JP2014034580A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition not only having smaller arithmetic average roughness of an insulator layer surface at a wet type roughening treatment step, but also having smaller root-mean-square roughness, and in addition, capable of forming a plated conductor layer having a stable peel strength and having lower dielectric loss tangent.SOLUTION: A resin composition includes: (A) a radical-polymerizable compound; (B) an epoxy resin; (C) a hardening agent and (D) a roughening treatment component.

Description

  The present invention relates to a resin composition. Furthermore, it is related with the sheet-like laminated material, multilayer printed wiring board, and semiconductor device containing the said resin composition.

  2. Description of the Related Art In recent years, electronic devices have been reduced in size and performance, and in multilayer printed wiring boards, build-up layers have been multilayered, and miniaturization and high density of wiring have been demanded. As the signal frequency increases, the build-up layer is also required to have a low dielectric loss tangent.

  Various approaches have been made against this. For example, Patent Document 1 discloses a thermosetting resin composition containing a polyfunctional vinylbenzyl ether compound, a solvent-soluble polyimide, and a thermosetting catalyst, but has a large surface roughness and a large dielectric loss tangent. The performance was not enough.

JP 2005-281673 A

  The problem to be solved by the present invention is that the plating conductor layer having not only a small arithmetic average roughness of the insulating layer surface in the wet roughening process but also a small root mean square roughness and a stable and sufficient peel strength. It is also possible to provide a resin composition having a low dielectric loss tangent.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention in a resin composition containing a radical polymerizable compound, an epoxy resin, a curing agent and a roughening component. It came.

［Ｒ_１〜Ｒ_６はそれぞれ独立に水素、炭素数１〜４のアルキル基である。Ａは下記式（２）又は下記式（３）である。］

［Ｂは下記構造式Ｂ−１、Ｂ−２又はＢ−３である。］

［Ｄは下記式（４）である。］

［Ｒ_７〜Ｒ_１４はそれぞれ独立に水素、炭素数６以下のアルキル基またはフェニル基である。ａ、ｂは、少なくとも一方が０でない０〜１００の整数である。Ｂは下記構造式Ｂ−１、Ｂ−２又はＢ−３である。］

［Ｒ_１５〜Ｒ_３４はそれぞれ独立に水素、炭素数６以下のアルキル基またはフェニル基である。Ｅは、炭素数２０以下の直鎖状、分岐状又は環状の２価の炭化水素基である。］
〔４〕 前記（Ａ）ラジカル重合性化合物の数平均分子量が、１００〜１００００の範囲であることを特徴とする〔１〕〜〔３〕のいずれか記載の樹脂組成物。
〔５〕 樹脂組成物中の不揮発成分を１００質量％とした場合、前記（Ａ）ラジカル重合性化合物の含有量が、５〜４０質量％であることを特徴とする〔１〕〜〔４〕のいずれか記載の樹脂組成物。
〔６〕 前記（Ｂ）エポキシ樹脂が、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、グリシジルエステル型エポキシ樹脂及びアントラセン型エポキシ樹脂より選択される１種以上であることを特徴とする〔１〕〜〔５〕のいずれか記載の樹脂組成物。
〔７〕 樹脂組成物中の不揮発成分を１００質量％とした場合、前記（Ｂ）エポキシ樹脂の含有量が、１〜３０質量％であることを特徴とする〔１〕〜〔６〕のいずれか記載の樹脂組成物。
〔８〕 前記（Ｃ）硬化剤が、活性エステル型硬化剤及び／又はシアネートエステル型硬化剤を含有することを特徴とする〔１〕〜〔７〕のいずれか記載の樹脂組成物。
〔９〕 前記（Ｃ）硬化剤が、活性エステル型硬化剤を含有することを特徴とする〔１〕〜〔８〕のいずれか記載の樹脂組成物。
〔１０〕 樹脂組成物中の不揮発成分を１００質量％とした場合、前記（Ｃ）硬化剤の含有量が、１〜３０質量％であることを特徴とする〔１〕〜〔９〕のいずれか記載の樹脂組成物。
〔１１〕 前記（Ｄ）粗化成分が、ポリブタジエン樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ポリイミド樹脂、ポリアセタール樹脂、ポリカーボネート樹脂、ポリメタクリル酸メチル樹脂、ポリエステル樹脂、ポリウレタン樹脂から選択される１種以上を含有することを特徴とする〔１〕〜〔１０〕のいずれか記載の樹脂組成物。
〔１２〕 前記（Ｄ）粗化成分が、ポリブタジエン樹脂を含有することを特徴とする〔１〕〜〔１１〕のいずれか記載の樹脂組成物。
〔１３〕 前記（Ｄ）粗化成分が、ブタジエン骨格と、反応性基とを有するポリブタジエン樹脂を含有することを特徴とする〔１〕〜〔１２〕のいずれか記載の樹脂組成物。
〔１４〕 前記（Ｄ）粗化成分の数平均分子量が、３００〜３００００の範囲であることを特徴とする〔１〕〜〔１３〕のいずれか記載の樹脂組成物。
〔１５〕 樹脂組成物中の不揮発成分を１００質量％とした場合、前記（Ｃ）粗化成分の含有量が、０．５〜２０質量％であることを特徴とする〔１〕〜〔１４〕のいずれか記載の樹脂組成物。
〔１６〕 （Ｅ）無機充填材を含有することを特徴とする〔１〕〜〔１５〕のいずれか記載の樹脂組成物。
〔１７〕 前記（Ｅ）無機充填材がスチリルシラン系カップリング剤で表面処理されていることを特徴とする〔１６〕記載の樹脂組成物。
〔１８〕 樹脂組成物を硬化して絶縁層を形成し、その絶縁層表面を粗化処理した後の算術平均粗さが１０〜３００ｎｍであり、二乗平均平方根粗さが１５〜４５０ｎｍであることを特徴とする〔１〕〜〔１７〕のいずれか記載の樹脂組成物。
〔１９〕 樹脂組成物を硬化して絶縁層を形成し、その絶縁層表面を粗化処理し、メッキして得られる導体層と絶縁層とのピール強度が０．３〜１．２ｋｇｆ／ｃｍであることを特徴とする〔１〕〜〔１８〕のいずれか記載の樹脂組成物。
〔２０〕 樹脂組成物の硬化物の誘電正接が０．００３以下であることを特徴とする〔１〕〜〔１９〕のいずれかに記載の樹脂組成物。
〔２１〕 多層プリント配線板の絶縁層用樹脂組成物であることを特徴とする〔１〕〜〔２０〕のいずれか記載の樹脂組成物。
〔２２〕 多層プリント配線板のビルドアップ層用樹脂組成物であることを特徴とする〔１〕〜〔２１〕のいずれか記載の樹脂組成物。
〔２３〕 〔１〕〜〔２２〕のいずれか記載の樹脂組成物を含有することを特徴とするシート状積層材料。
〔２４〕 〔２３〕記載のシート状積層材料を用いることを特徴とする多層プリント配線板。
〔２５〕 〔２４〕記載の多層プリント配線板を用いることを特徴とする半導体装置。 That is, the present invention includes the following contents.
[1] A resin composition comprising (A) a radical polymerizable compound, (B) an epoxy resin, (C) a curing agent, and (D) a roughening component.
[2] The resin according to [1], wherein the radically polymerizable compound (A) has at least one selected from a styryl group, an allyl group, a vinyl group, an acrylic group, a methacryl group, and a propenyl group. Composition.
[3] The resin composition according to [1] or [2], wherein the (A) radical polymerizable compound is a compound represented by the following formula (1).

[R _{1 to} R ₆ are each independently hydrogen and an alkyl group having 1 to 4 carbon atoms. A is the following formula (2) or the following formula (3). ]

[B is the following structural formula B-1, B-2, or B-3. ]

[D is the following formula (4). ]

[R _{7 to} R ₁₄ are each independently hydrogen, an alkyl group having 6 or less carbon atoms, or a phenyl group. a and b are integers of 0 to 100, at least one of which is not 0. B is the following structural formula B-1, B-2, or B-3. ]

[R _{15 to} R ₃₄ are each independently hydrogen, an alkyl group having 6 or less carbon atoms, or a phenyl group. E is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. ]
[4] The resin composition according to any one of [1] to [3], wherein the number average molecular weight of the radically polymerizable compound (A) is in the range of 100 to 10,000.
[5] When the nonvolatile component in the resin composition is 100% by mass, the content of the (A) radical polymerizable compound is 5 to 40% by mass. [1] to [4] The resin composition in any one of these.
[6] The epoxy resin (B) is bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, glycidyl ester type epoxy resin. And an anthracene-type epoxy resin, which is at least one selected from the group consisting of [1] to [5].
[7] Any of [1] to [6], wherein the content of the epoxy resin (B) is 1 to 30% by mass when the nonvolatile component in the resin composition is 100% by mass. A resin composition as described above.
[8] The resin composition according to any one of [1] to [7], wherein the (C) curing agent contains an active ester type curing agent and / or a cyanate ester type curing agent.
[9] The resin composition according to any one of [1] to [8], wherein the (C) curing agent contains an active ester type curing agent.
[10] Any of [1] to [9], wherein the content of the curing agent (C) is 1 to 30% by mass when the nonvolatile component in the resin composition is 100% by mass. A resin composition as described above.
[11] The roughening component (D) is one or more selected from polybutadiene resin, polyamide resin, polyamideimide resin, polyimide resin, polyacetal resin, polycarbonate resin, polymethyl methacrylate resin, polyester resin, and polyurethane resin. The resin composition according to any one of [1] to [10], which is contained.
[12] The resin composition according to any one of [1] to [11], wherein the roughening component (D) contains a polybutadiene resin.
[13] The resin composition according to any one of [1] to [12], wherein the roughening component (D) contains a polybutadiene resin having a butadiene skeleton and a reactive group.
[14] The resin composition according to any one of [1] to [13], wherein the number average molecular weight of the (D) roughening component is in the range of 300 to 30000.
[15] When the nonvolatile component in the resin composition is 100% by mass, the content of the roughening component (C) is 0.5 to 20% by mass [1] to [14] ] The resin composition in any one of these.
[16] The resin composition according to any one of [1] to [15], which contains an inorganic filler (E).
[17] The resin composition as described in [16], wherein the (E) inorganic filler is surface-treated with a styrylsilane coupling agent.
[18] The resin composition is cured to form an insulating layer, the arithmetic average roughness after roughening the surface of the insulating layer is 10 to 300 nm, and the root mean square roughness is 15 to 450 nm. The resin composition according to any one of [1] to [17].
[19] The resin composition is cured to form an insulating layer, the surface of the insulating layer is roughened, and the peel strength between the conductor layer and the insulating layer obtained by plating is 0.3 to 1.2 kgf / cm The resin composition according to any one of [1] to [18], wherein
[20] The resin composition according to any one of [1] to [19], wherein the dielectric loss tangent of the cured product of the resin composition is 0.003 or less.
[21] The resin composition according to any one of [1] to [20], which is a resin composition for an insulating layer of a multilayer printed wiring board.
[22] The resin composition according to any one of [1] to [21], which is a resin composition for a buildup layer of a multilayer printed wiring board.
[23] A sheet-like laminated material comprising the resin composition according to any one of [1] to [22].
[24] A multilayer printed wiring board using the sheet-like laminated material according to [23].
[25] A semiconductor device using the multilayer printed wiring board according to [24].

  By using a resin composition characterized by containing a radical polymerizable compound, an epoxy resin, a curing agent and a roughening component, not only the arithmetic average roughness of the insulating layer surface is small but also the square in the wet roughening step. A plated conductor layer having a small average square root roughness and a stable and sufficient peel strength can be formed thereon, and a resin composition having a low dielectric loss tangent can be provided.

  The present invention is a resin composition comprising (A) a radical polymerizable compound, (B) an epoxy resin, (C) a curing agent and (D) a roughening component. Hereinafter, the resin composition will be described in detail.

<(A) Radical polymerizable compound>
The radical polymerizable compound used in the present invention is not particularly limited as long as it has a radical polymerizable group. By using a radically polymerizable compound, the dielectric loss tangent of the cured product can be reduced. Examples of the radical polymerizable group include styryl group, allyl group, vinyl group, acrylic group, methacryl group, propenyl group, and the like, from the viewpoint of excellent storage stability, styryl group, allyl group, vinyl group, acrylic group, It preferably has one or more selected from a methacryl group and a propenyl group, and more preferably has a styryl group from the viewpoint of excellent heat resistance.

  Specifically, a compound represented by the following formula (1) is preferable.

［Ｒ_１〜Ｒ_６はそれぞれ独立に水素、炭素数１〜４のアルキル基であり、好ましくは水素である。Ａは下記式（２）又は下記式（３）である。］

[R _{1 to} R ₆ are each independently hydrogen and an alkyl group having 1 to 4 carbon atoms, preferably hydrogen. A is the following formula (2) or the following formula (3). ]

［Ｂは下記構造式Ｂ−１、Ｂ−２又はＢ−３である。］

[B is the following structural formula B-1, B-2, or B-3. ]

［Ｄは下記式（４）である。］

[D is the following formula (4). ]

［Ｒ_７〜Ｒ_１４はそれぞれ独立に水素、炭素数６以下のアルキル基またはフェニル基であり、好ましくは水素またはメチル基である。特にＲ_７、Ｒ_８、Ｒ_１３、Ｒ_１４はメチル基がより好ましい。ａ、ｂは、少なくとも一方が０でない０〜１００の整数である。Ｂは下記構造式Ｂ−１、Ｂ−２又はＢ−３である。］

[R _{7 to} R ₁₄ are each independently hydrogen, an alkyl group having 6 or less carbon atoms, or a phenyl group, preferably hydrogen or a methyl group. In particular, R ₇ , R ₈ , R ₁₃ and R ₁₄ are more preferably methyl groups. a and b are integers of 0 to 100, at least one of which is not 0. B is the following structural formula B-1, B-2, or B-3. ]

［Ｒ_１５〜Ｒ_３４はそれぞれ独立に水素、炭素数６以下のアルキル基またはフェニル基であり、好ましくは水素またはメチル基である。Ｅは、炭素数２０以下の直鎖状、分岐状又は環状の２価の炭化水素基である。］

[R _{15 to} R ₃₄ are each independently hydrogen, an alkyl group having 6 or less carbon atoms, or a phenyl group, preferably hydrogen or a methyl group. E is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. ]

  More specifically, a compound represented by the following formula (5) or the following formula (6) is more preferable.

［Ｒ_１〜Ｒ_６、Ｂ、ａ、ｂは、上記と同様である。］

[R _{1 to} R ₆ , B, a, and b are the same as described above. ]

  Examples of commercially available radical polymerizable compounds include styrene-modified polyphenylene ether resins ("OPE-2St (number average molecular weight 1200)" manufactured by Mitsubishi Gas Chemical Co., Ltd., equivalent to general formula (5)), bixylenol diallyl ether resins ( “YL7776 (number average molecular weight 331)” manufactured by Mitsubishi Chemical Corporation, corresponding to general formula (6)), and the like.

  The number average molecular weight of the radically polymerizable compound is preferably in the range of 100 to 10000 from the viewpoint of preventing volatilization when the resin varnish is dried and preventing the melt viscosity of the resin composition from being excessively increased. More preferably, it is the range. In addition, the number average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  In the resin composition of the present invention, from the viewpoint of improving the compatibility of the resin composition, when the nonvolatile component in the resin composition is 100% by mass, the content of the radical polymerizable compound is preferably 5 to 40% by mass, 10-30 mass% is more preferable.

<(B) Epoxy resin>
The epoxy resin used in the present invention is not particularly limited, but is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol. Type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, wire Aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type Carboxymethyl resin, trimethylol type epoxy resins, and halogenated epoxy resins. These may be used alone or in combination of two or more.

  Among these, from the viewpoint of improving peel strength while reducing surface roughness, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene It is preferable to use one or more selected from ether type epoxy resins, glycidyl ester type epoxy resins and anthracene type epoxy resins. Specifically, for example, bisphenol A type epoxy resin (“Epicoat 828EL”, “YL980” manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (“jER806H”, “YL983U” manufactured by Mitsubishi Chemical Corporation), Naphthalene type bifunctional epoxy resin (“HP4032”, “HP4032D”, “HP4032SS”, “EXA4032SS” manufactured by DIC Corporation), naphthalene type tetrafunctional epoxy resin (“HP4700”, “HP4710” manufactured by DIC Corporation), Naphthol type epoxy resin (“ESN-475V” manufactured by Nippon Steel Chemical Co., Ltd.), epoxy resin having biphenyl structure (“NC3000H”, “NC3000L”, “NC3100” manufactured by Nippon Kayaku Co., Ltd., Mitsubishi Chemical Corporation) ) "YX4000", "YX4000H", "YX4000HK" , “YL6121”), anthracene type epoxy resin (“YX8800” manufactured by Mitsubishi Chemical Corporation), naphthylene ether type epoxy resin (“EXA-7310”, “EXA-7311”, “EXA-7311L manufactured by DIC Corporation) ”,“ EXA7311-G3 ”), glycidyl ester type epoxy resin (“ EX711 ”manufactured by Nagase ChemteX Corporation,“ EX721 ”,“ R540 ”manufactured by Printec Co., Ltd.), and the like. In particular, biphenyl type epoxy resins are preferred because they exhibit low roughness and high peel strength.

  In the resin composition of the present invention, from the viewpoint of improving the mechanical strength and water resistance of the cured product of the resin composition, when the nonvolatile component in the resin composition is 100% by mass, the content of the epoxy resin is 1 to 1%. 30 mass% is preferable, 2-20 mass% is more preferable, and 3-10 mass% is still more preferable.

<(C) Curing agent>
The curing agent used in the present invention is not particularly limited, and examples thereof include an active ester type curing agent, a cyanate ester type curing agent, a phenol type curing agent, a benzoxazine type curing agent, and the like, further reducing the surface roughness, From the viewpoint of reducing the dielectric loss tangent, it is preferable to use an active ester type curing agent and / or a cyanate ester type curing agent, and it is more preferable to use an active ester type curing agent. These may be used alone or in combination of two or more.

  The active ester type curing agent is not particularly limited, but generally an ester group having high reaction activity such as phenol ester, thiophenol ester, N-hydroxyamine ester, heterocyclic hydroxy compound ester or the like in one molecule. A compound having two or more in the above is preferably used. The active ester type 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 type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester type curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. 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, phenolphthaline, 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, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like. The active ester type curing agent includes an active ester type curing agent having a dicyclopentadienyl diphenol structure, an active ester type curing agent having a naphthalene structure, an active ester type curing agent which is an acetylated product of phenol novolac, and phenol novolac. An active ester type curing agent that is a benzoylated product is preferable, and in particular, an active ester type curing agent containing a dicyclopentadienyl diphenol structure and an active ester type curing agent containing a naphthalene structure are excellent in terms of improving the peel strength. More preferred is an active ester type curing agent containing a dicyclopentadienyl diphenol structure.

  As the active ester type curing agent, an active ester type curing agent disclosed in JP-A-2004-277460 may be used, or a commercially available one may be used. Specifically, as an active ester type curing agent containing a dicyclopentadienyl diphenol structure, EXB9451, EXB9460, EXB9460S-65T, HPC-8000-65T (manufactured by DIC Corporation, active group equivalent of about 223), naphthalene structure EXB9416-70BK (manufactured by DIC Corporation, active group equivalent of about 274) as an active ester-type curing agent containing DC, and DC808 (manufactured by Mitsubishi Chemical Corporation, active group equivalent as an active ester type curing agent which is an acetylated product of phenol novolak) 149), YLH1026 (manufactured by Mitsubishi Chemical Corporation, active group equivalent of about 200), YLH1030 (manufactured by Mitsubishi Chemical Corporation, active group equivalent of about 201), YLH1048 as an active ester type curing agent which is a benzoylated phenol novolak (Mitsubishi Chemical Corporation, active group equivalent of about 245) And the like.

  Although there is no restriction | limiting in particular as a cyanate ester type hardening | curing agent, A novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening | curing agent, dicyclopentadiene type cyanate ester type hardening | curing agent, bisphenol type (bisphenol A type, bisphenol) Fate, bisphenol S type, etc.) cyanate ester type curing agents, and prepolymers in which these are partially triazines. Although the weight average molecular weight of a cyanate ester type hardening | curing agent is not specifically limited, 500-4500 are preferable and 600-3000 are more preferable. Specific examples of the cyanate ester type curing agent include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3, Bifunctional cyanate resins such as 5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether , Phenol novolac, Examples thereof include polyfunctional cyanate resins derived from resole novolac, dicyclopentadiene structure-containing phenol resins, prepolymers in which these cyanate resins are partially triazines, and these may be used alone or in combination of two or more. Examples of commercially available cyanate ester resins include phenol novolac polyfunctional cyanate ester resins (manufactured by Lonza Japan Co., Ltd., PT30, cyanate equivalent 124), and some or all of bisphenol A dicyanate are triazines and trimers. The prepolymer (Lonza Japan Co., Ltd. product, BA230, cyanate equivalent 232), dicyclopentadiene structure containing cyanate ester resin (Lonza Japan Co., Ltd. product, DT-4000, DT-7000) etc. are mentioned.

  The phenol type curing agent is not particularly limited, but a biphenyl type curing agent, a naphthalene type curing agent, a phenol novolac type curing agent, a naphthylene ether type curing agent, and a triazine skeleton-containing phenol type curing agent are preferable. Specifically, biphenyl type curing agents MEH-7700, MEH-7810, MEH-7785 (Maywa Kasei Co., Ltd.), naphthalene type curing agents NHN, CBN, GPH (Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Nippon Steel Chemical Co., Ltd.), EXB9500 (manufactured by DIC Corporation), phenol novolac type curing agent TD2090 (manufactured by DIC Corporation), Examples include naphthylene ether type curing agents EXB-6000 (manufactured by DIC Corporation), triazine skeleton-containing phenol type curing agents LA3018, LA7052, LA7054, LA1356 (manufactured by DIC Corporation), and the like.

  Although there is no restriction | limiting in particular as a benzoxazine type hardening | curing agent, As a specific example, Fa, Pd (made by Shikoku Kasei Co., Ltd.), HFB2006M (made by Showa Polymer Co., Ltd.), etc. are mentioned.

  In the resin composition of the present invention, from the viewpoint of reducing the dielectric loss tangent of the cured product of the resin composition, when the nonvolatile component in the resin composition is 100% by mass, the content of the curing agent is 1 to 30% by mass. Is preferable, 2-20 mass% is more preferable, and 3-10 mass% is still more preferable.

  In the resin composition of the present invention, from the viewpoint of improving the mechanical strength and water resistance of the cured product of the resin composition, the ratio of the total number of epoxy groups of the epoxy resin and the total number of reactive groups of the curing agent is: 1: 0.2-1: 2 is preferable, 1: 0.3-1: 1.5 is more preferable, and 1: 0.4-1: 1 is still more preferable. The total number of epoxy groups of the epoxy resin present in the resin composition is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the reactive group of the curing agent. The total number of is a value obtained by adding the values obtained by dividing the solid mass of each curing agent by the reactive group equivalent for all curing agents.

<(D) Roughening component>
The roughening component used in the present invention is not particularly limited as long as it can impart peel strength by roughening by desmear treatment. For example, as the roughening component, it is preferable to use at least one selected from polybutadiene resin, polyamide resin, polyamideimide resin, polyimide resin, polyacetal resin, polycarbonate resin, polymethyl methacrylate resin, polyester resin, and polyurethane resin. Of these, polybutadiene resin is more preferred from the viewpoint of low dielectric loss tangent and roughening property. Further, the roughening component preferably has a reactive group, and by having the reactive group, a uniform cured product is obtained, so that a sufficient peel strength can be obtained while keeping the surface roughness after the roughening treatment low. become. Examples of the reactive group include a carboxylic acid group, an acid anhydride group, a hydroxyl group, and an epoxy group. Among them, an acid anhydride group is preferable from the viewpoint of low dielectric loss tangent. Therefore, as one embodiment, a polybutadiene resin having a butadiene skeleton and a reactive group is preferable, and a polybutadiene resin having a butadiene skeleton, a reactive group, and a polyimide skeleton is preferable. In addition, it can be set as the roughening component which does not impair heat resistance by having a polyimide frame | skeleton.

  Specific examples of the roughening component include polybutadiene resins having a butadiene skeleton and a hydroxyl group (G-1000, G-3000, GI-1000, GI-3000, manufactured by Nippon Soda Co., Ltd.), and polybutadiene having a butadiene skeleton and a hydroxyl group. Resin (R-45EPI manufactured by Idemitsu Petrochemical Co., Ltd.), polybutadiene resin having butadiene skeleton and epoxy group (PB3600 manufactured by Daicel Chemical Industries, Ltd.), polybutadiene resin having butadiene skeleton, acid anhydride group and polyimide skeleton ( And the like described in JP-A-2006-37083).

  The number average molecular weight of the roughening component is preferably in the range of 300 to 30000, more preferably in the range of 800 to 15000. By setting the number average molecular weight within this range, compatibility and roughening properties in the resin composition can be achieved. In addition, the number average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  In the resin composition of the present invention, the content of the roughening component when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of enabling the production of a uniform cured product without impairing the compatibility of the resin. 0.5-20 mass% is preferable, and 1-10 mass% is more preferable.

<(E) Inorganic filler>
The resin composition of the present invention can lower the dielectric loss tangent by further containing an inorganic filler. Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Examples include strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, silica is preferable. In addition, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and mesoporous silica is preferable, and fused silica is more preferable. Further, the silica is preferably spherical. You may use these 1 type or in combination of 2 or more types. Examples of commercially available spherical fused silica include “SO-C2” and “SO-C1” manufactured by Admatechs.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less, from the viewpoint of forming fine wiring on the insulating layer. 7 μm or less is even more preferable. On the other hand, when the resin composition is a varnish, it is preferably 0.01 μm or more, more preferably 0.05 μm or more, and more preferably 0.1 μm from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from decreasing. The above is more preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-950 manufactured by Horiba, Ltd. or the like can be used.

  The content in the case of blending the inorganic filler is not particularly limited, but from the viewpoint of reducing the dielectric loss tangent and preventing the flexibility of the film form from being reduced, the nonvolatile component in the resin composition is 100%. When it is set as mass%, 40-85 mass% is preferable, 45-80 mass% is more preferable, 50-75 mass% is still more preferable.

  Inorganic fillers include amino silane coupling agents, ureido silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, silane coupling agents, vinyl silane coupling agents, and styryl silane coupling agents. Surface treatment with surface treatment agents such as acrylate silane coupling agents, isocyanate silane coupling agents, sulfide silane coupling agents, organosilazane compounds, titanate coupling agents, etc. to improve its moisture resistance and dispersibility Are preferred. These may be used alone or in combination of two or more.

  Specifically, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane Aminosilane coupling agents such as N-2 (-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, 3-ureidopropyltriethoxysilane, etc. Ureidosilane coupling agent, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane Epoxysilane coupling agents such as glycidylbutyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyl Mercaptosilane-based coupling agents such as dimethoxysilane and 11-mercaptoundecyltrimethoxysilane, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacroxypropyltrimethoxysilane, imidazolesilane, triazinesilane, t- Silane coupling agents such as butyltrimethoxysilane, vinylsilane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxysilane. Ring agent, styrylsilane coupling agent such as p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyltri Acrylate silane coupling agents such as ethoxysilane and 3-methacryloxypropyldiethoxysilane, isocyanate silane coupling agents such as 3-isocyanatopropyltrimethoxysilane, bis (triethoxysilylpropyl) disulfide, bis (triethoxysilyl) Propyl) sulfide silane coupling agents such as tetrasulfide, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexaphenyl Silazane, trisilazane, cyclotrisilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldi Silazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1, Organosilazane compounds such as 3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, tetramethyldisilazane, tetra-n -Butyl titanate dimer, titanium-i-propo Xyloctylene glycolate, tetra-n-butyl titanate, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate , Bis (dioctylpyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis ( Ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite Isopropyl trioctanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tridodecylbenzene sulfonyl titanate, isopropyl And titanate coupling agents such as tris (dioctylpyrophosphate) titanate and isopropyltri (N-amidoethyl / aminoethyl) titanate. Commercially available products include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM1403" manufactured by Shin-Etsu Chemical Co., Ltd. (P-styryltrimethoxysilane) and the like. Among these, when the inorganic filler is surface-treated with a styrylsilane coupling agent, it is excellent in reducing the dielectric loss tangent and is preferable.

<(F) Curing accelerator>
The resin composition of this invention can harden an epoxy resin and a hardening | curing agent efficiently by containing a hardening accelerator further. Although it does not specifically limit as a hardening accelerator, An amine hardening accelerator, a guanidine hardening accelerator, an imidazole hardening accelerator, a phosphonium hardening accelerator, a metal hardening accelerator, etc. are mentioned. These may be used alone or in combination of two or more.

  The amine curing accelerator is not particularly limited, but trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl). And amine compounds such as phenol and 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU). You may use these 1 type or in combination of 2 or more types.

  Although it does not specifically limit as a guanidine type hardening accelerator, Dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, dimethyl guanidine , 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-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl Rubiguanido, 1-(o-tolyl) biguanide, and the like. You may use these 1 type or in combination of 2 or more types.

  The imidazole curing accelerator is not particularly limited, but 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 tri Meritate 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-dihydroxymethyl Imidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1 Dodecyl-2-methyl-3-benzyl-imidazolium chloride, 2-methyl-imidazoline, adduct of 2-phenyl-imidazo imidazole compounds such as phosphorus and imidazole compound and an epoxy resin. You may use these 1 type or in combination of 2 or more types.

  Although it does not specifically limit as a phosphonium type hardening accelerator, Triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. You may use these 1 type or in combination of 2 or more types.

  Although content in particular when mix | blending a hardening accelerator (except a metal type hardening accelerator) is not restrict | limited, When the non-volatile component in a resin composition is 100 mass%, it is the range of 0.005-1 mass%. Is preferable, and the range of 0.01-0.5 mass% is more preferable. Within this range, thermosetting can be performed more efficiently, and the storage stability of the resin varnish is improved.

  Although it does not specifically limit as a metal type hardening accelerator, The organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned. 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. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.

  The addition amount in the case of adding a metal curing accelerator is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, the metal content based on the metal curing catalyst is in the range of 25 to 500 ppm. Is preferable, and the range of 40 to 200 ppm is more preferable. Within this range, a conductor layer having superior adhesion to the surface of the insulating layer is formed, and the storage stability of the resin varnish is also improved.

<(G) Polymerization initiator>
The resin composition of the present invention can efficiently cure the radical polymerizable compound by further containing a polymerization initiator. The type of the polymerization initiator is not particularly limited, but cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydro gen. Examples of the radical generator include peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, and 2,3-dimethyl-2,3-diphenylbutane. You may use these 1 type or in combination of 2 or more types.

  Although content in particular when mix | blending a polymerization initiator is not restrict | limited, When the non-volatile component in a resin composition is 100 mass%, 0.1-3 mass% is preferable, and 0.2-2 mass% is preferable. More preferred. Within this range, an increase in dielectric loss tangent can be prevented.

<(H) Rubber particles>
When the resin composition of the present invention further contains rubber particles, the plating peel strength can be improved, and drilling workability can be improved, the dielectric loss tangent can be reduced, and the stress relaxation effect can be obtained. The rubber particles that can be used in the present invention are, for example, those that do not dissolve in an organic solvent used when preparing the varnish of the resin composition and are incompatible with an epoxy resin or the like. Accordingly, the rubber particles exist in a dispersed state in the varnish of the resin composition of the present invention. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it does not dissolve in an organic solvent or resin and making it into particles.

  Preferable examples of the rubber particles include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which an outer shell layer is made of a glassy polymer and an inner core layer is made of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glassy polymer layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). Two or more rubber particles may be used in combination. Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N, AC3401N, IM-401 modified 7-17 (trade name, manufactured by Gantz Kasei Co., Ltd.), Metabrene KW-4426 (trade name, Mitsubishi Rayon Co., Ltd.) Manufactured). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size: 0.5 μm, manufactured by JSR Corporation). Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include Methbrene W300A (average particle size 0.1 μm) and W450A (average particle size 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.).

  The average particle size of the rubber particles is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of the rubber particles used in the present invention can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and a particle size distribution of rubber particles is created on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). And it can measure by making the median diameter into an average particle diameter.

  The content in the case of blending rubber particles is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, 0.05 to 10% by mass is preferable, and 0.5 to 5% by mass is more preferable. preferable.

<Other ingredients>
In the resin composition of the present invention, other components can be blended as necessary within a range not inhibiting the effects of the present invention. Other components include vinyl benzyl compounds, acrylic compounds, maleimide compounds, thermosetting resins such as blocked isocyanate compounds, organic fillers such as silicon powder, nylon powder and fluorine powder, thickeners such as Orben and Benton, Silicone-based, fluorine-based, polymer-based antifoaming agent or leveling agent, imidazole-based, thiazole-based, triazole-based, silane coupling agent and other adhesion-imparting agents, phthalocyanine blue, phthalocyanine green, iodin green, disazo Examples thereof include colorants such as yellow and carbon black, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, flame retardants such as metal hydroxides, and the like.

  The resin composition of the present invention is appropriately mixed with the above components and, if necessary, kneaded or mixed by a kneading means such as a three-roll, ball mill, bead mill, or sand mill, or a stirring means such as a super mixer or a planetary mixer. It can be adjusted by doing. Moreover, it can adjust also as a resin varnish by adding an organic solvent.

  In the resin composition of the present invention, a plated conductor layer having not only a small arithmetic average roughness on the surface of the insulating layer in the wet roughening step but also a small root mean square roughness and a stable and sufficient peel strength thereon. Can be formed, and the dielectric loss tangent can also be lowered. Therefore, it is suitably used as a resin composition (resin composition for an insulating layer of a multilayer printed wiring board) for forming an insulating layer in the production of a multilayer printed wiring board. And can be more suitably used as a resin composition for forming a conductor layer by plating (resin composition for an insulating layer of a multilayer printed wiring board on which a conductor layer is formed by plating). That is, it is suitable as a resin composition for buildup layers of multilayer printed wiring boards.

  The arithmetic average roughness (Ra value) after curing the resin composition of the present invention to form an insulating layer and roughening the surface of the insulating layer is described below <arithmetic average roughness (Ra Value) and root mean square roughness (Rq) measurement>. Specifically, the upper limit of the arithmetic average roughness (Ra value) is preferably 300 nm or less, more preferably 250 nm or less, still more preferably 200 nm or less, even more preferably 150 nm or less, and even more preferably 130 nm for the formation of fine wiring. The following are particularly preferred: The lower limit value of the arithmetic average roughness (Ra value) is not particularly limited, and is 10 nm or more, 50 nm or more, 80 nm or more, and the like.

  Since the root mean square roughness (Rq value) reflects the local state of the insulating layer surface, it was found that the surface of the insulating layer can be confirmed to be dense and smooth by grasping the Rq value. The upper limit of the root mean square roughness (Rq value) is preferably 450 nm or less, more preferably 400 nm or less, even more preferably 350 nm or less, and even more preferably 300 nm or less in order to obtain a dense and smooth insulating layer surface. 250 nm or less is particularly preferable. From the viewpoint of stabilizing the peel strength, the lower limit value of the root mean square roughness (Rq value) is preferably 15 nm or more, more preferably 70 nm or more, and further preferably 100 nm or more.

  The resin composition of the present invention is cured to form an insulating layer, the surface of the insulating layer is roughened, and the peel strength between the conductor layer and the insulating layer obtained by plating is described in <Plating conductor layer pulling> It can be grasped by the measurement method described in Measurement of Peel Strength (Peel Strength)>. Specifically, the peel strength is preferably 0.3 kgf / cm or more and more preferably 0.35 kgf / cm or more in order to keep the insulating layer and the conductor layer in close contact with each other. 0.4 kgf / cm or more is preferable. The upper limit of the peel strength is preferably as high as possible and is not particularly limited, but is generally 1.2 kgf / cm or less, 1.0 kgf / cm or less, or 0.8 kgf / cm or less.

  The dielectric loss tangent of the cured product of the resin composition of the present invention can be measured by <Measurement of dielectric loss tangent> described later. Specifically, it can be measured at a frequency of 5.8 GHz and a measurement temperature of 23 ° C. by the cavity resonance perturbation method. Specifically, the dielectric loss tangent is preferably 0.003 or less from the viewpoint of preventing heat generation at high frequencies, reducing signal delay, and signal noise. The lower limit value is not particularly limited and is 0.001, 0.0005, 0 or the like.

  Although the use of the resin composition of the present invention is not particularly limited, sheet-like laminated materials such as adhesive films and prepregs, circuit boards (for laminated boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, die It can be used in a wide range of applications where a resin composition is required, such as a bonding material, a semiconductor sealing material, a hole-filling resin, and a component-filling resin. The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but in general, it is preferably used in the form of a sheet-like laminated material such as an adhesive film or a prepreg. . The softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminate property of the sheet-like laminated material.

<Sheet laminated material>
(Adhesive film)
The adhesive film of the present invention is prepared by a method known to those skilled in the art, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish to a support using a die coater or the like. It can be produced by drying the organic solvent by heating or blowing hot air to form the resin composition layer.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. And aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Two or more organic solvents may be used in combination.

  The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. can do.

  The thickness of the resin composition layer formed in the adhesive film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm. From the viewpoint of thinning, 15 to 80 μm is more preferable.

  Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films. Various plastic films are listed. Moreover, you may use release foil, metal foil, such as copper foil and aluminum foil. Among these, from the viewpoint of versatility, a plastic film is preferable, and a polyethylene terephthalate film is more preferable. The support and a protective film described later may be subjected to surface treatment such as mud treatment or corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.

  Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.

  A protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can also be stored in a roll.

(Prepreg)
The prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing base material by a hot melt method or a solvent method, and heating and semi-curing it. That is, it can be set as the prepreg which will be in the state which impregnated the sheet-like reinforcement base material with the resin composition of this invention. As the sheet-like reinforcing base material, for example, a base material commonly used as a prepreg fiber such as glass cloth or aramid fiber can be used. And what formed the prepreg on the support body is suitable.

  In the hot melt method, the resin composition is once coated on a support without being dissolved in an organic solvent, and then laminated on a sheet-like reinforcing substrate, or directly applied to a sheet-like reinforcing substrate by a die coater. Thus, a prepreg is manufactured. In the solvent method, a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as the adhesive film, and a sheet-like reinforcing base material is immersed in the varnish, and then the resin-like varnish is impregnated into the sheet-like reinforcing base material. It is a method of drying. Alternatively, the adhesive film can be prepared by continuously laminating the adhesive film from both sides of the sheet-like reinforcing substrate under heating and pressure conditions. A support, a protective film, and the like can be used in the same manner as the adhesive film.

<Multilayer printed wiring board using sheet-like laminated material>
Next, a multilayer printed wiring board can be manufactured by using the sheet-like laminated material manufactured as described above. An example will be described below.

  First, a sheet-like laminated material is laminated (laminated) on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include 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. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

In the above laminate, when the sheet-like laminate material has a protective film, after removing the protective film, the sheet-like laminate material and the circuit board are preheated as necessary, and the sheet-like laminate material is pressurized and Laminate to circuit board while heating. In the sheet-like laminated material of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure (laminating pressure) is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), the pressure bonding time (laminating time) is preferably 5 to 180 seconds, and the lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll. The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.

  After laminating the sheet-like laminated material on the circuit board, after cooling to near room temperature, if the support is peeled off, it is peeled off, and the resin composition is thermally cured to form a cured product, thereby forming a cured product on the circuit board An insulating layer can be formed. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to 210 ° C. It is selected in the range of 30 to 120 minutes at ° C. After the insulating layer is formed, if the support is not peeled before curing, it can be peeled off here if necessary.

Moreover, a sheet-like laminated material can also be laminated | stacked on the single side | surface or both surfaces of a circuit board using a vacuum press machine. The lamination process for heating and pressurizing under reduced pressure can be performed using a general vacuum hot press machine. For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side. The pressing condition is that the degree of vacuum is usually 1 × 10 ⁻² MPa or less, preferably 1 × 10 ⁻³ MPa or less. Although heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the oozing of the resin. For example, the first stage press has a temperature of 70 to 150 ° C. and the pressure is in the range of 1 to 15 kgf / cm 2, and the second stage press has the temperature of 150 to 200 ° C. and the pressure is in the range of 1 to 40 kgf / cm 2 It is preferred to do so. The time for each stage is preferably 30 to 120 minutes. Thus, an insulating layer can be formed on a circuit board by thermosetting the resin composition layer. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

  Next, a hole is formed in the insulating layer formed on the circuit board to form a via hole and a through hole. For example, the drilling can be performed by a known method such as drilling, laser, or plasma, or a combination of these methods if necessary, but drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common. Is the method. If the support is not peeled off before drilling, it will be peeled off here.

  Next, a roughening process is performed on the surface of the insulating layer. In the case of dry-type roughening treatment, plasma treatment and the like can be mentioned, and in the case of wet-type roughening treatment, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid are performed in this order. It is done. The wet roughening treatment is preferable in that smear in the via hole can be removed while forming an uneven anchor on the surface of the insulating layer. The swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 5 to 20 minutes (preferably at 55 to 70 ° C. for 8 to 15 minutes). Examples of the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securiganth P (Swelling Dip Securiganth S) and Swelling Dip Securiganth SBU (ABUTEC Japan). be able to. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ° C. for 10 to 30 minutes (preferably at 70 to 80 ° C. for 15 to 25 minutes). Examples of the oxidizing agent include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is performed by immersing in a neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes (preferably at 35 to 45 ° C. for 3 to 8 minutes). As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.

  Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. Examples of wet plating include a method in which a conductive layer is formed by combining electroless plating and electrolytic plating, a method in which a plating resist having a pattern opposite to that of the conductive layer is formed, and a conductive layer is formed only by electroless plating. It is done. As a pattern formation method thereafter, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. By repeating the above-described series of steps a plurality of times, a multilayer in which build-up layers are stacked in multiple stages It becomes a printed wiring board. In the present invention, since it has low roughness, high peel, and low dielectric loss tangent, it can be suitably used as a build-up layer of a multilayer printed wiring board.

<Semiconductor device>
A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor chip in a conductive portion of the multilayer printed wiring board of the present invention. The “conduction location” is a “location where an electrical signal is transmitted in a multilayer printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. “Part” means part by mass.

<Measurement method / Evaluation method>
First, various measurement methods and evaluation methods will be described.

<Calculation of arithmetic average roughness (Ra value) root mean square roughness (Rq value) and peel strength measurement sample>
(1) Underlayer treatment of inner layer circuit board Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works R5715ES) on which an inner layer circuit is formed The copper surface was roughened by etching 1 μm with CZ8100 manufactured by MEC.

(2) Lamination of adhesive film The adhesive film created in Examples and Comparative Examples was laminated on both surfaces of the inner layer circuit board using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Co., Ltd.). . Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.

(3) Curing of Resin Composition The laminated adhesive film was cured at 200 ° C. under a curing condition of 60 minutes to form an insulating layer, and then the PET film was peeled off.

(4) Roughening treatment The inner layer circuit board on which the insulating layer is formed is immersed in a swelling liquid, diethylene glycol monobutyl ether-containing swelling dip securigant P, which is a swelling liquid, at 60 ° C. for 10 minutes, and then roughened. As a chemical solution, it is immersed in an Atotech Japan Co., Ltd. Concentrate Compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally as a neutralizing solution, Atotech Japan Co., Ltd. Were dipped in 40 g of reduction Shoryushin securigant P for 5 minutes. After drying at 80 ° C. for 30 minutes, arithmetic surface roughness (Ra value) and root mean square roughness (Rq value) were measured on the surface of the insulating layer after the roughening treatment.

(5) Plating by semi-additive method In order to form a circuit on the surface of the insulating layer, the inner layer circuit board is immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then in an electroless copper plating solution. It was immersed for 20 minutes at 25 ° C. After annealing at 150 ° C. for 30 minutes, an etching resist was formed. After pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 25 μm. Next, annealing treatment was performed at 180 ° C. for 30 minutes. The circuit board was measured for peel strength (peel strength) of the plated conductor layer.

<Measurement of arithmetic average roughness (Ra value) and root mean square roughness (Rq value) after roughening>
Using a non-contact type surface roughness meter (BYCO Instruments WYKO NT3300), the Ra value was determined by a numerical value obtained by setting the measurement range to 121 μm × 92 μm with a VSI contact mode and a 50 × lens. And it was set as the measured value by calculating | requiring the average value of 10 points | pieces.

<Measurement of peel strength (peel strength) of plated conductor layer>
Make a notch of width 10mm and length 100mm in the conductor layer of the circuit board, peel off one end and grasp it with a gripping tool (TSE Co., Ltd., Autocom type testing machine AC-50CSL) at room temperature The load (kgf / cm) when peeling 35 mm in the vertical direction at a speed of 50 mm / min was measured.

<Measurement of dielectric loss tangent>
The resin varnishes obtained in Examples and Comparative Examples were placed on a PET film (“PET501010”, manufactured by Lintec Co., Ltd.) having been subjected to a release treatment so that the thickness of the resin composition layer after drying was 40 μm. The film was uniformly coated with a tar and dried at 80 to 110 ° C. (average 95 ° C.) for 6 minutes. Then, it heat-processed for 90 minutes at 200 degreeC in nitrogen atmosphere, and obtained the hardened | cured material film by peeling from a support body. The cured film was cut into a length of 80 mm and a width of 2 mm and used as an evaluation sample. The dielectric loss tangent of this evaluation sample was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using an HP 8362B apparatus manufactured by Agilent Technologies. Two test pieces were measured, and the average value was calculated.

<Adjustment of polybutadiene resin A>
In a reaction vessel, 50 g of G-3000 (bifunctional hydroxyl group-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g / eq., Solid content: 100 w%, manufactured by Nippon Soda Co., Ltd.), ipzol 23.5 g of 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.005 g of dibutyltin dilaurate were mixed and dissolved uniformly. When the temperature became uniform, the temperature was raised to 50 ° C., and while further stirring, 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) Was added and the reaction was carried out for about 3 hours. The reaction was then cooled to room temperature before 8.96 g benzophenonetetracarboxylic dianhydride (acid anhydride equivalent = 161.1 g / eq.), 0.07 g triethylenediamine, and ethyl diglycol. 40.4 g of acetate (manufactured by Daicel Chemical Industries, Ltd.) was added, the temperature was raised to 130 ° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FT-IR. After confirming the disappearance of the NCO peak, the reaction is considered to be the end point of the reaction. The reaction product is cooled to room temperature and then filtered through a 100 mesh filter cloth to obtain a polybutadiene resin (polybutadiene resin A) having a butadiene skeleton, an acid anhydride group, and a polyimide skeleton Obtained.
Properties of the polybutadiene resin A:
Viscosity = 7.5 Pa · s (25 ° C, E-type viscometer)
Acid value = 16.9 mgKOH / g
Solid content = 50wt%
Number average molecular weight = 13723
Content ratio of polybutadiene structure portion = 50 / (50 + 4.8 + 8.96) * 100
= 78.4% by mass

<Example 1>
(Adjustment of resin varnish)
48 parts of styrene-modified polyphenylene ether resin (“OPE-2St (number average molecular weight 1200)” manufactured by Mitsubishi Gas Chemical Co., Ltd.), bixylenol diallyl ether resin (“YL7776 (number average molecular weight 331) manufactured by Mitsubishi Chemical Corporation)” 24 parts, 18 parts of biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd.), active ester type curing agent (“EXB9416-70BK” manufactured by DIC Corporation, methyl isobutyl ketone solution having a solid content of 70% by mass) A mixed solution of 26 parts, 20 parts of polybutadiene resin A, 30 parts of solvent naphtha and 25 parts of toluene was heated and dissolved while stirring. After cooling the mixed solution to room temperature, 3 parts of a curing accelerator (40% by mass MEK solution of “1B2PZ” manufactured by Shikoku Kasei Co., Ltd.), 4.8 parts of a polymerization initiator (“Perhexin 25B” manufactured by NOF Corporation) , 1.58 parts of rubber particles (manufactured by Ganz Kasei Co., Ltd., Staphyloid AC3816N), spherical silica (average particle diameter) surface-treated with a styrylsilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM1403”) A resin varnish was prepared by mixing 158 parts of 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd., and uniformly dispersing with a high-speed rotary mixer.

(Preparation of adhesive film)
Next, the above resin varnish is uniformly applied to a release-treated PET film (Lintec Co., Ltd., “PET501010”) with a die coater so that the thickness of the resin composition layer after drying is 40 μm. And dried at 80 to 110 ° C. (average 95 ° C.) for 6 minutes to prepare an adhesive film.

<Example 2>
48 parts of styrene-modified polyphenylene ether resin (“OPE-2St (number average molecular weight 1200)” manufactured by Mitsubishi Gas Chemical Co., Ltd.), bixylenol diallyl ether resin (“YL7776 (number average molecular weight 331) manufactured by Mitsubishi Chemical Corporation)” 24 parts, biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd.), active ester type curing agent (“EXB9416-70BK” manufactured by DIC Corporation, methyl isobutyl ketone solution having a solid content of 70% by mass) A mixed solution of 52 parts, 75 parts of polybutadiene resin A, 35 parts of solvent naphtha, and 50 parts of toluene was heated and dissolved while stirring. 6. After cooling the mixed solution to room temperature, 4.7 parts of curing accelerator (40% by mass MEK solution of “1B2PZ” manufactured by Shikoku Kasei Co., Ltd.), polymerization initiator (“Perhexine 25B” manufactured by NOF Corporation) 5 parts, 2.42 parts of rubber particles (manufactured by Ganz Kasei Co., Ltd., Staphyloid AC3816N), spherical silica surface treated with a styrylsilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM1403”) (average) A resin varnish was prepared by mixing 242 parts of a particle size of 0.5 μm and “SOC2” manufactured by Admatechs Co., Ltd. and uniformly dispersing with a high-speed rotary mixer. Thereafter, an adhesive film was produced in the same manner as in Example 1.

<Example 3>
48 parts of styrene-modified polyphenylene ether resin (“OPE-2St (number average molecular weight 1200)” manufactured by Mitsubishi Gas Chemical Co., Ltd.), bixylenol diallyl ether resin (“YL7776 (number average molecular weight 331) manufactured by Mitsubishi Chemical Corporation)” 24 parts, 18 parts of biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd.), 23 parts of active ester type curing agent (“HPC8000-65T” manufactured by DIC Corporation, toluene solution having a solid content of 65% by mass) Then, a mixed solution of 20 parts of polybutadiene resin A, 30 parts of solvent naphtha and 25 parts of toluene was heated and dissolved while stirring. After cooling the mixed solution to room temperature, 3 parts of a curing accelerator (40% by mass MEK solution of “1B2PZ” manufactured by Shikoku Kasei Co., Ltd.), 4.7 parts of a polymerization initiator (“Perhexine 25B” manufactured by NOF Corporation) , Spherical silica (average particle size) surface-treated with 1.54 parts of rubber particles (manufactured by Ganz Kasei Co., Ltd., Staphyloid AC3816N), styrylsilane coupling agent (“KBM1403” manufactured by Shin-Etsu Chemical Co., Ltd.) A resin varnish was prepared by mixing 154 parts of 0.5 μm and “SOC2” manufactured by Admatechs Co., Ltd. and uniformly dispersing with a high-speed rotary mixer. Thereafter, an adhesive film was produced in the same manner as in Example 1.

<Comparative Example 1>
48 parts of styrene-modified polyphenylene ether resin (“OPE-2St (number average molecular weight 1200)” manufactured by Mitsubishi Gas Chemical Co., Ltd.), bixylenol diallyl ether resin (“YL7776 (number average molecular weight 331) manufactured by Mitsubishi Chemical Corporation)” A mixed solution of 24 parts, polybutadiene resin A 37 parts, solvent naphtha 30 parts, and toluene 40 parts was heated and dissolved while stirring. After cooling the mixed solution to room temperature, 3.7 parts of a polymerization initiator (“Perhexin 25B” manufactured by NOF Corporation), 1.2 parts of rubber particles (STAFYROID AC3816N manufactured by Ganz Kasei Co., Ltd.), styrylsilane type 120 parts of spherical silica (average particle size 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd.) surface-treated with a coupling agent (“KBM1403” manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed, and a high-speed rotating mixer To uniformly disperse the resin varnish. Thereafter, an adhesive film was produced in the same manner as in Example 1.

<Comparative example 2>
48 parts of styrene-modified polyphenylene ether resin (“OPE-2St (number average molecular weight 1200)” manufactured by Mitsubishi Gas Chemical Co., Ltd.), bixylenol diallyl ether resin (“YL7776 (number average molecular weight 331) manufactured by Mitsubishi Chemical Corporation)” 24 parts, 18 parts of biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd.), active ester type curing agent (“EXB9416-70BK” manufactured by DIC Corporation, methyl isobutyl ketone solution having a solid content of 70% by mass) A mixed solution of 26 parts, 30 parts of solvent naphtha and 15 parts of toluene was heated and dissolved while stirring. 3. After cooling the mixed solution to room temperature, 2.8 parts of a curing accelerator (40% by mass MEK solution of “1B2PZ” manufactured by Shikoku Kasei Co., Ltd.), polymerization initiator (“Perhexin 25B” manufactured by NOF Corporation) 5 parts, 1.44 parts of rubber particles (manufactured by Ganz Kasei Co., Ltd., Staphyloid AC3816N), spherical silica surface treated with a styrylsilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM1403”) (average) A resin varnish was prepared by mixing 144 parts of a particle size of 0.5 μm and “SOC2” manufactured by Admatechs Co., Ltd. and uniformly dispersing with a high-speed rotary mixer. Thereafter, an adhesive film was produced in the same manner as in Example 1.

<Comparative Example 3>
48 parts of styrene-modified polyphenylene ether resin (“OPE-2St (number average molecular weight 1200)” manufactured by Mitsubishi Gas Chemical Co., Ltd.), bixylenol diallyl ether resin (“YL7776 (number average molecular weight 331) manufactured by Mitsubishi Chemical Corporation)” 24 parts, 18 parts of biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd.), active ester type curing agent (“EXB9416-70BK” manufactured by DIC Corporation, methyl isobutyl ketone solution having a solid content of 70% by mass) 26 parts, 34 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, MEK solution with a solid content of 30% by mass), 30 parts of solvent naphtha, 25 parts of toluene, and 10 parts of methyl ethyl ketone are heated and dissolved with stirring. It was. After cooling the mixed solution to room temperature, 3 parts of a curing accelerator (40% by mass MEK solution of “1B2PZ” manufactured by Shikoku Kasei Co., Ltd.), 4.9 parts of a polymerization initiator (“Perhexin 25B” manufactured by NOF Corporation) , 1.58 parts of rubber particles (manufactured by Ganz Kasei Co., Ltd., Staphyloid AC3816N), spherical silica (average particle diameter) surface-treated with a styrylsilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM1403”) A resin varnish was prepared by mixing 158 parts of 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd., and uniformly dispersing with a high-speed rotary mixer. Thereafter, an adhesive film was produced in the same manner as in Example 1.

  The results are shown in Table 1.

  From the results in Table 1, the resin compositions of the examples are stable with a low arithmetic average roughness, low root mean square roughness, a sufficient peel strength, and a low dielectric loss tangent. On the other hand, in Comparative Example 1, the arithmetic average roughness and the root mean square roughness are large, and the peel strength is also low. In Comparative Example 2, the peel strength is low. In Comparative Example 3, the peel strength is low and the dielectric loss tangent is also large.

  In the wet roughening process, not only the arithmetic average roughness of the insulating layer surface is small, but also the root mean square roughness is small, and a plated conductor layer having a stable peel strength can be formed thereon, and the dielectric loss tangent is also low. A resin composition can be provided. Furthermore, sheet-like laminated materials, multilayer printed wiring boards, and semiconductor devices using the resin composition can be provided. Furthermore, electric products such as computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, and airplanes equipped with these can be provided.

Claims (25)

  (A) A radically polymerizable compound, (B) an epoxy resin, (C) a curing agent, and (D) a roughening component.   The resin composition according to claim 1, wherein the radically polymerizable compound (A) has one or more selected from a styryl group, an allyl group, a vinyl group, an acrylic group, a methacryl group, and a propenyl group. The resin composition according to claim 1 or 2, wherein the (A) radical polymerizable compound is a compound represented by the following formula (1).

[R _{1 to} R ₆ are each independently hydrogen and an alkyl group having 1 to 4 carbon atoms. A is the following formula (2) or the following formula (3). ]

[B is the following structural formula B-1, B-2, or B-3. ]

[D is the following formula (4). ]

[R _{7 to} R ₁₄ are each independently hydrogen, an alkyl group having 6 or less carbon atoms, or a phenyl group. a and b are integers of 0 to 100, at least one of which is not 0. B is the following structural formula B-1, B-2, or B-3. ]

[R _{15 to} R ₃₄ are each independently hydrogen, an alkyl group having 6 or less carbon atoms, or a phenyl group. E is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. ]   The number average molecular weight of the said (A) radically polymerizable compound is the range of 100-10000, The resin composition of any one of Claims 1-3 characterized by the above-mentioned.   5. The content of the radically polymerizable compound (A) is 5 to 40% by mass when the non-volatile component in the resin composition is 100% by mass. 5. The resin composition as described.   The (B) epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, glycidyl ester type epoxy resin and anthracene type It is 1 or more types selected from an epoxy resin, The resin composition of any one of Claims 1-5 characterized by the above-mentioned.   The content of said (B) epoxy resin is 1-30 mass%, when the non-volatile component in a resin composition is 100 mass%, The any one of Claims 1-6 characterized by the above-mentioned. Resin composition.   The resin composition according to claim 1, wherein the (C) curing agent contains an active ester type curing agent and / or a cyanate ester type curing agent.   The resin composition according to claim 1, wherein the (C) curing agent contains an active ester type curing agent.   The content of the curing agent (C) is 1 to 30% by mass when the nonvolatile component in the resin composition is 100% by mass, according to any one of claims 1 to 9. Resin composition.   The roughening component (D) contains at least one selected from polybutadiene resin, polyamide resin, polyamideimide resin, polyimide resin, polyacetal resin, polycarbonate resin, polymethyl methacrylate resin, polyester resin, and polyurethane resin. The resin composition of any one of Claims 1-10 characterized by these.   The resin composition according to claim 1, wherein the roughening component (D) contains a polybutadiene resin.   The resin composition according to any one of claims 1 to 12, wherein the roughening component (D) contains a polybutadiene resin having a butadiene skeleton and a reactive group.   The resin composition according to any one of claims 1 to 13, wherein the number average molecular weight of the (D) roughening component is in the range of 300 to 30,000.   When the non-volatile component in a resin composition is 100 mass%, content of the said (C) roughening component is 0.5-20 mass%, Any one of Claims 1-14 characterized by the above-mentioned. The resin composition according to Item.   (E) Inorganic filler is contained, The resin composition of any one of Claims 1-15 characterized by the above-mentioned.   The resin composition according to claim 16, wherein the (E) inorganic filler is surface-treated with a styrylsilane coupling agent.   The arithmetic average roughness after the resin composition is cured to form an insulating layer, and the surface of the insulating layer is roughened is 10 to 300 nm, and the root mean square roughness is 15 to 450 nm. The resin composition according to any one of claims 1 to 17.   The resin composition is cured to form an insulating layer, the surface of the insulating layer is roughened, and the peel strength between the conductor layer and the insulating layer obtained by plating is 0.3 to 1.2 kgf / cm The resin composition of any one of Claims 1-18 characterized by these.   The resin composition according to any one of claims 1 to 19, wherein the dielectric loss tangent of the cured product of the resin composition is 0.003 or less.   The resin composition according to any one of claims 1 to 20, wherein the resin composition is a resin composition for an insulating layer of a multilayer printed wiring board. The resin composition according to any one of claims 1 to 21, which is a resin composition for a buildup layer of a multilayer printed wiring board. A sheet-like laminated material comprising the resin composition according to any one of claims 1 to 22. A multilayer printed wiring board comprising the sheet-like laminated material according to claim 23. A semiconductor device using the multilayer printed wiring board according to claim 24.