TW202012535A - Resin composition having excellent insulation reliability after a high temperature and high humidity environment test - Google Patents

Abstract

An object of the present invention is to provide: a resin composition, which is capable of obtaining a cured object with low dielectric tangent and having excellent insulation reliability after a high temperature and high humidity environment test; a resin sheet containing the resin composition; and a printed wiring board and a semiconductor device including an insulating layer formed by using the resin composition. The resin composition of the present invention includes: (A) an epoxy resin, (B) a curing agent, (C) a styrene-based elastomer, and (D-1) a resin having a (meth) acryloyl group.

Description

Resin composition

The present invention relates to a resin composition. Furthermore, it is about the resin sheet containing this resin composition, a printed wiring board, and a semiconductor device.

As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately stacked on an inner layer circuit board is known. In recent years, insulating layers have become required to reduce the loss of electrical signals at high frequencies, and require an insulating layer with a low dielectric tangent.

As a resin composition forming such an insulating layer, for example, Patent Literature 1 describes a resin composition including: (A) a thermosetting resin having a styrene group at the end and a molecular weight of 800 to 1500, and (B) liquid The epoxy resin, (C) styrene-based thermoplastic elastomer, (D) filler and (E) hardener are in the range of 30 to 70 parts by mass relative to 100 parts by mass of the resin composition. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2016-147945

[Problems to be solved by the invention]

In order to obtain an insulating layer having a low dielectric tangent, the present inventors conducted a study on a resin composition containing a radical polymerizable compound that can make the entire resin composition low in polarity. As a result, the following new problem was found: If a radical polymerizable compound is contained in the resin composition, the insulation reliability of the cured product of the resin composition after the high-temperature and high-humidity environment test deteriorates.

The object of the present invention is to provide a resin composition capable of obtaining a hardened product having a low dielectric tangent and excellent insulation reliability after a high temperature and high humidity environment test; a resin sheet containing the resin composition; A printed wiring board and a semiconductor device formed of an insulating layer formed of the resin composition. [Means to solve the problem]

In order to solve the aforementioned problems, the present inventors have conducted intensive studies and found that a resin composition, in addition to (A) epoxy resin and (B) hardener, also includes (C) styrene elastomer and ( D-1) A resin having a (meth)acryloyl group can solve the problems of the present invention, and thus completed the present invention. Furthermore, the present inventors discovered that a resin composition comprising: (A) an epoxy resin, (B) a hardener, (C) a styrene-based elastomer, and (D) has a radical polymerizable unsaturated group The resin has a moisture permeability coefficient of 0 g/mm･m ² ･24h or more and 10g/mm･m ² ･24h or less, which can solve the problems of the present invention. Thus, the present invention has been completed. That is, the present invention includes the following content.

[1]. A resin composition comprising: (A) an epoxy resin, (B) a hardener, (C) a styrene-based elastomer, and (D-1) a resin having a (meth)acryloyl group. [2]. A resin composition comprising: (A) an epoxy resin, (B) a hardener, (C) a styrene-based elastomer, and (D) a resin having a radical polymerizable unsaturated group, the resin The moisture permeability coefficient of the cured product obtained by thermally curing the composition at 200°C for 90 minutes is 0 g/mm･m ² ･24h or more and 10g/mm･m ² ･24h or less. [3]. The resin composition according to [2], wherein the component (D) contains (D-1) a resin having a (meth)acryloyl group. [4]. The resin composition according to [1] or [3], wherein the number average molecular weight of the component (D-1) is 3000 or less. [5]. The resin composition as described in any one of [1] to [4], wherein when the resin component in the resin composition is 100% by mass, the content of the (C) component is 0.5% by mass or more 18% by mass or less. [6]. The resin composition as described in any one of [1] to [5], wherein when the (C) component is 100% by mass, the (C) component contains 61% by mass or more of styrene units The content. [7]. The resin composition as described in any one of [1] to [6], wherein when the non-volatile component in the resin composition is 100% by mass, the content of the (B) component is 1% by mass 15% by mass or more. [8]. The resin composition according to any one of [1] to [7], which further contains (E) an inorganic filler. [9]. The resin composition according to [8], wherein the content of the (E) component is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass. [10]. The resin composition as described in any one of [1] to [9], which is for forming an insulating layer. [11]. The resin composition as described in any one of [1] to [10], which is used to form an insulating layer for forming a conductor layer. [12]. The resin composition as described in any one of [1] to [11], which is used to form an insulating layer for forming a conductor layer by sputtering or metal foil. [13]. The resin composition as described in any one of [1] to [12], which is for forming an insulating layer having a through hole having a top diameter of 45 μm or less. [14]. The resin composition according to any one of [1] to [13], which is used to form an insulating layer with a thickness of 20 μm or less. [15]. A resin sheet comprising: a support and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to any one of [1] to [14]. [16]. A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [14]. [17]. A semiconductor device including the printed wiring board according to [16]. [Effect of invention]

The present invention can provide: a resin composition capable of obtaining a hardened product having a low dielectric tangent and excellent insulation reliability after a high temperature and high humidity environment test; a resin sheet containing the resin composition; A printed wiring board and a semiconductor device formed of an insulating layer formed of the resin composition.

[Best form for carrying out the invention]

The following is an embodiment and examples to explain the present invention in detail. However, the present invention is not limited to the embodiments and examples given below, and can be arbitrarily changed and implemented without departing from the scope of the patent application of the present invention and its equivalent scope.

[Resin composition] The resin composition of the first embodiment of the present invention includes (A) an epoxy resin, (B) a hardener, (C) a styrene-based elastomer, and (D-1) has a (meth)acryloyl group Of resin. By using such a resin composition, it is possible to obtain a hardened product having a low dielectric tangent and excellent insulation reliability after a high temperature and high humidity environment test. Furthermore, by using such a resin composition, the peel strength with the conductor layer can be improved.

The resin composition of the first embodiment may further contain arbitrary components in combination with the components (A) to (D-1). Examples of optional components include (D-2) a resin having a vinyl phenyl group, (E) an inorganic filler, (F) a curing accelerator, (G) a polymerization initiator, and (H) other additives. .

Moreover, the resin composition of 2nd Embodiment of this invention contains (A) epoxy resin, (B) hardener, (C) styrene elastomer, and (D) has radical polymerizable unsaturated group The resin has a moisture permeability coefficient of 0 g/mm･m ² ･24h or more and 10g/mm･m ² ･24h or less of the cured product obtained by heat curing the resin composition at 200°C for 90 minutes. By using such a resin composition, it is possible to obtain a hardened product having a low dielectric tangent and excellent insulation reliability after a high temperature and high humidity environment test. Furthermore, by using such a resin composition, the peel strength with the conductor layer can be improved.

The resin composition of the second embodiment may further contain arbitrary components in combination with the components (A) to (D). Examples of arbitrary components include (E) inorganic fillers, (F) hardening accelerators, (G) polymerization initiators, and (H) other additives.

Here, (D-1) a resin having a (meth)acryloyl group and (D-2) a resin having a vinyl phenyl group are both included in "(D) a resin having a radical polymerizable unsaturated group ". In addition, the resin composition of the first embodiment and the resin composition of the second embodiment may be collectively referred to as a “resin composition”. The following is a detailed description of each component included in the resin composition.

＜(A) Epoxy resin＞ Examples of the (A) epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF Type epoxy resin, dicyclopentadiene type epoxy resin, trivalent phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin Resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, biphenyl ring Oxygen resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane epoxy resin , Cyclohexane dimethanol epoxy resin, naphthylene ether epoxy resin, trimethylol epoxy resin, tetraphenylethane epoxy resin, etc. One type of epoxy resin may be used alone, or two or more types may be used in combination.

In the resin composition, as the (A) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule is preferable. From the viewpoint that the desired effect of the present invention can be obtained remarkably, the proportion of epoxy resin having two or more epoxy groups per molecule with respect to (A) 100% by mass of the non-volatile content of the epoxy resin The system is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

Epoxy resins can be classified into epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resins”) and epoxy resins that are solid at a temperature of 20°C (sometimes called "Solid Epoxy"). In the resin composition, as the (A) epoxy resin system, it may include only liquid epoxy resin, solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin. . However, from the viewpoint that the desired effect of the present invention can be remarkably obtained, it is preferable to contain only the solid epoxy resin.

The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and is preferably an aromatic-based epoxy resin having three or more epoxy groups in one molecule. Solid epoxy resin.

The solid epoxy resin is preferably a bixylenol-type epoxy resin, a naphthalene-type epoxy resin, a naphthalene-type 4-functional epoxy resin, a cresol novolac-type epoxy resin, and a dicyclopentadiene-type epoxy resin. , Trihydric phenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type Epoxy resin, tetraphenylethane type epoxy resin, and preferably naphthalene type epoxy resin.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type 4-functional epoxy resin) manufactured by DIC ); "N-690" (cresol novolac epoxy resin) manufactured by DIC; "N-695" (cresol novolac epoxy resin) manufactured by DIC; "HP-7200" manufactured by DIC ", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC, "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (trivalent phenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl epoxy resin) manufactured by Nippon Kayaku; manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. "ESN475V" (naphthol epoxy resin); "ESN485" (naphthol novolac epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; "YX4000H", "YX4000", "YL6121" manufactured by Mitsubishi Chemical Corporation "(Biphenyl type epoxy resin); "YX4000HK" (bixylphenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; manufactured by OSAKA Gas chemical company "PG-100" and "CG-500"; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fusel epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "JER1010" (solid bisphenol A epoxy resin); "jER1031S" (tetraphenylethane epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These systems can be used alone or in combination of two or more.

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidol are preferred Amine epoxy resin, phenol novolak epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane epoxy resin, cyclohexane dimethanol epoxy resin, glycidylamine epoxy resin And the epoxy resin having a butadiene structure is preferably bisphenol A epoxy resin and bisphenol F epoxy resin.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828EL", "" "825", "Epikote 828EL" (bisphenol A epoxy resin); "jER807" and "1750" (bisphenol F epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac) manufactured by Mitsubishi Chemical Corporation Varnish epoxy resin); "630" and "630LSD" (glycidylamine epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A epoxy resin and double Phenol F type epoxy resin mixed product); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagasechemtex; "CELOXIDE2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel; Daicel Corporation's "PB-3600" (epoxy resin with butadiene structure); Nippon Steel & Sumitomo Chemical Corporation's "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl cyclohexane ring Oxygen resin), etc. These systems can be used alone or in combination of two or more.

When (A) epoxy resin is used in combination with liquid epoxy resin and solid epoxy resin, the quantity ratio (liquid epoxy resin: solid epoxy resin) is based on mass ratio, It is preferably 1:1 to 1:20, more preferably 1:1.5 to 1:15, and particularly preferably 1:2 to 1:10. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin in the above range, the desired effect of the present invention can be remarkably obtained. Furthermore, when it is generally used in the form of a resin sheet, moderate adhesion can be obtained. In addition, when generally used in the form of a resin sheet, sufficient flexibility can be obtained, so the operability is improved. Furthermore, in general, a cured product having sufficient breaking strength can be obtained.

(A) The epoxy equivalent of the epoxy resin is preferably 50 g/eq. to 5000 g/eq., more preferably 50 g/eq. to 3000 g/eq., and more preferably 80 g/eq. to 2000 g/eq. , And more preferably 110g/eq. ~ 1000g/eq. By being in this range, the cross-link density of the cured product of the resin composition layer becomes sufficient, so that an insulating layer with a small surface roughness can be obtained. Epoxy equivalent is the mass of epoxy resin containing 1 equivalent of epoxy group. This epoxy equivalent system can be measured according to JIS K7236.

(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to the viewpoint that the desired effect of the present invention can be remarkably obtained. 1500. The weight average molecular weight of the resin can be measured as a value converted to polystyrene by gel permeation chromatography (GPC) method.

(A) The content of the epoxy resin is from the viewpoint that an insulating layer exhibiting good mechanical strength and insulation reliability after a high-temperature and high-humidity environment test can be obtained, and the non-volatile component in the resin composition is set to 100 mass When it is %, it is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more. The upper limit of the content of the epoxy resin is preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less from the viewpoint that the desired effect of the present invention can be remarkably obtained. In addition, in the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass unless otherwise specified.

＜(B) Hardener＞ The resin composition contains a hardener as the (B) component. Generally, (B) hardener has a function of reacting with (A) epoxy resin to harden the resin composition.

Examples of the (B) hardener include active ester-based hardeners, phenol-based hardeners, naphthol-based hardeners, benzoxazine-based hardeners, cyanate-based hardeners, and carbodiimide ( carbodiimide) hardener, amine hardener, anhydride hardener, etc. (B) One type of hardener may be used alone, or two or more types may be used in combination.

As the active ester-based hardener, it can be used for compounds having one or more active ester groups in one molecule. Among them, as the active ester-based hardener, phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc., which have two or more reactive activities in one molecule are preferably Compounds with high ester groups. The active ester-based hardener is preferably obtained by condensation reaction of a carboxylic acid compound and/or thiocarboxylic acid compound with a hydroxyl compound and/or thiol compound. In particular, from the viewpoint of improving heat resistance, active ester-based hardeners obtained from carboxylic acid compounds and hydroxyl compounds are preferred, and active esters obtained from carboxylic acid compounds and phenol compounds and/or naphthol compounds are preferred The system hardener is also preferable.

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, methylated bisphenol A, methylated bisphenol F, and methyl Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene type diphenol compound, phenol novolac, etc. . Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene.

Preferred specific examples of the active ester-based hardener include active ester-based hardeners containing a dicyclopentadiene diphenol structure, active ester-based hardeners containing a naphthalene structure, and acetylated compounds containing phenol novolak. Active ester-based hardener, active ester-based hardener containing phenol novolak benzoate. Among them, active ester-based hardeners containing a naphthalene structure and active ester-based hardeners containing a dicyclopentadiene diphenol structure are also preferable. The so-called "dicyclopentadiene diphenol structure" refers to a divalent structural unit composed of phenylene-dicyclopentyl-phenylene.

Examples of commercially available products of active ester-based hardeners include "EXB9451", "EXB9460", "EXB9460S", "HPC8000-65T", and "HPC8000-65T" as active ester-based hardeners containing a dicyclopentadiene diphenol structure. "HPC8000H-65TM", "EXB8000L-65TM", "EXB8150-65T" (manufactured by DIC); "EXB9416-70BK" (manufactured by DIC) as an active ester hardener containing naphthalene structure; as a product containing phenol novolak "DC808" (manufactured by Mitsubishi Chemical Corporation), an active ester hardener of acetyl compounds; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), an active ester hardener of benzoyl compounds containing phenol novolac; as phenol novolac "DC808" (manufactured by Mitsubishi Chemical Corporation), an active ester hardener for acetal compounds of varnish; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" as an active ester hardener for phenol novolac varnishes "(Manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc.

As the phenol-based hardener and the naphthol-based hardener, those having a novolac structure are preferred from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based hardener is preferable, and a phenol-based hardener containing a triazine skeleton is more preferable.

Specific examples of the phenol-based hardener and the naphthol-based hardener include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemicals; "NHN" manufactured by Nippon Kayaku Co., Ltd. , "CBN", "GPH"; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. ; "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" manufactured by DIC Corporation, etc.

Specific examples of the benzoxazine-based hardener include "ODA-BOZ" manufactured by JFE Chemical Company, "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd.

Examples of the cyanate-based hardener include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), and 4,4′- Methylene bis (2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl) methane, 1,3 -Bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl) sulfide and bis(4-cyanate phenyl) ether, etc. 2 Functional cyanate resins; multifunctional cyanate resins derived from phenol novolak and cresol novolac; etc. These cyanate resins are partially triazineated prepolymers. Specific examples of the cyanate ester hardener include "PT30" and "PT60" (phenol novolak type multifunctional cyanate resin) manufactured by LONZA Japan, and "ULL-950S" (multifunctional cyanate Resin), "BA230", "BA230S75" (a part or all of bisphenol A dicyanate is triazineated to become a terpolymer prepolymer), etc.

Specific examples of the carbodiimide-based hardener include "V-03", "V-05", "V-07", and "V-09" manufactured by Nisshinbo Chemical; Statabaxol manufactured by Rhein Chemie. (Registered trademark) P, etc.

Examples of the amine-based hardener include hardeners having one or more amine groups in one molecule, and examples thereof include aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines. Among them, from the viewpoint of achieving the desired effect of the invention, aromatic amines are preferred. The amine-based hardener is preferably a first-level amine or a second-level amine, and more preferably a first-level amine. Specific examples of the amine-based hardener include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiamine sulfone, 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl ash, m-phenylenediamine, m-xylenediamine, diethyltoluenediamine, 4 ,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl Benzene, 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) satin, bis(4-(3-aminophenoxy)phenyl) satin, etc. Amine-based hardeners can also use commercially available products, such as "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS", and Mitsubishi, manufactured by Nippon Kayaku Co., Ltd. "Epicure W" manufactured by the Chemical Company, etc.

Examples of the acid anhydride-based hardener include hardeners having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride hardener include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic acid. Dicarboxylic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-bi- pendant tetrahydro-3 -Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl Tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyl ash tetracarboxylic dianhydride, 1,3,3a,4 ,5,9b-hexahydro-5-(tetrahydro-2,5-bi- pendant-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol Polymeric acid anhydrides such as bis (anhydrous trimellitate), styrene and maleic acid copolymerized with styrene and maleic acid resin, etc.

Among the above, from the viewpoint that the desired effect of the present invention can be remarkably obtained, the (B) hardener is preferably selected from phenol-based hardeners, active ester-based hardeners, and carbodiimide-based hardeners. More than one species.

(A) The amount ratio of epoxy resin and (B) hardener is calculated as the ratio of [total number of epoxy groups of component (A)]: [total number of reactive groups of (B) hardener], preferably It is in the range of 1:0.01 to 1:20, preferably 1:0.05 to 1:10, and more preferably 1:0.1 to 1:8. Here, the term "(A) epoxy resin number of epoxy resin" refers to the total value obtained by dividing the mass of the non-volatile component of (A) epoxy resin present in the resin composition by the epoxy equivalent. Value. In addition, the "(B) active group number of the hardener" refers to a value obtained by dividing the mass of the non-volatile component of the (B) hardener present in the resin composition by the equivalent of the active group and adding up all of them. By setting the amount ratio of (A) epoxy resin to (B) hardener within the above range, the desired effect of the present invention can be remarkably obtained, and further, it is usually a hardened product that can further enhance the resin composition layer Heat resistance.

(B) The content of the hardener, from the viewpoint that the desired effect of the present invention can be obtained remarkably, it is preferably 0.1% by mass or more, and more preferably 100% by mass of the nonvolatile component in the resin composition. 0.3% by mass or more, more preferably 0.5% by mass or more; preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less.

<(C) Styrene-based elastomer> The resin composition contains (C) a styrene-based elastomer. Generally, (C) a styrene-based elastomer, (A) an epoxy resin, (B) a hardener, and (D-1) a resin having a (meth)acryloyl group are highly compatible. Therefore, the phase separation of the component (A) and the component (B) and the component (D-1) can be suppressed. Therefore, since the generation of the phase interface where water easily penetrates can be suppressed, it is possible to obtain a cured product having excellent insulation reliability after a high-temperature and high-humidity environment test. Also, the moisture permeability coefficient can be adjusted to be low.

As the (C) styrene-based elastomer, any elastomer including a repeating unit (styrene unit) can be used, and the repeating unit has a structure obtained by polymerizing styrene. (C) The styrene-based elastomer may also be a copolymer, which is a copolymer containing any repeating unit different from the aforementioned styrene unit and combined with the styrene unit.

Examples of arbitrary repeating units include a repeating unit having a structure obtained by polymerizing a conjugated diene (conjugated diene unit), and a repeating unit having a structure obtained by hydrogenating the aforementioned repeating unit (hydrogenated conjugated diene) Ene units) etc.

Examples of conjugated dienes include aliphatic conjugates such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, and 1,3-hexadiene. Diene; halogenated aliphatic conjugated diene such as chloroprene. As the conjugated diene, from the viewpoint that the effect of the present invention can be obtained remarkably, the aliphatic conjugated diene is preferable, and the butadiene is also preferable. One type of conjugated diene can be used alone, or two or more types can be used in combination.

(C) The styrene-based elastomer may be a random copolymer, but from the viewpoint that the effect of the present invention can be obtained remarkably, a block copolymer is preferred. The (C) styrene-based elastomer is preferably a styrene-conjugated diene block copolymer or a hydrogenated styrene-conjugated diene copolymer. Examples of particularly preferred (C) styrene-based elastomers include block copolymers having a polymer block containing styrene units as at least one end block and having a conjugated diene unit or A block copolymer obtained by hydrogenating a polymerized block of a conjugated diene unit as at least one middle block.

The so-called hydrogenated styrene-conjugated diene block copolymer refers to a block copolymer having a structure obtained by hydrogenating the unsaturated bond of the styrene-conjugated diene block copolymer. Generally, the hydrogenated styrene-conjugated diene block copolymer-based aliphatic unsaturated bond is hydrogenated, while the aromatic unsaturated bond such as a benzene ring is not hydrogenated.

Specific examples of the (C) styrene-based elastomer include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), Styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butene-styrene block copolymer (SBBS), styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated benzene Ethylene-isoprene block copolymer, hydrogenated styrene-butadiene random copolymer, etc.

(C) The weight average molecular weight (Mw) of the styrene-based elastomer is preferably 1,000 to 500,000, more preferably 2,000 to 300,000, and more preferably from the viewpoint that the desired effect of the present invention can be remarkably obtained. 3000～200000. (C) The weight average molecular weight of the styrene-based elastomer can be measured in the same manner as (A) the weight average molecular weight of the epoxy resin.

As the content of styrene units in the (C) styrene-based elastomer, when the (C) component is set to 100% by mass, it is preferably 61% by mass or more, still preferably 63% by mass or more, and more preferably 65 Mass% or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. By setting the content of the styrene unit within the above range, the compatibility with the (A) epoxy resin and (B) hardener can be further improved, and the insulation reliability after the high-temperature and high-humidity environment test can be obtained with excellent curing Thing. Also, the moisture permeability coefficient can be adjusted to be low. The content of the aforementioned styrene unit can be measured, for example, based on the amount of the monomer constituting the component (C).

(C) As the component, commercially available products can be used, and examples include hydrogenated styrene-based thermoplastic elastomers "H1041", "Tuftec H1043", "Tuftec P2000", "Tuftec MP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene- Butadiene thermoplastic elastomer "Epofriend AT501", "CT310" (made by Daicel); modified styrene elastomer with hydroxyl group "Septon HG252" (made by Kuraray); modified styrene elastomer with carboxyl group" Tuftec N503M", modified styrene elastomer with amine group "Tuftec N501", modified styrene elastomer with acid anhydride group "Tuftec M1913" (made by Asahi Kasei Chemicals); unmodified styrene elastomer " Septon S8104" (manufactured by Kuraray), etc. (C) The component system can be used alone or in combination of two or more kinds.

(C) The content of the component is preferably 0.5% by mass or more, and preferably 0.6 when the nonvolatile component in the resin composition is 100% by mass from the viewpoint that the effect of the present invention can be obtained remarkably. The mass% or more, more preferably 0.7 mass% or more. In terms of the upper limit, it is preferably 18% by mass or less, and more preferably 15% by mass or less, more preferably 10% by mass or less, and 4% by mass or less.

The content of the (C) component when the non-volatile component in the resin composition is 100% by mass is defined as C1, and the content of the (B) component when the non-volatile component in the resin composition is 100% by mass is defined as B1. At this time, from the viewpoint that the effect of the present invention can be obtained remarkably, C1/B1 is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more; preferably 10 or less, and more preferably 5 Below, more preferably 3 or less.

<(D) Resin with radical polymerizable unsaturated group> In the resin composition of the first embodiment, (D) the resin having a radical polymerizable unsaturated group contains (D-1) a resin having a (meth)acryloyl group. The resin composition of the second embodiment contains (D) a resin having a radical polymerizable unsaturated group.

As one embodiment of the resin composition of the second embodiment, the component (D) is an aspect including (D-1) a resin having a (meth)acryloyl group. In addition, as another embodiment, it includes (D-1) a resin having a (meth)acryloyl group and (D-2) a resin having a vinyl phenyl group. From the viewpoint that the effect of the present invention can be obtained remarkably, the resin composition preferably contains both the component (D-1) and the component (D-2).

The so-called radical polymerizable unsaturated group refers to a group having an ethylenic double bond, and the ethylenic double bond is one that exhibits curing properties by irradiation of active energy rays. Examples of such a group include vinyl, vinylphenyl, acryl, methacryl, maleimide, fumaroyl, and cis-butadienyl. (maleoyl) is preferably one kind selected from vinylphenyl, acryl and methacryl.

-(D-1)Resin with (meth)acryloyl group- The resin composition is usually a resin containing (D-1) having a (meth)acryloyl group. By including (D-1) a resin having a (meth)acryloyl group in the resin composition, a hardened product having a low dielectric tangent can be obtained. When (D-1) a resin having a (meth)acryloyl group is used, the dielectric tangent of the cured product can generally be reduced, but the (D-1) component system has the same properties as (A) component and (B ) The components tend to separate. However, in the present invention, by further combining and containing the component (C), phase separation is suppressed, and a cured product having excellent insulation reliability after a high-temperature and high-humidity environment test and having a low dielectric tangent can be obtained. Also, by suppressing phase separation, the moisture permeability coefficient can be adjusted to be low. Here, the term "(meth)acrylic acid" includes acrylic acid and methacrylic acid and combinations of these.

From the viewpoint of obtaining a cured product having a low dielectric tangent, the (D-1) resin system having a (meth)acryloyl group preferably has two or more (meth)acryloyl groups per molecule. base. The term "(meth)acryloyl" refers to acryloyl and methacryloyl and combinations of these.

From the viewpoint of obtaining a cured product having a low dielectric tangent, (D-1) the resin having a (meth)acryloyl group preferably has a ring structure. The ring structure is preferably a divalent ring group. The divalent cyclic group may be any cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. In addition, it may have a plurality of divalent cyclic groups.

From the standpoint that the desired effect of the present invention can be obtained remarkably, the divalent cyclic group is preferably at least 3 member rings, more preferably at least 4 member rings, more preferably at least 5 member rings; preferably Below 20 member rings, preferably below 15 member rings, more preferably below 10 member rings. The bivalent cyclic group may have a single ring structure or a multi-ring structure.

In addition to carbon atoms, the ring in the divalent cyclic group may be constituted by a heteroatom. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, and the like, and oxygen atoms are preferred. The aforementioned ring may have one heteroatom or two or more.

As specific examples of the divalent cyclic group, the following divalent groups (i) to (xi) can be mentioned. Among them, the divalent cyclic group is preferably (x) or (xi).

The divalent cyclic group may have a substituent. Examples of such a substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfonic acid group, a cyano group, a nitro group, and a hydroxyl group , Mercapto, pendant, etc., preferably alkyl.

The (meth)acryloyl group may be directly bonded to a divalent cyclic group, or may be bonded via a divalent linking group. Examples of the divalent linking group include alkylene, alkenyl, aryl, heteroaryl, -C(=O)O-, -O-, -NHC(=O)-, and -NC (=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc., may also be a combination of a plurality of such bases. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group or carbon atom having 1 to 5 carbon atoms. Number 1 to 4 alkylene. The alkylene group may be any linear, branched or cyclic. Examples of such alkylene groups include methylene group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, 1,1-dimethylethyl group, etc. Methyl, ethylidene, 1,1-dimethylethylidene. The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkenyl group having 2 to 5 carbon atoms. The arylene group and the heteroarylene group are preferably a C 6-20 arylene group or a hetero aryl group, and more preferably a C 6-10 carbon arylene group or a heteroaryl group. The divalent linking group is preferably an alkylene group, and among them, methylene and 1,1-dimethylethylidene are preferable.

(式(1)中，R¹ 及R⁴ 分別獨立表示(甲基)丙烯醯基，R² 及R³ 分別獨立表示2價的連結基，環A表示2價的環狀基)。(D-1) A resin having a (meth)acryloyl group, preferably represented by the following formula (1).

(In formula (1), R ¹ and R ⁴ each independently represent a (meth)acryloyl group, R ² and R ³ each independently represent a divalent linking group, and ring A represents a divalent cyclic group).

R ¹ and R ⁴ each independently represent an acryl group or a methacryl group, preferably acryl group.

R ² and R ³ each independently represent a divalent linking group. The divalent linking group is the same as the above-mentioned divalent linking group.

Ring A represents a divalent cyclic group. The ring A is the same as the above-mentioned divalent cyclic group.

Ring A may have a substituent. As a substituent, it is the same as the substituent which the above-mentioned divalent cyclic group may have.

The following are specific examples showing the component (D-1), but the present invention is not limited thereto.

(D-1) A commercially available product can be used as a component, for example, "A-DOG" by Shin Nakamura Chemical Industry Co., Ltd., "DCP-A" by Kyoeisha Chemical Co., Ltd., etc. (D-1) The component system may be used alone or in combination of two or more kinds.

(D-1) The molecular weight of the component is preferably 2,000 or less, more preferably 1,000 or less, and even more preferably 500 or less from the viewpoint that the effect expected by the present invention can be remarkably obtained. In terms of the lower limit, it is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.

(D-1) The number average molecular weight of the component is preferably 3,000 or less, more preferably 2500 or less, and more preferably 2,000 or less and 1500 or less from the viewpoint that the desired effect of the present invention can be remarkably obtained. In terms of the lower limit, it is preferably 100 or more, more preferably 300 or more, and more preferably 500 or more and 1,000 or more. The number average molecular weight is the number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

(D-1) The content of the component is preferably 5% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint that the effect of the present invention can be obtained remarkably. 10% by mass or more, more preferably 15% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

(＊表示鍵結鍵)。-(D-2) Resin having a vinyl phenyl group-In addition to the (D-1) component, the resin composition preferably further contains (D-2) a resin having a vinyl phenyl group. The so-called vinyl phenyl group has a structure shown below.

(* indicates bonding key).

(D-2) From the viewpoint of obtaining a cured product having a low dielectric tangent, the resin having a vinyl phenyl group preferably has two or more vinyl phenyl groups per molecule.

(D-2) The resin having a vinyl phenyl group preferably has a ring structure from the viewpoint of obtaining a cured product having a low dielectric tangent. The ring structure is preferably a divalent ring group. The divalent cyclic group may be any cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. In addition, it may have a plurality of divalent cyclic groups.

From the standpoint that the desired effect of the present invention can be obtained remarkably, the divalent cyclic group is preferably at least 3 member rings, more preferably at least 4 member rings, more preferably at least 5 member rings; preferably Below 20 member rings, preferably below 15 member rings, more preferably below 10 member rings. The bivalent cyclic group may have a single ring structure or a multi-ring structure.

In addition to carbon atoms, the ring in the divalent cyclic group may be constituted by a heteroatom. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, and the like, and oxygen atoms are preferred. The aforementioned ring may have one heteroatom or two or more.

(2價的基(xii)、(xiii)中，R¹ 、R² 、R⁵ 、R⁶ 、R⁷ 、R¹¹ 及R¹² 分別獨立表示鹵素原子、碳原子數6以下的烷基或苯基，R³ 、R⁴ 、R⁸ 、R⁹ 及R¹⁰ 分別獨立表示氫原子、鹵素原子、碳原子數6以下的烷基或苯基)。As specific examples of the divalent cyclic group, the following divalent groups (xii) or (xiii) can be mentioned.

(In the divalent groups (xii) and (xiii), R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ¹¹ and R ¹² each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms or benzene Radicals, R ³ , R ⁴ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group).

Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of the alkyl group having 6 or less carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl, and methyl is preferred. R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ¹¹ and R ^{12 are} preferably represented by methyl groups. R ³ , R ⁴ , R ⁸ , R ⁹ and R ^{10 are} preferably a hydrogen atom or a methyl group.

(式(a)中，R²¹ 、R²² 、R²⁵ 、R²⁶ 、R²⁷ 、R³¹ 、R³² 、R³⁵ 及R³⁶ 分別獨立表示鹵素原子、碳原子數6以下的烷基或苯基，R²³ 、R²⁴ 、R²⁸ 、R²⁹ 、R³⁰ 、R³³ 及R³⁴ 分別獨立表示氫原子、鹵素原子、碳原子數6以下的烷基或苯基，n及m為表示0～300的整數，但不包括n及m之一方為0之情形)。In addition, the divalent cyclic group may be a combination of plural divalent cyclic groups. As a specific example of combining divalent cyclic groups, a divalent cyclic group (divalent group (a)) represented by the following formula (a) can be given.

(In formula (a), R ²¹ , R ²² , R ²⁵ , R ²⁶ , R ²⁷ , R ³¹ , R ³² , R ³⁵ and R ³⁶ each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group , R ²³ , R ²⁴ , R ²⁸ , R ²⁹ , R ³⁰ , R ³³ and R ³⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms, and n and m represent 0 to 300 ), but does not include the case where one of n and m is 0).

R ²¹ , R ²² , R ³⁵ and R ³⁶ are the same as R ¹ in the divalent group (xii). R ²³ , R ²⁴ , R ³³ and R ³⁴ are the same as R ³ in the divalent group (xii). R ²⁵ , R ²⁶ , R ²⁷ , R ³¹ and R ³² are the same as R ⁵ in formula (xiii). R ²⁸ , R ²⁹ and R ³⁰ are the same as R ⁸ in formula (xiii).

n and m are integers representing 0 to 300. It does not include the case where one of n and m is 0. As n and m, it is preferable that it represents the integer of 1-100, and it is still more preferable that it represents the integer of 1-50, and it is more preferable that it represents the integer of 1-10. n and m can be the same or different.

The divalent cyclic group may have a substituent. The substituent is the same as the substituent that the divalent cyclic group in the component (D-1) may have.

The vinyl phenyl group may be directly bonded to a divalent cyclic group, or may be bonded via a divalent linking group. The divalent linking group can be as explained in the column "-(D-1) Resin having (meth)acryloyl group-"). The divalent linking group is preferably an alkylene group, and among them, a methylene group is preferred.

(式(2)中，R⁴¹ 及R⁴² 分別獨立表示2價的連結基，環B表示2價的環狀基)。(D-2) A resin having a vinyl phenyl group, preferably represented by the following formula (2).

(In formula (2), R ⁴¹ and R ⁴² each independently represent a divalent linking group, and ring B represents a divalent cyclic group).

R ⁴¹ and R ⁴² each independently represent a divalent linking group. The divalent linking group is the same as the above-mentioned divalent linking group.

Ring B represents a divalent cyclic group. The ring B is the same as the above-mentioned divalent cyclic group.

Ring B may have a substituent. As a substituent, it is the same as the substituent which the above-mentioned divalent cyclic group may have.

(n1係與式(a)中的n為相同，m1係與式(a)中的m為相同)。The following are specific examples showing the component (D-2), but the present invention is not limited thereto.

(n1 is the same as n in formula (a), and m1 is the same as m in formula (a)).

(D-2) As a component, a commercial item can be used, For example, "OPE-2St" by Mitsubishi Gas Chemical company etc. are mentioned. (D-2) The component system may be used alone or in combination of two or more kinds.

(D-2) The number average molecular weight of the component is preferably 3000 or less, more preferably 2500 or less, and more preferably 2000 or less and 1500 or less from the viewpoint that the desired effect of the present invention can be remarkably obtained. In terms of the lower limit, it is preferably 100 or more, more preferably 300 or more, and more preferably 500 or more and 1,000 or more. The number average molecular weight system can be measured in the same manner as the component (D-1).

(D-2) The content of the component is preferably 5% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint that the effect of the present invention can be obtained remarkably. 10% by mass or more, more preferably 15% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

The resin composition preferably contains both the component (D-1) and the component (D-2). At this time, the content of the (D-1) component when the nonvolatile component in the resin composition is 100% by mass is defined as D1, and the (D-) when the nonvolatile component in the resin composition is 100% by mass. 2) When the content of the component is D2, D2/D1 is preferably 0.1 or more, more preferably 0.3 or more, and still more preferably 0.5 or more. The upper limit is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By setting D2/D1 within the above range, a cured product having excellent insulation reliability after a high-temperature and high-humidity environment test can be obtained. Also, the moisture permeability coefficient can be adjusted to be low.

<(E) Inorganic filler> In addition to the above components, the resin composition may further contain (E) an inorganic filler as an arbitrary component.

As the material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silicon dioxide, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, gibbsite, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate , Titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate and tungsten zirconium phosphate. Among these, silicon dioxide is particularly suitable. Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, and the like. Furthermore, spherical silica is preferred as the silica system. (E) One type of inorganic fillers may be used alone, or two or more types may be used in combination.

As a commercially available product of (E) an inorganic filler, for example, "UFP-30" by Denca; Nippon Steel & Sumikin "SP60-05" and "SP507-05" manufactured by Materials; Admatechs' "YC100C", "YA050C", " "YA050C-MJE", "YA010C"; "Tokuyama Corporation" Shirufiru NSS-3N", "Shirufiru NSS-4N", "Shirufiru NSS-5N"; Admatechs' "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", etc.

(E) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more from the viewpoint that the desired effect of the present invention can be remarkably obtained. It is preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

(E) The average particle diameter of the inorganic filler can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, the measurement is performed by the following method: a laser diffraction scattering type particle size distribution measuring device is used to prepare the particle size distribution of the inorganic filler on a volume basis, and the average particle size (median diameter) as the average particle diameter. For the measurement sample system, 100 mg of inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed by ultrasound for 10 minutes. Using a laser diffraction particle size distribution measuring device for the measurement sample, using blue and red as the wavelength of the light source, and measuring the volume-based particle size distribution of (E) the inorganic filler using a flow channel method, available from The average particle diameter is calculated as the average particle diameter of the particle size distribution of. As a laser diffraction type particle size distribution measuring apparatus, for example, "LA-960" manufactured by HORIBA, Ltd. may be mentioned.

The specific surface area (E) an inorganic filler, can be obtained significantly view of the desired effect of the present invention, it is preferably 1m ² / g or more, and preferably 2m ² / g or more, particularly preferably 3m ² /g or more. The upper limit is not particularly limited, but it is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area is based on the BET method, and a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) is used to adsorb nitrogen to the surface of the sample, and the specific surface area is calculated using the BET multipoint method.

(E) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, and organic silazane. Compounds, titanate-based coupling agents, etc. In addition, the surface treatment agent system may be used alone or in combination of two or more kinds arbitrarily.

Examples of commercially available products for surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyltrimethyl) manufactured by Shin-Etsu Chemical Co., Ltd. Oxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), 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), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The degree of surface treatment by the surface treatment agent is preferably limited to the specified range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, it is 100 parts by mass of the inorganic filler, and surface treatment with 0.2 to 5 parts by mass of surface treatment agent is preferred, and surface treatment with 0.2 to 3 parts by mass is preferred. It is preferable to perform surface treatment with 0.3 to 2 parts by mass.

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, and preferably 0.1 mg/m ² or more, 0.2 mg from the viewpoint of improving the dispersibility of the inorganic filler. /m ² or more is more preferable. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, 1 mg/m ² or less is preferable, and 0.8 mg/m ² or less is more preferable, and 0.5 Below mg/m ² is better.

The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler subjected to surface treatment with a surface treatment agent, and washed with ultrasonic waves 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 the carbon analysis system, "EMIA-320V" manufactured by HORIBA, Ltd. can be used.

(E) From the viewpoint of reducing the dielectric tangent, when the nonvolatile content in the resin composition is 100% by mass, it is preferably 50% by mass or more, and more preferably 51% by mass from the viewpoint of reducing the dielectric tangent The above is more preferably 52% by mass or more; preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

The content of the (E) component when the nonvolatile component in the resin composition is 100% by mass is defined as E1, and the content of the (D-2) component when the nonvolatile component in the resin composition is 100% by mass In the case of D2, D2+E1 is preferably 85% by mass or less, preferably 83% by mass or less, and more preferably 80% by mass or less. In terms of the lower limit, it is preferably 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass or more. By setting D2+E1 within the above range, a cured product having a lower moisture permeability coefficient can be obtained.

＜(F) Hardening accelerator＞ In addition to the above components, the resin composition may further contain (F) a hardening accelerator as an optional component.

Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among them, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are also preferred . One type of hardening accelerator may be used alone, or two or more types may be used in combination.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4 -Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, etc., preferably triphenylphosphine, tetrabutylphosphonium decanoic acid salt.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,- Ginseng (dimethylaminomethyl)phenol, 1,8-diazepine (5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-bis Acridine bicyclic (5,4,0)-undecene.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 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-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitic acid Ester, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-dec Monoalkyl 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 adduct, 2 -Phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro -1H-pyrrole[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc. The imidazole compound and the adduct of the imidazole compound and the epoxy resin are preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As the imidazole-based hardening accelerator, a commercially available product can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine hardening accelerator include dicyandiamine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, diacetyl Methylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triacbicyclo[4.4.0]dec-5-ene, 7-methyl-1 ,5,7-Triabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1 ,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., preferably Dicyandiamine, 1,5,7-triacryl bicyclo[4.4.0]dec-5-ene.

Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate, cobalt (III) acetoacetate, and copper (II) acetoacetate. Organic copper complexes, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, nickel (II) acetylacetonate Such as organic nickel complexes, organic manganese complexes such as manganese (II) acetonyl pyruvate, etc. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

(F) The content of the hardening accelerator, from the viewpoint that the desired effect of the present invention can be obtained remarkably, when the nonvolatile content in the resin composition is 100% by mass, it is preferably 0.01% by mass or more, and It is preferably 0.03% by mass or more, more preferably 0.05% by mass or more; preferably 0.3% by mass or less, still more preferably 0.2% by mass or less, more preferably 0.1% by mass or less.

<(G) polymerization initiator> In addition to the above components, the resin composition may further contain (G) a polymerization initiator as an optional component. Generally, the (G) polymerization initiator has a function of promoting the crosslinking of the radical polymerizable unsaturated group in the (D) component. (G) The polymerization initiator system may be used alone or in combination of two or more types.

Examples of the (G) polymerization initiator include t-butyl isophenylpropyl peroxide, t-butyl peroxyacetate, and α,α′-bis(t-butylperoxy) Diisopropylbenzene, t-butylperoxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy neodecanoate, t-butylperoxy Peroxides such as oxybenzoate.

Examples of commercially available products as (G) polymerization initiators include "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl O", and "Perbutyl ND" manufactured by NOF Corporation. , "Perbutyl Z", "Percumyl P", "Percumyl D", etc.

(G) The content of the polymerization initiator is preferably 0.01% by mass or more when the nonvolatile content in the resin composition is 100% by mass from the viewpoint that the desired effect of the present invention can be obtained remarkably. It is preferably 0.05% by mass or more, more preferably 0.1% by mass or more; preferably 1% by mass or less, still more preferably 0.5% by mass or less, more preferably 0.4% by mass or less.

＜(H)Other additives＞ In addition to the above components, the resin composition may further contain other additives as arbitrary components. Examples of such additives include thermoplastic resins (but excluding (C) and (D) components); organic fillers; tackifiers; defoamers; leveling agents; adhesion imparting agents, etc. Resin additives. One type of these additives may be used alone, or two or more types may be used in combination.

<Moisture permeability coefficient> The resin composition of the second embodiment is a cured product obtained by combining the components (A) to (D) and thermally curing the resin composition at 200°C for 90 minutes. The moisture permeability coefficient is 0g/mm･m ² ･24h or more and 10g/mm･m ² ･24h or less. From the viewpoint of making the insulation reliability after the high-temperature and high-humidity environment test good, the moisture permeability coefficient of the aforementioned hardened product is 10 g/mm･m ² ･24h or less, preferably 7g/mm･m ² ･24h or less It is preferably 5g/mm･m ² ･24h or less. The lower limit is 0g/mm･m ² ･24h or more, preferably 1g/mm･m ² ･24h or more, and preferably 1.3g/mm･m ² ･24h or more, more preferably 1.5g/mm･m ² ･More than 24h. In addition, the cured product obtained by thermally curing the resin composition of the first embodiment at 200° C. for 90 minutes is considered to be good in terms of insulation reliability after a high temperature and high humidity environment test. In other words, it is preferable to have a moisture permeability coefficient in the aforementioned range. The aforementioned measurement of the moisture permeability coefficient can be performed according to the method described in the examples described later.

<Physical properties and uses of resin composition> The cured product obtained by thermally curing the resin composition at 200°C for 90 minutes exhibits a characteristic that the dielectric tangent is low. Therefore, the aforementioned hardened system can obtain an insulating layer having a low dielectric tangent. The dielectric tangent is preferably 0.005 or less, and more preferably 0.0045 or less and 0.004 or less. On the other hand, the lower limit value of the dielectric tangent is not particularly limited, but can be set to 0.0001 or more. The aforementioned evaluation of the dielectric tangent can be measured according to the method described in the examples described later.

The cured product obtained by thermally curing the resin composition at 130°C for 30 minutes and then at 170°C for 30 minutes exhibits the so-called excellent insulation reliability even under high temperature and humidity conditions. Therefore, the aforementioned hardened system can obtain an insulating layer excellent in insulation reliability. When the thickness of the insulating layer is 10±1 μm, the insulation resistance value is preferably 10 ⁷ Ω or more, more preferably 10 ⁸ Ω or more, and more preferably 10 ⁹ Ω or more and 10 ¹⁰ Ω or more. The upper limit is not particularly limited, but may be 10 ¹⁵ Ω or less. The details of the measurement of the insulation resistance value can be measured according to the method described in the examples described later.

The cured product obtained by heat curing the resin composition at 130°C for 30 minutes and then at 170°C for 30 minutes is usually excellent in exhibiting the so-called adhesion strength (peel strength) with the plated conductor layer characteristic. Therefore, the aforementioned hardened system can obtain an insulating layer excellent in peel strength from the plated conductor layer. The peel strength is preferably 0.3 kgf/cm or more, more preferably 0.4 kgf/cm or more, and even more preferably 0.5 kgf/cm or more. On the other hand, the upper limit of the peel strength is not particularly limited, but may be 5 kgf/cm or less. The aforementioned evaluation of the peel strength can be measured according to the method described in the examples described later.

The resin composition of the present invention can reduce the dielectric tangent while generally obtaining an insulating layer with a large peel strength. Therefore, the resin composition system of the present invention can be suitably used as a resin composition for insulation applications. Specifically, it can be suitably used as: a resin composition for forming an insulating layer (including a redistribution layer) formed on an insulating layer (a resin composition for forming an insulating layer forming a conductive layer) Thing).

Moreover, in the multilayer printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a multilayer printed wiring board (a resin composition for forming an insulating layer of a multilayer printed wiring board), and for forming printing The resin composition of the interlayer insulating layer of the wiring board (the resin composition for forming the interlayer insulating layer of the printed wiring board). Among them, it can be particularly suitably used as: a resin composition for forming an insulating layer having a through hole having a top hole diameter of 45 μm or less; and can be particularly suitably used as: a resin composition for forming an insulating layer having a thickness of 20 μm or less .

Also, for example, when manufacturing a semiconductor chip package through the following steps (1) to (6), the resin composition of the present invention can also be suitably used as a rewiring as an insulating layer for forming a rewiring layer A resin composition for forming a layer (a resin composition for forming a rewiring formation layer) and a resin composition for sealing a semiconductor wafer (a resin composition for sealing a semiconductor wafer). When manufacturing a semiconductor chip package, a redistribution layer may be further formed on the sealing layer. (1) The step of laminating the temporary fixing film on the substrate, (2) The step of temporarily fixing the semiconductor wafer to the temporarily fixed film, (3) The step of forming the sealing layer on the semiconductor wafer, (4) The step of peeling the substrate and temporary fixing film from the semiconductor wafer, (5) Steps for forming a rewiring formation layer as an insulating layer on the surface where the substrate of the semiconductor wafer and the temporary fixing film are peeled off and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

In addition, the resin composition system of the present invention can obtain an insulating layer with good embedding properties of parts, so that the printed wiring board can be suitably used when the parts are embedded in a circuit board.

[Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

The thickness of the resin composition layer is preferably 30 μm or less from the viewpoint that the thickness of the printed wiring board and the cured product of the resin composition can provide a cured product with excellent insulation even if it is a thin film. It is 20 μm or less, more preferably 15 μm or less and 10 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but it can generally be 1 μm or more, 5 μm or more, and the like.

Examples of the support include films, metal foils, and release papers made of plastic materials, and films and metal foils made of plastic materials are preferred.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate. (Hereinafter sometimes abbreviated as "PEN") polyesters; polycarbonate (hereinafter sometimes abbreviated as "PC"); acrylic acid such as polymethyl methacrylate (PMMA); cyclic polyolefins; triethyl amide Cellulose (TAC); polyether sulfide (PES); polyether ketone; polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil. Among them, copper foil is preferred. As the copper foil, a foil made of a simple metal of copper, or a foil made of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. .

The support system may apply matting treatment, corona discharge treatment, and static electricity suppression treatment to the surface bonded to the resin composition layer.

As the support, a support with a release layer having a release layer on the surface joined to the resin composition layer can also be used. Examples of the mold release agent that can be used in the mold release layer of the support with a mold release layer include, for example, the group consisting of alkyd resin, polyolefin resin, urethane resin, and polysiloxane resin More than one release agent selected. As the support with a release layer, a commercially available product can be used, and examples thereof include "SK-1" and "SK-1" manufactured by LINTEC Corporation, which have a PET film made of a release layer mainly composed of an alkyd resin-based release agent. "AL-5", "AL-7", "Lumirror T60" manufactured by Toray, "PUREX" manufactured by Teijin, "Unipeel" manufactured by Unitika, etc.

The thickness of the support is not particularly limited, but it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when using the support body with a mold release layer, it is preferable to make the thickness of the whole support body with a mold release layer into the said range.

In one embodiment, the resin sheet may further include other layers as required. As the other layers described above, for example, a protective film may be provided in accordance with the support on the surface of the support that does not contact the resin composition layer (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion or scratching of dust and the like on the surface of the resin composition layer.

The resin sheet can be produced by, for example, dissolving the resin composition in an organic solvent to prepare a resin varnish, applying the resin varnish to a support using a die coater, etc., and then drying it A resin composition layer is formed.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether acetate Acetates such as carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethyl Acetamide-based solvents such as acetamide (DMAc) and N-methylpyrrolidone. One type of organic solvent can be used alone, or two or more types can be used in combination.

The drying system can be carried out by a well-known method such as heating and hot air blowing. The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, if a resin varnish containing 30% by mass to 60% by mass of organic solvent is used, it is dried at 50°C to 150°C for 3 minutes to 10 Minutes to form a resin composition layer.

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

[Printed wiring board] The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.

For example, using the above resin sheet, a printed wiring board can be manufactured by a method including the following steps (I) and (II). (I) The step of laminating on the inner substrate by bonding the resin composition layer of the resin sheet to the inner substrate, (II) The step of thermally curing the resin composition layer to form an insulating layer.

The "inner layer substrate" used in step (I) refers to a member that becomes a substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermal Hardened polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one or both sides, and the conductor layer may also be patterned. An inner layer substrate in which a conductor layer (circuit) is formed on one side or both sides of the substrate is sometimes called an "inner layer circuit substrate". In addition, when manufacturing a printed wiring board, an intermediate product of an insulating layer and/or a conductor layer to be formed is also included in the so-called "inner substrate" of the present invention. When the printed wiring board is a component-embedded circuit board, an inner substrate with embedded components can be used.

The lamination of the inner substrate and the resin sheet can be performed by, for example, heating and pressing the resin sheet and the inner substrate from the support side. Examples of the member that heat-pressure bonds the resin sheet and the inner layer substrate (hereinafter also referred to as "heat-pressure bonding member") include, for example, a heated metal plate (SUS mirror plate, etc.), a metal roll (SUS roll), and the like. In addition, in order to make the resin sheet sufficiently follow the surface unevenness of the inner layer substrate, it is not preferable to directly press the thermocompression bonding member and the resin sheet, but to press with an elastic material such as heat-resistant rubber.

The lamination of the inner substrate and the resin sheet can be carried out by vacuum lamination. In the vacuum lamination method, the heating and pressing temperature is preferably in the range of 60°C to 160°C, and preferably in the range of 80°C to 140°C, and the heating and pressing pressure is in the range of 0.098MPa to 1.77MPa, and preferably 0.29 In the range of MPa to 1.47 MPa, the heating and pressing time is preferably 20 seconds to 400 seconds, and more preferably 30 seconds to 300 seconds. The lamination system is preferably carried out under a reduced pressure of 26.7 hPa or less.

The lamination system can be performed by a commercially available vacuum laminator. As a commercially available vacuum bonding machine, for example, a vacuum press-type bonding machine made by Meiji Manufacturing Co., Ltd., a vacuum bonding machine made by Nikko･materials, a batch-type vacuum press bonding machine, etc. may be mentioned.

After lamination, the laminated resin sheet can be smoothed by pressing under normal pressure (at atmospheric pressure), for example, by pressing the heated pressure-bonding member from the support side. The pressing conditions of the smoothing treatment can be set to the same conditions as the above-mentioned laminating heat and pressure bonding conditions. The smoothing treatment can be performed by a commercially available bonding machine. Still, the lamination and smoothing treatment can also be continuously performed using the above-mentioned commercially available vacuum bonding machine.

The support body can be removed between step (I) and step (II), and can also be removed after step (II).

In step (II), the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions of the resin composition layer are not particularly limited, and conditions generally adopted when forming the insulating layer of the printed wiring board can be used.

For example, the thermosetting conditions of the resin composition layer vary depending on the type of resin composition, etc. The curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and more preferably 170°C 210℃. The hardening time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and more preferably 15 minutes to 100 minutes.

Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before the resin composition layer is thermally hardened, the resin composition layer may be applied at a temperature of 50°C or more but less than 120°C (preferably 60°C or more and 115°C or less, and more preferably 70°C or more and 110°C or less). Preheating for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, more preferably 15 minutes to 100 minutes).

Since the insulating layer is formed by the cured product of the resin composition of the present invention, the thickness of the insulating layer can be made thin. The thickness of the insulating layer is preferably 30 μm or less, further preferably 20 μm or less, and more preferably 15 μm or less and 10 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but it can generally be 1 μm or more, 5 μm or more, and the like.

When manufacturing a printed wiring board, it may be further implemented: (III) a step of opening the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer. These steps (III) to (V) can be carried out according to various methods well known to those used in the manufacture of printed wiring boards. Still, when the support is removed after step (II), the removal of the support may be between step (II) and step (III), between step (III) and step (IV), or in It is carried out between step (IV) and step (V). Furthermore, the multilayer wiring board may be formed by repeating the formation of the insulating layer and the conductor layer from step (II) to step (V) according to need.

Step (III) is a step of opening the insulating layer, whereby holes such as through holes, through holes, etc. can be formed on the insulating layer. Step (III) is performed in accordance with the composition of the resin composition used in the formation of the insulating layer, and can be performed using, for example, drilling, laser, plasma, or the like. The size or shape of the hole can be appropriately determined according to the design of the printed wiring board.

Since the insulating layer is formed by the cured product of the resin composition of the present invention, the top hole diameter can be made small. The top diameter of the aforementioned holes is preferably 45 μm or less, more preferably 40 μm or less, and still more preferably 35 μm or less. In terms of the lower limit, it can be set to 1 μm or more.

Step (IV) is a step of roughening the insulating layer. Generally speaking, the slag can also be removed in this step (IV). The procedures and conditions of the roughening treatment are not particularly limited, and well-known procedures and conditions generally used when forming an insulating layer of a printed wiring board can be adopted. In addition, a dry type or a wet type can be used. When the conductor layer is formed by sputtering, it is preferably performed in a dry method such as a slag removal process using plasma. In particular, if the opening of the above resin composition in step (III) is using UV (ultraviolet) laser, there is a tendency to effectively suppress slag, and it is suitable for dry slag removal.

Examples of the gas used in sputtering include argon, oxygen, and CF ₄ . These can be used alone or in combination of two or more.

In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after roughening is preferably 400 nm or less, more preferably 350 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited, but is preferably 0.5 nm or more, and more preferably 1 nm or more. Further, the square root roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited, but is preferably 0.5 nm or more, and more preferably 1 nm or more. The arithmetic average roughness (Ra) and the square root roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, which is to form a conductor layer on the insulating layer. The conductor material used as the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer includes one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium Above the metal. The conductor layer system may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel, chromium alloy, copper, nickel alloy, and copper, titanium) Alloy). Among them, from the viewpoints of versatility, cost, and ease of patterning of the conductor layer, a simple metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or nickel･ An alloy layer of chromium alloy, copper, nickel alloy, copper, and titanium alloy is preferred, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel and chromium alloy For better.

The conductor layer system may have a single-layer structure, or a multilayer structure in which two or more layers of a single metal layer or alloy layer composed of different kinds of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel and chromium alloy.

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

In one embodiment, the conductor layer may be formed by sputtering. In the sputtering method, first, a conductor seed layer is formed on the surface of the insulating layer by sputtering, and then a conductor sputtering layer is formed on the conductor seed layer by sputtering. Before the formation of the conductor seed layer by sputtering, the surface of the insulating layer can also be purified by reverse sputtering. As the gas used in the reverse sputtering, various gases can be used, but among them, Ar, O ₂ , and N ₂ are preferred. When the seed layer is Cu and Cu alloy, Ar or O ₂ or Ar, O ₂ mixed gas is preferred; when the seed layer is Ti, Ar or N ₂ or Ar, N ₂ Mixed gas is preferred; if the seed layer is Cr and Cr alloy (nickel-chromium alloy, etc.), Ar or O ₂ or Ar, O ₂ mixed gas is preferred. The sputtering system can be performed using various sputtering devices such as magnetron sputtering and mirrortron sputtering. Examples of the metal forming the conductor seed layer include Cr, Ni, Ti, and nickel-chromium alloy. In particular, Cr and Ti are preferred. The thickness of the conductor seed layer is generally formed as follows: preferably 5 nm or more, more preferably 10 nm or more; preferably 1000 nm or less, and more preferably 500 nm or less. Examples of the metal forming the conductor sputtering layer include Cu, Pt, Au, and Pd. In particular, Cu is preferred. The thickness of the conductor sputtering layer is generally formed as follows: preferably 50 nm or more, and more preferably 100 nm or more; preferably 3000 nm or less, and more preferably 1000 nm or less.

When the conductor seed layer is formed, the surface roughness (Ra value) formed on the surface of the insulating layer, the value measured after removing the conductor seed layer by etching is preferably 150 nm or less, preferably The range of 10 to 150 nm is more preferable, and more preferably 10 to 120 nm or less.

After the conductor layer is formed by the sputtering method, a copper plating layer can be further formed on the conductor layer by electrolytic copper plating. The thickness of the copper plating layer is generally formed as follows: preferably 5 μm or more, and more preferably 8 μm or more; preferably 75 μm or less, and more preferably 35 μm or less. A well-known method such as a subtractive method and a semi-additive method can be used for circuit formation.

In another embodiment, a metal foil may be used to form the conductor layer. In the case of using metal foil to form the conductor layer, step (V) is preferably implemented between step (I) and step (II). For example, after step (I), the support is removed, and the metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be carried out by vacuum lamination. The lamination conditions may be the same as the lamination conditions of the inner substrate and the resin sheet. Next, step (II) is performed to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern may be formed by a subtractive method, an improved semi-additive method, or the like.

The metal foil can be manufactured by a well-known method such as an electrolytic method or a rolling method. Examples of the metal foil include copper foil and aluminum foil. Copper foil is preferred. As the copper foil, a foil composed of a simple metal of copper, or a foil composed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can also be used . Examples of commercially available metal foil products include HLP foil made by JX Metals Corporation, JXUT-III foil, 3EC-III foil made by Mitsui Metals Mining Corporation, and TP-III foil.

Furthermore, in another embodiment, the conductor layer can be formed by plating. For example, by a conventionally well-known technique such as a semi-additive method or a full-additive method, a conductor layer having a desired wiring pattern can be formed by plating on the surface of an insulating layer, from the viewpoint of ease of manufacturing In particular, it is preferably formed by a semi-additive method. The following is an example of forming a conductor layer by a semi-additive method.

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 corresponding to a desired wiring pattern to expose a part of the plating seed layer. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, so that a conductor layer having a desired wiring pattern can be formed.

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

Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trams, ships, and airplanes).

The semiconductor device of the present invention can be manufactured by mounting components (semiconductor wafers) on the conductive portions of the printed wiring board. The so-called "conducting part" refers to "the part of the printed wiring board that transmits electrical signals", and its position may be the surface or the part where it is buried. In addition, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

The method of mounting a semiconductor wafer when manufacturing a semiconductor device is not particularly limited as long as the semiconductor wafer effectively functions, but specifically, a wire bonding mounting method, a flip chip mounting method, and bumpless Mounting method of build-up layer (BBUL), mounting method by anisotropic conductive film (ACF), mounting method by non-conductive film (NCF), etc. Here, the so-called "mounting method by bumpless build-up (BBUL)" refers to "mounting the semiconductor wafer directly into the recess of the printed wiring board to connect the semiconductor wafer to the wiring on the printed wiring board. method". [Example]

The present invention is specifically described below by showing examples. However, the present invention is not limited by the following examples. In the following description, "parts" and "%" indicating quantities, unless otherwise specified, represent the meaning of "parts by mass" and "mass %", respectively. In addition, the operation described below means that it is performed in an environment of normal temperature and normal pressure unless otherwise specified.

[Measurement of adhesion strength (peel strength) between insulating layer and conductor layer] <Fabrication of Evaluation Board A> (1) Base treatment of inner layer circuit board A micro-etching agent (manufactured by MEC Corporation) was used on both sides of the glass cloth substrate epoxy resin two-sided copper-clad laminated board (copper foil thickness 18 μm, substrate thickness 0.4 mm, "R1515A" manufactured by Panasonic Corporation) formed with an inner layer circuit CZ8101") etching 1μm to roughen the copper surface.

(2) Lamination of resin sheets The resin sheet a produced in the examples and comparative examples was batch-type vacuum press bonding machine ("MVLP-500" manufactured by Meiji Manufacturing Co., Ltd.), and the resin composition layer was in contact with the inner circuit board. To laminate on both sides of the inner circuit board. The lamination was performed by depressurizing for 30 seconds and then setting the air pressure to 13 hPa or less, and thereafter, by performing lamination treatment at 100° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Hardening of the resin composition layer The laminated resin sheet a was heated at 100° C. for 30 minutes and then at 170° C. for 30 minutes to thermally harden the resin composition layer to form an insulating layer.

(4) Formation of through-holes by UV-YAG laser After the support was peeled off, the surface of the insulating layer was exposed, and a through hole was formed to the insulating layer using the UV-YAG laser processing machine ("LU-2L212/M50L" manufactured by Via Mechanics) under the following conditions. Conditions: energy 0.30W, projection number 25, target top aperture 30μm

(5) After the dry slag removal treatment is used to form the through holes, the inner layer circuit board with the insulating layer formed using a vacuum plasma etching device (100-E PLASMA SYSTEM manufactured by Tepla Corporation), with O ₂ /CF ₄ (mixed Gas ratio) = 25/75 and a vacuum of 100 Pa for 5 minutes.

(6) Formation of conductor layer by dry method Using a sputtering apparatus ("E-400S" manufactured by Canon ANELVA), a titanium layer (thickness 30 nm) was formed on the insulating layer, and then a copper layer (thickness 300 nm) was formed. After the obtained substrate was annealed by heating at 150°C for 30 minutes, according to the semi-additive method, the pattern was formed by forming an etching resist and exposure and development, and then subjected to electrolytic plating with copper sulfate to form a thickness of 25 μm. Conductor layer. After the conductor pattern is formed, it is annealed by heating at 200°C for 60 minutes. The obtained printed wiring board is called "evaluation board A".

<Measurement of peel strength (peel strength)> The measurement of the peel strength of the insulating layer and the conductor layer was performed on the evaluation substrate A in accordance with JIS C6481. Specifically, a slit of a portion of 10 mm in width and 100 mm in length was placed on the conductor layer of the evaluation substrate A, and one end was peeled off and clamped with a clipper, and measured at a speed of 50 mm/min at room temperature The load (kgf/cm) at the time of peeling off 35 mm in the vertical direction to determine the peel strength. The measurement was performed using a tensile tester ("AC-50C-SL" manufactured by TSE).

[Determination of Dielectric Tangent] <Preparation of evaluation hardened product B> After the resin sheet a produced in the examples and the comparative examples was heated at 200° C. for 90 minutes to thermally harden the resin composition layer, the support was peeled off. The obtained hardened product is referred to as "evaluated hardened product B".

<Determination of dielectric tangent> The hardened product for evaluation B was cut into test pieces having a width of 2 mm and a length of 80 mm. For this test piece, "HP8362B" manufactured by Agilent Technologies was used, and the dielectric tangent was measured with a cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Two test pieces were measured, and the average value was calculated.

[Measurement of moisture permeability coefficient] ＜Measurement･Preparation of samples for evaluation＞ After the resin sheet b produced in Examples and Comparative Examples was heated at 200° C. for 90 minutes to thermally harden the resin composition layer, the support was peeled off. The obtained hardened product is referred to as "evaluated hardened product C".

<Measurement of Moisture Permeability Coefficient> The hardened material for evaluation C was cut into a circle with a diameter of 70 mm, and the moisture permeability was measured in accordance with the moisture permeability test method (cup method) of JIS Z0208. Specifically, the sample is left at 60°C, 85% RH for 24 hours, and the weight of water passing through the sample is measured to determine the moisture permeability (g/m ² ･24h), which is divided by the film thickness to calculate the permeability Wet coefficient (g/mm･m ² ･24h). Calculated from the average of 3 test pieces.

[Evaluation of insulation reliability after high temperature and high humidity environment test, measurement of thickness of insulation layer between conductor layers] <Modulation of Evaluation Board D> (1) Base treatment of inner layer circuit board As an inner-layer circuit board, prepare a glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm) on both sides with a wiring pattern of 1 mm square grid (residual copper rate 70%) to form a circuit conductor (copper) , Thickness of substrate 0.4mm, "R1515A" manufactured by Panasonic Corporation). Both surfaces of this inner layer circuit board were immersed in a micro-etching agent ("CZ8101" manufactured by MEC Corporation) to roughen the copper surface (copper etching amount 0.7 μm).

(2) Lamination of resin sheets The resin sheet c produced in the examples and the comparative examples was used a batch-type vacuum pressure bonding machine (manufactured by Nikko-Materials, two-stage build-up bonding machine, CVP700), using a resin composition layer and an inner layer circuit board The contact method is to laminate to both sides of the inner circuit board. The lamination is performed by depressurizing for 30 seconds, setting the air pressure to 13 hPa or less, and then pressing at 120° C. and a pressure of 0.74 MPa for 30 seconds. Next, hot press was performed at 120°C and a pressure of 0.5 MPa for 60 seconds.

(3) Hardening of the resin composition layer The inner layer circuit board laminated with the resin sheet c is heated at 100° C. for 30 minutes and then at 170° C. for 30 minutes to thermally harden the resin composition layer to form an insulating layer.

(4) Formation of through-holes by UV-YAG laser After peeling off the support, the surface of the insulating layer is exposed, using a UV-YAG laser processing machine ("LU-2L212/M50L" manufactured by Via Mechanics) to open the circuit conductors on the inner circuit board. The following conditions are used to form the through hole to the insulating layer. Conditions: energy 0.30W, projection number 25, target top aperture 30μm

(5) After the dry slag removal treatment is used to form the through holes, the inner layer circuit board with the insulating layer formed using a vacuum plasma etching device (100-E PLASMA SYSTEM manufactured by Tepla Corporation), with O ₂ /CF ₄ (mixed Gas ratio) = 25/75 and a vacuum of 100 Pa for 5 minutes.

(6) Formation of conductor layer by dry method A sputtering device ("E-400S" manufactured by Canon ANELVA) was used to form a titanium layer (thickness 30 nm), and then a copper layer (thickness 300 nm) was formed. The obtained substrate was heated at 150° C. for 30 minutes to perform annealing treatment.

(7) Electrolytic plating Next, using a chemical solution manufactured by Atotech Japan, the electrolytic copper plating step was performed under the condition that the through holes were filled with copper. Then, as a resist pattern for patterning by etching, the following land pattern and circular conductor pattern were used, and a pad and a conductor were formed on the surface of the insulating layer with a thickness of 10 μm Conductor layer of the pattern, the aforementioned pad pattern: a pad pattern with a diameter of 1 mm that communicates with the lower layer conductor (that is, the circuit conductor of the inner layer circuit board) through the through hole; the aforementioned conductor pattern: and the lower layer conductor are not Circular conductor pattern with a diameter of 10 mm. Next, annealing treatment was performed at 200°C for 90 minutes. This substrate is called an evaluation substrate D.

<Measurement of the thickness of the insulating layer between conductor layers> Use FIB-SEM composite device (SII) for evaluation substrate D NanoTechnology Co., Ltd. "SMI3050SE") for cross-sectional observation. Specifically, a cross section perpendicular to the surface of the conductor layer was cut out with FIB (Focused Ion Beam), and the thickness of the insulating layer between the conductor layers was measured from the cross-sectional SEM image. For each sample, a cross-sectional SEM image of five randomly selected sites was observed, and the average value was determined as the thickness of the insulating layer between the conductor layers.

<Evaluation of Insulation Reliability after High Temperature and High Humidity Environment Test of Insulation Layer> An inner layer circuit board connected to a pad having a diameter of 1 mm using the round conductor side of the evaluation substrate D obtained above with a diameter of 10 mm as the + electrode The side of the circuit conductor (copper) is an electrode, and a highly accelerated life test device ("PM422" manufactured by ETAC) is used to conduct a 500-hour test under the conditions of 130°C, 85% relative humidity, and a DC voltage of 3.3V. The insulation resistance value after the elapse of 500 hours was measured with an electrochemical migration tester ("ECM-100" manufactured by J-RAS). This measurement was repeated 6 times, and the average value was calculated. In addition, when the resistance value of all the test pieces for 6 times is 10 ⁷ Ω or more, it is evaluated as “○”; as long as one time is less than 10 ⁷ Ω, it is evaluated as “×”.

[Example 1] 15 parts of bisphenol AF epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight approximately 238), styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer "Tuftec" manufactured by Asahi Kasei Corporation) H1043", styrene content 67%) 3 parts, heated and dissolved in 25 parts of toluene and 15 parts of MEK while stirring. After cooling to room temperature, 46 parts of a resin having a vinyl phenyl group ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 1200, nonvolatile matter 65% by mass in toluene) were mixed with ) Acrylic-based resin ("NK Ester A-DOG" manufactured by Shin Nakamura Chemical Industry Co., Ltd., molecular weight 326) 30 parts, active ester type hardener ("HPC8000-65T" manufactured by DIC Corporation), solid content 65% by mass in toluene solution ) 30 parts, a phenolic hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC, 50% 2-methoxypropanol solution with a hydroxyl equivalent of about 151) 4 parts, carbodicarbonate 8 parts of amine-based hardener ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent of about 216, solid content 50% by mass in toluene), hardening accelerator (N,N-dimethyl-4-amino arsenic 6 parts of pyridine (DMAP), 5% by mass solids MEK solution, 1 part of polymerization initiator ("Perbutyl C" manufactured by NOF Corporation), via phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") 250 parts of spherical silica (average particle size 0.5 μm, specific surface area 5.9 m ² /g, "SO-C2" manufactured by Admatechs), uniformly dispersed by a high-speed rotary mixer Make resin varnish.

Next, on the release surface of the polyethylene terephthalate film ("AL5" manufactured by LINTEC, thickness 38 μm) with release treatment, the thickness of the resin composition layer after drying becomes 20 μm Method to uniformly apply resin varnish and dry it at 80 to 120°C (average 100°C) for 3 minutes to produce a resin sheet a.

In addition, for the measurement of the moisture permeability coefficient, the dried resin composition is applied to the release surface of a polyethylene terephthalate film ("AL5" manufactured by LINTEC Corporation, thickness 38 μm) with release treatment. The resin varnish was uniformly applied so that the thickness of the layer became 40 μm, and dried at 80 to 120° C. (average 100° C.) for 4 minutes to produce a resin sheet b.

For evaluation of insulation reliability after high-temperature and high-humidity environmental tests, on the release surface of a polyethylene terephthalate film ("AL5" manufactured by LINTEC, thickness 38 μm) with a release treatment, The resin varnish was uniformly coated so that the thickness of the resin composition layer after drying became 10 μm, and dried at 80° C. for 2 minutes to produce a resin sheet c.

[Example 2] 5 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269), bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent Approximately 238) 10 parts, styrene elastomer (hydrogenated styrene-based thermoplastic elastomer "Tuftec P2000" manufactured by Asahi Kasei Corporation, styrene content 67%) 20 parts, styrene elastomer (epoxidized styrene manufactured by Daicel Corporation) -20 parts of butadiene thermoplastic elastomer "Epofriend AT501" (styrene content 40%), dissolved in 50 parts of toluene and 20 parts of MEK while stirring and heating. After cooling to room temperature, 92 parts of a resin having a vinyl phenyl group ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 1200, nonvolatile matter 65% by mass in toluene) were mixed with (methyl ) Acrylic-based resin ("NK Ester A-DOG" manufactured by Shin Nakamura Chemical Industry Co., Ltd., molecular weight 326) 30 parts, active ester type hardener ("EXB9416-70BK" manufactured by DIC Corporation), non-volatile with equivalent active group equivalent of about 330 28 parts of a 70% by mass methyl isobutyl ketone solution), a phenolic hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, 50% solid content of 2-hydroxyl equivalent of about 151 Oxypropanol solution) 4 parts, carbodiimide-based hardener ("V-03" manufactured by Nisshinbo chemical company, active group equivalent of about 216, solid content 50% by mass in toluene solution) 8 parts, hardening accelerator (N , N-dimethyl-4-aminopyridine (DMAP), solids 5 mass% MEK solution) 6 parts, polymerization initiator ("Perbutyl C" manufactured by NOF Corporation) 1 part, via phenylamine Silane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") spherical silica (average particle size 0.3 μm, specific surface area 30.7 m ² /g, Denka Co., Ltd. "UFP-30") 200 The portions were uniformly dispersed using a high-speed rotary mixer to produce resin varnishes, and resin sheets a to c were produced in the same manner as in Example 1.

[Comparative Example 1] In Example 1, the amount of a resin having a vinyl phenyl group ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 1200, non-volatile matter 65% by mass toluene solution) was changed from 46 parts to 92 parts And 30 parts of (meth)acrylate ("NK Ester A-DOG" manufactured by Shin Nakamura Chemical Industry Co., Ltd., molecular weight 326) are not used. Except for the above matters, resin varnish and resin sheets a to c were produced in the same manner as in Example 1.

[Comparative Example 2] In Example 1, 3 parts of a styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer "Tuftec H1043" manufactured by Asahi Kasei Corporation, 67% styrene content) were not used. Except for the above matters, resin varnish and resin sheets a to c were produced in the same manner as in Example 1.

[Comparative Example 3] In Example 2, the amount of a resin having a vinyl phenyl group ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 1200, non-volatile matter 65% by mass toluene solution) was changed from 92 parts to 138 parts And 30 parts of (meth)acrylate ("NK Ester A-DOG" manufactured by Shin Nakamura Chemical Industry Co., Ltd., molecular weight 326) are not used. Except for the above matters, resin varnishes and resin sheets a to c were produced in the same manner as in Example 2.

[Comparative Example 4] In Example 2, 20 parts of styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer "Tuftec P2000" manufactured by Asahi Kasei Corporation, 67% styrene content) were not used, and styrene-based elastomer (Daicel Corporation) was not used Epoxy styrene-butadiene thermoplastic elastomer "Epofriend AT501", styrene content 40%) 20 parts. Except for the above matters, resin varnishes and resin sheets a to c were produced in the same manner as in Example 2.

In Examples 1 to 2, even if the components (D-2) to (H) were not included, although there were differences in the degree, it is confirmed that the same results as those in the above examples will be summarized.

Claims (17)

A resin composition characterized by comprising: (A) Epoxy resin, (B) Hardener, (C) Styrene elastomer and (D-1) A resin having a (meth)acryloyl group. A resin composition comprising: (A) an epoxy resin, (B) a hardener, (C) a styrene-based elastomer, and (D) a resin having a radical polymerizable unsaturated group, the resin composition The moisture permeability coefficient of the cured product obtained by heat curing at 200°C for 90 minutes is 0 g/mm･m ² ･24h or more and 10g/mm･m ² ･24h or less. The resin composition according to claim 2, wherein the component (D) contains (D-1) a resin having a (meth)acryloyl group. The resin composition according to claim 1 or 3, wherein the number average molecular weight of the component (D-1) is 3000 or less. The resin composition according to claim 1 or 2, wherein when the resin component in the resin composition is 100% by mass, the content of the (C) component is 0.5% by mass or more and 18% by mass or less. The resin composition according to claim 1 or 2, wherein when the component (C) is 100% by mass, the content of the styrene unit is 61% by mass or more in the component (C). The resin composition according to claim 1 or 2, wherein the content of the component (B) is 1% by mass or more and 15% by mass or less when the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1 or 2, which further contains (E) an inorganic filler. The resin composition according to claim 8, wherein the content of the (E) component is 50% by mass or more when the non-volatile content in the resin composition is 100% by mass. The resin composition according to claim 1 or 2 is used to form an insulating layer. The resin composition according to claim 1 or 2 is used to form an insulating layer for forming a conductor layer. The resin composition according to claim 1 or 2 is used to form an insulating layer for forming a conductor layer by sputtering or metal foil. The resin composition according to claim 1 or 2 is for forming an insulating layer having a through hole having a top hole diameter of 45 μm or less. The resin composition according to claim 1 or 2 is for forming an insulating layer with a thickness of 20 μm or less. A resin sheet characterized by comprising: Support and A resin composition layer provided on the support, The resin composition layer contains the resin composition of any one of claims 1 to 14. A printed wiring board including an insulating layer, wherein the insulating layer is formed by a cured product of the resin composition according to any one of claims 1 to 14. A semiconductor device characterized by a printed wiring board including claim 16.