JP7318699B2 - resin composition - Google Patents

Description

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

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

As a resin composition for forming such an insulating layer, for example, Patent Document 1 describes (A) a thermosetting resin having a molecular weight of 800 to 1500 having a styrene group at the end, (B) a liquid epoxy resin, and (C) A resin composition containing a styrenic thermoplastic elastomer, (D) a filler, and (E) a curing agent, wherein the component (D) is 30 to 70 parts by mass with respect to 100 parts by mass of the resin composition. ing.

JP 2016-147945 A

In order to obtain an insulating layer having a low dielectric loss tangent, the present inventors have investigated a resin composition containing a radically polymerizable compound that reduces the polarity of the entire resin composition. As a result, a new problem was found that the storage stability of a resin varnish obtained by dissolving the resin composition in an organic solvent deteriorates when the resin composition contains a radically polymerizable compound.

An object of the present invention is to provide a resin composition that is excellent in the storage stability of a resin varnish and that can provide a cured product with a low dielectric loss tangent; a resin sheet containing the resin composition; An object of the present invention is to provide a printed wiring board and a semiconductor device having an insulating layer.

As a result of extensive studies to solve the above problems, the present inventors have found that, in addition to (D) a resin having a radically polymerizable unsaturated group, (A) an epoxy resin, (B) a curing agent, and containing styrene units The present inventors have found that the above problems can be solved by a resin composition containing a combination of (C) a styrene-based elastomer whose amount is within a predetermined range, and have completed the present invention.
That is, the present invention includes the following contents.

[1] (A) epoxy resin,
(B) a curing agent;
(C) a styrene elastomer, and (D) a resin having a radically polymerizable unsaturated group,
A resin composition in which the content of styrene units in component (C) is 61% by mass or more when component (C) is taken as 100% by mass.
[2] The resin composition according to [1], wherein the content of component (C) is 0.5% by mass or more and 18% by mass or less when the resin component in the resin composition is taken as 100% by mass.
[3] The resin composition according to [1] or [2], wherein component (D) contains at least one selected from vinylphenyl groups, acryloyl groups, and methacryloyl groups.
[4] The resin composition according to any one of [1] to [3], wherein component (D) has a number average molecular weight of 3,000 or less.
[5] The resin composition according to any one of [1] to [4], further comprising (E) an inorganic filler.
[6] The resin composition according to [5], wherein the content of component (E) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[7] The resin composition according to any one of [1] to [6], which is for forming an insulating layer.
[8] The resin composition according to any one of [1] to [7], which is used for forming an insulating layer for forming a conductor layer.
[9] The resin composition according to any one of [1] to [8], which is for forming an insulating layer for forming a conductor layer by sputtering or metal foil.
[10] The resin composition according to any one of [1] to [9], which is for forming an insulating layer having via holes with a top diameter of 45 μm or less.
[11] The resin composition according to any one of [1] to [10], which is for forming an insulating layer having a thickness of 20 μm or less.
[12] A resin sheet comprising a support and a resin composition layer containing the resin composition according to any one of [1] to [11] provided on the support.
[13] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [11].
[14] A semiconductor device including the printed wiring board according to [13].

According to the present invention, a resin composition capable of obtaining a cured product having excellent storage stability of a resin varnish and a low dielectric loss tangent; a resin sheet containing the resin composition; A printed wiring board and a semiconductor device having an insulating layer can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

[Resin composition]
The resin composition of the present invention comprises (A) an epoxy resin, (B) a curing agent, (C) a styrene-based elastomer, and (D) a resin having a radically polymerizable unsaturated group. The content of styrene units is 61% by mass or more when the component (C) is 100% by mass. By using such a resin composition, it is possible to obtain a resin varnish having excellent storage stability and a cured product having a low dielectric loss tangent. Furthermore, by using such a resin composition, it is usually possible to increase the peel strength to the conductor layer.

The resin composition may further contain optional components in combination with components (A) to (D). Optional components include, for example, (E) an inorganic filler, (F) a styrene elastomer other than component (C), (G) a curing accelerator, (H) a polymerization initiator, and (I) other additives. etc. Each component contained in the resin composition will be described in detail below.

<(A) Epoxy resin>
(A) Epoxy resins include, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol type epoxy resins. Epoxy resin, naphthol novolak type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane Examples include dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin and the like. Epoxy resins may be used singly or in combination of two or more.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as (A) the epoxy resin. From the viewpoint of obtaining the desired effects of the present invention remarkably, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile components of the epoxy resin (A) is preferably 50% by mass. % or more, more preferably 60 mass % or more, and particularly preferably 70 mass % or more.

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

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

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin, and more preferably naphthalene type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; DIC's "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" ( Naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; YX8800" (anthracene type epoxy resin); Osaka Gas Chemicals Co., Ltd. "PG-100", "CG-500"; Mitsubishi Chemical Co., Ltd. "YL7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical Co., Ltd. "YL7800 (fluorene type epoxy resin); Mitsubishi Chemical Corp.'s "jER1010" (solid bisphenol A type epoxy resin); Mitsubishi Chemical Corp.'s "jER1031S" (tetraphenylethane type epoxy resin). These may be used individually by 1 type, and may be used in combination of 2 or more types.

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

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

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC; 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical Corporation "jER152" (phenol novolac type epoxy resin); Mitsubishi Chemical Corporation "630", "630LSD" (glycidylamine type epoxy resin); Nippon Steel & Sumikin Chemical Co., Ltd. "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX Co., Ltd. "EX -721" (glycidyl ester type epoxy resin); Daicel's "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton); Daicel's "PB-3600" (epoxy resin having a butadiene structure); Nippon Steel "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Sumikin Chemical Co., Ltd., and the like can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

(A) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the ratio by mass (liquid epoxy resin: solid epoxy resin) is preferably 1:1 to 1:20. , more preferably 1:1.5 to 1:15, particularly preferably 1:2 to 1:10. The desired effect of the present invention can be remarkably obtained by setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range. In addition, it usually provides moderate tackiness when used in the form of a resin sheet. In addition, when used in the form of a resin sheet, sufficient flexibility is usually obtained, and handleability is improved. Furthermore, usually, a cured product having sufficient breaking strength can be obtained.

(A) The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ~5000g/eq. , more preferably 50 g/eq. ~3000g/eq. , more preferably 80 g/eq. ~2000 g/eq. , even more preferably 110 g/eq. ~1000 g/eq. is. Within this range, the crosslink density of the cured product of the resin composition layer is sufficient, and an insulating layer with a small surface roughness can be obtained. Epoxy equivalent weight is the weight of an epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent 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, still more preferably 400 to 1500, from the viewpoint of significantly obtaining the desired effects of the present invention.
The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

(A) From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, the content of the epoxy resin is preferably 1% by mass or more, when the non-volatile component in the resin composition is 100% by mass. It is preferably 2% by mass or more, more preferably 3% by mass or more. The upper limit of the epoxy resin content 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 of significantly obtaining the desired effects of the present invention. 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) Curing agent>
The resin composition contains a curing agent as the (B) component. (B) Curing agent usually has a function of reacting with (A) epoxy resin to cure the resin composition.

(B) Curing agents include, for example, active ester curing agents, phenol curing agents, naphthol curing agents, benzoxazine curing agents, cyanate ester curing agents, carbodiimide curing agents, amine curing agents, and acid anhydrides. physical curing agents, and the like. (B) Curing agents may be used singly or in combination of two or more.

A compound having one or more active ester groups in one molecule can be used as the active ester curing agent. Among them, active ester curing agents include phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, and the like, and have two or more ester groups per molecule with high reaction activity. Preferred are compounds having The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. .

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

Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Preferred specific examples of the active ester curing agent include an active ester curing agent containing a dicyclopentadiene type diphenol structure, an active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylated phenol novolac, Examples include active ester curing agents containing benzoylated phenol novolacs. Among them, an active ester curing agent containing a naphthalene structure and an active ester curing agent containing a dicyclopentadiene type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC8000-65T", and "HPC8000H-65TM" as active ester curing agents containing a dicyclopentadiene type diphenol structure. , "EXB8000L-65TM", "EXB8150-65T" (manufactured by DIC); "EXB9416-70BK" (manufactured by DIC) as an active ester curing agent containing a naphthalene structure; active ester curing containing acetylated phenol novolak "DC808" (manufactured by Mitsubishi Chemical Corporation) as a curing agent; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing a benzoylated phenol novolac; "DC808" as an active ester curing agent that is an acetylated phenol novolac " (manufactured by Mitsubishi Chemical Corporation); "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester curing agents that are benzoyl compounds of phenol novolak. ; and the like.

From the viewpoint of heat resistance and water resistance, the phenol-based curing agent and naphthol-based curing agent preferably have a novolac structure. From the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable.

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

Specific examples of benzoxazine-based curing agents include "ODA-BOZ" manufactured by JFE Chemical Co., Ltd., "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Kasei Kogyo Co., Ltd. mentioned.

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate, oligo(3-methylene-1,5-phenylenecyanate), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4 '-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethyl Bifunctional cyanate resins such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether; polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc.; prepolymers obtained by partially triazinizing these cyanate resins; and the like. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resins), "ULL-950S" (polyfunctional cyanate ester resins) and "BA230" manufactured by Lonza Japan. , "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazined to form a trimer), and the like.

Specific examples of carbodiimide curing agents include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd., and the like.

Amine-based curing agents include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. Amine-based curing agents are preferably primary amines or secondary amines, more preferably primary amines. Specific examples of amine-based curing agents include 4,4′-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 3,3′. -diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane Diamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3- bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4′-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. Commercially available amine-based curing agents may be used. Kayahard AS", Mitsubishi Chemical's "Epicure W", and the like.

Acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride mellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1 , 3-dione, ethylene glycol bis(anhydrotrimellitate), polymer-type acid anhydrides such as styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid.

Among those mentioned above, the curing agent (B) is selected from phenol-based curing agents, active ester-based curing agents, carbodiimide-based curing agents, and benzoxazine-based curing agents from the viewpoint of significantly obtaining the desired effects of the present invention. One or more is preferable.

The ratio of (A) epoxy resin to (B) curing agent is [total number of epoxy groups of component (A)]:[total number of reactive groups of (B) curing agent], which is 1:0. A range of 0.01 to 1:20 is preferred, 1:0.05 to 1:10 is more preferred, and 1:0.1 to 1:8 is even more preferred. Here, "the number of epoxy groups of (A) the epoxy resin" is the sum of all the values obtained by dividing the mass of the non-volatile component of the (A) epoxy resin present in the resin composition by the epoxy equivalent. In addition, "(B) the number of active groups of the curing agent" is a value obtained by dividing the mass of the non-volatile component of the (B) curing agent present in the resin composition by the active group equivalent and totaling all the values. By setting the ratio between (A) the epoxy resin and (B) the curing agent within such a range, the desired effect of the present invention can be significantly obtained, and moreover, usually, the cured product of the resin composition layer Heat resistance is further improved.

(B) The content of the curing agent is preferably 0.1% by mass or more, more preferably 0% by mass, based on 100% by mass of non-volatile components in the resin composition, from the viewpoint of significantly obtaining the desired effects of the present invention. 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, and even more preferably 10% by mass or less.

<(C) Styrene-based elastomer>
The resin composition contains (C) a styrene elastomer. (C) The content of styrene units in the styrene-based elastomer is 61% by mass or more when the component (C) is taken as 100% by mass. Since the (C) styrene-based elastomer contains 61% by mass or more of styrene units, it is highly compatible with (A) an epoxy resin, (B) a curing agent, and (D) a resin having a radically polymerizable unsaturated group. Therefore, phase separation between the (A) component, the (B) component, and the (D) component can be suppressed. Therefore, the storage stability of the resin varnish can be improved.

The content of styrene units in the styrene-based elastomer (C) is 61% by mass or more, preferably 63% by mass or more, more preferably 65% by mass or more when component (C) is 100% by mass. be. 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 such a range, the compatibility between (A) the epoxy resin and (B) the curing agent and the (D) component can be further enhanced, and as a result, the storage stability of the resin varnish can be improved. can improve sexuality. The styrene unit content can be measured, for example, by the charged amount of the monomer constituting the component (C).

(C) As the styrene-based elastomer, any elastomer containing repeating units (styrene units) having a structure obtained by polymerizing styrene can be used. (C) The styrene-based elastomer may be a copolymer containing any repeating unit different from the styrene unit in combination with the styrene unit.

Examples of the optional repeating unit include a repeating unit having a structure obtained by polymerizing a conjugated diene (conjugated diene unit), a repeating unit having a structure obtained by hydrogenating it (hydrogenated conjugated diene unit), and the like. be done.

Examples of conjugated dienes include aliphatic conjugated dienes such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene and 1,3-hexadiene; and halogenated aliphatic conjugated dienes such as chloroprene. As the conjugated diene, an aliphatic conjugated diene is preferable, and butadiene is more preferable, from the viewpoint of significantly obtaining the effects of the present invention. Conjugated dienes may be used singly or in combination of two or more.

(C) The styrene-based elastomer may be a random copolymer, but is preferably a block copolymer from the viewpoint of significantly obtaining the effects of the present invention. (C) Styrene-based elastomers are preferably styrene-conjugated diene block copolymers and hydrogenated styrene-conjugated diene copolymers. A particularly preferred styrene-based elastomer (C) has, for example, a polymer block containing a styrene unit as at least one terminal block and a polymer block containing a conjugated diene unit or a hydrogenated conjugated diene unit as at least one intermediate block. Block copolymers containing

A hydrogenated styrene-conjugated diene block copolymer refers to a block copolymer having a structure obtained by hydrogenating the unsaturated bonds of a styrene-conjugated diene block copolymer. Generally, in this hydrogenated styrene-conjugated diene block copolymer, aliphatic unsaturated bonds are hydrogenated, and aromatic unsaturated bonds such as benzene rings are not hydrogenated.

(C) Specific examples of the styrene 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-butylene-styrene block copolymer (SBBS), Examples include styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene random copolymer and the like.

(C) The weight average molecular weight (Mw) of the styrene elastomer is preferably 1,000 to 500,000, more preferably 2,000 to 300,000, still more preferably 3,000 to 200,000, from the viewpoint of significantly obtaining the desired effects of the present invention. (C) The weight average molecular weight of the styrene-based elastomer can be measured by the same method as for the weight average molecular weight of (A) the epoxy resin.

Component (C) may be a commercially available product, for example, hydrogenated styrene thermoplastic elastomer "Tuftec H1043", "Tuftec P2000"; styrene thermoplastic elastomer "Septon 2104" (manufactured by Kuraray Co., Ltd.), etc. can be mentioned. (C) component may be used individually by 1 type, and may be used in combination of 2 or more types.

From the viewpoint of significantly obtaining the effect of the present invention, the content of component (C) is preferably 0.1% by mass or more, more preferably 0.3%, when the non-volatile component in the resin composition is 100% by mass. It is at least 0.5% by mass, more preferably at least 0.5% by mass. The upper limit is preferably 18% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and 4% by mass or less.

The content when the nonvolatile component in the resin composition of component (C) is 100% by mass is C1, and the content when the nonvolatile component in the resin composition of component (B) is 100% by mass is B1 and In this case, from the viewpoint of significantly obtaining the effects of the present invention, C1/B1 is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and preferably 10 or less. It is preferably 5 or less, more preferably 3 or less.

<(D) Resin Having a Radically Polymerizable Unsaturated Group>
The resin composition contains (D) a resin having a radically polymerizable unsaturated group. By including (D) a resin having a radically polymerizable unsaturated group in the resin composition, it is possible to obtain a cured product having a low dielectric loss tangent. (D) When a resin having a radically polymerizable unsaturated group is used, the cured product can usually have a low dielectric loss tangent, while the component (D) undergoes phase separation from components (A) and (B) to produce a resin varnish. storage stability tends to decrease. However, in the present invention, the combination of the component (C) suppresses the phase separation, making it possible to obtain a resin varnish with excellent storage stability and a cured product with a low dielectric loss tangent.

（＊は結合手を表す。） A radically polymerizable unsaturated group refers to a group having an ethylenic double bond that exhibits curability upon exposure to active energy rays. Such groups include, for example, a vinyl group, a vinylphenyl group, an acryloyl group, a methacryloyl group, a maleimide group, a fumaroyl group and a maleoyl group, and at least one group selected from a vinylphenyl group, an acryloyl group and a methacryloyl group. Seeds are preferred.
Here, an acryloyl group and a methacryloyl group may be collectively referred to as a "(meth)acryloyl group". A vinylphenyl group is a group having the structure shown below.

(* represents a bond.)

(D) The resin having a radically polymerizable unsaturated group preferably has two or more radically polymerizable unsaturated groups per molecule from the viewpoint of obtaining a cured product with a low dielectric loss tangent.

(D) The resin having a radically polymerizable unsaturated group preferably has a cyclic structure from the viewpoint of obtaining a cured product with a low dielectric loss tangent. As the cyclic structure, a divalent cyclic group is preferred. The divalent cyclic group may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Moreover, you may have two or more divalent cyclic groups.

From the viewpoint of significantly obtaining the desired effect of the present invention, the divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, still more preferably a 5-membered ring or more, and preferably a 20-membered ring. Below, it is more preferably a 15-membered ring or less, still more preferably a 10-membered ring or less. Moreover, the divalent cyclic group may have a monocyclic structure or a polycyclic structure.

The ring in the divalent cyclic group may have a ring skeleton composed of heteroatoms other than carbon atoms. The heteroatom includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc., and an oxygen atom is preferred. The ring may have one heteroatom, or may have two or more.

（２価の基（ｘｉｉ）、（ｘｉｉｉ）中、Ｒ^１、Ｒ^２、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^１１、及びＲ^１２は、それぞれ独立にハロゲン原子、炭素原子数が６以下のアルキル基、又はフェニル基を表し、Ｒ^３、Ｒ^４、Ｒ^８、Ｒ^９、及びＲ^１０は、それぞれ独立に水素原子、ハロゲン原子、炭素原子数６以下のアルキル基、又はフェニル基を表す。） Specific examples of divalent cyclic groups include the following divalent groups (i) to (xiii).

(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 and a represents an alkyl group or a phenyl group, and 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; )

Halogen atoms include fluorine, chlorine, bromine and iodine atoms. The alkyl group having 6 or less carbon atoms includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and the like, preferably methyl group. R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ¹¹ and R ¹² preferably represent a methyl group. R ³ , R ⁴ , R ⁸ , R ⁹ and R ¹⁰ are preferably hydrogen atoms or methyl groups.

（式（ａ）中、Ｒ^２１、Ｒ^２２、Ｒ^２５、Ｒ^２６、Ｒ^２７、Ｒ^３１、Ｒ^３２、Ｒ^３５及びＲ^３６は、それぞれ独立にハロゲン原子、炭素原子数が６以下のアルキル基、又はフェニル基を表し、Ｒ^２３、Ｒ^２４、Ｒ^２８、Ｒ^２９、Ｒ^３０、Ｒ^３３及びＲ^３４は、それぞれ独立に水素原子、ハロゲン原子、炭素原子数６以下のアルキル基、又はフェニル基を表す。ｎ及びｍは、０～３００の整数を表す。但し、ｎ及びｍの一方は０である場合を除く。） Moreover, the divalent cyclic group may be a combination of a plurality of divalent cyclic groups. A specific example of a combination of divalent cyclic groups includes a divalent cyclic group (divalent group (a)) represented by the following formula (a).

(In formula (a), R ²¹ , R ²² , R ²⁵ , R ²⁶ , R ²⁷ , R ³¹ , R ³² , R ³⁵ and R ³⁶ are each independently a halogen atom, an alkyl group having 6 or less carbon atoms, , or represents a phenyl group, and R ²³ , R ²⁴ , R ²⁸ , R ²⁹ , R ³⁰ , R ³³ and R ³⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group represents n and m are integers from 0 to 300, except when 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 represent integers from 0 to 300; However, the case where one of n and m is 0 is excluded. n and m preferably represent an integer of 1-100, more preferably an integer of 1-50, and even more preferably an integer of 1-10. n and m may be the same or different.

The divalent cyclic group is preferably a divalent group (x), a divalent group (xi), or a divalent group (a), and a divalent group (x) or a divalent group (a) is more preferred.

The bivalent cyclic group may have a substituent. Examples of such substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silyl groups, acyl groups, acyloxy groups, carboxy groups, sulfo groups, cyano groups, nitro groups, hydroxy groups, A mercapto group, an oxo group and the like can be mentioned, and an alkyl group is preferred.

The radically polymerizable unsaturated group may be directly bonded to the divalent cyclic group, or may be bonded via a divalent linking group. Examples of divalent linking groups include alkylene groups, alkenylene groups, arylene groups, heteroarylene groups, -C(=O)O-, -O-, -NHC(=O)-, and -NC(=O). Examples include N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, and -NH-, and may be a group combining a plurality of these. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms. is more preferred. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, 1,1-dimethylethylene group and the like. - dimethylethylene group is preferred. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and even more preferably an alkenylene group having 2 to 5 carbon atoms. As the arylene group and heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferable. As the divalent linking group, an alkylene group is preferable, and a methylene group and a 1,1-dimethylethylene group are particularly preferable.

（式（１）中、Ｒ^１及びＲ^４はそれぞれ独立にラジカル重合性不飽和基を表し、Ｒ^２及びＲ^３はそれぞれ独立に２価の連結基を表す。環Ａは、２価の環状基を表す。） (D) The resin having a radically polymerizable unsaturated group is preferably represented by the following formula (1).

(In formula (1), R ¹ and R ⁴ each independently represent a radically polymerizable unsaturated group, R ² and R ³ each independently represent a divalent linking group. Ring A is a divalent cyclic represents a group.)

R ¹ and R ⁴ each independently represent a radically polymerizable unsaturated group, preferably a vinylphenyl group or a (meth)acryloyl group.

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

Ring A represents a divalent cyclic group. Ring A is the same as the divalent cyclic group described above.

Ring A may have a substituent. The substituent is the same as the substituent that the divalent cyclic group may have.

（ｎ１は、式（ａ）中のｎと同じであり、ｍ１は、式（ａ）中のｍと同じである。） Specific examples of component (D) are shown below, 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).)

Component (D) may be a commercially available product, for example, "OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., "A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" manufactured by Kyoeisha Chemical Co., Ltd. ” and the like. Component (D) may be used singly or in combination of two or more.

The number average molecular weight of component (D) is preferably 3,000 or less, more preferably 2,500 or less, still more preferably 2,000 or less, and 1,500 or less, from the viewpoint of significantly obtaining the desired effects of the present invention. The lower limit is preferably 100 or more, more preferably 300 or more, still more preferably 500 or more, and 1000 or more. The number average molecular weight is a polystyrene equivalent number average molecular weight measured using gel permeation chromatography (GPC).

The content of component (D) is preferably 5% by mass or more, more preferably 10% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention. More preferably, it is 15% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

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

An inorganic compound is used as the material of the inorganic filler. Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide , barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as silica, spherical silica is preferable. (E) The inorganic filler may be used singly or in combination of two or more.

(E) Examples of commercially available inorganic fillers include "UFP-30" manufactured by Denka; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials; "YC100C" manufactured by Admatechs. ”, “YA050C”, “YA050C-MJE”, “YA010C”; “Silfil NSS-3N”, “Silfil NSS-4N”, “Silfil NSS-5N” manufactured by Tokuyama; “SC2500SQ” manufactured by Admatechs, "SO-C4", "SO-C2", "SO-C1";

(E) The average particle size 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 of significantly obtaining the desired effects of the present invention, It is preferably 5 µm or less, more preferably 2 µm or less, and still more preferably 1 µm or less.

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

(E) The specific surface area of the inorganic filler is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, and particularly preferably 3 m ² /g or more, from the viewpoint of significantly obtaining the desired effects of the present invention. be. Although there is no particular upper limit, 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 obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec) according to the BET method and calculating the specific surface area using the BET multipoint method. .

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

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

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2-5 parts by mass of a surface treatment agent, and is surface-treated with 0.2-3 parts by mass. preferably 0.3 parts by mass to 2 parts by mass of the surface treatment.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of suppressing the melt viscosity of the resin varnish and the melt viscosity in the sheet form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and further preferably 0.5 mg/m ² or less. preferable.

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

(E) The content of the inorganic filler is preferably 50% by mass or more, more preferably 51% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of lowering the dielectric loss tangent. , more preferably 52% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less.

<Styrene-based elastomer other than component (F) and (C)>
In addition to the component (C), the resin composition may further contain a styrenic elastomer other than the component (F) and (C) within a range that does not affect the effects of the present invention. (F) The styrene-based elastomer different from component (C) refers to a styrene-based elastomer having a styrene unit content of less than 61% by mass when component (F) is taken as 100% by mass. Elements other than the styrene unit content of component (F) may be as described in the section <(C) Styrene-based elastomer>.

The content of styrene units in component (F) is less than 61% by mass, more preferably 50% by mass or less, still more preferably 45% by mass or less when component (F) is 100% by mass. . The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more. The above styrene unit content can be measured, for example, by the charged amount of the monomer constituting the component (F).

Component (F) may be a commercially available product, for example, hydrogenated styrene thermoplastic elastomer “Tuftec MP10” (manufactured by Asahi Kasei Corporation); epoxidized styrene-butadiene thermoplastic elastomer “Epofriend AT501” (manufactured by Daicel Corporation) ) etc. can be mentioned. (F) component may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the component (F) is preferably 1% by mass or more, more preferably 2% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention. More preferably, it is 3% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 10% by mass or less.

<(G) Curing accelerator>
The resin composition may further contain (G) a curing accelerator as an optional component in addition to the components described above.

Examples of curing accelerators include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. Among them, phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, and metallic curing accelerators are preferred, and amine curing accelerators, imidazole curing accelerators, and metallic curing accelerators are more preferred. The curing accelerator may be used singly or in combination of two or more.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo (5,4,0)-undecene and the like, and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and the like, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

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

(G) The content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.01% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the desired effects of the present invention. is 0.03% by mass or more, more preferably 0.05% by mass or more, preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and still more preferably 0.1% by mass or less .

<(H) polymerization initiator>
The resin composition may further contain (H) a polymerization initiator as an optional component in addition to the components described above. (H) The polymerization initiator usually has a function of promoting cross-linking of the radically polymerizable unsaturated groups in the component (D). (H) The polymerization initiator may be used singly or in combination of two or more.

(H) Polymerization initiators include, for example, t-butyl cumyl peroxide, t-butyl peroxyacetate, α,α'-di(t-butylperoxy)diisopropylbenzene, t-butyl peroxylaurate, t -butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, t-butylperoxybenzoate and other peroxides.

(H) Commercially available polymerization initiators include, for example, “Perbutyl C”, “Perbutyl A”, “Perbutyl P”, “Perbutyl L”, “Perbutyl O”, “Perbutyl ND” and “Perbutyl ND” manufactured by NOF Corporation. Perbutyl Z”, “Perbutyl P”, “Perkmyl D” and the like.

(H) The content of the polymerization initiator is preferably 0.01% by mass or more, more preferably 0.01% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the desired effects of the present invention. is 0.05% by mass or more, more preferably 0.1% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.4% by mass or less.

<(I) Other Additives>
The resin composition may further contain other additives as optional components in addition to the components described above. Examples of such additives include thermoplastic resins (excluding components (C), (D) and (F)); organic fillers; thickeners, antifoaming agents, leveling agents, adhesion resin additives such as imparting agents; and the like. These additives may be used singly or in combination of two or more.

<Physical properties and applications of the resin composition>
A resin varnish obtained by dissolving a resin composition in an organic solvent exhibits excellent storage stability. For example, even if the resin varnish is stored at 5° C. for 100 hours and then returned to room temperature, aggregates of 1 mm or more are usually not observed in the resin varnish.

A cured product obtained by thermally curing the resin composition at 200° C. for 90 minutes exhibits a characteristic of low dielectric loss tangent. Thus, the cured product provides an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.005 or less, more preferably 0.0045 or less, and 0.004 or less. On the other hand, the lower limit of the dielectric loss tangent is not particularly limited, but may be 0.0001 or more. The dielectric loss tangent can be evaluated according to the method described in Examples below.

A cured product obtained by thermally curing the resin composition at 130° C. for 30 minutes and then at 170° C. for 30 minutes usually exhibits excellent adhesion strength (peel strength) to the plated conductor layer. Therefore, the cured product provides an insulating layer with excellent peel strength to the plated conductor layer. The peel strength is preferably 0.3 kgf/cm or more, more preferably 0.4 kgf/cm or more, and still 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 evaluation of the peel strength can be measured according to the method described in Examples below.

The resin composition of the present invention can provide an insulating layer having a low dielectric loss tangent and generally high peel strength. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation. Specifically, a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on an insulating layer (resin for forming an insulating layer for forming a conductor layer composition).

Further, in the multilayer printed wiring board described later, the resin composition for forming the insulating layer of the multilayer printed wiring board (the resin composition for forming the insulating layer of the multilayer printed wiring board) and the interlayer insulating layer of the printed wiring board are formed. (a resin composition for forming an interlayer insulating layer of a printed wiring board). Among them, it can be particularly preferably used as a resin composition for forming an insulating layer having a via hole with a top diameter of 45 μm or less, and is particularly preferably used as a resin composition for forming an insulating layer with a thickness of 20 μm or less. be able to.

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

Moreover, since the resin composition of the present invention provides an insulating layer having good component embedding properties, it can be suitably used when the printed wiring board is a component built-in 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, more It is preferably 20 μm or less, more preferably 15 μm or less, and 10 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 1 μm or more, 5 μm or more, or the like.

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

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

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

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

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

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

In one embodiment, the resin sheet may further contain other layers as necessary. Such other layers include, for example, a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, the surface of the resin composition layer can be prevented from being dusted or scratched.

For the resin sheet, for example, a resin varnish is prepared by dissolving a resin composition in an organic solvent, the resin varnish is applied onto a support using a die coater or the like, and dried to form a resin composition layer. It can be manufactured by

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol; carbitols; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

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

A printed wiring board can be manufactured, for example, using the resin sheet described above by a method including the following steps (I) and (II).
(I) Step of laminating the resin composition layer of the resin sheet on the inner layer substrate such that the resin composition layer is bonded to the inner layer substrate (II) Step of thermally curing the resin composition layer to form an insulating layer

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

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

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

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

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

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

In step (II), the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions for the resin composition layer are not particularly limited, and conditions that are commonly used for forming insulating layers of printed wiring boards may be used.

For example, although the thermosetting conditions for 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 still more preferably 170°C to 210°C. °C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 100 minutes.

Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is cured at a temperature of 50° C. or higher and less than 120° C. (preferably 60° C. or higher and 115° C. or lower, more preferably 70° C. or higher and 110° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes).

Since the insulating layer is formed of the cured product of the resin composition of the present invention, it is possible to reduce the thickness of the insulating layer. The thickness of the insulating layer is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less, and 10 μm or less. Although the lower limit is not particularly limited, it can usually be 1 μm or more, 5 μm or more, or the like.

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

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

Since the insulating layer is formed of the cured resin composition of the present invention, it is possible to reduce the top diameter. The top diameter of the hole is preferably 45 μm or less, more preferably 40 μm or less, and more preferably 35 μm or less. The lower limit can be, for example, 1 μm or more.

Step (IV) is a step of roughening the insulating layer. Smear is usually also removed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards can be employed. Moreover, either a dry method or a wet method may be used. When the conductor layer is formed by sputtering, it is preferable to use a dry process such as desmearing using plasma. In particular, the resin composition described above tends to effectively suppress smear when a UV (ultraviolet) laser is used for drilling in step (III), and is suitable for dry desmear.

Gases used in sputtering include, for example, argon, oxygen, and _CF4 . These may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

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

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

In one embodiment, the conductor layer may be formed by a sputtering method. In the sputtering method, a conductor seed layer is first formed on the surface of an insulating layer by sputtering, and then a conductor sputter layer is formed on the conductor seed layer by sputtering. Before forming the conductive seed layer by sputtering, the surface of the insulating layer may be cleaned by reverse sputtering. As the gas used for the reverse sputtering, various gases can be used, among which Ar, O ₂ and N ₂ are preferable. Ar or _O2 or Ar, O2 mixed gas when the seed layer is Cu and Cu alloy _, Ar or _N2 or Ar, _N2 mixed gas when the seed layer is Ti, Cr and Cr alloy (nichrome etc.), Ar or O ₂ or a mixed gas of Ar and O ₂ is preferable. Sputtering can be performed using various sputtering devices such as magnetron sputtering and mirrortron sputtering. Cr, Ni, Ti, nichrome, and the like are examples of metals that form the conductive seed layer. Cr and Ti are particularly preferred. The thickness of the conductor seed layer is usually preferably 5 nm or more, more preferably 10 nm or more, and preferably 1000 nm or less, more preferably 500 nm or less. Cu, Pt, Au, Pd, etc., can be used as the metal forming the conductor sputter layer. Cu is particularly preferred. The thickness of the conductor sputtered layer is usually preferably 50 nm or more, more preferably 100 nm or more, and preferably 3000 nm or less, 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 is preferably 150 nm or less, preferably in the range of 10 to 150 nm, as measured after the conductor seed layer is removed by etching. is more preferable, and 10 to 120 nm or less is more preferable.

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

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

A metal foil can be manufactured by a known method such as an electrolysis method or a rolling method. Examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Co., Ltd., and the like.

Also, in another embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method. An example of forming a conductor layer by a semi-additive method is shown below.

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

[Semiconductor device]
A 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 appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. A "conducting part" is a "part where an electric signal is transmitted on a printed wiring board", and the place may be a surface or an embedded part. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, and the like. Here, "a mounting method using a build-up layer without bumps (BBUL)" refers to a "mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected." is.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, unless otherwise specified, the operations described below were performed in an environment of normal temperature and normal pressure.

[Measurement of peel strength (adhesion strength) between insulating layer and conductor layer]
<Preparation of sample for measurement/evaluation>
(1) Surface treatment of inner layer circuit board Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") on which an inner layer circuit is formed, The copper surface was roughened by etching 1 μm with a micro-etching agent (“CZ8101” manufactured by MEC).

(2) Lamination of resin sheets The resin sheets prepared in Examples and Comparative Examples are batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.), and the resin composition layer is the inner layer circuit board. It laminated|stacked on both surfaces of the inner layer circuit board so that it might contact|connect. Lamination was carried out by reducing the pressure for 30 seconds to an air pressure of 13 hPa or less, followed by laminating at 100° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of Resin Composition Layer The laminated resin sheets were heated at 100° C. for 30 minutes and then at 170° C. for 30 minutes to thermally cure the resin composition layer to form an insulating layer.

(4) Via hole formation by UV-YAG laser Peel off the support to expose the surface of the insulating layer, and use a UV-YAG laser processing machine (“LU-2L212/M50L” manufactured by Via Mechanics Co., Ltd.) to insulate. Via holes were formed in the layer under the following conditions.
Conditions: power 0.30 W, number of shots 25, target top diameter 30 μm

(5) Dry desmear treatment After forming the via hole, the inner layer circuit board on which the insulating layer is formed is treated with O ₂ /CF ₄ (mixed gas ratio) using a vacuum plasma etching device (100-E PLASMA SYSTEM manufactured by Tepla). = 25/75 and a degree of vacuum of 100 Pa for 5 minutes.

(6) Formation of conductor layer by dry method A titanium layer (thickness 30 nm) and then a copper layer (thickness 300 nm) were formed using a sputtering apparatus ("E-400S" manufactured by Canon Anelva). After annealing the obtained substrate by heating it at 150° C. for 30 minutes, an etching resist is formed according to the semi-additive method. A conductor layer was formed with a thickness of After forming the conductor pattern, annealing was performed by heating at 200° C. for 60 minutes. The printed wiring board thus obtained is called "evaluation board A".

<Measurement of peel strength>
The peel strength between the insulating layer and the conductor layer was measured for the evaluation substrate A according to JIS C6481. Specifically, the conductor layer of the evaluation substrate A was cut into a portion having a width of 10 mm and a length of 100 mm. A load (kgf/cm) was measured when 35 mm was peeled off, and the peel strength was determined. A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the measurement.

[Measurement of dielectric loss tangent]
<Preparation of sample for measurement/evaluation>
The resin sheets prepared in Examples and Comparative Examples were heated at 200° C. for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off. The resulting cured product is referred to as “evaluation cured product B”.

<Measurement of dielectric loss tangent>
The cured product B for evaluation was cut into a test piece having a width of 2 mm and a length of 80 mm. The dielectric loss tangent of the test piece was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by the cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies. Two test pieces were measured, and the average value was calculated.

[Evaluation of storage stability of resin varnish]
The resin varnishes prepared in Examples and Comparative Examples were stored at 5° C. for 100 hours. After returning to room temperature (25° C.), aggregates were visually confirmed, and storage stability of the resin varnish was evaluated according to the following criteria.
◯: Aggregates of 1 mm or more are not observed.
×: aggregates of 1 mm or more are observed.

[Example 1]
15 parts of bisphenol A type epoxy resin (“828US” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180), 3 parts of styrene elastomer (hydrogenated styrenic thermoplastic elastomer “Tuftec H1043” manufactured by Asahi Kasei Corporation, styrene content 67%) The solution was heated and dissolved in 25 parts of toluene and 15 parts of MEK while stirring. After cooling to room temperature, 46 parts of a radically polymerizable compound ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., a number average molecular weight of 1200, a toluene solution with a nonvolatile content of 65% by mass), a radically polymerizable compound (Shin Nakamura Chemical Industry "NK Ester A-DOG", molecular weight 326) 30 parts, active ester type curing agent (DIC "EXB9416-70BK", methyl isobutyl ketone solution with active group equivalent weight of about 330 and nonvolatile content of 70% by mass) 28 parts , a triazine skeleton-containing phenolic curing agent (manufactured by DIC "LA-3018-50P", 2-methoxypropanol solution with a hydroxyl equivalent of about 151 and a solid content of 50%) 8 parts, a curing accelerator (N,N-dimethyl-4 -Aminopyridine (DMAP), MEK solution with a solid content of 5% by mass) 6 parts, polymerization initiator (manufactured by NOF Corporation "Percumyl P") 1 part, phenylaminosilane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573 ”) surface-treated spherical silica (average particle size 0.5 μm, specific surface area 5.9 m ² /g, “SO-C2” manufactured by Admatechs) 250 parts are mixed and uniformly dispersed with a high-speed rotating mixer. Then, a resin varnish was produced.

Next, a resin varnish was evenly applied onto the release surface of a release-treated polyethylene terephthalate film ("AL5" manufactured by Lintec, thickness 38 µm) so that the thickness of the resin composition layer after drying was 20 µm. , 80 to 120° C. (average 100° C.) for 3 minutes to prepare a resin sheet.

[Example 2]
15 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269), 3 parts of styrene elastomer (hydrogenated styrenic thermoplastic elastomer "Tuftec P2000" manufactured by Asahi Kasei Co., Ltd., styrene content 67%) The solution was heated and dissolved in 25 parts of toluene and 15 parts of MEK while stirring. After cooling to room temperature, 46 parts of a radically polymerizable compound ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., a number average molecular weight of 1200, a toluene solution with a nonvolatile content of 65% by mass), a radically polymerizable compound (Shin Nakamura Chemical Industry "NK Ester A-DOG" manufactured by DIC Corporation, molecular weight 326) 30 parts, active ester type curing agent ("HPC8000-65T" manufactured by DIC Corporation, a toluene solution with a solid content of 65% by mass) 30 parts, triazine skeleton-containing phenolic curing agent ("LA-3018-50P" manufactured by DIC Corporation, a 2-methoxypropanol solution with a solid content of 50% with a hydroxyl equivalent of about 151) 4 parts, a carbodiimide curing agent (manufactured by Nisshinbo Chemical Co., Ltd. "V-03", an active group equivalent of about 216, a toluene solution with a solid content of 50% by mass) 8 parts, a curing accelerator (N,N-dimethyl-4-aminopyridine (DMAP), a MEK solution with a solid content of 5% by mass) 6 parts, a polymerization initiator (NOF "Perbutyl C" manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part, spherical silica surface-treated with a phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") (average particle size 0.5 μm, specific surface area 5.9 m ² /g , "SO-C2" manufactured by Admatechs Co., Ltd.) were mixed and uniformly dispersed in a high-speed rotating mixer to prepare a resin varnish, and a resin sheet was prepared in the same manner as in Example 1.

[Example 3]
15 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269), 3 parts of styrene elastomer (hydrogenated styrenic thermoplastic elastomer "Tuftec P2000" manufactured by Asahi Kasei Co., Ltd., styrene content 67%) The solution was heated and dissolved in 25 parts of toluene and 15 parts of MEK while stirring. After cooling to room temperature, 60 parts of a radical polymerizable compound (manufactured by Shin-Nakamura Chemical Co., Ltd. "NK Ester A-DOG", molecular weight 326), a triazine skeleton-containing phenolic curing agent (manufactured by DIC "LA-3018-50P ”, 2-methoxypropanol solution with a hydroxyl equivalent of about 151 and a solid content of 50%) 8 parts, curing accelerator (N,N-dimethyl-4-aminopyridine (DMAP), a solid content of 5% by weight MEK solution) 6 parts , 1 part of a polymerization initiator (“PERBUTYL C” manufactured by NOF Corporation), spherical silica surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.5 μm, ratio Surface area 5.9 m ² /g, Admatechs "SO-C2") 250 parts were mixed and uniformly dispersed in a high-speed rotating mixer to prepare a resin varnish, and a resin sheet was prepared in the same manner as in Example 1. bottom.

[Example 4]
15 parts of bisphenol AF type epoxy resin (manufactured by Mitsubishi Chemical Corporation "YL7760", epoxy equivalent of about 238), 20 parts of styrene elastomer (manufactured by Asahi Kasei Corporation, hydrogenated styrenic thermoplastic elastomer "Tuftec H1043", styrene content 67%), 20 parts of another styrenic elastomer (hydrogenated styrenic thermoplastic elastomer “Tuftec MP10” manufactured by Asahi Kasei Corp., styrene content: 30%) was heated and dissolved in 50 parts of toluene and 20 parts of MEK with stirring. After cooling to room temperature, 46 parts of a radically polymerizable compound ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., a number average molecular weight of 1200, a toluene solution with a nonvolatile content of 65% by mass), a radically polymerizable compound (Shin Nakamura Chemical Industry Co., Ltd. "NK Ester A-DOG", molecular weight 326) 30 parts, carbodiimide curing agent (manufactured by Nisshinbo Chemical Co., Ltd. "V-03", active group equivalent weight of about 216, solid content 50 wt% toluene solution) 16 parts, curing Accelerator (N,N-dimethyl-4-aminopyridine (DMAP), MEK solution with a solid content of 5% by mass) 6 parts, polymerization initiator ("Perbutyl C" manufactured by NOF Corporation) 1 part, phenylaminosilane-based coupling 250 parts of spherical silica (average particle size 0.5 μm, specific surface area 5.9 m ² /g, Admatechs “SO-C2”) surface-treated with an agent (Shin-Etsu Chemical Co., Ltd., “KBM573”) is mixed. Then, the resin varnish was prepared by uniformly dispersing it with a high-speed rotating mixer, and a resin sheet was prepared in the same manner as in Example 1.

[Example 5]
15 parts of bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238), 40 parts of styrene elastomer (hydrogenated styrenic thermoplastic elastomer “Tuftec H1043” manufactured by Asahi Kasei Corporation, styrene content 67%) The solution was heated and dissolved in 50 parts of toluene and 20 parts of MEK while stirring. After cooling to room temperature, 46 parts of a radically polymerizable compound ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., a number average molecular weight of 1200, a toluene solution with a nonvolatile content of 65% by mass), a radically polymerizable compound (Shin Nakamura Chemical Industry Co., Ltd. "NK Ester A-DOG", molecular weight 326) 30 parts, benzoxazine-based curing agent (JFE Chemical Co., Ltd. "ODA-BOZ" solid content 50 wt% MEK solution) 16 parts, curing accelerator (N, N-dimethyl-4-aminopyridine (DMAP), MEK solution with a solid content of 5% by mass) 6 parts, polymerization initiator (NOF Corporation "Perbutyl C") 1 part, phenylaminosilane coupling agent (Shin-Etsu Chemical 250 parts of spherical silica (average particle diameter 0.5 μm, specific surface area 5.9 m ² /g, Admatechs “SO-C2”) surface-treated with “KBM573” manufactured by Admatechs) was mixed and mixed with a high-speed rotating mixer. to prepare a resin varnish, and a resin sheet was prepared in the same manner as in Example 1.

[Example 6]
15 parts of bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238), 3 parts of styrene elastomer (hydrogenated styrenic thermoplastic elastomer “Tuftec H1043” manufactured by Asahi Kasei Corporation, styrene content 67%) The solution was heated and dissolved in 25 parts of toluene and 15 parts of MEK while stirring. After cooling to room temperature, 92 parts of a radically polymerizable compound ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., a number average molecular weight of 1200, a toluene solution with a nonvolatile content of 65% by mass), a radically polymerizable compound (Shin Nakamura Chemical Industry Co., Ltd. "NK Ester A-DOG", molecular weight 326) 30 parts, active ester type curing agent (DIC Corporation "HPC8000-65T", solid content 65% by weight toluene solution) 30 parts, carbodiimide curing agent (Nisshinbo Chemical Co., Ltd. "V-03", active group equivalent of about 216, solid content of 50 wt% toluene solution) 16 parts, curing accelerator (N,N-dimethyl-4-aminopyridine (DMAP), solid content of 5 wt% MEK solution) 6 parts, polymerization initiator ("Perbutyl C" manufactured by NOF Corporation) 1 part, spherical silica surface-treated with a phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") (average particle size 0.3 μm, specific surface area 30.7 m ² /g, 200 parts of “UFP-30” manufactured by Denka) were mixed and uniformly dispersed in a high-speed rotating mixer to prepare a resin varnish. A resin sheet was produced.

[Example 7]
Biphenyl type epoxy resin (Nippon Kayaku "NC3000L", epoxy equivalent about 269) 5 parts, bisphenol AF type epoxy resin (Mitsubishi Chemical "YL7760", epoxy equivalent about 238) 10 parts, styrene elastomer (Asahi Kasei Co., Ltd.) Hydrogenated styrenic thermoplastic elastomer “Tuftec P2000”, styrene content 67%) 20 parts, styrene elastomer other than component (C) (Epoxidized styrene-butadiene thermoplastic elastomer “Epofriend AT501” manufactured by Daicel, styrene content of 40%) was dissolved in 50 parts of toluene and 20 parts of MEK by heating while stirring. After cooling to room temperature, 90 parts of a radical polymerizable compound (manufactured by Shin-Nakamura Chemical Co., Ltd. "NK Ester A-DOG", molecular weight 326), an active ester type curing agent (manufactured by DIC "HPC8000-65T", solid content 65 mass% toluene solution) 30 parts, triazine skeleton-containing phenolic curing agent (DIC Corporation "LA-3018-50P", 2-methoxypropanol solution with a hydroxyl equivalent of about 151 and a solid content of 50%) 4 parts, carbodiimide system Curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent weight of about 216, solid content of 50% by weight toluene solution) 8 parts, curing accelerator (N,N-dimethyl-4-aminopyridine (DMAP), solid 5% by weight MEK solution) 6 parts, polymerization initiator ("PERBUTYL C" manufactured by NOF Corporation) 1 part, phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") surface-treated spherical shape 200 parts of silica (average particle size: 0.3 μm, specific surface area: 30.7 m ² /g, “UFP-30” manufactured by Denka) was mixed and uniformly dispersed with a high-speed rotating mixer to prepare a resin varnish. A resin sheet was produced in the same manner as in 1.

[Comparative Example 1]
In Example 1, 3 parts of the styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer "Tuftec H1043" manufactured by Asahi Kasei Co., Ltd., styrene content: 67%) was not used. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

[Comparative Example 2]
In Example 1,
1) Without using 3 parts of styrene elastomer (hydrogenated styrene thermoplastic elastomer "Tuftec H1043" manufactured by Asahi Kasei Corporation, styrene content 67%),
2) Without using 28 parts of an active ester curing agent (“EXB9416-70BK” manufactured by DIC, a methyl isobutyl ketone solution with an active group equivalent of about 330 and a non-volatile content of 70% by mass),
3) 8 parts of a triazine skeleton-containing phenol-based curing agent (“LA-3018-50P” manufactured by DIC, a 2-methoxypropanol solution with a hydroxyl equivalent of about 151 and a solid content of 50%) was added to a carbodiimide-based curing agent (manufactured by Nisshinbo Chemical Co., Ltd. "V-03", active group equivalent weight about 216, toluene solution with a solid content of 50% by mass) changed to 16 parts,
4) 1 part of the polymerization initiator ("Perbutyl P" manufactured by NOF Corporation) was replaced with 1 part of the polymerization initiator ("PERBUTYL C" manufactured by NOF Corporation).
A resin varnish was produced in the same manner as in Example 1 except for the above matters. An attempt was made to produce a resin sheet from this resin varnish in the same manner as in Example 1, but after dispersion with a high-speed rotating mixer, 10 or more aggregates of 1 mm or more were visually observed, so production of the resin sheet was discontinued.

[Comparative Example 3]
In Example 6, 3 parts of styrene elastomer (hydrogenated styrene thermoplastic elastomer "Tuftec H1043" manufactured by Asahi Kasei Co., Ltd., styrene content: 67%) was not used. A resin varnish and a resin sheet were produced in the same manner as in Example 6 except for the above matters.

In Examples 1 to 7, even if the components (E) to (H) are not contained, although there is a difference in degree, it has been confirmed that results similar to those of the above Examples are obtained.

Claims (13)

(A) an epoxy resin,
(B) a curing agent;
(C) a styrenic elastomer,
(D) a resin having a radically polymerizable unsaturated group, and (E) an inorganic filler,
(B) component contains one or more selected from phenol-based curing agents, active ester-based curing agents, carbodiimide-based curing agents, and benzoxazine-based curing agents;
The content of styrene units in component (C) is 61% by mass or more when component (C) is 100% by mass,
(D) component includes those having a cyclic structure and two or more (meth)acryloyl groups per molecule ,
(E) A resin composition in which the content of component is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass (provided by the following formula (1):

(In the formula, each R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an allyl group, or an aryl group having 6 to 10 carbon atoms, and Ar ¹ represents an aromatic hydrocarbon group having 6 to 50 carbon atoms. Each R ² represents a hydrogen group and independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a vinylbenzyl group, and the proportion of the vinylbenzyl group in R ² is 60 to 100 mol %. is an average value in the range of 1 to 20, m is a number from 1 to 6, and r is a number from 1 to 3, provided that m + r does not exceed 6 or 7.) And, in ¹³ C-NMR measurement, the peak area derived from the aldehyde group at 200 to 204 ppm is 10.0% or less with respect to the total peak area including the peak area of the vinyl group at 112 to 115 ppm. A resin composition containing both a (vinylbenzyl) ether compound and a vinyl compound having a number average molecular weight of 100 or more is excluded. ). (A) an epoxy resin,
(B) a curing agent;
(C) a styrenic elastomer,
(D) a resin having a radically polymerizable unsaturated group, and (E) an inorganic filler,
(B) component contains one or more selected from phenol-based curing agents, active ester-based curing agents, carbodiimide-based curing agents, and benzoxazine-based curing agents;
The content of styrene units in component (C) is 61% by mass or more when component (C) is 100% by mass,
Component (D) has a (meth)acryloyl group and has the following formulas (i) to (xiii):

(in formulas (xii) and (xiii), R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ¹¹ , and R ¹² are each independently a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and 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.)
Including those having one or more divalent cyclic groups selected from
A resin composition in which the content of component (E) is 50% by mass or more when the non-volatile component in the resin composition is taken as 100% by mass. (A) an epoxy resin,
(B) a curing agent;
(C) a styrenic elastomer,
(D) a resin having a radically polymerizable unsaturated group, and (E) an inorganic filler,
(B) component contains a phenolic curing agent ,
The content of styrene units in component (C) is 61% by mass or more when component (C) is 100% by mass,
(D) component includes those having a cyclic structure and two or more (meth)acryloyl groups per molecule ,
A resin composition in which the content of component (E) is 50% by mass or more when the non-volatile component in the resin composition is taken as 100% by mass. Claim 1, wherein (F) contains a styrene-based elastomer other than component (C), and the content of styrene units in component (F) is less than 61% by mass when component (F) is taken as 100% by mass. 4. The resin composition according to any one of 3 . 5. The resin composition according to any one of claims 1 to 4 , wherein component (D) has a number average molecular weight of 3,000 or less. The resin composition according to any one of claims 1 to 5 , which is used for forming an insulating layer. The resin composition according to any one of claims 1 to 6 , which is used for forming an insulating layer for forming a conductor layer. The resin composition according to any one of claims 1 to 7 , which is for forming an insulating layer for forming a conductor layer by sputtering or metal foil. The resin composition according to any one of claims 1 to 8 , which is for forming an insulating layer having a via hole with a top diameter of 45 µm or less. The resin composition according to any one of claims 1 to 9 , which is for forming an insulating layer having a thickness of 20 µm or less. A resin sheet comprising a support and a resin composition layer containing the resin composition according to any one of claims 1 to 10 provided on the support. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 10 . A semiconductor device comprising the printed wiring board according to claim 12 .