JP2019206622A - Resin composition - Google Patents

Abstract

To provide a resin composition that makes it possible to obtain a cured product that has a low dielectric loss tangent, prevents the holoing phenomenon, and has excellent adhesion to a conductor layer; a resin sheet containing the resin composition; a printed wiring board including an insulating layer formed with the resin composition; and a semiconductor device.SOLUTION: A resin composition contains (A) an epoxy resin, (B) a (meth) acrylate having two or less functional groups, (C) a (meth) acrylate having three or more functional groups, and (D) inorganic filler.SELECTED DRAWING: None

Description

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

  As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked on an inner layer circuit board is known. The insulating layer is generally formed by curing a resin composition. For example, Patent Document 1 describes a resin composition containing (A) a radical polymerizable compound, (B) an epoxy resin, (C) a curing agent, and (D) a roughening component.

JP 2014-034580 A

  Many proposals of a resin composition suitable for forming an insulating layer of an inner circuit board have been made including the resin composition described in Patent Document 1, but in recent years, there has been a demand for an insulating layer having a low dielectric loss tangent. It is increasing.

  As a result of the study by the present inventors, the cured product of the resin composition containing a material that lowers the dielectric loss tangent is difficult to obtain adhesiveness with a conductor layer or the like, and has a haloing phenomenon that reduces conduction reliability. It has been found that it occurs. In recent years, in the production of multilayer printed wiring boards, the cured product of the resin composition for forming an insulating layer has sufficient adhesion and conductivity in addition to low dielectric loss tangent even in the miniaturization and densification of wiring. Although it is required to have reliability, the current situation is that these have not been sufficiently satisfied. Here, the haloing phenomenon means that delamination occurs between the insulating layer and the inner layer substrate around the via hole. Such a haloing phenomenon usually occurs when the resin around the via hole is deteriorated during the formation of the via hole, and the deteriorated portion is eroded during the roughening treatment. The deteriorated portion is usually observed as a discolored portion.

  An object of the present invention is to provide a resin composition having a low dielectric loss tangent, capable of suppressing a haloing phenomenon, and capable of obtaining a cured product having excellent adhesion to a conductor layer; a resin sheet containing the resin composition; A printed wiring board including an insulating layer formed using a resin composition; and a semiconductor device including the printed wiring board.

As a result of intensive studies to solve the above problems, the present inventor has (A) an epoxy resin, (B) a bifunctional or lower (meth) acrylic ester, and (C) a trifunctional or higher (meth) acrylic ester. And (D) It discovered that the said subject could be solved with the resin composition containing combining an inorganic filler, and completed this invention.
That is, the present invention includes the following contents.

（式（Ｂ−１）中、Ｒ^１及びＲ^４はそれぞれ独立にアクリロイル基又はメタクリロイル基を表し、Ｒ^２及びＲ^３はそれぞれ独立に２価の連結基を表す。環Ａは、２価の環状基を表す。）
［７］ （Ｃ）成分が、３価以上のアルコールの（メタ）アクリレート、３価以上のアルコールの環状エーテル付加物の（メタ）アクリレート、３価以上のアルコールの環状エステル付加物の（メタ）アクリレート、又はリン酸トリエステル（メタ）アクリレートである、［１］〜［６］のいずれかに記載の樹脂組成物。
［８］ さらに、（Ｅ）硬化剤を含む、［１］〜［７］のいずれかに記載の樹脂組成物。
［９］ （Ｅ）成分が、ベンゾオキサジン系硬化剤、カルボジイミド系硬化剤、フェノール系硬化剤、及び活性エステル系硬化剤からなる選択される１種以上である、［８］に記載の樹脂組成物。
［１０］ 絶縁用途に用いる、［１］〜［９］のいずれかに記載の樹脂組成物。
［１１］ 絶縁層形成用である、［１］〜［１０］のいずれかに記載の樹脂組成物。
［１２］ 導体層を形成するための絶縁層形成用である、［１］〜［１１］のいずれかに記載の樹脂組成物。
［１３］ 半導体チップの封止用である、［１］〜［１２］のいずれかに記載の樹脂組成物。
［１４］ 支持体と、該支持体上に設けられた、［１］〜［１３］のいずれかに記載の樹脂組成物を含む樹脂組成物層とを含む、樹脂シート。
［１５］ ［１］〜［１３］のいずれかに記載の樹脂組成物の硬化物により形成された絶縁層を含む、プリント配線板。
［１６］ ［１５］に記載のプリント配線板を含む、半導体装置。 [1] (A) epoxy resin,
(B) a bifunctional or lower (meth) acrylic acid ester,
(C) Trifunctional or higher functional (meth) acrylic acid ester, and (D) an inorganic filler.
[2] The resin composition according to [1], wherein the content of the component (B) is 0.1% by mass or more and 10% by mass or less when the nonvolatile component in the resin composition is 100% by mass.
[3] The content of the component (C) is 0.1% by mass or more and 3% by mass or less when the nonvolatile component in the resin composition is 100% by mass, according to [1] or [2] Resin composition.
[4] The content of the component (B) when the nonvolatile component in the resin composition is 100% by mass is b1, and the content of the component (C) when the nonvolatile component in the resin composition is 100% by mass The resin composition according to any one of [1] to [3], wherein b1 / c1 satisfies a relationship of 1 or more and 10 or less when the amount is c1.
[5] The resin composition according to any one of [1] to [4], wherein the component (B) has a cyclic structure.
[6] The resin composition according to any one of [1] to [5], wherein the component (B) has a structure represented by the following formula (B-1).

(In Formula (B-1), R ¹ and R ⁴ each independently represent an acryloyl group or a methacryloyl group, R ² and R ³ each independently represent a divalent linking group. Ring A is a divalent group. Represents a cyclic group.)
[7] The component (C) is a (meth) acrylate of a trivalent or higher alcohol (meth) acrylate, a (meth) acrylate of a cyclic ether adduct of a trivalent or higher alcohol, or a (meth) of a cyclic ester adduct of a trivalent or higher alcohol. The resin composition according to any one of [1] to [6], which is an acrylate or a phosphoric acid triester (meth) acrylate.
[8] The resin composition according to any one of [1] to [7], further comprising (E) a curing agent.
[9] The resin composition according to [8], wherein the component (E) is at least one selected from a benzoxazine-based curing agent, a carbodiimide-based curing agent, a phenol-based curing agent, and an active ester-based curing agent. Stuff.
[10] The resin composition according to any one of [1] to [9], which is used for insulating purposes.
[11] The resin composition according to any one of [1] to [10], which is for forming an insulating layer.
[12] The resin composition according to any one of [1] to [11], which is for forming an insulating layer for forming a conductor layer.
[13] The resin composition according to any one of [1] to [12], which is used for sealing a semiconductor chip.
[14] A resin sheet comprising a support and a resin composition layer including the resin composition according to any one of [1] to [13] provided on the support.
[15] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [13].
[16] A semiconductor device including the printed wiring board according to [15].

  According to the present invention, a resin composition having a low dielectric loss tangent, capable of suppressing a haloing phenomenon, and capable of obtaining a cured product having excellent adhesion to a conductor layer; a resin sheet containing the resin composition; A printed wiring board provided with an insulating layer formed using a resin composition; and a semiconductor device including the printed wiring board can be provided.

FIG. 1 is a cross-sectional view schematically showing an insulating layer obtained by curing the resin composition of the present invention into a sheet shape together with an inner layer substrate. FIG. 2 is a plan view schematically showing the surface of the insulating layer obtained by curing the resin composition of the present invention in a sheet shape on the side opposite to the conductor layer. FIG. 3 is a cross-sectional view schematically showing an insulating layer after the roughening treatment obtained by curing the resin composition of the present invention into a sheet shape together with the inner layer substrate.

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

[Resin composition]
The resin composition of the present invention comprises (A) an epoxy resin, (B) a bifunctional or lower (meth) acrylic ester, (C) a trifunctional or higher (meth) acrylic ester, and (D) an inorganic filler, Is a resin composition. By using such a resin composition, the desired effect of the present invention is that the dielectric loss tangent is low, the haloing phenomenon can be suppressed, and a cured product having excellent adhesion to the conductor layer can be obtained. can get.

  The resin composition may further contain an optional component in combination with the components (A) to (D). Examples of optional components include (E) a curing agent, (F) a curing accelerator, (G) a polymerization initiator, (H) a thermoplastic resin, (I) a flame retardant, and (J) other additives. Is mentioned. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Epoxy resin>
Examples of (A) epoxy resins include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol types. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin , Cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin Heterocyclic epoxy resins, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  It is preferable that a resin composition contains the epoxy resin which has a 2 or more epoxy group in 1 molecule as (A) epoxy resin. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule with respect to 100% by mass of the nonvolatile component (A) of the epoxy resin is preferably 50 masses. % Or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

  The epoxy resin may be an epoxy resin that is liquid at a temperature of 20 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) and an epoxy resin that is a solid at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). ) The resin composition (A) may contain only a liquid epoxy resin or only a solid epoxy resin as an epoxy resin, but may contain a combination of a liquid epoxy resin and a solid epoxy resin. Is preferred. (A) By using a combination of a liquid epoxy resin and a solid epoxy resin as the epoxy resin, sufficient flexibility is obtained when used in the form of a resin sheet, or the cured product of the resin composition is broken. Strength can be improved.

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

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

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

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

  Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, bisphenol AF type epoxy resin, biphenyl type epoxy resin, bixylenol A type epoxy resin is more preferable.

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

  (A) When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably a mass ratio, preferably 1: 1 to 1:20. More preferably, it is 1: 1.5-1: 15, Most preferably, it is 1: 2-1: 10. When the quantity ratio between the liquid epoxy resin and the solid epoxy resin is within such a range, the desired effect of the present invention can be remarkably obtained. Furthermore, usually, when used in the form of a resin sheet, moderate tackiness is brought about. Moreover, normally, when using with the form of a resin sheet, sufficient flexibility is acquired and a handleability improves. Furthermore, usually, a cured product having a sufficient breaking strength can be obtained.

  (A) The epoxy equivalent of the epoxy resin is preferably 50 g / eq to 5000 g / eq, more preferably 50 g / eq to 3000 g / eq, still more preferably 80 g / eq to 2000 g / eq, and even more preferably 110 g / eq to 1000 g / eq. By being in this range, the crosslinked density of the cured product of the resin composition layer is sufficient, and an insulating layer having a small surface roughness can be provided. Epoxy equivalent is the mass of resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

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

  (A) The content of the epoxy resin is preferably 1% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. Preferably it is 3 mass% or more, More preferably, it is 5 mass% or more. The upper limit of the content of the epoxy resin is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention. In addition, in this invention, content of each component in a resin composition is a value when the non-volatile component in a resin composition shall be 100 mass% unless there is separate description.

<(B) Bifunctional or lower (meth) acrylic acid ester>
The resin composition contains (B) a bifunctional or lower (meth) acrylic ester. (B) By containing a bifunctional or lower (meth) acrylic ester in the resin composition, a cured product having a low dielectric loss tangent and excellent adhesion can be obtained. Here, the term “(meth) acrylic acid” includes acrylic acid and methacrylic acid, and combinations thereof.

  (B) Bifunctional or lower (meth) acrylic acid esters include monofunctional (meth) acrylic acid esters and bifunctional (meth) acrylic acid esters. Among these, from the viewpoint of obtaining a cured product having a low dielectric loss tangent, (B) a bifunctional (meth) acrylic acid ester is preferably a bifunctional (meth) acrylic acid ester. Here, the monofunctional (meth) acrylic acid ester has one (meth) acryloyl group per molecule, and the bifunctional (meth) acrylic acid ester has two (meth) acryloyl groups per molecule. Have. The term “(meth) acryloyl group” includes acryloyl and methacryloyl groups and combinations thereof.

  (B) The bifunctional or lower (meth) acrylic acid ester preferably has a cyclic structure from the viewpoint of obtaining a cured product having a low dielectric loss tangent. As the cyclic structure, a divalent cyclic group is preferable. As a bivalent cyclic group, any of the cyclic group containing an alicyclic structure and the cyclic group containing an aromatic ring structure may be sufficient. Especially, it is preferable that it is a cyclic group containing an alicyclic structure from a viewpoint which obtains the desired effect of this invention notably.

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

  In the ring in the divalent cyclic group, a ring skeleton may be constituted by a hetero atom in addition to a carbon atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom, and an oxygen atom is preferable. One hetero atom may be present in the ring, or two or more hetero atoms may be present.

Specific examples of the divalent cyclic group include the following divalent groups (i) to (xi). Among these, as the divalent cyclic group, (x) or (xi) is preferable.

  The divalent cyclic group may have a substituent. Examples of such substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silyl groups, acyl groups, acyloxy groups, carboxy groups, sulfo groups, cyano groups, nitro groups, hydroxy groups, A mercapto group, an oxo group, etc. are mentioned, An alkyl group is preferable.

  The (meth) acryloyl group may be directly bonded to the divalent cyclic group or may be bonded via a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, —C (═O) O—, —O—, —NHC (═O) —, and —NC (═O). N—, —NHC (═O) O—, —C (═O) —, —S—, —SO—, —NH— and the like may be mentioned, and a group obtained by combining a plurality of these may be used. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms. Is more preferable. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a 1,1-dimethylethylene group. -A dimethylethylene group is preferred. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and still more preferably an alkenylene group having 2 to 5 carbon atoms. As an arylene group and heteroarylene group, a C6-C20 arylene group or heteroarylene group is preferable, and a C6-C10 arylene group or heteroarylene group is more preferable. As the divalent linking group, an alkylene group is preferable, and a methylene group and a 1,1-dimethylethylene group are particularly preferable.

（式（Ｂ−１）中、Ｒ^１及びＲ^４はそれぞれ独立にアクリロイル基又はメタクリロイル基を表し、Ｒ^２及びＲ^３はそれぞれ独立に２価の連結基を表す。環Ａは、２価の環状基を表す。） (B) The bifunctional or lower (meth) acrylic acid ester is preferably represented by the following formula (B-1).

(In Formula (B-1), R ¹ and R ⁴ each independently represent an acryloyl group or a methacryloyl group, R ² and R ³ each independently represent a divalent linking group. Ring A is a divalent group. Represents a cyclic group.)

R ¹ and R ⁴ each independently represents an acryloyl group or a methacryloyl group, and an acryloyl group is preferred.

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

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

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

Hereinafter, although the specific example of (B) component is shown, this invention is not limited to this.

  As the component (B), commercially available products may be used. For example, “NK ester A-DOG” ((meth) acryloyl group equivalent 163), “NK ester A-DCP” ((meta ) Acryloyl group equivalent 152), “NK ester DCP” ((meth) acryloyl group equivalent 166), “DCP-A” ((meth) acryloyl group equivalent 152) manufactured by Kyoeisha Chemical Co., Ltd., “NPDGA” manufactured by Nippon Kayaku Co., Ltd. ((Meth) acryloyl group equivalent 106), “FM-400” ((meth) acryloyl group equivalent 156), “R-604” ((meth) acryloyl group equivalent 163), “R-684” ((meth) acryloyl) Group equivalent 152), “R-687” ((meth) acryloyl group equivalent 187), “HX-220” ((meth) acryloyl group equivalent 270), “HX-620” ( Meth) acryloyl group equivalent 384), and the like. (B) A component may be used individually by 1 type and may be used in combination of 2 or more types.

  The (meth) acryloyl group equivalent of the component (B) is preferably 30 g / eq. From the viewpoint of obtaining a cured product having a low dielectric loss tangent and excellent adhesion. -400 g / eq. , More preferably 50 g / eq. -300 g / eq. And more preferably 75 g / eq. -200 g / eq. It is. The (meth) acryloyl group equivalent is the mass of the component (B) containing 1 equivalent of the (meth) acryloyl group.

  The content of the component (B) is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, in order to obtain a cured product having a low dielectric loss tangent and excellent adhesion when the nonvolatile component in the resin composition is 100% by mass. Is 1% by mass or more, more preferably 1.5% by mass or more. From the viewpoint of suppressing the haloing phenomenon, the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less.

<(C) Trifunctional or higher (meth) acrylic acid ester>
The resin composition contains (C) a trifunctional or higher functional (meth) acrylic ester. (C) It becomes possible to obtain the hardened | cured material which can suppress a haloing phenomenon by containing (meth) acrylic acid ester more than trifunctional in a resin composition. Bifunctional or lower (meth) acrylic acid esters usually do not react with epoxy resins. Therefore, in the cured product of the resin composition, since there is no bond between the part derived from the epoxy resin and the part derived from the bifunctional or lower (meth) acrylic acid ester, the bifunctional or lower (meth) acrylic acid It is considered that the portion derived from the ester is easily eroded and a halo phenomenon occurs. In the present invention, in addition to a bifunctional or lower (meth) acrylic acid ester, a trifunctional or higher functional (meth) acrylic acid ester is contained. Trifunctional or higher (meth) acrylic acid ester has a three-dimensional network structure by combining bifunctional or lower (meth) acrylic acid ester, so that bifunctional or lower (meth) acrylic acid ester is prevented from being eroded. To do. As a result, it is considered that the haloing phenomenon can be suppressed.

  (C) Trifunctional or higher (meth) acrylic acid ester is a (meth) acrylic acid ester having 3 or more (meth) acryloyl groups, preferably 4 functional or higher, more preferably 5 functional or higher, preferably Is 10 functions or less, more preferably 8 functions or less, and even more preferably 6 functions or less.

  (C) As trifunctional or higher functional (meth) acrylic acid ester, for example, (meth) acrylate of trivalent or higher alcohol, (meth) acrylate of trivalent or higher alcohol cyclic ether adduct, trivalent or higher alcohol (Meth) acrylate of a cyclic ester adduct or a phosphate triester (meth) acrylate is preferable, and a (meth) acrylate of a trivalent or higher alcohol or a cyclic ester adduct of a trivalent or higher alcohol ( More preferred is a (meth) acrylate. Examples of the trihydric or higher alcohol include trimethylolpropane, pentaerythritol, dipentaerythritol, and the like. Examples of the cyclic ether include ethylene oxide and propylene oxide. Examples of the cyclic ester include ε-caprolactone.

  Examples of the trivalent or higher alcohol (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetrafurfuryl alcohol oligo (meth) acrylate, Ethyl carbitol oligo (meth) acrylate, 1,4-butanediol oligo (meth) acrylate, 1,6-hexanediol oligo (meth) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate, Tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, N, N, N ', N'- tetrakis (beta-hydroxyethyl) ethyl diamine (meth) acrylic acid ester.

  Examples of the (meth) acrylate of a cyclic ether adduct of a trivalent or higher alcohol include trimethylolpropane EO-added tri (meth) acrylate and glycerin PO-added tri (meth) acrylate.

  Examples of the (meth) acrylate of a cyclic ester adduct of a trivalent or higher valent alcohol include (meth) acrylic acid ester of dipentaerythritol caprolactone.

  Examples of the phosphoric acid triester (meth) acrylate include tri (2- (meth) acryloyloxyethyl) phosphate, tri (2- (meth) acryloyloxypropyl) phosphate, and tri (3- (meth) acryloyloxypropyl) phosphate. , Tri (3- (meth) acryloyl-2-hydroxyloxypropyl) phosphate, di (3- (meth) acryloyl-2-hydroxyloxypropyl) (2- (meth) acryloyloxyethyl) phosphate, (3- (meta And acryloyl-2-hydroxyloxypropyl) di (2- (meth) acryloyloxyethyl) phosphate.

  (C) Trifunctional or higher (meth) acrylic acid ester may be used alone or in combination of two or more.

  (C) Trifunctional or higher functional (meth) acrylic acid ester may be a commercially available product. Specific examples include “DPHA”, “D-310”, “DPCA-20” manufactured by Nippon Kayaku Co., Ltd. “DPCA-30”, “DPCA-60”, “DPCA-120”, “GPO-303”, “TMPTA”, “PET-30”, “T-1420 (T)”, “RP-1040”, “ DPEA-12 "," THE-330 "," TMP-A "," PE-3A "," PE-4A "," DPE-6A "manufactured by Kyoeisha Chemical Co., Ltd. and the like.

  The content of the component (C) is preferably 0.1% by mass or more, more preferably 0.2% by mass, when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of suppressing haloing. As mentioned above, More preferably, it is 0.3 mass% or more. From the viewpoint of maintaining adhesion, the upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less.

  Since the resin composition contains (B) a bifunctional or lower (meth) acrylic ester and (C) a trifunctional or higher (meth) acrylic ester, the dielectric loss tangent is low and the haloing phenomenon can be suppressed. A cured product having excellent adhesion between the layers can be obtained. When the content (mass%) of the component (B) in the resin composition is b1, and the content (mass%) of the component (C) in the resin composition is c1, b1 / c1 From the viewpoint of maintaining, it is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more. From the viewpoint of suppressing haloing, the upper limit is preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less. By making b1 / c1 within such a range, the effect of the present invention can be remarkably obtained.

<(D) Inorganic filler>
The resin composition contains (D) an inorganic filler. Thereby, a cured product having a low dielectric loss tangent can be obtained. An inorganic compound is used as the material of the inorganic filler. Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide , Barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly preferred. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as silica, spherical silica is preferable. (D) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

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

  (D) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. Preferably it is 5 micrometers or less, More preferably, it is 2 micrometers or less, More preferably, it is 1 micrometer or less.

  (D) The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering particle size distribution measuring device and setting the median diameter as the average particle size. As the measurement sample, 100 mg of an inorganic filler and 10 g of methyl ethyl ketone are weighed in a vial and can be dispersed by ultrasonic for 10 minutes. Particles obtained by measuring the volume-based particle size distribution of the (D) inorganic filler using a flow cell method, using a laser diffraction particle size distribution measuring device as the measurement light source, using blue and red as the light source wavelength. The average particle diameter was calculated as the median diameter from the diameter distribution. Examples of the laser diffraction particle size distribution measuring apparatus include “LA-960” manufactured by Horiba, Ltd.

(D) The specific surface area of the inorganic filler is preferably 1 m ² / g or more, more preferably 2 m ² / g or more, and particularly preferably 3 m ² / g or more from the viewpoint of remarkably obtaining the desired effect of the present invention. is there. Although there is no special restriction | limiting in an upper limit, Preferably it is 60 m < ² > / g or less, 50 m < ² > / g or less, or 40 m < ² > / g or less. The specific surface area can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method. .

  (D) It is preferable that the inorganic filler is treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanates. A coupling agent etc. are mentioned. Moreover, a surface treating agent may be used individually by 1 type, and may be used combining two or more types arbitrarily.

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

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

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

  The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.

  (D) From the viewpoint of lowering the dielectric loss tangent, the content of the inorganic filler is preferably 50% by mass or more, more preferably 53% by mass or more when the nonvolatile component in the resin composition is 100% by mass. More preferably, it is 55% by mass or more. Moreover, from a viewpoint of maintaining adhesiveness, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less, More preferably, it is 80 mass% or less.

<(E) Curing agent>
The resin composition may further contain (E) a curing agent as an optional component in addition to the components described above. (E) The curing agent usually has a function of reacting with the component (A) to cure the resin composition. (E) A hardening | curing agent may be used individually by 1 type, and may use 2 or more types together.

  (E) Examples of the curing agent include an active ester curing agent, a phenol curing agent, a naphthol curing agent, a benzoxazine curing agent, a cyanate ester curing agent, a carbodiimide curing agent, an amine curing agent, and an acid anhydride. Examples thereof include physical curing agents.

  As the active ester curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, as the active ester curing agent, two or more ester groups having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters in one molecule are used. The compound which has is preferable. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester 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, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

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

  As an active ester type curing agent commercially available as an active ester type curing agent having a dicyclopentadiene type diphenol structure, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T”, “HPC-” "8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC); "EXB9416-70BK", "EXB-8150-65T" (manufactured by DIC) as an active ester-based curing agent containing a naphthalene structure; phenol novolac “DC808” (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent containing an acetylated product; “YLH1026” (manufactured by Mitsubishi Chemical) as an active ester-based curing agent containing a benzoylated product of phenol novolac; Active ester “DC808” (manufactured by Mitsubishi Chemical Corporation) as a curing agent; “YLH1026” (manufactured by Mitsubishi Chemical Corporation), “YLH1030” (manufactured by Mitsubishi Chemical Corporation), “YLH1048” (manufactured by Mitsubishi Chemical Corporation) Mitsubishi Chemical Co., Ltd.);

  As a phenol type hardening | curing agent and a naphthol type | system | group hardening | curing agent, what has a novolak structure from a heat resistant and water-resistant viewpoint is preferable. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | curing agent is more preferable.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd .; “NHN” manufactured by Nippon Kayaku Co., Ltd. “CBN”, “GPH”: “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN-495V”, “SN375” manufactured by Nippon Steel & Sumikin Chemical; “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500”;

  Specific examples of the benzoxazine-based curing agent include “JBZ-OD100” (benzoxazine ring equivalent 218), “JBZ-OP100D” (benzoxazine ring equivalent 218), and “ODA-BOZ” (benzoxazine) manufactured by JFE Chemical Co., Ltd. Ring equivalent 218); “Pd” (benzoxazine ring equivalent 217), “Fa” (benzoxazine ring equivalent 217), manufactured by Shikoku Kasei Kogyo Co., Ltd .; “HFB2006M” (benzoxazine ring, manufactured by Showa Polymer Co., Ltd.) Equivalent 432) and the like.

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

  Specific examples of the carbodiimide curing agent include Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216, V-05 (carbodiimide group equivalent: 262), V-07 (carbodiimide group equivalent: 200) manufactured by Nisshinbo Chemical Co., Ltd. ); V-09 (carbodiimide group equivalent: 200); Stabuxol (registered trademark) P (carbodiimide group equivalent: 302) manufactured by Rhein Chemie.

  Examples of the amine curing agent include curing agents having one or more amino groups in one molecule. For example, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like. Among them, aromatic amines are preferable from the viewpoint of achieving the desired effect of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine curing agent include 4,4′-methylenebis (2,6-dimethylaniline), diphenyldiaminosulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3,3 ′. -Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl- 4,4′-diaminobiphenyl, 3,3′-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane Diamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- (4 Aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4 ′ -Bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, and the like. Commercially available amine-based curing agents may be used. For example, “KAYABOND C-200S”, “KAYABOND C-100”, “Kayahard A-A”, “Kayahard A-B”, “Kayahard AB” manufactured by Nippon Kayaku Co., Ltd. Kayahard AS, “Epicure W” manufactured by Mitsubishi Chemical Corporation, and the like.

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

  (E) As a hardening | curing agent, from the viewpoint which acquires the desired effect of this invention notably, 1 or more types selected from a benzoxazine type hardening | curing agent, a carbodiimide type hardening | curing agent, a phenol type hardening | curing agent, and an active ester type hardening | curing agent. Preferably, it is at least one selected from benzoxazine-based curing agents, carbodiimide-based curing agents, and active ester-based curing agents. Among these, (E) the curing agent preferably contains a benzoxazine curing agent or a carbodiimide curing agent in addition to the active ester curing agent, and in addition to the active ester curing agent and the phenol curing agent. More preferably, it contains a benzoxazine-based curing agent or a carbodiimide-based curing agent.

  (E) When an active ester type curing agent is included as the curing agent, the dielectric loss tangent can be lowered, and from the viewpoint of obtaining a cured product having excellent adhesion, the amount ratio of the component (A) and the active ester type curing agent is a predetermined amount. It is preferable to adjust the amount of the component (A) and the active ester curing agent so as to be within the range. Specifically, a1 is a value obtained by dividing the mass of the component (A) by the epoxy equivalent. This value “a1” indicates the equivalent number (eq.) Of the epoxy group contained in the component (A). In addition, a value obtained by dividing the mass of the active ester curing agent by the active ester group equivalent is defined as e1. This value “e1” indicates the number of equivalents (eq.) Of the active ester group. In this case, e1 / a1 is 0.1 or more, preferably 0.3 or more, more preferably 0.5 or more. The upper limit is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less. Here, when 2 or more types of (A) component are contained in a resin composition, said a1 is the value which totaled all the values which remove | divided the mass of each epoxy resin which exists in a resin composition by each epoxy equivalent. is there. Moreover, when two or more types of active ester type curing agents are contained, the above e1 is a value obtained by adding up all values obtained by dividing the mass of each active ester type curing agent present in the resin composition by the equivalent amount of each active ester group. is there.

  (E) When a benzoxazine-based curing agent is included as the curing agent, from the viewpoint of obtaining a cured product having excellent adhesion, the amount ratio of the component (B), the component (C) and the benzoxazine-based curing agent is within a predetermined range. It is preferable to adjust the amounts of the component (B), the component (C) and the benzoxazine-based curing agent so that Specifically, b2 is a value obtained by dividing the mass of the component (B) by the (meth) acryloyl group equivalent of the component (B). This value “b2” represents the number of equivalents (eq.) Of the (meth) acryloyl group equivalent contained in the component (B). The value obtained by dividing the (C) component by the (meth) acryloyl group equivalent is defined as c2. This value “c2” represents the equivalent number (eq.) Of the (meth) acryloyl group equivalent contained in the component (C). In addition, a value obtained by dividing the mass of the benzoxazine-based curing agent by the benzoxazine ring equivalent is defined as e2. This value “e2” represents the number of equivalents (eq.) Of the benzoxazine ring. In this case, e2 / (b2 + c2) is 0.08 or more, preferably 0.1 or more, more preferably 0.13 or more. The upper limit is 2.5 or less, preferably 2 or less, more preferably 1 or less. When two or more types of component (B) are contained in the resin composition, b2 is a value obtained by dividing the mass of each (meth) acrylic acid ester present in the resin composition by each (meth) acryloyl group equivalent. This is the total value. In addition, when two or more kinds of benzoxazine-based curing agents are contained in the resin composition, the above e2 is obtained by dividing the mass of the nonvolatile component of each benzoxazine-based curing agent present in the resin composition by each benzoxazine ring equivalent. This is the total value of all the values.

  (E) When a carbodiimide curing agent is included as the curing agent, the mass ratio of the component (B), the component (C) and the carbodiimide curing agent is within a predetermined range from the viewpoint of obtaining a cured product having excellent adhesion. Thus, it is preferable to adjust the amounts of the component (B), the component (C) and the carbodiimide curing agent. Specifically, when the content (% by mass) of the carbodiimide curing agent in the resin composition is e3, e3 / (b1 + c1) is 0.1 or more, preferably 0.2 or more, more preferably It is 0.25 or more. The upper limit is 1.5 or less, preferably 1.3 or less, more preferably 1.0 or less.

  The amount ratio of (A) epoxy resin to all (E) curing agents is a ratio of [total number of epoxy groups of component (A)]: [total number of reactive groups of (E) curing agent], 1 : The range of 0.01 to 1: 5 is preferable, 1: 0.5 to 1: 3 is more preferable, and 1: 1 to 1: 2 is more preferable. Here, “(A) the number of epoxy groups of the epoxy resin” is a value obtained by adding up all the values obtained by dividing the mass of the nonvolatile component of the (A) epoxy resin present in the resin composition by the epoxy equivalent. Further, “(E) the number of active groups of the curing agent” is a value obtained by adding all values obtained by dividing the mass of the non-volatile component of the (E) curing agent present in the resin composition by the active group equivalent. By making the amount ratio of (A) epoxy resin and (E) curing agent within such a range, the desired effect of the present invention can be remarkably obtained.

  (E) The content of the curing agent is preferably 5% by mass or more, more preferably 8% by mass with respect to 100% by mass of the nonvolatile component in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. More preferably, it is 10% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.

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

  Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among these, a phosphorus curing accelerator, an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

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

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

  Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  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, for example. 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.

  (F) The content of the curing accelerator is preferably 0.01% by mass or more, more preferably 100% by mass when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. Is 0.03% by mass or more, more preferably 0.05% by mass or more, preferably 0.5% by mass or less, more preferably 0.4% by mass or less, and further preferably 0.3% by mass or less. .

<(G) Polymerization initiator>
In addition to the components described above, the resin composition may further contain (G) a polymerization initiator as an optional component. (G) A polymerization initiator has a function which accelerates | stimulates the bridge | crosslinking of the (meth) acryloyl group in (B) component and (C) component normally. (G) A polymerization initiator may be used individually by 1 type, or may use 2 or more types together.

  (G) As a polymerization initiator, for example, t-butylcumyl peroxide, t-butylperoxyacetate, α, α′-di (t-butylperoxy) diisopropylbenzene, t-butylperoxylaurate, t -Peroxides such as butylperoxy-2-ethylhexanoate t-butylperoxyneodecanoate and t-butylperoxybenzoate.

  (G) Examples of commercially available polymerization initiators include “PARK Mill P”, “PARK Mill D”, “Perbutyl C”, “Perbutyl A”, “Perbutyl P”, “Perbutyl L”, “ “Perbutyl O”, “Perbutyl ND”, “Perbutyl Z” and the like.

  (G) The content of the polymerization initiator is preferably 0.01% by mass or more, more preferably 100% by mass, when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. Is 0.02% by mass or more, more preferably 0.03% by mass or more, preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and further preferably 0.1% by mass or less. .

<(H) Thermoplastic resin>
In addition to the components described above, the resin composition may further contain (H) a thermoplastic resin as an optional component.

  Examples of the thermoplastic resin as component (H) include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, and polyphenylene ether resin. , Polycarbonate resin, polyether ether ketone resin, polyester resin and the like. Among these, a phenoxy resin is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention and a viewpoint of obtaining an insulating layer having a small surface roughness and particularly excellent adhesion to the conductor layer. Moreover, a thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more types.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include a phenoxy resin having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

  Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resins) manufactured by Mitsubishi Chemical; “YX8100” (bisphenol S skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical; “YX6954” (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel &Chemicals; “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical; “YL7500BH30”, “YX6954BH30”, “YX7553”, “YX7553BH30” manufactured by Mitsubishi Chemical “YL7769BH30”, “YL6794”, “YL7213”, “YL7290”, “YL7482”;

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include SLECK BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd .;

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamide-imide resin include modified polyamide-imides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polyphenylene ether resin include oligophenylene ether / styrene resin “OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Company.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers.

  (H) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferably 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less.

  (H) The content of the thermoplastic resin is preferably 0.01% by mass or more, more preferably 100% by mass or more, more preferably 100% by mass, from the viewpoint of remarkably obtaining the desired effect of the present invention. Is 0.05% by mass or more, more preferably 0.1% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less.

<(I) Flame retardant>
The resin composition may contain (I) a flame retardant as an optional component. Examples of the flame retardant (I) include phosphazene compounds, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides, and the like, and phosphazene compounds are preferred. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

  The phosphazene compound is a cyclic compound having nitrogen and phosphorus as constituent elements, and the phosphazene compound is preferably a phosphazene compound having a phenolic hydroxyl group. Specific examples of the phosphazene compound include, for example, “SPH-100”, “SPS-100”, “SPB-100”, “SPE-100” manufactured by Otsuka Chemical Co., Ltd., and “FP-100” manufactured by Fushimi Pharmaceutical Co., Ltd. , “FP-110”, “FP-300”, “FP-400” and the like.

  Commercially available products may be used as the flame retardant other than the phosphazene compound, and examples thereof include “HCA-HQ” manufactured by Sanko Co., Ltd. and “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd. As the flame retardant, those which are difficult to hydrolyze are preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

  When the resin composition contains (I) a flame retardant, the amount of (I) the flame retardant is when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. The content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more. An upper limit becomes like this. Preferably it is 3 mass% or less, More preferably, it is 2 mass% or less, More preferably, it is 1 mass% or less.

<(J) Other additives>
The resin composition may further contain other additives as optional components in addition to the components described above. Examples of such additives include organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; thickeners; antifoaming agents; leveling agents; adhesion imparting agents; resin additives such as colorants. Is mentioned. These additives may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

<Characteristics of resin composition>
By curing the resin composition of the present invention, an insulating layer formed of a cured product of the resin composition can be obtained. When a via hole is formed in this insulating layer and a roughening process is performed, the haloing phenomenon can be suppressed. Hereinafter, these effects will be described with reference to the drawings.

  FIG. 1 is a cross-sectional view schematically showing an insulating layer 100 obtained by curing the resin composition of the present invention into a sheet shape together with an inner layer substrate 200. FIG. 1 shows a cross section of the insulating layer 100 taken along a plane passing through the center 120C of the bottom 120 of the via hole 110 and parallel to the thickness direction of the insulating layer 100.

  As shown in FIG. 1, the insulating layer 100 is a layer obtained by curing a resin composition formed on an inner layer substrate 200 including a conductor layer 210, and is made of a cured product of the resin composition. A via hole 110 is formed in the insulating layer 100. The via hole 110 is generally formed in a forward tapered shape having a larger diameter as it is closer to the surface 100U of the insulating layer 100 on the side opposite to the conductor layer 210, and a smaller diameter as it is closer to the conductor layer 210. It is formed in a columnar shape having a constant diameter in the thickness direction of 100. The via hole 110 is usually formed by irradiating the surface 100U of the insulating layer 100 opposite to the conductor layer 210 with laser light to remove a part of the insulating layer 100.

  The bottom of the via hole 110 on the conductor layer 210 side is appropriately referred to as a “via bottom” and denoted by reference numeral 120. The diameter of the via bottom 120 is referred to as a bottom diameter Lb. An opening formed on the opposite side of the via hole 110 from the conductor layer 210 is appropriately referred to as a “via top” and is denoted by reference numeral 130. The diameter of the via top 130 is referred to as a top diameter Lt. Normally, the via bottom 120 and the via top 130 are formed in a circular shape when viewed from the thickness direction of the insulating layer 100, but may be elliptical. When the planar shapes of the via bottom 120 and the via top 130 are elliptical, the bottom diameter Lb and the top diameter Lt respectively represent the major axis of the elliptical shape.

  At this time, the shape of the via hole 110 is better as the taper ratio Lb / Lt obtained by dividing the bottom diameter Lb by the top diameter Lt is closer to 100%. If the resin composition of the present invention is used, the shape of the normal via hole 110 can be easily controlled, so that the via hole 110 having a taper ratio Lb / Lt close to 100% can be realized.

  The taper ratio Lb / Lt of the via hole 110 can be calculated from the bottom diameter Lb and the top diameter Lt of the via hole 110. Further, the bottom diameter Lb and the top diameter Lt of the via hole 110 have a cross section through the insulating layer 100 parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the via bottom 120 using FIB (focused ion beam). After cutting out, the cross section can be measured by observing it with an electron microscope.

  FIG. 2 is a plan view schematically showing a surface 100U on the side opposite to the conductor layer 210 (not shown in FIG. 2) of the insulating layer 100 obtained by curing the resin composition of the present invention.

  As shown in FIG. 2, when the insulating layer 100 in which the via hole 110 is formed is seen, the insulating layer 100 is formed around the via hole 110 from the edge 180 of the via top 130 to the edge 190 on the outer peripheral side of the discoloration portion 140. A discolored portion 140 that has been discolored may be observed. The discolored portion 140 can be formed by resin degradation when the via hole 110 is formed, and is usually formed continuously from the via hole 110. In many cases, the discoloration portion 140 is a whitened portion.

FIG. 3 is a cross-sectional view schematically showing the roughened insulating layer 100 together with the inner layer substrate 200 obtained by curing the resin composition of the present invention. 3 shows a cross section of the insulating layer 100 taken along a plane passing through the center 120C of the via bottom 120 of the via hole 110 and parallel to the thickness direction of the insulating layer 100.
As shown in FIG. 3, when a roughening process is performed on the insulating layer 100 in which the via hole 110 is formed, a haloing phenomenon occurs, and the insulating layer 100 of the discolored portion 140 is peeled off from the conductor layer 210 and the edge of the via bottom 120 is formed. A gap 160 continuous from 150 may be formed.

  The haloing phenomenon can be suppressed by using the resin composition of the present invention. Therefore, peeling of the insulating layer 100 from the conductor layer 210 can be suppressed, so that the size of the gap 160 can be reduced.

  The edge 150 of the via bottom 120 corresponds to the inner peripheral edge of the gap 160. Therefore, the distance Wb from the edge 150 of the via bottom 120 to the outer peripheral end portion 170 of the gap portion 160 (that is, the end portion far from the center 120C of the via bottom 120) is the size in the in-plane direction of the gap portion 160. Equivalent to. Here, the in-plane direction refers to a direction perpendicular to the thickness direction of the insulating layer 100. In the following description, the distance Wb may be referred to as a haloing distance Wb from the edge 150 of the via bottom 120 of the via hole 110. The degree of suppression of the haloing phenomenon can be evaluated by the haloing distance Wb from the edge 150 of the via bottom 120. Specifically, it can be evaluated that the haloing phenomenon can be effectively suppressed as the haloing distance Wb from the edge 150 of the via bottom 120 is smaller.

For example, a resin composition layer including a resin composition formed on a copper foil is heated at 130 ° C. for 30 minutes and then heated at 170 ° C. for 30 minutes to be cured, and the insulating layer 100 obtained by heating is then subjected to CO ₂ laser. By irradiating light, a via hole 110 having a top diameter Lt of about 50 μm or about 30 μm is formed. Then, it is immersed in the swelling solution at 60 ° C. for 10 minutes, then immersed in the oxidant solution at 80 ° C. for 20 minutes, then immersed in the neutralizing solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 30 minutes. If the resin composition of the present invention is used, the haloing distance Wb from the edge 150 of the via bottom 120 of the via hole 110 of the insulating layer 100 thus obtained is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably. Can be 4.5 μm or less, particularly preferably 4 μm or less.

The CO ₂ laser light irradiation conditions are as follows: when the top diameter Lt is about 50 μm, the mask diameter is 1.60 mm, the focus offset value is 0.050, the pulse width is 25 μs, the power is 0.66 W, the aperture is 13, the number of shots is 2, burst. The mode (10 kHz) is set.
When the top diameter Lt is about 30 μm, the mask diameter is 1 mm, the pulse width is 16 μs, the energy is 0.2 mJ / shot, the number of shots is 2, and the burst mode (10 kHz).

  The haloing distance Wb from the edge 150 of the via bottom 120 is such that a cross section appears through the insulating layer 100 parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the via bottom 120 using FIB (focused ion beam). It can be measured by observing the cross section with an electron microscope.

  Moreover, since the shape of the via hole 110 in the insulating layer 100 before the roughening treatment can be easily controlled by using the resin composition of the present invention, the shape of the via hole 110 is usually also in the insulating layer 100 after the roughening treatment. Can be easily controlled. Therefore, the shape of the via hole 110 can be improved even after the roughening treatment, as in the case before the roughening treatment. Therefore, if the resin composition of the present invention is used, a via hole 110 having a taper ratio Lb / Lt close to 100% can be realized in the insulating layer after the roughening treatment.

For example, the insulating layer 100 obtained by heating the resin composition at 130 ° C. for 30 minutes and then curing at 170 ° C. for 30 minutes is irradiated with CO ₂ laser light to have a top diameter Lt of about 50 μm or about 30 μm. The via hole 110 is formed. Then, it is immersed in the swelling solution at 60 ° C. for 10 minutes, then immersed in the oxidant solution at 80 ° C. for 20 minutes, then immersed in the neutralizing solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 30 minutes. In these cases, the taper ratio Lb / Lt of the via hole 110 is preferably 70% to 100%, more preferably 75% to 100%, and particularly preferably 80% to 100%.

The CO ₂ laser light irradiation conditions are as follows: when the top diameter Lt is about 50 μm, the mask diameter is 1.60 mm, the focus offset value is 0.050, the pulse width is 25 μs, the power is 0.66 W, the aperture is 13, the number of shots is 2, burst. The mode (10 kHz) is set.
When the top diameter Lt is about 30 μm, the mask diameter is 1 mm, the pulse width is 16 μs, the energy is 0.2 mJ / shot, the number of shots is 2, and the burst mode (10 kHz).

  The taper rate Lb / Lt of the via hole 110 after the roughening process can be calculated from the bottom diameter Lb and the top diameter Lt of the via hole 110. Further, the bottom diameter Lb and the top diameter Lt of the via hole 110 have a cross section through the insulating layer 100 parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the via bottom 120 using FIB (focused ion beam). After cutting out, the cross section can be measured by observing it with an electron microscope.

  Further, according to the study of the present inventors, it has been found that the size of the gap 160 tends to increase as the via hole diameter increases. Therefore, the degree of suppression of the haloing phenomenon can be evaluated by the ratio of the size of the gap 160 to the diameter of the via hole 110. For example, the evaluation can be performed based on the haloing ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110. Here, the bottom radius Lb / 2 of the via hole 110 refers to the radius of the via bottom 120 of the via hole 110. Further, the haloing ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110 is a ratio obtained by dividing the haloing distance Wb from the edge 150 of the via bottom 120 by the bottom radius Lb / 2 of the via hole 110. The smaller the haloing ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110, the more effectively the haloing phenomenon can be suppressed.

For example, the resin composition formed on the copper foil is heated at 130 ° C. for 30 minutes and then heated at 170 ° C. for 30 minutes to be cured and irradiated with CO ₂ laser light. A via hole 110 having a top diameter Lt of about 50 μm or about 30 μm is formed. Then, it is immersed in the swelling solution at 60 ° C. for 10 minutes, then immersed in the oxidant solution at 80 ° C. for 20 minutes, then immersed in the neutralizing solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 30 minutes. The halo ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110 formed in the insulating layer 100 thus obtained can be preferably 35% or less, more preferably 30% or less, and even more preferably 25% or less. .

The CO ₂ laser light irradiation conditions are as follows: when the top diameter Lt is about 50 μm, the mask diameter is 1.60 mm, the focus offset value is 0.050, the pulse width is 25 μs, the power is 0.66 W, the aperture is 13, the number of shots is 2, burst. The mode (10 kHz) is set.
When the top diameter Lt is about 30 μm, the mask diameter is 1 mm, the pulse width is 16 μs, the energy is 0.2 mJ / shot, the number of shots is 2, and the burst mode (10 kHz).

  The haloing ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110 can be calculated from the bottom diameter Lb of the via hole 110 and the haloing distance Wb from the edge 150 of the via bottom 120 of the via hole 110.

  In the process of manufacturing a printed wiring board, the via hole 110 is usually formed in a state where another conductor layer (not shown) is not provided on the surface 100U of the insulating layer 100 opposite to the conductor layer 210. Therefore, if the manufacturing process of the printed wiring board is known, a structure in which the via bottom 120 is provided on the conductor layer 210 side and the via top 130 is opened on the opposite side to the conductor layer 210 can be clearly recognized. However, in the completed printed wiring board, a conductor layer may be provided on both sides of the insulating layer 100. In this case, it may be difficult to distinguish the via bottom 120 and the via top 130 depending on the positional relationship with the conductor layer. However, the top diameter Lt of the via top 130 is usually larger than the bottom diameter Lb of the via bottom 120. Therefore, in the above case, it is possible to distinguish the via bottom 120 and the via top 130 according to the diameter.

  In addition to suppressing the haloing phenomenon, the resin composition of the present invention provides an insulating layer having a low dielectric loss tangent and excellent adhesion to the conductor layer.

  A cured product obtained by thermally curing the resin composition at 200 ° C. for 90 minutes exhibits a characteristic that the dielectric loss tangent is low. Thus, the cured product provides an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.006 or less, more preferably 0.0055 or less, and still more preferably 0.0053 or less. On the other hand, the lower limit value of the dielectric loss tangent is not particularly limited, but may be 0.0001 or more. The evaluation of the dielectric loss tangent can be measured according to the method described in Examples described later.

  A cured product obtained by thermosetting the resin composition at 130 ° C. for 30 minutes and then at 170 ° C. for 30 minutes exhibits the property of excellent adhesion (peel strength) between the plated conductor layers. Therefore, the said hardened | cured material brings about the insulating layer excellent in adhesiveness with a plating conductor layer. The peel strength with the plated conductor layer is preferably 0.35 kgf / cm or more, more preferably 0.4 kgf / cm or more, and further preferably 0.45 kgf / cm or more. On the other hand, the upper limit of the peel strength is not particularly limited, but may be 5 kgf / cm or less. The evaluation of the peel strength with the plated conductor layer can be measured according to the method described in Examples described later.

  The resin composition of the present invention has a low dielectric loss tangent, can suppress the haloing phenomenon, and can provide an insulating layer having excellent adhesion with the conductor layer. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating purposes. Specifically, a resin composition for forming a conductive layer (including a rewiring layer) formed on the insulating layer (resin for forming an insulating layer for forming a conductive layer) It can be suitably used as a composition.

  Further, in a multilayer printed wiring board to be described later, a resin composition for forming an insulating layer of the multilayer printed wiring board (resin composition for forming an insulating layer of the multilayer printed wiring board) and an interlayer insulating layer of the printed wiring board are formed. Therefore, it can be suitably used as a resin composition (resin composition for forming an interlayer insulating layer of a printed wiring board).

For example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is used for a rewiring layer as an insulating layer for forming a rewiring layer. The resin composition (resin composition for forming a rewiring layer) and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip) can be suitably used. When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer.
(1) Laminating a temporary fixing film on a substrate;
(2) a step of temporarily fixing the semiconductor chip on the temporary fixing film;
(3) forming a sealing layer on the semiconductor chip;
(4) The process of peeling a base material and a temporary fixing film from a semiconductor chip,
(5) a step of forming a rewiring formation layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip are peeled; and (6) a rewiring layer as a conductor layer on the rewiring formation layer. Forming process

  Moreover, since the resin composition of this invention brings about an insulating layer favorable for component embedding property, it can be used conveniently also when a printed wiring board is a component built-in circuit board.

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

  The thickness of the resin composition layer is preferably 50 μm or less from the viewpoint of making the printed wiring board thinner and providing a cured product having excellent insulation even if the cured product of the resin composition is a thin film. Preferably it is 40 micrometers or less, More preferably, it is 30 micrometers or less. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it can be set as 5 micrometers or more.

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

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). It may be used.

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

  Further, as the support, a support with a release layer having a release layer on the surface bonded to the resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1”, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. AL-5 ”,“ AL-7 ”,“ Lumirror T60 ”manufactured by Toray Industries, Inc.,“ Purex ”manufactured by Teijin Limited,“ Unipeel ”manufactured by Unitika Ltd., and the like.

  Although it does not specifically limit as thickness of a support body, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. In addition, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include a protective film according to the support provided on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). It is done. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to suppress adhesion and scratches of dust and the like on the surface of the resin composition layer.

  The resin sheet is prepared by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer. Can be manufactured.

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

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

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

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

A printed wiring board can be manufactured by the method including the process of following (I) and (II), for example using the above-mentioned resin sheet.
(I) The process of laminating | stacking so that the resin composition layer of a resin sheet may join to an inner layer board | substrate on an inner layer board | substrate (II) The process of thermosetting a resin composition layer and forming an insulating layer

  The “inner layer substrate” used in the step (I) is a member that becomes a printed wiring board substrate, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate. Etc. Moreover, this board | substrate may have a conductor layer in the single side | surface or both surfaces, and this conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be referred to as an “inner layer circuit board”. Further, when the printed wiring board is manufactured, an intermediate product in which an insulating layer and / or a conductor layer is to be formed is also included in the “inner layer substrate” in the present invention. When the printed wiring board is a circuit board with a built-in component, an inner layer board with a built-in component can be used.

  Lamination | stacking of an inner layer board | substrate and a resin sheet can be performed by heat-pressing a resin sheet to an inner layer board | substrate from the support body side, for example. Examples of the member that heat-presses the resin sheet to the inner layer substrate (hereinafter, also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate) or a metal roll (SUS roll). It is preferable that the thermocompression-bonding member is not pressed directly on the resin sheet, but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

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

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurizing laminator.

  After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

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

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

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

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

  When manufacturing a printed wiring board, you may further implement (III) the process of drilling in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used for manufacturing printed wiring boards. In addition, when removing a support body after process (II), removal of this support body is performed between process (II) and process (III), between process (III) and process (IV), or process ( It may be carried out between IV) and step (V). Moreover, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

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

  Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear is also removed. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof 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. preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 100 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizers include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan. Moreover, as a neutralization liquid used for a roughening process, acidic aqueous solution is preferable, As a commercial item, the "Reduction Solution Securigant P" by Atotech Japan is mentioned, for example. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 1 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 120 nm or less, more preferably 110 nm or less, and further preferably 100 nm or less. Although it does not specifically limit about a minimum, Preferably it is 30 nm or more, More preferably, it is 40 nm or more, More preferably, it is 50 nm or more. The arithmetic average roughness (Ra) of the insulating layer surface can be measured using a non-contact type surface roughness meter.

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

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

  Although the thickness of a conductor layer is based on the design of a desired printed wiring board, generally it is 3 micrometers-35 micrometers, Preferably it is 5 micrometers-30 micrometers.

  In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full additive method. It is preferable to form by a method. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. A metal layer is formed by electrolytic plating on the exposed plating seed layer, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

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

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

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conduction location” is a “location where an electrical signal is transmitted on a 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 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 build-up layer are used. (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, and the like. Here, “a mounting method using a bumpless buildup layer (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and a wiring on the printed wiring board are connected”. It is.

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

<Example 1: Production of resin composition 1>
10 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation “828US”, epoxy equivalent of about 180), bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation “YL7760”, epoxy equivalent of about 238), and biphenyl type epoxy resin ( Nippon Kayaku Co., Ltd. “NC3000L”, epoxy equivalent of about 269) 20 parts, phosphazene resin (Otsuka Chemical Co., Ltd. “SPH-100”) 3 parts, phenoxy resin (Mitsubishi Chemical Co., Ltd. “YX7553BH30”, solid content 30 mass% 10 parts of MEK and cyclohexanone (1: 1 solution) were dissolved in 20 parts of MEK and 40 parts of solvent naphtha with stirring. After cooling to room temperature, 94 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC, toluene solution having an active group equivalent of about 223 and a solid content of 65% by mass), a phenolic curing agent (manufactured by DIC) 10 parts of “LA-3018-50P”, 2-methoxypropanol solution having an active group equivalent of about 151 and a solid content of 50%, a benzoxazine-based curing agent (“ODA-BOZ” manufactured by JFE Chemical Co., Ltd.) having a solid content of 50% by mass. MEK solution, 6 parts of benzoxazine ring equivalent 218), bifunctional acrylate (Shin Nakamura Chemical Co., Ltd. “NK Ester A-DOG”, molecular weight 326, (meth) acryloyl group equivalent 163) 10 parts, polyfunctional acrylate (Japan) “DPHA” manufactured by Kayaku Co., Ltd., 2 parts of (meth) acryloyl group equivalent 96), curing accelerator (4-dimethylaminopyridine (DMAP), solid Surface treated with 8 parts of MEK solution (5% by mass), 0.2 part of a polymerization initiator (“Perbutyl C” manufactured by NOF Corporation), and a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 400 parts of spherical silica (average particle size 0.5 μm, specific surface area 5.9 m ² / g, “SO-C2” manufactured by Admatechs) is mixed and uniformly dispersed with a high-speed rotary mixer, and then a cartridge filter (ROKITETECHNO The resin composition 1 was produced by filtration through “SHP100” manufactured by the company.

ａ＝５、ｂ＝１、及びａ＝６、ｂ＝０の混合物 DPHA has the structure shown below.

A mixture of a = 5, b = 1, and a = 6, b = 0

A-DOG has the structure shown below.

<Example 2: Production of resin composition 2>
In Example 1,
1) 20 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238) is changed to 20 parts of bixylenol type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation, about 190 equivalents of epoxy),
2) 94 parts of an active ester type curing agent (“HPC-8000-65T” manufactured by DIC, toluene solution having an active group equivalent of about 223 and a solid content of 65% by mass) was added to an active ester type curing agent (“EXB9416-” manufactured by DIC). 70BK ", a methyl isobutyl ketone solution having a non-volatile content of 70% by mass with an active group equivalent of about 330) and 86 parts.
3) 6 parts of a benzoxazine-based curing agent (MEK solution having a solid content of 50% by mass of “ODA-BOZ” manufactured by JFE Chemical Co., Ltd., about 218 benzoxazine ring equivalent) is added to a carbodiimide-based curing agent (“V- manufactured by Nisshinbo Chemical Co., Ltd.). 03 ", a toluene solution having an active group equivalent of about 216 and a solid content of 50% by mass), 10 parts,
4) Multifunctional acrylate (Nippon Kayaku Co., Ltd. “DPHA”, (meth) acryloyl group equivalent 96) 2 parts polyfunctional acrylate (Nippon Kayaku Co., Ltd. “DPCA-60”, (meth) acryloyl group equivalent 211) Changed to 2 parts.
A resin composition 2 was produced in the same manner as in Example 1 except for the above items.

DPCA-60 has the structure shown below.

<Example 3: Production of resin composition 3>
5 parts of bisphenol A type epoxy resin (Mitsubishi Chemical "828 US", epoxy equivalent of about 180), biphenyl type epoxy resin (Nippon Kayaku "NC3000L", epoxy equivalent of about 269), and bixylenol type epoxy resin (Mitsubishi Chemical "YX4000H", epoxy equivalent of about 190) 25 parts, phosphazene resin (Otsuka Chemical "SPH-100") 3 parts, phenoxy resin (Mitsubishi Chemical "YX7553BH30", solid content 30 mass% 10 parts of MEK and cyclohexanone (1: 1 solution) were dissolved in 40 parts of MEK and 40 parts of toluene with heating while stirring. After cooling to room temperature, 94 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC, toluene solution having an active group equivalent of about 223 and a solid content of 65% by mass), a phenolic curing agent (manufactured by DIC) “LA-3018-50P”, 10 parts of active group equivalent of 151, 2-methoxypropanol solution having a solid content of 50%, carbodiimide curing agent (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent of about 216, solid 10 parts by weight of 50% by weight toluene solution), 15 parts by weight, bifunctional acrylate (Shin Nakamura Chemical Co., Ltd. “NK Ester A-DOG”, molecular weight 326), polyfunctional acrylate (by Nippon Kayaku Co., Ltd. “DPCA-60”), 2 parts of (meth) acryloyl group equivalent 211), 8 parts of curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass), polymerization initiator Spherical silica (average particle size of 0.3 μm, specific surface area of 30 μm, surface treated with a phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”)) 7 m ² / g, 200 parts of Denka's “UFP-30”) was mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered through a cartridge filter (“SHP020”, manufactured by ROKITECHNO). Produced.

<Example 4: Production of resin composition 4>
In Example 3,
1) 20 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000L”, epoxy equivalent of about 269) is changed to 20 parts of bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 238),
2) Change the amount of phenolic curing agent (“LA-3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution having an active group equivalent of about 151 and a solid content of 50%) from 10 parts to 5 parts,
3) 10 parts of a carbodiimide-based curing agent (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution having an active group equivalent of about 216 and a solid content of 50% by mass) was added to a benzoxazine-based curing agent (“ODA-BOZ” manufactured by JFE Chemical). ”Of MEK solution having a solid content of 50 mass%)
4) Polyfunctional acrylate (Nippon Kayaku Co., Ltd. “DPCA-60”, (meth) acryloyl group equivalent 211) 2 parts polyfunctional acrylate (Nippon Kayaku Co., Ltd. “D-310”, (meth) acryloyl group equivalent 116) Changed to 2 parts.
A resin composition 4 was produced in the same manner as in Example 3 except for the above items.

D-310 has the structure shown below.

<Comparative Example 1: Production of Comparative Resin Composition 1>
In Example 1, the amount of bifunctional acrylate (“NK Ester A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326, (meth) acryloyl group equivalent 163) was changed from 10 parts to 12 parts to obtain polyfunctional acrylate (Japan) "DPHA" manufactured by Kayaku Co., Ltd. (meth) acryloyl group equivalent 96) 2 parts was not used. A comparative resin composition 1 was produced in the same manner as in Example 1 except for the above items.

<Comparative Example 2: Production of Comparative Resin Composition 2>
In Example 3, the amount of a bifunctional acrylate (“NK Ester A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326, (meth) acryloyl group equivalent 163) was changed from 15 parts to 17 parts to obtain a polyfunctional acrylate (Japan) “DPCA-60” manufactured by Kayaku Co., Ltd. (meth) acryloyl group equivalent 211) 2 parts was not used. A comparative resin composition 2 was produced in the same manner as in Example 3 except for the above items.

<Comparative Example 3: Production of Comparative Resin Composition 3>
In Example 1, a polyfunctional acrylate (manufactured by Nippon Kayaku Co., Ltd.) was used without using 10 parts of a bifunctional acrylate (“NK Ester A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326, (meth) acryloyl group equivalent 163). The amount of “DPHA”, (meth) acryloyl group equivalent 96) was changed from 2 parts to 12 parts. A comparative resin composition 3 was produced in the same manner as in Example 1 except for the above items.

<Comparative Example 4: Production of Comparative Resin Composition 4>
In Example 3, the amount of polyfunctional acrylate (“DPCA-60” manufactured by Nippon Kayaku Co., Ltd.) was added without adding 15 parts of bifunctional acrylate (“NK Ester A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd., molecular weight 326). Changed from 2 to 17 parts. A comparative resin composition 4 was produced in the same manner as in Example 3 except for the above items.

<Measurement of average particle size of inorganic filler>
100 mg of an inorganic filler, 0.1 g of a dispersant (“SN9228” manufactured by San Nopco) and 10 g of methyl ethyl ketone were weighed in a vial and dispersed with an ultrasonic wave for 20 minutes. Using a laser diffraction particle size distribution measuring device (“SALD-2200” manufactured by Shimadzu Corporation), the particle size distribution was measured by a batch cell method, and the average particle size according to the median diameter was calculated.

＊表中、「ａ１」は（Ａ）成分の質量をエポキシ当量で除した値を表し、「ｅ１」は活性エステル系硬化剤の質量を活性エステル基当量で除した値を表し、「ｅ２」はベンゾオキサジン系硬化剤の質量をベンゾオキサジン環当量で除した値を表し、「ｂ２」は（Ｂ）成分の質量を（メタ）アクリロイル基当量で除した値を表し、「ｃ２」は（Ｃ）成分の質量を（メタ）アクリロイル基当量で除した値を表し、「ｅ３」は樹脂組成物中のカルボジイミド系硬化剤の含有量を表し、「ｂ１」は樹脂組成物中の（Ｂ）成分の含有量を表し、「ｃ１」は樹脂組成物中の（Ｃ）成分の含有量を表す。

* In the table, “a1” represents the value obtained by dividing the mass of the component (A) by the epoxy equivalent, “e1” represents the value obtained by dividing the mass of the active ester curing agent by the active ester group equivalent, and “e2”. Represents a value obtained by dividing the mass of the benzoxazine-based curing agent by the benzoxazine ring equivalent, “b2” represents a value obtained by dividing the mass of the component (B) by the (meth) acryloyl group equivalent, and “c2” represents (C ) Represents the value obtained by dividing the mass of the component by the (meth) acryloyl group equivalent, “e3” represents the content of the carbodiimide curing agent in the resin composition, and “b1” represents the component (B) in the resin composition. The “c1” represents the content of the component (C) in the resin composition.

[Production of resin sheet]
As a support, a PET film (“Lumirror R80” manufactured by Toray Industries, Inc., having a thickness of 38 μm, a softening point of 130 ° C., hereinafter referred to as “release PET”, which has been release-treated with an alkyd resin release agent (“AL-5” manufactured by Lintec) I prepared.)

<Preparation of resin sheet A>
In Resin Compositions 1 and 2, and Comparative Resin Compositions 1 and 3, each resin composition was uniformly coated on a release PET with a die coater so that the thickness of the resin composition layer after drying was 40 μm. And it was made to dry at 80-120 degreeC (average 100 degreeC) for 4 minutes, and the resin composition layer was obtained on mold release PET. Next, a rough surface of a polypropylene film (“Alphan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) as a protective film is formed on the surface of the resin composition layer not bonded to the release PET, and the resin composition layer Lamination was performed so as to join. Thereby, the resin sheet A which consists of order of mold release PET (support body), a resin composition layer, and a protective film was obtained.

<Preparation of resin sheet B>
In Resin Compositions 3 and 4 and Comparative Resin Compositions 2 and 4, apply the resin composition uniformly on the release PET with a die coater so that the thickness of the resin composition layer after drying is 10 μm. And it dried at 80 degreeC for 2 minute (s), and the resin composition layer was obtained on mold release PET. Next, a rough surface of a polypropylene film (“Alphan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) as a protective film is bonded to the surface of the resin composition layer not bonded to the support. Laminated so that. Thereby, the resin sheet B which consists of order of mold release PET (support body), a resin composition layer, and a protective film was obtained.

[Measurement of dielectric loss tangent]
The protective film was peeled off from the resin sheet A or B obtained in the examples and comparative examples, and was cured by heating at 200 ° C. for 90 minutes, and the support was peeled off to obtain a sheet-like cured product. The cured product 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. Measurement was performed on three test pieces, and an average value was calculated.

[Measurement of peeling strength (peel strength) of haloing and plating conductor layer]
<Production of samples for evaluation of haloing and measurement of peel strength>
(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 0.4 mm, Panasonic R1515A) on which an inner layer circuit is formed are microetching agents (Rough etching of the copper surface was performed by 1 μm etching with CZ8101 manufactured by Mec).

(2) Lamination of resin sheet with support The protective film is peeled off from each of the produced resin sheets A or B, and both sides of the inner layer circuit board are used using a batch type vacuum pressure laminator (MVLP-500, manufactured by Meiki Co., Ltd.). Laminated. 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 resin sheet was cured at 130 ° C. for 30 minutes and the resin composition layer was cured at 170 ° C. for 30 minutes to form an insulating layer.

(4) Via hole formation In Examples 1 and 2 and Comparative Examples 1 and 3, a CO ₂ laser processing machine (manufactured by Hitachi Via Mechanics, LC-2E21B / 1C) was used, mask diameter 1.60 mm, focus offset value The insulating layer is drilled under the conditions of 0.050, pulse width 25 μs, power 0.66 W, aperture 13, number of shots 2, burst mode (10 kHz), and the top diameter (diameter) of the via hole on the insulating layer surface is about 50 μm. A plurality of via holes were formed so that Thereafter, the release PET was peeled off.

In Examples 3 and 4 and Comparative Examples 2 and 4, a CO ₂ laser processing machine (“605GTWIII (−P)” manufactured by Mitsubishi Electric Corporation) was used, mask diameter 1 mm, pulse width 16 μs, energy 0.2 mJ / shot. A plurality of via holes were formed by punching the insulating layer under conditions of 2 shots and burst mode (10 kHz) so that the top diameter (diameter) of the via hole on the insulating layer surface was about 30 μm. Thereafter, the release PET was peeled off.

(5) Roughening treatment The inner layer circuit board on which the insulating layer is formed is added to a swelling liquid, diethylene glycol monobutyl ether-containing swelling dip securigant P (glycol ethers, aqueous solution of sodium hydroxide) 60, which is a swelling liquid. Soak at 10 ° C for 10 minutes, and then as a roughening solution, soak in 20 minutes at 80 ° C for concentrate compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) manufactured by Atotech Japan. As a neutralizing solution, it was immersed in Reduction Sholysin Securigant P (an aqueous solution of sulfuric acid) manufactured by Atotech Japan for 5 minutes at 40 ° C. and then dried at 80 ° C. for 30 minutes. This substrate was designated as evaluation substrate A.

(6) Plating by semi-additive method Evaluation substrate A was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. After annealing for 30 minutes at 150 ° C., 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 20 μm. Next, annealing was performed at 200 ° C. for 60 minutes. This substrate was designated as evaluation substrate B.

<Measurement of via hole dimensions, haloing distance, and haloing ratio after roughening>
About evaluation board | substrate A, cross-sectional observation was performed using FIB-SEM composite apparatus ("SMI3050SE" by SII nanotechnology company). Specifically, using an FIB (focused ion beam), the insulating layer was cut out so that a cross section parallel to the thickness direction of the insulating layer and passing through the center of the via bottom of the via hole appeared. This cross section was observed by SEM. From the observed image, the bottom diameter and top diameter of the via hole were measured.
Further, in the image observed by SEM, a gap portion formed by peeling off the insulating layer from the copper foil layer of the inner substrate was seen continuously from the edge of the via bottom. Therefore, from the observed image, the distance from the center of the via bottom to the edge of the via bottom (corresponding to the inner radius of the gap) r1, and the distance from the center of the via bottom to the far end of the gap (gap) R2) was measured, and a difference r2-r1 between the distance r1 and the distance r2 was calculated as a haloing distance from the edge of the via bottom at the measurement point.

  The above measurements were made at 5 randomly selected via holes. Then, the average of the measured top diameters of the five via holes was adopted as the top diameter Lt after the roughening treatment of the sample. Further, the average of the measured bottom diameters of the five via holes was adopted as the bottom diameter Lb after the roughening treatment of the sample. Furthermore, the average of the measured haloing distances of the five via holes was adopted as the haloing distance Wb from the edge of the via bottom of the sample.

  From the measurement results, the taper ratio (ratio “Lb / Lt” between the top diameter Lt and the bottom diameter Lb of the via hole after the roughening treatment) and the haloing ratio Hb (haloing from the edge of the via bottom after the roughening treatment). A ratio “Wb / (Lb / 2)” between the distance Wb and the radius (Lb / 2) of the via bottom of the via hole after the roughening treatment was calculated. When this haloing ratio Hb was 35% or less, it was determined as “◯”, and when the haloing ratio Ht was greater than 35%, it was determined as “x”.

<Measurement and evaluation of adhesion (peel strength) between plating conductor layers>
The conductor layer of the evaluation board B is cut with a 10 mm width and a length of 100 mm. One end is peeled off, and is gripped with a gripping tool (manufactured by TS E Corp., Autocom type tester AC-50C-SL). The load (kgf / cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min at room temperature was measured.

  In Examples 1-4, even if it does not contain (E) component-(I) component, although it has a difference in a grade, it has confirmed that it results in the same result as the above-mentioned example.

DESCRIPTION OF SYMBOLS 100 Insulating layer 100U The surface of the insulating layer on the opposite side to a conductor layer 110 Via hole 120 Via bottom 120C Center of via bottom 130 Via top 140 Discolored part 150 Edge of via bottom of via hole 160 Gap part 170 Edge part on the outer periphery side of a gap part 180 Via top Edge 190 on the outer peripheral side of the discolored portion 200 Inner layer substrate 210 Conductor layer Lb Bottom diameter of via hole Lt Top diameter of via hole Wb Halo ing distance from edge of via bottom

Claims (16)

(A) epoxy resin,
(B) a bifunctional or lower (meth) acrylic acid ester,
(C) Trifunctional or higher functional (meth) acrylic acid ester, and (D) an inorganic filler.   (B) The resin composition of Claim 1 whose content of a component is 0.1 to 10 mass% when the non-volatile component in a resin composition is 100 mass%.   (C) The resin composition of Claim 1 or 2 whose content of a component is 0.1 to 3 mass% when the non-volatile component in a resin composition is 100 mass%.   The content of the component (B) when the nonvolatile component in the resin composition is 100% by mass is b1, and the content of the component (C) when the nonvolatile component in the resin composition is 100% by mass is c1. The resin composition according to any one of claims 1 to 3, wherein b1 / c1 satisfies a relationship of 1 or more and 10 or less.   The resin composition according to any one of claims 1 to 4, wherein the component (B) has a cyclic structure. The resin composition according to any one of claims 1 to 5, wherein the component (B) has a structure represented by the following formula (B-1).

(In Formula (B-1), R ¹ and R ⁴ each independently represent an acryloyl group or a methacryloyl group, R ² and R ³ each independently represent a divalent linking group. Ring A is a divalent group. Represents a cyclic group.)   The component (C) is a (meth) acrylate of a trivalent or higher alcohol, a (meth) acrylate of a cyclic ether adduct of a trivalent or higher alcohol, a (meth) acrylate of a cyclic ester adduct of a trivalent or higher alcohol, or The resin composition according to any one of claims 1 to 6, which is a phosphoric acid triester (meth) acrylate.   Furthermore, the resin composition of any one of Claims 1-7 containing (E) hardening | curing agent.   The resin composition according to claim 8, wherein the component (E) is at least one selected from a benzoxazine-based curing agent, a carbodiimide-based curing agent, a phenol-based curing agent, and an active ester-based curing agent.   The resin composition of any one of Claims 1-9 used for an insulation use.   The resin composition according to any one of claims 1 to 10, which is used for forming an insulating layer.   The resin composition according to any one of claims 1 to 11, which is used for forming an insulating layer for forming a conductor layer.   The resin composition according to claim 1, which is used for sealing a semiconductor chip.   The resin sheet containing the support body and the resin composition layer provided on this support body containing the resin composition of any one of Claims 1-13.   The printed wiring board containing the insulating layer formed with the hardened | cured material of the resin composition of any one of Claims 1-13.   A semiconductor device comprising the printed wiring board according to claim 15.

Images