TWI811356B - resin composition - Google Patents

Abstract

An object of the present invention is to provide: a resin composition capable of obtaining a hardened product with a low dielectric tangent and capable of suppressing blooming; a resin sheet containing the resin composition; and an insulation device formed using the resin composition. a printed wiring board composed of layers; and a semiconductor device including the aforementioned printed wiring board. The resin composition of the present invention that solves the problem includes: (A) epoxy resin, (B) (meth)acrylate, (C) aromatic ring containing two or more hydroxyl groups as a single ring or condensed ring Aromatic hydrocarbon resin and (D) inorganic filler.

Description

resin composition

The present invention relates to a resin composition. Furthermore, it relates to resin sheets, printed wiring boards, and semiconductor devices containing the resin composition.

As a manufacturing technology for printed wiring boards, a build-up manufacturing method in which insulating layers and conductive layers are alternately stacked on an inner 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 Document]

[Patent Document 1] Japanese Patent Application Publication No. 2014-034580

[Problem to be solved by the invention]

There have been many proposals for resin compositions suitable for forming the insulating layer of the inner circuit board, including the resin composition described in Patent Document 1. However, in recent years, insulating layers with low dielectric tangent have been proposed. The requirements gradually become higher.

As a result of examination, the inventor found that the cured product of a resin composition containing a material that lowers the dielectric tangent will produce haloing, which reduces conduction reliability. In recent years, in the manufacture of multilayer printed wiring boards, cured resin compositions used to form insulating layers are required to have a lower dielectric tangent in addition to a lower dielectric tangent in order to achieve miniaturization and high-density wiring. It has sufficient conduction reliability, but the current situation is that it still cannot fully satisfy these characteristics. Here, the halo phenomenon refers to the delamination between the insulating layer and the inner substrate that occurs around the through hole. Such 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 etched during the roughening process. Furthermore, the aforementioned deteriorated portion is generally observed as a discolored portion.

An object of the present invention is to provide: a resin composition capable of obtaining a hardened product with a low dielectric tangent and capable of suppressing blooming; a resin sheet containing the resin composition; and an insulation device formed using the resin composition. a printed wiring board composed of layers; and a semiconductor device including the aforementioned printed wiring board. [Means to solve the problem]

As a result of in-depth research in order to solve the aforementioned problems, the inventor found that a resin composition containing: (A) epoxy resin, (B) (meth)acrylate, (C) containing two or more The aromatic hydrocarbon resin in which the hydroxyl group is a monocyclic or condensed aromatic ring and the (D) inorganic filler can solve the above-mentioned problems, and thus the present invention has been completed. That is, the present invention includes the following contents.

[1]. A resin composition containing: (A) epoxy resin, (B) (meth)acrylate, (C) an aromatic ring containing two or more hydroxyl groups as a single ring or a condensed ring. Aromatic hydrocarbon resin and (D) inorganic filler. [2]. The resin composition according to [1], wherein the content of component (B) is 0.1 mass% or more and 10 mass% or less when the non-volatile components in the resin composition are 100 mass%. [3]. The resin composition according to [1] or [2], wherein the component (B) has a cyclic structure. [4]. The resin composition according to 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 each independently represent an acryl group or a methacryloyl group, R ² and R ³ each independently represent a divalent linking group, and ring A represents a divalent cyclic group. ). [5]. The resin composition according to 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 each independently represents a divalent hydrocarbon group, and n1 represents an integer from 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 component (C) is 0.1 mass % or more relative to 100 mass % of the resin component in the resin composition. %the following. [8]. The resin composition according to any one of [1] to [7], further comprising (E) a hardener. [9]. The resin composition according to [8], wherein component (E) is selected from the group consisting of benzoxazine-based hardeners, carbodiimide-based hardeners, phenol-based hardeners, and One or more types of active ester hardeners in the group. [10]. The resin composition described in any one of [1] to [9] is used for insulation purposes. [11]. The resin composition as described in any one of [1] to [10], which is used for forming an insulating layer. [12]. The resin composition according to any one of [1] to [11] 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 semiconductor wafers. [14]. A resin sheet, which includes: a support body and a resin composition layer provided on the support body, where the resin composition layer contains the resin composition described in any one of [1] to [13]. [15]. A printed wiring board including an insulating layer formed from a cured product of the resin composition described in any one of [1] to [13]. [16]. A semiconductor device including the printed wiring board described in [15]. [Effects of the invention]

The present invention can provide: a resin composition capable of obtaining a hardened product with a low dielectric tangent and capable of suppressing blooming; a resin sheet containing the resin composition; and an insulation device formed using the resin composition. a printed wiring board composed of layers; and a semiconductor device including the aforementioned printed wiring board.

[The best way to implement the invention]

The present invention will be described in detail below by showing embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and can be arbitrarily modified and implemented without departing from the patentable scope of the present invention and its equivalent range.

[Resin composition] The resin composition of the present invention is a resin composition containing the following (A) to (D) components: (A) epoxy resin, (B) (meth)acrylate, (C) containing 2 Aromatic hydrocarbon resin composed of an aromatic ring containing more than one hydroxyl group as a single ring or condensed ring, and (D) inorganic filler. By using such a resin composition, it is possible to obtain the desired effect of the present invention, which is "it is possible to obtain a cured product with a low dielectric tangent and excellent suppression of blooming phenomena." Furthermore, by using such a resin composition, the adhesion with the conductor layer can generally be improved.

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

＜(A) Epoxy resin＞ The resin composition contains (A) epoxy resin as (A) component. Examples of (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, trihydric phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy Resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin Oxygen resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane-type epoxy resin , cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. One type of epoxy resin can be used alone, or two or more types can be used in combination.

In the resin composition, (A) the epoxy resin is preferably an epoxy resin containing two or more epoxy groups per molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the ratio of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the non-volatile component of the epoxy resin (A) The content is preferably 50 mass% or more, more preferably 60 mass% or more, and particularly preferably 70 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 referred to as "liquid epoxy resins"). "Solid epoxy resin"). In the resin composition, the epoxy resin (A) may contain only a liquid epoxy resin or only a solid epoxy resin, but it is preferably a combination of a liquid epoxy resin and a solid epoxy resin. . By combining liquid epoxy resin and solid epoxy resin and using it as (A) epoxy resin, when used in the form of a resin sheet, sufficient flexibility can be obtained or the cured product of the resin composition can be improved. breaking strength.

As the liquid epoxy resin, one having two or more epoxy groups per molecule is preferred.

As the liquid epoxy resin, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, and glycidyl ester type epoxy resin. Amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin And epoxy resin with butadiene structure, preferably bisphenol A type epoxy resin.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D" and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "jER828EL" and " 825", "Epikote 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation's "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical Corporation's "jER152" (phenol novolac Varnish type epoxy resin); "630" and "630LSD" (glycidyl amine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A type epoxy resin and bisphenol A type epoxy resin) manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation Mixed product of phenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagasechemtex Corporation; "CELOXIDE2021P" (alicyclic epoxy resin with an ester skeleton) manufactured by Daicel Corporation; "PB-3600" manufactured by Daicel Co., Ltd. (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd. (liquid 1,4-glycidyl cyclohexane type cyclic resin) Oxygen resin) etc. These can be used individually by 1 type, or can be used in combination of 2 or more types.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups per molecule is preferred, and an aromatic resin having three or more epoxy groups per molecule is more preferred. Solid epoxy resin.

As the solid epoxy resin, preferred are dixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, and 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 Epoxy resin, tetraphenyl ethane type epoxy resin, more preferably bisphenol AF type epoxy resin, biphenyl type epoxy resin, dixylenol type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation Resin); "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP- 7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" made by DIC Corporation , "EXA-7311-G4S", "HP6000" (alkylene ether type epoxy resin); "EPPN-502H" (trihydric phenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; manufactured by Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Chemical Corporation; Nippon Steel & Sumitomo Metal Chemical Co., Ltd. "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; "YX4000H", "YX4000", " 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 Co., Ltd. "PG-100" and "CG-500" manufactured by Mitsubishi Chemical Corporation; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (N-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These can be used individually by 1 type, or can be used in combination of 2 or more types.

When the epoxy resin (A) is used in combination with a liquid epoxy resin and a solid epoxy resin, the quantitative ratio (liquid epoxy resin: solid epoxy resin) is based on the mass ratio, The preferred range is 1:1~1:20, the preferred range is 1:1.5~1:15, and the particularly preferred range is 1:2~1:10. By setting the quantitative ratio of the liquid epoxy resin to the solid epoxy resin within the above range, the desired effects of the present invention can be significantly obtained. Furthermore, when used in the form of a resin sheet, moderate adhesion can generally be obtained. In addition, if it is generally used in the form of a resin sheet, sufficient flexibility can be obtained, so the operability is improved. Furthermore, a hardened material having sufficient breaking strength can usually be obtained.

(A) The epoxy equivalent of the epoxy resin is preferably 50g/eq.~5000g/eq., more preferably 50g/eq.~3000g/eq., and more preferably 80g/eq.~2000g/eq. , and preferably 110g/eq.~1000g/eq. By entering this range, the crosslinking 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. The epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured based on JIS K7236.

(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 400 in order to significantly obtain the desired effects of the present invention. 1500. The weight average molecular weight of the resin can be measured as a value converted to polystyrene by gel permeation chromatography (GPC).

(A) The content of the epoxy resin is preferably 1 when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. % by mass or more, preferably 3 % by mass or more, more preferably 5 % by mass or more. The upper limit of the content of the epoxy resin is preferably 30 mass% or less, more preferably 25 mass% or less, and particularly preferably 20 mass% or less from the viewpoint of significantly obtaining the desired effects of the present invention. Furthermore, in the present invention, the content of each component in the resin composition is the 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 component (B). By containing (B) (meth)acrylate in the resin composition, a cured product having a low dielectric tangent can be obtained. Here, the term "(meth)acrylic acid" includes acrylic acid, methacrylic acid, and combinations thereof.

From the viewpoint of obtaining a cured product with a low dielectric tangent, the (B) (meth)acrylate system preferably has two or more (meth)acrylyl groups per molecule. The term "(meth)acrylyl group" includes acrylyl group, methacrylyl group and combinations thereof.

From the viewpoint of obtaining a cured product with a low dielectric tangent, the (B) (meth)acrylate preferably has a cyclic structure. As the cyclic structure, a divalent cyclic group is preferred. 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 of significantly obtaining the desired effects of the present invention, a cyclic group containing an alicyclic structure is preferred.

From the viewpoint of significantly obtaining the desired effects of the present invention, the divalent cyclic group is preferably a ring with 3 members or more, more preferably a ring with 4 members or more, and more preferably a ring with 5 members or more; preferably The number of members is less than 20 members, preferably less than 15 members, and more preferably less than 10 members. In addition, the divalent cyclic group may have a monocyclic structure or a polycyclic structure.

In addition to carbon atoms, the ring in the divalent cyclic group may also be composed of heteroatoms to form the skeleton of the ring. Examples of the hetero atom include oxygen atom, sulfur atom, nitrogen atom, etc., and an oxygen atom is preferred. The aforementioned ring may have one heteroatom or two or more heteroatoms.

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

The divalent cyclic group may have a substituent. Examples of such substituents include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a silyl group, a hydroxyl group, a hydroxyl group, a carboxyl group, a sulfonic acid group, a cyano group, a nitro group, and a hydroxyl group. , mercapto group, side oxygen group, etc., preferably alkyl group.

The (meth)acrylyl group may be directly bonded to a divalent cyclic group, or may be bonded via a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an aryl group, a heteroaryl group, -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 these groups. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferred, an alkylene group having 1 to 6 carbon atoms is more preferred, and an alkylene group having 1 to 5 carbon atoms or a carbon atom is more preferred. Alkylene groups with numbers 1 to 4. The alkylene group can be optionally linear, branched or cyclic. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1,1-dimethylethylene, and the like. Methyl, ethylidene, 1,1-dimethylethylidene. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferred, an alkenylene group having 2 to 6 carbon atoms is more preferred, and an alkenylene group having 2 to 5 carbon atoms is more preferred. As the aryl group or heteroaryl group, an aryl group or heteroaryl group having 6 to 20 carbon atoms is preferred, and an aryl group or heteroaryl group having 6 to 10 carbon atoms is more preferred. As the divalent linking group, an alkylene group is preferred, and among these, a methylene group and a 1,1-dimethylethylene group are preferred.

(B) (Meth)acrylate is preferably represented by the following formula (B-1). (In formula (B-1), R ¹ and R ⁴ each independently represent an acryl group or a methacryloyl group, 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 independently represent an acrylic group or a methacrylic group, preferably an acrylic group.

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

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

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

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

Commercially available products can be used as the component (B). Examples include "NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. ((meth)acrylyl equivalent: 163 g/eq.) and "NK Ester A-DOG" manufactured by Kyoeisha Chemical Co., Ltd. DCP-A" ((meth)acrylyl equivalent 152g/eq.), Nippon Kayaku Co., Ltd. "NPDGA" ((meth)acrylyl equivalent 106g/eq.), "FM-400" ((meth)acrylyl equivalent ((meth)acrylyl equivalent weight 156g/eq.), "R-687" ((meth)acrylyl equivalent weight 187g/eq.), "THE-330" ((meth)acrylyl equivalent weight 143g/eq. ), "PET-30" ((meth)acrylyl equivalent weight 88g/eq.), "DPHA" ((meth)acrylyl equivalent weight 96g/eq.), etc. (B) Component system can be used individually by 1 type, or can be used in combination of 2 or more types.

From the viewpoint of obtaining a hardened material with a low dielectric tangent, the (meth)acrylyl group equivalent of component (B) is preferably 30 g/eq.~400 g/eq., and more preferably 50 g/eq.~ 300g/eq., preferably 75g/eq.~200g/eq. The (meth)acrylyl group equivalent refers to the mass of component (B) including 1 equivalent of (meth)acrylyl group.

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

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

Generally speaking, when forming a via hole, energy such as heat or light is applied to a portion of the insulating layer where the via 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 haloing. However, since the aromatic ring of component (C) has two or more hydroxyl groups, the progress of the oxidation reaction of the resin can be inhibited by the steric hindrance effect of the hydroxyl groups. Therefore, the insulating layer obtained 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 single ring such as a benzene ring and an aromatic ring that is a condensed ring such as a naphthalene ring. The number of carbon atoms per one of the aforementioned aromatic rings contained in component (C) is preferably 6 or more, and more preferably 14, from the viewpoint that the desired effects of the present invention can be significantly obtained. or less, and preferably less than 10.

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

At least one of the aromatic rings contained in the aromatic hydrocarbon resin as component (C) has two or more hydroxyl groups per aromatic ring. The number of hydroxyl groups per aromatic ring is preferably 3 or less, and particularly preferably 2, from the viewpoint of significantly obtaining the desired effects of the present invention.

The number of aromatic rings having two or more hydroxyl groups per molecule of component (C) is usually one or more, and from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferably two. More than 3, and preferably more than 3. 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 each 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, and preferably 3 or more, 6 or more, or 7 or more in order to significantly obtain the desired effects of the present invention. The upper limit of the number of carbon atoms mentioned above is preferably 20 or less, 15 or less, or 10 or less from the viewpoint of significantly obtaining the desired effects of the present invention.

Specific examples of R ⁰ include the following hydrocarbon groups.

In formula (1), n1 represents an integer from 0 to 6. Among these, n1 is preferably 1 or more, and more preferably 2 or more, and is preferably 4 or less, and more preferably 3 or less, in order to significantly obtain the desired effects of the present invention.

By using the aromatic hydrocarbon resin represented by the formula (1), 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 of significantly obtaining the desired effect of the present invention, an aliphatic hydrocarbon group is preferred, a saturated aliphatic hydrocarbon group is more preferred, and a chain saturated aliphatic hydrocarbon group is particularly preferred. The number of carbon atoms of the monovalent hydrocarbon group is usually 1 or more, but is preferably 20 or less, and more preferably 15 or less, 10 or less, or 8 or less in order to significantly obtain the desired effects of the present invention. Preferable examples of R ¹ to R ⁴ include hydrogen atoms; alkyl groups such as methyl, ethyl, propyl, butyl, and hexyl. If the aromatic hydrocarbon resin represented by formula (2) is used, peeling off of the halo portion caused by etching during the roughening treatment can be effectively suppressed.

Among them, particularly preferred aromatic hydrocarbon resins as the component (C) include the aromatic hydrocarbon resin represented by the following formula (3) and the aromatic hydrocarbon resin represented by the following formula (4). n2 in formula (3) represents an integer with the same definition as n1 in formula (1), and the preferred range is also the same. In addition, R ¹ to R ⁴ in the formula (4) are synonymous with R ¹ to R ⁴ in the formula (2).

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

The aromatic hydrocarbon resin system as (C) component may be used individually by 1 type, or may be used in combination of 2 or more types.

The hydroxyl equivalent of component (C) is preferably 50 g/ eq. or more, preferably 60g/eq. or more, more preferably 70g/eq. or more, and preferably 200g/eq. or less, more preferably 150g/eq. or less, particularly preferably 120g/eq. the following. The hydroxyl equivalent weight refers to the mass of the resin containing 1 equivalent of hydroxyl groups.

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

The amount of component (C) based on 100 mass% of (A) epoxy resin is preferably 1 mass% or more, further preferably 2 mass% or more, particularly preferably 3 mass% or more; more preferably 10 mass% or less, preferably 8 mass% or less, particularly preferably 5 mass% or less. By setting the amount of component (B) within 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 component (C) is preferably 0.01 or more, more preferably 0.03 or more, more preferably 0.05 or more; preferably 2 or less, and more preferably The optimum value is 1.5 or less, the more preferred value is 1 or less, and the particularly preferred value is 0.5 or less. Here, the "epoxy group number of (A) epoxy resin" refers to the total value obtained by dividing the mass of non-volatile components of component (A) present in the resin composition by the epoxy equivalent. value. In addition, the "number of hydroxyl groups of component (C)" refers to the total value obtained by dividing the mass of non-volatile components of component (C) present in the resin composition by the hydroxyl equivalent. When the number of epoxy groups of the epoxy resin (A) is 1 and the number of hydroxyl groups of the component (C) is within the aforementioned range, the blooming phenomenon can be effectively suppressed.

＜(D) Inorganic filler＞ The resin composition contains (D) an inorganic filler. Therefore, a hardened material with a low dielectric tangent can be obtained. As the material of the inorganic filler, inorganic compounds are used. Examples of materials for the inorganic filler include silica, 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, titanate Bismuth, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungsten phosphate, etc. Among these, silicon dioxide is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. In addition, as the silica system, spherical silica is preferred. (D) Inorganic filler system can be used individually by 1 type, or can be used in combination of 2 or more types.

(D) Commercially available inorganic fillers include, for example, "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 Corporation; "SC2500SQ" manufactured by Admatechs Corporation, "SO-C4", "SO-C2", "SO-C1", etc.

(D) The average particle size 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, in order to significantly obtain the desired effects of the present invention; It is preferably 5 μm or less, more preferably 2 μm or less, and more preferably 1 μm or less.

(D) The average particle size of the inorganic filler can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, the measurement is performed in the following manner: using a laser diffraction and scattering particle size distribution measuring device, the particle size distribution of the inorganic filler is measured on a volume basis, and the average particle size (median particle size) is calculated. diameter) as the average particle diameter. To measure the sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed using ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction particle size distribution measuring device, using blue and red as the light source wavelengths, and measured the volume-based particle size distribution of (D) the inorganic filler using the flow cell method. From the obtained Particle size distribution The average particle size was calculated and used as the average particle size. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

(D) The specific surface area of the inorganic filler is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, and particularly preferably 3 m ² from the viewpoint of significantly obtaining the desired effects of the present invention. /g or above. The upper limit is not particularly limited, but is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area is based on the BET method. Nitrogen gas is adsorbed on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Corporation), and the specific surface area is calculated using the BET multi-point method.

(D) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane, and organosilazane. compounds, titanate coupling agents, etc. Moreover, the surface treatment agent can be used individually by 1 type, and can also be used in combination of 2 or more types arbitrarily.

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

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably limited to a specified range. Specifically, 100 parts by mass of the inorganic filler is preferably surface treated with a surface treatment agent of 0.2 to 5 parts by mass, preferably 0.2 to 3 parts by mass, and preferably 0.2 to 3 parts by mass. It is better to perform surface treatment with 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. From the viewpoint of improving the dispersibility 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, more preferably 0.1 mg/m ² or more, and 0.2 mg /m ² or more is better. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg/m ² or less is preferred, 0.8 mg/m ² or less is more preferred, and 0.5 is preferred. mg/m ² or less is better.

The carbon amount per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning was performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer system, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd., etc. can be used.

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

＜(E) Hardener＞ In addition to the above-mentioned components, the resin composition may further contain (E) a hardener as an optional component. However, component (C) is not included in (E) hardener. Generally speaking, (E) hardening agent has the following function: It reacts with (A) component and hardens a resin composition. (E) The hardener system may be used individually by 1 type, or may use 2 or more types together.

Examples of (E) the curing agent include active ester curing agents, phenol curing agents, naphthol curing agents, benzoxazine curing agents, cyanate ester curing agents, carbodiimide curing agents, Amine-based hardener, acid anhydride-based hardener, etc.

As the active ester type curing agent, a compound having one or more active ester groups per molecule can be used. Among them, as the active ester-based hardener, preferred are phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxyl compounds, etc., which have two or more reactive activities per molecule. Compounds with high ester base. The active ester hardener is preferably obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester hardener obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is preferred. It is better to use hardener.

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

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, methyl Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, phloroglucinol, dicyclopentadiene-type diphenol compounds, phenol novolac, etc. . Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol into one molecule of dicyclopentadiene.

Preferable specific examples of the active ester-based hardener include an active ester-based hardener containing a dicyclopentadiene-type diphenol structure, an active ester-based hardener containing a naphthalene structure, and an acetate containing phenol novolak. An active ester hardener, an active ester hardener containing a benzyl compound of phenol novolak. Among these, an active ester-based hardener containing a naphthalene structure and an active ester-based hardening agent containing a dicyclopentadiene-type diphenol structure are more preferred. The so-called "dicyclopentadiene-type diphenol structure" represents a divalent structure composed of phenylene-dicyclopentylene-phenylene group.

Examples of commercially available active ester-based hardeners include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T", which are active ester-based hardeners containing a dicyclopentadiene-type diphenol structure. ", "HPC-8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC Corporation); "EXB9416-70BK" and "EXB-8150-65T" (manufactured by DIC Corporation), which are active ester-based hardeners containing a naphthalene structure "DC808" (manufactured by Mitsubishi Chemical Corporation), which is an active ester-based hardener containing an acetate of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), which is an active ester-based hardener containing an acetate of phenol novolac "DC808" (manufactured by Mitsubishi Chemical Corporation), which is an active ester-based hardener for the acetyl compound of phenol novolac; "YLH1026", which is an active ester-based hardener for the benzyl compound of phenol novolac (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc.

As the phenol-based hardener and the naphthol-based hardener, those having a novolak structure are preferred from the viewpoint of heat resistance and water resistance. Furthermore, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based hardening agent is preferred, and a phenol-based hardening agent containing a triazine skeleton is further preferred.

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

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

Examples of the cyanate-based hardener include bisphenol A dicyanate, polyhydric phenol 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-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1, 3-Bis(4-cyanatophenyl-1-(methylethylene))benzene, bis(4-cyanatephenyl)sulfide and bis(4-cyanatephenyl)ether, etc. 2-functional cyanate ester resin; multi-functional cyanate ester resin derived from phenol novolac and cresol novolac; prepolymers in which these cyanate ester resins are partially triazinized, etc. Specific examples of cyanate ester-based hardeners include "PT30" and "PT60" (phenol novolak type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin) manufactured by LONZA Japan Resin), "BA230", "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazinated to form a tripartite), etc.

Specific examples of carbodiimide-based hardeners include Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216 g/eq.) and V-05 (carbodiimide) manufactured by Nisshinbo Chemical Co., Ltd. Base equivalent: 262g/eq.), V-07 (carbodiimide base equivalent: 200g/eq.); V-09 (carbodiimide base equivalent: 200g/eq.); Stabaxol manufactured by Rhein Chemie ( Registered trademark)P (carbodiimide equivalent: 302g/eq.).

Examples of the amine-based curing agent include those having one or more amine groups per molecule. Examples include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. , among them, from the viewpoint of achieving the desired effects of the present 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), diphenyldiaminotriene, and 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylenediamine, diethyltoluenediamine, 4 ,4'-Diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl ether 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)sine, bis(4-(3-aminophenoxy)phenyl)sine, etc. Commercially available amine hardeners can also be used, such as "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S" manufactured by Nippon Kayaku Co., Ltd., Mitsubishi "Epicure W" produced by a chemical company, etc.

Examples of the acid anhydride-based curing agent include those having one or more acid anhydride groups per molecule. Specific examples of the acid anhydride-based hardener include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Dicarboxylic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-di-oxytetrahydro-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'-diphenyltetracarboxylic dianhydride, 1,3,3a,4 ,5,9b-hexahydro-5-(tetrahydro-2,5-bisoxy-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol Bis(anhydrous trimellitate), polymer-type acid anhydrides such as styrene and maleic acid resin copolymerized by styrene and maleic acid, etc.

(E) The hardener is preferably selected from the group consisting of benzoxazine-based hardeners, carbodiimide-based hardeners, phenol-based hardeners and reactive hardeners from the viewpoint of significantly obtaining the desired effects of the present invention. One or more types of ester hardeners, preferably one selected from the group consisting of benzoxazine hardeners, carbodiimide hardeners and active ester hardeners More than one species. Among them, (E) the hardening agent preferably contains, in addition to the active ester type hardening agent, a benzoxazine type hardening agent or a carbodiimide type hardening agent; and further preferably, in addition to the active ester type hardening agent, In addition to phenol-based hardeners, benzoxazine-based hardeners or carbodiimide-based hardeners are also included.

When the curing agent (E) contains an active ester-based curing agent, from the viewpoint of obtaining a cured product with excellent adhesion while lowering the dielectric tangent, it is preferable to use the component (A) and the active ester-based curing agent. The amounts of component (A) and active ester-based hardener are adjusted so that the amount ratio of the hardener falls within the specified range. Specifically, let the value obtained by dividing the mass of the component (A) by the epoxy equivalent be a1. This value "a1" represents the equivalent number (eq.) of the epoxy group contained in the component (A). In addition, the value obtained by dividing the mass of the active ester-based hardener by the active ester group equivalent is set to e1. This value "e1" represents the equivalent number (eq.) of the active ester group. In this case, e1/a1 is usually 0.1 or more, preferably 0.3 or more, and still more preferably 0.5 or more. The upper limit is usually preferably 5 or less, more preferably 3 or less, and more preferably 2 or less. Here, when the resin composition contains two or more types of (A) components, the above-mentioned 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 all the values. Moreover, when two or more types of active ester-based hardeners are contained, the above-mentioned e1 is the value obtained by dividing the mass of each active ester-based hardener present in the resin composition by the equivalent weight of each active ester group and adding all the values.

When the curing agent (E) contains a benzoxazine-based curing agent, from the viewpoint of obtaining a cured product with excellent adhesion, a combination of component (B) and a benzoxazine-based curing agent is preferred. The amounts of component (B) and benzoxazine-based hardener are adjusted so that the amount ratio falls within the specified range. Specifically, the value obtained by dividing the mass of component (B) by the (meth)acrylyl group equivalent of component (B) is b2. This value "b2" represents the number of equivalents (eq.) of the (meth)acrylyl group equivalent contained in the component (B). Moreover, the value obtained by dividing the mass of the benzoxazine-based hardening agent by the benzoxazine ring equivalent is set to e2. This value "e2" represents the equivalent number (eq.) of the benzoxazine ring. In this case, e2/b2 is usually 0.08 or more, preferably 0.1 or more, and further preferably 0.13 or more. The upper limit is usually 2.5 or less, preferably 2 or less, and still more preferably 1 or less. When the resin composition contains two or more types of (B) components, the above b2 is the value obtained by dividing the mass of each (meth)acrylate present in the resin composition by the equivalent weight of each (meth)acrylyl group. The total value obtained. In addition, when the resin composition contains two or more benzoxazine-based hardeners, the above e2 is the mass of the non-volatile component of each benzoxazine-based hardener present in the resin composition divided by the mass of each benzo The value of the oxazine ring equivalent is the value obtained by adding all the values.

When the curing agent (E) contains a carbodiimide-based curing agent, from the viewpoint of obtaining a cured product with excellent adhesion, a combination of component (B) and a carbodiimide-based curing agent is preferred. The amounts of component (B) and carbodiimide-based hardener are adjusted so that the mass ratio falls within the specified range. Specifically, let the content (mass %) of the component (B) in the resin composition be b1, and let the content (mass %) of the carbodiimide-based hardener in the resin composition be 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 is usually 1.5 or less, preferably 1.3 or less, further preferably 1.0 or less.

The amount ratio of (A) epoxy resin to all (E) hardener is calculated as the ratio of [the total number of epoxy groups of component (A)]: [the total number of reactive groups of (E) hardener], The preferred range is 1:0.01~1:5, the preferred range is 1:0.3~1:3, and the preferred range is 1:0.5~1:2. Here, the "epoxy group number of (A) epoxy resin" refers to the total value obtained by dividing the mass of non-volatile components of (A) epoxy resin present in the resin composition by the epoxy equivalent. value. In addition, the "number of active groups of (E) hardener" refers to the total value obtained by dividing the mass of non-volatile components of (E) hardener present in the resin composition by the active group equivalent. By setting the amount ratio of (A) epoxy resin and (E) hardener within the above range, the desired effects of the present invention can be significantly obtained.

(E) The content of the hardener is preferably 5 mass% or more based on 100 mass% of the non-volatile components in the resin composition, and more preferably 8% by mass or more, more preferably 10% by mass or more; 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-mentioned components, the resin composition may further contain (F) a hardening accelerator as an optional component.

Examples of the hardening accelerator include phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and metal-based hardening 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 further 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 compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4 -Methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine and tetrabutylphosphonium decanoic acid salt.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6- (Dimethylaminomethyl)phenol, 1,8-diazinebicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-dimethylaminopyridine, etc. Acridinebicyclo(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 trimellitate Ester, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-deca 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 isocyanuric acid adduct, 2 -Phenylimidazole isocyanuric acid 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, commercially available products can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, and dicyanodiamine. Methylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1 ,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1 , 1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc., preferably Dicyanodiamide, 1,5,7-triazinebicyclo[4.4.0]dec-5-ene.

Examples of metal-based hardening accelerators include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetylpyruvate and cobalt (III) acetylpyruvate, and copper (II) acetylpyruvate. Organic copper complexes, organic zinc complexes such as zinc (II) acetylpyruvate, organic iron complexes such as iron (III) acetylpyruvate, nickel (II) acetylpyruvate Organic nickel complexes such as manganese acetylpyruvate (II) and other organic manganese complexes. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

(F) The content of the hardening accelerator is preferably 0.01 mass% or more when the non-volatile components in the resin composition are 100 mass%, so as to significantly obtain the desired effects of the present invention. It is preferably 0.03 mass% or more, more preferably 0.05 mass% or more; it is preferably 0.5 mass% or less, and more preferably 0.4 mass% or less, and more preferably 0.3 mass% or less.

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

Examples of the (G) polymerization initiator include t-butylisopropyl peroxide, t-butylperoxyacetate, and α,α'-di(t-butylperoxy). Diisopropylbenzene, t-butylperoxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, t-butylperoxynedecanoate Peroxides such as oxybenzoates.

Examples of commercially available polymerization initiators (G) 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 mass% or more when the non-volatile component in the resin composition is 100 mass%, so as to significantly obtain the desired effects of the present invention. It is also preferably 0.02 mass% or more, more preferably 0.03 mass% or more; more preferably 0.5 mass% or less, more preferably 0.3 mass% or less, more preferably 0.1 mass% or less.

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

Examples of the thermoplastic resin of component (H) include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamide imine resin, and polyether. Imide resin, polystyrene resin, polyether styrene resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. Among them, phenoxy resin is preferable from the viewpoint that the desired effects of the present invention can be significantly obtained and from the viewpoint that an insulating layer with small surface roughness and particularly excellent adhesion to the conductor layer can be obtained. . Moreover, the thermoplastic resin system can be used individually by 1 type, or can be used in combination of 2 or more types.

Examples of the phenoxy resin include those having a skeleton selected from a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorine skeleton, and a dicyclopentadiene skeleton. , phenoxy resins with one or more types of skeletons from 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" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (containing a bisphenol A skeleton) Phenoxy resin with phenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation; Mitsubishi "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Chemical Company.

Examples of the polyvinyl acetal resin include polyvinyl formaldehyde resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. 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 Industry Co., Ltd.

Specific examples of the polyimide resin include "RIKA COAT SN20" and "RIKA COAT PN20" manufactured by New Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (Japanese Patent Application Laid-Open No. 2006-37083 Polyimide described in Japanese Patent Application Publication No. 2002-12667 and Japanese Patent Application Publication No. 2000-319386, etc. modified polyimide.

Specific examples of the polyamide imide resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamide imine resin include modified polyamides such as "KS9100" and "KS9300" (polyamide imine containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd. acyl imine.

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

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

Specific examples of polystyrene resins include polystyrene "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

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

(H) The content of the thermoplastic resin is preferably 0.01 mass% or more when the non-volatile component in the resin composition is 100 mass%, so as to significantly obtain the desired effects of the present invention. It is preferably 0.05% by mass or more, more preferably 0.1% by mass or more; it is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 1% by mass or less.

＜(I) Flame retardant＞ The resin composition may contain (I) a flame retardant as an optional component. Examples of the (I) flame retardant include phosphazene compounds, organophosphorus-based flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, polysiloxane-based flame retardants, metal hydroxides, etc., with phosphorus Nitrogen ring compounds are preferred. One type of flame retardant agent may be used alone, or two or more types may be used in combination.

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", and "SPE-100" manufactured by Otsuka Chemical Co., Ltd., and "FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd. 100", "FP-110", "FP-300", "FP-400", etc.

As the flame retardant other than the phosphorus nitrogen ring compound, commercially available products can be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. As a flame retardant, one that is difficult to hydrolyze is preferred. For example, 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene-10-peroxide is preferred. good.

When the resin composition contains (I) a flame retardant, from the viewpoint of significantly obtaining the desired effects of the present invention, when the non-volatile component in the resin composition is 100% by mass, the (I) flame retardant The amount is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, and more preferably 0.3 mass% or more. The upper limit is preferably 3 mass% or less, more preferably 2 mass% or less, and more preferably 1 mass% or less.

＜(J)Other additives＞ In addition to the above-mentioned components, the resin composition may further contain other additives as optional components. Examples of such additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; tackifiers; defoaming agents; leveling agents; adhesion-imparting agents; and resins such as colorants. Additives. These additives can be used individually by 1 type, or can be used in combination of 2 or more types at arbitrary ratios.

＜Characteristics of resin composition＞ By curing the resin composition of the present invention, an insulating layer formed of a cured product of the resin composition can be obtained. When through-holes are formed in the insulating layer and roughened, the halo phenomenon can be suppressed. These effects will be described below with reference to the drawings.

FIG. 1 is a cross-sectional view schematically showing an insulating layer 100 (which is obtained by hardening the resin composition of the present invention into a sheet shape) and an inner layer substrate 200. FIG. 1 shows a cross section of the insulating layer 100 cut 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 curing a resin composition layer formed on the inner substrate 200 including the conductor layer 210 , and is made of a cured product of the resin composition. . In addition, a through hole 110 is formed in the insulating layer 100 . Generally speaking, the closer the through hole 110 is to the surface 100U of the insulating layer 100 on the opposite side to the conductive layer 210, the larger the hole diameter will be, and the closer the through hole 110 is to the conductive layer 210, the smaller the hole diameter will be. It forms a forward cone shape; ideally, it forms a columnar shape with a certain aperture in the thickness direction of the insulating layer 100 . Usually, the surface 100U of the insulating layer 100 opposite 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 conductor layer 210 side is appropriately called a “through hole bottom” and is represented by a symbol 120 . Then, the hole diameter of the through hole bottom 120 is called bottom hole diameter Lb. In addition, the opening formed on the side of the via hole 110 opposite to the conductor layer 210 is appropriately called a “via hole top” and is represented by a symbol 130 . Then, the hole diameter of the through hole top 130 is called top hole diameter Lt. Generally speaking, when the planar shape is viewed from the thickness side of the insulating layer 100, the through hole bottom 120 and the through hole top 130 are formed into a circular shape, but they may also be elliptical. When the planar shapes of the through hole bottom 120 and the through hole top 130 are elliptical shapes, the bottom hole diameter Lb and the top hole diameter Lt respectively represent the major diameter of the aforementioned elliptical shape.

At this time, when the taper rate 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 the through hole 110 with a taper ratio Lb/Lt 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 through hole bottom 120 The insulating layer 100 is cut to reveal a cross section, and then the cross section is observed using an electron microscope.

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

As shown in FIG. 2 , when the insulating layer 100 in which the through hole 110 is formed is viewed, around the through hole 110 , from the edge 180 of the through hole top 130 to the outer peripheral edge 190 of the discolored portion 140 , In some cases, the insulating layer 100 may be observed to have a discolored portion 140 that changes color. The discolored portion 140 may be formed due to resin degradation during the formation of the through hole 110 , and is usually formed continuously from the through hole 110 . In addition, in most cases, the discolored portion 140 is a whitened portion.

FIG. 3 is a cross-sectional view schematically showing the roughened insulating layer 100 (which is obtained by hardening the resin composition of the present invention into a sheet shape) and the inner layer substrate 200 . The cross section shown in FIG. 3 is a cross section through which the insulating layer 100 is cut on a plane passing through the center 120C of the through hole 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 with the through hole 110 is roughened, a halo phenomenon will occur, and the insulating layer 100 in the discolored portion 140 will be peeled off from the conductor layer 210 , and will be separated from the through hole. The edge 150 of the bottom 120 forms a continuous gap portion 160 .

By using the resin composition of the present invention, the aforementioned blooming 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 through hole bottom 120 corresponds to the edge on the inner peripheral side of the gap 160 . Therefore, the distance Wb from the edge 150 of the through-hole bottom 120 to the outer peripheral end 170 of the gap 160 (that is, the far side end from the center 120C of the through-hole bottom 120) is equivalent to The size of the gap portion 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 addition, in the following description, the aforementioned distance Wb is referred to as the blooming distance Wb from the edge 150 of the through-hole bottom 120 of the through-hole 110 . The degree of suppression of the blooming phenomenon can be evaluated based on the blooming distance Wb from the edge 150 of the through hole bottom 120 . Specifically, the smaller the blooming distance Wb from the edge 150 of the through hole bottom 120 is, the more effectively the blooming 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 harden and obtain the 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. Thereafter, it was immersed in a swelling solution at 60°C for 10 minutes, then immersed in an oxidizing agent solution at 80°C for 20 minutes, then immersed in a neutralizing solution 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 blooming distance Wb of the insulating layer 100 obtained in this way from the edge 150 of the through hole bottom 120 of the through hole 110 can be preferably 10 μm or less, and more preferably 5 μm or less. , the best can be below 4.5μm, the best can be below 4μm.

The aforementioned CO ₂ laser light irradiation conditions, if the top aperture Lt is about 50 μm, are set to a mask diameter of 1.60 mm, a focal length deviation value of 0.050, a pulse width of 25 μs, an energy of 0.66 W, an aperture (aperture) of 13, and a 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 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 The insulating layer 100 is cut to reveal a cross section, and then the cross section is observed using an electron microscope.

In addition, by using the resin composition of the present invention, the shape of the through holes 110 of the insulating layer 100 before roughening can be easily controlled. Generally, the shape of the through holes can also be easily controlled even in the insulating layer 100 after roughening. 110 shape. Therefore, even after the roughening process, the shape of the through hole 110 can be improved in the same manner as before the roughening process. Therefore, as long as the resin composition of the present invention is used, in the insulating layer after roughening treatment, a through hole 110 with a taper ratio Lb/Lt close to 100% can be achieved.

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 and obtain the insulating layer 100. The insulating layer 100 is irradiated with _CO2 laser light to form a top aperture Lt of approximately 50 μm or approximately 30 μm via 110. Thereafter, it was immersed in a swelling solution at 60°C for 10 minutes, then immersed in an oxidizing agent solution at 80°C for 20 minutes, then immersed in a neutralizing solution at 40°C for 5 minutes, and then dried at 80°C for 30 minutes. In this case, the taper ratio Lb/Lt of the through hole 110 can be preferably 70% to 100%, more preferably 75% to 100%, and particularly preferably 80% to 100%.

The aforementioned CO ₂ laser light irradiation conditions, if the top aperture Lt is about 50 μm, are set to a mask diameter of 1.60 mm, a focal length deviation value of 0.050, a pulse width of 25 μs, an energy of 0.66 W, an aperture (aperture) of 13, and a 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 taper ratio Lb/Lt of the roughened 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 through hole bottom 120 The insulating layer 100 is cut to reveal a cross section, and then the cross section is observed using an electron microscope.

Furthermore, according to the research of the present inventor, it can be found that when the diameter of the through hole becomes larger, the size of the gap portion 160 also tends to become larger. Therefore, the degree of suppression of the blooming phenomenon can be evaluated based on the ratio of the size of the gap portion 160 relative to the hole diameter of the through hole 110 . For example, the evaluation can be performed by the halo ratio Hb relative to the bottom radius Lb/2 of the through hole 110 . Here, the so-called bottom radius Lb/2 of the through hole 110 refers to the radius of the through hole bottom 120 of the through hole 110 . In addition, the so-called halo ratio Hb with respect to the bottom radius Lb/2 of the through hole 110 refers to the halo distance Wb from the edge 150 of the through hole bottom 120 divided by the bottom radius Lb/2 of the through hole 110. obtained ratio. The smaller the halo ratio Hb relative to the bottom radius Lb/2 of the through hole 110 is, the more effectively the halo phenomenon can be suppressed.

For example, the resin composition formed on the copper foil is heated at 130°C for 30 minutes, and then heated at 170°C for 30 minutes to harden it to obtain the insulating layer 100, and the insulating layer 100 is irradiated with CO ₂ laser light to form The top hole diameter Lt is about 50 μm or about 30 μm of the through hole 110 . Thereafter, it was immersed in a swelling solution at 60°C for 10 minutes, then immersed in an oxidizing agent solution at 80°C for 20 minutes, then immersed in a neutralizing solution 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 formed in this way with respect to the bottom radius Lb/2 of the through hole 110 is preferably 35% or less, more preferably 30% or less, and still more preferably It can become less than 25%.

The aforementioned CO ₂ laser light irradiation conditions, if the top aperture Lt is about 50 μm, are set to a mask diameter of 1.60 mm, a focal length deviation value of 0.050, a pulse width of 25 μs, an energy of 0.66 W, an aperture (aperture) of 13, and a 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/shot, the number of shots 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 no other conductive layer (not shown) is provided on the surface 100U of the insulating layer 100 (the side opposite to the conductive layer 210). . Therefore, as long as one understands the manufacturing process of the printed wiring board, it can be clearly understood that the conductor layer 210 side has a structure with a through hole bottom 120 and a through hole top 130 opening on the opposite side to the conductor layer 210 . However, in the completed printed wiring board, it is still possible to provide conductor layers on both sides of the insulating layer 100 . In this case, depending on the positional relationship with the conductor layer, it may be difficult to distinguish the via bottom 120 and the via top 130 . However, generally speaking, the top hole diameter Lt of the through-hole top 130 is larger than the bottom hole diameter Lb of the through-hole bottom 120 . Therefore, in the aforementioned situation, the through hole bottom 120 and the through hole top 130 can be distinguished according to the size of the hole diameter.

The resin composition of the present invention can not only suppress the blooming phenomenon, but also provide an insulating layer with a low dielectric tangent and excellent adhesion to the conductor layer.

The cured product obtained by thermally curing the resin composition at 200° C. for 90 minutes exhibits the so-called low dielectric tangent characteristic. Therefore, the aforementioned hardened material system can obtain an insulating layer with a low dielectric tangent. The dielectric tangent is preferably 0.006 or less, more preferably 0.0055 or less, and more preferably 0.0053 or less. On the other hand, the lower limit value of the dielectric tangent is not particularly limited, but may 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 to be described later.

A cured product obtained by thermally curing the resin composition at 130°C for 30 minutes and then at 170°C for 30 minutes generally exhibits so-called adhesion (peel strength) to the plated conductor layer: Excellent characteristics. Therefore, the above-described hardened material system can obtain an insulating layer having excellent adhesion to the plated conductor layer. The peeling strength from the plated conductor layer is preferably 0.3 kgf/cm or more, more preferably 0.35 kgf/cm or more, and 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 peeling strength from the plated conductor layer can be measured according to the method described in the Examples to be described later.

The resin composition system of the present invention can obtain an insulating layer with a low dielectric tangent, suppressed halo phenomenon, and generally has excellent adhesion to the conductor layer. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation purposes. Specifically, it can be suitably used as a resin composition for forming a conductor layer (including a rewiring layer) on an insulating layer (a resin composition for forming an insulating layer forming a conductor layer) for forming the insulating layer. things).

Furthermore, in the multilayer printed wiring board described below, 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), or for forming a printed circuit board. Resin composition for interlayer insulating layers of wiring boards (resin composition for forming interlayer insulating layers of printed wiring boards).

Furthermore, for example, when a semiconductor chip package is manufactured 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 forming layer) and a resin composition for sealing a semiconductor wafer (a resin composition for sealing a semiconductor wafer). When manufacturing the semiconductor chip package, a rewiring layer may be further formed on the sealing layer. (1) The steps of laminating the temporary fixing film on the base material, (2) The steps of temporarily fixing the semiconductor chip to the temporary fixing film, (3) The steps of forming a sealing layer on a semiconductor wafer, (4) The steps of peeling off the base material and temporary fixing film from the semiconductor wafer, (5) The step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor wafer from which the base material and the temporary fixing film have been peeled off, and (6) A step of forming a rewiring layer as a conductor layer on the rewiring forming layer.

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

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

The thickness of the resin composition layer is preferably 50 μm or less, and more preferably 50 μm or less, from the viewpoint of thinning the printed wiring board and the fact that the cured product of the resin composition can provide a cured product with excellent insulation properties even if it is a film. It is 40 μm or less, more preferably, it is 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but it can usually be set to 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"), polyethylene naphthalate Polyesters such as (hereinafter sometimes referred to as "PEN"); polycarbonate (hereinafter sometimes referred to as "PC"); acrylics such as polymethylmethacrylate (PMMA); cyclic polyolefins; triacetyl 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, aluminum foil, and the like. Among them, copper foil is preferred. As the copper foil, foils made of copper as a single metal or foils made of alloys of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used. .

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

Moreover, as a support body, the support body with a release layer which has a release layer on the surface joined to a resin composition layer can also be used. Examples of the release agent that can be used in the release layer of a support with a release layer include alkyd resins, polyolefin resins, urethane resins, and polysiloxane resins. One or more selected release agents. As a support with a release layer, commercially available products can be used. Examples include "SK-1" and "SK-1" manufactured by LINTEC Corporation, which are PET films having a release layer containing an alkyd resin release agent as the main component. AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "PUREX", Unitika's "Unipeel", etc.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. Furthermore, when using a support with a release layer, it is preferable that the thickness of the entire support with a release layer is within the above range.

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

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, and 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. and acetate esters such as carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethyl Acetamide (DMAc) and amide-based solvents such as N-methylpyrrolidone, etc. One type of organic solvent may be used alone, or two or more types may be used in combination.

Drying can be carried out by well-known methods such as heating and blowing hot air. Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer becomes 10 mass% or less, preferably 5 mass% or less. It varies depending on the boiling point of the organic solvent in the resin varnish. For example, when using a resin varnish containing 30% to 60% by mass of organic solvent, dry it at 50°C to 150°C for 3 minutes to 10 minutes to form a resin composition layer.

The resin sheet can be rolled up into a roll shape and stored. If the resin sheet has a protective film, the protective film can be peeled off to become a usable resin sheet.

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

The "inner layer substrate" used in step (I) refers to a member that becomes the substrate of a printed wiring board, and includes, for example, glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermal substrate 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 substrate with a conductor layer (circuit) formed on one or both sides of the substrate is sometimes called an "inner circuit substrate". In addition, the intermediate product of the insulating layer and/or the conductor layer that should be formed when manufacturing the printed wiring board is also included in the so-called "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with embedded components, an inner substrate with embedded components can be used.

The inner layer substrate and the resin sheet can be laminated, for example, by heating and pressing the resin sheet and the inner layer substrate from the support side. Examples of the member for heat and pressure bonding the resin sheet and the inner substrate (hereinafter also referred to as "heat and pressure bonding member") include a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller). Furthermore, in order to make the resin sheet fully follow the surface irregularities of the inner substrate, it is better not to directly press the heat-pressing member and the resin sheet, but to press them with an elastic material such as heat-resistant rubber interposed.

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 system is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and pressing pressure system is preferably in the range of 0.098MPa to 1.77MPa, and more preferably 0.29 In the range of MPa~1.47MPa, the heating and pressing viscosity time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. The lamination system is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

The lamination system can be performed by a commercially available vacuum laminating machine. Examples of commercially available vacuum laminating machines include a vacuum pressure laminating machine manufactured by Meiki Seisakusho Co., Ltd., a vacuum laminating machine manufactured by Nikko Materials Co., Ltd., and a batch type vacuum pressure laminating machine.

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

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

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

For example, the thermal hardening conditions of the resin composition layer will vary depending on the type of the resin composition. The curing temperature is preferably 120°C~240°C, more preferably 150°C~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 also be preheated at a temperature lower than the curing temperature. For example, before thermally hardening the lipid composition layer, the resin composition layer can be cured at a temperature of 50°C or more and less than 120°C (preferably 60°C or more and 115°C or less, and more preferably 70°C or more and 110°C or less). Preheat for more than 5 minutes (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 is also possible to further implement: (III) a step of opening holes in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer. These steps (III) to steps (V) can be implemented according to various methods well known in the industry and used for manufacturing printed wiring boards. Furthermore, when the support is removed after step (II), the removal of the support can be between step (II) and step (III), between step (III) and step (IV), or between Implemented between step (IV) and step (V). In addition, by repeating the formation of the insulating layer and the conductor layer of steps (II) to (V) as required, a multi-layer wiring board can also be formed.

Step (III) is a step of opening holes in the insulating layer, whereby holes such as through-holes and through-holes can be formed on the insulating layer. Step (III) can be implemented using, for example, drilling, laser, plasma, etc., depending on the composition of the resin composition used in forming the insulating layer. 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. For example, the roughening treatment of the insulating layer can be carried out in sequence, such as swelling treatment by swelling liquid, roughening treatment by oxidant, and neutralization treatment by neutralizing liquid. The swelling liquid used in the roughening treatment is not particularly limited, and examples thereof include alkali solutions, surfactant solutions, etc., and an alkali solution is preferred. As the alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are preferred. good. Examples of commercially available swelling solutions 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, for example, by 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 a swelling liquid of 40°C to 80°C for 5 minutes to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, but may include, for example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment by 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 to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Atotech Japan. In addition, an acidic aqueous solution is preferably used as the neutralizing liquid used in the roughening treatment. An example of a commercially available product is "Reduction solution Securiganth P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be performed by immersing the treated surface roughened by the oxidizing agent in a neutralizing solution at 30°C to 80°C for 1 to 30 minutes. In terms of workability, etc., the method of immersing the object roughened by an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes is preferred.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening is preferably 120 nm or less, more preferably 110 nm or less, and more preferably 100 nm or less. The lower limit is not particularly limited, but it is preferably 30 nm or more, more preferably 40 nm or more, and more preferably 50 nm or more. The arithmetic mean 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 the 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 The above metals. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the above groups (such as nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). alloy). Among them, from the viewpoint of versatility, cost, ease of patterning, etc. of conductor layer formation, single metal layers 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, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy It is better to use a single metal layer of copper.

The conductor layer system may have a single-layer structure or a multi-layer structure in which two or more simple metal layers or alloy layers composed of different types of metals or alloys are laminated. If the conductor layer has a multi-layer structure, the layer connected to the insulating layer is preferably a single 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 may be formed by plating. For example, by plating the surface of the insulating layer using conventionally known techniques such as the semi-additive method and the fully-additive method, a conductor layer having a desired wiring pattern can be formed. From the viewpoint of ease of production, Generally speaking, it is better to form it by the semi-additive method. The following is an example of forming a conductor layer by the 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 to expose a part of the plating seed layer in accordance with a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like, thereby forming a conductor layer having a desired wiring pattern.

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

Examples of 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, trains, ships, and airplanes).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The so-called "conducting part" refers to the "part of the printed wiring board that transmits electrical signals", and its location can be on the surface or a buried part. 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 mounting method of the semiconductor chip when manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip can effectively function. However, specific examples include wire bonding mounting method, flip chip mounting method, and bumpless mounting method. The installation method of build-up layer (BBUL), the installation method of anisotropic conductive film (ACF), the installation method of non-conductive film (NCF), etc. Here, the so-called "mounting method by bump-less build-up (BBUL)" refers to "mounting in which the semiconductor chip is directly embedded in the recessed portion of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board. method". [Example]

The present invention will be described in detail below by showing examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" expressing amounts, unless otherwise specified, represent "parts by mass" and "% by mass" respectively. In addition, the operations described below are performed in an environment of normal temperature and pressure unless otherwise specified.

<Example 1: Preparation of resin composition 1> Mix 10 parts of bisphenol A-type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight: about 180 g/eq.), bisphenol AF-type epoxy resin (Mitsubishi Chemical Corporation "828US", 20 parts of "YL7760" made by Chemical Co., Ltd., epoxy equivalent weight is about 238g/eq.), 20 parts of biphenyl-type epoxy resin ("NC3000L" made by Nippon Kayaku Co., Ltd., epoxy equivalent weight is about 269g/eq.), phosphorus nitrogen ring 3 parts of resin ("SPH-100" manufactured by Otsuka Chemical Corporation), 10 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), in MEK20 40 parts of solvent naphtha and 40 parts of solvent naphtha are heated and dissolved while stirring. After cooling to room temperature, 94 parts of an active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution with an active group equivalent of approximately 223 g/eq. and a solid content of 65% by mass) and a phenol-based hardener ( "LA-3018-50P" made by DIC, 10 parts of 2-methoxypropanol solution with an active radical equivalent of about 151g/eq. and a solid content of 50%, and a benzoxazine-based hardener (made by JFE Chemical) MEK solution with a solid content of 50% by mass of "ODA-BOZ", 6 parts of benzoxazine ring equivalent (approximately 218g/eq.), (meth)acrylate ("NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Molecular weight 326, (meth)acrylyl equivalent weight 163 g/eq.) 12 parts, hardener as component (C) (aromatic hydrocarbon represented by formula (4), "GRA13H" manufactured by Gunei Chemical Industry Co., Ltd., hydroxyl group Equivalent of about 75g/eq.) 2 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 5 mass% solid content) 8 parts, polymerization initiator ("Perbutyl" manufactured by NOF Corporation C") 0.2 parts of spherical silica (average particle diameter 0.5 μm, specific surface area 5.9 m ² /g, Admatechs 400 parts of "SO-C2" manufactured by ROKITECHNO Co., Ltd.) was uniformly dispersed using a high-speed rotary mixer, and then filtered with a filter cartridge ("SHP100" manufactured by ROKITECHNO Co., Ltd.) to prepare 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-type epoxy resin ("NC3000L" manufactured by Nippon Chemical Company, epoxy equivalent: approximately 269g/eq.) to dixylenol-type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation, Oxygen equivalent is about 190g/eq.) 20 parts; 2) Change 94 parts of active ester type hardener ("HPC-8000-65T" manufactured by DIC Corporation, toluene solution with active group equivalent of approximately 223g/eq., solid content of 65% by mass) to active ester type hardener (DIC Corporation Prepare 86 parts of "EXB9416-70BK", a non-volatile 70 mass% methyl isobutyl ketone solution with an active radical equivalent of about 330g/eq.); 3) Change 6 parts of benzoxazine-based hardener (MEK solution with a solid content of 50% by mass of "ODA-BOZ" manufactured by JFE Chemical Co., Ltd., benzoxazine ring equivalent of approximately 218g/eq.) to carbodiimide 10 parts of hardening agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., toluene solution with active radical equivalent of approximately 216g/eq. and solid content of 50% by mass); 4) Change 2 parts of the hardener (aromatic hydrocarbon represented by the formula (4), "GRA13H" manufactured by Gunei Chemical Industry Co., Ltd., hydroxyl equivalent: about 75g/eq.) as the component (C) to the component (C) 2 parts of hardener (aromatic hydrocarbon represented by formula (5), "SN395" manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd., hydroxyl equivalent: 107g/eq.). Except for the above-mentioned matters, the resin composition 2 was produced in the same manner as in Example 1.

<Example 3: Preparation of Resin Composition 3> Mix 5 parts of bisphenol A-type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 180g/eq.), biphenyl-type epoxy resin (Japanese "NC3000L" manufactured by a pharmaceutical company, epoxy equivalent of approximately 269g/eq.) 20 parts, 25 parts of dixylenol type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of approximately 190g/eq.), phosphorus nitrogen 3 parts of cycloresin ("SPH-100" manufactured by Otsuka Chemical Company), 10 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Company, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass), in 40 parts of MEK and 40 parts of toluene were heated and dissolved with stirring. After cooling to room temperature, 94 parts of an active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution with an active group equivalent of approximately 223 g/eq. and a solid content of 65% by mass) and a phenol-based hardener ( "LA-3018-50P" manufactured by DIC Corporation, 10 parts of 2-methoxypropanol solution with an active radical equivalent of approximately 151g/eq. and a solid content of 50%, carbodiimide-based hardener (produced by Nisshinbo Chemical Corporation) V-03", 10 parts of toluene solution with active group equivalent of about 216g/eq., solid content of 50% by mass), (meth)acrylate ("NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326) 17 parts, 2 parts of hardening agent as component (C) (aromatic hydrocarbon represented by formula (5), "SN395" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., hydroxyl equivalent: 107g/eq.), hardening accelerator (4- 8 parts of dimethylaminopyridine (DMAP, MEK solution with 5% solid content by mass), 0.2 part of polymerization initiator ("Perbutyl C" manufactured by NOF Corporation), phenylaminosilane coupling agent ( 200 parts of surface-treated spherical silica (average particle diameter 0.3 μm, specific surface area 30.7 m ² /g, Denca Co., Ltd. "UFP-30") surface-treated "KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd., and mixed by high-speed rotation After evenly dispersing the mixture with a machine, the resin composition 3 was produced by filtering with a filter cartridge ("SHP020" manufactured by ROKITECHNO).

<Example 4: Preparation of resin composition 4> The changes in Example 3 are as follows: 1) Change 20 parts of biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Chemical Company, epoxy equivalent: approximately 269g/eq.) to bisphenol AF-type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy Equivalent about 238g/eq.) 20 parts; 2) Change the amount of phenolic hardener ("LA-3018-50P" manufactured by DIC Corporation, active group equivalent of about 151g/eq., 50% solid content of 2-methoxypropanol solution) from 10 parts to 5 servings; 3) Change 10 parts of carbodiimide-based hardener ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active radical equivalent of about 216g/eq., solid content 50 mass% toluene solution) to benzoxazine-based hardener (MEK solution of "ODA-BOZ" manufactured by JFE Chemical Co., Ltd. with a solid content of 50% by mass and a benzoxazine ring equivalent of approximately 218g/eq.) 10 parts; 4) Change 2 parts of the hardener (aromatic hydrocarbon represented by formula (5), "SN395" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., hydroxyl equivalent: 107 g/eq.) as component (C) to component (C) 2 parts of hardener (aromatic hydrocarbon represented by formula (4), "GRA13H" manufactured by Gunei Chemical Industry Co., Ltd., hydroxyl equivalent weight is 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 hardener (aromatic hydrocarbon represented by the formula (4), "GRA13H" manufactured by Gunei Chemical Industry Co., Ltd., hydroxyl equivalent weight of about 75 g/eq.) as the component (C) was not used. Except for the above-mentioned matters, the 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 the hardener (aromatic hydrocarbon represented by the formula (5), "SN395" manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd., hydroxyl equivalent: 107 g/eq.) as the component (C) was not used. Except for the above-mentioned matters, the 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 Co., Ltd.), and 10 g of methyl ethyl ketone into a vial, and disperse them using ultrasonic waves for 20 minutes. A laser diffraction particle size distribution measuring device ("SALD-2200" manufactured by Shimadzu Corporation) was used to measure the particle size distribution using a batch tank method, and the average particle size was calculated as the average particle size.

*In the table, "a1" represents the value obtained by dividing the mass of component (A) by the epoxy equivalent; "e1" represents the value obtained by dividing the mass of the active ester hardener by the active ester group equivalent; "e2" ” represents the value obtained by dividing the mass of the benzoxazine-based hardener by the benzoxazine ring equivalent; “b2” represents the value obtained by dividing the mass of component (B) by the (meth)acrylyl group equivalent ; "e3" represents the content of the carbodiimide-based hardener in the resin composition; "b1" represents the content of component (B) in the resin composition.

[Preparation of resin sheets] As a support, a PET film ("Lumirror R80" made by Toray Co., Ltd., thickness 38 μm, softening point 130°C or less) was prepared by releasing treatment with an alkyd resin release agent ("AL-5" produced by LINTEC Co., Ltd.). There is a situation called "release PET").

＜Preparation of Resin Sheet A＞ Use a die coater to evenly apply resin compositions 1 and 2 and comparative example resin composition 1 onto the release PET so that the thickness of the resin composition layer after drying each resin composition becomes 40 μm. , and after drying at 80~120°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 a polypropylene film ("Arufan MA-411" manufactured by Oji F-Tex Co., Ltd., thickness: 15 μm) as a protective film was combined with the resin. Lamination is carried out by joining layers of materials. Thereby, a resin sheet A composed of release PET (support), a resin composition layer, and a protective film is obtained in this order.

＜Preparation of Resin Sheet B＞ Use a die coater to evenly apply resin compositions 3 and 4 and comparative example resin composition 2 onto the release PET so that the thickness of the resin composition layer after drying becomes 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 bonded to the support, the rough surface of a polypropylene film ("Arufan MA-411" manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) as a protective film and the resin composition are Lamination is carried out by layer joining. Thereby, a resin sheet B composed of release PET (support), a resin composition layer, and a protective film is obtained in this order.

[Measurement of dielectric tangent] The protective film was peeled off from the resin sheet A or B obtained in the Examples and Comparative Examples, heated at 200° C. for 90 minutes to thermally cure, and the support was peeled off to obtain a sheet-like cured product. The hardened material was cut into a length of 80 mm and a width of 2 mm to prepare an evaluation sample. For this evaluation sample, the dielectric tangent was measured using the HP8362B device manufactured by Agilent Technologies using the cavity resonance perturbation method at a frequency of 5.8 GHz and a measurement temperature of 23°C. Measurement was performed on three test pieces, and the average value was calculated.

[Measurement of blooming and peeling strength (peel strength) of plated conductor layers] ＜Preparation of samples for evaluation of blooming and measurement of peel strength＞ (1) Substrate treatment of inner circuit substrate Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, R1515A manufactured by Panasonic Corporation) with an inner circuit formed thereon were etched with a microetchant (CZ8101 manufactured by MEC Corporation) 1μm to roughen the copper surface.

(2) Lamination of resin sheets The protective film was peeled off from each of the resin sheets A or B that had been produced, and was laminated on both sides of the inner circuit board using a batch-type vacuum pressure laminating machine (MVLP-500 manufactured by Meiji Co., Ltd.). Lamination was performed by reducing the pressure for 30 seconds and setting the air pressure to 13 hPa or less, and then performing pressure bonding at 100° C. and a pressure of 0.74 MPa for 30 seconds.

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

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

In Examples 3 and 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, an energy of 0.2 mJ/projection, and a number of projections. 2. Under the condition of pulse intermittent mode (10kHz), open holes in the insulating layer to form a plurality of through holes so that the top hole diameter (diameter) of the through hole on the surface of the insulating layer becomes about 30 μm. After that, the release PET is peeled off.

(5) Roughening treatment: The inner circuit board with the insulating layer formed on it is immersed in Swelling Dip Securiganth P (diol containing diethylene glycol monobutyl ether manufactured by Atotech Japan) at 60°C as a swelling liquid. ether, sodium hydroxide aqueous solution) for 10 minutes, and then immersed in an aqueous solution of Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L) manufactured by Atotech Japan 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 solution at 40°C for 5 minutes, and then dried at 80°C for 30 minutes. This substrate was used as evaluation substrate A.

(6) By semi-additive plating, the evaluation substrate A is immersed in an electroless plating solution containing PdCl ₂ at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C. 20 minutes. After heating at 150° C. for 30 minutes and annealing, an etching resist was formed. After pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 20 μm. Next, annealing treatment was performed at 200° C. for 60 minutes. This substrate was used as evaluation substrate B.

＜Measurement of dimensions, halo distance and halo ratio of through-holes after roughening treatment＞ Regarding the evaluation substrate A, cross-sectional observation was performed using a FIB-SEM hybrid device ("SMI3050SE" manufactured by SII NanoTechnology Co., Ltd.). Specifically, FIB (focused ion beam) is used to cut the insulating layer in such a manner 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 emerges. The cross section was observed by SEM. The bottom hole diameter and the top hole diameter of the through hole are measured from the observed picture. In addition, in the picture observed by SEM, it can be seen that there is a continuous gap portion starting from the edge of the bottom of the through hole, and the insulating layer is peeled off from the copper foil layer of the inner substrate. Here, "distance r1" and "distance r2" are measured from the observed screen. The distance r1 is the distance from the center of the through hole bottom to the edge of the through hole bottom (corresponding to the inner circumferential radius of the gap portion). ); this distance r2 is the distance from the center of the bottom of the through hole to the far end of the gap (corresponding to the outer circumferential radius of the gap), and the difference r2- between the equidistant 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.

Five through-holes were randomly selected to perform the aforementioned measurement. Then, the average of the measured top hole diameters of the five through holes was used as the top hole diameter Lt of the sample after the roughening process. In addition, the average of the measured bottom hole diameters of the five through holes was used as the bottom hole diameter Lb of the sample after the roughening process. Furthermore, the average of the measured blooming distances of the through-holes at five locations was used as the blooming distance Wb from the edge of the through-hole bottom of the sample.

From the above measurement results, the taper ratio (the ratio of the top hole diameter Lt and the bottom hole diameter Lb of the roughened through hole "Lb/Lt") and the halo penetration ratio Hb (from the edge of the roughened through hole bottom) were calculated. The ratio of the halo distance Wb and the radius (Lb/2) of the through hole bottom of the roughened through hole (Wb/(Lb/2)"). If the bloom ratio Hb is 35% or less, it is judged as "○", and if the bloom ratio Ht is greater than 35%, it is judged as "×".

<Measurement and evaluation of adhesion (peel strength) to the plated conductor layer> A cutout of a 10 mm wide and 100 mm long portion was placed on the conductor layer of the evaluation substrate B, and the end was peeled off and clamped with a clamp (Auto Rubber type testing machine AC-50C-SL manufactured by TSE). 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 when components (E) to (I) are not contained, it was confirmed that the same results as in the above examples were obtained, although there were differences in degree.

100‧‧‧insulation layer 100U‧‧‧The side of the insulating layer opposite to the conductor layer 110‧‧‧through hole 120‧‧‧Through hole bottom 120C‧‧‧Center of the bottom of the through hole 130‧‧‧Through hole top 140‧‧‧Discoloration part 150‧‧‧The edge of the bottom of the through hole 160‧‧‧Gap 170‧‧‧End of the outer peripheral side of the gap 180‧‧‧The edge of the top of the through hole 190‧‧‧The outer edge of the discolored part 200‧‧‧Inner substrate 210‧‧‧Conductor layer Lb‧‧‧Bottom diameter of through hole Lt‧‧‧Top aperture of through hole Wb‧‧‧The blooming distance from the edge of the bottom of the through hole

[Fig. 1] Fig. 1 is a cross-sectional view schematically showing an insulating layer (which is obtained by curing the resin composition of the present invention into a sheet shape) and an inner layer substrate. [Fig. 2] Fig. 2 is a plan view schematically showing the surface of the insulating layer (which is obtained by hardening the resin composition of the present invention into a sheet shape) and the conductive layer on the opposite side. [Fig. 3] Fig. 3 is a cross-sectional view schematically showing a roughened insulating layer (which is obtained by curing the resin composition of the present invention into a sheet shape) and an inner substrate.

Claims (14)

A resin composition characterized by containing: (A) epoxy resin, (B) (meth)acrylate, (C) aromatic ring containing two or more hydroxyl groups as a single ring or condensed ring Aromatic hydrocarbon resin and (D) inorganic filler, the amount of component (C) is 0.1 mass % or more and 10 mass % or less based on 100 mass % of the resin component in the resin composition, and component (C) is represented by the following formula ( 1) or formula (2),

(In formula (1), R ⁰ each independently represents a divalent hydrocarbon group, and n1 represents an integer from 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 of claim 1, wherein the content of component (B) is 0.1 mass% or more and 10 mass% or less when the non-volatile components in the resin composition are 100 mass%. The resin composition according to claim 1, wherein the component (B) has a cyclic structure. The resin composition of 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 each independently represent an acryl group or a methacryloyl group, R ² and R ³ each independently represent a divalent linking group, and ring A represents a divalent cyclic group. ). The resin composition of 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 of claim 1, further comprising (E) a hardener. The resin composition of claim 6, wherein component (E) is selected from the group consisting of benzoxazine-based hardeners, carbodiimide-based hardeners, phenol-based hardeners, and active ester-based hardeners. More than 1 species. For example, the resin composition of claim 1 is used for insulation purposes. The resin composition of claim 1 is used for forming an insulating layer. The resin composition according to claim 1 is used to form an insulating layer for forming a conductor layer. The resin composition of claim 1 is used for sealing semiconductor wafers. A resin sheet, characterized by comprising: a support body and a resin composition layer provided on the support body, the resin composition layer containing the resin composition of any one of claims 1 to 11. A printed wiring board including an insulating layer, characterized in that the insulating layer is formed by a cured product of the resin composition in any one of claims 1 to 11. A semiconductor device characterized by including the printed wiring board of claim 13.