JP6694833B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition. Further, the present invention relates to a sheet-shaped laminated material, a multilayer printed wiring board and a semiconductor device containing the resin composition.

  2. Description of the Related Art In recent years, electronic devices have become smaller and higher in performance, and in a multilayer printed wiring board, build-up layers are multi-layered, and finer wiring and higher density are required. In addition, as the frequency of signals increases, the buildup layer is also required to have a low dielectric loss tangent.

  Various efforts have been made to address 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 not only the arithmetic mean roughness of the surface of the insulating layer in the wet roughening step is small, but also the root mean square roughness is small, and a plated conductor layer having a stable and sufficient peel strength. And a low dielectric loss tangent.

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

［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 containing (A) a radically 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 styryl group, allyl group, vinyl group, acryl group, methacryl group and propenyl group. Composition.
[3] The resin composition according to [1] or [2], wherein the radically polymerizable compound (A) is a compound represented by the following formula (1).

[R _{1 to} R ₆ are each independently hydrogen or 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 in which at least one 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 radically polymerizable compound (A) is 5 to 40% by mass [1] to [4]. The resin composition according to any one of 1.
[6] The (B) epoxy resin is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, a glycidyl ester type epoxy resin. And at least one selected from anthracene type epoxy resins, [1] to [5].
[7] Any of [1] to [6], wherein the content of the (B) epoxy resin is 1 to 30 mass% when the nonvolatile component in the resin composition is 100 mass%. Or the resin composition as described above.
[8] The resin composition according to any one of [1] to [7], wherein the curing agent (C) 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 curing agent (C) contains an active ester type curing agent.
[10] Any of [1] to [9], wherein the content of the (C) curing agent is 1 to 30% by mass, when the nonvolatile component in the resin composition is 100% by mass. Or the resin composition as described above.
[11] The (D) roughening component is one or more selected from polybutadiene resin, polyamide resin, polyamideimide resin, polyimide resin, polyacetal resin, polycarbonate resin, polymethyl methacrylate resin, polyester resin, polyurethane resin. The resin composition according to any one of [1] to [10], which further comprises:
[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 (D) roughening component 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 roughening component (D) is in the range of 300 to 30,000.
[15] When the nonvolatile component in the resin composition is 100% by mass, the content of the (C) roughening component 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 (E) an inorganic filler.
[17] The resin composition according to [16], wherein the inorganic filler (E) is surface-treated with a styrylsilane coupling agent.
[18] The resin composition is cured to form an insulating layer, and the arithmetic mean roughness after roughening the insulating layer surface 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].
[20] The resin composition according to any one of [1] to [19], wherein the cured product of the resin composition has a dielectric loss tangent of 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-shaped laminated material containing 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 radically polymerizable compound, an epoxy resin, a curing agent and a roughening component, not only the arithmetic average roughness of the insulating layer surface in the wet roughening step is small, but also the square. It has become possible to provide a resin composition having a small average square root roughness, a stable plated conductor layer having a sufficient peel strength, and a low dielectric loss tangent.

  The present invention is a resin composition containing (A) a radically 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 radically polymerizable group include a styryl group, an allyl group, a vinyl group, an acryl group, a methacryl group, and a propenyl group, and from the viewpoint of excellent storage stability, a styryl group, an allyl group, a vinyl group, an acryl group, It is preferable to have one or more selected from a methacryl group and a propenyl group, and it is more preferable to have 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 or 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, and 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 in which at least one 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 each independently represent 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 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., Inc., equivalent to general formula (5)), bixylenol diallyl ether resins ( “YL7776 (number average molecular weight 331)” manufactured by Mitsubishi Chemical Corporation, equivalent to general formula (6), and the like can be mentioned.

  The number average molecular weight of the radically polymerizable compound is preferably in the range of 100 to 10,000, from the viewpoint of preventing volatilization at the time of drying the resin varnish and preventing the melt viscosity of the resin composition from rising too much, and 200 to 3,000. The range is more preferably. The number average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (polystyrene conversion). The number average molecular weight by the GPC method is specifically 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 calculated by using chloroform as a mobile phase at a column temperature of 40 ° C and using a calibration curve of standard polystyrene.

  In the resin composition of the present invention, from the viewpoint of improving the compatibility of the resin composition, when the non-volatile component in the resin composition is 100% by mass, the content of the radically polymerizable compound is preferably 5 to 40% by mass, 10 to 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, glycidyl amine 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 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. You may use these 1 type or in combination of 2 or more types.

  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 Co., Ltd.), bisphenol F type epoxy resin (“jER806H”, “YL983U” manufactured by Mitsubishi Chemical Co., Ltd.), 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 a 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-7331”, “EXA-7331L” manufactured by DIC Corporation). , "EXA7311-G3"), glycidyl ester type epoxy resin ("EX711", "EX721" manufactured by Nagase Chemtex Co., Ltd., "R540" manufactured by Printec Co., Ltd.), and the like. Biphenyl type epoxy resin is particularly preferable because it exhibits 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 a 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, 3-10 mass% is still more preferable.

<(C) Curing agent>
The curing agent used in the present invention is not particularly limited, but examples thereof include active ester type curing agents, cyanate ester type curing agents, phenol type curing agents, benzoxazine type curing agents, etc., to further reduce the surface roughness, In addition, from the viewpoint that the dielectric loss tangent can be lowered, it is preferable to use the active ester type curing agent and / or the cyanate ester type curing agent, and it is more preferable to use the active ester type curing agent. You may use these 1 type or in combination of 2 or more types.

  The active ester type curing agent is not particularly limited, but in general, an ester group having a high reaction activity such as a phenol ester, a thiophenol ester, an N-hydroxyamine ester, and an ester of a heterocyclic hydroxy compound is contained in one molecule. Compounds having two or more of them are 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.

  Particularly, from the viewpoint of improving heat resistance, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type 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, 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. As the active ester type curing agent, an active ester type curing agent containing a dicyclopentadienyl diphenol structure, an active ester type curing agent containing a naphthalene structure, an active ester type curing agent which is an acetylated product of phenol novolac, and a phenol novolak An active ester type curing agent which is a benzoyl compound is preferable, and among them, an active ester type curing agent containing a dicyclopentadienyl diphenol structure and an active ester type curing agent containing a naphthalene structure are preferable because they are excellent in improving the peel strength. More preferred is an active ester type curing agent containing a dicyclopentadienyl diphenol structure, and further preferred.

  As the active ester type curing agent, the 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: 223), naphthalene structure. EXB9416-70BK (manufactured by DIC Corporation, active group equivalent: about 274) as an active ester type curing agent containing DC, and DC808 (manufactured by Mitsubishi Chemical Corporation, active group equivalent: active ester type curing agent which is an acetylated product of phenol novolac). 149), YLH1026 (manufactured by Mitsubishi Chemical Corporation, active group equivalent: about 200), YLH1030 (manufactured by Mitsubishi Chemical Corporation, active group equivalent: about 201), YLH1048 as an active ester type curing agent which is a benzoylated product of phenol novolac. (Mitsubishi Chemical Corporation, active group equivalent of about 245) And the like.

  The cyanate ester type curing agent is not particularly limited, but is a novolac type (phenol novolac type, alkylphenol novolac type, etc.) cyanate ester type curing agent, dicyclopentadiene type cyanate ester type curing agent, bisphenol type (bisphenol A type, bisphenol Cyanate ester type curing agents such as F type and bisphenol S type, and prepolymers obtained by partially converting these into triazine. The weight average molecular weight of the cyanate ester type curing agent is not particularly limited, but is preferably 500 to 4500, more preferably 600 to 3000. 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′-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenyl propane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3, Bifunctional cyanate resins such as 5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether. , Phenol novolac, Examples include polyfunctional cyanate resins derived from resole novolacs, phenolic resins containing dicyclopentadiene structure, and prepolymers obtained by partially converting these cyanate resins into triazines. Examples of commercially available cyanate ester resins include phenol novolac-type polyfunctional cyanate ester resins (PT30, cyanate equivalent 124, manufactured by Lonza Japan Co., Ltd.), and some or all of bisphenol A dicyanate is triazined to form a trimer. The following prepolymers (BA230, cyanate equivalent 232, manufactured by Lonza Japan Co., Ltd.), cyanate ester resins containing a dicyclopentadiene structure (DT-4000, DT-7000, manufactured by Lonza Japan Co., Ltd.) and the like can be 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-7851 (manufactured by Meiwa Kasei Co., Ltd.), naphthalene type curing agents NHN, CBN, GPH (manufactured by Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Nippon Steel Chemical Co., Ltd.), EXB9500 (manufactured by DIC Co., Ltd.), TD2090 (manufactured by DIC Co., Ltd.) as a phenol novolac type curing agent, 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.

  The benzoxazine type curing agent is not particularly limited, but specific examples thereof include Fa, Pd (manufactured by Shikoku Kasei Co., Ltd.), HFB2006M (manufactured by Showa High Polymer Co., Ltd.) and the like.

  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 preferred, 2 to 20 mass% is more preferred, and 3 to 10 mass% is even more preferred.

  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, 1: 0.2 to 1: 2 is preferable, 1: 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1 is further preferable. Incidentally, 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. Is the total value of all the curing agents obtained by dividing the solid content mass of each curing agent by the reactive group equivalent.

<(D) Roughening component>
The roughening component used in the present invention is not particularly limited as long as it can impart peel strength by being roughened by desmear treatment. For example, as the roughening component, it is preferable to use one or more selected from polybutadiene resin, polyamide resin, polyamideimide resin, polyimide resin, polyacetal resin, polycarbonate resin, polymethylmethacrylate resin, polyester resin, and polyurethane resin. Among them, polybutadiene resin is more preferable because it has low dielectric loss tangent and roughening property. Further, the roughening component preferably has a reactive group, and by having the reactive group, it becomes a uniform cured product, and it is possible to obtain sufficient peel strength while suppressing the surface roughness after the roughening treatment to be 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, the 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. By having a polyimide skeleton, it can be a roughening component that does not impair heat resistance.

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

  The number average molecular weight of the roughening component is preferably in the range of 300 to 30,000, more preferably 800 to 15,000. By setting the number average molecular weight within this range, compatibility and roughening properties in the resin composition can be compatible. The number average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (polystyrene conversion). The number average molecular weight by the GPC method is specifically 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 calculated by using chloroform as a mobile phase at a column temperature of 40 ° C and using a calibration curve of standard polystyrene.

  In the resin composition of the present invention, the content of the roughening component is 100% by mass of the non-volatile component in the resin composition from the viewpoint of enabling the production of a uniform cured product without impairing the compatibility of the resin. Is preferably 0.5 to 20% by mass, more preferably 1 to 10% by mass.

<(E) Inorganic filler>
The resin composition of the present invention can lower the dielectric loss tangent by further containing an inorganic filler. As the inorganic filler, for example, 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 thereof include strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, silica is preferred. Further, 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, spherical silica is preferable. 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 Co., Ltd.

  Although the average particle diameter of the inorganic filler is not particularly limited, it 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. It is even more preferably 7 μm or less. On the other hand, when the resin composition is a varnish, 0.01 μm or more is preferable, 0.05 μm or more is more preferable, and 0.1 μm is 0.1 μm or more from the viewpoint of preventing the viscosity of the varnish from increasing and the handleability 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 the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction / scattering particle size distribution measuring device, and the median diameter can be used as the average particle diameter for measurement. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring device, LA-950 manufactured by Horiba, Ltd. can be used.

  The content of the inorganic filler in the case of being blended is not particularly limited, but from the viewpoint of reducing the dielectric loss tangent and preventing the flexibility of the film form from decreasing, the content of the nonvolatile component in the resin composition is 100. When it is defined as mass%, 40 to 85 mass% is preferable, 45 to 80 mass% is more preferable, and 50 to 75 mass% is further 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, styryl silane coupling agents. Surface treatment with surface treatment agents such as acrylate silane coupling agents, isocyanate silane coupling agents, sulfide silane coupling agents, silane silane coupling agents, organosilazane compounds, and titanate coupling agents to improve their moisture resistance and dispersibility. Those that are preferred. You may use these 1 type or in combination of 2 or more types.

  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-based coupling agents such as glycidylbutyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyl Mercaptosilane-based coupling agents such as dimethoxysilane, 11-mercaptoundecyltrimethoxysilane, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolesilane, triazinesilane, t- Silane-based coupling agents such as butyltrimethoxysilane, vinylsilane-based coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxysilane. Ring agent, styrylsilane-based 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-isocyanatepropyltrimethoxysilane, bis (triethoxysilylpropyl) disulfide, bis (triethoxysilyl) Propyl) tetrasulfide and other sulfide silane coupling agents, 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 Xyoctylene glycolate, tetra-n-butyl titanate, titanium octylene glycolate, diisopropoxy titanium bis (triethanol aminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate , Bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxy titanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis ( Ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite Nate, isopropyl trioctanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tridodecylbenzene sulfonyl titanate, isopropyl Examples of titanate coupling agents such as tris (dioctyl pyrophosphate) titanate and isopropyltri (N-amidoethylaminoamino) titanate. As commercial products, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical 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-based coupling agent, it is excellent in reducing the dielectric loss tangent and is preferable.

<(F) Curing accelerator>
When the resin composition of the present invention further contains a curing accelerator, the epoxy resin and the curing agent can be efficiently cured. The curing accelerator is not particularly limited, and examples thereof include an amine curing accelerator, a guanidine curing accelerator, an imidazole curing accelerator, a phosphonium curing accelerator, and a metal curing accelerator. You may use these 1 type or in combination of 2 or more types.

  The amine curing accelerator is not particularly limited, but trialkylamine such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl). Examples thereof include 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.

  The guanidine curing accelerator is not particularly limited, but includes 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-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-fe Rubiguanido, 1-(o-tolyl) biguanide, and the like. You may use these 1 type or in combination of 2 or more types.

  The imidazole-based curing accelerator is not particularly limited, 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-5-hydroxymethylimidazole, 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.

  The phosphonium-based curing accelerator is not particularly limited, but includes triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like can be mentioned. You may use these 1 type or in combination of 2 or more types.

  The content of the curing accelerator (excluding the metal-based curing accelerator) is not particularly limited, but is 0.005 to 1% by mass when the nonvolatile component in the resin composition is 100% by mass. Is preferable, and the range of 0.01-0.5 mass% is more preferable. Within this range, thermosetting can be made more efficient and the storage stability of the resin varnish is also improved.

  The metal-based curing accelerator is not particularly limited, and examples thereof include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, zinc (II) acetylacetonate. And the like, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. You may use these 1 type or in combination of 2 or more types.

  The addition amount of the metal-based curing accelerator is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, the content of the metal based on the metal-based 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 excellent adhesion to the surface of the insulating layer is formed, and the storage stability of the resin varnish is also improved.

<(G) Polymerization initiator>
When the resin composition of the present invention further contains a polymerization initiator, the radical polymerizable compound can be efficiently cured. 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 hydrol Radical generators such as peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, and 2,3-dimethyl-2,3-diphenylbutane are mentioned. You may use these 1 type or in combination of 2 or more types.

  The content in the case of adding the polymerization initiator is not particularly limited, but when the nonvolatile component in the resin composition is 100% by mass, 0.1 to 3% by mass is preferable, and 0.2 to 2% by mass is More preferable. 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, drill workability can be improved, dielectric loss tangent can be reduced, and stress relaxation effect can be obtained. The rubber particles that can be used in the present invention are, for example, those that are insoluble in an organic solvent used when preparing a varnish of the resin composition, and are also incompatible with an epoxy resin and the like. Therefore, the rubber particles are present 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 the rubber component does not dissolve in the organic solvent or the resin and forming the rubber particles.

  Preferable examples of the rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked 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 the outer shell layer is composed of a glassy polymer and the inner core layer is composed of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is composed of a glassy polymer, the intermediate layer is composed of a rubbery polymer, and the core layer is composed 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). The rubber particles may be used in combination of two or more kinds. Specific examples of the core-shell type rubber particles include staphyloid AC3832, AC3816N, AC3401N, IM-401 Kai 7-17 (trade name, manufactured by Ganz Kasei Co., Ltd.), and METABLEN 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 Metablen W300A (average particle size 0.1 μm) and W450A (average particle size 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.).

  The average particle diameter of the rubber particles is preferably in the range of 0.005 to 1 μm, more preferably 0.2 to 0.6 μm. The average particle size of the rubber particles used in the present invention can be measured by 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 prepared on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). However, it can be measured by setting the median diameter to the average particle diameter.

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

<Other ingredients>
Other components can be added to the resin composition of the present invention, if necessary, within a range that does not impair the effects of the present invention. As other components, vinylbenzyl compounds, acrylic compounds, maleimide compounds, thermosetting resins such as blocked isocyanate compounds, silicone powder, nylon powder, organic fillers such as fluorine powder, orben, thickeners such as Benton, Adhesion imparting agents such as silicone type, fluorine type, polymer type antifoaming agents or leveling agents, imidazole type, thiazole type, triazole type, silane coupling 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 prepared by appropriately mixing the above components, and if necessary, kneading or mixing by a kneading means such as a triple roll, a ball mill, a bead mill, a sand mill, or a stirring means such as a super mixer or a planetary mixer. It can be adjusted by Further, a resin varnish can be prepared by further adding an organic solvent.

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

  The arithmetic average roughness (Ra value) after the resin composition of the present invention is cured to form an insulating layer and the surface of the insulating layer is subjected to a roughening treatment will be described later. Value) and measurement of root mean square roughness (Rq)>. Specifically, the upper limit of the arithmetic average roughness (Ra value) is preferably 300 nm or less, more preferably 250 nm or less, further preferably 200 nm or less, still more preferably 150 nm or less, and even more preferably 130 nm for forming fine wiring. The following are particularly preferred. The lower limit 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.

  Since the root mean square roughness (Rq value) reflects the local state of the surface of the insulating layer, it was found that it is possible to confirm that the surface of the insulating layer is 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, still more preferably 350 nm or less, still more preferably 300 nm or less, in order to obtain a dense and smooth insulating layer surface. A thickness of 250 nm or less is particularly preferable. The lower limit of the root mean square roughness (Rq value) is preferably 15 nm or more, more preferably 70 nm or more, still more preferably 100 nm or more, from the viewpoint of stabilizing the peel strength.

  The peel strength between the conductor layer and the insulating layer obtained by curing the resin composition of the present invention to form the insulating layer, roughening the surface of the insulating layer, and plating is described below. Measurement of peeling strength (peel strength)> can be understood. 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. It is preferably 0.4 kgf / cm or more. The higher the upper limit of the peel strength, the better, and there is no particular limitation, but it is generally 1.2 kgf / cm or less, 1.0 kgf / cm or less, and 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 below. Specifically, it can be measured by a cavity resonance perturbation method at a frequency of 5.8 GHz and a measurement temperature of 23 ° C. 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 reducing signal noise. The lower limit value is not particularly limited and is 0.001, 0.0005, 0 or the like.

  The use of the resin composition of the present invention is not particularly limited, but includes adhesive films, sheet-like laminated materials such as prepregs, circuit boards (used for laminated boards, used for multilayer printed wiring boards, etc.), solder resists, underfill materials, dies. It can be used in a wide range of applications where a resin composition is required, such as a bonding material, a semiconductor encapsulating material, a hole filling resin, 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 it is generally industrially preferable to use it in the form of a sheet-like laminated material such as an adhesive film and a prepreg. .. The softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminating property of the sheet-shaped laminated material.

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

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, acetic ester such as cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, carbitol 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 kinds of organic solvents may be used in combination.

  The drying condition is not particularly limited, but the resin composition layer is dried 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 varies 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 the 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 not less 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, the thickness is more preferably 15 to 80 μm.

  Examples of the support include films of polyolefins 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. Examples include various plastic films. Further, release paper or metal foil such as copper foil and aluminum foil may be used. Among them, a plastic film is preferable, and a polyethylene terephthalate film is more preferable, from the viewpoint of versatility. The support and the protective film described later may be subjected to surface treatment such as mud treatment and corona treatment. Further, 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.

  The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm.

  A protective film conforming to the support can be further laminated on the surface of the resin composition layer on which the support is not adhered. The thickness of the protective film is not particularly limited, but is, for example, 1 to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and prevent scratches. The adhesive film can be wound into a roll and stored.

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

  In the hot-melt method, the resin composition is not dissolved in an organic solvent and is once coated on a support and then laminated on a sheet-shaped reinforcing base material, or is directly applied to the sheet-shaped reinforcing base material by a die coater. It is a method of manufacturing a prepreg by performing the above. Further, the solvent method, the resin is dissolved in an organic solvent in the same manner as the adhesive film to prepare a resin varnish, the sheet-shaped reinforcing base material is immersed in this varnish, and the resin varnish is impregnated into the sheet-shaped reinforcing base material. It is a method of drying. Alternatively, the adhesive film may be prepared by continuously heat laminating the adhesive film from both sides of the sheet-like reinforcing base material under heating and pressurizing conditions. A support, a protective film, etc. can be used similarly to 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-shaped laminated material manufactured as described above. An example will be described below.

  First, the sheet-shaped laminated material is laminated (laminated) on one side or both sides of the 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, and a thermosetting polyphenylene ether substrate. The term "circuit board" used herein refers to a board on which a patterned conductor layer (circuit) is formed on one side or both sides of the board. Further, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one or both outermost layers of the multilayer printed wiring board are patterned conductor layers (circuits). It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening treatment, copper etching or the like.

In the above laminate, when the sheet-shaped laminated material has a protective film, after removing the protective film, the sheet-shaped laminated material and the circuit board are preheated if necessary, and the sheet-shaped laminated material is pressed and Laminate on circuit board while heating. In the sheet-shaped laminated material of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used. The laminating conditions are not particularly limited, but for example, the pressure bonding temperature (lamination temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure (lamination 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 a reduced pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using rolls. Vacuum lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum applicators manufactured by Nichigo Morton Co., Ltd., vacuum press laminators manufactured by Meiki Co., Ltd., roll dry coaters manufactured by Hitachi Industries Co., Ltd., Hitachi AIC Co., Ltd. ) Vacuum laminator etc. made by the above can be mentioned.

  After laminating the sheet-shaped laminated material on the circuit board, and then cooling it to around room temperature, if the support is peeled off, peel the resin composition and heat cure the resin composition to form a cured product. An insulating layer can be formed. The conditions for thermosetting may be appropriately selected depending on the type and content of the resin component in the resin composition, but are 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 off before curing, it may be peeled off here if necessary.

Further, the sheet-shaped laminated material can be laminated on one side or both sides of the circuit board by using a vacuum press machine. The lamination process of 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 conditions are such that the degree of pressure reduction is usually 1 × 10 ⁻² MPa or less, preferably 1 × 10 ⁻³ MPa or less. The heating and pressurizing can be carried out in one step, but it is preferable to carry out the conditions divided into two or more steps from the viewpoint of controlling the exudation of the resin. For example, the first-stage press has a temperature of 70 to 150 ° C. and a pressure of 1 to 15 kgf / cm 2, and the second stage of the press has a temperature of 150 to 200 ° C. and a pressure of 1 to 40 kgf / cm 2. It is preferable to carry out. The time of each step is preferably 30 to 120 minutes. By thermally curing the resin composition layer in this manner, an insulating layer can be formed on the circuit board. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho Co., Ltd.) and VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.).

  Next, the insulating layer formed on the circuit board is perforated to form via holes and through holes. The drilling process can be carried out, for example, by a known method such as a drill, a laser, a plasma, or a combination of these methods, if necessary, but the drilling process by a laser such as a carbon dioxide gas laser or a YAG laser is the most common. Is the way. If the support has not been peeled off before drilling, it is peeled off here.

  Then, the surface of the insulating layer is roughened. In the case of dry-type roughening treatment, plasma treatment and the like can be mentioned. In the case of wet-type roughening treatment, a method of performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent and neutralization treatment with a neutralizing liquid in this order can be given. Be done. The wet roughening treatment is preferable because the smear in the via hole can be removed while forming the 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 55 to 70 ° C. for 8 to 15 minutes). Examples of the swelling solution include an alkaline solution and a surfactant solution, preferably an alkaline solution. 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 SBU, manufactured by Atotech Japan Co., Ltd. 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 70 to 80 ° C for 15 to 25 minutes). Examples of the oxidizing agent include alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate 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 permanganate solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan Co., Ltd. The neutralization treatment with the neutralizing solution is carried out by immersing in the 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 solution Securigant 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, known methods such as vapor deposition, sputtering and ion plating can be used. Examples of the wet plating include a method of forming a conductor layer by combining electroless plating and electrolytic plating, a method of forming a plating resist having a pattern opposite to that of the conductor layer, and forming a conductor layer only by electroless plating. Be done. As a method for pattern formation thereafter, for example, a subtractive method, a semi-additive method or the like known to those skilled in the art can be used, and by repeating the above-mentioned series of steps a plurality of times, a multi-layered buildup layer is laminated. 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 on a conductive portion of the multilayer printed wiring board of the present invention. The "conducting place" is a "place for transmitting an electric signal in the multilayer printed wiring board", and the place may be a surface or an embedded place. 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. Specifically, the wire bonding mounting method, the flip chip mounting method, and the bumpless method are used. Examples thereof 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).

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, "part" means a mass part.

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

<Preparation of Samples for Arithmetic Mean Roughness (Ra Value) Root Mean Square Roughness (Rq Value) and Peel Strength Measurement>
(1) Undercoating of inner layer circuit board Both sides of the glass cloth base material epoxy resin double-sided copper clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, R5715ES manufactured by Matsushita Electric Works, Ltd.) on which the inner layer circuit is formed A copper surface was roughened by etching with CZ8100 manufactured by MEC Co., Ltd. by 1 μm.

(2) Lamination of Adhesive Film The adhesive films prepared in Examples and Comparative Examples were 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 decompressing for 30 seconds so that the atmospheric pressure was 13 hPa or less, and then performing 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 by curing the resin composition under a curing condition of 200 ° C for 60 minutes to form an insulating layer, and then the PET film was peeled off.

(4) Roughening treatment The inner layer circuit board having the insulating layer formed thereon was immersed in a swelling solution, Swelling Dip Securigant P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. at 60 ° C. for 10 minutes, and then roughened. As a solution, Atotech Japan Co., Ltd. Concentrate Compact P (KMnO4: 60 g / L, aqueous solution of NaOH: 40 g / L) is immersed at 80 ° C. for 20 minutes, and finally as a neutralizing solution, Atotech Japan Co., Ltd. It was immersed for 5 minutes at 40 ° C. in the reduction SHORYUSIN SECURIGANT P. After drying at 80 ° C. for 30 minutes, arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) of the roughened insulating layer surface were measured.

(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 a solution for electroless plating containing PdCl ₂ at 40 ° C. for 5 minutes, and then an electroless copper plating solution. It was immersed at 25 ° C. for 20 minutes. After heating at 150 ° C. for 30 minutes to perform an annealing treatment, an etching resist was formed, and after forming a pattern 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 peeling strength (peel strength) of the plated conductor layer was measured for this circuit board.

<Measurement of arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) after roughening treatment>
Using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Becoin Instruments Co., Ltd.), Ra value was determined by a numerical value obtained by setting the measurement range to 121 μm × 92 μm with a 50 × lens in VSI contact mode. Then, an average value of 10 points was obtained to obtain a measured value.

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

<Measurement of dielectric loss tangent>
The resin varnishes obtained in Examples and Comparative Examples were coated on a release-treated PET film (“PET501010” manufactured by Lintec Co., Ltd.) so that the resin composition layer after drying had a thickness of 40 μm. It was evenly coated with a coater and dried at 80 to 110 ° C. (average 95 ° C.) for 6 minutes. Then, it was heat-treated at 200 ° C. for 90 minutes in a nitrogen atmosphere and peeled from the support to obtain a cured product film. The cured film was cut into a length of 80 mm and a width of 2 mm to give 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. The measurement was performed on two test pieces, and the average value was calculated.

<Preparation of polybutadiene resin A>
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.) in a reaction vessel, and Ipsol 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 uniformly dissolved. When the temperature became uniform, the temperature was raised to 50 ° C., and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) Was added with stirring, and the reaction was carried out for about 3 hours. Then, this reaction product was cooled to room temperature, and then 8.96 g of benzophenonetetracarboxylic dianhydride (acid anhydride equivalent = 161.1 g / eq.), 0.07 g of triethylenediamine, and ethyldiglycol were added. 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. Upon confirmation of the disappearance of the NCO peak, the reaction was considered to be the end point of the reaction, and the reaction product was cooled to room temperature and filtered with 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 mg KOH / g
Solid content = 50 wt%
Number average molecular weight = 13723
Content of polybutadiene structure = 50 / (50 + 4.8 + 8.96) * 100
= 78.4 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., Inc.), bixylenol diallyl ether resin ("YL7776 (number average molecular weight 331)" manufactured by Mitsubishi Chemical Co., Ltd.) 24 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L") 18 parts, active ester type curing agent (DIC Co., Ltd. "EXB9416-70BK", solid content 70 mass% methyl isobutyl ketone solution) 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.) and 4.8 parts of a polymerization initiator ("Perhexin 25B" manufactured by NOF CORPORATION) , Spherical particles (average particle size) surface-treated with 1.58 parts of rubber particles (Ganzu Kasei Co., Ltd., Staphyloid AC3816N), styrylsilane coupling agent (Shin-Etsu Chemical Co., Ltd., "KBM1403") A resin varnish was prepared by mixing 158 parts of 0.5 μm and “SOC2” manufactured by Admatechs Co., Ltd. and uniformly dispersing them with a high-speed rotary mixer.

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

<Example 2>
Styrene-modified polyphenylene ether resin ("OPE-2St (number average molecular weight 1200)" manufactured by Mitsubishi Gas Chemical Co., Inc.) 48 parts, bixylenol diallyl ether resin ("YL7776 (number average molecular weight 331)" manufactured by Mitsubishi Chemical Co., Ltd.) 24 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L") 36 parts, active ester type curing agent (DIC Co., Ltd. "EXB9416-70BK", solid content 70 mass% methyl isobutyl ketone solution) A mixed solution of 52 parts, polybutadiene resin A 75 parts, solvent naphtha 35 parts, and toluene 50 parts was heated and dissolved with stirring. After cooling the mixed solution to room temperature, 4.7 parts of a curing accelerator (40% by mass MEK solution of "1B2PZ" manufactured by Shikoku Kasei Co., Ltd.) and a polymerization initiator ("Perhexin 25B" manufactured by NOF CORPORATION) 7. 5 parts, 2.42 parts of staphyloid AC3816N, rubber particles (manufactured by Ganz Kasei Co., Ltd.), 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 them with a high-speed rotary mixer. Then, an adhesive film was prepared in the same manner as in Example 1.

<Example 3>
Styrene-modified polyphenylene ether resin ("OPE-2St (number average molecular weight 1200)" manufactured by Mitsubishi Gas Chemical Co., Inc.) 48 parts, bixylenol diallyl ether resin ("YL7776 (number average molecular weight 331)" manufactured by Mitsubishi Chemical Co., Ltd.) 24 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L") 18 parts, active ester type curing agent (DIC Co., Ltd. "HPC8000-65T", solid content 65 mass% toluene solution) 23 parts A mixed solution of 20 parts of polybutadiene resin A, 30 parts of solvent naphtha, and 25 parts of toluene was heated and dissolved with 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.) and 4.7 parts of a polymerization initiator ("Perhexin 25B" manufactured by NOF CORPORATION) , Spherical particles (average particle size) surface-treated with rubber particles (Ganzu Kasei Co., Ltd., Staphyloid AC3816N) 1.54 parts, styrylsilane coupling agent (Shin-Etsu Chemical Co., Ltd., "KBM1403") A resin varnish was prepared by mixing 154 parts of 0.5 μm and “SOC2” manufactured by Admatechs Co., Ltd. and uniformly dispersing them with a high-speed rotary mixer. Then, an adhesive film was prepared 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., Inc.), bixylenol diallyl ether resin ("YL7776 (number average molecular weight 331)" manufactured by Mitsubishi Chemical Co., Ltd.) A mixed solution of 24 parts, 37 parts of polybutadiene resin A, 30 parts of solvent naphtha, and 40 parts of toluene 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 (Staffloid AC3816N manufactured by Gantz Kasei Co., Ltd.), a styrylsilane system. 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 is mixed. Was evenly dispersed to prepare a resin varnish. Then, an adhesive film was prepared 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., Inc.), bixylenol diallyl ether resin ("YL7776 (number average molecular weight 331)" manufactured by Mitsubishi Chemical Co., Ltd.) 24 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L") 18 parts, active ester type curing agent (DIC Co., Ltd. "EXB9416-70BK", solid content 70 mass% methyl isobutyl ketone solution) A mixed solution of 26 parts, 30 parts of solvent naphtha and 15 parts of toluene was heated and dissolved with stirring. 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.) and a polymerization initiator ("Perhexin 25B" manufactured by NOF CORPORATION) 4. Spherical silica (average) surface-treated with 5 parts, rubber particles (Ganzu Kasei Co., Ltd., Staphyloid AC3816N) 1.44 parts, styrylsilane coupling agent (Shin-Etsu Chemical Co., Ltd., "KBM1403") 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 them with a high-speed rotary mixer. Then, an adhesive film was prepared 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., Inc.), bixylenol diallyl ether resin ("YL7776 (number average molecular weight 331)" manufactured by Mitsubishi Chemical Co., Ltd.) 24 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L") 18 parts, active ester type curing agent (DIC Co., Ltd. "EXB9416-70BK", solid content 70 mass% methyl isobutyl ketone solution) A mixed solution of 26 parts, phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK solution having a solid content of 30% by mass), 30 parts solvent naphtha, 25 parts toluene, and 10 parts methyl ethyl ketone was 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.) and 4.9 parts of a polymerization initiator ("Perhexin 25B" manufactured by NOF CORPORATION) , Spherical particles (average particle size) surface-treated with 1.58 parts of rubber particles (Ganzu Kasei Co., Ltd., Staphyloid AC3816N), styrylsilane coupling agent (Shin-Etsu Chemical Co., Ltd., "KBM1403") A resin varnish was prepared by mixing 158 parts of 0.5 μm and “SOC2” manufactured by Admatechs Co., Ltd. and uniformly dispersing them with a high-speed rotary mixer. Then, an adhesive film was prepared in the same manner as in Example 1.

  The results are shown in Table 1.

  From the results shown in Table 1, the resin compositions of Examples have low arithmetic mean roughness, low root mean square roughness, stable peel strength, and low dielectric loss tangent. On the other hand, in Comparative Example 1, the arithmetic mean roughness and the root mean square roughness are large and the peel strength is 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 high.

  In the wet roughening step, not only the arithmetic mean roughness of the surface of the insulating layer is small, but also the root mean square roughness is small, and it is possible to form a plated conductor layer having a stable peel strength on it, and the dielectric loss tangent is also low. It has become possible to provide a resin composition. Further, it has become possible to provide a sheet-shaped laminated material, a multilayer printed wiring board and a semiconductor device using the resin composition. Furthermore, it has become possible to provide electric products such as computers, mobile phones, digital cameras, televisions, etc., on which these are mounted, and vehicles such as motorcycles, automobiles, trains, ships, and aircraft.

Claims (21)

Contains (A) a radically polymerizable compound, (B) an epoxy resin, (C) a curing agent and (D) a roughening component,
Wherein the radically polymerizable compound (A) having a styryl group, an allyl group, an acrylic group, and one or more selected from a methacrylic group,
The (C) curing agent contains an active ester type curing agent and / or a cyanate ester type curing agent,
The (D) roughening component is selected from polybutadiene resin, polyamide resin, polyamideimide resin, polyimide resin, polycarbonate resin, polyester resin, polyurethane resin having a number average molecular weight of 300 to 30,000 or having a reactive group. A resin composition for forming a plated conductor layer, which comprises one or more of the following:   The resin composition according to claim 1, wherein the number-average molecular weight of the radically polymerizable compound (A) is in the range of 100 to 10,000.   The resin composition according to claim 1 or 2, wherein the content of the radically polymerizable compound (A) is 5 to 40% by mass, when the nonvolatile component in the resin composition is 100% by mass. object.   The (B) epoxy resin is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, a glycidyl ester type epoxy resin and an anthracene type. It is 1 or more types selected from an epoxy resin, The resin composition of any one of Claims 1-3 characterized by the above-mentioned.   The content of the (B) epoxy resin is 1 to 30% by mass when the nonvolatile component in the resin composition is 100% by mass, and the content of the epoxy resin is 1 to 30% by mass. Resin composition.   The resin composition according to any one of claims 1 to 5, wherein the (C) curing agent contains an active ester type curing agent.   Content of the said (C) hardening | curing agent 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 any one of claims 1 to 7, wherein the roughening component (D) contains a polybutadiene resin having a number average molecular weight of 300 to 30,000. The (D) roughening component contains a polybutadiene resin having a butadiene skeleton and a reactive group,
The resin composition according to any one of claims 1 to 8, wherein the reactive group is selected from a carboxylic acid group, an acid anhydride group, a hydroxyl group, and an epoxy group.   The content of the (D) roughening component is 0.5 to 20 mass% when the non-volatile component in the resin composition is 100 mass%, any one of claims 1 to 9 characterized in that The resin composition according to item.   (E) The inorganic filler is contained, The resin composition of any one of Claims 1-10 characterized by the above-mentioned.   The resin composition according to claim 11, wherein the inorganic filler (E) is surface-treated with a styrylsilane-based coupling agent.   The resin composition according to claim 11 or 12, wherein the content of the inorganic filler (E) is 40 to 85 mass% when the nonvolatile component in the resin composition is 100 mass%. ..   The resin composition is cured to form an insulating layer, and the surface of the insulating layer is roughened to have an arithmetic mean roughness of 10 to 300 nm and a root mean square roughness of 15 to 450 nm. The resin composition according to any one of claims 1 to 13.   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 (2. 94 to 11.8 N / cm), The resin composition according to claim 1.   The resin composition according to any one of claims 1 to 15, wherein the cured product of the resin composition has a dielectric loss tangent of 0.003 or less.   It is a resin composition for insulating layers of a multilayer printed wiring board, The resin composition of any one of Claims 1-16 characterized by the above-mentioned.   It is a resin composition for buildup layers of a multilayer printed wiring board, The resin composition of any one of Claims 1-17 characterized by the above-mentioned.   A sheet-shaped laminated material comprising the resin composition according to any one of claims 1 to 18.   A multilayer printed wiring board using the sheet-shaped laminated material according to claim 19.   A semiconductor device using the multilayer printed wiring board according to claim 20.