JP2023093025A - resin composition - Google Patents

Abstract

To provide a resin composition or the like that can form an insulating layer having excellent flame retardancy, dielectric properties, and high-temperature reflow expansion resistance.SOLUTION: A resin composition contains (A) curable resin, (B) inorganic filler, and (C) non-inflammable gas.SELECTED DRAWING: None

Description

The present invention relates to resin compositions.

2. Description of the Related Art As a technique for manufacturing printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed from a cured product obtained by curing a resin composition (Patent Document 1).

JP 2020-23714 A

By the way, in recent years, in the production of multilayer printed wiring boards, cured products of resin compositions for forming insulating layers are required to be excellent in flame retardancy and dielectric properties including dielectric constant and dielectric loss tangent. there is Moreover, when both flame retardancy and dielectric properties are excellent, the heat resistance after curing is lowered, and swelling may occur during reflow. Therefore, it is required to have excellent flame retardancy and dielectric properties, as well as excellent resistance to reflow swelling at high temperatures.

The present invention was invented in view of the above problems, and includes a resin composition capable of forming an insulating layer having excellent flame retardancy, dielectric properties, and high-temperature reflow swelling resistance; a cured product of the resin composition; A sheet-like laminated material containing the composition; A resin sheet having a resin composition layer formed from the resin composition; A printed wiring board having an insulating layer containing a cured product of the resin composition; A semiconductor device comprising:

The inventors have made extensive studies to solve the above problems. As a result, the present inventors have found that the above problems can be solved by including (C) a nonflammable gas in the resin composition, and completed the present invention.
That is, the present invention includes the following.

[1] (A) a curable resin,
(B) an inorganic filler; and (C) a nonflammable gas.
[2] The resin composition according to [1], wherein the content of component (C) is 3% by volume or more when the non-volatile component in the resin composition is 100% by volume.
[3] The resin composition according to [1] or [2], wherein component (C) is one or more selected from nitrogen gas, argon gas, carbon dioxide gas, helium gas, and neon gas.
[4] Component (B) contains (B-1) a hollow inorganic filler having voids therein, and Component (C) is contained within the voids of Component (B-1), [1 ] The resin composition according to any one of [3].
[5] The resin composition according to [4], wherein component (B-1) has an average particle size of 0.01 μm or more and 5 μm or less.
[6] The resin composition according to [4] or [5], wherein the component (B-1) has a porosity of 10% by volume or more and 80% by volume or less.
[7] The resin composition according to any one of [4] to [6], wherein component (B) comprises component (B-1) and solid inorganic filler (B-2).
[8] Any one of [1] to [7], wherein component (A) contains at least one selected from the group consisting of epoxy resins, phenol resins, active ester resins, cyanate resins and radically polymerizable resins. of the resin composition.
[9] The resin composition according to any one of [1] to [8], further comprising (D) organic particles.
[10] The resin composition according to any one of [1] to [9], which is used for forming an insulating layer.
[11] A cured product of the resin composition according to any one of [1] to [10].
[12] A sheet-like laminate material containing the resin composition according to any one of [1] to [10].
[13] A resin sheet comprising a support and a resin composition layer formed on the support from the resin composition according to any one of [1] to [10].
[14] A printed wiring board comprising an insulating layer containing a cured product of the resin composition according to any one of [1] to [10].
[15] A semiconductor device comprising the printed wiring board according to [14].

According to the present invention, a resin composition capable of forming an insulating layer having excellent flame retardancy, dielectric properties, and high-temperature reflow swelling resistance; a cured product of the resin composition; a sheet-like laminate material containing the resin composition; A resin sheet having a resin composition layer formed from the resin composition; a printed wiring board having an insulating layer containing a cured product of the resin composition; and a semiconductor device having the printed wiring board.

Hereinafter, the present invention will be described with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be arbitrarily modified without departing from the scope of the claims and their equivalents.

In the following description, the term "(meth)acrylic" includes acrylic, methacrylic and combinations thereof. The term "(meth)acrylate" also includes acrylates, methacrylates and combinations thereof. A "(meth)acryloyloxy group" includes an acryloyloxy group, a methacryloyloxy group, and combinations thereof. Furthermore, the term "(meth)acrylonitrile" includes acrylonitrile, methacrylonitrile and combinations thereof.

[Resin composition]
The resin composition of the present invention includes (A) a curable resin, (B) an inorganic filler, and (C) a nonflammable gas in combination. A resin composition that satisfies such requirements can form an insulating layer that is excellent in flame retardancy, dielectric properties, and resistance to high-temperature reflow swelling. In addition, the resin composition generally has a low coefficient of thermal expansion, excellent dielectric properties even at high temperatures, and can form an insulating layer excellent in elongation (rate of elongation at break).

The resin composition of the present invention, in combination with (A) a curable resin, (B) an inorganic filler, and (C) a nonflammable gas, (D) organic particles, (E) a curing accelerator, (F) a thermoplastic A resin, (G) a flame retardant, and (H) other additives may be included. Each component that can be contained in the resin composition will be described in detail below.

<(A) Curable resin>
The resin composition contains (A) a curable resin as the (A) component. (A) The curable resin can be a resin that can be cured when heat is applied. Moreover, curable resin may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of curable resins include epoxy resins, phenolic resins, active ester resins, cyanate resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, thiol resins, and radical polymerizable resins. One type of curable resin may be used alone, or two or more types may be used in combination. Among them, the curable resin preferably contains at least one selected from the group consisting of epoxy resins, active ester resins, cyanate resins and radically polymerizable resins.

In particular, from the viewpoint of significantly obtaining the effects of the present invention, it is preferable to use an epoxy resin in combination with a resin capable of reacting with the epoxy resin to cure the resin composition. A resin that can react with an epoxy resin to cure a resin composition is sometimes referred to as a "curing agent" hereinafter. Examples of curing agents include phenol resins, active ester resins, cyanate resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, and thiol resins. Among them, phenol resins, active ester resins, cyanate resins and carbodiimide resins are preferable, phenol resins, active ester resins and cyanate resins are more preferable, active ester resins and cyanate resins are more preferable, and active ester resins are particularly preferable. Moreover, one type of curing agent may be used alone, or two or more types may be used in combination.

Epoxy resins are curable resins having epoxy groups. Examples of epoxy resins 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, trisphenol type epoxy resin, Naphthol novolak type epoxy resin, phenol novolak 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, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, isocyanurate-type epoxy resins, phenolphthalimidine-type epoxy resins, and the like. One type of epoxy resin may be used alone, or two or more types may be used in combination.

The epoxy resin preferably contains an epoxy resin containing an aromatic structure from the viewpoint of obtaining a cured product having excellent high-temperature reflow swelling resistance. Aromatic structures are chemical structures generally defined as aromatic and also include polycyclic aromatic and heteroaromatic rings. Examples of epoxy resins containing an aromatic structure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol novolak type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bixylenol type epoxy resin, glycidylamine type epoxy having an aromatic structure Resin, glycidyl ester type epoxy resin having aromatic structure, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having aromatic structure, epoxy resin having butadiene structure having aromatic structure, aromatic Structured alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin having aromatic structure, cyclohexane dimethanol type epoxy resin having aromatic structure, naphthylene ether type epoxy resin, having aromatic structure A trimethylol type epoxy resin, a tetraphenylethane type epoxy resin having an aromatic structure, and the like are included.

(A) The curable resin preferably contains, as an epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. The ratio of the 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 with respect to 100% by mass of the non-volatile component of the epoxy resin. % or more.

Epoxy resins include liquid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resins”). ). As the epoxy resin, the resin composition may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. good.

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, and an ester skeleton. An alicyclic epoxy resin, a cyclohexane-type epoxy resin, a cyclohexanedimethanol-type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a bisphenol A-type epoxy resin and a naphthalene-type epoxy resin are more preferable.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation; ", "Epikote 828EL" (bisphenol A type epoxy resin); "jER807" and "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" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycirrol type epoxy resin) manufactured by ADEKA; "EP-3950L" manufactured by ADEKA; "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; Bisphenol F type epoxy resin mixture); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celoxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); Daicel "PB-3600" manufactured by Nippon Soda Co., Ltd., "JP-100" and "JP-200" (epoxy resins having a butadiene structure) manufactured by Nippon Soda Co., Ltd.; 1,4-glycidylcyclohexane type epoxy resin) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolak type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol phthalate Midine-type epoxy resins are preferred, and biphenyl-type epoxy resins and naphthylene ether-type epoxy resins are more preferred.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac 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); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" ", "HP6000" (naphthylene ether type epoxy resin); Nippon Kayaku "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku; epoxy resin); "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "YX4000H" manufactured by Mitsubishi Chemical, "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin); "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Company "YX7700" (phenol aralkyl type epoxy resin); Osaka Gas Chemicals Co., Ltd. "PG-100", "CG-500"; Mitsubishi Chemical Co., Ltd. "YX7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical Company "YL7800" (fluorene type epoxy resin); Mitsubishi Chemical Corporation "jER1010" (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation "jER1031S" (tetraphenylethane type epoxy resin); Nippon Kayaku "WHR991S" (phenolphthalimidine-type epoxy resin) manufactured by Co., Ltd., and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the mass ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1:0.01 to 1:20, more preferably 1:0.05 to 1:10, particularly preferably 1:0.1 to 1:7.

The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ~5,000g/eq. , more preferably 60 g/eq. ~3,000 g/eq. , more preferably 80 g/eq. ~2,000 g/eq. , particularly preferably 110 g/eq. ~1,000 g/eq. is. Epoxy equivalent weight represents the mass of resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin is preferably 100-5,000, more preferably 250-3,000, and still more preferably 400-1,500. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the epoxy resin in the resin composition is preferably 1% by mass or more when the non-volatile component in the resin composition is 100% by mass. , more preferably 5% by mass or more, particularly preferably 10% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

As the phenolic resin, a compound having one or more, preferably two or more hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring per molecule can be used. A phenolic resin is sometimes referred to as a "phenolic curing agent" because, when combined with an epoxy resin, it can react with the epoxy resin to cure the resin composition. Phenolic resins having a novolac structure are preferred from the viewpoint of high-temperature reflow swelling resistance and water resistance. Moreover, from the viewpoint of adhesion, a nitrogen-containing phenolic resin is preferable, and a triazine skeleton-containing phenolic resin is more preferable. Among them, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying high-temperature reflow swelling resistance, water resistance, and adhesion. Specific examples of phenolic resins include "MEH-7700", "MEH-7810" and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN", "CBN" and "GPH" manufactured by Nippon Kayaku Co., Ltd. , Nippon Steel Chemical & Material Co., Ltd. "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375" , "SN-395", DIC's "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD- 2090-60M” and the like.

Active ester resins generally include compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. It is preferably used. When combined with an epoxy resin, the active ester resin can react with the epoxy resin to cure the resin composition, so it is sometimes referred to as an "active ester curing agent". The active ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving high-temperature reflow swelling resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, the active ester resin includes a dicyclopentadiene-type active ester resin, a naphthalene-type active ester resin containing a naphthalene structure, an active ester resin containing an acetylated phenol novolac, and an active ester resin containing a benzoylated phenol novolac. is preferred, and at least one selected from dicyclopentadiene-type active ester resins and naphthalene-type active ester resins is more preferred. As the dicyclopentadiene-type active ester resin, an active ester resin containing a dicyclopentadiene-type diphenol structure is preferable.

Commercially available active ester resins include, for example, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", and "EXB-8000L-65M" as active ester resins containing a dicyclopentadiene type diphenol structure. , "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC); "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK" as active ester resins containing a naphthalene structure, "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); "EXB9401" (manufactured by DIC Corporation) as a phosphorus-containing active ester resin; acetylated phenol novolac "DC808" (Mitsubishi Chemical Co., Ltd.) as an active ester resin; "YLH1026", "YLH1030", and "YLH1048" (Mitsubishi Chemical Co., Ltd.) as active ester resins that are benzoylated phenol novolacs; containing a styryl group and a naphthalene structure Examples of active ester resins include "PC1300-02-65MA" (manufactured by Air Water).

As the cyanate resin, a compound having one or more, preferably two or more cyanate groups in one molecule can be used. A cyanate resin is sometimes referred to as a "cyanate-based curing agent" because, when combined with an epoxy resin, it can react with the epoxy resin to cure the resin composition. Examples of cyanate resins include bisphenol A dicyanate, polyphenolcyanate (oligo(3-methylene-1,5-phenylenecyanate)), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4′- ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethylphenyl) Bifunctional cyanate resins such as methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, phenol novolak and Polyfunctional cyanate resins derived from cresol novolak and the like, and prepolymers obtained by partially triazinizing these cyanate resins. Specific examples of cyanate resins include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate resins) manufactured by Lonza Japan, "BA230" and "BA230S75" (part or all of bisphenol A dicyanate is triazine and trimerized prepolymers).

As the carbodiimide resin, a compound having one or more, preferably two or more carbodiimide structures in one molecule can be used. When combined with an epoxy resin, the carbodiimide resin can react with the epoxy resin to cure the resin composition, so it is sometimes referred to as a "carbodiimide-based curing agent." Specific examples of carbodiimide resins include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexanebis(methylene-t-butylcarbodiimide); aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide). biscarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), poly(isophoronecarbodiimide) and other aliphatic polycarbodiimides; poly(phenylenecarbodiimide), poly( naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly (xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), poly[methylenebis(methylphenylene)carbodiimide] and other aromatic polycarbodiimides. Examples of commercially available carbodiimide resins include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07" and "Carbodilite V-09" manufactured by Nisshinbo Chemical Co.; "Stabaxol P", "Stabaxol P400", "Hykasil 510" and the like manufactured by Rhein Chemie.

As the acid anhydride resin, a compound having one or more, preferably two or more acid anhydride groups in one molecule can be used. Acid anhydride resins are sometimes referred to as "acid anhydride-based curing agents" because when combined with epoxy groups, they can react with epoxy resins to cure the resin composition. Specific examples of acid anhydride resins include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic anhydride. , trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride , pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3′-4,4′-diphenylsulfone Tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3 - polymer-type acid anhydrides such as dione, ethylene glycol bis(anhydrotrimellitate), styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid, and the like. Commercially available acid anhydride resins include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA" and "OSA" manufactured by Shin Nippon Rika; YH-306", "YH-307"; "HN-2200", "HN-5500" manufactured by Hitachi Chemical; "EF-30", "EF-40", "EF-60", "EF -80” and the like.

As the amine resin, a compound having one or more, preferably two or more amino groups in one molecule can be used. Amine resins are sometimes referred to as "amine-based curing agents" because, when combined with epoxy groups, they can react with the epoxy resin to cure the resin composition. Examples of amine resins include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred. Amine resins are preferably primary amines or secondary amines, more preferably primary amines. Specific examples of amine resins include 4,4′-methylenebis(2,6-dimethylaniline), 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, m -phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diamino biphenyl, 3,3′-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)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, and the like. Commercially available amine resins include, for example, "SEIKACURE-S" manufactured by Seika; B", "Kayahard AS"; "Epicure W" manufactured by Mitsubishi Chemical; "DTDA" manufactured by Sumitomo Seika.

Benzoxazine resins are sometimes referred to as "benzoxazine-based curing agents" because, when combined with epoxy resins, they can react with the epoxy resins to cure the resin composition. Specific examples of benzoxazine resins include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co.; -a” and the like.

A thiol resin is sometimes referred to as a "thiol-based curing agent" because, when combined with an epoxy resin, it can react with the epoxy resin to cure the resin composition. Examples of thiol resins include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl) isocyanurate and the like.

The active group equivalent of the curing agent is preferably 50 g/eq. ~3000g/eq. , more preferably 100 g/eq. ~1000g/eq. , more preferably 100 g/eq. ~500 g/eq. , particularly preferably 100 g/eq. ~300 g/eq. is. Active group equivalents are the mass of curing agent per equivalent of active groups.

When the number of epoxy groups in the epoxy resin is 1, the number of active groups in the curing agent is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.5 or more, and preferably 5.0 or less. It is more preferably 4.0 or less, particularly preferably 3.0 or less. The “epoxy group number of the epoxy resin” represents the sum of all the values obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, "the number of active groups of the curing agent" represents the sum of all the values obtained by dividing the mass of the non-volatile component of the curing agent present in the resin composition by the active group equivalent.

From the viewpoint of significantly obtaining the effect of the present invention, the content of the curing agent in the resin composition is preferably 1% by mass or more, more preferably 2% by mass, when the non-volatile component in the resin composition is 100% by mass. % or more, particularly preferably 5 mass % or more, preferably 40 mass % or less, more preferably 30 mass % or less, and particularly preferably 25 mass % or less.

A compound having an ethylenically unsaturated bond can be used as the radically polymerizable resin. Therefore, the radically polymerizable resin can have a radically polymerizable group containing an ethylenically unsaturated bond. Examples of radically polymerizable groups include unsaturated hydrocarbons such as vinyl groups, allyl groups, 3-cyclohexenyl groups, 3-cyclopentenyl groups, 2-vinylphenyl groups, 3-vinylphenyl groups, and 4-vinylphenyl groups. groups; α,β-unsaturated carbonyl groups such as acryloyl group, methacryloyl group, maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group), and the like. The number of radically polymerizable groups contained in one molecule of the radically polymerizable resin may be one, but preferably two or more. One type of radically polymerizable resin may be used alone, or two or more types may be used in combination.

Preferred radically polymerizable resins include, for example, styrene-based radically polymerizable resins. The styrenic radically polymerizable resin can be a compound having one or more, preferably two or more vinyl groups directly bonded to an aromatic carbon atom. Styrenic radically polymerizable resins include, for example, divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4′-divinylbiphenyl, 1,2-bis(4 -vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, bis(4-vinylphenyl)ether, etc., low molecular weight (molecular weight less than 1000) styrenic compounds; vinylbenzyl-modified polyphenylene ether resin, styrene - high molecular weight (molecular weight 1000 or more) styrene compounds such as divinylbenzene copolymer;

A modified polyphenylene ether resin having a vinylphenyl group is preferable as the styrene-based radically polymerizable resin. Vinylphenyl groups can include 2-vinylphenyl groups, 3-vinylphenyl groups, 4-vinylphenyl groups, or groups in which these aromatic carbon atoms are further substituted with one or more alkyl groups. Among them, a resin represented by the following formula (A-1) is particularly preferable as the styrene-based radically polymerizable resin.

(In formula (A-1),
R ¹¹ and R ¹² each independently represent an alkyl group;
R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group;
R ³¹ and R ³² each independently represent a vinylphenyl group;
Y ¹ represents a single bond, -C(R ^y ) ₂ -, -O-, -CO-, -S-, -SO-, or -SO ₂ -;
R ^y each independently represents a hydrogen atom or an alkyl group;
Y ² represents a single bond or an alkylene group;
p represents 0 or 1;
q and r each independently represent an integer of 1 or more. )
The q unit and the r unit may be the same or different for each unit.

In formula (A-1), R ¹¹ and R ¹² each independently represent an alkyl group, preferably a methyl group.

In formula (A-1), R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom.

In formula (A-1), R ²¹ and R ²² each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, more preferably a methyl group.

In formula (A-1), R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

In formula (A-1), R ³¹ and R ³² each independently represent a vinylphenyl group.

In formula (A-1), Y ² represents a single bond or an alkylene group. An alkylene group means a linear, branched and/or cyclic divalent saturated aliphatic hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 14 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and particularly preferably an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group include -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH(CH ₃ )-, -CH(CH ₃ )-CH ₂ -, -C(CH ₃ ) ₂ - and the like. Y ² is preferably an alkylene group (particularly -CH ₂ -).

In formula (A-1), Y ¹ represents a single bond, —C(R ^y ) ₂ —, —O—, —CO—, —S—, —SO—, or —SO ₂ —, preferably , a single bond, —C(R ^y ) ₂ —, or —O—, particularly preferably a single bond. Each R ^y independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

In formula (A-1), p represents 0 or 1, preferably 1.

In formula (A-1), q and r each independently represent an integer of 1 or more, preferably an integer of 1-200, more preferably an integer of 1-100.

Specific examples of the resin represented by the formula (A-1) include resins represented by the following formula (A-1-1). Examples of resins represented by formula (A-1-1) include “OPE-2St 1200” and “OPE-2St 2200” (vinylbenzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Company.

Another preferred radically polymerizable resin is, for example, a maleimide-based radically polymerizable resin. The maleimide-based radically polymerizable resin can be a compound having one or more, preferably two or more maleimide groups. The maleimide-based radically polymerizable resin may be an aliphatic maleimide compound containing an aliphatic amine skeleton, or an aromatic maleimide compound containing an aromatic amine skeleton. Among them, as the maleimide-based radically polymerizable resin, a resin represented by the following formula (A-2) is particularly preferable.

(In formula (A-2),
R ^a each independently represents a hydrogen atom or an alkyl group;
Ring E, ring F and ring G each independently represent an aromatic ring optionally having a substituent;
Z each independently represents a single bond, -C(R ^z ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO- indicate;
R ^z each independently represents a hydrogen atom or an alkyl group;
s represents an integer of 1 or more;
t each independently represents 0 or 1;
u represents 0, 1, 2 or 3 independently. )
The s unit, t unit and u unit may be the same or different for each unit.

In formula (A-2), each R ^a independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

In formula (A-2), ring E, ring F and ring G each independently represents an optionally substituted aromatic ring, preferably optionally substituted benzene It is a ring, more preferably a benzene ring optionally substituted with a group selected from an alkyl group and an aryl group, particularly preferably an unsubstituted benzene ring.

In formula (A-2), each Z is independently a single bond, -C(R ^z ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, - represents CONH- or -NHCO-, preferably a single bond, -C(R ^z ) ₂ - or -O-, more preferably a single bond or -C(R ^z ) ₂ - , particularly preferably a single bond. Each ^Rz independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

In formula (A-2), s represents an integer of 1 or more, preferably an integer of 1-10.

In formula (A-2), each t independently represents 0 or 1, preferably 1.

In formula (A-2), u each independently represents 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, particularly preferably 1.

Specific examples of the resin represented by the formula (A-2) include resins represented by the following formula (A-2-1). Examples of the resin represented by formula (A-2-1) include "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., and the like.

Still another preferred radically polymerizable resin is, for example, a (meth)acrylic radically polymerizable resin. The (meth)acrylic radically polymerizable resin can be a compound having one or more, preferably two or more acryloyl groups and/or methacryloyl groups. Examples of (meth)acrylic radically polymerizable resins include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, neo Pentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol Di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylic acid ester compounds such as; 9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene , ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate and other low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylic acid ester compounds; Low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylic acid ester compounds such as (meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate; High molecular weight (molecular weight 1000 or more) acrylic acid ester compounds such as (meth)acrylic-modified polyphenylene ether resins and the like can be mentioned. Commercially available (meth)acrylic radical polymerizable resins include, for example, Shin-Nakamura Chemical Co., Ltd. "A-DOG" (dioxane glycol diacrylate), Kyoeisha Chemical Co., Ltd. "DCP-A" (tricyclode candimethanol diacrylate), "DCP" (tricyclodecanedimethanol dimethacrylate), Nippon Kayaku Co., Ltd.'s "KAYARAD R-684" (tricyclodecanedimethanol diacrylate), "KAYARAD R-604" (dioxane glycol diacrylate), and "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether) manufactured by SABIC Innovative Plastics.

Further preferred radically polymerizable resins include, for example, allyl-based radically polymerizable resins. The allyl-based radically polymerizable resin can be a compound having one or more, preferably two or more allyl groups. Examples of allyl-based radically polymerizable resins include diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and diallyl 2,3-naphthalenecarboxylate. aromatic carboxylic acid allyl ester compounds; 1,3,5-triallyl isocyanurate, isocyanurate allyl ester compounds such as 1,3-diallyl-5-glycidyl isocyanurate; 2,2-bis[3-allyl-4 -epoxy-containing aromatic allyl compounds such as (glycidyloxy)phenyl]propane; bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane benzoxazine-containing aromatic allyl compounds; ether-containing aromatic allyl compounds such as 1,3,5-triallyletherbenzene; and allylsilane compounds such as diallyldiphenylsilane. Examples of commercially available allyl-based radical polymerizable resins include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd., and "DAD" (diallyl diphenate) manufactured by Nissho Techno Fine Chemical Co., Ltd. , "TRIAM-705" manufactured by Wako Pure Chemical Industries, Ltd. (triallyl trimellitate), trade name "DAND" manufactured by Nippon Distillery Co., Ltd. (diallyl 2,3-naphthalenecarboxylate), manufactured by Shikoku Chemical Industry Co., Ltd. "ALP- d” (Bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane), “RE-810NM” manufactured by Nippon Kayaku Co., Ltd. (2, 2-bis[3-allyl-4-(glycidyloxy)phenyl]propane), "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Kasei Co., Ltd., and the like.

The ethylenically unsaturated bond equivalent of the radically polymerizable resin is preferably 20 g/eq. ~3000g/eq. , more preferably 50 g/eq. ~2500 g/eq. , more preferably 70 g/eq. ~2000g/eq. , particularly preferably 90 g/eq. ~1500 g/eq. is. The ethylenically unsaturated bond equivalent represents the mass of the radically polymerizable resin per equivalent of ethylenically unsaturated bond.

The weight average molecular weight (Mw) of the radically polymerizable resin is preferably 40,000 or less, more preferably 10,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, but may be 150 or more, for example.

The content of the radical polymerizable resin in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 0.5% by mass or more, when the non-volatile component in the resin composition is 100% by mass. is 1.0% by mass or more, preferably 10% by mass or less, more preferably 5.0% by mass or less, and particularly preferably 3.0% by mass or less. When the amount of the radically polymerizable resin is within the above range, it is possible to effectively improve the impact peel resistance and impact crack resistance of the insulating layer containing the cured product of the resin composition.

From the viewpoint of significantly obtaining the effects of the present invention, the content of (A) the curable resin in the resin composition is preferably 10% by mass or more, when the non-volatile component in the resin composition is 100% by mass. It is preferably 20% by mass or more, particularly preferably 25% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

<(B) Inorganic filler>
The resin composition contains (B) an inorganic filler as the (B) component. (B) The inorganic filler is usually contained in the resin composition in the form of particles.

(B) An inorganic compound can be used as the material for the inorganic filler. (B) Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, 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 zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate.

Inorganic composite oxides may also be used as the material for the inorganic filler (B). An inorganic complex oxide represents an oxide containing two or more kinds of atoms selected from the group consisting of metal atoms and metalloid atoms. Such an inorganic composite oxide is preferably an oxide containing a combination of silicon and one or more atoms selected from the group consisting of metal atoms other than silicon and metalloid atoms. Metal atoms to be combined with silicon include aluminum, lead, nickel, cobalt, copper, zinc, zirconium, iron, lithium, magnesium, barium, potassium, calcium, titanium, boron, sodium, etc. Among them, aluminum is particularly preferred. . Therefore, as the inorganic composite oxide, an oxide containing silicon and aluminum is preferable, and an aluminosilicate is particularly preferable.

Among these (B) inorganic filler materials, silica, alumina and aluminosilicate are preferable, and silica is particularly preferable. (B) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

(B) Inorganic fillers can be classified into (B-1) hollow inorganic fillers having internal voids and (B-2) solid inorganic fillers having no internal voids. (B) The inorganic filler preferably includes (B-1) a hollow inorganic filler and (B-2) a solid inorganic filler. In addition, (B-2) the solid inorganic filler preferably contains (C) a nonflammable gas, which will be described later, in its pores.

(B-1) The hollow inorganic filler may be a single hollow particle having only one hole inside the particle, or may be a multi-hollow particle having two or more holes inside the particle. , a combination of single hollow particles and other hollow particles.

(B-1) Since the hollow inorganic filler has pores, it usually has a porosity greater than 0% by volume. From the viewpoint of including the component (C) inside the pores of the component (B-1), the porosity of the hollow inorganic filler (B-1) is preferably 10% by volume or more, more preferably 15% by volume or more. , particularly preferably 20% by volume or more. Further, from the viewpoint of the mechanical strength of the cured product of the resin composition, the porosity of the hollow inorganic filler (B-1) is preferably 80% by volume or less, more preferably 75% by volume or less, and particularly preferably 70% by volume. % by volume or less.

The porosity P (% by volume) of a particle is the volume-based ratio of the total volume of one or more pores present inside the particle to the volume of the entire particle based on the outer surface of the particle (total volume of pores /particle volume). The porosity P is obtained by using the measured value D _M (g/cm ³ ) of the actual density of the particles and the theoretical value D _T (g/cm ³ ) of the substance density of the material forming the particles. It can be calculated by the formula (X2).

(B) Hollow inorganic particles generally have voids formed within the particles and outer shells formed of an inorganic material surrounding the voids. The pores are usually separated from the outside of the particle by the outer shell. At this time, it is desirable that the pores do not communicate with the outside of the particles. Therefore, it is desirable that the outer shell portion be a non-porous shell that does not have pores communicating with the outside of the particle. It can be confirmed by observing with a transmission electron microscope (TEM) that the outer shell is non-porous.

(B-1) The average particle size of the hollow inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, and particularly preferably 0.3 μm or more, from the viewpoint of significantly obtaining the effects of the present invention. , preferably 5 μm or less, more preferably 4 μm or less, particularly preferably 3 μm or less.

The average particle size of particles can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of particles is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring apparatus, and the median diameter thereof can be used as the average particle size for measurement. A measurement sample of the inorganic filler can be obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them ultrasonically for 10 minutes. A measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle size can be calculated as the median size. Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

(B-1) The BET specific surface area of the hollow inorganic filler is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, and particularly preferably 5 m ² /g, from the viewpoint of significantly obtaining the effects of the present invention. or more, preferably 100 m ² /g or less, more preferably 50 m ² /g or less, and particularly preferably 30 m ² /g or less. According to the BET method, the BET specific surface area of the particles is calculated by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen gas on the sample surface and calculating the specific surface area using the BET multipoint method. can be measured by

(B-1) A commercially available hollow inorganic filler may be used. Commercially available (B-1) hollow inorganic fillers include, for example, “MG-005” manufactured by Taiheiyo Cement Co., Ltd. The (B-1) hollow inorganic filler may be produced, for example, by the method described in Japanese Patent No. 5940188 or a method based thereon. To give a specific example, (B-1) Hollow silica particles as an example of the hollow inorganic filler are a step of preparing an aqueous solution containing a substance capable of forming pores and a basic compound; A step of mixing and stirring to precipitate silica particles; a step of removing substances that can form pores from the silica particles to obtain a hollow silica precursor; and a step of firing the hollow silica precursor; It can be manufactured by a method including:

(B-1) The hollow inorganic filler is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate compounds. A coupling agent etc. are mentioned. One type of surface treatment agent may be used alone, or two or more types may be used in combination.

Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" ( Hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM- 7103” (3,3,3-trifluoropropyltrimethoxysilane).

From the viewpoint of improving dispersibility, the degree of surface treatment with a surface treatment agent is preferably within a specific range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% to 8% by mass, and a surface treatment agent of 0.2% to 5% by mass. It is more preferably surface-treated, and more preferably surface-treated with 0.3% by mass to 3% by mass of a surface treating agent.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of preventing the melt viscosity of the resin composition from increasing, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and even more preferably 0.5 mg/m ² or less.

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

The amount (% by mass) of the hollow inorganic filler (B-1) in the resin composition is preferably It is 1% by mass or more, more preferably 3% by mass or more, particularly preferably 5% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

The amount (% by volume) of the hollow inorganic filler (B-1) in the resin composition is preferably It is 1% by volume or more, more preferably 3% by volume or more, particularly preferably 5% by volume or more, preferably 70% by volume or less, more preferably 60% by volume or less, and particularly preferably 50% by volume or less.

The specific gravity of component (B-1) is preferably 3.50 g/cm 3 or less, more preferably 3.00 g/cm ³ or less, and still more preferably 2.50 g/cm ³ from the viewpoint of significantly obtaining the effects of the present invention. ³ or less, preferably 0.05 g/cm ³ or more, more preferably 0.5 g/cm ³ or more, and particularly preferably 1.0 g/cm ³ or more. The specific gravity can be measured by the method described in Examples below.

(B) The inorganic filler preferably contains (B-2) a solid inorganic filler together with (B-1) the hollow inorganic filler. (B-2) Commercially available solid inorganic fillers include, for example, “UFP-30” manufactured by Denka Kagaku Kogyo; “SP60-05” and “SP507-05” manufactured by Nippon Steel & Sumikin Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Matex; "UFP-30" manufactured by Denka; "Silfil NSS-5N"; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs; "DAW-03", "FB-105FD" manufactured by Denka, etc. are mentioned.

(B-2) The average particle size of the solid inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, particularly preferably 0.3 μm or more, preferably 10 μm or less, more preferably 5 μm. Below, it is particularly preferably 3 μm or less. The average particle size of component (B-2) can be measured by the same method as for the average particle size of hollow inorganic filler (B-1).

(B-2) The BET specific surface area of the solid inorganic filler is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, particularly preferably 1 m ² /g or more, and preferably It is 100 m ² /g or less, more preferably 70 m ² /g or less, and particularly preferably 40 m ² /g or less. The BET specific surface area of component (B-2) can be measured by the same method as for the BET specific surface area of component (B-2).

(B-2) The solid inorganic filler is preferably treated with a surface treatment agent, as with the (B-1) hollow inorganic filler.

The amount (% by mass) of the solid inorganic filler (B-2) in the resin composition may be 0% by mass or more than 0% by mass when the non-volatile component in the resin composition is 100% by mass. Also preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 30% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, particularly preferably 40% by mass or less is.

The amount (% by volume) of the solid inorganic filler (B-2) in the resin composition may be 0% by volume or more than 0% by volume when the non-volatile component in the resin composition is 100% by volume. well, preferably 5% by volume or more, more preferably 10% by volume or more, particularly preferably 20% by volume or more, preferably 50% by volume or less, more preferably 40% by volume or less, particularly preferably 30% by volume or less is.

(B-1) Hollow inorganic filler and (B-2) solid inorganic filler The proportion of pores contained in the entire inorganic filler (B) containing both the inorganic filler is It is calculated as a rate (% by volume). (B) The porosity (% by volume) of the inorganic filler is a representative value representing the ratio of pores to the volume of the (B) inorganic filler on a volume basis, and is expressed as "total volume of pores / (B) The total volume of inorganic fillers”. (B) The specific range of the porosity of the inorganic filler is preferably 10% by volume or more, more preferably 15% by volume or more, particularly preferably 20% by volume or more, and preferably 80% by volume or less. It is preferably 70% by volume or less, particularly preferably 60% by volume or less.

The average particle diameter of the entire (B) inorganic filler including both the (B-1) hollow inorganic filler and (B-2) solid inorganic filler is preferable from the viewpoint of significantly obtaining the effects of the present invention. is 0.01 μm or more, more preferably 0.1 μm or more, particularly preferably 0.3 μm or more, preferably 5 μm or less, more preferably 4 μm or less, and particularly preferably 3 μm or less.

The BET specific surface area of the entire (B) inorganic filler including both the (B-1) hollow inorganic filler and (B-2) the solid inorganic filler is preferable from the viewpoint of significantly obtaining the effects of the present invention. is 1 m ² /g or more, more preferably 2 m ² /g or more, particularly preferably 5 m ^{2 /g or more, preferably 100 m 2 /} g or less, more preferably 50 m ² /g or less, particularly preferably 30 m ² /g g or less.

The content (% by mass) of the inorganic filler (B) in the resin composition is preferably 20% by mass when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention. % or more, more preferably 30 mass % or more, particularly preferably 40 mass % or more, preferably 80 mass % or less, more preferably 70 mass % or less, and particularly preferably 65 mass % or less. Even if the component (C) is contained inside the pores of the component (B-1), the mass of the component (C) itself is so light that it can be ignored, so the content (% by mass) of the inorganic filler (B) is It is determined by the sum of the content of component (B-1) and the content of component (B-2).

The content (% by volume) of the inorganic filler (B) in the resin composition is preferably 20 vol. % or more, more preferably 30 volume % or more, particularly preferably 40 volume % or more, preferably 80 volume % or less, more preferably 75 volume % or less, and particularly preferably 70 volume % or less.

<(C) nonflammable gas>
The resin composition contains (C) a nonflammable gas as the (C) component. (C) Component usually functions as a flame retardant. By including the component (C) in the resin composition, it is possible to improve the flame retardancy of the cured product of the resin composition. Conventionally, it has been said that the presence of a gas such as a nonflammable gas in a resin composition adversely affects the cured product of the resin composition. However, in the present invention, by including the component (C) in the resin composition, it is possible to improve the flame retardancy of the cured product of the resin composition. In addition, since gases such as nonflammable gases have almost no polarization, by including the component (C) in the resin composition, the dielectric properties such as the dielectric constant and the dielectric loss tangent of the cured product of the resin composition can be lowered. can.

Component (C) can be a gas that is chemically stable and hardly reacts with other compounds. Examples of such gas include inert gas and rare gas. Among them, the component (C) is preferably one or more selected from nitrogen gas, argon gas, carbon dioxide gas, helium gas, and neon gas.

The component (C) is contained inside the pores of the hollow inorganic filler (B-1) having pores therein in order to stably exist in the resin composition and in the cured product of the resin composition. preferably. (B-1) The hollow inorganic filler is as described above.

As the content (% by volume) of component (C) contained inside the pores of component (B-1), from the viewpoint of significantly obtaining the effects of the present invention, When the volume is 100% by volume, it is preferably 80% by volume or more, more preferably 85% by volume or more, still more preferably 90% by volume or more, 95% by volume or more, and preferably 100% by volume or less (all the inside of the pores is the (C) component). The content of component (C) is calculated from the specific gravity of component (B-1) before inclusion of component (C) and the specific gravity of component (B-1) after inclusion of component (C). can be done.

As a method for including the component (C) in the pores of the component (B-1), for example, a manufacturing method including the following steps (a) and (b) can be used.
(a) a step of including a nonflammable gas in the pores of the precursor of the hollow inorganic filler (that is, the precursor of the component (B-1));
(b) a step of firing a precursor of a hollow inorganic filler containing a non-combustible gas inside the pores;

As one embodiment of the step (a), the precursor of the component (B-1) is placed in a closed container such as a desiccator, and the atmosphere in the closed container is replaced with a non-flammable gas atmosphere to perform a non-flammable gas purge. The precursor of component (B-1) represents a material from which component (B-1) can be obtained by firing. The precursor of component (B-1) usually has a hollow portion open to the outside. Therefore, the non-combustible gas can be taken into the hollow portion by purging the non-combustible gas. The non-combustible gas purge may be performed only once, or may be performed multiple times.

The nonflammable gas purge time varies depending on the content of component (C) contained in the pores of component (B-1), but is preferably 0.5 hours or longer, more preferably 1 hour or longer, and more preferably 1 hour or longer. It is preferably 2 hours or longer, preferably 24 hours or shorter, more preferably 20 hours or shorter, and still more preferably 15 hours or shorter.

The nonflammable gas purge is preferably performed under reduced pressure. As the reduced pressure condition, for example, the ultimate pressure is preferably 1000 Pa or less, more preferably 300 Pa or less, still more preferably 100 Pa or less, preferably 0.01 Pa or more, more preferably 0.03 Pa or more, and still more preferably 0.1 Pa. That's it. The temperature during decompression is preferably 20° C. or higher, more preferably 30° C. or higher, still more preferably 40° C. or higher, preferably 200° C. or lower, more preferably 120° C. or lower, and still more preferably 80° C. or lower. .

As an embodiment of the step (b), after the completion of the nonflammable gas purging, the precursor of the component (B-1) containing the component (C) inside the pores is taken out from the sealed container, and the nonflammable gas is removed using an electric furnace or the like. Firing under ambient conditions. By performing this step, the (B-1) component is obtained from the precursor, and the (C) component is sealed in the (B-1) component, and the resin composition and the cured product of the resin composition It will become possible to exist stably inside. The non-combustible gas atmosphere during firing may be the same non-combustible gas as the component (C) contained in the pores, or may be a different non-combustible gas.

The firing temperature of the precursor of component (B-1) in which the component (C) is included in the pores is preferably 600° C. or higher, more preferably 750° C. or higher, and still more preferably 900° C. or higher. is 1200° C. or lower, more preferably 1100° C. or lower, and still more preferably 1000° C. or lower.

The firing time of the precursor of the component (B-1) in which the component (C) is included in the pores is preferably 12 hours or longer, more preferably 24 hours or longer, and still more preferably 48 hours or longer. is 200 hours or less, more preferably 150 hours or less, still more preferably 100 hours or less.

The content of component (C) in the resin composition is preferably 100% by volume of non-volatile components in the resin composition from the viewpoint of obtaining a cured product having excellent flame retardancy, high-temperature reflow swelling resistance, and dielectric properties. is 1% by volume or more, more preferably 2% by volume or more, still more preferably 3% by volume or more, preferably 50% by volume or less, more preferably 40% by volume or less, and particularly preferably 30% by volume or less. The content of component (C) is assuming that the mass of component (C) itself is so light that it can be ignored, and the specific gravity of the cured resin composition before containing component (C) and the content of component (C) It can be calculated from the specific gravity of the cured product of the resin composition after curing.

<(D) Organic particles>
The resin composition preferably contains (D) organic particles as component (D) in combination with (A) curable resin, (B) inorganic filler, and (C) nonflammable gas as optional components. (D) The organic particles are present in a particulate form in the resin composition, and are usually included in the cured product while maintaining the particulate form. Components (D) do not include those corresponding to the above components (A) to (C).

Since the (D) organic particles contain an organic material, they usually have a higher thermal expansion coefficient than the (B) inorganic filler and a lower specific gravity than the (B) inorganic filler. Therefore, by using the component (D), the coefficient of thermal expansion and the specific gravity of the cured product of the resin composition can be adjusted. In general, the (D) component tends to have higher flexibility than the (B) component, so the (D) component can increase the resistance to stress of the cured product of the resin composition.

As component (D), particles having a uniform composition as a whole may be used, but particles having a non-uniform composition may also be used. For example, multi-layered particles having a shell portion and a built-in portion formed in the shell portion are preferred. Moreover, the multi-layered particle may contain a portion other than the shell portion and the built-in portion. For example, the multi-layered particle may further contain an optional portion within the built-in portion. Further, for example, the multi-layered particle may contain any layer between the shell portion and the internal portion. Since the built-in portion is usually covered with the shell portion, the multi-layered particles can be highly dispersed in the resin composition regardless of the composition of the built-in portion. can. Therefore, since it is possible to employ an internal portion having a composition suitable for the insulating layer, the characteristics of the insulating layer can be improved. The term “multilayered particles” as used herein does not necessarily refer only to particles in which the shell part and the internal part can be clearly distinguished, and includes particles in which the boundary between the shell part and the internal part is unclear, and the internal part is the shell. It does not have to be completely covered with parts.

The shell portion of multi-layered particles is usually made of a polymer. The polymer forming the shell portion may be a homopolymer as a polymer of one type of monomer, or a copolymer as a copolymer of two or more types of monomers. It is preferable to select the types of the polymer and its monomer that form the shell portion so as to suppress aggregation of the component (D) and to disperse well in the resin composition. Specific types may depend on the composition of the (A) curable resin, but preferred examples of monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth) ) cyclohexyl acrylate, octyl (meth)acrylate, glycidyl (meth)acrylate and other (meth)acrylic acid esters; (meth)acrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimide α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene and α-methylstyrene; and (meth)acrylonitrile. One type of these monomers may be used alone, or two or more types may be used in combination.

Preferably, the internal portion of the multi-layered particle contains an organic material different from that contained in the shell portion. A multi-layered particle having a built-in portion containing an organic material can have a core portion corresponding to the built-in portion and a shell portion covering the core portion, and thus is sometimes called a “core-shell particle”. Especially, it is preferable that the built-in part contains a rubber component. When the (C) organic particles contain multilayer particles containing a rubber component in the built-in portion, the impact peel resistance and impact crack resistance of the insulating layer containing the cured product of the resin composition can be effectively improved. As the rubber component, for example, a resin that exhibits an elastic modulus of 1 GPa or less when a tensile test is performed at a temperature of 25° C. and a humidity of 40% RH according to Japanese Industrial Standards (JIS K7161) can be used. As the rubber component, for example, a resin having a glass transition temperature of preferably 0° C. or lower, more preferably -10° C. or lower, still more preferably -20° C. or lower, particularly preferably -30° C. or lower can be used. The glass transition temperature can be measured by DSC (differential scanning calorimetry) at a heating rate of 10°C/min. These rubber components are selected, for example, from 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. It can be provided as a resin having one or more structures.

Specific examples of rubber components include silicone elastomers such as polydimethylsiloxane; polybutadiene, polyisoprene, polychlorobutadiene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene- Olefins such as isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, ethylene-propylene-butene terpolymer thermoplastic elastomers; thermoplastic elastomers such as acrylic thermoplastic elastomers such as poly(meth)acrylate, poly(meth)butyl acrylate, poly(meth)cyclohexyl acrylate, and poly(meth)octyl acrylate); mentioned. Further, the rubber component may be mixed with silicone rubber such as polyorganosiloxane rubber.

In the multi-layer particles containing the rubber component, the amount of the rubber component is preferably 40% by mass or more, more preferably 50% by mass or more, and particularly preferably 60% by mass or more. Although there is no particular upper limit, it may be, for example, 95% by mass or less, 90% by mass, or the like, from the viewpoint of sufficiently covering the internal portion with the shell portion.

A multi-layered particle having a built-in part containing a rubber component can be produced by, for example, preparing a core particle containing a rubber component, and graft-copolymerizing a monomer component copolymerizable with the rubber component contained in the core particle to form a shell part. It can be manufactured by a manufacturing method including the step of forming Moreover, a commercial product may be used for the multi-layered particles having a built-in part containing a rubber component. Commercially available products include, for example, “CHT” manufactured by Cheil Industries; “B602” manufactured by UMGABS; ”, “Paraloid EXL-2311”, “Paraloid-EXL2313”, “Paraloid EXL-2315”, “Paraloid KM-330”, “Paraloid KM-336P”, “Paraloid KCZ-201”; C-223A", "METABLEN E-901", "METABLEN S-2001", "METABLEN W-450A", "METABLEN SRK-200"; Kaneka's "Kaneace M-511", "Kaneace M-600", "Kane Ace M-400", "Kane Ace M-580", "Kane Ace MR-01"; Staphyloid "AC3832", "AC3816N" manufactured by Aica Kogyo Co., Ltd., and the like.

It is preferable that the built-in portion of the multi-layered particle is a hollow portion. That is, it is preferable that the multi-layered particles have hollow portions as pores surrounded by shell portions. A multi-layered particle having a hollow portion as a built-in portion is sometimes called a “hollow organic particle”. When component (D) contains multi-layered particles having hollow portions as built-in portions, it is possible to effectively improve the impact peel resistance and impact crack resistance of the insulating layer containing the cured product of the resin composition.

A multi-layered particle containing hollow portions usually has a porosity greater than 0% by volume. From the viewpoint of effectively improving the impact peel resistance and impact crack resistance of the insulating layer containing the cured product of the resin composition, the porosity of the multilayer particles is preferably 10% by volume or more, more preferably 15% by volume or more. , particularly preferably 20% by volume or more. From the viewpoint of mechanical strength of the cured product of the resin composition, the porosity of the multilayer particles is preferably 90% by volume or less, more preferably 90% by volume or less, and particularly preferably 80% by volume or less.

Multilayer particles containing a hollow portion, for example, JP 2006-265394, JP 2007-238792, WO 2011/040376, JP 2016-190980, WO 2018/051794 , Japanese Patent Laid-Open No. 2020-189978. Moreover, a commercial product may be used for the multi-layered particles having a hollow portion. Commercially available products include, for example, “XX-5598Z” manufactured by Sekisui Plastics Co., Ltd.

Component (D) may be used singly or in combination of two or more.

(D) The component may be treated with a surface treatment agent. Examples of surface treatment agents for component (D) include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid; carboxylic acids such as acetic acid, propionic acid, butyric acid, and acrylic acid; Sulfonic acid such as benzenesulfonic acid, phosphoric acid such as polyoxyethylene alkyl ether phosphoric acid, phosphonic acid, organic acid such as phosphinic acid; tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, 3-(meth)acryl silane coupling agents such as roxypropyltrimethoxysilane and 8-(meth)acryloxyoctyltrimethoxysilane; and isocyanate compounds such as ethyl isocyanate.

The average particle size of component (D) is preferably smaller than the average particle size of hollow inorganic filler (B-1). The specific average particle diameter of component (D) is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.10 μm or more, preferably 5 μm or less, more preferably 2 μm or less, and It is preferably 1 μm or less. The average particle size of component (D) can be measured using a zeta potential particle size distribution analyzer.

The amount (% by mass) of component (D) in the resin composition is preferably 0.1% by mass when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention. Above, more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

The amount (% by volume) of component (D) in the resin composition is preferably 0.5% by volume when the non-volatile component in the resin composition is 100% by volume, from the viewpoint of significantly obtaining the effects of the present invention. Above, more preferably 1.5% by volume or more, particularly preferably 2.0% by volume or more, preferably 20% by volume or less, more preferably 15% by volume or less, and particularly preferably 10% by volume or less.

The specific gravity of the component (D) is preferably 2.5 g/cm ³ or less, more preferably 2.0 g/cm ³ or less, and preferably 0.8 g/cm ³ from the viewpoint of significantly obtaining the effects of the present invention. Above, more preferably 0.9 g/cm ³ or more, particularly preferably 1.0 g/cm ³ or more. The specific gravity can be measured by the method described in Examples below.

<(E) Curing accelerator>
The resin composition may further contain (E) a curing accelerator as an optional component in combination with the components (A) to (C) described above. The (E) curing accelerator as the (E) component does not include those corresponding to the above-described components (A) to (D). (E) The curing accelerator functions as a curing catalyst that accelerates the curing of the (A) curable resin.

As the (E) curing accelerator, an appropriate one can be used according to the type of the (A) curable resin. For example, when the (A) curable resin contains an epoxy resin, the (E) curing accelerator that can accelerate the curing of the epoxy resin includes, for example, a phosphorus-based curing accelerator, a urea-based curing accelerator, and a guanidine-based curing accelerator. accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, and the like. (E) The curing accelerator may be used alone or in combination of two or more.

Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydro Aliphatic phosphonium salts such as genhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl phosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 -methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, aromatic phosphonium salts such as butyltriphenylphosphonium thiocyanate; aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; 2-butenyl)phosphine, aliphatic phosphines such as tricyclohexylphosphine; -tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butyl) phenyl)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 other aromatic phosphines. be done.

Urea-based curing accelerators include, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 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) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] etc.

Guanidine curing accelerators include, 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.

Examples of imidazole curing accelerators include 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'-undecyl imidazolyl-(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 isocyanurate, 2-phenylimidazole isocyanurate, 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 other imidazole compounds, and adducts of imidazole compounds and epoxy resins. Examples of commercially available imidazole curing accelerators include, for example, Shikoku Kasei Co., Ltd. "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK- PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "C11Z-A"; and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. and the like, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo (5,4,0)-undecene and the like. As the amine-based curing accelerator, a commercially available product may be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like.

The amount of the (E) curing accelerator in the resin composition may be 0% by mass, or greater than 0% by mass, when the non-volatile component in the resin composition is 100% by mass, preferably 0.01% by mass or more, more preferably 0.02% by mass or more, particularly preferably 0.05% by mass or more, preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and particularly preferably is 0.2% by mass or less.

<(F) Thermoplastic resin>
The resin composition may further contain (F) a thermoplastic resin as an optional component in combination with the components (A) to (C) described above. The (F) thermoplastic resin as the (F) component does not include those corresponding to the above-described components (A) to (E).

(F) Thermoplastic resins include, for example, phenoxy resins, polyimide resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, and polycarbonate resins. , polyether ether ketone resin, polyester resin, and the like. (F) The thermoplastic resin may be used singly or in combination of two or more.

Examples of phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, and terpene. Examples include phenoxy resins having one or more skeletons selected from the group consisting of skeletons and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of the phenoxy resin include Mitsubishi Chemical's "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins); Mitsubishi Chemical's "YX8100" (bisphenol S skeleton-containing phenoxy resin); Mitsubishi Chemical "YX6954" (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30";

Specific examples of the polyimide resin include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "Likacoat SN20" and "Ricacoat PN20" manufactured by New Japan Chemical Co., Ltd., and the like.

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, and Denka Butyral 6000-EP manufactured by Sekisui Chemical Co., Ltd. S-LEC BH series, BX series (eg BX-5Z), KS series (eg KS-1), BL series, BM series;

Examples of polyolefin resins include ethylene-based copolymers such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer. Resin: polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.

Polybutadiene resins include, for example, hydrogenated polybutadiene skeleton-containing resins, hydroxyl group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxyl group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, and isocyanate group-containing resins. Examples include polybutadiene resin, urethane group-containing polybutadiene resin, polyphenylene ether-polybutadiene resin, and the like.

Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimides) manufactured by Hitachi Chemical Co., Ltd.

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Specific examples of the polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of the polyetherimide resin include "Ultem" manufactured by GE.

Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxy group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, "C-1090" and "C-2090" manufactured by Kuraray Co., Ltd. , “C-3090” (polycarbonate diol), and the like. Specific examples of the polyetheretherketone resin include "Sumiproy K" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethyl terephthalate resin, and the like.

(F) The weight average molecular weight (Mw) of the thermoplastic resin is preferably greater than 5,000, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, and preferably is 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less.

The amount of the (F) thermoplastic resin in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, when the non-volatile component in the resin composition is 100% by mass, especially It is preferably 1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

<(G) Flame Retardant>
The resin composition may further contain (G) a flame retardant as an optional component in combination with the components (A) to (C) described above. The (G) flame retardant as the (G) component does not include those corresponding to the above-described components (A) to (F). (G) Flame retardants include, for example, phosphazene compounds, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides, with phosphazene compounds being preferred. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

The phosphazene compound is not particularly limited as long as it is a cyclic compound containing nitrogen and phosphorus as constituent elements, but the phosphazene compound is preferably a phosphazene compound having a phenolic hydroxyl group.

Specific examples of the phosphazene compound include "SPH-100", "SPS-100", "SPB-100" and "SPE-100" manufactured by Otsuka Chemical Co., Ltd., "FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd., "FP-110", "FP-300", "FP-400" and the like can be mentioned, and "SPH-100" manufactured by Otsuka Chemical Co., Ltd. is preferable.

As the flame retardant other than the phosphazene compound, commercially available products may be used, and examples thereof include “HCA-HQ” manufactured by Sanko Co., Ltd., and “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd. As the flame retardant, one that is difficult to hydrolyze is preferable, and for example, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide is preferable.

(G) The content of the flame retardant is preferably 0.1% by mass or more, more preferably 0.1% by mass, based on 100% by mass of non-volatile components in the resin composition, from the viewpoint of significantly obtaining the effects of the present invention. It is 2% by mass or more, more preferably 0.3% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

<(H) Optional Additives>
The resin composition may further contain (H) an optional additive as an optional non-volatile component in combination with the components (A) to (C) described above. (H) Optional additives include, for example, polymerization initiators; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, oxidation Colorants such as titanium and carbon black; Polymerization inhibitors such as hydroquinone, catechol, pyrogallol and phenothiazine; Leveling agents such as silicone leveling agents and acrylic polymer leveling agents; Thickeners such as bentone and montmorillonite; Defoamers such as agents, acrylic defoaming agents, fluorine defoaming agents, vinyl resin defoaming agents; UV absorbers such as benzotriazole UV absorbers; Adhesion improvers such as urea silane; Adhesion-imparting agents such as property-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as surfactants, silicone-based surfactants; Flame retardants such as inorganic flame retardants (for example, antimony trioxide); Dispersants: Stabilizers such as borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, carboxylic anhydride stabilizers; tertiary photopolymerization initiation aids such as amines; photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, and thioxanthones; (H) Optional additives may be used singly or in combination of two or more.

<(I) Solvent>
The resin composition may contain (I) a solvent as an optional volatile component in combination with the non-volatile components such as components (A) to (H) described above. (I) As the solvent, an organic solvent is usually used. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol; acetic acid Ether ester solvents such as 2-ethoxyethyl, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, etc. ester alcohol solvents; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol) and other ether alcohol solvents; N,N-dimethylformamide, N, Amide solvents such as N-dimethylacetamide and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethylsulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatics such as hexane, cyclopentane, cyclohexane, and methylcyclohexane Hydrocarbon-based solvents: aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, and the like can be mentioned. (I) Solvents may be used singly or in combination of two or more.

(I) The amount of the solvent is not particularly limited. It may be 0% by mass or less, 15% by mass or less, 10% by mass or less, or the like.

The specific gravity of the resin component in the cured product of the resin composition is preferably 1.58 g/cm ³ or less, more preferably 1.56 g/cm ³ or less, from the viewpoint of significantly obtaining the effects of the present invention. The lower limit of the specific gravity of the cured product is preferably 1.0 g/cm ³ or higher, more preferably 1.02 g/cm ³ or higher, and particularly preferably 1.05 g/cm ³ or higher. The resin component represents the non-volatile components of the resin composition excluding (B) the inorganic filler and (D) the organic particles. The specific gravity can be measured by the method described in Examples below.

The content (% by volume) of the resin component in the cured product obtained by heating the resin composition at 180° C. for 90 minutes is preferably 20% by volume or more, more preferably 30% by volume, from the viewpoint of significantly obtaining the effects of the present invention. It is vol% or more, more preferably 40 vol% or more, preferably 80 vol% or less, more preferably 70 vol% or less, still more preferably 60 vol% or less.

The resin composition can be produced, for example, by mixing components that can be included in the resin composition. Some or all of the components described above may be mixed at the same time, or may be mixed in order. During the course of mixing each component, the temperature may be set accordingly, and thus may be temporarily or permanently heated and/or cooled. Moreover, you may perform stirring or shaking in the process of mixing each component.

The thermal expansion coefficient of the cured product of the resin composition can be adjusted according to the composition of the resin composition. For example, (B) the method of increasing the amount of the inorganic filler can reduce the coefficient of thermal expansion. Moreover, according to the method of increasing a resin component, a thermal expansion coefficient can be enlarged. Furthermore, the thermal expansion coefficient may be changed by adjusting the types of the inorganic filler and the resin component.

A cured product obtained by heating the resin composition at 180° C. for 90 minutes can have a low dielectric constant. Therefore, an insulating layer having a low relative dielectric constant can be formed from a cured product of these resin compositions. In one example, the relative permittivity of the cured product at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by the cavity resonance perturbation method is preferably less than 3.30, more preferably 3.15 or less, and particularly preferably 3.00 or less. , is less than 3.00. The lower limit is not particularly limited, and can be, for example, 2.00 or more. The relative permittivity can be measured according to the method described in Examples below.

A cured product obtained by heating the resin composition at 180° C. for 90 minutes can have a low dielectric constant. Therefore, an insulating layer having a low relative dielectric constant can be formed from a cured product of these resin compositions. In one example, the relative permittivity of the cured product at a measurement frequency of 5.8 GHz and a measurement temperature of 90° C. by the cavity resonance perturbation method is preferably less than 3.30, more preferably 3.15 or less, and particularly preferably 3.00 or less. , is less than 3.00. The lower limit is not particularly limited, and can be, for example, 2.00 or more. The relative permittivity can be measured according to the method described in Examples below.

A cured product obtained by heating the resin composition at 180° C. for 90 minutes can have a low dielectric loss tangent. Therefore, an insulating layer having a low dielectric loss tangent can be formed from a cured product of these resin compositions. In one example, the dielectric loss tangent of the cured product at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by the cavity resonance perturbation method is preferably 0.020 or less, more preferably 0.018 or less, and particularly preferably 0.015 or less. be. The lower limit is not particularly limited, and can be, for example, 0.001 or more, 0.002 or more. The dielectric loss tangent can be measured according to the method described in Examples below.

A cured product obtained by heating the resin composition at 180° C. for 90 minutes can have a low dielectric loss tangent. Therefore, an insulating layer having a low dielectric loss tangent can be formed from a cured product of these resin compositions. In one example, the dielectric loss tangent of the cured product at a measurement frequency of 5.8 GHz and a measurement temperature of 90° C. is preferably 0.020 or less, more preferably 0.018 or less, and particularly preferably 0.015 or less by the cavity resonance perturbation method. be. The lower limit is not particularly limited, and can be, for example, 0.001 or more, 0.002 or more. The dielectric loss tangent can be measured according to the method described in Examples below.

The cured product obtained by heating the resin composition at 180 ° C. for 90 minutes is usually the dielectric loss tangent between the dielectric loss tangent of the cured product at a measurement temperature of 90 ° C. and the dielectric loss tangent of the cured product at a measurement temperature of 23 ° C. The rate of change can be lowered. Therefore, an insulating layer having a low rate of change in dielectric loss tangent can be formed from a cured product of these resin compositions. In one example, the rate of change in dielectric loss tangent of the cured product of the resin composition is preferably less than 30%, more preferably 29% or less, and particularly preferably 25% or less. The lower limit is not particularly limited, and may be, for example, 1% or more, 2% or more. The rate of change in dielectric loss tangent can be measured according to the method described in Examples below.

A cured product obtained by thermally curing the resin composition of the present invention at 180° C. for 90 minutes exhibits excellent flame retardancy. Therefore, an insulating layer having excellent flame retardancy can be formed from a cured product of these resin compositions. The flame retardancy is preferably "V-1", "V-0" or better in the UL flame resistance test (UL94V). Flame retardancy can be measured according to the method described in the examples below.

A cured product obtained by thermally curing the resin composition at 100° C. for 30 minutes and then at 190° C. for 120 minutes exhibits excellent high-temperature reflow blistering resistance. Therefore, it is possible to form an insulating layer exhibiting a property (reflow resistance) that no abnormalities such as blisters are observed even after the reflow process is performed. Even if the cured product is passed 10 times through a reflow device that reproduces a solder reflow temperature with a peak temperature of 260° C., no abnormality such as blistering is observed in the small piece of the insulating layer. High-temperature reflow blistering resistance can be measured according to the method described in Examples below.

A cured product obtained by heating the resin composition at 180° C. for 90 minutes usually has a coefficient of thermal expansion within a specific range. A specific range of the thermal expansion coefficient of the cured product is usually 40 ppm or less, preferably 30 ppm or less, more preferably 25 ppm or less. The lower limit of the coefficient of thermal expansion of the cured product is preferably 5 ppm or more, more preferably 10 ppm or more, and particularly preferably 15 ppm or more.

A cured product obtained by heating the resin composition at 180° C. for 90 minutes can usually have a large elongation (elongation at break). Therefore, an insulating layer having a high elongation at break can be formed from a cured product of these resin compositions. In one example, the elongation at break of the cured product is preferably 0.5% or more, more preferably 1.0% or more, and particularly preferably 1.2% or more. The upper limit is not particularly limited, and may be, for example, 10% or less, or 5.0% or less. The elongation can be measured according to the method described in the examples below.

The resin composition described above can be used as a resin composition for insulation, and can be particularly suitably used as a resin composition for forming an insulation layer (resin composition for forming an insulation layer). For example, the resin composition described above can be used as a resin composition for forming an insulating layer of a printed wiring board, and is suitable as a resin composition for forming an interlayer insulating layer (resin composition for interlayer insulation). Available.

Further, the resin composition described above may be used as a resin composition for forming a rewiring layer (resin composition for forming a rewiring layer). A rewiring formation layer represents an insulating layer for forming a rewiring layer. Further, the rewiring layer represents a conductor layer formed on a rewiring forming layer as an insulating layer. For example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition described above may be used as a resin composition for forming a rewiring layer. Further, when the semiconductor chip package is manufactured by the following steps (1) to (6), a rewiring layer may be further formed on the sealing layer.
(1) a step of laminating a temporary fixing film on a substrate;
(2) temporarily fixing the semiconductor chip on the temporary fixing film;
(3) forming a sealing layer on the semiconductor chip;
(4) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;
(5) Forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been removed; and (6) Forming a rewiring layer as a conductor layer on the rewiring layer. forming process

Furthermore, the resin composition described above includes, for example, a resin sheet, a sheet-like laminate material such as prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole-filling resin, a part-embedding resin, etc. It can be used in a wide range of applications.

[Sheet-like laminated material]
Although the resin composition described above may be applied in the form of a varnish, it is industrially preferable to use it in the form of a sheet-like laminated material containing the resin composition.

As the sheet-like laminate material, resin sheets and prepregs shown below are preferable.

In one embodiment, the resin sheet includes a support and a resin composition layer provided on the support. The resin composition layer is formed of the resin composition described above. Therefore, the resin composition layer usually contains the resin composition, and preferably contains only the resin composition.

The thickness of the resin composition layer is preferably 50 μm or less, more It is preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be 5 μm or more, 10 μm or more, or the like.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

The support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the resin composition layer.

As the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

In one embodiment, the resin sheet may further contain any layer as necessary. Examples of such an optional layer include a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dust and scratches on the surface of the resin composition layer.

For the resin sheet, for example, a liquid (varnish) resin composition is used as it is, or a liquid (varnish) resin composition is prepared by dissolving the resin composition in a solvent, and this is applied to a coating device such as a die coater. and then dried to form a resin composition layer.

Examples of the solvent include the same solvents as those described as components of the resin composition. A solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

Drying may be carried out by a method such as heating or blowing hot air. Although the drying conditions are not particularly limited, drying is performed so that the solvent content in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the solvent in the resin composition, for example, when using a resin composition containing 30% by mass to 60% by mass of solvent, the resin composition is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. layer can be formed.

The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition described above.

As the sheet-like fiber base material used for the prepreg, for example, those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited, and is usually 10 μm or more.

A prepreg can be produced by a hot melt method, a solvent method, or the like.

The thickness of the prepreg may be in the same range as the resin composition layer in the resin sheet described above.

The sheet-like laminate material can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). for interlayer insulating layers).

[Printed wiring board]
A printed wiring board according to one embodiment of the present invention includes an insulating layer containing a cured product obtained by curing the resin composition described above. This printed wiring board can be manufactured, for example, using the resin sheet described above by a method including the following steps (I) and (II).
(I) A step of laminating a resin sheet on the inner layer substrate such that the resin composition layer of the resin sheet is bonded to the inner layer substrate.
(II) A step of curing the resin composition layer to form an insulating layer.

The "inner layer substrate" used in step (I) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. The substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Further, an intermediate product on which an insulating layer and/or a conductor layer are further formed when manufacturing a printed wiring board is also included in the above-mentioned "inner layer board". When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components may be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C., and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa, and the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions with a pressure of 26.7 hPa or less.

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch-type vacuum pressurized laminator, and the like.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. Pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned commercially available vacuum laminator.

The support may be removed between steps (I) and (II) or after step (II).

In step (II), the resin composition layer is cured to form an insulating layer made of a cured product of the resin composition. As the specific curing conditions for the resin composition layer, the conditions normally employed for forming the insulating layer of the printed wiring board may be used, and the resin composition layer is usually thermally cured by heating.

The thermosetting conditions for the resin composition layer may vary depending on the type of resin composition. For example, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, even more preferably 170°C to 210°C. Also, the curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 100 minutes.

Further, when the resin composition layer is thermally cured, the method for manufacturing a printed wiring board may include preheating the resin composition layer at a temperature lower than the curing temperature before the thermal curing. preferable. For example, prior to thermosetting the resin composition layer, the resin composition layer is usually cured at a temperature of 50° C. to 150° C., preferably 60° C. to 140° C., more preferably 70° C. to 130° C. for 5 minutes. As above, preheating may be preferably performed for 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes.

When manufacturing a printed wiring board, (III) the step of drilling holes in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or step ( It may be carried out between IV) and step (V). If necessary, the steps (I) to (V) of forming the insulating layer and the conductor layer may be repeated to form a multilayer wiring board.

In other embodiments, printed wiring boards can be manufactured using the prepregs described above. The manufacturing method can be basically the same as in the case of using a resin sheet.

Step (III) is a step of making holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Smear is usually also removed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order.

The swelling liquid used for the roughening treatment includes, for example, an alkaline solution, a surfactant solution, etc., preferably an alkaline solution. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferred. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment with a swelling liquid can be performed, for example, by immersing the insulating layer in a swelling liquid at 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.

Examples of the oxidizing agent used for the roughening treatment include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 to 30 minutes. The permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan.

As the neutralizing solution used for the roughening treatment, an acidic aqueous solution is preferable, and commercially available products include, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.

Step (V) is a step of forming a conductor layer, in which the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred. A metal layer is more preferred.

The conductor layer may have a single layer structure, or may have a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has a multilayer 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.

The thickness of the conductor layer is generally between 3 μm and 35 μm, preferably between 5 μm and 30 μm, depending on the desired printed wiring board design.

In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. A semi-additive method is preferable from the viewpoint of manufacturing simplicity. An example of forming a conductor layer by a semi-additive method is shown below.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

In other embodiments, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, step (V) is preferably performed between step (I) and step (II). For example, after step (I), the support is removed and a metal foil is laminated on the exposed surface of the resin composition layer. Lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Then, step (II) is performed to form an insulating layer. After that, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventional known techniques such as the subtractive method and the modified semi-additive method.

A metal foil can be manufactured by a known method such as an electrolysis method or a rolling method. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Co., Ltd., and the like.

[Semiconductor device]
A semiconductor device according to an embodiment of the present invention includes the printed wiring board described above. A semiconductor device can be manufactured using a printed wiring board.

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "mass parts" and "mass%", respectively, unless otherwise specified. Further, the temperature and pressure conditions were room temperature (25° C.) and atmospheric pressure (1 atm) unless otherwise specified. In addition, hollow inorganic fillers containing noncombustible gas inside pores are sometimes referred to as “flame retardants”.

<Synthesis Example 1. Production of flame retardant 1>
40 g of methanol, 0.3 g of an aqueous tetramethylammonium hydroxide solution having a solid content of 25%, 0.7 g of dodecyltrimethylammonium chloride, and 0.4 g of hexane were placed in a reactor and dissolved by stirring. 120 g of ion-exchanged water was added to the methanol solution to precipitate emulsified droplets of hexane. Then, 0.85 g of tetramethoxysilane was slowly added, stirred at room temperature (25° C.) for 8 hours, and aged for 12 hours. Next, the resulting white precipitate was filtered through Advantech filter paper (5C), washed with 300 mL of water, and dried at a temperature of 90° C. for 8 hours to obtain a dry powder. The resulting dry powder was heated to 600° C. at a rate of 1° C./min with an air flow (3 L/min) using a high-speed heating electric furnace (“SK-2535E” manufactured by Motoyama Co., Ltd.). C. for 2 hours to remove organic components and obtain precursor particles of hollow silica. 0.5 g of this hollow silica precursor particle was placed in an alumina crucible, transferred to a desiccator, and nitrogen purge was repeated 5 times using nitrogen gas ( _N gas) with a purity of over 99.999% under reduced pressure. . After that, the alumina crucible is taken out from the desiccator and fired in the electric furnace at 1000 ° C. for 72 hours in a nitrogen atmosphere, so that the inside of the pores is all replaced with N ₂ gas Flame retardant 1 (average particle diameter 1 .6 μm, a BET specific surface area of 12 m ² /g, and a porosity of 50% by volume).

<Synthesis Example 2. Production of flame retardant 2>
In Synthesis Example 1, nitrogen gas with a purity of over 99.999% was replaced with carbon dioxide gas (CO ₂ gas) with a purity of over 99.995%. Flame retardant 2 (average particle diameter 1.6 μm, BET specific surface area 12 m ² /g, porosity 50% by volume) in which all the inside of the pores are replaced with CO ₂ gas in the same manner as in Synthesis Example 1 except for the above items got

<Synthesis Example 3. Production of flame retardant 3>
In Synthesis Example 1, nitrogen gas with a purity of over 99.999% was replaced with helium gas (He gas) with a purity of over 99.999%. Flame retardant 3 (average particle diameter 1.6 μm, BET specific surface area 12 m ² /g, porosity 50% by volume) in which all the inside of the pores are replaced with He gas in the same manner as in Synthesis Example 1 except for the above items Obtained.

<Synthesis Example 4. Production of flame retardant 4>
In Synthesis Example 1, nitrogen gas with a purity of over 99.999% was replaced with neon gas (Ne gas) with a purity of over 99.999%. Flame retardant 4 (average particle diameter 1.6 μm, BET specific surface area 12 m ² /g, porosity 50% by volume) in which all the inside of the pores are replaced with Ne gas in the same manner as in Synthesis Example 1 except for the above items. Obtained.

<Synthesis Example 5. Production of flame retardant 5>
In Synthesis Example 1, nitrogen gas with a purity of over 99.999% was replaced with argon gas (Ar gas) with a purity of over 99.999%. Flame retardant 5 (average particle diameter 1.6 μm, BET specific surface area 12 m ² /g, porosity 50% by volume) in which all the inside of the pores are replaced with Ar gas in the same manner as in Synthesis Example 1 except for the above items. Obtained.

<Synthesis Example 6. Production of flame retardant 6>
Flame retardant 6 was synthesized according to the description in Japanese Patent No. 5940188. Specifically, flame retardant 6 was synthesized by the following procedure.
Using 300 g of water glass aqueous solution (SiO ₂ /Na ₂ O molar ratio 3.2, SiO ₂ concentration 24% by weight), one of the two-fluid nozzles is supplied with a flow rate of 0.12 kg / hr, and the other nozzle is supplied with air at 31800 L / Hot air at an inlet temperature of 400° C. was sprayed at a flow rate of hr (air/liquid volume ratio: 31,800) to obtain silica-based particle precursor particles (1). At this time, the outlet temperature was 150°C. Then, 50 g of silica-based particle precursor particles (1) were immersed in 500 g of an aqueous sulfuric acid solution having a concentration of 10% by weight and stirred for 2 hours. Then, it was dried and heat-treated in a dryer at 90° C. for 12 hours to obtain a dry powder.
The resulting dry powder was heated to 600° C. at a rate of 1° C./min with an air flow (3 L/min) using a high-speed heating electric furnace (“SK-2535E” manufactured by Motoyama Co., Ltd.). C. for 2 hours to obtain hollow silica particles. 0.5 g of the hollow silica particles were placed in an alumina crucible, transferred to a desiccator, and vacuumed and nitrogen purged five times using nitrogen gas with a purity of >99.999%. After that, the alumina crucible is taken out from the desiccator and fired in the electric furnace at 1000 ° C. for 72 hours in a nitrogen atmosphere, so that the inside of the pores is all replaced with N ₂ gas Flame retardant 6 (average particle diameter 2 0 μm, a BET specific surface area of 3.8 m ² /g, and a porosity of 20% by volume).

<Example 1>
Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd. "828EL", epoxy equivalent of about 180) 25 parts, biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent of about 269 g / eq.) 10 parts of methyl ethyl ketone 50 parts was added and dissolved by heating with stirring. This was cooled to room temperature to prepare an epoxy resin solution composition. To this dissolved composition, 10 parts of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC, active group equivalent of about 151 g/eq., 2-methoxypropanol solution with a nonvolatile content of 50%), naphthol type Curing agent ("SN-485" manufactured by Nippon Steel Chemical & Materials Co., Ltd., hydroxyl equivalent of about 205 g / eq.) 10 parts, phenoxy resin (manufactured by Mitsubishi Chemical Corporation "YX7553BH30", 1 of MEK and cyclohexanone with a nonvolatile content of 30% by mass: 1 solution) 15 parts, spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) 80 parts, 10 parts of flame retardant 1 (average particle size 1.6 μm, containing _N gas, porosity 50% by volume) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.), rubber particles ( Aica Kogyo Co., Ltd. "Staphyloid AC3816N") 3 parts, amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass) are mixed, and evenly dispersed with a high-speed rotating mixer. Then, a resin varnish was prepared.

Next, a resin varnish is evenly applied to the release surface of a release-treated polyethylene terephthalate film (Lintec Co., Ltd. "AL5", thickness 38 µm), which is a support, so that the resin composition layer has a thickness of 40 µm. and dried at 80 to 120° C. (average 100° C.) for 5 minutes to prepare a support-attached resin sheet.

<Example 2>
In Example 1, flame retardant 1 (average particle size 1.6 μm, _N gas content, porosity 50% by volume) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) 10 10 parts of flame retardant 2 (average particle size 1.6 μm, containing _CO2 gas, porosity 50% by volume) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) replaced. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

<Example 3>
In Example 1, flame retardant 1 (average particle size 1.6 μm, _N gas content, porosity 50% by volume) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) 10 10 parts of flame retardant 3 (average particle size 1.6 μm, containing He gas, porosity 50% by volume) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.). rice field. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

<Example 4>
In Example 1, flame retardant 1 (average particle size 1.6 μm, _N gas content, porosity 50% by volume) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) 10 10 parts of flame retardant 4 (average particle size 1.6 μm, containing Ne gas, porosity 50% by volume) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.). rice field. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

<Example 5>
50 parts of methyl ethyl ketone was added to 12 parts of a naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, epoxy equivalent of about 144), and the mixture was heated with stirring to homogenize. This was cooled to room temperature to prepare an epoxy resin solution composition. To this dissolved composition, 30 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC, an active ester group equivalent of about 223 g/eq., a toluene solution with a nonvolatile content of 65%), a triazine skeleton-containing phenolic curing agent ( DIC's "LA-3018-50P", active group equivalent of about 151 g / eq., 2-methoxypropanol solution with a non-volatile content of 50%) 2 parts, carbodiimide curing agent (Nisshinbo Chemical Co., Ltd. "V-03", Active group equivalent of about 216 g / eq., toluene solution with a nonvolatile content of 50%) 5 parts, vinylbenzyl-modified polyphenylene ether ("OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Co., a toluene solution with a nonvolatile content of 65%) 2 parts , 30 parts of spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.), a silane coupling agent ( Shin-Etsu Chemical Co., Ltd. "KBM-573") surface-treated flame retardant 5 (average particle size 1.6 μm, containing Ar gas, porosity 50% by volume) 30 parts, imidazole curing accelerator (Shikoku Kasei Kogyo 0.1 part of "1B2PZ" (1-benzyl-2-phenylimidazole manufactured by Co., Ltd.) was mixed and uniformly dispersed with a high-speed rotating mixer to prepare a resin varnish.

Next, a resin varnish is evenly applied to the release surface of a release-treated polyethylene terephthalate film (Lintec Co., Ltd. "AL5", thickness 38 µm), which is a support, so that the resin composition layer has a thickness of 40 µm. and dried at 80 to 120° C. (average 100° C.) for 5 minutes to prepare a support-attached resin sheet.

<Example 6>
Bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. "828EL", epoxy equivalent about 180) 20 parts, naphthylene ether type epoxy resin (epoxy equivalent about 250, DIC, "HP6000") 15 parts and methyl ethyl ketone 50 was added and dissolved by heating while stirring. This was cooled to room temperature to prepare an epoxy resin solution composition. To this dissolved composition, 15 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC, an active ester group equivalent of about 223 g/eq., a toluene solution with a non-volatile content of 65%), a prepolymer of bisphenol A dicyanate (Lonza Japan Co., Ltd. "BA230S75", cyanate equivalent of about 232, MEK solution with a nonvolatile content of 75% by mass) 20 parts, biphenyl aralkyl novolac type maleimide (manufactured by Nippon Kayaku Co., Ltd. "MIR-3000-70MT", MEK with a nonvolatile content of 70% / toluene mixed solution) 2 parts, organic phosphorus flame retardant (“PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.) 1 part, phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, non-volatile content 30% by mass of MEK and cyclohexanone 1:1 solution) 8 parts, spherical silica (“SO-C2” manufactured by Admatex Co., Ltd., average particle size 0.5 μm) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) 60 Part, flame retardant 6 (average particle size 2.0 μm, BET specific surface area 3.8 m / g, _N gas content, voids ratio 20% by volume) 48 parts, rubber particles ("Staphyloid AC3816N" manufactured by Aica Kogyo Co., Ltd.) 2 parts, amine curing accelerator (4-dimethylaminopyridine (DMAP), solid content 5% by mass MEK solution) 4 parts , and 1 part of a 1% by weight MEK solution of cobalt (III) acetylacetonate (manufactured by Tokyo Kasei Co., Ltd.) were mixed and dispersed uniformly with a high-speed rotating mixer to prepare a resin varnish.

Next, a resin varnish is evenly applied to the release surface of a release-treated polyethylene terephthalate film (Lintec Co., Ltd. "AL5", thickness 38 µm), which is a support, so that the resin composition layer has a thickness of 40 µm. and dried at 80 to 120° C. (average 100° C.) for 5 minutes to prepare a support-attached resin sheet.

<Comparative Example 1>
In Example 1, the amount of spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) was increased to 80 Change the part to 100 parts, flame retardant 1 (average particle size 1.6 μm, containing _N gas, porosity 50 volume %) 10 parts were not used. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

<Comparative Example 2>
In Example 1, flame retardant 1 (average particle size 1.6 μm, _N gas content, porosity 50% by volume) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) 10 The part was changed to 10 parts of an organic phosphorus-based flame retardant (“PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.). A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

<Measurement of specific gravity>
The specific gravity was calculated by measuring the weight in air and the weight in water using an analytical balance "XP105" (using a specific gravity measurement kit) manufactured by Mettler Toledo. Five samples were measured, and an average value was calculated.

<Preparation of cured product for evaluation>
A release agent-treated PET film (“501010” manufactured by Lintec, thickness 50 μm, 240 mm square) was coated with a glass cloth-based epoxy resin double-sided copper-clad laminate (“R5715ES” manufactured by Panasonic, 0.7 mm thick, 255 mm square) were stacked and fixed on four sides with polyimide adhesive tape (width 10 mm) (hereinafter sometimes referred to as "fixed PET film").

The resin varnishes prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were applied onto the release-treated surface of the "fixed PET film" using a die coater so that the thickness of the resin composition layer after drying was 40 μm. It was applied and dried at 80° C. to 120° C. (average 100° C.) for 10 minutes to obtain a resin sheet. Then, the resin composition layer was heat-cured under curing conditions for 90 minutes after being placed in an oven at 180°C. After thermal curing, the polyimide adhesive tape was peeled off, the cured product was removed from the glass cloth-based epoxy resin double-sided copper-clad laminate, and the PET film ("501010" manufactured by Lintec Co., Ltd.) was also peeled off to obtain a sheet-like cured product. rice field. The resulting cured product is referred to as "evaluation cured product".

<Measurement of dielectric constant and dielectric loss tangent>
A cured product for evaluation was cut into a piece having a length of 80 mm and a width of 2 mm to obtain an evaluation sample. For this evaluation sample, the relative dielectric constant (Dk _23deg.C ) and the dielectric dissipation factor (Df _23deg.C ) at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. are measured by a cavity resonance perturbation method using an HP8362B device manufactured by Agilent Technologies. ), and the dielectric constant (Dk _90deg.C ) and dielectric loss tangent (Df _90deg.C ) at a measurement temperature of 90°C were measured. Two specimens were measured and an average value was calculated. Also, the dielectric constant and dielectric loss tangent at each temperature were evaluated according to the following evaluation criteria.

·Evaluation Criteria for Relative Permittivity A: Relative permittivity is less than 3.00.
○: Relative permittivity is 3.00 or more and less than 3.30.
x: Relative permittivity is 3.30 or more.

• Evaluation criteria for dielectric loss tangent ⊚: The rate of change in dielectric loss tangent represented by the following formula (1) is less than 30%.
x: The rate of change in dielectric loss tangent represented by the following formula (1) is 30% or more.
Change rate of dielectric loss tangent (%) = {(Df _90deg.C )-(Df _23deg.C )}/(Df _23deg.C ) x 100 (1)

<Evaluation of thermal expansion coefficient>
The cured product for evaluation was cut into a test piece having a length of about 15 mm and a width of about 5 mm, and thermomechanical analysis was performed by a tensile loading method using a thermomechanical analyzer (Thermo Plus TMA8310) manufactured by Rigaku. After mounting the test piece on the apparatus, the measurement was performed twice continuously under the measurement conditions of a load of 1 g and a temperature increase rate of 5° C./min. In the second measurement, the glass transition temperature and the thermal expansion coefficient from 25°C to 150°C were calculated. The coefficient of thermal expansion was evaluated according to the following evaluation criteria.
- Evaluation criteria ◯: The thermal expansion coefficient is less than 30 ppm.
x: The coefficient of thermal expansion is 30 or more.

<Measurement of elongation (elongation at break)>
The cured product for evaluation was cut into a dumbbell-shaped No. 1 specimen to obtain a test piece. The test piece was subjected to tensile strength measurement using a tensile tester "RTC-1250A" manufactured by Orientec Co., Ltd., and the elongation at break at 23°C was determined. The measurement was performed according to JIS K7127, and the average value of 5 measurements was calculated.

<Evaluation of flame retardancy>
The resin sheets prepared in Examples and Comparative Examples were applied to both sides of a base material obtained by etching away the copper foil of a copper-clad laminate (“MCL-E-700G” manufactured by Hitachi Chemical Co., Ltd.) having a thickness of 0.2 mm. Using a vacuum pressurized laminator MVLP-500 (manufactured by Meiki Co., Ltd.), both surfaces of the laminate were laminated. Lamination was performed by reducing the pressure for 30 seconds to an air pressure of 13 hPa or less, and then pressing for 30 seconds at 100° C. and a pressure of 0.74 MPa. After peeling off the PET film of the support, a resin sheet having a thickness of 40 μm was again laminated on both sides under the same conditions. Thereafter, the PET film was peeled off and heat cured at 180° C. for 90 minutes to obtain a flame retardant test sample. A width of 12.7 mm and a length of 127 mm were cut out, and the cut surface was polished with a polishing machine (RotoPol-22 manufactured by Struers). A set of the above five samples was subjected to a flame retardancy test according to the UL94 vertical flame retardance test.

<Evaluation of high-temperature reflow blistering resistance>
The resin varnishes prepared in Examples and Comparative Examples are applied on a copper foil (“JDLC” manufactured by JX Metals Co., Ltd., thickness 12 μm, 240 mm square), and a die coater is applied so that the thickness of the resin composition layer after drying is 40 μm. and dried at 80° C. to 120° C. (average 100° C.) for 10 minutes to obtain a resin-coated copper foil sheet. This resin-coated copper foil sheet is processed into a copper-clad laminate using a vacuum hot press (manufactured by Kitagawa Seiki Co., Ltd., VH1-1603) so that the resin composition layer of the resin-coated copper foil sheet is in contact with the copper-clad laminate. laminated on both sides of the Pressing conditions are under reduced pressure of 1×10 ⁻³ MPa or less, under pressure conditions of 20 kgf/cm ² , and as heating conditions, the first stage pressing is performed at a temperature of 100° C. for 30 minutes and 2 The press at the stage was performed at a temperature of 190° C. for 120 minutes to obtain a substrate for heat resistance evaluation. The evaluation board was cut into small pieces of 100 mm × 50 mm, and passed through a reflow device ("HAS-6116" manufactured by Nippon Antom Co., Ltd.) that reproduces a solder reflow temperature with a peak temperature of 260 ° C. 10 times (The reflow temperature profile is IPC / JEDEC conforming to J-STD-020C). Evaluation was performed on two small pieces and evaluated by visual observation according to the following evaluation criteria.
O: No abnormality at all in all small pieces.
Δ: Abnormality such as 1 to 4 blisters.
x: There are 5 or more abnormalities such as swelling.

Claims (15)

(A) a curable resin,
(B) an inorganic filler; and (C) a nonflammable gas. 2. The resin composition according to claim 1, wherein the content of component (C) is 3% by volume or more based on 100% by volume of non-volatile components in the resin composition. 3. The resin composition according to claim 1, wherein component (C) is one or more selected from nitrogen gas, argon gas, carbon dioxide gas, helium gas, and neon gas. Claims 1 to 3, wherein the component (B) contains a hollow inorganic filler (B-1) having voids therein, and the component (C) is contained within the voids of the component (B-1). The resin composition according to any one of. 5. The resin composition according to claim 4, wherein component (B-1) has an average particle size of 0.01 μm or more and 5 μm or less. 6. The resin composition according to claim 4, wherein component (B-1) has a porosity of 10% by volume or more and 80% by volume or less. The resin composition according to any one of claims 4 to 6, wherein component (B) comprises component (B-1) and solid inorganic filler (B-2). The resin composition according to any one of claims 1 to 7, wherein component (A) contains at least one selected from the group consisting of epoxy resins, phenolic resins, active ester resins, cyanate resins and radically polymerizable resins. thing. The resin composition according to any one of claims 1 to 8, further comprising (D) organic particles. The resin composition according to any one of claims 1 to 9, which is used for forming an insulating layer. A cured product of the resin composition according to any one of claims 1 to 10. A sheet-like laminate material containing the resin composition according to any one of claims 1 to 10. A resin sheet comprising a support and a resin composition layer formed on the support from the resin composition according to any one of claims 1 to 10. A printed wiring board comprising an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 10. A semiconductor device comprising the printed wiring board according to claim 14 .