JP2020015859A - Resin composition - Google Patents

Abstract

To provide a resin composition that makes it possible to obtain a cured product that is excellent in storage stability of resin varnish and low in dielectric loss tangent; a resin sheet containing the resin composition; a printed wiring board including an insulating layer formed using the resin composition; and a semiconductor device.SOLUTION: A resin composition contains (A) an epoxy resin, (B) a curing agent, (C) a styrenic elastomer, and (D) a resin having a radical polymerizable unsaturated group, wherein the content of styrene units in (C) component is 61 mass% or more when (C) component is 100 mass%.SELECTED DRAWING: None

Description

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

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

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

JP-A-2006-147945

  The present inventors have studied a resin composition containing a radically polymerizable compound that makes the entire resin composition less polar in order to obtain an insulating layer having a low dielectric loss tangent. As a result, a new problem has been found that when the radical polymerizable compound is contained in the resin composition, the storage stability of the resin varnish obtained by dissolving the resin composition in an organic solvent is inferior.

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

The present inventors have conducted intensive studies in order to solve the above-described problems, and as a result, in addition to (D) a resin having a radically polymerizable unsaturated group, containing (A) an epoxy resin, (B) a curing agent, and a styrene unit. The present inventors have found that the above-mentioned problems can be solved by a resin composition containing (C) a styrene-based elastomer in a predetermined amount in combination, and completed the present invention.
That is, the present invention includes the following contents.

[1] (A) epoxy resin,
(B) a curing agent,
(C) a styrene-based elastomer, and (D) a resin having a radically polymerizable unsaturated group,
The resin composition, wherein the content of the styrene unit in the component (C) is 61% by mass or more when the component (C) is 100% by mass.
[2] The resin composition according to [1], wherein the content of the component (C) is 0.5% by mass or more and 18% by mass or less when the resin component in the resin composition is 100% by mass.
[3] The resin composition according to [1] or [2], wherein the component (D) includes at least one selected from a vinylphenyl group, an acryloyl group, and a methacryloyl group.
[4] The resin composition according to any one of [1] to [3], wherein the component (D) has a number average molecular weight of 3000 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 the component (E) is 50% by mass or more when the nonvolatile 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 used 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 used for forming an insulating layer having a via hole having 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 including the resin composition according to any one of [1] to [11] provided on the support.
[13] A printed wiring board including 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 having excellent storage stability of a resin varnish and capable of obtaining a cured product having a low dielectric loss tangent; a resin sheet containing the resin composition; formed using the resin composition A printed wiring board and a semiconductor device having an insulating layer can be provided.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and equivalents thereof.

[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 the styrene unit 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 cured product having excellent storage stability of a resin varnish and a low dielectric loss tangent. Furthermore, by using such a resin composition, it is usually possible to increase the peel strength between the conductive layer and the conductive layer.

  The resin composition may further include optional components in combination with the components (A) to (D). Examples of the optional components include (E) an inorganic filler, (F) a styrene-based elastomer other than the (C) component, (G) a curing accelerator, (H) a polymerization initiator, and (I) other additives. And the like. Hereinafter, each component contained in the resin composition will be described in detail.

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

  The resin composition preferably contains, as the epoxy resin (A), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of remarkably obtaining the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass based on 100% by mass of the nonvolatile component of the epoxy resin (A). % Or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more.

  The epoxy resin may be a liquid epoxy resin at a temperature of 20 ° C. (hereinafter, sometimes referred to as “liquid epoxy resin”) or a solid epoxy resin at a temperature of 20 ° C. (hereinafter, “solid epoxy resin”). ). The resin composition may contain only the liquid epoxy resin as the epoxy resin (A), may contain only the solid epoxy resin, or may contain the liquid epoxy resin and the solid epoxy resin in combination. Is also good.

  As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

  Examples of the solid epoxy resin include a bixylenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type epoxy resin is more preferable.

  Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type four-functional epoxy resin) manufactured by DIC; "N-690" (cresol novolak type epoxy resin); DIC "N-695" (cresol novolak type epoxy resin); DIC "HP-7200" (dicyclopentadiene type epoxy resin); “HP-7200HH”, “HP-7200H”, “EXA-7311”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000” (manufactured by DIC Corporation) Naphthylene ether type epoxy resin); "EPPN-502H" (Trisphenol type epoxy resin) manufactured by Nippon Kayaku Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolak type epoxy resin); Nippon Kayaku Co., Ltd. "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); Nippon Steel & Sumitomo Metal Corporation "ESN475V" (naphthol type epoxy resin) manufactured by Chemical Company; "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation; "YX4000H", "YX4000", "YL6121" (biphenyl type) manufactured by Mitsubishi Chemical Corporation. "Epoxy resin"; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-" manufactured by Osaka Gas Chemical Company. 500 ”;“ YL ”manufactured by Mitsubishi Chemical Corporation 760 "(bisphenol AF type epoxy resin);" YL7800 "(fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation;" jER1010 "(solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation;" jER1031S "manufactured by Mitsubishi Chemical Corporation (Tetraphenylethane-type epoxy resin). These may be used alone or in combination of two or more.

  As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

  As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin, ester skeleton Preferred are alicyclic epoxy resins, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, glycidylamine type epoxy resins, and epoxy resins having a butadiene structure, and more preferably bisphenol A type epoxy resins and bisphenol F type epoxy resins.

  Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, and “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC; “828US”, “jER828EL”, “825”, and “Epicoat” manufactured by Mitsubishi Chemical Corporation. "828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical Corporation; manufactured by Mitsubishi Chemical Corporation “630” and “630LSD” (glycidylamine type epoxy resin); “ZX1059” (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical; “EX” manufactured by Nagase ChemteX Corporation -721 "(glycidyl (Stell type epoxy resin); "CELLOXIDE 2021P" (manufactured by Daicel) (alicyclic epoxy resin having an ester skeleton); "PB-3600" (manufactured by Daicel) (epoxy resin having a butadiene structure); "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) and the like. These may be used alone or in combination of two or more.

  (A) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their ratio (liquid epoxy resin: solid epoxy resin) is preferably in a mass ratio of 1: 1 to 1:20. , More preferably 1: 1.5 to 1:15, particularly preferably 1: 2 to 1:10. When the ratio between the liquid epoxy resin and the solid epoxy resin is within the above range, the desired effects of the present invention can be remarkably obtained. Furthermore, when used in the form of a resin sheet, moderate tackiness is usually provided. In addition, usually, when used in the form of a resin sheet, sufficient flexibility is obtained and handleability is improved. Further, usually, a cured product having a sufficient breaking strength can be obtained.

  (A) The epoxy equivalent of the epoxy resin is preferably 50 g / eq. ~ 5000 g / eq. , More preferably 50 g / eq. ~ 3000 g / eq. , More preferably 80 g / eq. ~ 2000 g / eq. , Even more preferably 110 g / eq. ~ 1000 g / eq. It is. Within this range, the crosslinked density of the cured product of the resin composition layer becomes sufficient, and an insulating layer with small surface roughness can be provided. Epoxy equivalent 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, and still more preferably 400 to 1500, from the viewpoint of obtaining the desired effect of the present invention remarkably.
The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

  (A) The content of the epoxy resin is preferably 1% by mass or more, when the nonvolatile component in the resin composition is 100% by mass, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. It is preferably at least 2% by mass, more preferably at least 3% by mass. The upper limit of the content of the epoxy resin is preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less, from the viewpoint 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 nonvolatile component in the resin composition is 100% by mass, unless otherwise specified.

<(B) Curing agent>
The resin composition contains a curing agent as the component (B). The curing agent (B) usually has a function of curing the resin composition by reacting with the epoxy resin (A).

  (B) Examples of the curing agent include an active ester curing agent, a phenol curing agent, a naphthol curing agent, a benzoxazine curing agent, a cyanate ester curing agent, a carbodiimide curing agent, an amine curing agent, and acid anhydride. Physical hardener and the like. (B) As the curing agent, one type may be used alone, or two or more types may be used in combination.

  As the active ester-based curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, as the active ester-based curing agent, two or more ester groups having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. Is preferred. The active ester-based 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-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. .

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

  Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, 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, phloroglucin, Examples include benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolak, and the like. Here, the “dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Preferred specific examples of the active ester-based curing agent include an active ester-based curing agent containing a dicyclopentadiene-type diphenol structure, an active ester-based curing agent containing a naphthalene structure, an active ester-based curing agent containing an acetylated phenol novolak, An active ester-based curing agent containing a benzoylated product of phenol novolak is exemplified. Among them, an active ester-based curing agent containing a naphthalene structure and an active ester-based curing agent containing a dicyclopentadiene-type diphenol structure are more preferable. The “dicyclopentadiene-type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

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

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

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

  Specific examples of the benzoxazine-based curing agent include “ODA-BOZ” manufactured by JFE Chemical Co., “HFB2006M” manufactured by Showa Polymer Co., Ltd., and “Pd” and “Fa” manufactured by Shikoku Chemicals. No.

  Examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4 '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; Phenol novolak and Polyfunctional cyanate resin derived from resol novolac; prepolymer these cyanate resin is partially triazine of; and the like. Specific examples of the cyanate ester-based curing agent include “PT30” and “PT60” (phenol novolak type polyfunctional cyanate ester resin), “ULL-950S” (polyfunctional cyanate ester resin), and “BA230” manufactured by Lonza Japan. , "BA230S75" (a prepolymer in which a part or all of bisphenol A dicyanate is triazined to be a trimer), and the like.

  Specific examples of the carbodiimide-based curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical.

  Examples of the amine-based curing agent include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines. Among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine-based curing agent include 4,4′-methylenebis (2,6-dimethylaniline), diphenyldiaminosulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 3,3 ′. -Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylether, 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. As the amine-based curing agent, a commercially available product may be used. For example, “KAYABOND C-200S”, “KAYABOND C-100”, “Kayahard AA”, “Kayahard AB”, “Kayahard AB”, manufactured by Nippon Kayaku Co., Ltd. "Kayahard AS" and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

  Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic acid Anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride Melitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfonetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hex Hydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione, ethylene glycol bis (anhydrotrimellitate), styrene and maleic acid And a polymer type acid anhydride such as styrene / maleic acid resin copolymerized with

  Among the above, the curing agent (B) is selected from a phenol-based curing agent, an active ester-based curing agent, a carbodiimide-based curing agent, and a benzoxazine-based curing agent, from the viewpoint of significantly obtaining the desired effects of the present invention. It is preferable that at least one kind is used.

  The amount ratio of the epoxy resin (A) to the curing agent (B) is 1: 0 in the ratio of [total number of epoxy groups of component (A)]: [total number of reactive groups of (B) curing agent]. 0.01 to 1:20, more preferably 1: 0.05 to 1:10, and even more preferably 1: 0.1 to 1: 8. Here, “(A) the number of epoxy groups of the epoxy resin” is a value obtained by summing all values obtained by dividing the mass of the nonvolatile component of the (A) epoxy resin present in the resin composition by the epoxy equivalent. Further, “(B) the number of active groups in the curing agent” is a value obtained by summing all values obtained by dividing the mass of the nonvolatile component of the (B) curing agent present in the resin composition by the equivalent of the active group. By setting the ratio of the (A) epoxy resin to the (B) curing agent in such a range, the desired effects of the present invention can be remarkably obtained, and more usually, the cured product of the resin composition layer is used. Heat resistance is further improved.

  The content of the (B) curing agent is preferably 0.1% by mass or more, more preferably 0% by mass, based on 100% by mass of the nonvolatile component in the resin composition, from the viewpoint of obtaining the desired effects of the present invention remarkably. It is at least 0.3% by mass, more preferably at least 0.5% by mass, preferably at most 20% by mass, more preferably at most 15% by mass, further preferably at most 10% by mass.

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

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

  As the styrene-based elastomer (C), any elastomer containing a repeating unit (styrene unit) having a structure obtained by polymerizing styrene can be used. (C) The styrene-based elastomer may be a copolymer containing an arbitrary 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) and a repeating unit having a structure obtained by hydrogenating the same (hydrogenated conjugated diene unit). Can be

  Examples of the conjugated diene 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 remarkably obtaining the effects of the present invention. The conjugated diene may be used alone 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) As the styrene-based elastomer, a styrene-conjugated diene block copolymer and a hydrogenated styrene-conjugated diene copolymer are preferable. As a particularly preferred (C) styrene-based elastomer, for example, a polymer block containing a styrene unit as at least one end block, and a polymer block containing a conjugated diene unit or a hydrogenated conjugated diene unit as at least one intermediate block Block copolymers.

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

  (C) Specific examples of the styrene elastomer include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and 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), Styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene random copolymer and the like can be mentioned.

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

  As the component (C), a commercially available product may be used, and examples thereof include a hydrogenated styrene-based thermoplastic elastomer “TUFTEC H1043” and “TUFTEC P2000”; Can be mentioned. As the component (C), one type may be used alone, or two or more types may be used in combination.

  The content of the component (C) is preferably 0.1% by mass or more, more preferably 0.3% by mass, when the nonvolatile component in the resin composition is 100% by mass, from the viewpoint of remarkably obtaining the effects of the present invention. % By mass or more, more preferably 0.5% by mass or more. The upper limit is preferably 18% by mass or less, more preferably 15% by mass or less, and 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 the component (C) is 100% by mass is C1, and the content when the nonvolatile component in the resin composition of the component (B) is 100% by mass is B1. And In this case, from the viewpoint of remarkably obtaining the effects of the present invention, C1 / B1 is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, and preferably 10 or less, more preferably 10 or less. Preferably it is 5 or less, more preferably 3 or less.

<(D) Resin having radically polymerizable unsaturated group>
The resin composition contains (D) a resin having a radically polymerizable unsaturated group. By including (D) a resin having a radical polymerizable unsaturated group in the resin composition, a cured product having a low dielectric loss tangent can be obtained. When a resin having a radically polymerizable unsaturated group (D) is used, the cured product thereof can usually have a low dielectric loss tangent, while the component (D) undergoes phase separation with the components (A) and (B) to form a resin varnish. Tends to decrease in storage stability. However, in the present invention, by further incorporating the component (C) in combination, phase separation is suppressed, and a cured product having excellent storage stability of the resin varnish and a low dielectric loss tangent can be obtained.

（＊は結合手を表す。） The radically polymerizable unsaturated group refers to a group having an ethylenic double bond that shows curability upon irradiation with active energy rays. Examples of such a group include 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. Preferably it is a seed.
Here, the acryloyl group and the methacryloyl group may be collectively referred to as “(meth) acryloyl group”. Further, a vinylphenyl group is a group having a structure shown below.

(* Represents a bond)

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

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

  The divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, further preferably a 5-membered ring or more, and preferably a 20-membered ring, from the viewpoint of remarkably obtaining the desired effects of the present invention. The number is more preferably 15 or less, more preferably 10 or less. Further, the divalent cyclic group may have a monocyclic structure or a polycyclic structure.

  In the ring of the divalent cyclic group, the ring skeleton may be constituted by hetero atoms other than carbon atoms. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like, and an oxygen atom is preferable. The ring may have one hetero atom or two or more hetero atoms.

（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 the divalent cyclic group 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 carbon atom number of 6 or less. 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. )

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 6 or less carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is preferable. 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 a hydrogen atom or a methyl group.

（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。） Further, the divalent cyclic group may be a combination of a plurality of divalent cyclic groups. As a specific example when a divalent cyclic group is combined, a divalent cyclic group (a divalent group (a)) represented by the following formula (a) can be given.

(In the formula (a), R ²¹ , R ²² , R ²⁵ , R ²⁶ , R ²⁷ , R ³¹ , R ³² , R ³⁵ and R ³⁶ each independently represent a halogen atom or an alkyl group having 6 or less carbon atoms. Or a phenyl group, and R ²³ , R ²⁴ , R ²⁸ , R ²⁹ , R ³⁰ , R ³³ and R ³⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group And n and m represent an integer of 0 to 300, except that 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 the formula (xiii).

  n and m represent an integer of 0 to 300. However, this excludes the case where one of n and m is 0. n and m preferably represent an integer of 1 to 100, more preferably represent an integer of 1 to 50, and still more preferably represent an integer of 1 to 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 is preferably a divalent group (x) or a divalent group (a). Is more preferred.

  The divalent cyclic group may have a substituent. Examples of such a substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, Examples thereof include a mercapto group and an oxo group, and an alkyl group is preferable.

  The radical polymerizable unsaturated group may be directly bonded to a divalent cyclic group, or may be bonded via a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C (= O) O-, -O-, -NHC (= O)-, -NC (= O) Examples include N-, -NHC (= O) O-, -C (= O)-, -S-, -SO-, -NH-, and the like. 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, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a 1,1-dimethylethylene group. -Dimethylethylene groups are 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 still more preferably an alkenylene group having 2 to 5 carbon atoms. As the arylene group and the heteroarylene group, an arylene group or a heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or a heteroarylene group having 6 to 10 carbon atoms is more preferable. As the divalent linking group, an alkylene group is preferable, and among them, a methylene group and a 1,1-dimethylethylene group are 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 the formula (1), R ¹ and R ⁴ each independently represent a radically polymerizable unsaturated group, and R ² and R ³ each independently represent a divalent linking group. Ring A is a divalent cyclic group. Represents a group.)

R ¹ and R ⁴ each independently represent a radically polymerizable unsaturated group, and are 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-described divalent linking group.

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

  Ring A may have a substituent. 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。） Hereinafter, specific examples of the component (D) are shown, but the present invention is not limited thereto.

(N1 is the same as n in the formula (a), and m1 is the same as m in the formula (a).)

  As the component (D), commercially available products may be used. For example, “OPE-2St” manufactured by Mitsubishi Gas Chemical Company, “A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd., and “DCP-A” manufactured by Kyoeisha Chemical Co., Ltd. And the like. As the component (D), one type may be used alone, or two or more types may be used in combination.

  The number average molecular weight of the component (D) is preferably 3,000 or less, more preferably 2,500 or less, further preferably 2,000 or less, from the viewpoint of obtaining the desired effects of the present invention remarkably. 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 number average molecular weight in terms of polystyrene measured using gel permeation chromatography (GPC).

  The content of the component (D) is preferably 5% by mass or more, more preferably 10% by mass or more, when the nonvolatile component in the resin composition is 100% by mass, from the viewpoint of remarkably 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 still more preferably 30% by mass or less.

<(E) Inorganic filler>
The resin composition may further contain (E) an inorganic filler as an optional component other than the components described above.

  An inorganic compound is used as a 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, zirconium tungstate phosphate, and the like. Among these, silica is particularly preferred. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As the silica, spherical silica is preferable. (E) One kind of inorganic filler may be used alone, or two or more kinds may be used in combination.

  (E) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials; "YC100C" manufactured by Admatechs. ", YA050C", "YA050C-MJE", "YA010C"; "Sillfill NSS-3N", "Sillfill NSS-4N", "Sillfill NSS-5N", manufactured by Tokuyama Corporation; "SC2500SQ", manufactured by Admatex, "SO-C4", "SO-C2", "SO-C1"; and the like.

  (E) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, from the viewpoint of obtaining the desired effects of the present invention remarkably. Preferably it is 5 μm or less, more preferably 2 μm or less, further 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 the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter can be measured by setting the median diameter as the average particle diameter. As the measurement sample, a sample in which 100 mg of an inorganic filler and 10 g of methyl ethyl ketone are weighed in a vial and dispersed with ultrasonic waves for 10 minutes can be used. Using a laser diffraction type particle size distribution measuring apparatus, the wavelength of the light source used was set to blue and red, and the volume-based particle size distribution of the inorganic filler (E) was measured by a flow cell method. The average particle diameter can be calculated as the median diameter from the diameter distribution. As the laser diffraction type particle size distribution measuring device, for example, "LA-960" manufactured by Horiba, Ltd. and the like can be mentioned.

(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, particularly preferably 3 m ² / g or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. is there. The upper limit is not particularly limited, but 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 Mountech) 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 improving moisture resistance and dispersibility. Examples of the surface treatment agent include a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane, an organosilazane compound, and a titanate compound. Coupling agents and the like can be mentioned. Further, the surface treatment agent may be used alone or in a combination of two or more.

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

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

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

  The amount of carbon per unit surface area of the inorganic filler can be measured after the inorganic filler after the surface treatment is washed with a solvent (for example, 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 and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. or the like 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 nonvolatile component in the resin composition is 100% by mass, from the viewpoint of reducing the dielectric loss tangent. It is more preferably at least 52% by mass, preferably at most 90% by mass, more preferably at most 85% by mass, further preferably at most 80% by mass.

<Styrene elastomer other than (F) and (C) components>
The resin composition may further contain, in addition to the component (C), a styrene-based elastomer other than the components (F) and (C) as long as the effects of the present invention are not affected. (F) The styrene-based elastomer different from the component (C) means a styrene-based elastomer having a styrene unit content of less than 61% by mass when the component (F) is 100% by mass. Elements other than the styrene unit content of the component (F) may be the same as those described in the section <(C) Styrene-based elastomer>.

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

  As the component (F), a commercially available product may be used. For example, a hydrogenated styrene-based thermoplastic elastomer “Tuftec MP10” (manufactured by Asahi Kasei Corporation); an epoxidized styrene-butadiene thermoplastic elastomer “Epofriend AT501” (manufactured by Daicel Corporation) ) And the like. As the component (F), one type may be used alone, or two or more types may be used in combination.

  The content of the component (F) is preferably 1% by mass or more, more preferably 2% by mass or more, when the nonvolatile component in the resin composition is 100% by mass, from the viewpoint of remarkably obtaining the effects of the present invention. More preferably, it is at least 3% by mass. 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 the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, and a metal-based curing accelerator. Among them, a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are preferred, and an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are more preferred. The curing accelerator may be used alone or in combination of two or more.

  Examples of the phosphorus-based curing accelerator include triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

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

  Examples of the imidazole-based curing accelerator include, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-Ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl Imidazole compounds such as -3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline and adducts of imidazole compounds and epoxy resins; 2-ethyl-4-methylimidazole, 1-benzyl-2- Phenylimidazole is preferred.

  As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine curing accelerator include 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] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  Examples of the metal-based curing accelerator include an organic metal complex or an organic metal salt of a metal such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. And the like, an organic iron complex such as iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

  (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 nonvolatile component in the resin composition is 100% by mass, from the viewpoint of obtaining the desired effect of the present invention remarkably. 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, further 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 generally has a function of promoting the crosslinking of the radically polymerizable unsaturated group in the component (D). (H) The polymerization initiator may be used alone or in combination of two or more.

  (H) Examples of the polymerization initiator include t-butylcumyl peroxide, t-butylperoxyacetate, α, α′-di (t-butylperoxy) diisopropylbenzene, t-butylperoxylaurate, and t-butylperoxylaurate. Peroxides such as -butylperoxy-2-ethylhexanoate t-butylperoxyneodecanoate and t-butylperoxybenzoate.

  (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 "," Park Mill P "," Park Mill 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, assuming that the nonvolatile component in the resin composition is 100% by mass, from the viewpoint of remarkably obtaining the desired effect 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 (however, components (C), (D) and (F) are excluded); organic fillers; thickeners, defoamers, leveling agents, and adhesiveness. Resin additives such as imparting agents; and the like. These additives may be used alone or in a combination of two or more.

<Physical properties and applications of resin composition>
A resin varnish obtained by dissolving a resin composition in an organic solvent exhibits characteristics of being excellent in storage stability. For example, even if the resin varnish is stored at 5 ° C. for 100 hours and then returned to room temperature, usually, no aggregate of 1 mm or more is observed in the resin varnish.

  A cured product obtained by thermally curing the resin composition at 200 ° C. for 90 minutes has a characteristic of a low dielectric loss tangent. Therefore, the cured product provides an insulating layer having 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 value of the dielectric loss tangent is not particularly limited, but may be 0.0001 or more. The evaluation of the dielectric loss tangent can be measured according to the method described in Examples described later.

  A cured product obtained by thermally curing the resin composition at 130 ° C. for 30 minutes and then at 170 ° C. for 30 minutes generally exhibits excellent adhesion strength (peel strength) with the plated conductor layer. Therefore, the cured product provides an insulating layer having excellent peel strength with 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 described later.

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

  In a multilayer printed wiring board described later, a resin composition for forming an insulating layer of the multilayer printed wiring board (resin composition for forming an insulating layer of the multilayer printed wiring board) and an interlayer insulating layer of the printed wiring board are formed. (A resin composition for forming an interlayer insulating layer of a printed wiring board) can be suitably used. Above all, it can be used particularly preferably as a resin composition for forming an insulating layer having a via hole having a top diameter of 45 μm or less, and is particularly preferably used as a resin composition for forming an insulating layer having 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 for a rewiring forming layer as an insulating layer for forming a rewiring layer. (A resin composition for forming a rewiring formation layer) and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer.
(1) a step of laminating a temporary fixing film on a substrate,
(2) temporarily fixing the semiconductor chip on the temporary fixing film,
(3) forming a sealing layer on the semiconductor chip;
(4) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;
(5) a step of forming a rewiring forming layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off; and (6) forming a rewiring layer as a conductor layer on the rewiring forming layer. Forming process

  Further, since the resin composition of the present invention provides an insulating layer having a good component embedding property, it can be suitably used even 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 on the support and formed of the resin composition of the present invention.

  The thickness of the resin composition layer is preferably 30 μm or less, from the viewpoint that the thickness of the printed wiring board can be reduced, and a cured product having excellent insulation properties can be provided even when the cured product of the resin composition is a thin film. Preferably it is 20 μm or less, more preferably 15 μm or less, 10 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can usually be 1 μm or more, 5 μm or more.

  Examples of the support include a film made of a plastic material, a metal foil, and 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, the plastic material may be, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) or polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”). .), Acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), and polyethers. Ketone, polyimide and the like can be mentioned. 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 a copper foil and an aluminum foil, and a copper foil is preferable. 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 another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. May be used.

  The support may have been subjected to a mat treatment, a corona treatment, or an antistatic treatment on the surface to be joined to the resin composition layer.

  Further, as the support, a support with a release layer having a release layer on the surface to be joined to the resin composition layer may be used. Examples of the release agent used in the release layer of the support having a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . The support with a release layer may be a commercially available product, for example, "SK-1" manufactured by Lintec, which is a PET film having a release layer containing an alkyd resin-based release agent as a main component. AL-5 "," AL-7 "," Lumirror T60 "manufactured by Toray Industries," Purex "manufactured by Teijin Limited," Unipeal "manufactured by Unitika, and the like.

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

  In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include, for example, a protective film similar to the support provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Can be Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the attachment and scratches of dust and the like to the surface of the resin composition layer.

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

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetates 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. The organic solvent may be used alone or in combination of two or more.

  Drying may be performed by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it depends 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 an organic solvent, the resin composition is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. An object layer can be formed.

  The resin sheet can be wound and stored in a roll shape. 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.

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

  The “inner layer substrate” used in the step (I) is a member to be a substrate of a printed wiring board, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate And the like. Further, the substrate may have a conductor layer on one or both surfaces thereof, and the conductor layer may be patterned. An inner substrate having a conductor layer (circuit) formed on one or both surfaces of the substrate may be referred to as an “inner circuit substrate”. In the manufacture of a printed wiring board, an intermediate product on which an insulating layer and / or a conductor layer is to be formed is also included in the “inner substrate” of the present invention. When the printed wiring board is a circuit board with a built-in component, an inner layer board with a built-in component 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 a member (hereinafter, also referred to as a “thermocompression member”) that heat-presses the resin sheet to the inner layer substrate include, for example, a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll). It is preferable that the thermocompression bonding member is not pressed directly on the resin sheet, but is pressed via an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner substrate.

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

  Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials Co., Ltd., and a batch vacuum pressurized laminator.

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

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

  In the step (II), the insulating layer is formed by thermosetting the resin composition layer. The thermosetting conditions of the resin composition layer are not particularly limited, and conditions usually employed when forming an insulating layer of a printed wiring board may be used.

  For example, the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition and the like, but 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 from 5 minutes to 120 minutes, more preferably from 10 minutes to 100 minutes, even more preferably from 15 minutes to 100 minutes.

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

  Since the insulating layer is formed from a cured product of the resin composition of the present invention, the thickness of the insulating layer can be reduced. The thickness of the insulating layer is preferably 30 μm or less, more preferably 20 μm or less, and 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.

  In manufacturing the printed wiring board, (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) may be performed according to various methods used for manufacturing a printed wiring board and known to those skilled in the art. 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 It may be performed between IV) and step (V). If necessary, the formation of the insulating layer and the conductor layer in the steps (II) to (V) may be repeated to form a multilayer wiring board.

  The step (III) is a step of forming a hole in the insulating layer, whereby a hole such as a via hole or a through hole 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 size and shape of the hole may be appropriately determined according to the design of the printed wiring board.

  Since the insulating layer is formed of a cured product of the resin composition of the present invention, the top diameter can be reduced. 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 may be 1 μm or more.

  Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear is also removed. The procedure and conditions of the roughening treatment are not particularly limited, and well-known procedures and conditions usually used when forming an insulating layer of a printed wiring board can be adopted. Further, either a dry type or a wet type may be used. When the conductor layer is formed by sputtering, it is preferable that the conductor layer be formed by a dry method such as desmear treatment using plasma. In particular, the above-mentioned resin composition tends to be able to effectively suppress smear when a UV (ultraviolet) laser is used for drilling in the step (III), and is suitable for dry desmear.

As a gas used for sputtering, for example, argon, oxygen, CF _{4 and the} like can be mentioned. These may be used alone or in combination of two or more.

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

  Step (V) is a step of forming a conductor layer, and 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 conductive layer is 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. Including metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper Nickel alloy and copper-titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper An alloy layer of a nickel alloy or a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable.

  The conductor layer may have a single-layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are stacked. 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 a nickel-chromium alloy.

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

In one embodiment, the conductor layer may be formed by a sputtering method. In the sputtering method, first, a conductor seed layer is formed on the insulating layer surface by sputtering, and then a conductor sputter layer is formed on the conductor seed layer by sputtering. Before forming the conductor seed layer by sputtering, the surface of the insulating layer may be cleaned by reverse sputtering. Various gases can be used as the gas used for the reverse sputtering, but among them, Ar, O ₂ , and N ₂ are preferable. Ar or O ₂ or a mixed gas of Ar and O ₂ when the seed layer is Cu and a Cu alloy; Ar or N ₂ or a mixed gas of Ar and N ₂ when the seed layer is Ti; and a Cr and Cr alloy (Nichrome In this case, Ar or O ₂ or a mixed gas of Ar and O ₂ is preferable. Sputtering can be performed using various sputtering apparatuses such as magnetron sputtering and mirrortron sputtering. Examples of the metal forming the conductor seed layer include Cr, Ni, Ti, nichrome, and the like. Particularly, Cr and Ti are preferable. The thickness of the conductor seed layer is usually preferably 5 nm or more, more preferably 10 nm or more, preferably 1000 nm or less, more preferably 500 nm or less. Examples of the metal forming the conductor sputter layer include Cu, Pt, Au, Pd, and the like. Particularly, Cu is preferable. The thickness of the conductor sputtered layer is usually preferably 50 nm or more, more preferably 100 nm or more, preferably 3000 nm or less, more preferably 1000 nm or less.

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

  After forming the conductor layer by the sputtering method, 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, preferably 75 μm or less, more preferably 35 μm or less. 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 a conductor layer is formed using a metal foil, step (V) is preferably performed between step (I) and step (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. The lamination of the resin composition layer and the metal foil may be performed by a vacuum lamination method. The conditions for lamination may be the same as the conditions for laminating the inner layer substrate and the resin sheet. Next, the step (II) is performed to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern may be formed by a subtractive method, a modified semi-additive method, or the like.

  The metal foil can be manufactured by a known method such as an electrolytic method and a rolling method. Examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferable. 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 another metal (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, JXUT-III foil, 3EC-III foil, TP-III foil, etc., manufactured by Mitsui Kinzoku Mining Co., Ltd.

  In another embodiment, the conductor layer may be formed by plating. For example, a semi-additive method, plating on the surface of the insulating layer by a conventionally known technique such as a full-additive method can form a conductor layer having a desired wiring pattern, and from the viewpoint of simplicity of manufacture, semi-additive. It is preferably formed by a method. Hereinafter, an example in which a conductor layer is formed by a semi-additive method will be described.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern for exposing a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like, so that a conductor layer having a desired wiring pattern can be formed.

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

  Examples of the semiconductor device include various semiconductor devices used for electric appliances (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  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. The “conduction point” is a “point where an electric signal is transmitted on the printed wiring board”, and the point may be a surface or an embedded point. 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. Specifically, a wire bonding mounting method, a flip chip mounting method, a bumpless build-up layer, and the like. (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the “mounting method using the bump-less build-up layer (BBUL)” refers to a “mounting method for directly embedding a semiconductor chip in a recess of a printed wiring board and connecting the semiconductor chip to wiring on the printed wiring board”. It is.

  Hereinafter, the present invention will be described specifically 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. The operations described below were performed in a normal temperature and normal pressure environment unless otherwise specified.

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

(2) Lamination of Resin Sheets The resin sheets prepared in the Examples and Comparative Examples were prepared by using a batch-type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.) so that the resin composition layer and the inner circuit board were used. They were laminated on both sides of the inner circuit board so as to be in contact with each other. The lamination was performed by reducing the pressure to 13 hPa or less by reducing the pressure for 30 seconds, and then performing a lamination treatment at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of Resin Composition Layer The laminated resin sheet was 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) Formation of via holes by UV-YAG laser The support was peeled off to expose the surface of the insulating layer, and the insulation was performed using a UV-YAG laser processing machine ("LU-2L212 / M50L" manufactured by Via Mechanics). 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 the formation of the via holes, the inner layer circuit board on which the insulating layer was formed was subjected to O ₂ / CF ₄ (mixed gas ratio) using a vacuum plasma etching apparatus (Tepla 100-E PLASMA SYSTEM). = 25/75 and a degree of vacuum of 100 Pa for 5 minutes.

(6) Formation of Conductive 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 heating the obtained substrate at 150 ° C. for 30 minutes to perform an annealing process, an etching resist is formed according to a semi-additive method, and after patterning by exposure and development, copper sulfate electrolytic plating is performed to obtain a 25 μm To form a conductor layer. After the formation of the conductor pattern, annealing was performed by heating at 200 ° C. for 60 minutes. The obtained printed wiring board is referred to as “evaluation board A”.

<Measurement of peel strength>
The measurement of the peel strength between the insulating layer and the conductor layer was performed on the evaluation substrate A in accordance with JIS C6481. Specifically, a cut of 10 mm in width and 100 mm in length is made in the conductor layer of the evaluation board A, and one end thereof is peeled off and gripped with a gripper, and is vertically moved at room temperature at a speed of 50 mm / min. The load (kgf / cm) when 35 mm was peeled off was measured to determine the peel strength. For the measurement, a tensile tester (“AC-50C-SL” manufactured by TSE) was used.

[Measurement of dielectric loss tangent]
<Preparation of sample for measurement and evaluation>
The resin sheet prepared in each of Examples and Comparative Examples was heated at 200 ° C. for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off. The obtained cured product is referred to as “evaluated 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 a cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies. The measurement was performed on two test pieces, 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 the temperature was returned to room temperature (25 ° C.), the aggregate was visually confirmed, and the storage stability of the resin varnish was evaluated according to the following criteria.
〇: Aggregates of 1 mm or more are not observed.
X: 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: about 180) and 3 parts of styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer “Tuftec H1043” manufactured by Asahi Kasei Corporation, 67% of styrene content) were used. The mixture 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 radical polymerizable compound (“OPE-2St” manufactured by Mitsubishi Gas Chemical Company, a toluene solution having a number average molecular weight of 1200 and a nonvolatile content of 65% by mass) and a radical polymerizable compound (Shin-Nakamura Chemical Co., Ltd.) 30 parts of "NK Ester A-DOG" (manufactured by DIC Corporation), 28 parts of an active ester-type curing agent ("EXB9416-70BK" manufactured by DIC, a solution of 70% by mass of a nonvolatile content of 70% by mass of methyl isobutyl ketone having an active group equivalent of about 330) 8 parts of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC, 2-methoxypropanol solution having a hydroxyl equivalent of about 151 and a solid content of 50%), and a curing accelerator (N, N-dimethyl-4) -Aminopyridine (DMAP), 6 parts by weight of MEK solution having a solid content of 5 parts), 1 part of a polymerization initiator ("Park Mill P" manufactured by NOF Corporation) Aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd., "KBM573") surface-treated with a spherical silica (average particle size 0.5 [mu] m, a specific surface area of 5.9 m ² / g, Admatechs Co., "SO-C2") 250 parts were mixed and uniformly dispersed by a high-speed rotation mixer to prepare a resin varnish.

  Next, a resin varnish was uniformly applied on the release surface of a release-treated polyethylene terephthalate film (“AL5” manufactured by Lintec Co., thickness 38 μm) so that the thickness of the resin composition layer after drying was 20 μm. , And dried at 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., epoxy equivalent about 269) and 3 parts of styrene elastomer (hydrogenated styrene thermoplastic elastomer “Tuftec P2000” manufactured by Asahi Kasei Corporation, styrene content 67%) The mixture 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 radical polymerizable compound (“OPE-2St” manufactured by Mitsubishi Gas Chemical Company, a toluene solution having a number average molecular weight of 1200 and a nonvolatile content of 65% by mass) and a radical polymerizable compound (Shin-Nakamura Chemical Co., Ltd.) 30 parts of "NK Ester A-DOG" (manufactured by DIC Corporation), 30 parts of an active ester type curing agent ("HPC8000-65T" manufactured by DIC, a toluene solution having a solid content of 65% by mass), and a phenolic curing agent having a triazine skeleton. 4 parts of (LA-3018-50P manufactured by DIC, 2-methoxypropanol solution having a hydroxyl equivalent of about 151 and a solid content of 50%), carbodiimide-based curing agent (“V-03” manufactured by Nisshinbo Chemical Inc., active group equivalent: about 216, 8 parts of a toluene solution having a solid content of 50% by mass), a curing accelerator (N, N-dimethyl-4-aminopyridine (DMAP), a solid content of 5 % Of MEK solution), 1 part of a polymerization initiator ("Perbutyl C" manufactured by NOF CORPORATION), and spherical silica ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) surface-treated with a phenylaminosilane coupling agent ("KBM573"). 250 parts of an average particle diameter of 0.5 μm, a specific surface area of 5.9 m ² / g, and “SO-C2” manufactured by Admatechs Co., Ltd. were mixed and uniformly dispersed with a high-speed mixer to produce a resin varnish. In the same manner as in the above, a resin sheet was produced.

[Example 3]
15 parts of a biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., epoxy equivalent: about 269) and 3 parts of a styrene elastomer (hydrogenated styrene thermoplastic elastomer "Tuftec P2000" manufactured by Asahi Kasei Corporation, 67% styrene content) were used. The mixture 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 (“NK Ester A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight: 326) and a phenolic curing agent containing a triazine skeleton (“LA-3018-50P” manufactured by DIC) 8 parts of a 50% solids 2-methoxypropanol solution having a hydroxyl equivalent of about 151) and 6 parts of a curing accelerator (N, N-dimethyl-4-aminopyridine (DMAP), a 5% by mass solids MEK solution) 1 part of a polymerization initiator (“Perbutyl C” manufactured by NOF CORPORATION) and spherical silica (average particle size: 0.5 μm, surface ratio) treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 250 parts of a surface area of 5.9 m ² / g, “SO-C2” manufactured by Admatechs Co., Ltd.) were mixed and uniformly dispersed with a high-speed rotating mixer to prepare a resin varnish. Thus, a resin sheet was produced.

[Example 4]
15 parts of bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 238), 20 parts of styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer “Tuftec H1043” manufactured by Asahi Kasei Corporation, styrene content: 67%), 20 parts of another styrene-based elastomer (Hydrogenated styrene-based thermoplastic elastomer “Toughtec MP10” manufactured by Asahi Kasei Corporation, styrene content 30%) 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 radical polymerizable compound (“OPE-2St” manufactured by Mitsubishi Gas Chemical Company, a toluene solution having a number average molecular weight of 1200 and a nonvolatile content of 65% by mass) and a radical polymerizable compound (Shin-Nakamura Chemical Co., Ltd.) 30 parts of "NK Ester A-DOG" (molecular weight: 326), 16 parts of a carbodiimide-based curing agent ("V-03" manufactured by Nisshinbo Chemical Inc., active group equivalent: about 216, toluene solution having a solid content of 50% by mass), and curing 6 parts of accelerator (N, N-dimethyl-4-aminopyridine (DMAP), MEK solution having a solid content of 5% by mass), 1 part of polymerization initiator ("Perbutyl C" manufactured by NOF Corporation), phenylaminosilane coupling Silica (average particle size: 0.5 μm, specific surface area: 5.9 m ² / g, surface-treated with an agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), “SO-C manufactured by Admatechs Co., Ltd.” 2)) 250 parts were mixed and uniformly dispersed with a high-speed rotary mixer to produce a resin varnish, and a resin sheet was produced 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: about 238) and 40 parts of a styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer “Tuftec H1043” manufactured by Asahi Kasei Corporation, 67% styrene content) were used. The mixture 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 radical polymerizable compound (“OPE-2St” manufactured by Mitsubishi Gas Chemical Company, a toluene solution having a number average molecular weight of 1200 and a nonvolatile content of 65% by mass) and a radical polymerizable compound (Shin-Nakamura Chemical Co., Ltd.) 30 parts of "NK Ester A-DOG" (molecular weight: 326), 16 parts of a benzoxazine-based curing agent (MEK solution having a solid content of 50% by mass of "ODA-BOZ" manufactured by JFE Chemical Company), and a curing accelerator (N, 6 parts of N-dimethyl-4-aminopyridine (DMAP), MEK solution having a solid content of 5% by mass), 1 part of polymerization initiator ("Perbutyl C" manufactured by NOF CORPORATION), phenylaminosilane-based coupling agent (Shin-Etsu Chemical Co., Ltd.) 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 KK Were mixed and uniformly dispersed by a high-speed rotary mixer to produce a resin varnish, and a resin sheet was produced 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: about 238) and 3 parts of styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer “Tuftec H1043” manufactured by Asahi Kasei Corporation, 67% of styrene content) were used. The mixture was heated and dissolved in 25 parts of toluene and 15 parts of MEK while stirring. After cooling to room temperature, there are 92 parts of a radical polymerizable compound (“OPE-2St” manufactured by Mitsubishi Gas Chemical Company, a toluene solution having a number average molecular weight of 1200 and a nonvolatile content of 65% by mass), and a radical polymerizable compound (Shin Nakamura Chemical Industry) 30 parts of "NK Ester A-DOG" (manufactured by DIC Corporation), 30 parts of an active ester type curing agent ("HPC8000-65T" manufactured by DIC, a toluene solution having a solid content of 65% by mass), and a carbodiimide-based curing agent (Nisshinbo Chemical) 16 parts of "V-03", an active group equivalent of about 216, a solid solution of 50% by mass in toluene solution, a curing accelerator (N, N-dimethyl-4-aminopyridine (DMAP), 5% by mass of solid content) 6 parts of MEK solution), 1 part of polymerization initiator ("Perbutyl C" manufactured by NOF Corporation), phenylaminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) Surface-treated spherical silica was mixed (average particle size 0.3 [mu] m, a specific surface area of 30.7m ² / g, Denka Co. "UFP-30") 200 parts, uniformly dispersed in a resin varnish in a high-speed rotary mixer A resin sheet was prepared in the same manner as in Example 1.

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

[Comparative Example 1]
In Example 1, 3 parts of a styrene-based elastomer (a hydrogenated styrene-based thermoplastic elastomer “TUFTEC H1043” manufactured by Asahi Kasei Corporation, styrene content: 67%) was not used. Except for the above, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Comparative Example 2]
In Example 1,
1) Without using 3 parts of a styrene-based elastomer (Hydrogenated styrene-based thermoplastic elastomer “Tuftec H1043” manufactured by Asahi Kasei Corporation, styrene content 67%),
2) without using 28 parts of an active ester type curing agent ("EXB9416-70BK" manufactured by DIC, a solution of 70% by mass of a nonvolatile content of a methyl isobutyl ketone having an active group equivalent of about 330);
3) 8 parts of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC, a 2-methoxypropanol solution having a hydroxyl equivalent of about 151 and a solid content of 50%) are combined with a carbodiimide-based curing agent (manufactured by Nisshinbo Chemical Inc.). "V-03", an active group equivalent of about 216, a solid solution of 50% by mass in toluene solution) was changed to 16 parts,
4) 1 part of the polymerization initiator ("Park Mill P" manufactured by NOF Corporation) was changed to 1 part of the polymerization initiator ("PERBUTYL C" manufactured by NOF Corporation).
A resin varnish was prepared in the same manner as in Example 1 except for the above. An attempt was made to prepare a resin sheet from this resin varnish in the same manner as in Example 1. However, after dispersion by a high-speed rotary mixer, 10 or more aggregates having a size of 1 mm or more were visually observed, and the preparation of the resin sheet was stopped.

[Comparative Example 3]
In Example 6, 3 parts of a styrene-based elastomer (a hydrogenated styrene-based thermoplastic elastomer “ToughTech H1043” manufactured by Asahi Kasei Corporation, styrene content: 67%) was not used. A resin varnish and a resin sheet were prepared in the same manner as in Example 6 except for the above.

  In Examples 1 to 7, it was confirmed that even when the components (E) to (H) were not contained, the results were similar to those of the above examples, although the degree was different.

Claims (14)

(A) epoxy resin,
(B) a curing agent,
(C) a styrene-based elastomer, and (D) a resin having a radically polymerizable unsaturated group,
The resin composition, wherein the content of the styrene unit in the component (C) is 61% by mass or more when the component (C) is 100% by mass.   The resin composition according to claim 1, wherein the content of the component (C) is 0.5% by mass or more and 18% by mass or less when the resin component in the resin composition is 100% by mass.   3. The resin composition according to claim 1, wherein the component (D) includes at least one selected from a vinylphenyl group, an acryloyl group, and a methacryloyl group. 4.   The resin composition according to any one of claims 1 to 3, wherein the number average molecular weight of the component (D) is 3,000 or less.   The resin composition according to any one of claims 1 to 4, further comprising (E) an inorganic filler.   The resin composition according to claim 5, wherein the content of the component (E) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass.   The resin composition according to any one of claims 1 to 6, which is used for forming an insulating layer.   The resin composition according to any one of claims 1 to 7, which is used for forming an insulating layer for forming a conductor layer.   The resin composition according to any one of claims 1 to 8, which is used 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 9, which is for forming an insulating layer having a via hole having a top diameter of 45 µm or less.   The resin composition according to any one of claims 1 to 10, which is used for forming an insulating layer having a thickness of 20 µm or less.   A resin sheet comprising: a support; and a resin composition layer including the resin composition according to claim 1 provided on the support.   A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to claim 1.   A semiconductor device comprising the printed wiring board according to claim 13.