 15,000 to 80,000. The weight average molecular weight of the (F) component is a weight average molecular weight converted to polystyrene, measured using gel permeation chromatography (GPC).

[0182] (F) component has a functional group, the functional group equivalent of the (F) component is preferably 100 g / eq. or more, more preferably 200 g / eq. or more, further preferably 300 g / eq. or more, particularly preferably 400 g / eq. or more, and preferably 50,000 g / eq. or less, more preferably 30,000 g / eq. or less, further preferably 10,000 g / eq. or less, particularly preferably 5,000 g / eq. or less. The functional group equivalent is the number of grams of a resin containing 1 gram equivalent of the functional group. For example, the epoxy equivalent can be measured according to JIS K 7236. In addition, for example, the hydroxyl equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K 1557-1.

[0183] The glass transition temperature (Tg) of the (F) elastomer is, for example, 30°C or lower, and preferably 0°C or lower.

[0184] The content of the (F) elastomer in the resin composition is not particularly limited, and is preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, further more preferably 40% by mass or less, and particularly preferably 35% by mass or less, based on 100% by mass of the nonvolatile components in the resin composition. The lower limit of the content of the (F) elastomer in the resin composition is not particularly limited, and can be, for example, 0% by mass or more, 0.1% by mass or more, 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, or the like, based on 100% by mass of the nonvolatile components in the resin composition.

[0185] (G) Thermoplastic Resin

[0186] The resin composition of the present application sometimes contains a (G) thermoplastic resin as an arbitrary component. As the (G) thermoplastic resin, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyimide resin, polyamide-imide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyether ether ketone resin, polyester resin, and the like can be given, and a phenoxy resin is preferred. The thermoplastic resin can be used alone or in combination of two or more. The (G) thermoplastic resin herein is a component other than the (F) elastomer.

[0187] (G) The weight average molecular weight of the thermoplastic resin is preferably 38000 or more, more preferably 40000 or more, and further preferably 42000 or more. The upper limit is preferably 100000 or less, more preferably 70000 or less, and further preferably 60000 or less. The weight average molecular weight of the thermoplastic resin can be measured by gel permeation chromatography (GPC) (in terms of polystyrene). Specifically, for the weight average molecular weight of the thermoplastic resin in terms of polystyrene, LC-9A / RID-6A manufactured by Shimadzu Corporation can be used as a measuring device, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko K.K. can be used as a column, and chloroform or the like can be used as a mobile phase, and the measurement can be performed at a column temperature of 40°C, and the calculation can be performed using a standard curve of a standard polystyrene.

[0188] As the phenoxy resin, for example, a phenoxy resin having one or more skeletons selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton can be given. The terminal of the phenoxy resin can be any functional group such as a phenolic hydroxyl group, an epoxy group, or the like. The phenoxy resin can be used alone or in combination with two or more. As specific examples of the phenoxy resin, "1256" and "4250" (both are phenoxy resins containing a bisphenol A skeleton), "YX8100" (a phenoxy resin containing a bisphenol S skeleton), and "YX6954" (a phenoxy resin containing a bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation, and "FX280" and "FX293" manufactured by JFE Chemicals Corporation, "YX7200B35", "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482" manufactured by Mitsubishi Chemical Corporation, and the like can be given.

[0189] As the polyvinyl acetal resin, for example, a polyvinyl formal resin, a polyvinyl butyral resin, and preferably a polyvinyl butyral resin can be given. As specific examples of the polyvinyl acetal resin, for example, "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", "Denka Butyral 6000-EP" manufactured by Denki Kagaku Kogyo K.K., S-LEC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series, and the like manufactured by Sekisui Chemical Co., Ltd. can be given.

[0190] As specific examples of the polyimide resin, "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Shokubai Co., Ltd. can be given. As specific examples of the polyimide resin, modified polyimides such as a linear polyimide obtained by reacting a difunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetraacid anhydride (polyimide described in Japanese Patent Application Publication No. 2006-37083), a polyimide containing a polysiloxane skeleton (polyimide described in Japanese Patent Application Publication No. 2002-12667 and Japanese Patent Application Publication No. 2000-319386, and the like) can also be given.

[0191] As specific examples of the polyamide-imide resin, "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. can be given. As specific examples of the polyamide-imide resin, modified polyamide-imides such as "KS9100", "KS9300" (polyamide-imide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd. can also be given.

[0192] As specific examples of the polyether ether ketone resin, "SUMIPLOY K" manufactured by Sumitomo Chemical Co., Ltd. and the like can be given. As specific examples of the polyether imide resin, "ULTEM" manufactured by GE Co. and the like can be given.

[0193] As specific examples of the polysulfone resin, polysulfones "P1700", "P3500" manufactured by Solvay Advanced Polymers Co. and the like can be given.

[0194] As the polyolefin resin, for example, low-density polyethylene, ultralow-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, and the like ethylene-based copolymer resins; polypropylene, ethylene-propylene block copolymer, and the like polyolefin-based elastomers, and the like can be given.

[0195] As the polyester resin, for example, polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, poly-1,3-propylene terephthalate resin, poly-1,3-propylene naphthalate resin, poly(cyclohexane dimethanol) terephthalate resin, and the like can be given.

[0196] Among them, as the (G) thermoplastic resin, a phenoxy resin is preferred. Thus, as the preferred thermoplastic resin, a phenoxy resin is preferred, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferred.

[0197] The content of the (G) thermoplastic resin in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100% by mass, it is preferably 30% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, further more preferably 3% by mass or less, and particularly preferably 1% by mass or less. The lower limit of the content of the (G) thermoplastic resin in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100% by mass, it can be, for example, 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, or the like.

[0198] <(H) Other additives>

[0199] For the resin composition of the present application, as the nonvolatile component, any additive can be further included. As such an additive, there can be mentioned, for example, organic metal compounds such as organic copper compounds, organic zinc compounds, organic cobalt compounds, and the like; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazonium yellow, crystal violet, titanium oxide, carbon black, and the like; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine, and the like; leveling agents such as silicone-based leveling agents, acrylic polymer-based leveling agents, and the like; thickening agents such as Benton, montmorillonite, and the like; defoaming agents such as silicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, vinyl resin-based defoaming agents, and the like; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers, and the like; adhesion improvers such as urea silane, and the like; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, triazine-based adhesion imparting agents, and the like; antioxidants such as hindered phenol-based antioxidants, hindered amine-based antioxidants, and the like; fluorescent brightening agents such as stilbene derivatives, and the like; surfactants such as fluorine-based surfactants, silicone-based surfactants, and the like; and the like. The additive can be used alone as one kind, or two or more kinds can be used in combination at an arbitrary ratio. The content of the (H) other additive can be appropriately set by those skilled in the art.

[0200] <(I) Organic solvent>

[0201] For the resin composition of the present application, in addition to the above-mentioned nonvolatile component, an arbitrary organic solvent is sometimes contained as a volatile component. As the (I) organic solvent, a publicly known organic solvent can be appropriately used, and the kind thereof is not particularly limited. As the (I) organic solvent, mention can be made of, for example: ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, and the like; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and the like; alcohol-based solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, and the like; ether ester-based solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, carbitol acetate (ethyl diglycol acetate), γ-butyrolactone, methyl methoxypropionate, and the like; ester alcohol-based solvents such as methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, and the like; ether alcohol-based solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol), and the like; amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like; sulfoxide-based solvents such as dimethyl sulfoxide, and the like; nitrile-based solvents such as acetonitrile, propionitrile, and the like; aliphatic hydrocarbon-based solvents such as hexane, cyclopentane, cyclohexane, methylcyclohexane, and the like; aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, mesitylene, and the like. The (I) organic solvent can be used alone as one kind, or two or more kinds can be used in combination at an arbitrary ratio.

[0202] In one embodiment, the content of the (I) organic solvent is not particularly limited, and when the total components in the resin composition are taken as 100% by mass, it can be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, and the like.

[0203] <Method for producing resin composition>

[0204] The resin composition of the present application can be produced, for example, by adding (A) hollow organic polymer particles, (B) an epoxy resin, (C) a curing agent, (A') non-hollow organic polymer particles as needed, (D) an inorganic filler as needed, (E) a flame retardant as needed, (F) an elastomer as needed, (G) a thermoplastic resin as needed, (H) other additives as needed, and (I) an organic solvent as needed, in any order and / or all at once or in parts, into any reaction vessel, and mixing them. In addition, during the addition of the respective components and the mixing, the temperature can be appropriately set, and heating and / or cooling can be performed temporarily or throughout. In addition, during the addition of the respective components and the mixing, stirring or shaking can be performed. In addition, at or after the addition and the mixing, the resin composition can be stirred using a stirring device such as a mixer, so as to be uniformly dispersed.

[0205] <Properties of the resin composition>

[0206] The resin composition of the present application can obtain a cured product having excellent stain removal properties, because it contains (A) hollow organic polymer particles. In addition, in one embodiment, the cured product of the resin composition of the present application can have excellent reflow soldering resistance. In addition, in one embodiment, the cured product of the resin composition of the present application can suppress warping and cracking at the time of curing. In addition, in one embodiment, the cured product of the resin composition of the present application can have excellent electrical properties.

[0207] The cured product of the resin composition of the present application has excellent stain removal properties, and therefore, in one embodiment, for example, when a through-hole is formed in the cured product of the resin composition and roughening treatment is performed, and the maximum stain length is measured, the maximum stain length can be preferably less than 5 μm, more preferably less than 3 μm. Note that the maximum stain length refers to the maximum length of the stain from the circumference of the bottom surface of the through-hole to the center of the circle.

[0208] In one embodiment, the cured product of the resin composition of the present application can also have excellent electrical properties, and therefore, the dielectric loss tangent of the cured product of the resin composition when measured at 5.8 GHz and 23°C, as in Test Example 1 below, can be preferably 0.020 or less, more preferably 0.017 or less, further preferably 0.015 or less, particularly preferably 0.013 or less. In addition, in one embodiment, the relative dielectric constant of the cured product of the resin composition when measured at 5.8 GHz and 23°C, as in Test Example 1 below, can be preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.5 or less, particularly preferably 3.0 or less.

[0209] In one embodiment, the cured product of the resin composition of the present application can have excellent reflow soldering resistance, and thus, for example, as in Test Example 2 described below, a cured product of the resin composition is cut into a small piece of 100 mm x 50 mm, and even if this is subjected to reflow soldering 10 times at a reflow soldering temperature of a solder having a peak temperature of 260°C, the small piece can be inhibited from being abnormal, and in a particular embodiment, the small piece does not become abnormal.

[0210] In one embodiment, the resin composition of the present application can inhibit warping at the time of curing, and thus, for example, as in Test Example 4 described below, the warping of a metal foil having a cured layer is measured, and the amount of warping can be preferably less than 10 mm, more preferably less than 5 mm, further preferably less than 3 mm, and particularly preferably less than 1 mm.

[0211] In one embodiment, the resin composition of the present application can inhibit the occurrence of cracks, and thus, for example, as in Test Example 5 described below, 100 copper pad portions of a roughened circuit substrate are observed, and the number of cracks occurring in the resin composition layer can be preferably 20 or less, more preferably 15 or less, and further preferably 10 or less.

[0212] <Usage of the resin composition>

[0213] The resin composition of the present application can be suitably used as a resin composition for an insulating purpose, and particularly a resin composition for forming an insulating layer. Specifically, it can be suitably used as a resin composition for forming an insulating layer (insulating layer-forming resin composition for forming a conductor layer) which is an insulating layer for forming a conductor layer (including a rewiring layer) formed on the insulating layer. In addition, in the printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (insulating layer-forming resin composition for a printed wiring board). The resin composition of the present application can also be widely used in sheet-like laminated materials such as a resin sheet, a prepreg, and the like, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a filling resin, a component embedding resin, and the like, which require a resin composition.

[0214] In addition, for example, in the case of manufacturing a semiconductor chip package by the following (1) to (6) processes, the resin composition of the present application can also be suitably used as a resin composition for a rewiring layer-forming layer (resin composition for forming a rewiring layer-forming layer) as an insulating layer for forming a rewiring layer, and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). In the manufacturing of a semiconductor chip package, a rewiring layer can be further formed on a sealing layer;

[0215] (1) a process of laminating a temporary fixing film on a substrate;

[0216] (2) a process of temporarily fixing the semiconductor chip on the temporary fixing film;

[0217] (3) a process of forming a sealing layer on the semiconductor chip;

[0218] (4) a process of peeling the substrate and the temporary fixing film from the semiconductor chip;

[0219] (5) a process of forming a rewiring formation layer as an insulating layer on a surface of the semiconductor chip from which the substrate and the temporary fixing film are peeled; and

[0220] (6) a process of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0221] In addition, the resin composition of the present application is excellent in component embedding property, and thus can be suitably used even when the printed wiring board is a component-embedded circuit board.

[0222] <Sheet-shaped Laminated Material>

[0223] The resin composition of the present application can be used by being coated in a varnish state, but in industry, it is generally preferable to use in the form of a sheet-shaped laminated material containing the resin composition.

[0224] As the sheet-shaped laminated material, a resin sheet and a prepreg shown below are preferable.

[0225] In one embodiment, the resin sheet contains a support and a resin composition layer provided on the support, and the resin composition layer is formed of the resin composition of the present application.

[0226] The thickness of the resin composition layer is preferably 50 μm or less, and more preferably 40 μm or less, from the viewpoint of thinning of the printed wiring board and the fact that an excellent insulating property can be provided even when the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, and can be, for example, 5 μm or more, 10 μm or more, or the like.

[0227] As the support, a film formed of a plastic material, a metal foil, and a release paper can be mentioned, and a film formed of a plastic material and a metal foil are preferable.

[0228] In the case of using a film formed of a plastic material as the support, as the plastic material, for example, polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PEN"), and the like polyester, polycarbonate (hereinafter sometimes referred to as "PC"), polymethyl methacrylate (PMMA), and the like acrylic polymer, cyclic polyolefin, triacetyl cellulose (TAC), polyethersulfide (PES), polyetherketone, polyimide, and the like can be given. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

[0229] In the case of using a metal foil as the support, as the metal foil, for example, a copper foil, an aluminum foil, and the like can be given, and a copper foil is preferable. As the copper foil, a foil formed of a single metal of copper, or a foil formed of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, and the like) can be used.

[0230] For the support, a surface to be joined to the resin composition layer can be subjected to a mat treatment, a corona treatment, an antistatic treatment.

[0231] In addition, as the support, a support with a release layer having a release layer on a surface to be joined to the resin composition layer can be used. As the release agent used in the release layer of the support with a release layer, for example, a release agent selected from one or more of an alkyd resin, a polyolefin resin, a polyurethane resin, and a silicone resin can be given. The support with a release layer can use a commercially available product, and for example, "SK-1", "AL-5", "AL-7" manufactured by Linde Company, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipeel" manufactured by UNITIKA, and the like as a PET film having a release layer in which an alkyd resin-based release agent is a main component can be given.

[0232] The thickness of the support is not particularly limited, and is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. Note that in the case of using a support with a release layer, the thickness of the support with a release layer as a whole is preferably in the above range.

[0233] In one embodiment, the resin sheet can further include an arbitrary layer as needed. As the arbitrary layer, for example, a protective film or the like provided on a surface of the resin composition layer which is not joined to the support (i.e., a surface on the opposite side to the support) can be given. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, attachment of dust or the like to the surface of the resin composition layer or generation of damage on the surface of the resin composition layer can be suppressed.

[0234] The resin sheet can be produced, for example, by directly applying a liquid resin composition to a support using a die coater or the like, or by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish to a support using a die coater or the like, and further drying the same to form a resin composition layer.

[0235] As the organic solvent, the same organic solvents as those described as the component of the resin composition can be mentioned. The organic solvent can be used alone or in combination of two or more.

[0236] Drying can be performed by a publicly known method such as heating or blowing hot air. The drying conditions are not particularly limited, and the drying is performed in such a manner that the content of the organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although it differs depending on the boiling point of the organic solvent in the resin composition or the resin varnish, when, for example, a resin composition or a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0237] The resin sheet can be stored in a roll shape by being wound into a roll. When the resin sheet has a protective film, the protective film can be peeled off to use.

[0238] In one embodiment, the prepreg is formed by impregnating the resin composition of the present application in a sheet-shaped fibrous base material.

[0239] The sheet-shaped fibrous base material used in the prepreg is not particularly limited, and a sheet-shaped fibrous base material commonly used as a base material for a prepreg, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, or the like, can be used. From the viewpoint of thinning of the printed wiring board, the thickness of the sheet-shaped fibrous base material is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-shaped fibrous base material is not particularly limited. It is usually 10 μm or more.

[0240] The prepreg can be produced by a publicly known method such as a hot melt method or a solvent method.

[0241] The thickness of the prepreg can be in the same range as that of the resin composition layer in the resin sheet described above.

[0242] The sheet-shaped laminated material of the present application can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board).

[0243] <Printed wiring board>

[0244] The printed wiring board of the present application comprises an insulating layer formed of a cured product of the resin composition of the present application.

[0245] The printed wiring board can be manufactured, for example, using the resin sheet described above, by a method comprising the following (I) and (II),

[0246] (I) a step of laminating the resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is joined to the inner layer substrate;

[0247] (II) a step of curing (e.g., thermally curing) the resin composition layer to form an insulating layer.

[0248] The "inner layer substrate" used in the step (I) refers to a member that becomes a substrate of the printed wiring board, and examples include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermally cured polyphenylene ether substrate, and the like. In addition, the substrate can have a conductor layer on one or both sides thereof, and the conductor layer can be subjected to pattern processing. Sometimes, the inner layer substrate having a conductor layer (circuit) formed on one or both sides thereof is referred to as an "inner layer circuit substrate". In addition, in the manufacture of the printed wiring board, an intermediate product to be further formed with an insulating layer and / or a conductor layer is also included in the "inner layer substrate" in the present application. When the printed wiring board is a component-embedded circuit board, an inner layer substrate having a component embedded therein can be used.

[0249] The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-press bonding the resin sheet to the inner layer substrate from the support side. As a member for heat-press bonding the resin sheet to the inner layer substrate (hereinafter also referred to as a "heat-press bonding member"), examples include a heated metal plate (SUS end plate or the like) or a metal roller (SUS roller), and the like. Note that it is preferable that the heat-press bonding member is not pressed directly to the resin sheet, but is pressed through an elastic material such as heat-resistant rubber, so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

[0250] The lamination of the inner layer substrate and the resin sheet can be performed by a vacuum lamination method. In the vacuum lamination method, the heat-press bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heat-press bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the heat-press bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination can be preferably performed under reduced pressure conditions at a pressure of 26.7 hPa or less.

[0251] The lamination can be performed by a commercially available vacuum laminator. As the commercially available vacuum laminator, for example, a vacuum press-type laminator manufactured by Seiko Instruments Inc., a vacuum applicator manufactured by Nikko-Materials, Inc., and an intermittent vacuum press laminator can be mentioned.

[0252] After the lamination, the smoothing treatment of the laminated resin sheet can be performed by, for example, pressing the heat-pressing member from the support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment can be set to the same conditions as the above-mentioned heat-pressing conditions for the lamination. The smoothing treatment can be performed by using a commercially available laminator. Note that the lamination and the smoothing treatment can be continuously performed by using the above-mentioned commercially available vacuum laminator.

[0253] The support can be removed between the process (I) and the process (II), or can be removed after the process (II).

[0254] In the process (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer formed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions generally used when forming an insulating layer of a printed wiring board can be used.

[0255] For example, the thermal curing conditions of the resin composition layer vary depending on the kind of the resin composition, and the like, and the curing temperature is preferably from 120°C to 240°C, more preferably from 150°C to 220°C, and further preferably from 170°C to 210°C. The curing time can be preferably from 5 minutes to 120 minutes, more preferably from 10 minutes to 100 minutes, and further preferably from 15 minutes to 100 minutes.

[0256] The resin composition layer can be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer can be preheated at a temperature of from 50°C to 120°C, preferably from 60°C to 115°C, more preferably from 70°C to 110°C, for 5 minutes or more, preferably from 5 minutes to 150 minutes, more preferably from 15 minutes to 120 minutes, and further preferably from 15 minutes to 100 minutes, before the resin composition layer is thermally cured.

[0257] In the production of the printed wiring board, the process (III) of forming a hole in the insulating layer, the process (IV) of performing a roughening treatment on the insulating layer, and the process (V) of forming a conductor layer can be further performed. These processes (III) to (V) can be performed according to various methods that can be used in the production of the printed wiring board and are known to those skilled in the art. Note that, in the case where the support is removed after the process (II), the removal of the support can be performed between the process (II) and the process (III), between the process (III) and the process (IV), or between the process (IV) and the process (V). In addition, the formation of the insulating layer and the conductor layer of the processes (II) to (V) can be repeatedly performed as necessary to form a multilayer wiring board.

[0258] In other embodiments, the printed wiring board of the present application can be produced using the prepreg described above. The production method is basically the same as in the case of using a resin sheet.

[0259] The process (III) is a process of forming a hole in the insulating layer, and thus a through hole, a through hole, or the like can be formed in the insulating layer. For the process (III), a drill, a laser, plasma, or the like can be used according to the composition of the resin composition used in the formation of the insulating layer, or the like. The size and shape of the hole can be appropriately determined according to the design of the printed wiring board.

[0260] The process (IV) is a process of performing a roughening treatment on the insulating layer. In this process (IV), removal of contamination is also generally performed. The steps and conditions of the roughening treatment are not particularly limited, and known steps and conditions generally used in the formation of the insulating layer of the printed wiring board can be employed. For example, the insulating layer can be subjected to a roughening treatment by sequentially performing a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing liquid.

[0261] The swelling liquid used in the roughening treatment is not particularly limited, and an alkali solution, a surfactant solution, or the like can be used, and an alkali solution is preferred, and a sodium hydroxide solution or a potassium hydroxide solution is more preferred as the alkali solution. As commercially available swelling liquids, "Swelling Dip Securiganth P", "Swelling Dip Securiganth SBU", and the like manufactured by ATOTECH JAPAN Co., Ltd. can be used. The swelling treatment using the swelling liquid is not particularly limited, and for example, the insulating layer can be immersed in the swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, the insulating layer is preferably immersed in the swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0262] As the oxidizing agent used in the roughening treatment, there is no particular limitation, and examples include an alkaline permanganate solution prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of the permanganate salt in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. As commercially available oxidizing agents, examples include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Asahi M&C Corporation.

[0263] In addition, as the neutralizing solution used in the roughening treatment, an acidic aqueous solution is preferable, and as commercially available products, examples include "Reduction Solution Securiganth P" manufactured by Asahi M&C Corporation.

[0264] The treatment using a neutralizing solution can be performed by immersing the treatment surface on which the roughening treatment using an oxidizing agent has been completed in a neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, the method in which the object on which the roughening treatment using an oxidizing agent has been completed is immersed in a neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

[0265] In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is not particularly limited, and is preferably 500 nm or less, more preferably 400 nm or less, and further preferably 300 nm or less. There is no particular limitation on the lower limit, and it can be, for example, 1 nm or more, 2 nm or more, or the like. In addition, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and further preferably 300 nm or less. There is no particular limitation on the lower limit, and it can be, for example, 1 nm or more, 2 nm or more, or the like. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

[0266] The step (V) is a step of forming a conductor layer on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In the preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer can be a single metal layer or an alloy layer. As the alloy layer, for example, a layer formed of an alloy of two or more metals selected from the above metals (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) can be given. Among them, from the viewpoint of the versatility of the conductor layer formation, cost, easiness of patterning and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is more preferred, and a single metal layer of copper is further preferred.

[0267] The conductor layer can be a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers of different kinds of metals or alloys are stacked. When the conductor layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

[0268] The thickness of the conductor layer depends on the design of the printed wiring board desired and is usually 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0269] In one embodiment, the conductor layer can be formed by plating. For example, a technology conventionally known such as a semi-additive method, a full-additive method or the like can be used to perform plating on the surface of the insulating layer to form a conductor layer having a desired wiring pattern. From the viewpoint of the easiness of manufacture, it is preferred to form the conductor layer using the semi-additive method. Hereinafter, an example of forming the conductor layer using the semi-additive method will be shown.

[0270] First, a plating seed layer is formed on the surface of the insulating layer by non-electrolytic plating. Next, a mask pattern is formed on the formed plating seed layer so as to expose a part of the plating seed layer corresponding to a desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0271] In other embodiments, the conductor layer can be formed using a metal foil. In the case where the conductor layer is formed using a metal foil, process (V) is preferably performed between process (I) and process (II). For example, after process (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be performed using a vacuum lamination method. The conditions for lamination can be the same as those described for process (I). Next, process (II) is performed to form the insulating layer. Then, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed using a technology known in the art such as subtractive method, modified semi-additive method, and the like.

[0272] The metal foil can be manufactured using a known method such as electrolysis method, rolling method, and the like. As commercially available products of the metal foil, for example, HLP foil, JX UT-III foil, 3EC-III foil, TP-III foil, and the like manufactured by JX Nippon Mining & Metal Corporation can be mentioned.

[0273] <semiconductor device>

[0274] The semiconductor device of the present application includes the printed wiring board of the present application. The semiconductor device of the present application can be manufactured using the printed wiring board of the present application.

[0275] As the semiconductor device, various semiconductor devices that can be used for electrical products (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, electric cars, ships, airplanes, and the like), and the like can be mentioned.

[0276] Examples

[0277] Hereinafter, the present application will be specifically described by examples. The present application is not limited by these examples. Note that, hereinafter, "parts" and "%" indicating amounts mean "mass parts" and "mass %", respectively, unless otherwise explicitly stated.

[0278] <synthesis example 1: synthesis of elastomer (butadiene resin containing phenolic hydroxyl group)>

[0279] A reaction vessel was charged with difunctional hydroxyl-terminated polybutadiene ("G-3000" manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxyl equivalent weight = 1800 g / eq.), 69 g, an aromatic hydrocarbon-based mixed solvent ("Ipzole 150" manufactured by Idemitsu Petrochemical Co., Ltd.), 40 g, and dibutyltin laurate, 0.005 g, and mixed to uniformly dissolve. After becoming uniform, the temperature was raised to 60°C, and further, isophorone diisocyanate ("IPDI" manufactured by Evonik Degussa Japan, isocyanate group equivalent weight = 113 g / eq.), 8 g, was added while stirring, and reaction was performed for about 3 hours.

[0280] Next, to the reactant, cresol novolak resin ("KA-1160" manufactured by DIC Corporation, hydroxyl equivalent = 117 g / eq.) 23 g, and ethyl diglycol acetate (ethyl diglycol acetate) manufactured by DKS Co., Ltd.) 60 g were added, and the temperature was raised to 150°C while stirring, and the reaction was performed for about 10 hours. Disappearance of the NCO peak at 2250 cm -1 was confirmed by FT-IR. Based on the confirmation of the disappearance of the NCO peak, the reaction was considered to be complete, and the reactant was cooled to room temperature. Then, the reactant was filtered with a filter cloth of 100 mesh to obtain an elastomer having a butadiene structure and a phenolic hydroxyl group (butadiene resin containing a phenolic hydroxyl group: nonvolatile content 50 mass%). The number average molecular weight of the elastomer was 5900, and the glass transition temperature was -7°C.

[0281] <SYNTHESIS EXAMPLE 2: SYNTHESIS OF HOLLOW STYRENE PARTICLES>

[0282] According to the description of Example 2 of Japanese Patent Application Publication No. 2017-119843, styrene-based hollow particles were obtained. The average particle diameter was 8 μm, and the porosity was 50 vol%.

[0283] <EXAMPLE 1>

[0284] A resin composition was prepared by mixing 20 parts of a biphenyl-type epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent about 269 g / eq.), 5 parts of an epoxy resin ("WHR-991S" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent about 265 g / eq.), 50 parts of the elastomer obtained in Synthesis Example 1 (nonvolatile content 50 mass%), 15 parts of spherical silica ( "UFP-30" manufactured by Epolin Co., Ltd., average particle diameter 0.3 μm) which had been surface-treated with an amino silane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), 10 parts of hollow acrylic polymer particles ("XX-5598Z" manufactured by Sekisui Plastics Co., Ltd., average particle diameter 0.5 μm, porosity 35 vol%), 5 parts of a flame retardant ("HCA-HQ-HST" manufactured by Sanshin Co., Ltd., 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 1.5 μm), 2 parts of 1-benzyl-2-phenylimidazole (a 10 mass% solid content solution in methyl ethyl ketone of "1B2PZ" manufactured by Shikoku Chemicals Corporation) as a curing accelerator, and 25 parts of methyl ethyl ketone, and uniformly dispersing them with a high-speed rotary mixer.

[0285] <EXAMPLE 2>

[0286] The hollow acrylic polymer particles ("XX-5598Z" manufactured by Seiko PMC Corp., average particle diameter 0.5 μm, porosity 35 vol%) were used in an amount of 3 parts instead of 10 parts, and otherwise the same operation as in Example 1 was performed to produce a resin composition.

[0287] Example 3

[0288] The spherical silica ("UFP-30" manufactured by Kanto Chemical Co., Inc., average particle diameter 0.3 μm) surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was used in an amount of 10 parts instead of 15 parts, and the hollow acrylic polymer particles ("XX-5598Z" manufactured by Seiko PMC Corp., average particle diameter 0.5 μm, porosity 35 vol%) were used in an amount of 35 parts instead of 10 parts, and otherwise the same operation as in Example 1 was performed to produce a resin composition.

[0289] Example 4

[0290] The spherical silica ("UFP-30" manufactured by Kanto Chemical Co., Inc., average particle diameter 0.3 μm) surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was not used, and otherwise the same operation as in Example 3 was performed to produce a resin composition.

[0291] Example 5

[0292] The hollow acrylic polymer particles ("XX-5598Z" manufactured by Seiko PMC Corp., average particle diameter 0.5 μm, porosity 35 vol%) were used in an amount of 5 parts instead of 10 parts, and the core-shell rubber particles ("IM401-4-14" manufactured by AICA Corp., core: polybutadiene, shell: copolymer of styrene and divinylbenzene) were additionally used in an amount of 5 parts, and otherwise the same operation as in Example 1 was performed to produce a resin composition.

[0293] Example 6

[0294] The hollow styrene particles (average particle diameter 8 μm, porosity 50 vol%) obtained in Synthesis Example 2 were used in an amount of 10 parts instead of the hollow acrylic polymer particles ("XX-5598Z" manufactured by Seiko PMC Corp., average particle diameter 0.5 μm, porosity 35 vol%) 10 parts, and otherwise the same operation as in Example 1 was performed to produce a resin composition.

[0295] Example 7

[0296] The amount of biphenyl-type epoxy resin (NC-3000-L manufactured by Nippon Kayaku Co., Ltd., with an epoxy equivalent of approximately 269 g / eq.) was changed from 20 parts to 10 parts, and 10 parts of liquid bisphenol A-type epoxy resin (jER828EL manufactured by Mitsubishi Chemical Co., Ltd., with an epoxy equivalent of approximately 180 g / eq.) were added. Otherwise, the resin composition was prepared in the same manner as in Example 1.

[0297] <Example 8>

[0298] Instead of 20 parts of biphenyl-type epoxy resin (NC-3000-L manufactured by Nippon Kayaku Co., Ltd., with an epoxy equivalent of approximately 269 g / eq.), 10 parts of liquid bisphenol A-type epoxy resin (jER828EL manufactured by Mitsubishi Chemical Co., Ltd., with an epoxy equivalent of approximately 180 g / eq.) and 10 parts of bisphenol AF-type epoxy resin (YX7760 manufactured by Mitsubishi Chemical Co., Ltd., with an epoxy equivalent of approximately 238 g / eq.) were used to prepare the resin composition in the same manner as in Example 1.

[0299] <Example 9>

[0300] Instead of 20 parts of biphenyl-type epoxy resin (NC-3000-L manufactured by Nippon Kayaku Co., Ltd., with an epoxy equivalent of approximately 269 g / eq.), 10 parts of liquid bisphenol A-type epoxy resin (jER828EL manufactured by Mitsubishi Chemical Co., Ltd., with an epoxy equivalent of approximately 180 g / eq.) and 10 parts of dicyclopentadiene-type epoxy resin (HP-7200L manufactured by DIC Co., Ltd., with an epoxy equivalent of approximately 250 g / eq.) were used to prepare the resin composition in the same manner as in Example 1.

[0301] <Example 10>

[0302] Instead of 20 parts of biphenyl-type epoxy resin (NC-3000-L manufactured by Nippon Kayaku Co., Ltd., with an epoxy equivalent of approximately 269 g / eq.), 10 parts of liquid bisphenol A-type epoxy resin (jER828EL manufactured by Mitsubishi Chemical Co., Ltd., with an epoxy equivalent of approximately 180 g / eq.) and 10 parts of modified naphthalene-type epoxy resin (ESN-475V manufactured by Nippon Steel Chemical Co., Ltd., with an epoxy equivalent of approximately 330 g / eq.) were used to prepare the resin composition in the same manner as in Example 1.

[0303] <Example 11>

[0304] Instead of the biphenyl type epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: about 269 g / eq.) 20 parts, a naphthalene type epoxy resin ("HP-4032SS" manufactured by DIC Corporation, epoxy equivalent weight: about 144 g / eq.) 7 parts, a naphthalene type multifunctional epoxy resin ("HP-4710" manufactured by DIC Corporation, epoxy equivalent weight: about 170 g / eq.) 3 parts, and a naphthalene type epoxy resin ("HP-6000" manufactured by DIC Corporation, epoxy equivalent weight: about 250 g / eq.) 10 parts were used, and otherwise, the same operation as in Example 1 was performed to produce a resin composition.

[0305] <Example 12>

[0306] Instead of the biphenyl type epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: about 269 g / eq.) 20 parts, a naphthalene type epoxy resin ("HP-4032SS" manufactured by DIC Corporation, epoxy equivalent weight: about 144 g / eq.) 10 parts, and a naphthalene type epoxy resin ("HP-6000" manufactured by DIC Corporation, epoxy equivalent weight: about 250 g / eq.) 10 parts were used, and otherwise, the same operation as in Example 1 was performed to produce a resin composition.

[0307] <Example 13>

[0308] Instead of the spherical silica ("UFP-30" manufactured by Kanto Chemical Co., Inc., average particle diameter: 0.3 μm) 15 parts, which was surface-treated with an amino silane type coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), the spherical silica ("SOC2" manufactured by Admatechs Co., Ltd., average particle diameter: 0.5 μm) 30 parts, which was surface-treated with an amino silane type coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), was used, and otherwise, the same operation as in Example 7 was performed to produce a resin composition.

[0309] <Example 14>

[0310] The amount of the flame retardant ("HCA-HQ-HST" manufactured by Sanso Corporation, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) was changed from 5 parts to 2 parts, and the flame retardant ("SPS-100" manufactured by Otsuka Chemical Co., Ltd.) 3 parts was additionally used, and otherwise, the same operation as in Example 7 was performed to produce a resin composition.

[0311] <Example 15>

[0312] A resin composition was prepared by mixing 30 parts of a biphenyl type epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: about 269 g / eq.), 5 parts of an epoxy resin ("WHR-991S" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: about 265 g / eq.), 10 parts of a liquid bisphenol A type epoxy resin ("jER828EL" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight: about 180 g / eq.), 50 parts of an active ester curing agent ("HPC8000-65T" manufactured by DIC Corporation, active group equivalent weight: about 223 g / eq., toluene solution of 65 mass% nonvolatile component), 10 parts of a phenol-based curing agent containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, hydroxyl equivalent weight: about 151 g / eq., 2-methoxypropanol solution of 50% solid component), 5 parts of a phenoxy resin (weight average molecular weight: 35,000, "YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK and cyclohexanone of 30 mass% nonvolatile component), 10 parts of hollow acrylic polymer particles ("XX-5598Z" manufactured by Sekisui Plastics Co., Ltd., average particle diameter: 0.5 μm, porosity: 35 vol%), 100 parts of spherical silica ("SOC2" manufactured by Admatechs Co., Ltd., average particle diameter: 0.5 μm) surface-treated with an amino silane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), 5 parts of a flame retardant ("HCA-HQ-HST" manufactured by San-Aid Co., Ltd., 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter: 1.5 μm), 2 parts of 1-benzyl-2-phenylimidazole (methyl ethyl ketone solution of 10 mass% solid component of "1B2PZ" manufactured by Shikoku Chemicals Corporation) as a curing accelerator, and 25 parts of methyl ethyl ketone, and uniformly dispersing them with a high-speed rotary mixer.

[0313] Example 16

[0314] Instead of 50 parts of active ester curing agent (DIC Corporation "HPC8000-65T", active group equivalent weight about 223 g / eq., toluene solution of nonvolatile component 65 mass%), and 10 parts of phenol-based curing agent containing triazine skeleton (DIC Corporation "LA-3018-50P", hydroxyl group equivalent weight about 151 g / eq., 2-methoxypropanol solution of solid content 50%), 30 parts of cresol novolak resin (DIC Corporation "KA-1160", hydroxyl group equivalent weight 117 g / eq.) was used; instead of 2 parts of curing accelerator (1-benzyl-2-phenylimidazole (solid content 10 mass% of methyl ethyl ketone solution of "1B2PZ" of Shikoku Chemicals Corporation), 2 parts of curing accelerator (4-dimethylaminopyridine (DMAP), methyl ethyl ketone solution of solid content 5 mass%) was used, and otherwise, similarly to Example 15, a resin composition was prepared.

[0315] <Example 17>

[0316] Instead of 30 parts of cresol novolak resin (DIC Corporation "KA-1160", hydroxyl group equivalent weight 117 g / eq.), 30 parts of prepolymer of bisphenol A dicyanate (Lonza Japan Corporation "BA230S75", cyanate equivalent weight about 232 g / eq., MEK solution of nonvolatile component 75 mass%) and 5 parts of phenol novolak type polyfunctional cyanate ester resin (Lonza Japan Corporation "PT30", cyanate equivalent weight about 124 g / eq., MEK solution of nonvolatile component 80 mass%) of bisphenol A dicyanate were used, and 2 parts of curing accelerator (1 mass% of MEK solution of cobalt (III) acetylacetonate (Tokyo Chemical Industry Co., Ltd.)) was additionally used, and otherwise, similarly to Example 16, a resin composition was prepared.

[0317] <Example 18>

[0318] Instead of 30 parts of a biphenyl type epoxy resin ("NC-3000-L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: about 269 g / eq.) and 5 parts of an epoxy resin ("WHR-991S" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: about 265 g / eq.), 10 parts of a bisphenol AF type epoxy resin ("YX7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight: about 238 g / eq.), 20 parts of a modified naphthalene type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent weight: about 330 g / eq.), and 5 parts of a naphthalene type multifunctional epoxy resin ("HP-4710" manufactured by DIC Corporation, epoxy equivalent weight: about 170 g / eq.) were used; instead of 5 parts of a flame retardant ("HCA-HQ-HST" manufactured by Sankyo Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide), 3 parts of a flame retardant ("SPS-100" manufactured by Otsuka Chemical Co., Ltd.) was used, and otherwise, the same operation as in Example 15 was performed to produce a resin composition.

[0319] <Example 19>

[0320] Instead of 50 parts of an active ester curing agent ("HPC8000-65T" manufactured by DIC Corporation, active group equivalent weight: about 223 g / eq., toluene solution of 65 mass% nonvolatile component), 46 parts of an active ester curing agent ("EXB9460S-65T" manufactured by DIC Corporation, active group equivalent weight: about 223 g / eq., toluene solution of 65 mass% nonvolatile component) was used, and otherwise, the same operation as in Example 15 was performed to produce a resin composition.

[0321] <Example 20>

[0322] The use amount of an active ester curing agent ("HPC8000-65T" manufactured by DIC Corporation, active group equivalent weight: about 223 g / eq., toluene solution of 65 mass% nonvolatile component) was changed from 50 parts to 45 parts, the use amount of a phenol-based curing agent containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, hydroxyl equivalent weight: about 151 g / eq., 2-methoxypropanol solution of 50% solid component) was changed from 10 parts to 5 parts, a benzoaxazine compound ("ODA-BOZ" manufactured by JFE Chemical Co., Ltd.) was additionally used in an amount of 4.5 parts, and a carbodiimide-based curing agent ("V-03" manufactured by Nippon Shokubai Co., Ltd., active group equivalent weight: about 216 g / eq., toluene solution of 50 mass% solid component) was additionally used in an amount of 10 parts, and otherwise, the same operation as in Example 15 was performed to produce a resin composition.

[0323] <Comparative Example 1>

[0324] Instead of 10 parts of the hollow acrylic polymer particles ("XX-5598Z" manufactured by Seiko PMC Corp., average particle diameter: 0.5 μm, porosity: 35 vol%), 10 parts of the core-shell type rubber particles ("IM401-4-14" manufactured by AICA Corp., core: polybutadiene, shell: copolymer of styrene and divinylbenzene) were used, and otherwise, the same operation as in Example 1 was performed to produce the resin composition.

[0325] <Comparative Example 2>

[0326] Instead of 10 parts of the hollow acrylic polymer particles ("XX-5598Z" manufactured by Seiko PMC Corp., average particle diameter: 0.5 μm, porosity: 35 vol%), the same operation as in Example 1 was performed except that the hollow acrylic polymer particles were not used to produce the resin composition.

[0327] <Comparative Example 3>

[0328] Instead of 10 parts of the hollow acrylic polymer particles ("XX-5598Z" manufactured by Seiko PMC Corp., average particle diameter: 0.5 μm, porosity: 35 vol%), 10 parts of the core-shell type rubber particles ("IM401-4-14" manufactured by AICA Corp., core: polybutadiene, shell: copolymer of styrene and divinylbenzene) were used, and otherwise, the same operation as in Example 15 was performed to produce the resin composition.

[0329] <Comparative Example 4>

[0330] Instead of 10 parts of the hollow acrylic polymer particles ("XX-5598Z" manufactured by Seiko PMC Corp., average particle diameter: 0.5 μm, porosity: 35 vol%), the same operation as in Example 15 was performed except that the hollow acrylic polymer particles were not used to produce the resin composition.

[0331] <Comparative Example 5>

[0332] Instead of 10 parts of the hollow acrylic polymer particles ("XX-5598Z" manufactured by Seiko PMC Corp., average particle diameter: 0.5 μm, porosity: 35 vol%), 10 parts of the hollow aluminosilicate particles ("MG-005" manufactured by Pacific Cement Co., average particle diameter: 1.6 μm, porosity: 80 vol%) were used, and otherwise, the same operation as in Example 15 was performed to produce the resin composition.

[0333] <Experimental Example 1: Measurement of Dielectric Constant and Dielectric Loss Tangent

[0334] (1) Production of cured product for evaluation

[0335] On the release agent non-treated surface of a release agent treated PET film ("501010" manufactured by Linde Corporation, thickness: 50 μm, 240 mm square), a glass cloth substrate epoxy resin two-sided copper clad laminate ("R5715ES" manufactured by Matsushita Electric Works, Ltd., thickness: 0.7 mm, 255 mm square) was overlapped, and the four edges were fixed with a polyimide tape (width: 10 mm) (hereinafter sometimes referred to as "fixed PET film").

[0336] The resin composition prepared in the Examples and Comparative Examples was applied to the release treated surface of the above "fixed PET film" in such a manner that the thickness of the dried resin composition layer became 40 μm using a kiss coater, and dried at 80 to 120°C (average: 100°C) for 10 minutes to obtain a resin sheet.

[0337] Next, the resin composition layer was heat cured by being put into an oven at 180°C and then left for 90 minutes under curing conditions.

[0338] After heat curing, the polyimide tape was peeled off, the cured product was removed from the glass cloth substrate epoxy resin two-sided copper clad laminate, and further the PET film ("501010" manufactured by Linde Corporation) was peeled off to obtain a sheet-shaped cured product. The obtained cured product was referred to as "cured product for evaluation".

[0339] (2) Measurement of Relative Dielectric Constant and Dielectric Loss Tangent

[0340] The cured product for evaluation was cut into a size of 80 mm in length and 2 mm in width to prepare an evaluation sample. The relative dielectric constant and dielectric loss tangent (tan δ) were measured using a HP8362B device manufactured by Agilent Technologies, by the resonant cavity perturbation method, under conditions of a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. The measurement was performed on two test pieces, and the average value was calculated.

[0341] < Test Example 2: Evaluation of Reflow Soldering Resistance >

[0342] (1) Lamination of Resin-attached Copper Foil Sheet

[0343] The resin composition prepared in the Examples and Comparative Examples was coated on a copper foil (manufactured by JX Metal Co., Ltd., "JDLC", thickness 12 μm, 240 mm square) using a slot die coater in such a manner that the thickness of the dried resin composition layer became 40 μm, and dried at 80 to 120°C (average 100°C) for 10 minutes to obtain a resin-coated copper foil sheet. The resin-coated copper foil sheet was laminated to both sides of a prepreg (glass cloth substrate epoxy resin two-sided copper clad laminate, thickness of copper foil 18 μm, thickness of substrate 0.4 mm, "R1515A" manufactured by Matsushita Electric Works, Ltd.) using an intermittent vacuum press laminator (manufactured by Nissei Machine Co., Ltd., MVLP-500) in such a manner that the resin composition layer was in contact with both sides of the prepreg. Lamination was performed by reducing the air pressure to 13 hPa or less for 30 seconds, and then pressing under conditions of 100°C, 0.74 MPa for 30 seconds.

[0344] (2) Curing of the resin composition layer

[0345] The resin composition layer of the prepreg to which the resin-coated copper foil sheet was laminated was cured under curing conditions of 180°C for 30 minutes to form an insulating layer. This is referred to as "evaluation substrate A".

[0346] (3) Evaluation of expansion in the reflow soldering step

[0347] Evaluation substrate A was cut into small pieces of 100 mm x 50 mm, and reflow soldering was performed 10 times in a reflow soldering apparatus (manufactured by ANTEK Co., Ltd., "HAS-6116") at a reflow soldering temperature of 260°C (reflow temperature profile according to IPC / JEDEC J-STD-020C).

[0348] Evaluation was performed on 2 small pieces, and the presence of 5 or more abnormalities such as expansion in the conductor layer was evaluated as "X" by visual observation, the presence of 1 to 4 abnormalities such as expansion in the conductor layer was evaluated as "Δ", and the absence of abnormalities in all small pieces was evaluated as "O".

[0349] < Test Example 3: Evaluation of stain removability >

[0350] (1) Production of evaluation substrate

[0351] The two surfaces of a glass cloth substrate epoxy resin two-sided copper clad laminate (thickness of copper foil 18 μm, thickness of substrate 0.4 mm, "R1515A" manufactured by Matsushita Electric Works, Ltd.) on which a circuit substrate was formed were roughened by etching the copper surfaces with a micro-etching agent (manufactured by MEC Co., Ltd., "CZ8100") by 1 μm.

[0352] (2) Lamination of resin sheet

[0353] The resin sheet produced in Test Example 1(1) was laminated to both sides of the circuit board in a manner that the resin composition layer was bonded to the circuit board using an intermittent vacuum press lamination machine (two-stage stack lamination machine "CVP700" manufactured by Nichigo-Morton Co., Ltd.). The lamination was performed by performing 30 seconds of depressurization to make the air pressure 13 hPa or less, and then performing 30 seconds of press bonding under conditions of a temperature of 110°C and a pressure of 0.74 MPa. Next, the resin sheet after lamination was subjected to 60 seconds of heat press under conditions of a temperature of 110°C and a pressure of 0.5 MPa at atmospheric pressure, and smoothing was performed.

[0354] (3) Curing of the resin composition layer

[0355] After the lamination of the resin sheet, the resin composition layer was thermally cured, and a cured body was formed on both sides of the circuit board. The thermal curing of the resin composition layer was performed by the following thermal curing treatment. The thermal curing was performed under conditions of 100°C (after being put into an oven at 100°C) for 30 minutes, and then 180°C (after being moved to an oven at 180°C) for 30 minutes. Then, the board was taken out to an atmosphere at room temperature.

[0356] (4) Formation of through-holes

[0357] Under a state with a support (PET film), the insulating layer was perforated to form through-holes using a CO2 laser processing machine ("LC-2E21B / 1C" manufactured by Hitachi Via Mechanics Co., Ltd.) under conditions of a mask diameter of 1.60 mm, a focus offset value of 0.050, a pulse width of 25 μs, a power of 0.66 W, an aperture of 13, a shot number of 2, and a burst mode. The top diameter (diameter) of the through-holes on the surface of the insulating layer was 50 μm. After the formation of the through-holes, the support (PET film) was peeled off.

[0358] (5) Roughening treatment

[0359] The substrate on which the through-holes were formed was immersed in a swelling liquid ("Swelling Dip Securiganth P" manufactured by Asahi Denka Kogyo K.K., an aqueous solution containing diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 10 minutes, in an oxidizing agent ("Concentrate Compact CP" manufactured by Asahi Denka Kogyo K.K., an aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L) at 80°C for 20 minutes, and finally, in a neutralizing liquid ("Reduction Solution Securiganth P" manufactured by Asahi Denka Kogyo K.K., an aqueous solution of sulfuric acid) at 40°C for 5 minutes, and then dried at 80°C for 30 minutes, to form a roughened cured body on both sides of the circuit substrate. The obtained substrate was referred to as "evaluation substrate B".

[0360] (6) Evaluation of stain removal

[0361] The bottom of the through-hole of the evaluation substrate B was observed with a scanning electron microscope (S-4800 manufactured by Hitachi High-Technologies Co., Ltd.), and the maximum stain length from the wall surface of the bottom of the through-hole was measured from the obtained image. The case where the maximum stain length was less than 3 μm was evaluated as "O", and the case where the maximum stain length was 3 μm or more was evaluated as "X".

[0362] < Test Example 4: Evaluation of warpage >

[0363] (1) Lamination of resin sheet

[0364] The resin sheet produced in Test Example 1 (1) was cut into a size of 9.5 cm square, and laminated to the roughened surface of a copper foil (3EC-III, thickness: 35 μm) manufactured by Mitsui Mining Co., Ltd. having a size of 10 cm square using an intermittent vacuum press lamination machine ("MVLP-500" manufactured by Meicoh Co., Ltd.). For the lamination, 30 seconds of pressure reduction was performed so that the air pressure became 13 hPa or less, and then, pressure bonding was performed at 120°C for 30 seconds at a pressure of 0.74 MPa, whereby a metal foil having a resin composition layer was produced, and then, the PET film was peeled off.

[0365] (2) Curing of resin composition layer

[0366] The four edges of the metal foil having a resin composition layer obtained in the above (1) were attached to a SUS plate having a thickness of 1 mm with polyimide tape so that the resin composition layer was on the top, and the resin composition layer was cured under curing conditions of 180°C for 30 minutes.

[0367] (3) Measurement of warpage

[0368] The polyimide adhesive tape was peeled off from three sides of the metal foil with the cured layer in the above (2), and the height from the SUS plate to the highest point was measured to obtain the value of the warpage. Further, the case where the warpage was less than 1 cm was recorded as "O", the case where the warpage was 1 cm or more and less than 3 cm was recorded as "Δ", and the case where the warpage was 3 cm or more was recorded as "X".

[0369] <Experiment Example 5: Evaluation of cracks after desmear (roughening treatment)>

[0370] The resin composition prepared in the Examples and Comparative Examples was coated on the release-treated surface of the "fixed PET film" using a kiss coater in such a manner that the thickness of the dried resin composition layer became 25 μm, and dried at 80 to 120°C (average 100°C) for 10 minutes to obtain a resin sheet. A core material (Hitachi Chemical, Ltd., "E705GR", thickness 400 μm) in which circular copper pads (copper thickness 35 μm) of 350 μm in diameter were formed in a lattice shape at intervals of 400 μm in such a manner that the residual copper rate became 60% was used, and the resin sheet was laminated to both surfaces of the inner layer substrate in such a manner that the resin composition layer was bonded to the inner layer substrate using an intermittent vacuum press laminator (Nikko-Materials Co., Ltd., two-stage stacking laminator "CVP700"). The lamination was performed by reducing the pressure for 30 seconds to make the air pressure 13 hPa or less, and then, pressure-bonding under the conditions of a temperature of 100°C and a pressure of 0.74 MPa for 30 seconds. This was put into an oven at 130°C and heated for 30 minutes, and then, moved to an oven at 170°C and heated for 30 minutes. Further, the support layer was peeled off, and the obtained circuit substrate was immersed in Swelling Dip Securiganth P (Asahi Japan, swelling liquid) at 60°C for 10 minutes. Next, it was immersed in Concentrate Compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) (Asahi Japan, roughening liquid) at 80°C for 30 minutes. Finally, it was immersed in Reduction Solution Securiganth P (Asahi Japan, neutralizing liquid) at 40°C for 5 minutes. 100 copper pad portions of the circuit substrate after the roughening treatment were observed, and the presence or absence of cracks in the resin composition layer was confirmed. If the number of cracks was 10 or less, it was evaluated as "O", and if the number of cracks was more than 10, it was evaluated as "X".

[0371] The amount of use of the non-volatile component of the resin composition of the Examples and Comparative Examples, the measurement results and evaluation results of the Experiment Examples, and the like are shown in Table 1 below.

[0372] [Table 1]

[0373]

[0374] According to the above, by using the resin composition containing the (A) hollow organic polymer particles, a cured product having excellent stain removability can be obtained. Also, for the cured product of the resin composition containing the (A) hollow organic polymer particles, in one embodiment, excellent reflow soldering resistance can be obtained, warping and cracking at the time of curing can be suppressed, and excellent electrical properties can also be obtained.

[0375] Reference Example 1: Cross Section of Cured Product

[0376] An image of the cross section of the cured product of the resin composition based on Example 1 obtained in Test Example 1 was taken. A FIB-SEM composite device (SII Nano Technology Co., Ltd. "SMI3050SE") was used in the taking. The image obtained by the taking is shown in FIG. 1. As is clear from the image of FIG. 1, even in the cured product obtained after curing the resin composition of the present application, the pores of the (A) hollow organic polymer particles remain. Figure 1 Figure 1 As is clear from the image of FIG. 1, even in the cured product obtained after curing the resin composition of the present application, the pores of the (A) hollow organic polymer particles remain.​

Claims

1. A resin composition for an interlayer insulating layer of a printed wiring board, comprising: (A) hollow organic polymer particles, (B) epoxy resin, (C) a curing agent, (D) an inorganic filler, and (E) a flame retardant. (A) The organic polymer contained in the ingredients is: an organic polymer composed of monomers containing styrene, or an organic polymer composed of monomers containing (meth)acrylates. (D) is composed of spherical silicon dioxide. When the non-volatile component in the resin composition is set as 100% by mass, the content of component (A) is 5.1% by mass or more and 50% by mass or less. When the non-volatile component in the resin composition is set at 100% by mass, the content of component (B) is 10% by mass or more and 40% by mass or less. When the non-volatile component in the resin composition is set as 100% by mass, the content of component (C) is 0.01% by mass or more and 30% by mass or less. When the non-volatile component in the resin composition is set at 100% by mass, the content of component (D) is 10% by mass or more and 60% by mass or less. When the non-volatile component in the resin composition is set at 100% by mass, the content of component (E) is 0.1% by mass or more and 10% by mass or less. (A) The average particle size of the component is 0.5~8μm. The average particle size of component (D) is 0.2~10 μm.

2. The resin composition according to claim 1, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (A) is 5.1% by mass or more and 40% by mass or less.

3. The resin composition according to claim 1, wherein, (A) is composed of single hollow particles.

4. The resin composition according to claim 1, wherein, (A) The porosity of the component is above 20% by volume and below 99% by volume.

5. The resin composition according to claim 1, wherein, (A) The porosity of the component is above 25% by volume and below 99% by volume.

6. The resin composition according to claim 1, wherein, (A) The porosity of the component is less than 99% by volume.

7. The resin composition according to claim 1, wherein, (A) The porosity of the component is less than 60% by volume.

8. The resin composition according to claim 1, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (B) is 10% by mass or more and 35% by mass or less.

9. The resin composition according to claim 1, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (B) is 15% by mass or more and 40% by mass or less.

10. The resin composition according to claim 1, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (C) is 0.01% by mass or more and 25% by mass or less.

11. The resin composition according to claim 1, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (C) is 0.2% by mass or more and 30% by mass or less.

12. The resin composition according to claim 1, wherein, (C) The curing agent contains (C-1) epoxy curing agent, and when the non-volatile component in the resin composition is set to 100% by mass, the content of component (C-1) is 30% by mass or less.

13. The resin composition according to claim 1, wherein, (C) The curing agent contains (C-1) epoxy curing agent, and when the non-volatile component in the resin composition is set to 100% by mass, the content of component (C-1) is 25% by mass or less.

14. The resin composition according to claim 1, wherein, (C) The curing agent includes (C-1) epoxy curing agent, and when the non-volatile component in the resin composition is set to 100% by mass, the content of component (C-1) is 0.01% by mass or more and 30% by mass or less.

15. The resin composition according to claim 1, wherein, (C) The curing agent contains (C-1) epoxy curing agent, and when the non-volatile component in the resin composition is set to 100% by mass, the content of component (C-1) is 10% by mass or more and 30% by mass or less.

16. The resin composition according to claim 1, wherein, (C) The curing agent contains (C-2) curing accelerator, and when the non-volatile component in the resin composition is set to 100% by mass, the content of component (C-2) is less than 10% by mass.

17. The resin composition according to claim 1, wherein, (C) The curing agent contains (C-2) curing accelerator, and when the non-volatile component in the resin composition is set to 100% by mass, the content of component (C-2) is 0.5% by mass or less.

18. The resin composition according to claim 1, wherein, (C) The curing agent contains a (C-2) curing accelerator, and when the non-volatile component in the resin composition is set to 100% by mass, the content of component (C-2) is 0.001% by mass or more and 10% by mass or less.

19. The resin composition according to claim 1, wherein, (C) The curing agent contains a (C-2) curing accelerator, and when the non-volatile component in the resin composition is set to 100% by mass, the content of component (C-2) is 0.2% by mass or more and 10% by mass or less.

20. The resin composition according to claim 1, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (D) is 10% by mass or more and 55% by mass or less.

21. The resin composition according to claim 1, wherein, (E) contains phosphorus-based flame retardants.

22. The resin composition according to claim 21, wherein, (E) The ingredients include: phosphorus-based flame retardants containing phenolic hydroxyl groups.

23. The resin composition according to claim 1, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (E) is 0.1% by mass or more and 8% by mass or less.

24. The resin composition according to claim 1, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (E) is 1% by mass or more and 10% by mass or less.

25. The resin composition according to claim 1, further comprising (F) an elastomer.

26. The resin composition according to claim 25, wherein, (F) is a resin having one or more structures selected from polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure.

27. The resin composition according to claim 26, wherein, (F) Components include: a resin having a polybutadiene structure.

28. The resin composition according to claim 27, wherein, (F) Components include: polybutadiene resin containing phenolic hydroxyl groups.

29. The resin composition according to claim 25, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (F) is 80% by mass or less.

30. The resin composition according to claim 25, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (F) is 35% by mass or less.

31. The resin composition according to claim 25, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (F) is 0.1% by mass or more and 80% by mass or less.

32. The resin composition according to claim 25, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (F) is 20% by mass or more and 80% by mass or less.

33. The resin composition according to claim 1, further comprising (G) a thermoplastic resin.

34. The resin composition according to claim 33, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (G) is 30% by mass or less.

35. The resin composition according to claim 33, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (G) is less than 1% by mass.

36. The resin composition according to claim 33, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (G) is 0.01% by mass or more and 30% by mass or less.

37. The resin composition according to claim 33, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (G) is 0.5% by mass or more and 30% by mass or less.

38. A cured product, which is a cured product of the resin composition according to any one of claims 1 to 37.

39. A sheet-like laminated material comprising the resin composition according to any one of claims 1 to 37.

40. A resin sheet, comprising: Support body, and A resin composition layer formed of any one of claims 1 to 37 is disposed on the support.

41. A printed wiring board having an insulating layer formed from a cured resin composition according to any one of claims 1 to 37.

42. A semiconductor device comprising the printed wiring board of claim 41.

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