TW202003619A - Resin composition capable of obtaining a cured product having a low dielectric tangent and suppressing a haloing phenomenon - Google Patents

Abstract

An object of the present invention is to provide a resin composition capable of obtaining a cured product having a low dielectric tangent and suppressing a haloing phenomenon, a resin sheet containing the resin composition, a printed wiring board including an insulating layer formed by using the resin composition, and a semiconductor device including the printed wiring board. To achieve the object, the resin composition of the present invention includes (A) an epoxy resin, (B) a (meth)acrylate, (C) an aromatic hydrocarbon resin containing an aromatic ring having two or more hydroxyl groups for serving as monocyclic or condensed ring, and (D) an inorganic filler.

Description

Resin composition

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

As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately stacked on an inner layer circuit board is known. Generally, the insulating layer is formed by hardening the resin composition. For example, Patent Document 1 describes a resin composition containing (A) a radically polymerizable compound, (B) an epoxy resin, (C) a hardener, and (D) a roughening component. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2014-034580

[Problems to be solved by the invention]

Proposals for resin compositions suitable for forming the insulating layer of the inner-layer circuit board include the resin composition described in Patent Document 1. There have been many proposals, but in recent years, the insulating layer is low in dielectric tangent (dielectric tangent) The requirements gradually become higher.

As a result of review, the present inventors have learned that a cured product of a resin composition containing a material that reduces dielectric tangent may cause haloing that reduces conduction reliability. In recent years, in the manufacture of multilayer printed wiring boards, the hardened resin composition used to form the insulating layer requires, in addition to lower dielectric tangent, finer and higher-density wiring. It has sufficient conduction reliability, but the status quo is still unable to fully meet these characteristics. Here, the so-called blooming phenomenon refers to delamination between the insulating layer and the inner substrate generated around the through hole. Such a halo phenomenon is generally caused by the deterioration of the resin around the through hole when the through hole is formed, and the deteriorated portion is eroded during the roughening process. In addition, the aforementioned deteriorated part is generally observed as a discolored part.

The object of the present invention is to provide: a resin composition which can obtain a hardened product having a low dielectric tangent and capable of suppressing halo phenomenon; a resin sheet containing the resin composition; and having an insulation formed using the resin composition A layered printed wiring board; and a semiconductor device including the above printed wiring board. [Means to solve the problem]

In order to solve the aforementioned problems, the present inventors have conducted intensive studies and found that a resin composition comprising: (A) epoxy resin, (B) (meth)acrylate, and (C) containing more than two The aromatic hydrocarbon resin and the (D) inorganic filler having a hydroxyl group as an aromatic ring of a monocyclic ring or a condensed ring can solve the aforementioned problems, and thus the present invention has been completed. That is, the present invention includes the following content.

(式(B-1)中，R¹ 及R⁴ 分別獨立表示丙烯醯基或甲基丙烯醯基，R² 及R³ 分別獨立表示2價的連結基，環A表示2價的環狀基)。 [5]. 如[1]~[4]中任一項記載之樹脂組成物，其中，(C)成分係以下述式(1)或式(2)表示，

(式(1)中，R⁰ 分別獨立表示2價的烴基，n1表示0~6的整數)

(式(2)中，R¹ ~R⁴ 分別獨立表示氫原子或1價的烴基)。 [6]. 如[1]~[5]中任一項記載之樹脂組成物，其中，(C)成分係以下述式(3)或式(4)表示，

(式(3)中，n2表示0~6的整數)

(式(4)中，R¹ ~R⁴ 分別獨立表示氫原子或1價的烴基)。 [7]. 如[1]~[6]中任一項記載之樹脂組成物，其中，相對於樹脂組成物中的樹脂成分100質量%，(C)成分的量為0.1質量%以上10質量%以下。 [8]. 如[1]~[7]中任一項記載之樹脂組成物，其中，進一步包含(E)硬化劑。 [9]. 如[8]記載之樹脂組成物，其中，(E)成分係選自由苯并噁嗪(benzoxazine)系硬化劑、碳二亞胺(carbodiimide)系硬化劑、酚系硬化劑及活性酯系硬化劑所成之群組中的1種以上。 [10]. 如[1]~[9]中任一項記載之樹脂組成物，其係使用於絕緣用途。 [11]. 如[1]~[10]中任一項記載之樹脂組成物，其係絕緣層形成用。 [12]. 如[1]~[11]中任一項記載之樹脂組成物，其係用來形成導體層的絕緣層形成用。 [13]. 如[1]~[12]中任一項記載之樹脂組成物，其係半導體晶片的密封用。 [14]. 一種樹脂薄片，其包含： 支撐體與 設置於該支撐體上的樹脂組成物層， 該樹脂組成物層包含[1]~[13]中任一項記載之樹脂組成物。 [15]. 一種包含絕緣層的印刷配線板，該絕緣層係藉由[1]~[13]中任一項記載之樹脂組成物的硬化物所形成者。 [16]. 一種半導體裝置，其包含[15]記載之印刷配線板。 [發明的效果][1]. A resin composition comprising: (A) an epoxy resin, (B) (meth)acrylate, (C) an aromatic ring containing two or more hydroxyl groups as a monocyclic ring or a condensed ring Aromatic hydrocarbon resin and (D) inorganic filler. [2]. The resin composition as described in [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 resin composition according to [1] or [2], wherein the component (B) has a ring structure. [4]. The resin composition as described in any one of [1] to [3], wherein the component (B) has a structure represented by the following formula (B-1),

(In formula (B-1), R ¹ and R ⁴ independently represent acryl or methacryl, R ² and R ³ each independently represent a divalent linking group, and ring A represents a divalent cyclic group ). [5]. The resin composition as described in any one of [1] to [4], wherein the component (C) is represented by the following formula (1) or formula (2),

(In formula (1), R ⁰ independently represents a divalent hydrocarbon group, and n 1 represents an integer of 0 to 6)

(In formula (2), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group). [6]. The resin composition according to any one of [1] to [5], wherein the component (C) is represented by the following formula (3) or formula (4),

(In formula (3), n2 represents an integer from 0 to 6)

(In formula (4), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group). [7]. The resin composition according to any one of [1] to [6], wherein the amount of the component (C) is 0.1% by mass or more and 10% by mass with respect to 100% by mass of the resin component in the resin composition. %the following. [8]. The resin composition according to any one of [1] to [7], which further contains (E) a hardener. [9]. The resin composition as described in [8], wherein the component (E) is selected from the group consisting of benzoxazine-based hardener, carbodiimide-based hardener, phenol-based hardener and One or more of the group consisting of active ester hardeners. [10]. The resin composition as described in any one of [1] to [9], which is used for insulation purposes. [11]. The resin composition as described in any one of [1] to [10], which is used to form an insulating layer. [12]. The resin composition as described in any one of [1] to [11], which is used to form an insulating layer for forming a conductor layer. [13]. The resin composition as described in any one of [1] to [12], which is used for sealing a semiconductor wafer. [14]. A resin sheet comprising: a support and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to any one of [1] to [13]. [15]. A printed wiring board including an insulating layer formed by 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]. [Effect of invention]

The present invention can provide: a resin composition capable of obtaining a hardened product having a low dielectric tangent and suppressing halo phenomenon; a resin sheet containing the resin composition; and having an insulation formed using the resin composition A layered printed wiring board; and a semiconductor device including the above printed wiring board.

[Best form for carrying out the invention]

The following is an embodiment and examples to explain the present invention in detail. However, the present invention is not limited to the embodiments and examples given below, and can be arbitrarily changed and implemented without departing from the scope of the patent application of the present invention and its equivalent scope.

[Resin composition] The resin composition of the present invention is a resin composition comprising the following components (A) to (D): (A) epoxy resin, (B) (meth)acrylate, (C) containing 2 An aromatic hydrocarbon resin which is a single ring or an aromatic ring of a condensed ring or more hydroxyl groups, and (D) an inorganic filler. By using such a resin composition, the desired effect of the present invention that "the dielectric tangent is low and the halo phenomenon is excellent in suppression can be obtained" can be obtained. Furthermore, by using such a resin composition, generally, the adhesion with the conductor layer can be improved.

The resin composition may further contain arbitrary components in combination with the components (A) to (D). Examples of optional components include (E) curing agent, (F) curing accelerator, (G) polymerization initiator, (H) thermoplastic resin, (I) flame retardant, and (J) other additives. . The following is a detailed description of each component included in the resin composition.

＜(A) Epoxy resin＞ The resin composition contains (A) epoxy resin as (A) component. Examples of the (A) epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF Type epoxy resin, dicyclopentadiene type epoxy resin, trivalent phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin Resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, biphenyl ring Oxygen resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane epoxy resin , Cyclohexane dimethanol epoxy resin, naphthylene ether epoxy resin, trimethylol epoxy resin, tetraphenylethane epoxy resin, etc. One type of epoxy resin may be used alone, or two or more types may be used in combination.

In the resin composition, as the (A) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule is preferable. From the viewpoint that the desired effect of the present invention can be obtained remarkably, the proportion of epoxy resin having two or more epoxy groups per molecule with respect to (A) 100% by mass of the non-volatile content of the epoxy resin The system is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

Epoxy resins can be classified into epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resins”) and epoxy resins that are solid at a temperature of 20°C (sometimes called "Solid Epoxy"). In the resin composition, as the (A) epoxy resin system, only liquid epoxy resins or solid epoxy resins may be included, but it is preferable to include liquid epoxy resins and solid epoxy resins in combination. . By combining liquid epoxy resin and solid epoxy resin as (A) epoxy resin, when used in the form of a resin sheet, sufficient flexibility can be obtained, or a cured product that can enhance the resin composition Breaking strength.

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

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidol are preferred Amine epoxy resin, phenol novolak epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane epoxy resin, cyclohexane dimethanol epoxy resin, glycidylamine epoxy resin And the epoxy resin having a butadiene structure is preferably a bisphenol A epoxy resin.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828EL", "" "825", "Epikote 828EL" (bisphenol A epoxy resin); "jER807" and "1750" (bisphenol F epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac) manufactured by Mitsubishi Chemical Corporation Varnish epoxy resin); "630" and "630LSD" (glycidylamine epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A epoxy resin and double Phenol F type epoxy resin mixed product); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagasechemtex; "CELOXIDE2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel; Daicel Corporation's "PB-3600" (epoxy resin with butadiene structure); Nippon Steel & Sumitomo Chemical Corporation's "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl cyclohexane ring Oxygen resin), etc. These systems can be used alone or in combination of two or more.

The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and is preferably an aromatic-based epoxy resin having three or more epoxy groups in one molecule. Solid epoxy resin.

The solid epoxy resin is preferably a bixylenol-type epoxy resin, a naphthalene-type epoxy resin, a naphthalene-type 4-functional epoxy resin, a cresol novolac-type epoxy resin, and a dicyclopentadiene-type epoxy resin. , Trihydric phenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type The epoxy resin, tetraphenylethane type epoxy resin, and preferably bisphenol AF type epoxy resin, biphenyl type epoxy resin, and bixylenol type epoxy resin.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type 4-functional epoxy manufactured by DIC). Resin); "N-690" (cresol novolac epoxy resin) made by DIC; "N-695" (cresol novolac epoxy resin) made by DIC; "HP-" made by DIC "7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC Corporation , "EXA-7311-G4S", "HP6000" (naphthyl ether epoxy resin); "EPPN-502H" (trivalent phenol epoxy resin) manufactured by Nippon Kayaku Co.; manufactured by Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl epoxy resin) manufactured by Nippon Kayaku; Nippon Steel & Sumitomo Chemical Co., Ltd. "ESN475V" (naphthol-type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. "ESN485" (naphthol novolac epoxy resin); "YX4000H", "YX4000" manufactured by Mitsubishi Chemical Corporation, " "YL6121" (biphenyl type epoxy resin); "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; OSAKA Gas chemical company "PG-100" and "CG-500" manufactured by Mitsubishi Chemical Corporation; "YL7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (tungsten epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "JER1010" (solid bisphenol A epoxy resin) manufactured by the company; "jER1031S" (tetraphenylethane epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These systems can be used alone or in combination of two or more.

When (A) epoxy resin is used in combination with liquid epoxy resin and solid epoxy resin, the quantity ratio (liquid epoxy resin: solid epoxy resin) is based on mass ratio, It is preferably 1:1~1:20, more preferably 1:1.5~1:15, and particularly preferably 1:2~1:10. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin in the above range, the desired effect of the present invention can be remarkably obtained. Furthermore, when it is generally used in the form of a resin sheet, moderate adhesion can be obtained. In addition, when generally used in the form of a resin sheet, sufficient flexibility can be obtained, so the operability is improved. Furthermore, in general, a cured product having sufficient breaking strength can be obtained.

(A) The epoxy equivalent of the epoxy resin is preferably 50g/eq. to 5000g/eq., and more preferably 50g/eq. to 3000g/eq., more preferably 80g/eq. to 2000g/eq. , And more preferably 110g/eq.~1000g/eq. By being in this range, the cross-link density of the cured product of the resin composition layer becomes sufficient, so that an insulating layer with a small surface roughness can be obtained. Epoxy equivalent is the mass of resin containing 1 equivalent of epoxy groups. This epoxy equivalent system can be measured according to JIS K7236.

(A) From the viewpoint that the weight-average molecular weight (Mw) of the epoxy resin can remarkably obtain the desired effect of the present invention, it is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. The weight average molecular weight of the resin can be measured as a value converted to polystyrene by gel permeation chromatography (GPC) method.

(A) The content of the epoxy resin is preferably 1 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 The mass% or more is preferably 3 mass% or more, and more preferably 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 that the desired effect of the present invention can be remarkably obtained. In addition, in the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass unless otherwise specified.

＜(B)(meth)acrylate＞ The resin composition contains (meth)acrylate as the (B) component. By containing (B) (meth)acrylate in the resin composition, a hardened product having a low dielectric tangent can be obtained. Here, the term "(meth)acrylic acid" includes acrylic acid and methacrylic acid and combinations of these.

From the viewpoint of obtaining a hardened product with a low dielectric tangent, the (B) (meth)acrylate system preferably has two or more (meth)acryloyl groups per molecule. The term "(meth)acryloyl" refers to acryloyl and methacryloyl and combinations of these.

From the viewpoint of obtaining a hardened product having a low dielectric tangent, (B) (meth)acrylate preferably has a ring structure. The ring structure is preferably a divalent ring group. The divalent cyclic group may be any cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Among them, from the viewpoint that the desired effect of the present invention can be remarkably obtained, it is preferable to include a cyclic group having an alicyclic structure.

From the standpoint that the desired effect of the present invention can be obtained remarkably, the divalent cyclic group is preferably at least 3 member rings, more preferably at least 4 member rings, more preferably at least 5 member rings; preferably Below 20 member rings, preferably below 15 member rings, more preferably below 10 member rings. The bivalent cyclic group may have a single ring structure or a multi-ring structure.

In addition to carbon atoms, the ring in the divalent cyclic group may be constituted by a heteroatom. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, and the like, and oxygen atoms are preferred. The aforementioned ring may have one heteroatom or two or more.

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

The divalent cyclic group may have a substituent. Examples of such a substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfonic acid group, a cyano group, a nitro group, and a hydroxyl group , Mercapto, pendant, etc., preferably alkyl.

The (meth)acryloyl group may be directly bonded to a divalent cyclic group, or may be bonded via a divalent linking group. Examples of the divalent linking group include alkylene, alkenyl, aryl, heteroaryl, -C(=O)O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S- , -SO-, -NH-, etc., may also be a combination of a plurality of such bases. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group or carbon atom having 1 to 5 carbon atoms. Number 1~4 alkylene. The alkylene group may be any linear, branched or cyclic. Examples of such alkylene groups include methylene group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, 1,1-dimethylethyl group, etc. Methyl, ethylidene, 1,1-dimethylethylidene. The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkenyl group having 2 to 5 carbon atoms. As the arylene group and the heteroarylene group, a aryl group or a heteroaryl group having 6 to 20 carbon atoms is preferred, and an aryl group or a heteroaryl group having 6 to 10 carbon atoms is preferred. The divalent linking group is preferably an alkylene group, and among them, methylene and 1,1-dimethylethylidene are preferable.

(式(B-1)中，R¹ 及R⁴ 分別獨立表示丙烯醯基或甲基丙烯醯基，R² 及R³ 分別獨立表示2價的連結基，環A表示2價的環狀基)。(B) (Meth)acrylate is preferably represented by the following formula (B-1).

(In formula (B-1), R ¹ and R ⁴ independently represent acryl or methacryl, R ² and R ³ each independently represent a divalent linking group, and ring A represents a divalent cyclic group ).

R ¹ and R ⁴ each independently represent an acryl group or a methacryl group, preferably acryl group.

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

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

Ring A may have a substituent. As a substituent, it is the same as the substituent which the above-mentioned divalent cyclic group may have.

The following are specific examples showing the component (B), but the present invention is not limited thereto.

(B) A commercially available product can be used as the component. For example, "NK Ester A-DOG" ((meth)acrylic acid equivalent of 163g/eq.) manufactured by Shin Nakamura Chemical Industry Co., Ltd. and "" DCP-A'' ((meth)acryl acetyl equivalent 152g/eq.), Nippon Kayaku Co., Ltd. ``NPDGA'' ((meth)acryl acetyl equivalent 106g/eq.), ``FM-400'' ((A )) Acryloyl equivalent of 156g/eq.), ``R-687'' ((meth)acrylic equivalent of 187g/eq.), ``THE-330'' ((meth)acrylic equivalent of 143g/eq. ), "PET-30" ((meth)acryl acetyl equivalent 88g/eq.), "DPHA" ((meth)acryl acetyl equivalent 96g/eq.), etc. (B) The component system can be used alone or in combination of two or more kinds.

From the viewpoint of obtaining a hardened product having a low dielectric tangent, the (meth)acryl acetyl equivalent of the component (B) is preferably 30 g/eq. to 400 g/eq., and preferably 50 g/eq.~ 300g/eq., more preferably 75g/eq.~200g/eq. The (meth)acryl acetyl equivalent is the mass of the component (B) containing 1 equivalent of (meth)acryl acetyl.

From the viewpoint of obtaining a cured product having a low dielectric tangent and excellent adhesion, when the nonvolatile component in the resin composition is 100% by mass, the content of the component (B) is preferably 0.1% by mass or more It is preferably 1% by mass or more, and more preferably 1.5% by mass or more. From the viewpoint of suppressing the halo phenomenon, the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less.

<(C) Aromatic hydrocarbon resin containing an aromatic ring having two or more hydroxyl groups as a monocyclic ring or a condensed ring> The resin composition contains "an aromatic hydrocarbon resin containing an aromatic ring as a single ring or a condensed ring having two or more hydroxyl groups" as the component (C). Generally, the hydroxyl group of the aromatic ring allows the (C) component to react with the (A) epoxy resin, so the (C) component can function as a curing agent for curing the resin composition. Then, by the action of the component (C), the halo phenomenon can be suppressed.

Generally, when forming a through hole, energy such as heat and light is applied to a portion of the insulating layer where the through hole is to be formed. Part of the energy applied at this time will be conducted around the part where the through hole is to be formed, which may cause oxidation of the resin. If such oxidation occurs, the resin will deteriorate and may appear as a halo phenomenon. However, since the aromatic ring of the component (C) has two or more hydroxyl groups, the steric hindrance of the hydroxyl groups can suppress the progress of the oxidation reaction of the resin. Therefore, the insulating layer obtained by using the resin composition of the present invention can suppress the blooming phenomenon.

Here, the term "aromatic ring" includes both an aromatic ring that is a monocyclic ring like a benzene ring and an aromatic ring that is a condensed ring like a naphthalene ring. (C) The number of carbon atoms in each of the aforementioned aromatic rings contained in the component is preferably 6 or more, preferably 14 from the viewpoint that the desired effect of the present invention can be remarkably obtained Below, it is more preferably 10 or less.

Examples of aromatic rings include benzene ring, naphthalene ring, and anthracene ring. The type of aromatic ring contained in one molecule of the aromatic hydrocarbon resin may be one type, or two or more types.

Among the aromatic rings contained in the aromatic hydrocarbon resin as the component (C), at least one of the aromatic rings has two or more hydroxyl groups per one of the aromatic rings. The number of hydroxyl groups per aromatic ring is preferably 3 or less, and particularly preferably 2 from the viewpoint that the desired effect of the present invention can be remarkably obtained.

The number of aromatic rings having two or more hydroxyl groups per molecule of the component (C) is usually one or more. From the viewpoint that the desired effect of the present invention can be obtained remarkably, 2 is preferred More than 3, preferably 3 or more. The upper limit is not particularly limited, but from the viewpoint of suppressing steric hindrance and improving reactivity with the epoxy resin, it is preferably 6 or less, and more preferably 5 or less.

Examples of suitable components (C) include aromatic hydrocarbon resins represented by the following formula (1) and aromatic hydrocarbon resins represented by the following formula (2).

In formula (1), R ⁰ independently represents a divalent hydrocarbon group. The divalent hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the divalent hydrocarbon group is usually 1 or more. From the viewpoint that the desired effect of the present invention can be remarkably obtained, it is preferably 3 or more, 6 or more, or 7 or more. The aforementioned upper limit of the number of carbon atoms is preferably 20 or less, 15 or less, or 10 or less from the viewpoint that the desired effect of the present invention can be remarkably obtained.

Specific examples of R ⁰ include the following hydrocarbon groups.

In formula (1), n1 represents an integer of 0 or more and 6 or less. Among them, n1 is preferably 1 or more, more preferably 2 or more, preferably 4 or less, and more preferably 3 or less from the viewpoint that the desired effect of the present invention can be significantly obtained.

As long as the aromatic hydrocarbon resin represented by formula (1) is used, the halo phenomenon can be effectively suppressed.

In formula (2), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group. The monovalent hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Among them, from the viewpoint that the desired effect of the present invention can be remarkably obtained, an aliphatic hydrocarbon group is preferred, a saturated aliphatic hydrocarbon group is also preferred, and a chain-shaped saturated aliphatic hydrocarbon group is particularly preferred. The number of carbon atoms of the monovalent hydrocarbon group is usually 1 or more. From the viewpoint that the desired effect of the present invention can be remarkably obtained, it is preferably 20 or less, and more preferably 15 or less, 10 or less, or 8 or less. Preferable examples of R ¹ to R ⁴ include a hydrogen atom and an alkyl group such as methyl, ethyl, propyl, butyl, and hexyl. As long as the aromatic hydrocarbon resin represented by the formula (2) is used, in particular, the peeling of the halo portion caused by the etching during the roughening treatment can be effectively suppressed.

Among them, as the component (C), particularly preferred aromatic hydrocarbon resins include aromatic hydrocarbon resins represented by the following formula (3) and aromatic hydrocarbon resins represented by the following formula (4). N2 in formula (3) represents an integer defined the same as n1 in formula (1), and the preferred range is also the same. In addition, R ¹ to R ⁴ in formula (4) are synonymous with R ¹ to R ⁴ in formula (2).

As a commercially available product of the aromatic hydrocarbon resin represented by the formula (3), for example, a naphthol-based hardener "SN395" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. represented by the following formula (5) may be mentioned. In formula (5), n3 represents 2 or 3. Moreover, as a commercial item of the aromatic hydrocarbon resin represented by Formula (4), the phenolic hardener "GRA13H" by Qunrong Chemical Industry Co., Ltd. is mentioned, for example.

The aromatic hydrocarbon resin system as the component (C) can be used alone or in combination of two or more kinds.

(C) The hydroxyl equivalent of the component is preferably 50 g/ from the viewpoint of increasing the crosslinking density of the insulating layer as the cured product of the resin composition layer, and from the viewpoint that the desired effect of the present invention can be obtained remarkably eq. or more, preferably 60g/eq. or more, more preferably 70g/eq. or more, and more preferably 200g/eq. or less, still more preferably 150g/eq. or less, particularly preferably 120g/eq. the following. The hydroxyl equivalent is the mass of the resin containing 1 equivalent of hydroxyl.

When the amount of the (C) component in the resin composition is 100% by mass of the non-volatile component in the resin composition, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and particularly preferably 0.3% by mass % Or more; preferably 10% by mass or less, and more preferably 5% by mass or less, 3% by mass or less, or 1% by mass or less. By making the amount of the (C) component into the aforementioned range, the halo phenomenon can be effectively suppressed.

The amount of the (C) component relative to (A) 100% by mass of the epoxy resin is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 3% by mass or more; preferably 10% by mass Below, it is further preferably 8% by mass or less, and particularly preferably 5% by mass or less. By setting the amount of the component (B) to the aforementioned range, the halo phenomenon can be effectively suppressed.

When the number of epoxy groups of (A) epoxy resin is 1, the number of hydroxyl groups of (C) component is preferably 0.01 or more, preferably 0.03 or more, more preferably 0.05 or more; preferably 2 or less, and more It is preferably 1.5 or less, more preferably 1 or less, and particularly preferably 0.5 or less. Here, the "epoxy group number of (A) epoxy resin" refers to the total value obtained by dividing the mass of the non-volatile component of the (A) component present in the resin composition by the epoxy equivalent and adding up all value. In addition, the "number of hydroxyl groups of (C) component" refers to a value obtained by dividing the mass of the non-volatile component of the (C) component present in the resin composition by the hydroxyl equivalent and adding up all of them. When the number of epoxy groups of the (A) epoxy resin is 1, the number of hydroxyl groups of the (C) component is within the aforementioned range, whereby the halo phenomenon can be effectively suppressed.

<(D) inorganic filler> The resin composition contains (D) an inorganic filler. Therefore, a hardened product with a low dielectric tangent can be obtained. As the material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silicon dioxide, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and gibbsite. , 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, titanic acid Bismuth, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, tungsten zirconium phosphate, etc. Among these, silicon dioxide is particularly suitable. Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, and the like. Furthermore, spherical silica is preferred as the silica system. (D) Inorganic fillers can be used alone or in combination of two or more.

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

(D) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more from the viewpoint that the desired effect of the present invention can be remarkably obtained. It is preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

(D) The average particle diameter of the inorganic filler can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, the measurement is performed by the following method: a laser diffraction scattering type particle size distribution measuring device is used to prepare the particle size distribution of the inorganic filler on a volume basis, and the average particle size (median diameter) as the average particle diameter. For the measurement sample system, 100 mg of inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed by ultrasound for 10 minutes. Using a laser diffraction type particle size distribution measuring device for the measurement sample, using blue and red as the wavelength of the light source, and measuring (D) the volume-based particle size distribution of the inorganic filler using a flow cell method, from the obtained The particle size distribution calculates the average particle size as the average particle size. As a laser diffraction type particle size distribution measuring apparatus, for example, "LA-960" manufactured by HORIBA, Ltd. may be mentioned.

The specific surface area (D) an inorganic filler, can be obtained significantly view of the desired effect of the present invention, it is preferably 1m ² / g or more, and preferably 2m ² / g or more, particularly preferably 3m ² /g or more. The upper limit is not particularly limited, but it is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area is based on the BET method, and a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) is used to adsorb nitrogen to the surface of the sample, and the specific surface area is calculated using the BET multipoint method.

(D) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, and organic silazane. Compounds, titanate-based coupling agents, etc. In addition, the surface treatment agent system may be used alone or in combination of two or more kinds arbitrarily.

Examples of commercially available products for surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyltrimethyl) manufactured by Shin-Etsu Chemical Co., Ltd. Oxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (Long-chain epoxy type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The degree of surface treatment by the surface treatment agent is preferably limited to the specified range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, it is 100 parts by mass of the inorganic filler, and surface treatment with 0.2 parts by mass to 5 parts by mass of surface treatment agent is preferred, and surface treatment with 0.2 parts by mass to 3 parts by mass is preferred. It is preferable to perform surface treatment through 0.3 parts by mass to 2 parts by mass.

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

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

(D) The content of the inorganic filler is preferably 50% by mass or more, and preferably 53% by mass when the non-volatile content in the resin composition is 100% by mass from the viewpoint of reducing the dielectric tangent Above, more preferably 55% by mass or more. In addition, from the viewpoint of maintaining adhesion, it is preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less.

＜(E) Hardener＞ In addition to the above components, the resin composition may further contain (E) a hardener as an optional component. However, component (C) is not included in (E) hardener. In general, the (E) hardener has a function of reacting with the (A) component to harden the resin composition. (E) One type of hardener may be used alone, or two or more types may be used in combination.

Examples of (E) hardeners include active ester hardeners, phenol hardeners, naphthol hardeners, benzoxazine hardeners, cyanate ester hardeners, and carbodiimide hardeners. Amine hardeners, anhydride hardeners, etc.

As the active ester-based hardener, it can be used for compounds having one or more active ester groups in one molecule. Among them, as the active ester-based hardener, phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc., which have two or more reactive activities in one molecule are preferably Compounds with high ester groups. The active ester-based hardener is preferably obtained by condensation reaction of a carboxylic acid compound and/or thiocarboxylic acid compound with a hydroxyl compound and/or thiol compound. In particular, from the viewpoint of improving heat resistance, active ester-based hardeners obtained from carboxylic acid compounds and hydroxyl compounds are preferred, and active esters obtained from carboxylic acid compounds and phenol compounds and/or naphthol compounds are preferred The system hardener is also 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, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, methylated bisphenol A, methylated bisphenol F, and methyl Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene type diphenol compound, phenol novolac, etc. . Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene.

Preferred specific examples of the active ester-based hardener include active ester-based hardeners containing a dicyclopentadiene diphenol structure, active ester-based hardeners containing a naphthalene structure, and acetylated compounds containing phenol novolak. Active ester-based hardener, active ester-based hardener containing phenol novolak benzoate. Among them, active ester-based hardeners containing a naphthalene structure and active ester-based hardeners containing a dicyclopentadiene diphenol structure are also preferable. The so-called "dicyclopentadiene-type diphenol structure" refers to a divalent structure formed by phenylene-dicyclopentyl-phenylene.

Examples of commercially available products of active ester-based hardeners include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" as active ester-based hardeners containing a dicyclopentadiene diphenol structure. ", "HPC-8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC Corporation); "EXB9416-70BK", "EXB-8150-65T" (DIC Corporation) as active ester hardeners containing naphthalene structure (Manufactured); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based hardener containing phenol novolak acetal; "YLH1026" as an active ester-based hardener containing phenol novolak benzoate Mitsubishi Chemical Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester hardener for phenol novolak acetal; "YLH1026" as an active ester hardener for phenol novolak acetalate (Mitsubishi Chemical Corporation), "YLH1030" (Mitsubishi Chemical Corporation), "YLH1048" (Mitsubishi Chemical Corporation), etc.

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

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

Specific examples of the benzoxazine-based hardener include "JBZ-OD100" (benzoxazine ring equivalent 218g/eq.) and "JBZ-OP100D" (benzoxazine ring equivalent) manufactured by JFE Chemical. 218g/eq.), "ODA-BOZ" (benzoxazine ring equivalent 218g/eq.); Shikoku Chemical Industry Co., Ltd. "Pd" (benzoxazine ring equivalent 217g/eq.), "Fa" (Benzoxazine ring equivalent 217g/eq.); Showa Polymer Co., Ltd. "HFB2006M" (benzoxazine ring equivalent 432g/eq.), etc.

Examples of the cyanate-based hardener include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), and 4,4′. -Methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl) methane, 1, 3-bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl) sulfide and bis(4-cyanate phenyl) ether 2-functional cyanate ester resin; multifunctional cyanate ester resin derived from phenol novolak and cresol novolak; etc. These cyanate ester resins are partially triazineated prepolymers. Specific examples of the cyanate ester hardener include "PT30" and "PT60" (phenol novolak type multifunctional cyanate resin) manufactured by LONZA Japan, and "ULL-950S" (multifunctional cyanate Resin), "BA230", "BA230S75" (a part or all of bisphenol A dicyanate is triazineated to become a terpolymer prepolymer), etc.

Specific examples of the carbodiimide-based hardener include Carbodilite (registered trademark) V-03 (carbodiimide equivalent: 216 g/eq.) and V-05 (carbodiimide) manufactured by Nisshinbo Chemical Company. Radical equivalent: 262g/eq.), V-07 (carbodiimide equivalent: 200g/eq.); V-09 (carbodiimide equivalent: 200g/eq.); Stabaxol (Stabaxol (Rhein Chemie) Registered trademark) P (carbodiimide equivalent: 302g/eq.).

Examples of the amine-based hardener include hardeners having one or more amine groups in one molecule, and examples thereof include aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines. Among them, from the viewpoint of achieving the desired effect of the invention, aromatic amines are preferred. The amine-based hardener is preferably a first-level amine or a second-level amine, and more preferably a first-level amine. Specific examples of the amine-based hardener include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiamine sulfone, 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl ash, m-phenylenediamine, m-xylenediamine, diethyltoluenediamine, 4 ,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl Benzene, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4 -Diphenylmethanediamine, 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) satin, bis(4-(3-aminophenoxy)phenyl) satin, etc. Amine-based hardeners can also use commercially available products, such as "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS", and Mitsubishi, manufactured by Nippon Kayaku Co., Ltd. "Epicure W" manufactured by the Chemical Company, etc.

Examples of the acid anhydride-based hardener include hardeners having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride hardener include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic acid. Dicarboxylic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-bi- pendant tetrahydro-3 -Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl Tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyl ash tetracarboxylic dianhydride, 1,3,3a,4 ,5,9b-hexahydro-5-(tetrahydro-2,5-bi- pendant-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol Polymeric acid anhydrides such as bis(anhydrous trimellitate), styrene and maleic acid copolymerized with styrene and maleic acid, etc.

The (E) hardener is preferably selected from the group consisting of benzoxazine-based hardeners, carbodiimide-based hardeners, phenol-based hardeners and active agents from the viewpoint that the desired effect of the present invention can be remarkably obtained. One or more of the group consisting of ester-based hardeners, and preferably one selected from the group consisting of benzoxazine-based hardeners, carbodiimide-based hardeners, and active ester-based hardeners More than one species. Among them, as the (E) hardener, it is preferable to contain a benzoxazine-based hardener or a carbodiimide-based hardener in addition to the active ester-based hardener; and it is more preferable to: in addition to the active ester-based hardener In addition to phenol-based hardeners, it also contains benzoxazine-based hardeners or carbodiimide-based hardeners.

If the (E) hardener contains an active ester-based hardener, from the viewpoint of obtaining a cured product that can reduce the dielectric tangent while having excellent adhesion, it is preferable to use the (A) component and the active ester-based hardener. The amount ratio of the hardener is adjusted so that the amount of the component (A) and the active ester-based hardener is adjusted within the specified range. Specifically, the value obtained by dividing the mass of the component (A) by the epoxy equivalent is defined as a1. This value "a1" represents the number of equivalents (eq.) of epoxy groups contained in the component (A). In addition, the value obtained by dividing the mass of the active ester-based hardener by the equivalent of active ester groups was defined as e1. This value "e1" represents the equivalent number of active ester groups (eq.). In this case, e1/a1 is usually 0.1 or more, preferably 0.3 or more, and more preferably 0.5 or more. The upper limit value is usually preferably 5 or less, and more preferably 3 or less, and more preferably 2 or less. Here, when two or more components (A) are contained in the resin composition, the a1 is the value obtained by dividing the mass of each epoxy resin present in the resin composition by the value of each epoxy equivalent and adding up all of them. In addition, when two or more kinds of active ester-based hardeners are contained, the above-mentioned e1 is a value obtained by dividing the mass of each active ester-based hardener present in the resin composition by the value of the equivalent of each active ester group and adding up all.

When the (E) hardener includes a benzoxazine-based hardener, it is preferable to use the component (B) and the benzoxazine-based hardener from the viewpoint of obtaining a cured product excellent in adhesion. The amount ratio is adjusted within the specified range to adjust the amount of the component (B) and the benzoxazine-based hardener. Specifically, the value obtained by dividing the mass of the (B) component by the (meth)acryloyl equivalent of the (B) component is defined as b2. This value "b2" represents the equivalent number (eq.) of the (meth)acryloyl equivalent contained in the component (B). In addition, the value obtained by dividing the mass of the benzoxazine-based hardener by the benzoxazine ring equivalent is defined as e2. This value "e2" represents the equivalent number of benzoxazine ring (eq.). In this case, e2/b2 is usually 0.08 or more, preferably 0.1 or more, and more preferably 0.13 or more. The upper limit value is usually 2.5 or less, preferably 2 or less, and more preferably 1 or less. If two or more (B) components are contained in the resin composition, the above b2 is the value of the mass of each (meth)acrylate present in the resin composition divided by the equivalent of each (meth)acryl group The total value obtained. In addition, when two or more benzoxazine-based hardeners are contained in the resin composition, the above e2 is the mass of the non-volatile components of each benzoxazine-based hardener present in the resin composition divided by each benzox The value of the oxazine ring equivalent is taken as the total value.

When the (E) hardener contains a carbodiimide-based hardener, it is preferable to use a component (B) and a carbodiimide-based hardener from the viewpoint of obtaining a cured product excellent in adhesion. The mass ratio is adjusted within the specified range to adjust the amount of the component (B) and the carbodiimide-based hardener. Specifically, the content (mass %) of the component (B) in the resin composition is b1, and the content (mass %) of the carbodiimide-based curing agent in the resin composition is e3. In this case, e3/b1 is usually 0.1 or more, preferably 0.2 or more, and more preferably 0.25 or more. The upper limit value is usually 1.5 or less, preferably 1.3 or less, and more preferably 1.0 or less.

(A) The amount ratio of epoxy resin to all (E) hardeners is calculated as the ratio of [total number of epoxy groups of (A) component]: [total number of reactive groups of (E) hardeners], It is preferably in the range of 1:0.01 to 1:5, more preferably 1:0.3 to 1:3, and even more preferably 1:0.5 to 1:2. Here, the term "(A) epoxy resin number of epoxy resin" refers to the total value obtained by dividing the mass of the non-volatile component of (A) epoxy resin present in the resin composition by the epoxy equivalent. Value. In addition, the "(E) number of active groups of the hardener" refers to a value obtained by dividing the mass of the non-volatile components of the (E) hardener present in the resin composition by the equivalent of active groups and adding up all of them. By setting the amount ratio of (A) epoxy resin to (E) hardener within the above range, the desired effect of the present invention can be obtained remarkably.

(E) From the viewpoint that the content of the hardener can be remarkably obtained in the present invention, it is preferably 5% by mass or more relative to 100% by mass of the nonvolatile component in the resin composition, and is more preferably 8% by mass or more, more preferably 10% by mass or more; preferably 35% by mass or less, more preferably 30% by mass or less, more preferably 25% by mass or less.

＜(F) Hardening accelerator＞ In addition to the above components, the resin composition may further contain (F) a hardening 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 them, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are also preferred . One type of hardening accelerator may be used alone, or two or more types may be used in combination.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4 -Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, etc., preferably triphenylphosphine, tetrabutylphosphonium decanoic acid salt.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,- Ginseng (dimethylaminomethyl)phenol, 1,8-diazepine (5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-bis Acridine bicyclic (5,4,0)-undecene.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 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-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitic acid Ester, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-dec Monoalkyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')] -Ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate adduct, 2 -Phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro -1H-pyrrole[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc. The imidazole compound and the adduct of the imidazole compound and the epoxy resin are preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As the imidazole-based hardening accelerator, a commercially available product can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine hardening accelerator include dicyandiamine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, diacetyl Methylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triacbicyclo[4.4.0]dec-5-ene, 7-methyl-1 ,5,7-Triabicyclo[4.4.0]dec-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-(o-tolyl) biguanide, etc., preferably Dicyandiamine, 1,5,7-triacryl bicyclo[4.4.0]dec-5-ene.

Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate, cobalt (III) acetoacetate, and copper (II) acetoacetate. Organic copper complexes, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, nickel (II) acetylacetonate Such as organic nickel complexes, organic manganese complexes such as manganese (II) acetonyl pyruvate, etc. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

(F) The content of the hardening accelerator, from the viewpoint that the desired effect of the present invention can be obtained remarkably, when the nonvolatile content in the resin composition is 100% by mass, it is preferably 0.01% by mass or more, and It is preferably 0.03 mass% or more, more preferably 0.05 mass% or more; preferably 0.5 mass% or less, still more preferably 0.4 mass% or less, more preferably 0.3 mass% or less.

<(G) polymerization initiator> In addition to the above components, the resin composition may further contain (G) a polymerization initiator as an optional component. Generally, the (G) polymerization initiator has a function of promoting the crosslinking of the (meth)acryloyl group in the (B) component and (C) component. (G) The polymerization initiator system can be used alone or in combination of two or more kinds.

Examples of the (G) polymerization initiator include t-butyl isophenylpropyl peroxide, t-butyl peroxyacetate, and α,α′-bis(t-butylperoxy) Diisopropylbenzene, t-butylperoxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy neodecanoate, t-butylperoxy Peroxides such as oxybenzoate.

Examples of commercially available products of (G) polymerization initiators include "Percumyl P", "Percumyl D", "Perbutyl C", "Perbutyl A", "Perbutyl P", and "Perbutyl L" manufactured by NOF Corporation. , "Perbutyl O", "Perbutyl ND", "Perbutyl Z", etc.

(G) The content of the polymerization initiator is preferably 0.01% by mass or more when the nonvolatile content in the resin composition is 100% by mass from the viewpoint that the desired effect of the present invention can be obtained remarkably. It is preferably 0.02% by mass or more, more preferably 0.03% by mass or more; preferably 0.5% by mass or less, still more preferably 0.3% by mass or less, more preferably 0.1% by mass or less.

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

Examples of the thermoplastic resin of the component (H) include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamidimide resins, and polyethers. Acetamide resin, polyphenol resin, polyether resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. Among them, phenoxy resins are preferred from the viewpoints that the effects expected by the present invention can be obtained remarkably, and the insulating layer having a small surface roughness and particularly excellent adhesion to the conductor layer can be obtained. . The thermoplastic resin system can be used alone or in combination of two or more kinds.

Examples of the phenoxy resin include a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a stilbene skeleton, and a dicyclopentadiene skeleton. , One or more types of phenoxy resins in the group consisting of norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton and trimethylcyclohexane skeleton. The terminal system of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

Specific examples of phenoxy resins include "1256" and "4250" (both are phenoxy resins containing a bisphenol A skeleton) manufactured by Mitsubishi Chemical Corporation; "YX8100" (including double Phenoxy resin with phenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin with bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Chemical Corporation; Mitsubishi "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by the Chemical Company.

Examples of the polyvinyl acetal resin include polyethylene formaldehyde resin and polyvinyl butyral resin, and preferably polyvinyl butyral resin. Specific examples of the polyvinyl acetal resin include S-LEC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Sekisui Chemical Industries, Ltd.

As specific examples of the polyimide resin, "RIKA COAT SN20" and "RIKA COAT PN20" manufactured by Shin Nippon Physical and Chemical Corporation can be cited. As a specific example of the polyimide resin, a linear polyimide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (Japanese Patent Laid-Open No. 2006-37083) Polyimide described in Japanese Patent Publication), polyimide containing a polysiloxane skeleton (polyimide described in Japanese Patent Application Publication No. 2002-12667 and Japanese Patent Application Publication No. 2000-319386, etc.), etc. Of modified polyimide.

Specific examples of the polyimide amide imine resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo. As specific examples of the polyimide amide imide resin, modified polyamides such as "KS9100" and "KS9300" (polyamide amide imide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd. can also be mentioned. Amide imine.

Specific examples of polyether resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. and the like.

Specific examples of the polyphenylene ether resin include oligophenyl ether/styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd. and the like.

As specific examples of the poly-resin resin, poly-resin "P1700", "P3500" manufactured by Solvay Advanced Polymers, etc. may be mentioned.

(H) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, and particularly preferably 20,000 or more from the viewpoint that the desired effect of the present invention can be significantly obtained. 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, from the viewpoint that the desired effect of the present invention can be obtained remarkably, when the nonvolatile content in the resin composition is 100% by mass, it is preferably 0.01% by mass or more, and It is preferably 0.05% by mass or more, more preferably 0.1% by mass or more; preferably 5% by mass or less, still more preferably 3% by mass or less, more preferably 1% by mass or less.

＜(I) flame retardant＞ The resin composition may contain (I) a flame retardant as an arbitrary component. Examples of (I) flame retardants include phosphazene compounds, organic phosphorus-based flame retardants, organic phosphorus-containing phosphorus compounds, nitrogen compounds, polysiloxane-based flame retardants, metal hydroxides, etc. Nitrogen ring compounds are preferred. The flame retardant system can be used alone or in combination of two or more.

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

As a flame retardant other than the phosphorus-nitrogen ring compound, a commercially available product can be used, and examples thereof include "HCA-HQ" manufactured by Sanko Corporation, and "PX-200" manufactured by Taiba Chemical Industry Corporation. As the flame retardant system, those that are difficult to hydrolyze are preferred. For example, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-peroxide and the like are preferred. good.

When the resin composition contains (I) a flame retardant, from the viewpoint that the desired effect of the present invention can be obtained remarkably, when the nonvolatile component in the resin composition is 100% by mass, (I) the flame retardant The amount is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more. 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.

＜(J)Other additives＞ In addition to the above components, the resin composition may further contain other additives as arbitrary components. Examples of such additives include organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; tackifiers; defoamers; leveling agents; adhesion imparting agents; resins such as colorants additive. One type of these additives can be used alone, or two or more types can be combined in any ratio.

<Characteristics of resin composition> By hardening the resin composition of the present invention, it is possible to obtain an insulating layer formed of a cured product of the resin composition. When a through hole is formed on this insulating layer and roughening treatment is applied, the blooming phenomenon can be suppressed. Hereinafter, these effects will be described with reference to the drawings.

FIG. 1 is a cross-sectional view showing the insulating layer 100 (which is obtained by curing the resin composition of the present invention into a sheet shape) and the inner layer substrate 200 together. This FIG. 1 is a cross-sectional view of the insulating layer 100 cut by a plane passing through the center 120C of the bottom 120 of the through 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 hardening the resin composition layer formed on the inner substrate 200 including the conductor layer 210, and it is made of the hardened material of the resin composition . In addition, a through hole 110 is formed in the insulating layer 100. In general, the through hole 110 is closer to the surface 100U of the insulating layer 100 on the opposite side to the conductor layer 210, the larger the aperture, and the closer to the conductor layer 210, the smaller the aperture, and Forming a regular cone shape; ideally, a columnar shape having a certain aperture is formed in the thickness direction of the insulating layer 100. Normally, the surface 100U of the insulating layer 100 on the opposite side to the conductor layer 210 is irradiated with laser light to remove a part of the insulating layer 100 to form the through hole 110.

The bottom of the aforementioned through-hole 110 on the side of the conductor layer 210 is appropriately referred to as "through-hole bottom" and indicated by the symbol 120. Then, the diameter of the bottom 120 of the through hole is referred to as bottom diameter Lb. In addition, the opening formed on the opposite side of the via hole 110 from the conductor layer 210 is appropriately referred to as "top of the via hole" and indicated by the symbol 130. Then, the diameter of the top 130 of the through hole is referred to as the top diameter Lt. Generally, when the planar shape is viewed from the thickness side of the insulating layer 100, the bottom portion 120 and the top portion 130 of the through hole are formed into a circular shape, but they may also be oval. When the planar shapes of the bottom portion 120 of the through hole and the top portion 130 of the through hole are elliptical, the bottom hole diameter Lb and the top hole diameter Lt respectively represent the long diameters of the aforementioned elliptical shape.

At this time, when the taper ratio Lb/Lt obtained by dividing the bottom hole diameter Lb by the top hole diameter Lt is closer to 100%, the shape of the through hole 110 is better. As long as the resin composition of the present invention is used, the shape of the through-hole 110 can be easily controlled, so that the through-hole 110 whose taper ratio Lb/Lt is close to 100% can be realized.

The taper ratio Lb/Lt of the through hole 110 can be calculated from the bottom hole diameter Lb and the top hole diameter Lt of the through hole 110. In addition, the bottom hole diameter Lb and the top hole diameter Lt of the through hole 110 can be measured as follows: using FIB (focused ion beam), parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the bottom 120 of the through hole The cross-section is a way to cut the insulating layer 100, and then the cross-section is observed with an electron microscope.

2 is a simulation representation of a surface 100U on the opposite side of the insulating layer 100 (which is obtained by curing the resin composition of the present invention into a sheet shape) and the conductor layer 210 (not shown in FIG. 2). Floor plan.

As shown in FIG. 2, when viewing the insulating layer 100 in which the through-hole 110 is formed, around the through-hole 110, from the edge 180 of the top 130 of the through-hole to the edge 190 on the outer peripheral side of the discoloration part 140, It may be observed that the insulating layer 100 is a discolored portion 140 that changes color. The discolored portion 140 may be formed due to the deterioration of the resin during the formation of the through-hole 110, and is usually formed continuously from the through-hole 110. In most cases, the color-changing portion 140 becomes a whitened portion.

FIG. 3 is a cross-sectional view of the insulating layer 100 after roughening (which is obtained by curing the resin composition of the present invention into a sheet shape) and the inner substrate 200 together. The section shown in FIG. 3 is a section through which the insulating layer 100 is cut on a plane passing through the center 120C of the bottom 120 of the through hole 110 and parallel to the thickness direction of the insulating layer 100 . As shown in FIG. 3, when the insulating layer 100 having the through hole 110 is subjected to roughening treatment, a halo phenomenon may occur, and the insulating layer 100 of the discolored portion 140 may be peeled off from the conductive layer 210, and there may be a through hole The edge 150 of the bottom 120 forms a continuous gap 160.

By using the resin composition of the present invention, the aforementioned halo phenomenon can be suppressed. Therefore, peeling of the conductor layer 210 from the insulating layer 100 can be suppressed, so that the size of the gap portion 160 can be reduced.

The edge 150 of the bottom portion 120 of the through hole corresponds to the edge of the gap 160 on the inner peripheral side. Therefore, the distance Wb from the edge 150 of the through-hole bottom 120 to the end on the outer peripheral side of the gap 160 (that is, the end on the far side from the center 120C of the through-hole bottom 120) 170 is equivalent to The dimension of the gap 160 in the in-plane direction. Here, the so-called in-plane direction refers to a direction perpendicular to the thickness direction of the insulating layer 100. In the following description, the aforementioned distance Wb is referred to as the halo distance Wb from the edge 150 of the through-hole bottom 120 of the through-hole 110. With this halo distance Wb from the edge 150 of the bottom 120 of the through hole, the degree of suppression of halo phenomenon can be evaluated. Specifically, the smaller the halo distance Wb from the edge 150 of the bottom 120 of the through hole, the more effectively the halo phenomenon can be suppressed.

For example, a resin composition layer containing 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 to obtain an insulating layer 100, and the insulating layer 100 is irradiated with CO ₂ Laser light to form a through hole 110 with a top aperture Lt of about 50 μm or about 30 μm. After that, it was immersed in the swelling liquid at 60°C for 10 minutes, then immersed in the oxidizing agent solution at 80°C for 20 minutes, then immersed in the neutralization liquid at 40°C for 5 minutes, and then dried at 80°C for 30 minutes. As long as the resin composition of the present invention is used, the insulating layer 100 obtained in such a manner, the halo distance Wb from the edge 150 of the bottom 120 of the through hole 110 of the through hole 110 may preferably be 10 μm or less, and more preferably 5 μm or less , More preferably, it can be 4.5 μm or less, and especially good can be 4 μm or less.

In the aforementioned CO ₂ laser irradiation conditions, if the top aperture Lt is about 50 μm, the mask diameter is 1.60 mm, the focal length deviation value is 0.050, the pulse width is 25 μs, the energy is 0.66 W, the aperture 13 and the number of projections 2. Pulse intermittent mode (10kHz). In addition, when the top aperture Lt is about 30 μm, the mask diameter is 1 mm, the pulse width is 16 μs, the energy is 0.2 mJ/projection, the projection number is 2, and the pulse intermittent mode (10 kHz) is used.

The halo distance Wb from the edge 150 of the through-hole bottom 120 can be measured as follows: using FIB (focused ion beam), parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the through-hole bottom 120 Is to cut the insulating layer 100 in a visible manner, and then observe the cross section with an electron microscope.

In addition, by using the resin composition of the present invention, the shape of the through-hole 110 of the insulating layer 100 before roughening can be easily controlled, and generally even the insulating layer 100 after roughening can easily control the through-hole 110 shapes. Therefore, even after the roughening treatment, the shape of the through-hole 110 can be made good as in the case before the roughening treatment. Therefore, as long as the resin composition of the present invention is used, the through hole 110 having a taper ratio Lb/Lt close to 100% can be realized in the roughened insulating layer.

For example, the resin composition is heated at 130°C for 30 minutes, and then heated at 170°C for 30 minutes to harden it to obtain an insulating layer 100, and the insulating layer 100 is irradiated with CO ₂ laser light to form a top aperture Lt of about The through hole 110 of 50 μm or about 30 μm. After that, it was immersed in the swelling liquid at 60°C for 10 minutes, then immersed in the oxidizing agent solution at 80°C for 20 minutes, then immersed in the neutralization liquid at 40°C for 5 minutes, and then dried at 80°C for 30 minutes. In such cases, the taper ratio Lb/Lt of the through hole 110 may be preferably 70% to 100%, preferably 75% to 100%, and particularly preferably 80% to 100%.

In the aforementioned CO ₂ laser irradiation conditions, if the top aperture Lt is about 50 μm, the mask diameter is 1.60 mm, the focal length deviation value is 0.050, the pulse width is 25 μs, the energy is 0.66 W, the aperture 13 and the number of projections 2. Pulse intermittent mode (10kHz). In addition, when the top aperture Lt is about 30 μm, the mask diameter is 1 mm, the pulse width is 16 μs, the energy is 0.2 mJ/projection, the projection number is 2, and the pulse intermittent mode (10 kHz) is used.

The taper Lb/Lt of the through-hole 110 after the roughening treatment can be calculated from the bottom hole diameter Lb and the top hole diameter Lt of the through-hole 110. In addition, the bottom hole diameter Lb and the top hole diameter Lt of the through hole 110 can be measured as follows: using FIB (focused ion beam), parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the bottom 120 of the through hole The cross-section is a way to cut the insulating layer 100, and then the cross-section is observed with an electron microscope.

Furthermore, according to the research of the present inventors, it can be known that the larger the diameter of the through hole, the larger the size of the gap 160 tends to be. Therefore, according to the ratio of the size of the gap portion 160 with respect to the diameter of the through hole 110, the degree of suppression of the halo phenomenon can be evaluated. For example, it can be evaluated by the halo ratio Hb with respect to the bottom radius Lb/2 of the through hole 110. Here, the bottom radius Lb/2 of the through hole 110 refers to the radius of the bottom 120 of the through hole 110. In addition, the so-called halo ratio Hb relative to the bottom radius Lb/2 of the through hole 110 refers to the halo distance Wb from the edge 150 of the bottom 120 of the through hole divided by the bottom radius Lb/2 of the through hole 110 The ratio obtained. When the halo ratio Hb with respect to the bottom radius Lb/2 of the through hole 110 is smaller, it means that the halo phenomenon can be more effectively 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 hardened to obtain the insulating layer 100, and the insulating layer 100 is irradiated with CO ₂ laser light to form The through hole 110 having a top hole diameter Lt of about 50 μm or about 30 μm. After that, it was immersed in the swelling liquid at 60°C for 10 minutes, then immersed in the oxidizing agent solution at 80°C for 20 minutes, then immersed in the neutralization liquid at 40°C for 5 minutes, and then dried at 80°C for 30 minutes. The halo ratio Hb formed on the insulating layer 100 obtained in such a manner with respect to the bottom radius Lb/2 of the through hole 110 may preferably be 35% or less, and more preferably 30% or less, more preferably It can be below 25%.

In the aforementioned CO ₂ laser irradiation conditions, if the top aperture Lt is about 50 μm, the mask diameter is 1.60 mm, the focal length deviation value is 0.050, the pulse width is 25 μs, the energy is 0.66 W, the aperture 13 and the number of projections 2. Pulse intermittent mode (10kHz). In addition, when the top aperture Lt is about 30 μm, the mask diameter is 1 mm, the pulse width is 16 μs, the energy is 0.2 mJ/projection, the number of projections is 2, and the pulse intermittent mode (10 kHz) is used.

The halo ratio Hb relative to the bottom radius Lb/2 of the through hole 110 can be calculated from the bottom hole diameter Lb of the through hole 110 and the halo distance Wb from the edge 150 of the through hole bottom 120 of the through hole 110.

In the manufacturing process of the printed wiring board, the through hole 110 is usually formed in a state where the surface 100U of the insulating layer 100 (which is opposite to the conductive layer 210) is not provided with another conductive layer (not shown) . Therefore, as long as the manufacturing process of the printed wiring board is understood, it can be clearly understood that the conductor layer 210 side has a structure having a via bottom 120 and a via top 130 opening on the opposite side to the conductor layer 210. However, it is still possible to provide conductor layers on both sides of the insulating layer 100 for the printed wiring board that has been completed. In this case, depending on the positional relationship with the conductor layer, it is difficult to distinguish between the bottom 120 of the via and the top 130 of the via. However, in general, the top hole diameter Lt of the top portion 130 of the through hole has a size larger than the bottom hole diameter Lb of the bottom portion 120 of the through hole. Therefore, in the foregoing case, the bottom 120 of the through hole and the top 130 of the through hole can be distinguished according to the size of the aperture.

In addition to suppressing the blooming phenomenon, the resin composition of the present invention can also obtain an insulating layer whose dielectric tangent is low and which generally has excellent adhesion to the conductor layer.

The cured product obtained by thermally curing the resin composition at 200°C for 90 minutes exhibits a characteristic that the dielectric tangent is low. Therefore, the aforementioned hardened system can obtain an insulating layer having a low dielectric tangent. The dielectric tangent is preferably 0.006 or less, more preferably 0.0055 or less, and even more preferably 0.0053 or less. On the other hand, the lower limit value of the dielectric tangent is not particularly limited, but can be set to 0.0001 or more. The aforementioned evaluation of the dielectric tangent can be measured according to the method described in the examples described later.

The cured product obtained by heat curing the resin composition at 130°C for 30 minutes and then at 170°C for 30 minutes usually exhibits the so-called adhesion (peel strength) to the plated conductor layer as Excellent characteristics. Therefore, the aforementioned hardened system can obtain an insulating layer excellent in adhesion to the plated conductor layer. The peel strength from the plated conductor layer is preferably 0.3 kgf/cm or more, more preferably 0.35 kgf/cm or more, and even more preferably 0.4 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 aforementioned evaluation of the peel strength from the plated conductor layer can be measured according to the method described in the examples described later.

The resin composition system of the present invention can obtain an insulating layer having a low dielectric tangent, suppressing blooming, and generally having excellent adhesion to a conductor layer. Therefore, the resin composition system of the present invention can be suitably used as a resin composition for insulation applications. Specifically, it can be suitably used as: a resin composition for forming an insulating layer (including a redistribution layer) formed on an insulating layer (a resin composition for forming an insulating layer forming a conductive layer) Thing).

Moreover, in the multilayer printed wiring board described later, it can be suitably used as a resin composition for forming an insulating layer of a multilayer printed wiring board (a resin composition for forming an insulating layer of a multilayer printed wiring board), and for forming printing The resin composition of the interlayer insulating layer of the wiring board (the resin composition for forming the interlayer insulating layer of the printed wiring board).

In addition, for example, when manufacturing a semiconductor chip package through the following steps (1) to (6), the resin composition of the present invention can also be suitably used as a rewiring as an insulating layer for forming a rewiring layer A resin composition for forming a layer (a resin composition for forming a rewiring formation layer) and a resin composition for sealing a semiconductor wafer (a resin composition for sealing a semiconductor wafer). When manufacturing a semiconductor chip package, a redistribution layer may be further formed on the sealing layer. (1) The step of laminating the temporary fixing film on the substrate, (2) The step of temporarily fixing the semiconductor wafer to the temporary fixing film, (3) The steps of forming the sealing layer on the semiconductor wafer, (4) The steps of peeling the substrate and temporary fixing film from the semiconductor wafer, (5) Steps for forming a rewiring formation layer as an insulating layer on the surface where the substrate of the semiconductor wafer and the temporary fixing film are peeled off and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

In addition, the resin composition system of the present invention can obtain an insulating layer with good embedding properties of parts, so that the printed wiring board can be suitably used when the parts are embedded in a circuit board.

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

The thickness of the resin composition layer is preferably 50 μm or less from the viewpoint that the thickness of the printed wiring board and the cured product of the resin composition can provide a cured product with excellent insulation even if it is a thin film. It is 40 μm or less, more preferably 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but it can generally be 5 μm or more.

Examples of the support include films, metal foils, and release papers made of plastic materials, and films and metal foils made of plastic materials are preferred.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate. (Hereinafter sometimes abbreviated as "PEN") polyesters; polycarbonate (hereinafter sometimes abbreviated as "PC"); acrylic acid such as polymethyl methacrylate (PMMA); cyclic polyolefins; triethyl amide Cellulose (TAC); polyether sulfide (PES); polyether ketone; polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil. Among them, copper foil is preferred. As the copper foil, a foil made of a simple metal of copper, or a foil made of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. .

The support system may apply matting treatment, corona discharge treatment, and static electricity suppression treatment to the surface bonded to the resin composition layer.

As the support, a support with a release layer having a release layer on the surface joined to the resin composition layer can also be used. Examples of the mold release agent that can be used in the mold release layer of the support with a mold release layer include, for example, the group consisting of alkyd resin, polyolefin resin, urethane resin, and polysiloxane resin More than one release agent selected. As the support with a release layer, a commercially available product can be used, and examples thereof include "SK-1" and "SK-1" manufactured by LINTEC Corporation, which have a PET film made of a release layer mainly composed of an alkyd resin-based release agent. "AL-5", "AL-7", "Lumirror T60" manufactured by Toray, "PUREX" manufactured by Teijin, "Unipeel" manufactured by Unitika, etc.

The thickness of the support is not particularly limited, but it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when using the support body with a mold release layer, it is preferable to make the thickness of the whole support body with a mold release layer into the said range.

In one embodiment, the resin sheet may further include other layers as required. As the above-mentioned other layer, for example, a protective film may be provided on the surface of the support body not to be in contact with the resin composition layer (that is, the surface opposite to the support body) according to the support body. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion or scratching of dust and the like on the surface of the resin composition layer.

The resin sheet can be produced by, for example, dissolving the resin composition in an organic solvent to prepare a resin varnish, applying the resin varnish to a support using a die coater, etc., and then drying it A resin composition layer is formed.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether acetate Acetates such as carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethyl Acetamide-based solvents such as acetamide (DMAc) and N-methylpyrrolidone. One type of organic solvent can be used alone, or two or more types can be used in combination.

The drying system can be carried out by a well-known method such as heating and 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, if a resin varnish containing 30% by mass to 60% by mass of organic solvent is used, it is dried at 50°C to 150°C for 3 minutes to 10 Minutes to form a resin composition layer.

The resin sheet system can be wound into a roll shape and stored. If the resin sheet has a protective film, it can be used as a resin sheet 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.

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

The "inner layer substrate" used in step (I) refers to a member that becomes a substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermal Hardened polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one or both sides, and the conductor layer may also be patterned. An inner layer substrate in which a conductor layer (circuit) is formed on one side or both sides of the substrate is sometimes called an "inner layer circuit substrate". In addition, when manufacturing a printed wiring board, an intermediate product of an insulating layer and/or a conductor layer to be formed is also included in the so-called "inner substrate" of the present invention. When the printed wiring board is a component-embedded circuit board, an inner substrate with embedded components can be used.

The lamination of the inner substrate and the resin sheet can be performed by, for example, heating and pressing the resin sheet and the inner substrate from the support side. Examples of the member that heat-pressure bonds the resin sheet and the inner layer substrate (hereinafter also referred to as "heat-pressure bonding member") include, for example, a heated metal plate (SUS mirror plate, etc.), a metal roll (SUS roll), and the like. In addition, in order to make the resin sheet sufficiently follow the surface unevenness of the inner layer substrate, it is not preferable to directly press the thermocompression bonding member and the resin sheet, but to press with an elastic material such as heat-resistant rubber.

The lamination of the inner substrate and the resin sheet can be carried out by vacuum lamination. In the vacuum lamination method, the heating and pressing temperature is preferably in the range of 60°C to 160°C, and preferably in the range of 80°C to 140°C, and the heating and pressing pressure is preferably in the range of 0.098MPa to 1.77MPa, and preferably 0.29 In the range of MPa to 1.47 MPa, the heating and pressing time is preferably 20 seconds to 400 seconds, and more preferably 30 seconds to 300 seconds. The lamination system is preferably carried out under a reduced pressure of 26.7 hPa or less.

The lamination system can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminating machine, for example, a vacuum pressurizing laminating machine manufactured by Meiji Co., Ltd., a vacuum laminating machine manufactured by Nikko Materials Co., Ltd., a batch-type vacuum pressurizing laminating machine, etc. may be mentioned.

After lamination, the laminated resin sheet can be smoothed by pressing under normal pressure (at atmospheric pressure), for example, by pressing the heated pressure-bonding member from the support side. The pressing conditions of the smoothing treatment can be set to the same conditions as the above-mentioned laminating heat and pressure bonding conditions. The smoothing treatment can be performed by a commercially available bonding machine. Still, the lamination and smoothing treatment can also be continuously performed using the above-mentioned commercially available vacuum bonding machine.

The support body can be removed between step (I) and step (II), and can also be removed after step (II).

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

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

Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before thermally hardening the fat composition layer, the resin composition layer may be applied at a temperature of 50°C or higher but less than 120°C (preferably 60°C or higher and 115°C or lower, and more preferably 70°C or higher and 110°C or lower). Preheating for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, more preferably 15 minutes to 100 minutes).

When manufacturing a printed wiring board, it may be further implemented: (III) a step of opening the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer. These steps (III) to (V) can be carried out according to various methods well known to those used in the manufacture of printed wiring boards. Still, when the support is removed after step (II), the removal of the support may be between step (II) and step (III), between step (III) and step (IV), or in It is carried out between step (IV) and step (V). Furthermore, by repeating the formation of the insulating layer and the conductor layer from step (II) to step (V) as required, a multilayer wiring board can also be formed.

Step (III) is a step of opening the insulating layer, whereby holes such as through holes, through holes, etc. can be formed on the insulating layer. Step (III) is performed in accordance with the composition of the resin composition used in the formation of the insulating layer, and can be performed using, for example, drilling, laser, plasma, or the like. The size or shape of the hole can be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Generally speaking, the slag can also be removed in this step (IV). The procedures and conditions of the roughening treatment are not particularly limited, and well-known procedures and conditions generally used when forming an insulating layer of a printed wiring board can be adopted. The insulating layer may be roughened by, for example, swelling treatment by swelling solution, roughening treatment by oxidizing agent, and neutralization treatment by neutralizing solution. The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, and the like is preferably an alkaline solution. The alkaline solution includes sodium hydroxide solution and potassium hydroxide solution. good. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment by the swelling liquid is not particularly limited, and can be performed by, for example, immersing the insulating layer in a swelling liquid of 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling liquid at 40°C to 80°C for 5 to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. 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°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidants include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Atotech Japan. In addition, an acidic aqueous solution is preferable as the neutralizing liquid used in the roughening treatment, and examples of commercially available products include "Reduction solution Securiganth P" manufactured by Atotech Japan. The treatment with the neutralizing liquid can be performed by immersing the treated surface roughened with an oxidizing agent in the neutralizing liquid at 30°C to 80°C for 1 to 30 minutes. In terms of workability and the like, a method of immersing the object after roughening treatment with an oxidizing agent in a neutralizing liquid at 40°C to 70°C for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after roughening is preferably 120 nm or less, more preferably 110 nm or less, and even more preferably 100 nm or less. The lower limit is not particularly limited, and it is preferably 30 nm or more, more preferably 40 nm or more, and still more preferably 50 nm or more. The arithmetic average roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, which is to form a conductor layer on the insulating layer. The conductor material used as the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer includes one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium Above the metal. The conductor layer system may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel·chromium alloy, copper·nickel alloy, and copper·titanium) Alloy). Among them, from the viewpoints of versatility, cost, and ease of patterning of the conductor layer, a simple metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or nickel An alloy layer of chromium alloy, copper/nickel alloy, copper/titanium alloy is preferred, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel/chromium alloy For further preference, a simple metal layer of copper is more preferred.

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

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

In one embodiment, the conductor layer can be formed by plating. For example, by a conventionally well-known technique such as a semi-additive method or a full-additive method, a conductor layer having a desired wiring pattern can be formed by plating on the surface of an insulating layer, from the viewpoint of ease of manufacturing In particular, it is preferably formed by a semi-additive method. The following is an example of forming a conductor layer by a semi-additive method.

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

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

Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trams, ships, and airplanes).

The semiconductor device of the present invention can be manufactured by mounting components (semiconductor wafers) on the conductive portions of the printed wiring board. The so-called "conducting part" refers to "the part of the printed wiring board that transmits electrical signals", and its position may be the surface or the part where it is buried. In addition, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

The method of mounting a semiconductor wafer when manufacturing a semiconductor device is not particularly limited as long as the semiconductor wafer effectively functions, but specifically, a wire bonding mounting method, a flip chip mounting method, and bumpless Mounting method of build-up layer (BBUL), mounting method by anisotropic conductive film (ACF), mounting method by non-conductive film (NCF), etc. Here, the so-called "mounting method by bumpless build-up (BBUL)" refers to "mounting the semiconductor wafer directly into the recess of the printed wiring board to connect the semiconductor wafer to the wiring on the printed wiring board. method". [Example]

The present invention is specifically described below by showing examples. However, the present invention is not limited by the following examples. In the following description, "parts" and "%" indicating quantities, unless otherwise specified, represent the meaning of "parts by mass" and "mass %", respectively. In addition, the operation described below means that it is performed in an environment of normal temperature and normal pressure unless otherwise specified.

<Example 1: Preparation of resin composition 1> 10 parts of bisphenol A epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180 g/eq.), and bisphenol AF epoxy resin (Mitsubishi 20 parts of "YL7760" manufactured by Chemical Company, epoxy equivalent of about 238g/eq.) and 20 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., equivalent of epoxy equivalent of about 269g/eq.), phosphorus nitrogen 3 parts of resin ("SPH-100" manufactured by Otsuka Chemical Co., Ltd.), 10 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), in MEK20 In 40 parts of solvent petroleum naphtha, it was heated and dissolved while stirring. After cooling to room temperature, 94 parts of active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223 g/eq., solid content of 65% by mass in toluene solution) were mixed, and 94 parts of phenolic hardener ( DIC's "LA-3018-50P", active group equivalent of about 151g/eq., solid content 50% 2-methoxypropanol solution) 10 parts, benzoxazine hardener (made by JFE Chemical company) ODA-BOZ" solid content 50% by mass MEK solution, benzoxazine ring equivalent of about 218g/eq.) 6 parts, (meth)acrylate ("NK Ester A-DOG" manufactured by Shin Nakamura Chemical Industry Co., Ltd., Molecular weight 326, (meth)acryloyl equivalent 163g/eq.) 12 parts, hardener (aromatic hydrocarbon represented by formula (4), "GRA13H" manufactured by Qunrong Chemical Industry Co., Ltd., hydroxyl group) as component (C) Equivalent of about 75g/eq.) 2 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5 mass% MEK solution) 8 parts, polymerization initiator ("Perbutyl" manufactured by NOF Corporation) C'') 0.2 parts of spherical silica (average particle size 0.5 μm, specific surface area 5.9 m ² /g, Admatechs) surface-treated with phenylaminosilane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”) 400 parts "SO-C2" manufactured by the company, evenly dispersed by a high-speed rotary mixer, and then filtered through a filter cartridge ("SHP100" manufactured by ROKITECHNO) to produce a resin composition 1.

A-DOG has the structure shown below.

<Example 2: Preparation of resin composition 2> The changes in Example 1 are as follows: 1) Change 20 parts of biphenyl epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd. with an epoxy equivalent of about 269g/eq.) to a bixylenol epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation, ring Oxygen equivalent is about 190g/eq.) 20 servings; 2) Change 94 parts of active ester hardener ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223g/eq., solid content 65% by mass in toluene solution) to active ester type hardener (DIC Corporation) Prepare 86 parts of "EXB9416-70BK", a non-volatile 70% by mass methyl isobutyl ketone solution with an active group equivalent of about 330g/eq.); 3) 6 parts of benzoxazine hardener ("ODA-BOZ" made by JFE Chemical company, solid content 50% by mass, benzoxazine ring equivalent of about 218g/eq.) were changed to carbodiimide 10 parts of hardener ("V-03" manufactured by Nisshinbo Chemical Company, active group equivalent of about 216g/eq., solid content 50% by mass in toluene solution); 4) 2 parts of the hardener (aromatic hydrocarbon represented by formula (4), "GRA13H" manufactured by Qunrong Chemical Industry Co., Ltd., hydroxyl equivalent of about 75g/eq.) as the (C) component are changed to (C) component 2 parts of the curing agent (aromatic hydrocarbon represented by formula (5), "SN395" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., hydroxyl equivalent 107g/eq.). Except for the above matters, the resin composition 2 was produced in the same manner as in Example 1.

<Example 3: Preparation of resin composition 3> Bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180g/eq.) 5 parts, biphenyl type epoxy resin (Japanese made Pharmaceutical company "NC3000L", epoxy equivalent of about 269g/eq.) 20 parts and bixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy equivalent of about 190g/eq.) 25 parts, phosphorus nitrogen 3 parts of cyclic resin ("SPH-100" manufactured by Otsuka Chemical Company), 10 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Company, 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), in Among 40 parts of MEK and 40 parts of toluene, it was heated and dissolved while stirring. After cooling to room temperature, 94 parts of active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223 g/eq., solid content of 65% by mass in toluene solution) were mixed, and 94 parts of phenolic hardener ( DIC's "LA-3018-50P", active group equivalent of about 151g/eq., solid content 50% 2-methoxypropanol solution) 10 parts, carbodiimide-based hardener (Nisshinbo chemical company's "V-03'', active group equivalent of about 216g/eq., solid content 50% by mass in toluene solution) 10 parts, (meth)acrylate ("NK Ester A-DOG" manufactured by Shin Nakamura Chemical Industry Co., Ltd., molecular weight 326) 17 parts, curing agent (aromatic hydrocarbon represented by formula (5), "SN395" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., hydroxyl equivalent of 107g/eq.) as component (C), 2 parts, curing accelerator (4- 8 parts of dimethylaminopyridine (DMAP), MEK solution with 5 mass% solid content), 0.2 parts of polymerization initiator ("Perbutyl C" manufactured by NOF Corporation), phenylaminosilane-based coupling agent ( Shin-Etsu Chemical Co., Ltd., "KBM573") surface-treated spherical silica (average particle size 0.3 μm, specific surface area 30.7 m ² /g, Denca Co., Ltd. "UFP-30") 200 parts, mixed by high-speed rotation After the machine was evenly dispersed, it was filtered with a filter cartridge ("SHP020" manufactured by ROKITECHNO) to produce a resin composition 3.

<Example 4: Preparation of resin composition 4> In Example 3, the changes are as follows: 1) Change 20 parts of biphenyl epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269g/eq.) to bisphenol AF epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy Equivalent about 238g/eq.) 20 servings; 2) Change the amount of phenolic hardener ("LA-3018-50P" manufactured by DIC Corporation, active group equivalent of about 151g/eq., solid content 50% 2-methoxypropanol solution) from 10 parts to 5 copies; 3) Change 10 parts of carbodiimide-based hardener ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent of about 216 g/eq., solid content of 50% by mass in toluene solution) to benzoxazine-based hardener (The "ODA-BOZ" made by JFE Chemical company has a solid content of 50% by mass of MEK solution and a benzoxazine ring equivalent of about 218 g/eq.) 10 parts; 4) Two parts of the curing agent (aromatic hydrocarbon represented by formula (5), "SN395" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., hydroxyl equivalent of 107 g/eq.) are changed to (C) component 2 parts of the curing agent (aromatic hydrocarbon represented by formula (4), "GRA13H" manufactured by Qunrong Chemical Industry Co., Ltd., hydroxyl equivalent of about 75g/eq.). Except for the above matters, the resin composition 4 was produced in the same manner as in Example 3.

<Comparative Example 1: Preparation of Comparative Resin Composition 1> In Example 1, the curing agent (aromatic hydrocarbon represented by the formula (4), "GRA13H" manufactured by Qunrong Chemical Industry Co., Ltd., having a hydroxyl equivalent of about 75 g/eq.) was not used. Except for the above matters, a comparative resin composition 1 was produced in the same manner as in Example 1.

<Comparative Example 2: Preparation of Comparative Resin Composition 2> In Example 3, 2 parts of a curing agent (aromatic hydrocarbon represented by formula (5), "SN395" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., hydroxyl equivalent of 107 g/eq.) was not used. Except for the above matters, a comparative resin composition 2 was produced in the same manner as in Example 3.

<Measurement of average particle size of inorganic filler> Weigh 100 mg of inorganic filler, 0.1 g of dispersant ("SN9228" manufactured by San nopco), and 10 g of methyl ethyl ketone into a vial, and disperse it for 20 minutes by ultrasound. Using a laser diffraction particle size distribution measuring device ("SALD-2200" manufactured by Shimadzu Corporation), the particle size distribution was measured by a batch tank method, and the average particle size was calculated from the average particle size.

＊表中，「a1」表示將(A)成分的質量除以環氧當量而得到的值；「e1」表示將活性酯系硬化劑的質量除以活性酯基當量而得到的值；「e2」表示將苯并噁嗪系硬化劑的質量除以苯并噁嗪環當量而得到的值；「b2」表示將(B)成分的質量除以(甲基)丙烯醯基當量而得到的值；「e3」表示樹脂組成物中的碳二亞胺系硬化劑的含量；「b1」表示樹脂組成物中的(B)成分的含量。

* In the table, "a1" represents the value obtained by dividing the mass of (A) component by the epoxy equivalent; "e1" represents the value obtained by dividing the mass of the active ester-based hardener by the equivalent of active ester groups; "e2 "Indicates the value obtained by dividing the mass of the benzoxazine-based hardener by the benzoxazine ring equivalent; "b2" indicates the value obtained by dividing the mass of the (B) component by the (meth)acryloyl equivalent ; "E3" indicates the content of the carbodiimide-based hardener in the resin composition; "b1" indicates the content of the (B) component in the resin composition.

[Production of Resin Sheet] As a support, a PET film ("Lumirror R80" manufactured by Toray Co., Ltd.) with a thickness of 38 μm and a softening point of 130° C. or less prepared by release treatment with an alkyd resin-based mold release agent (“AL-5” manufactured by LINTEC) is prepared. (There is a case called "release PET").

<Production of Resin Sheet A> Using a die coater, the resin composition 1, 2 and the resin composition 1 for comparative examples were uniformly coated on the release PET so that the thickness of the dried resin composition layer of each resin composition became 40 μm After drying at 80 to 120°C (average 100°C) for 4 minutes, a resin composition layer was obtained on the release PET. Next, on the surface of the resin composition layer that is not bonded to the release PET, the rough surface of the polypropylene film ("Arufan MA-411" manufactured by Oji F-Tex Corporation, thickness 15 μm) and the resin composition are used as the protective film Lamination is carried out by means of object layer bonding. Thereby, the resin sheet A formed by releasing PET (support), a resin composition layer, and a protective film in this order is obtained.

<Preparation of resin sheet B> Using a die coater, the resin composition 3, 4 and the resin composition 2 for comparative examples were uniformly coated on the mold release PET so that the thickness of the resin composition layer after the resin composition was dried became 10 μm. After drying at 80°C for 2 minutes, a resin composition layer was obtained on the release PET. Next, on the surface of the resin composition layer that is not joined to the support, the rough surface of the polypropylene film ("Arufan MA-411" manufactured by Oji F-Tex Corporation, thickness 15 μm) and the resin composition are used as the protective film Lamination is carried out by layer bonding. Thereby, the resin sheet B formed by releasing PET (support), a resin composition layer, and a protective film in this order is obtained.

[Determination of Dielectric Tangent] The protective film was peeled off from the resin sheets A or B obtained in Examples and Comparative Examples, and heated at 200° C. for 90 minutes to thermally harden it, and by peeling off the support, a sheet-shaped hardened product was obtained. The hardened material was cut out to have a length of 80 mm and a width of 2 mm as evaluation samples. For this evaluation sample, the dielectric tangent was measured by using the HP8362B device manufactured by Agilent Technologies and using the cavity resonance perturbation method to measure the cycle number at 5.8 GHz and the measurement temperature at 23°C. The three test pieces were measured, and the average value was calculated.

[Measurement of tear strength (peel strength) of halo and plated conductor layer] <Preparation of samples for evaluation of halo and measurement of peel strength> (1) Base treatment of inner circuit board Both sides of the glass cloth substrate epoxy resin two-sided copper-clad laminate (with copper foil thickness 18 μm, substrate thickness 0.4 mm, R1515A manufactured by Panasonic Corporation) with an inner layer circuit formed were etched with a micro-etchant (CZ8101 manufactured by MEC Corporation) 1μm to roughen the copper surface.

(2) Lamination of resin sheets The protective film was peeled from each prepared resin sheet A or B, and laminated to both sides of the inner-layer circuit board using a batch-type vacuum pressure bonding machine (MVLP-500 manufactured by Mingji Corporation). The lamination is performed by depressurizing for 30 seconds and setting the air pressure to 13 hPa or less, and thereafter, by performing pressure bonding at 30 seconds, 100° C., and a pressure of 0.74 MPa.

(3) Hardening of resin composition The laminated resin sheet was cured at 130°C for 30 minutes and then at 170°C for 30 minutes to harden the resin composition layer to form an insulating layer.

(4) In Examples 1, 2 and Comparative Example 1 for forming a through hole, a CO ₂ laser processing machine (manufactured by Hitachi Via Mechanics, LC-2E21B/1C) was used with a mask diameter of 1.60 mm and a focal length deviation value of 0.050, Under the conditions of pulse width 25μs, energy 0.66W, aperture 13, projection number 2, pulse intermittent mode (10kHz), the insulating layer is opened, so that the top diameter (diameter) of the through hole on the surface of the insulating layer becomes In a manner of about 50 μm, a plurality of through holes are formed. After that, the release PET is peeled off.

In Examples 3, 4, and Comparative Example 2, a CO ₂ laser processing machine ("605GTWIII (-P)" manufactured by Mitsubishi Electric Corporation) was used with a mask diameter of 1 mm, a pulse width of 16 μs, and an energy of 0.2 mJ/projection number. 2. Under the condition of the pulse intermittent mode (10 kHz), the insulating layer is opened to form a plurality of through holes so that the top diameter (diameter) of the through holes on the surface of the insulating layer becomes about 30 μm. After that, the release PET is peeled off.

(5) Roughening treatment: The inner layer circuit board on which the insulating layer is formed is immersed at 60° C. in a swelling liquid made by Atotech Japan Corporation containing diethylene glycol monobutyl ether Swelling Dip·Securiganth P (diol 10 minutes in ethers and aqueous solution of sodium hydroxide, and then immersed in an aqueous solution of Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L) manufactured by Atotech Japan Co., Ltd. as a roughening liquid at 80°C ) For 20 minutes, and finally immersed in Reduction solution·Securiganth P (aqueous solution of sulfuric acid) manufactured by Atotech Japan as a neutralizing liquid at 40°C for 5 minutes, and then dried at 80°C for 30 minutes. Let this board be evaluation board A.

(6) Immerse the evaluation substrate A in a solution for electroless plating containing PdCl ₂ at 40°C for 5 minutes by plating using a semi-additive method, and then immerse it in an electroless copper plating solution at 25°C 20 minutes. After heating at 150° C. for 30 minutes and performing annealing treatment, an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 20 μm. Next, annealing treatment was performed at 200°C for 60 minutes. Let this board be the evaluation board B.

<Measurement of the size of the through hole after roughening treatment, the distance of halo and halo ratio> For the evaluation substrate A, a FIB-SEM composite device ("SMI3050SE" manufactured by SII NanoTechnology) was used for cross-sectional observation. In detail, using FIB (Focused Ion Beam), the insulating layer is cut so that a cross section parallel to the thickness direction of the insulating layer and passing through the center of the bottom of the through hole of the through hole appears. The cross section was observed by SEM. The bottom hole diameter and top hole diameter of the through hole are measured from the observed screen. In addition, the screen observed by SEM shows a gap formed by peeling off the insulating layer from the copper foil layer of the inner substrate, which is continuous from the edge of the bottom of the through hole. Here, the "distance r1" and "distance r2" are measured from the observed screen, and the distance r1 is the distance from the center of the bottom of the through hole to the edge of the bottom of the through hole (equivalent to the inner circumferential radius of the gap portion) ); The distance r2 is the distance from the center of the bottom of the through hole to the far end of the gap (equivalent to the outer radius of the gap), and the difference r2 between the distance r1 and the distance r2 is calculated r1, and use the difference as the halo distance from the edge of the bottom of the through hole at the measurement location.

Randomly selected five parts of through holes to perform the aforementioned measurement. Then, the average of the top hole diameters of the five through-holes measured was used as the top hole diameter Lt of the sample after roughening. In addition, the average bottom hole diameter of the five through-holes measured was used as the bottom hole diameter Lb of the sample after roughening. Furthermore, the average of the measured halo distances of the five through holes was used as the halo distance Wb from the edge of the bottom of the through hole for this sample.

From the aforementioned measurement results, the taper ratio (ratio of the top hole diameter Lt of the through hole after roughening to the bottom hole diameter Lb "Lb/Lt"), the halo ratio Hb (from the edge of the bottom of the through hole after roughening treatment) are calculated The ratio of the resulting halo distance Wb to the radius (Lb/2) of the through-hole bottom of the through-hole after roughening is "Wb/(Lb/2)"). If the halo ratio Hb is 35% or less, it is judged as "○", and if the halo ratio Ht is more than 35%, it is judged as "×".

<Measurement and evaluation of adhesion (peel strength) with plated conductor layer> A slit with a width of 10 mm and a length of 100 mm was placed on the conductor layer of the evaluation substrate B, one end was peeled off, and the clip was clamped (Automatic Rubber Tester AC-50C-SL manufactured by TSE Corporation). At room temperature, the load (kgf/cm) when peeling 35 mm in the vertical direction at a speed of 50 mm/min was measured.

In Examples 1 to 4, even if the components (E) to (I) are not contained, although there are differences in the degree, it is confirmed that the same results as in the above examples will be summarized.

100‧‧‧Insulation 100U‧‧‧The surface of the insulating layer opposite to the conductor layer 110‧‧‧Through hole 120‧‧‧Bottom hole 120C‧‧‧ Center of bottom of through hole 130‧‧‧Top of through hole 140‧‧‧Discoloration Department 150‧‧‧Through hole bottom edge 160‧‧‧Gap 170‧‧‧The outer peripheral end of the gap 180‧‧‧The edge of the top of the through hole 190‧‧‧The outer edge of the color-changing part 200‧‧‧Inner substrate 210‧‧‧Conductor layer Lb‧‧‧Bottom hole diameter of through hole Lt‧‧‧Top aperture of through hole Wb‧‧‧Blood distance from the edge of the bottom of the through hole

[FIG. 1] FIG. 1 is a cross-sectional view showing a simulation of an insulating layer (which is obtained by curing the resin composition of the present invention into a sheet shape) together with an inner layer substrate. [FIG. 2] FIG. 2 is a plan view showing the surface of the insulating layer (which is obtained by curing the resin composition of the present invention into a sheet shape) opposite to the conductor layer. [FIG. 3] FIG. 3 is a cross-sectional view showing the insulating layer after roughening treatment (which is obtained by curing the resin composition of the present invention into a sheet shape) together with the inner layer substrate.

Claims (16)

A resin composition characterized by comprising: (A) Epoxy resin, (B) (meth)acrylate, (C) An aromatic hydrocarbon resin containing an aromatic ring as a single ring or a condensed ring having two or more hydroxyl groups and (D) Inorganic filler. The resin composition according to claim 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. The resin composition according to claim 1, wherein the component (B) has a ring structure. The resin composition according to claim 1, wherein the component (B) has a structure represented by the following formula (B-1),

(In formula (B-1), R ¹ and R ⁴ independently represent acryl or methacryl, R ² and R ³ each independently represent a divalent linking group, and ring A represents a divalent cyclic group ). The resin composition according to claim 1, wherein the component (C) is represented by the following formula (1) or formula (2),

(In formula (1), R ⁰ independently represents a divalent hydrocarbon group, and n 1 represents an integer of 0 to 6)

(In formula (2), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group). The resin composition according to claim 1, wherein component (C) is represented by the following formula (3) or formula (4),

(In formula (3), n2 represents an integer from 0 to 6)

(In formula (4), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group). The resin composition according to claim 1, wherein the amount of the component (C) is 0.1% by mass or more and 10% by mass or less with respect to 100% by mass of the resin component in the resin composition. The resin composition according to claim 1, which further contains (E) a hardener. The resin composition according to claim 8, wherein the (E) component is selected from the group consisting of a benzoxazine-based hardener, a carbodiimide-based hardener, a phenol-based hardener, and an active ester-based hardener More than one species. The resin composition of claim 1 is used for insulation purposes. The resin composition according to claim 1 is used for forming an insulating layer. The resin composition according to claim 1, which is used to form an insulating layer for forming a conductor layer. The resin composition according to claim 1 is used for sealing a semiconductor wafer. A resin sheet characterized by comprising: Support and A resin composition layer provided on the support, The resin composition layer contains the resin composition of any one of claims 1 to 13. A printed wiring board including an insulating layer, characterized in that the insulating layer is formed by a cured product of the resin composition of any one of claims 1 to 13. A semiconductor device characterized by a printed wiring board including claim 15.

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