JP2018188625A - Resin composition layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition layer capable of obtaining an insulating layer which can suppress a haloing phenomenon even when a thickness is thin and can form a via hole having a good shape.SOLUTION: A resin composition layer contains a resin composition and has a thickness of 15 μm or less, and the resin composition contains (A) an epoxy resin, (B) an aromatic hydrocarbon resin containing an aromatic ring having two or more hydroxyl groups as a monocycle or condensed ring, and (C) an inorganic filler having at least one of an average particle diameter of 100 nm or less and a specific surface area of 15 m/g or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin composition layer. Furthermore, this invention relates to the printed wiring board and semiconductor device containing the insulating layer formed with the resin sheet containing the said resin composition layer; and the hardened | cured material of the resin composition layer.

  In recent years, printed wiring boards have been further reduced in thickness in order to achieve miniaturization of electronic devices. Along with this, miniaturization of the wiring circuit in the inner layer substrate has been promoted. For example, Patent Document 1 describes a resin sheet (adhesive film) that can support fine wiring, including a support and a resin composition layer.

JP 2014-36051 A

  The present inventor has studied thinning the resin composition layer of the resin sheet in order to achieve further miniaturization and thinning of electronic devices. As a result of the study, the present inventors have found that a haloing phenomenon occurs after the formation of a via hole when a thin resin composition layer is applied to an insulating layer. Here, the haloing phenomenon refers to a phenomenon in which the resin of the insulating layer changes color around the via hole. Such a haloing phenomenon usually occurs when the resin around the via hole deteriorates. Further, when a roughening treatment is applied to the insulating layer in which the haloing phenomenon has occurred, the resin in the portion of the insulating layer in which the haloing phenomenon has occurred (hereinafter sometimes referred to as “haloing portion”) is eroded during the roughening treatment. It has been found that delamination occurs between the insulating layer and the inner layer substrate.

  Furthermore, the present inventor has found that when a thin resin composition layer is applied to the insulating layer, it becomes difficult to control the shape of the via hole and it is difficult to obtain a well-shaped via hole. Here, “the shape of the via hole is“ good ”” means that the taper ratio of the via hole is close to 1. The via hole taper ratio is the ratio of the bottom diameter to the top diameter of the via hole.

  All of the above-mentioned problems are caused only by reducing the thickness of the resin composition layer, and are new problems that have not been conventionally known. From the viewpoint of improving the conduction reliability between the layers of the printed wiring board, it is desired to solve these problems.

  The present invention was devised in view of the above problems, and a resin composition layer capable of suppressing a haloing phenomenon even when the thickness is small and obtaining an insulating layer capable of forming a well-shaped via hole. A resin sheet including the resin composition layer; a printed wiring board including a thin insulating layer capable of suppressing a haloing phenomenon and capable of forming a well-shaped via hole; and a semiconductor device including the printed wiring board The purpose is to provide;

As a result of intensive studies to solve the above problems, the present inventor has (A) an epoxy resin, (B) an aromatic hydrocarbon resin containing an aromatic ring as a single ring or a condensed ring having two or more hydroxyl groups, And (C) the resin composition containing a combination of an inorganic filler having an average particle diameter of 100 nm or less and a specific surface area of 15 m ² / g or more, and found that the above-mentioned problems can be solved, and the present invention Completed.
That is, the present invention includes the following contents.

（式（１）において、Ｒ^０は、それぞれ独立して、２価の炭化水素基を表し、ｎ１は、０〜６の整数を表す。）

（式（２）において、Ｒ^１〜Ｒ^４は、それぞれ独立して、水素原子又は１価の炭化水素基を表す。）
〔４〕 （Ｂ）成分が、下記の式（３）又は式（４）で表される、〔１〕〜〔３〕のいずれか一項に記載の樹脂組成物層。

（式（３）において、ｎ２は、０〜６の整数を表す。）

（式（４）において、Ｒ^１〜Ｒ^４は、それぞれ独立して、水素原子又は１価の炭化水素基を表す。）
〔５〕 （Ｂ）成分の量が、樹脂組成物中の樹脂成分１００質量％に対して、５質量％〜５０質量％である、〔１〕〜〔４〕のいずれか一項に記載の樹脂組成物層。
〔６〕 （Ｃ）成分の量が、樹脂組成物中の不揮発成分１００質量％に対して、５０質量％以上である、〔１〕〜〔５〕のいずれか一項に記載の樹脂組成物層。
〔７〕 導体層を形成するための絶縁層形成用である、〔１〕〜〔６〕のいずれか一項に記載の樹脂組成物層。
〔８〕 プリント配線板の層間絶縁層形成用である、〔１〕〜〔７〕のいずれか一項に記載の樹脂組成物層。
〔９〕 トップ径３５μｍ以下のビアホールを有する絶縁層形成用である、〔１〕〜〔８〕のいずれか一項に記載の樹脂組成物層。
〔１０〕 支持体と、
支持体上に設けられた、〔１〕〜〔９〕のいずれか一項に記載の樹脂組成物層とを含む、樹脂シート。
〔１１〕 〔１〕〜〔９〕のいずれか一項に記載の樹脂組成物層の硬化物で形成された絶縁層を含む、プリント配線板。
〔１２〕 第１の導体層、第２の導体層、及び、第１の導体層と第２の導体層との間に形成された絶縁層を含むプリント配線板であって、
絶縁層の厚みが、１５μｍ以下であり、
絶縁層が、トップ径３５μｍ以下のビアホールを有し、
該ビアホールのテーパー率が、８０％以上であり、
該ビアホールのボトムのエッジからのハローイング距離が、５μｍ以下であり、
該ビアホールのボトム半径に対するハローイング比が、３５％以下である、プリント配線板。
〔１３〕 該ビアホールのボトム半径に対するハローイング比が、５％以上である、〔１２〕記載のプリント配線板。
〔１４〕 〔１１〕〜〔１３〕のいずれか一項に記載のプリント配線板を含む、半導体装置。 [1] A resin composition layer containing a resin composition and having a thickness of 15 μm or less,
The resin composition comprises (A) an epoxy resin, (B) an aromatic hydrocarbon resin containing a monocyclic or condensed ring having two or more hydroxyl groups, and (C) an inorganic material having an average particle size of 100 nm or less. A resin composition layer containing a filler.
[2] A resin composition layer containing a resin composition and having a thickness of 15 μm or less,
The resin composition is (A) an epoxy resin, (B) an aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring having two or more hydroxyl groups, and (C) a specific surface area of 15 m ² / g or more. A resin composition layer comprising an inorganic filler.
[3] The resin composition layer according to [1] or [2], wherein the component (B) is represented by the following formula (1) or formula (2).

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

(In Formula (2), R ^{1 to} R ⁴ each independently represents a hydrogen atom or a monovalent hydrocarbon group.)
[4] The resin composition layer according to any one of [1] to [3], wherein the component (B) is represented by the following formula (3) or formula (4).

(In Formula (3), n2 represents the integer of 0-6.)

(In Formula (4), R ^{1 to} R ⁴ each independently represents a hydrogen atom or a monovalent hydrocarbon group.)
[5] The amount of the component (B) is 5% to 50% by mass with respect to 100% by mass of the resin component in the resin composition, according to any one of [1] to [4]. Resin composition layer.
[6] The resin composition according to any one of [1] to [5], wherein the amount of the component (C) is 50% by mass or more with respect to 100% by mass of the non-volatile component in the resin composition. layer.
[7] The resin composition layer according to any one of [1] to [6], which is for forming an insulating layer for forming a conductor layer.
[8] The resin composition layer according to any one of [1] to [7], which is for forming an interlayer insulating layer of a printed wiring board.
[9] The resin composition layer according to any one of [1] to [8], which is for forming an insulating layer having a via hole having a top diameter of 35 μm or less.
[10] a support;
The resin sheet containing the resin composition layer as described in any one of [1]-[9] provided on the support body.
[11] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition layer according to any one of [1] to [9].
[12] A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
The insulating layer has a thickness of 15 μm or less;
The insulating layer has a via hole with a top diameter of 35 μm or less,
The taper ratio of the via hole is 80% or more,
The haloing distance from the bottom edge of the via hole is 5 μm or less,
The printed wiring board whose haloing ratio with respect to the bottom radius of this via hole is 35% or less.
[13] The printed wiring board according to [12], wherein a haloing ratio of the via hole with respect to a bottom radius is 5% or more.
[14] A semiconductor device including the printed wiring board according to any one of [11] to [13].

  According to the present invention, even if the thickness is small, the resin composition layer capable of suppressing the halo phenomenon and obtaining an insulating layer capable of forming a via hole having a good shape; a resin comprising the resin composition layer described above It is possible to provide a sheet; a printed wiring board including a thin insulating layer capable of suppressing a haloing phenomenon and capable of forming a well-shaped via hole; and a semiconductor device including the printed wiring board.

FIG. 1 is a cross-sectional view schematically showing an insulating layer obtained by curing the resin composition layer according to the first embodiment of the present invention together with an inner layer substrate. FIG. 2 is a plan view schematically showing the surface of the insulating layer obtained by curing the resin composition layer according to the first embodiment of the present invention on the side opposite to the conductor layer. FIG. 3 is a cross-sectional view schematically showing the roughened insulating layer together with the inner layer substrate obtained by curing the resin composition layer according to the first embodiment of the present invention. FIG. 4 is a schematic cross-sectional view of a printed wiring board according to the second embodiment of the present invention.

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

  In the following description, the “resin component” of the resin composition refers to a component excluding the inorganic filler among the non-volatile components contained in the resin composition.

[1. Outline of Resin Composition Layer]
The resin composition layer of the present invention is a thin resin composition layer having a thickness of a predetermined value or less. Moreover, the resin composition included in the resin composition layer of the present invention is:
(A) epoxy resin,
(B) an aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring having two or more hydroxyl groups, and
(C) an inorganic filler having at least one of an average particle diameter of 100 nm or less and a specific surface area of 15 m ² / g or more.
Thus, the resin composition included in the resin composition layer of the present invention can include any of the following first resin composition and second resin composition.

  (A) an epoxy resin, (B) an aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring having two or more hydroxyl groups, and (C) an inorganic filler having an average particle size of 100 nm or less, 1st resin composition.

(A) an epoxy resin, (B) an aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring having two or more hydroxyl groups, and (C) an inorganic filler having a specific surface area of 15 m ² / g or more. A second resin composition comprising.

  By using such a resin composition layer, a thin insulating layer can be obtained. And the desired effect of this invention that the via hole of a favorable shape can be formed in the obtained insulating layer, suppressing a haloing phenomenon can be acquired.

[2. (A) component: epoxy resin]
Examples of the epoxy resin as the component (A) include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, Trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester Type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic Poxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. . An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

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

  As the epoxy resin, an epoxy resin that is liquid at a temperature of 20 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) and an epoxy resin that is a solid at a temperature of 20 ° C. (sometimes referred to as “solid epoxy resin”). There is. The resin composition (A) may contain only a liquid epoxy resin or only a solid epoxy resin as an epoxy resin, but may contain a combination of a liquid epoxy resin and a solid epoxy resin. Is preferred. (A) By using a combination of a liquid epoxy resin and a solid epoxy resin as an epoxy resin, the flexibility of the resin composition layer is improved, or the breaking strength of the cured product of the resin composition layer is improved. it can.

  The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, and more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule. Here, the “aromatic” epoxy resin means an epoxy resin having an aromatic ring in the molecule.

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

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

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

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

  Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin) manufactured by DIC; “HP-4700” and “HP-4710” (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC; “HP-7200HH”, “HP-7200H”, “EXA-7311”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000” (manufactured by DIC) Naphthylene ether type epoxy resin) “EPPN-502H” (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Resin); “NC7000L” (naphthol novolak type epoxy resin) manufactured by Nippon Kayaku; “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin) manufactured by Nippon Kayaku; Nippon Steel & Sumitomo Metal "ESN475V" (naphthalene type epoxy resin) manufactured by Chemical Co .; "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co .; "YX4000H", "YX4000", "YL6121" (biphenyl type) manufactured by Mitsubishi Chemical Corporation Epoxy resin); "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-" manufactured by Osaka Gas Chemical Co., Ltd. 500 ";" YL7760 "(bis "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" manufactured by Mitsubishi Chemical Corporation (Tetra) Phenylethane type epoxy resin). These may be used alone or in combination of two or more.

  (A) When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably a mass ratio, preferably 1: 1 to 1:20. More preferably, it is 1: 2 to 1:15, and particularly preferably 1: 5 to 1:13. When the quantity ratio between the liquid epoxy resin and the solid epoxy resin is within such a range, the desired effect of the present invention can be remarkably obtained. Furthermore, usually, when used in the form of a resin sheet, moderate tackiness is brought about. Moreover, normally, when using with the form of a resin sheet, sufficient flexibility is acquired and a handleability improves. Furthermore, usually, a cured product having a sufficient breaking strength can be obtained.

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

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

  The amount of the (A) epoxy resin in the resin composition is preferably 10% by mass with respect to 100% by mass of the resin component in the resin composition from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. As mentioned above, More preferably, it is 20 mass% or more, More preferably, it is 30 mass% or more. The upper limit of the content of the epoxy resin is preferably 90% by mass or less, more preferably 85% by mass or less, and particularly preferably 80% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

[3. (B) Component: Aromatic hydrocarbon resin containing an aromatic ring as a single ring or condensed ring having two or more hydroxyl groups]
The resin composition includes an aromatic hydrocarbon resin containing an aromatic ring having two or more hydroxyl groups as the component (B). Usually, since the (B) component can react with the (A) epoxy resin by the hydroxyl group of the aromatic ring, the (B) component can function as a curing agent for curing the resin composition. The haloing phenomenon can be suppressed by the action of the component (B).

  Here, the term “aromatic ring” includes both an aromatic ring as a single ring such as a benzene ring and an aromatic ring as a condensed ring such as a naphthalene ring. The number of carbon atoms per aromatic ring contained in the component (B) is preferably 6 or more, preferably 14 or less, more preferably from the viewpoint of remarkably obtaining the desired effect of the present invention. 10 or less.

  Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. Moreover, the kind of aromatic ring contained in one molecule of the aromatic hydrocarbon resin may be one kind or two or more kinds.

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

  The number of aromatic rings having 2 or more hydroxyl groups per molecule of component (B) is usually 1 or more, and preferably 2 or more from the viewpoint of remarkably obtaining the desired effect of the present invention. Preferably it is 3 or more. The upper limit is not particularly limited, but is preferably 6 or less, more preferably 5 or less, from the viewpoint of suppressing steric hindrance and increasing the reactivity with the epoxy resin.

  Examples of suitable component (B) include an aromatic hydrocarbon resin represented by the following formula (1) and an aromatic hydrocarbon resin represented by the following formula (2).

In the 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 group obtained by combining 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 can be preferably 3 or more, 6 or more, or 7 or more from the viewpoint of remarkably obtaining the desired effect of the present invention. The upper limit of the number of carbon atoms is preferably 20 or less, 15 or less, or 10 or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

Specific examples of R ⁰ include the following hydrocarbon groups.

  In Formula (1), n1 represents an integer of 0 or more and 6 or less. Among them, n1 is preferably 1 or more, more preferably 2 or more, preferably 4 or less, more preferably 3 or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

  If the aromatic hydrocarbon resin represented by the formula (1) is used, the haloing phenomenon can be particularly 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 these, from the viewpoint of remarkably obtaining the desired effect of the present invention, an aliphatic hydrocarbon group is preferable, a saturated aliphatic hydrocarbon group is more preferable, and a chain saturated aliphatic hydrocarbon group is particularly preferable. The number of carbon atoms of the monovalent hydrocarbon group is usually 1 or more, and is preferably 20 or less, more preferably 15 or less, 10 or less, or 8 or less from the viewpoint of remarkably obtaining the desired effect of the present invention. Preferable examples of R ^{1 to} R ⁴ include a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. If the aromatic hydrocarbon resin represented by Formula (2) is used, peeling of the halo portion due to erosion during the roughening treatment can be particularly effectively suppressed.

Among these, the aromatic hydrocarbon resin particularly preferable as the component (B) includes an aromatic hydrocarbon resin represented by the following formula (3) and an aromatic hydrocarbon resin represented by the following formula (4). It is done. In formula (3), n2 represents an integer defined in the same manner as n1 in formula (1), and the preferred range is also the same. Further, in the equation ^(4), R 1 to R ⁴ have the same meanings as ^R 1 to R ⁴ in Formula (2).

  As a commercial item of the aromatic hydrocarbon resin represented by Formula (3), the naphthol type hardening | curing agent "SN395" by Nippon Steel & Sumikin Chemical Co., Ltd. represented by following formula (5) is mentioned, for example. In Formula (5), n3 represents 2 or 3. Moreover, as a commercial item of the aromatic hydrocarbon resin represented by Formula (4), the phenol type hardening | curing agent "GRA13H" by Gunei Chemical Industry Co., Ltd. is mentioned, for example.

  (B) The aromatic hydrocarbon resin as a component may be used individually by 1 type, and may be used in combination of 2 or more type.

  The hydroxyl equivalent of the component (B) is preferably 50 g / eq or more from the viewpoint of increasing the crosslinking density of the insulating layer as a cured product of the resin composition layer and from the viewpoint of remarkably obtaining the desired effect of the present invention. Preferably it is 60 g / eq or more, more preferably 70 g / eq or more, preferably 200 g / eq or less, more preferably 150 g / eq or less, and particularly preferably 120 g / eq or less. Hydroxyl equivalent weight is the mass of a resin containing 1 equivalent of hydroxyl groups.

  The amount of the component (B) in the resin composition is preferably 5% by mass or more, more preferably 7% by mass or more, and particularly preferably 9% by mass or more with respect to 100% by mass of the resin component in the resin composition. The amount is preferably 50% by mass or less, more preferably 40% by mass or less, 30% by mass or less, or 20% by mass or less. When the amount of the component (B) is in the above range, the haloing phenomenon can be effectively suppressed.

  The amount of the component (B) relative to 100% by mass of the (A) epoxy resin is preferably 5% by mass or more, more preferably 8% by mass or more, particularly preferably 10% by mass or more, and preferably 100% by mass or less. Preferably it is 50 mass% or less, Most preferably, it is 30 mass% or less. When the amount of the component (B) is in the above range, the haloing phenomenon can be effectively suppressed.

  When the number of epoxy groups in the (A) epoxy resin is 1, the number of hydroxyl groups in the component (B) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, preferably 2 or less, more preferably 1.5 or less, still more preferably 1 or less, particularly preferably 0.5 or less. Here, “(A) the number of epoxy groups of the epoxy resin” is a value obtained by adding up all values obtained by dividing the mass of the nonvolatile component of the component (A) present in the resin composition by the epoxy equivalent. The “number of hydroxyl groups in component (B)” is a value obtained by adding all the values obtained by dividing the mass of the nonvolatile component of component (B) present in the resin composition by the hydroxyl equivalent. (A) When the number of epoxy groups of the epoxy resin is 1, the number of hydroxyl groups of the component (B) is in the above range, whereby the haloing phenomenon can be effectively suppressed.

[4. (C) Component: Inorganic filler having at least one of an average particle diameter of 100 nm or less and a specific surface area of 15 m ² / g or more]
The resin composition contains an inorganic filler as the component (C). According to the inorganic filler, since the thermal expansion coefficient of the cured product of the resin composition layer can be reduced, an insulating layer in which reflow warpage is suppressed can be obtained. Moreover, the inorganic filler as the component (C) has at least one of an average particle diameter of 100 nm or less and a specific surface area of 15 m ² / g or more. As the inorganic filler, an insulating layer capable of forming a via hole having a good shape by using the component (C) having at least one of the average particle diameter and the specific surface area in such a range in combination with the component (B). Can be realized.

  An inorganic compound is used as the material of the inorganic filler. Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide , Barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly preferred. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as silica, spherical silica is preferable. One kind of inorganic filler may be used alone, or two or more kinds may be used in combination.

  The average particle diameter of the component (C) is usually 100 nm or less, preferably 90 nm or less, more preferably 80 nm, from the viewpoint of thinning the insulating layer and realizing a good shape by enabling control of the shape of the via hole. It is as follows. Although the minimum of this average particle diameter is not specifically limited, Preferably it is 50 nm or more, 60 nm or more, or 70 nm or more. Examples of commercially available inorganic fillers having such an average particle diameter include “UFP-30” and “UFP-40” manufactured by Denki Kagaku Kogyo Co., Ltd.

  The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering particle size distribution measuring device and setting the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring device, “LA-500” manufactured by Horiba, “SALD-2200” manufactured by Shimadzu, etc. can be used.

The specific surface area of the component (C) is usually 15 m ² / g or more, preferably 20 m ² / g or more, particularly preferably 30 m ² / g or more, from the viewpoint of easily controlling the shape of the via hole and realizing a good shape. It is. Further, the component (C) having a large specific surface area as described above generally has a small particle size, so that the insulating layer can be made thin. Although there is no special restriction | limiting in an upper limit, Preferably it is 60 m < ² > / g or less, 50 m < ² > / g or less, or 40 m < ² > / g or less. The specific surface area of the inorganic filler can be measured by the BET method.

  The inorganic filler as the component (C) 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, alkoxysilanes, organosilazane compounds, and titanates. A coupling agent etc. are mentioned. Moreover, a surface treating agent may be used individually by 1 type, and may be used combining two or more types arbitrarily.

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

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

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

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

  The amount of the component (C) in the resin composition is preferably 30% by mass or more, more preferably 35% by mass with respect to 100% by mass of the non-volatile component in the resin composition from the viewpoint of lowering the dielectric loss tangent of the insulating layer. As mentioned above, More preferably, it is 40 mass% or more. Conventionally, when the layer of the resin composition containing such a large amount of inorganic filler is thin, it is difficult to improve the shape of the via hole, and in particular, inorganic filling with respect to 100% by mass of the nonvolatile component in the resin composition. When the amount of the material was 50% by mass or more, formation of a well-shaped via hole was particularly difficult. Therefore, from the viewpoint of effectively utilizing the advantage of the present invention that it is possible to form a well-shaped via hole that has been particularly difficult in the past, the amount of the component (C) with respect to 100% by mass of the nonvolatile component in the resin composition. Is preferably 50% by mass or more, particularly preferably 54% by mass or more. The upper limit of the amount of the component (C) with respect to 100% by mass of the non-volatile component in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% from the viewpoint of increasing the mechanical strength of the insulating layer. It is not more than mass% or not more than 75 mass%.

[5. (D) component: thermoplastic resin]
In addition to the components described above, the resin composition may further contain (D) a thermoplastic resin as an optional component.

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

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

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

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, and “Electrical butyral 6000-EP” manufactured by Denki Kagaku Kogyo Co., Ltd .; Examples include S-LEC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series;

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

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

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

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

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

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

  When (D) a thermoplastic resin is used, the amount of (D) the thermoplastic resin in the resin composition is based on 100% by mass of the resin component in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. And preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, preferably 15% by mass or less, more preferably 12% by mass or less, and still more preferably 10%. It is below mass%.

[6. (E) component: curing agent]
The resin composition may further contain (E) a curing agent other than the component (B) as an optional component in addition to the components described above.

  (E) As a hardening | curing agent as a component, what has the effect | action which hardens (A) component can be used. Examples of the (E) curing agent include an active ester curing agent, a phenol curing agent, a naphthol curing agent, a benzoxazine curing agent, a cyanate ester curing agent, and a carbodiimide curing agent. Moreover, a hardening | curing agent may be used individually by 1 type, or may use 2 or more types together. Among these, an active ester curing agent is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention.

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

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

  Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Preferable specific examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac. The active ester compound containing is mentioned. Of these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. 65TM "," EXB-8000L-65TM "," EXB-8150-65T "(manufactured by DIC);" EXB9416-70BK "(manufactured by DIC) as an active ester compound containing a naphthalene structure; including an acetylated product of phenol novolac “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound; “YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac; "C808" (manufactured by Mitsubishi Chemical Corporation); "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) );

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

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

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd. and “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

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

  Specific examples of the carbodiimide curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

  When (E) a curing agent is used, the amount of the (E) curing agent in the resin composition is based on 100% by mass of the resin component in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. Preferably it is 0.1 mass% or more, More preferably, it is 0.5 mass% or more, More preferably, it is 1 mass% or more, Preferably it is 20 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 12 mass% It is as follows.

  Moreover, when using (E) hardening | curing agent, the quantity of (E) hardening | curing agent in a resin composition is preferable with respect to 100 mass% of (B) component from a viewpoint which acquires the desired effect of this invention notably. Is 40% by mass or more, more preferably 50% by mass or more, particularly preferably 60% by mass or more, preferably 120% by mass or less, more preferably 100% by mass or less, and particularly preferably 90% by mass or less.

  Furthermore, when the number of epoxy groups in the (A) epoxy resin is 1, the number of active groups in the component (E) is preferably 0.1 or more, more preferably 0.2 or more, preferably 2 or less, more Preferably it is 1.5 or less, More preferably, it is 1 or less, Most preferably, it is 0.5 or less. Here, the “number of active groups of the (E) component” is a value obtained by adding up all values obtained by dividing the mass of the non-volatile component of the (E) component present in the resin composition by the active group equivalent. (A) When the number of active groups of the (E) component when the number of epoxy groups of the epoxy resin is 1, the insulating layer having particularly excellent mechanical strength can be obtained.

[7. (F) Component: Curing accelerator]
In addition to the components described above, the resin composition may further contain (F) a curing accelerator as an optional component.

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

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

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

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

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

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

  As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

  When using the (F) curing accelerator, the amount of the (F) curing accelerator in the resin composition is based on 100% by mass of the resin component of the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. , Preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably It is 1.5 mass% or less.

[8. (G) Component: Arbitrary additive]
The resin composition may further contain an optional additive as an optional component in addition to the components described above. Examples of such additives include organic fillers; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; flame retardants, thickeners, antifoaming agents, leveling agents, adhesion imparting agents, Resin additives such as colorants; and the like. These additives may be used alone or in combination of two or more.

[9. Thickness of resin composition layer]
The resin composition layer is a layer formed of the above-described resin composition and has a thickness equal to or less than a predetermined value. The specific thickness of the resin composition layer is usually 15 μm or less, preferably 14 μm or less, and more preferably 12 μm or less. Conventionally, the thickness of the resin composition layer for forming an insulating layer of a printed wiring board is generally thicker than this. On the other hand, when the present inventor thins the resin composition layer having a general composition as described above, the thin resin composition layer generates haloing phenomenon and controls the shape of the via hole. We have found that a problem that has not been known in the past arises. From the viewpoint of solving such a new problem and contributing to thinning of the printed wiring board, the resin composition layer of the present invention is provided thin as described above. The lower limit of the thickness of the resin composition layer is arbitrary, and can be, for example, 1 μm or more and 3 μm or more.

[10. Characteristics of resin composition layer]
By curing the resin composition layer of the present invention, a thin insulating layer formed of a cured product of the resin composition layer can be obtained. A well-shaped via hole can be formed in this insulating layer. Moreover, when forming a via hole in this insulating layer, the haloing phenomenon can be suppressed. Hereinafter, these effects will be described with reference to the drawings.

FIG. 1 is a cross-sectional view schematically showing an insulating layer 100 obtained by curing a resin composition layer according to a first embodiment of the present invention, together with an inner layer substrate 200. FIG. 1 shows a cross section of the insulating layer 100 taken along a plane passing through the center 120C of the bottom 120 of the via hole 110 and parallel to the thickness direction of the insulating layer 100.
As shown in FIG. 1, the insulating layer 100 according to the first embodiment of the present invention is a layer obtained by curing a resin composition layer formed on an inner substrate 200 including a conductor layer 210, It consists of the hardened | cured material of the said resin composition layer. A via hole 110 is formed in the insulating layer 100. The via hole 110 is generally formed in a forward tapered shape having a larger diameter as it is closer to the surface 100U of the insulating layer 100 on the side opposite to the conductor layer 210 and smaller as it is closer to the conductor layer 210. It is formed in a columnar shape having a constant diameter in the thickness direction of 100. The via hole 110 is usually formed by irradiating the surface 100U of the insulating layer 100 opposite to the conductor layer 210 with laser light to remove a part of the insulating layer 100.

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

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

For example, the insulating layer 100 obtained by heating the resin composition layer at 100 ° C. for 30 minutes and then curing at 180 ° C. for 30 minutes has a mask diameter of 1 mm, a pulse width of 16 μs, an energy of 0.2 mJ / shot, and a shot. When a via hole 110 having a top diameter Lt of 30 μm ± 2 μm is formed by irradiating CO ₂ laser light under the conditions of Equation 2 and burst mode (10 kHz), the taper ratio Lb / Lt of the via hole 110 is preferably 60%. To 100%, more preferably 70% to 100%, particularly preferably 80% to 100%.

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

FIG. 2 schematically shows a surface 100U on the opposite side of the conductor layer 210 (not shown in FIG. 2) of the insulating layer 100 obtained by curing the resin composition layer according to the first embodiment of the present invention. FIG.
As shown in FIG. 2, when the insulating layer 100 in which the via hole 110 is formed is seen, a halo portion 140 in which the insulating layer 100 is discolored may be observed around the via hole 110. The haloing portion 140 can be formed by a haloing phenomenon when the via hole 110 is formed, and is usually formed continuously from the via hole 110. In many cases, the haloing portion 140 is a whitened portion.

  By using the resin composition layer of the present invention, the haloing phenomenon can be suppressed. Therefore, the size of the haloing portion 140 can be reduced, and ideally the haloing portion 140 can be eliminated. The size of the haloing portion 140 can be evaluated by the haloing distance Wt from the edge 150 of the via top 130 of the via hole 110.

  The edge 150 of the via top 130 corresponds to the inner peripheral edge of the halo 140. The haloing distance Wt from the edge 150 of the via top 130 represents the distance from the edge 150 of the via top 130 to the edge 160 on the outer peripheral side of the haloing part 140. It can be evaluated that the haloing phenomenon can be effectively suppressed as the haloing distance Wt from the edge 150 of the via top 130 is smaller.

For example, the insulating layer 100 obtained by heating the resin composition layer at 100 ° C. for 30 minutes and then curing at 180 ° C. for 30 minutes has a mask diameter of 1 mm, a pulse width of 16 μs, an energy of 0.2 mJ / shot, and a shot. When a via hole 110 having a top diameter Lt of 30 μm ± 2 μm is formed by irradiating CO ₂ laser light under the conditions of Equation 2 and burst mode (10 kHz), the haloing distance Wt from the edge 150 of the via top 130 is preferably Can be 6 μm or less, more preferably 5 μm or less.

  The haloing distance Wt from the edge 150 of the via top 130 can be measured by observation with an optical microscope.

  Further, according to the study by the present inventor, it has been found that in general, the size of the haloing portion 140 tends to increase as the diameter of the via hole 110 increases. Therefore, the degree of suppression of the haloing phenomenon can be evaluated by the ratio of the size of the haloing portion 140 to the diameter of the via hole 110. For example, the evaluation can be performed based on the halo ratio Ht with respect to the top radius Lt / 2 of the via hole 110. Here, the top radius Lt / 2 of the via hole 110 refers to the radius of the via top 130 of the via hole 110. The haloing ratio Ht with respect to the top radius Lt / 2 of the via hole 110 is a ratio obtained by dividing the haloing distance Wt from the edge 150 of the via top 130 by the top radius Lt / 2 of the via hole 110. The smaller the haloing ratio Ht with respect to the top radius Lt / 2 of the via hole 110, the more effectively the haloing phenomenon can be suppressed.

For example, the insulating layer 100 obtained by heating the resin composition layer at 100 ° C. for 30 minutes and then curing at 180 ° C. for 30 minutes has a mask diameter of 1 mm, a pulse width of 16 μs, an energy of 0.2 mJ / shot, and a shot. When a via hole 110 having a top diameter Lt of 30 μm ± 2 μm is formed by irradiating CO ₂ laser light under the condition of Equation 2, burst mode (10 kHz), the haloing ratio Ht with respect to the top radius Lt / 2 of the via hole 110 is Preferably it can be 45% or less, more preferably 40% or less, and still more preferably 35% or less.

  The haloing ratio Ht with respect to the top radius Lt / 2 of the via hole 110 can be calculated from the top diameter Lt of the via hole 110 and the haloing distance Wt from the edge 150 of the via top 130 of the via hole 110.

FIG. 3 is a cross-sectional view schematically showing the insulating layer 100 after the roughening treatment, obtained by curing the resin composition layer according to the first embodiment of the present invention, together with the inner layer substrate 200. 3 shows a cross section of the insulating layer 100 taken along a plane passing through the center 120C of the via bottom 120 of the via hole 110 and parallel to the thickness direction of the insulating layer 100.
As shown in FIG. 3, when the insulating layer 100 in which the via hole 110 is formed is roughened, the insulating layer 100 of the halo portion 140 is peeled off from the conductor layer 210, and a continuous gap from the edge 170 of the via bottom 120 is formed. Part 180 may be formed. The gap portion 180 is usually formed by eroding the halo portion 140 during the roughening process.

  By using the resin composition layer of the present invention, the haloing phenomenon can be suppressed as described above. Therefore, the size of the haloing portion 140 can be reduced, and ideally the haloing portion 140 can be eliminated. Therefore, peeling of the insulating layer 100 from the conductor layer 210 can be suppressed, and the size of the gap 180 can be reduced.

  The edge 170 of the via bottom 120 corresponds to the inner peripheral edge of the gap 180. Therefore, the distance Wb from the edge 170 of the via bottom 120 to the outer peripheral end of the gap 180 (ie, the end far from the center 120C of the via bottom 120) 190 is the size in the in-plane direction of the gap 180. Equivalent to. Here, the in-plane direction refers to a direction perpendicular to the thickness direction of the insulating layer 100. In the following description, the distance Wb may be referred to as a haloing distance Wb from the edge 170 of the via bottom 120 of the via hole 110.

  The degree of suppression of the formation of the gap 180 can be evaluated by the haloing distance Wb from the edge 170 of the via bottom 120. Specifically, it can be evaluated that the formation of the gap portion 180 can be effectively suppressed as the haloing distance Wb from the edge 170 of the via bottom 120 is smaller.

  In addition, since the gap portion 180 is formed by peeling off the insulating layer 100 of the halo portion 140, the size thereof is correlated with the size of the halo phenomenon 140. Therefore, it can be evaluated that the haloing phenomenon can be effectively suppressed as the haloing distance Wb from the edge 170 of the via bottom 120 is smaller.

For example, the insulating layer 100 obtained by heating the resin composition layer at 100 ° C. for 30 minutes and then curing at 180 ° C. for 30 minutes has a mask diameter of 1 mm, a pulse width of 16 μs, an energy of 0.2 mJ / shot, and a shot. By irradiation with CO ₂ laser light under the condition of Equation 2 and burst mode (10 kHz), a via hole 110 having a top diameter Lt of 30 μm ± 2 μm is formed. Then, it is immersed in the swelling solution at 60 ° C. for 10 minutes, then immersed in the oxidant solution at 80 ° C. for 20 minutes, then immersed in the neutralizing solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 15 minutes. When such roughening treatment is performed, the haloing distance Wb from the edge 170 of the via bottom 120 is preferably 60 μm or less, more preferably 50 μm or less, and particularly preferably 40 μm or less.

  The haloing distance Wb from the edge 170 of the via bottom 120 is such that a cross section appears through the insulating layer 100 parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the via bottom 120 using FIB (focused ion beam). It can be measured by observing the cross section with an electron microscope.

  Further, according to the study by the present inventor, it has been found that in general, the larger the diameter of the via hole 110, the larger the size of the haloing portion 140, and thus the size of the gap portion 180 tends to increase. Yes. Therefore, the degree of suppression of the haloing phenomenon can be evaluated by the ratio of the size of the gap 180 to the diameter of the via hole 110, and thus the degree of suppression of the formation of the gap 180 can be evaluated. For example, the evaluation can be performed based on the haloing ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110. Here, the bottom radius Lb / 2 of the via hole 110 refers to the radius of the via bottom 120 of the via hole 110. The haloing ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110 is a ratio obtained by dividing the haloing distance Wb from the edge 170 of the via bottom 120 by the bottom radius Lb / 2 of the via hole 110. The smaller the halo ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110, the more effectively the formation of the gap 180 can be suppressed.

For example, the insulating layer 100 obtained by heating the resin composition layer at 100 ° C. for 30 minutes and then curing at 180 ° C. for 30 minutes has a mask diameter of 1 mm, a pulse width of 16 μs, an energy of 0.2 mJ / shot, and a shot. By irradiation with CO ₂ laser light under the condition of Equation 2 and burst mode (10 kHz), a via hole 110 having a top diameter Lt of 30 μm ± 2 μm is formed. Then, it is immersed in the swelling solution at 60 ° C. for 10 minutes, then immersed in the oxidant solution at 80 ° C. for 20 minutes, then immersed in the neutralizing solution at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 15 minutes. When such roughening treatment is performed, the haloing ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110 can be preferably 60% or less, more preferably 50% or less, and even more preferably 40% or less.

  The haloing ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110 can be calculated from the bottom diameter Lb of the via hole 110 and the haloing distance Wb from the edge 170 of the via bottom 120 of the via hole 110.

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

  The inventor presumes the mechanism by which the above-described effect can be obtained by the resin composition layer of the present invention as follows. However, the technical scope of the present invention is not limited by the mechanism described below.

  Usually, when the via hole 110 is formed, energy such as heat and light is applied to a portion of the insulating layer 100 where the via hole 110 is to be formed. Part of the energy applied at this time is transmitted to the periphery of the portion where the via hole 110 is to be formed, which may cause oxidation of the resin. When such oxidation occurs, the resin deteriorates and may appear as a haloing phenomenon. However, since the component (B) has an aromatic ring having two or more hydroxyl groups, the progress of the oxidation reaction of the resin can be suppressed by the steric hindrance action of the hydroxyl groups. Therefore, the haloing phenomenon can be suppressed in the insulating layer 100 obtained using the resin composition layer of the present invention.

  Moreover, as can be seen from the description of the average particle diameter and the specific surface area, the particle diameter of the component (C) contained in the resin composition layer is usually small. Since the particle size of the component (C) is small, the energy given to the insulating layer 100 can be transmitted well in the thickness direction of the insulating layer 100. For example, when thermal energy or light energy is applied to the surface 100U of the insulating layer 100, the energy can be transmitted in the thickness direction without causing significant attenuation. Therefore, since the via hole 110 having a large taper rate can be easily formed, the shape of the via hole 110 can be improved.

[11. Application of resin composition layer]
The resin composition layer of the present invention can be suitably used as a resin composition layer for insulating applications. Specifically, the resin composition layer of the present invention is preferably used as a resin composition layer (resin composition layer for forming an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board. Furthermore, it can be more suitably used as a resin composition layer (resin composition layer for forming an interlayer insulating layer of a printed wiring board) for forming an interlayer insulating layer of a printed wiring board. Further, the resin composition layer of the present invention is a resin composition layer (for forming a conductor layer) for forming the insulating layer for forming a conductor layer (including a rewiring layer) on the insulating layer. The resin composition layer for forming an insulating layer can be suitably used.

  In particular, from the viewpoint of effectively utilizing the advantage that a haloing phenomenon can be suppressed and a via hole having a good shape can be formed, the resin composition layer is used for forming an insulating layer having a via hole. It is suitable as a resin composition layer (resin composition layer for forming an insulating layer having a via hole), and particularly suitable as a resin composition layer for forming an insulating layer having a via hole having a top diameter of 35 μm or less.

[12. Resin sheet]
The resin sheet of this invention contains a support body and the resin composition layer of this invention provided on this support body.

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

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). Acrylic polymers such as polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (hereinafter sometimes abbreviated as “PMMA”), cyclic polyolefin, and triacetylcellulose (hereinafter referred to as “PC”). "TAC" may be abbreviated), polyether sulfide (hereinafter may be abbreviated as "PES"), polyether ketone, polyimide and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

  The support may be subjected to a treatment such as a mat treatment, a corona treatment, or an antistatic treatment on the surface to be joined to the resin composition layer.

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

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

  Moreover, the resin sheet may contain arbitrary layers other than a support body and a resin composition layer as needed. Examples of such an optional layer include a protective film according to the support provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). It is done. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By the protective film, it is possible to suppress the adhesion and scratches of dust and the like to the surface of the resin composition layer.

  The resin sheet is prepared, for example, by preparing a resin varnish containing an organic solvent and a resin composition, and applying the resin varnish on a support using a coating device such as a die coater and further drying the resin composition layer. It can be manufactured by forming.

  Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol. Solvents; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; One organic solvent may be used alone, or two or more organic solvents may be used in combination.

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

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

[13. Printed wiring board]
As described above, the printed wiring board of the present invention includes an insulating layer formed of a cured product of a thin resin composition layer. In addition, this insulating layer can suppress a haloing phenomenon when forming a via hole, and can form a well-shaped via hole. Therefore, by using the resin composition layer of the present invention, it is possible to reduce the thickness of the printed wiring board while suppressing the performance degradation due to the haloing phenomenon or the deterioration of the via hole shape.

  The via hole is usually provided for conducting a conductor layer provided on both sides of the insulating layer having the via hole. Therefore, the printed wiring board of the present invention usually includes a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer. A via hole is formed in the insulating layer, and the first conductor layer and the second conductor layer can be conducted through the via hole.

By utilizing the advantage of the resin composition layer that can suppress the haloing phenomenon and form a well-shaped via hole, it is possible to realize a specific printed wiring board that has been difficult to realize in the past. it can. The specific printed wiring board is a printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, All the following requirements (i) to (v) are satisfied.
(I) The insulating layer has a thickness of 15 μm or less.
(Ii) The insulating layer has a via hole having a top diameter of 35 μm or less.
(Iii) The taper ratio of the via hole is 80% or more.
(Iv) The haloing distance from the edge of the via bottom of the via hole is 5 μm or less.
(V) The haloing ratio with respect to the bottom radius of the via hole is 35% or less.

  The specific printed wiring board will be described below with reference to the drawings. FIG. 4 is a schematic cross-sectional view of a printed wiring board 300 according to the second embodiment of the present invention. FIG. 4 shows a cross section of the printed wiring board 300 taken along a plane passing through the center 120C of the via bottom 120 of the via hole 110 and parallel to the thickness direction of the insulating layer 100. Further, in FIG. 4, portions corresponding to the elements described in FIGS. 1 to 3 are denoted by the same reference numerals as those used in FIGS. 1 to 3.

  As shown in FIG. 4, the specific printed wiring board 300 according to the second embodiment of the present invention includes a first conductor layer 210, a second conductor layer 220, and the first conductor layer 210 and the second conductor. Insulating layer 100 formed between layers 220 is included. A via hole 110 is formed in the insulating layer 100. In general, the second conductor layer 220 is provided after the via hole 110 is formed. Therefore, the second conductor layer 220 is usually formed not only in the surface 100U of the insulating layer 100 but also in the via hole 110, and the first conductor layer 210 and the second conductor layer 220 are electrically connected through the via hole 110. doing.

  The thickness T of the insulating layer 100 included in the specific printed wiring board 300 is usually 15 μm or less, preferably 12 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. Since the specific printed wiring board 300 has such a thin insulating layer 100, the specific printed wiring board 300 itself can be thinned. The lower limit of the thickness T of the insulating layer 100 is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably 3 μm or more from the viewpoint of enhancing the insulating performance of the insulating layer 100. Here, the thickness T of the insulating layer 100 represents the dimension of the insulating layer 100 between the first conductor layer 210 and the second conductor layer 220, and the first conductor layer 210 or the second conductor layer 220. It does not represent the dimension of the insulating layer 100 at a position where there is no symbol. The thickness T of the insulating layer 100 usually corresponds to the distance between the main surface 210U of the first conductor layer 210 and the main surface 220D of the second conductor layer 220 facing each other through the insulating layer 100, and This corresponds to the depth of the via hole 110.

  The top diameter Lt of the via hole 110 included in the insulating layer 100 included in the specific printed wiring board 300 is usually 35 μm or less, preferably 33 μm or less, and particularly preferably 32 μm or less. Since the specific printed wiring board 300 includes the insulating layer 100 having the via hole 110 having the small top diameter Lt as described above, the miniaturization of the wiring including the first conductor layer 210 and the second conductor layer 220 can be promoted. it can. From the viewpoint of easily forming the via hole 110, the lower limit of the top diameter Lt of the via hole 110 is preferably 3 μm or more, more preferably 10 μm or more, and particularly preferably 15 μm or more.

  The taper ratio Lb / Lt (%) of the via hole 110 included in the insulating layer 100 included in the specific printed wiring board 300 is usually 80% to 100%. The specific printed wiring board 300 includes the insulating layer 100 having the well-shaped via hole 110 having a high taper ratio Lb / Lt. Therefore, the specific printed wiring board 300 can usually improve the reliability of conduction between the first conductor layer 210 and the second conductor layer 220.

  The haloing distance Wb from the edge 170 of the via bottom 120 of the via hole 110 included in the insulating layer 100 included in the specific printed wiring board 300 is usually 5 μm or less, preferably 4 μm or less. In the specific printed wiring board 300, the haloing distance Wb from the edge 170 of the via bottom 120 is thus small, and therefore, the peeling of the insulating layer 100 from the first conductor layer 210 is small. Therefore, the specific printed wiring board 300 can usually improve the reliability of conduction between the first conductor layer 210 and the second conductor layer 220.

  The haloing ratio Hb with respect to the bottom radius Lb / 2 of the via hole 110 included in the insulating layer 100 included in the specific printed wiring board 300 is usually 35% or less, preferably 33% or less, and more preferably 31% or less. The specific printed wiring board 300 has such a small halo ratio Hb with respect to the bottom radius Lb / 2, and thus the peeling of the insulating layer 100 from the first conductor layer 210 is small. As described above, the specific printed wiring board 300 including the insulating layer 100 having a small haloing ratio Hb can usually improve the reliability of conduction between the first conductor layer 210 and the second conductor layer 220. The lower limit of the halo ratio Hb with respect to the bottom radius Lb / 2 is ideally zero, but is usually 5% or more.

  The number of via holes 110 included in the insulating layer 100 included in the specific printed wiring board 300 may be one or two or more. When the insulating layer 100 has two or more via holes 110, some of them may satisfy the requirements (ii) to (v), but it is preferable that all of them satisfy the requirements (ii) to (v). . For example, it is preferable that the five via holes 110 randomly selected from the insulating layer 100 satisfy the requirements (ii) to (v) on average.

  The specific printed wiring board 300 described above can be realized by forming the insulating layer 100 with a cured product of the resin composition layer of the present invention. At this time, the planar shapes of the via bottom 120 and the via top 130 of the via hole 110 formed in the insulating layer 100 are arbitrary, but are usually circular or elliptical, and preferably circular.

A printed wiring board such as a specific printed wiring board can be manufactured, for example, by performing a manufacturing method including the following steps (I) to (III) using a resin sheet.
(I) A step of laminating a resin sheet on the inner layer substrate so that the resin composition layer is bonded to the inner layer substrate.
(II) A step of thermally curing the resin composition layer to form an insulating layer.
(III) A step of forming a via hole in the insulating layer.

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

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

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

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

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

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

  For example, although the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, the curing temperature is usually in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably 170 ° C. C. to 200.degree. C.) and the curing time can usually be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

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

  In step (III), a via hole is formed in the insulating layer. Examples of the method for forming the via hole include laser light irradiation, etching, mechanical drilling, and the like. Among these, irradiation with laser light generally tends to cause a haloing phenomenon. Therefore, laser light irradiation is preferable from the viewpoint of effectively utilizing the effect of suppressing the halo phenomenon.

This laser light irradiation can be performed using, for example, a laser processing machine having a laser light source such as a carbon dioxide laser, a YAG laser, or an excimer laser as a light source. The laser processing machine which may be used, for example, Via Mechanics, Ltd. CO ₂ laser processing machine "LC-2k212 / 2C", Mitsubishi Electric Corporation of 605GTWIII (-P), Matsushita Welding Systems Co., Ltd. Laser processing machine, etc. Is mentioned.

  Laser light irradiation conditions such as laser light wavelength, number of pulses, pulse width, and output are not particularly limited, and appropriate conditions may be set according to the type of laser light source.

  By the way, the support may be removed between step (I) and step (II), or may be removed between step (II) and step (III), and after step (III). It may be removed. Especially, it is preferable to remove after the process (III) which forms a via hole in an insulating layer from a viewpoint of suppressing generation | occurrence | production of a bending part more. For example, when a support is peeled after a via hole is formed in an insulating layer by laser light irradiation, a well-shaped via hole is easily formed.

  The method for manufacturing a printed wiring board may further include (IV) a step of roughening the insulating layer and (V) a step of forming a conductor layer. You may implement these process (IV) and process (V) according to the various methods used for manufacture of a printed wiring board. When the support is removed after the step (III), the support may be removed between the step (III) and the step (IV), and the step (IV) and the step (V). You may carry out between.

  Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and any procedure and conditions used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

  Although it does not specifically limit as a swelling liquid, For example, an alkaline solution, surfactant solution, etc. are mentioned, Preferably an alkaline solution is mentioned. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan. Moreover, a swelling liquid may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes.

  Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. Moreover, an oxidizing agent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizers include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan.

  As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, for example, “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. may be mentioned. Moreover, a neutralization liquid may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

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

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

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

  The conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by a technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Especially, it is preferable to form by a semi-additive method from a viewpoint of the simplicity of manufacture.

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

  Moreover, if necessary, the multilayer printed wiring board may be manufactured by repeatedly forming the insulating layer and the conductor layer in the steps (I) to (V).

[14. Semiconductor device]
A semiconductor device of the present invention includes the printed wiring board. This semiconductor device can be manufactured using a printed wiring board.

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

  The semiconductor device can be manufactured, for example, by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conduction location” is a “location where an electrical signal is transmitted on a printed wiring board”, and the location may be a surface or an embedded location. In addition, an electric circuit element made of a semiconductor can be arbitrarily used for the semiconductor chip.

  The semiconductor chip mounting method for manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Examples of mounting methods include wire bonding mounting methods, flip chip mounting methods, mounting methods using a bumpless buildup layer (BBUL), mounting methods using an anisotropic conductive film (ACF), mounting using a nonconductive film (NCF) Method, etc. Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

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

[Description of inorganic filler]
<Measuring method of average particle diameter of inorganic filler>
100 mg of inorganic filler, 0.1 g of a dispersant (“SN9228” manufactured by San Nopco) and 10 g of methyl ethyl ketone were weighed in a vial and dispersed with ultrasound for 20 minutes. Using a laser diffraction particle size distribution measuring apparatus (“SALD-2200” manufactured by Shimadzu Corporation), the particle size distribution of the inorganic filler was measured on a volume basis by a batch cell method. And the average particle diameter of the inorganic filler was computed from the obtained particle size distribution as a median diameter.

<Method for measuring specific surface area of inorganic filler>
The specific surface area of the inorganic filler was measured using a BET fully automatic specific surface area measuring device ("Macsorb HM-1210" manufactured by Mountec Co., Ltd.).

<Type of inorganic filler>
Inorganic filler 1: N-phenyl-3-aminopropyltri to 100 parts of spherical silica (“UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.078 μm, specific surface area 30.7 m ² / g) Surface treated with 2 parts of methoxysilane (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.).

Inorganic filler 2: N-phenyl-3-aminopropyltrimethoxysilane (100 parts by weight of spherical silica (“SC2500SQ” manufactured by Admatechs, average particle size 0.77 μm, specific surface area 5.9 m ² / g)) Surface treated with 1 part KBM573) manufactured by Shin-Etsu Chemical Co., Ltd.

[Example 1. Preparation of Resin Composition 1]
6 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 5 parts of naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical Corporation "YL7760", epoxy equivalent of about 238) 15 parts, cyclohexane type epoxy resin (Mitsubishi Chemical Corporation "ZX1658GS", epoxy equivalent of about 135), and phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", 2 parts of a cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution having a nonvolatile content of 30% by mass, Mw = 35000) was dissolved in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone with stirring. The resulting solution was cooled to room temperature. Thereafter, 5 parts of a naphthol-based curing agent (aromatic hydrocarbon resin represented by the formula (5). “SN395”, hydroxyl equivalent 107) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Hardener (“EXB-8000L-65TM” manufactured by DIC, approximately 220 active group equivalent, non-volatile component 65 mass% toluene: MEK 1: 1 solution) 6 parts, inorganic filler 1 50 parts, and amine-based 0.05 part of a curing accelerator (4-dimethylaminopyridine (DMAP)) was mixed and uniformly dispersed with a high-speed rotary mixer to obtain a mixture. This mixture was filtered through a cartridge filter (“SHP020” manufactured by ROKITECHNO) to obtain a resin composition 1.

[Example 2. Preparation of Resin Composition 2]
Resin composition 2 was prepared in the same manner as in Example 1 except that the types and amounts of reagents used were changed as shown in Table 1. Specific changes from Example 1 are as follows.
Instead of 2 parts of cyclohexane type epoxy resin (Mitsubishi Chemical "ZX1658GS", epoxy equivalent of about 135), bisphenol type epoxy resin (Nippon Steel Sumikin Chemical Co., Ltd. "ZX1059", epoxy equivalent of about 169, bisphenol A type and bisphenol F type) 4 parts) and 2 parts of a naphthylene ether type epoxy resin (“EXA-7311-G4” manufactured by DIC, epoxy equivalent of about 213).
Further, instead of 2 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a nonvolatile content of 30% by mass, Mw = 35000), phenoxy resin (“YL7500BH30 manufactured by Mitsubishi Chemical Corporation) was used. 2 parts of a cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution having a nonvolatile content of 30% by mass, Mw = 44000) was used.
Further, as component (B), instead of 5 parts of a naphthol-based curing agent (“NS395” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 107), a phenol-based curing agent (aromatic hydrocarbon resin represented by the formula (4)) 4 parts of “GRA13H” manufactured by Gunei Chemical Industry Co., Ltd., hydroxyl equivalent of about 75) were used.

[Comparative Example 1. Preparation of Resin Composition 3]
Resin composition 3 was prepared in the same manner as in Example 1 except that the type and amount of the reagent used were changed as shown in Table 1. Specific changes from Example 1 are as follows.
Instead of 2 parts of cyclohexane type epoxy resin (Mitsubishi Chemical "ZX1658GS", epoxy equivalent of about 135), bisphenol type epoxy resin (Nippon Steel Sumikin Chemical Co., Ltd. "ZX1059", epoxy equivalent of about 169, bisphenol A type and bisphenol F type) 4 parts) and 2 parts of a naphthylene ether type epoxy resin (“EXA-7311-G4” manufactured by DIC, epoxy equivalent of about 213).
Further, instead of 2 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a nonvolatile content of 30% by mass, Mw = 35000), phenoxy resin (“YL7500BH30 manufactured by Mitsubishi Chemical Corporation) was used. 2 parts of a cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution having a nonvolatile content of 30% by mass, Mw = 44000) was used.
Further, instead of 5 parts of a naphthol-based curing agent (“SN395” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 107), a triazine skeleton-containing cresol novolak-based curing agent (“LA-3018-50P” manufactured by DIC) ”, 10 parts of a 2-methoxypropanol solution having a hydroxyl group equivalent of about 151 and a non-volatile component of 50%.

[Comparative Example 2. Preparation of Resin Composition 4]
Resin composition 4 was prepared in the same manner as in Example 1 except that the types and amounts of reagents used were changed as shown in Table 1. Specific changes from Example 1 are as follows.
Instead of 5 parts of a naphthol-based curing agent (“SN395” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 107), a triazine skeleton-containing cresol novolac-based curing agent (“LA-3018-50P” manufactured by DIC, 4 parts of a 2-methoxypropanol solution having a hydroxyl group equivalent of about 151 and a non-volatile component of 50% was used.
Furthermore, instead of using 50 parts of the inorganic filler 1, 80 parts of the inorganic filler 2 were used.

[Comparative Example 3. Preparation of Resin Composition 5]
Resin composition 5 was prepared in the same manner as in Example 1 except that the types and amounts of reagents used were changed as shown in Table 1. Specific changes from Example 1 are as follows.
Instead of 5 parts of naphthol-based curing agent (“NS395” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 107), naphthol-based curing agent (“SN485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent of about 215) 4 And 4 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution with 50% nonvolatile component) were used.

[Comparative Example 4. Preparation of Resin Composition 6]
Resin composition 6 was prepared in the same manner as in Example 1 except that the types and amounts of reagents used were changed as shown in Table 1. Specific changes from Example 1 are as follows.
As a curing agent, 5 parts of a naphthol-based curing agent (“NS395” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 107), and an active ester curing agent (“EXB-8000L-65TM” manufactured by DIC Co., active group equivalent of about 220, In addition, a triazine skeleton-containing cresol novolac-based curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl group) as a component (E) 4 parts of 2-methoxypropanol solution having an equivalent weight of about 151 and a non-volatile component of 50% was used.
Moreover, instead of using 50 parts of the inorganic filler 1, 80 parts of the inorganic filler 2 were used.

[Composition of resin composition]
The components used for the preparation of the resin compositions 1 to 6 and their blending amounts (parts by mass of nonvolatile content) are shown in Table 1 below. Abbreviations in the table below are as follows.
Content of curing agent: Content of curing agent with respect to 100% by mass of the resin component in the resin composition.
Content of active ester curing agent: Content of active ester curing agent relative to 100% by mass of the resin component in the resin composition.
Content of inorganic filler: Content of inorganic filler with respect to 100% by mass of the nonvolatile component in the resin composition.

[Manufacture of resin sheets]
As a support, a polyethylene terephthalate film (“Lumirror R80” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C.) subjected to release treatment with an alkyd resin release agent (“AL-5” manufactured by Lintec) was prepared. .

  By applying each of the resin compositions 1 to 6 uniformly on a support with a die coater so that the thickness of the resin composition layer after drying is 10 μm, and drying at 70 to 95 ° C. for 2 minutes. Then, a resin composition layer was formed on the support. Next, a rough surface of a polypropylene film (“Alphan MA-411” manufactured by Oji F-tex Co., Ltd., thickness: 15 μm) as a protective film was bonded to the surface of the resin composition layer not bonded to the support. Thereby, the resin sheet A which has a support body, a resin composition layer, and a protective film in this order was obtained.

[Method for measuring thickness]
The thickness of a layer such as a resin composition layer was measured using a contact-type film thickness meter (“MCD-25MJ” manufactured by Mitutoyo Corporation).

[Evaluation of via holes after laser via processing]
Using the resin sheet A manufactured using each of the resin compositions 1 to 6, an insulating layer having a via hole was formed by the following method, and the via hole was evaluated.

<Preparation of sample for evaluation>
(1) Preparation of inner layer substrate:
Glass cloth base epoxy resin double-sided copper-clad laminate with copper foil layers on both sides as inner layer substrate (copper foil thickness 3 μm, substrate thickness 0.15 mm, “HL832NSF LCA” manufactured by Mitsubishi Gas Chemical Company, 255 × 340 mm size) Prepared.

(2) Lamination of resin sheet:
The protective film was peeled off from the resin sheet A to expose the resin composition layer. Using a batch type vacuum pressure laminator (manufactured by Nikko Materials, 2-stage build-up laminator “CVP700”), the resin composition layer was laminated on both surfaces of the inner layer substrate so as to be in contact with the inner layer substrate. Lamination was carried out by reducing the pressure for 30 seconds and adjusting the pressure to 13 hPa or less, followed by pressure bonding at 130 ° C. and a pressure of 0.74 MPa for 45 seconds. Next, hot pressing was performed at 120 ° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermosetting of resin composition layer:
Thereafter, the inner layer substrate on which the resin sheet is laminated is put into an oven at 100 ° C. and heated for 30 minutes, then transferred to an oven at 180 ° C. and heated for 30 minutes to thermally cure the resin composition layer, An insulating layer was formed. The thickness of the insulating layer was 10 μm. Thereby, the hardening substrate A which has a support body, an insulating layer, an inner layer board | substrate, an insulating layer, and a support body in this order was obtained.

(4) Laser via processing:
Using a CO ₂ laser processing machine ("605GTWIII (-P)" manufactured by Mitsubishi Electric Corporation), the insulating layer is irradiated with laser light through a support, and the insulating layer has a plurality of top diameters (diameters) of about 30 μm. Via holes were formed. The laser light irradiation conditions were a mask diameter of 1 mm, a pulse width of 16 μs, an energy of 0.2 mJ / shot, a shot number of 2, and a burst mode (10 kHz).

(5) Roughening treatment:
After forming a via hole in the insulating layer, the support was peeled off to obtain a via-processed substrate A having an insulating layer, an inner layer substrate, and an insulating layer in this order. Thereafter, desmear processing as roughening processing was performed on the via-processed substrate A. As the desmear treatment, the following wet desmear treatment was performed.

(Wet desmear treatment)
The via-processed substrate A is immersed in a swelling solution (“Swelling Dip Securigant P” manufactured by Atotech Japan, aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 10 minutes, and then an oxidizing agent solution (Atotech Japan). Soaked in “Concentrate Compact CP”, an aqueous solution with a potassium permanganate concentration of approximately 6% and a sodium hydroxide concentration of approximately 4% at 80 ° C. for 20 minutes, and then neutralized (“Reduction” manufactured by Atotech Japan) (Solution Securigant P ", sulfuric acid aqueous solution) at 40 ° C for 5 minutes and then dried at 80 ° C for 15 minutes. The via-processed substrate A that has been subjected to the wet desmear process is referred to as a roughened substrate A.

<Measurement of via hole dimensions before roughening>
A via-processed substrate A before roughening treatment was prepared as a sample. The via-processed substrate A was subjected to cross-sectional observation using a FIB-SEM composite apparatus (“SMI3050SE” manufactured by SII Nanotechnology). Specifically, using an FIB (focused ion beam), the insulating layer was cut out so that a cross section parallel to the thickness direction of the insulating layer and passing through the center of the via bottom of the via hole appeared. This cross section was observed by SEM (scanning electron microscope), and the top diameter and bottom diameter of the via hole were measured from the observed image.

  The above measurements were made at 5 randomly selected via holes. And the average of the measured value of the measured top diameter of the five via holes was adopted as the top diameter Lt1 of the via hole of the sample. Moreover, the average of the measured values of the measured bottom diameters of the five via holes was adopted as the bottom diameter Lb1 of the via hole of the sample.

<Measurement of via hole dimensions after roughening>
As a sample, a roughened substrate A was used instead of the via-processed substrate A. Except for the above, the same operation as the above <Measurement of via hole dimensions before roughening treatment> was performed to measure the top diameter Lt2 and bottom diameter Lb2 of the via holes after roughening treatment.

<Measurement of halo distance before roughening>
The via processed substrate A before the roughening treatment was observed with an optical microscope (“KH8700” manufactured by Hilox). Specifically, the insulating layer around the via hole was observed from above the via-processed substrate A using an optical microscope (CCD). This observation was performed with the optical microscope focused on the via top. As a result of observation, a donut-shaped haloing portion in which the insulating layer was turned white was continuously observed around the via hole from the edge of the via top of the via hole. Therefore, from the observed image, the radius of the via top of the via hole (corresponding to the inner peripheral radius of the haloing portion) r1 and the outer peripheral radius r2 of the haloing portion are measured, and the difference r2 between the radius r1 and the radius r2 -R1 was calculated as the haloing distance from the edge of the via top of the measurement point.

  The above measurements were made at 5 randomly selected via holes. And the average of the measured value of the measured haloing distance of five via holes was adopted as the haloing distance Wt from the edge of the via top of the sample.

<Dimension measurement of halo distance after roughening>
About roughening board | substrate A, cross-sectional observation was performed using FIB-SEM composite apparatus ("SMI3050SE" by SII nanotechnology company). Specifically, using an FIB (focused ion beam), the insulating layer was cut out so that a cross section parallel to the thickness direction of the insulating layer and passing through the center of the via bottom of the via hole appeared. This cross section was observed by SEM (scanning electron microscope). As a result of the observation, a gap formed by peeling the insulating layer from the copper foil layer of the inner substrate was observed continuously from the edge of the via bottom. From the observed image, the distance from the center of the via bottom to the edge of the via bottom (corresponding to the inner peripheral radius of the haloing portion) r3, and the distance from the center of the via bottom to the far end of the gap (the haloing portion) R4) was measured, and the difference r4-r3 between the distance r3 and the distance r4 was calculated as a haloing distance from the edge of the via bottom at the measurement point.

  The above measurements were made at 5 randomly selected via holes. And the average of the measured value of the measured haloing distance of five via holes was adopted as the haloing distance Wb from the edge of the via bottom of the sample.

[result]
The evaluation results of the examples and comparative examples are shown in Table 2 below.
In Table 2, the taper ratio represents a ratio “Lb1 / Lt1” between the top diameter Lt1 and the bottom diameter Lb1 of the via hole before the roughening treatment. When the taper ratio Lb1 / Lt1 is 75% or more, the via processability is determined as “good”, and when the taper ratio Lb1 / Lt1 is less than 75%, the via processability is determined as “bad”.

  In Table 2, the haloing ratio Ht before the roughening process is the haloing distance Wt from the edge of the via top before the roughening process, and the via top radius (Lt1 / 2) of the via hole before the roughening process. The ratio “Wt / (Lt1 / 2)”. When the haloing ratio Ht is 35% or less, the haloing evaluation is determined as “good”, and when the haloing ratio Ht is greater than 35%, the haloing evaluation is determined as “bad”.

  In Table 2, the haloing ratio Hb after the roughening process is the ratio of the haloing distance Wb from the edge of the via bottom after the roughening process to the radius (Lb2 / 2) of the via bottom of the via hole after the roughening process. “Wb / (Lb2 / 2)” is represented. When the haloing ratio Hb is 35% or less, the haloing evaluation is determined as “good”, and when the haloing ratio Ht is greater than 35%, the haloing evaluation is determined as “bad”.

[Consideration]
As can be seen from Table 2, in the example, a via hole having a high taper ratio can be formed in the insulating layer while forming the insulating layer using a thin resin composition layer having a thickness of 10 μm. From this result, it was confirmed that the resin composition layer of the present invention can realize an insulating layer capable of forming a well-shaped via hole even if the thickness is small.

  In addition, as can be seen from Table 2, in the examples, the haloing ratio of the halo portion generated along with the formation of the via hole is small while the insulating layer is formed using the resin composition layer as thin as 10 μm. . From this result, it was confirmed that the insulating layer capable of suppressing the haloing phenomenon can be realized even if the resin composition layer of the present invention is thin.

  In particular, as obtained in Examples 1 and 2 above, the thickness is 15 μm or less, the via hole top diameter is 35 μm or less, the via hole taper rate is 80% or more, and the via hole bottom edge An insulating layer having a haloing distance of 5 μm or less and a haloing ratio with respect to the bottom radius of the via hole of 35% or less has not been realized conventionally. Therefore, the realization of such an insulating layer has significant technical significance in recent printed wiring boards in which a thinning of the insulating layer is desired.

In Examples 1 and 2, specific results when the conductor layer is formed on the insulating layer of the roughened substrate A are not shown, but if the results of the above-described examples are seen, the insulation of the roughened substrate A is shown. It can be clearly understood by those skilled in the art that a specific printed wiring board that satisfies the requirements (i) to (v) can be obtained by forming a conductor layer on the layer.
Moreover, even if it is a case where it does not contain (D) component-(F) component in Examples 1-2, although it has a difference in a grade, it has confirmed that it results in the same result as the said Example. .

DESCRIPTION OF SYMBOLS 100 Insulating layer 100U The surface of the insulating layer opposite to a conductor layer 110 Via hole 120 Via bottom 120C Center of via bottom 130 Via top 140 Hallowing part 150 Edge of via top of via hole 160 Edge of outer side of haloing part 170 Via hole Edge of via bottom 180 Gap portion 190 End portion on outer peripheral side of gap portion 200 Inner layer substrate 210 Conductor layer (first conductor layer)
220 Second conductor layer 300 Printed wiring board Lb Bottom diameter of via hole Lt Top diameter of via hole T Thickness of insulating layer Wt Haloing distance from edge of viatop Wb Haloing distance from edge of via bottom

Claims (14)

A resin composition layer containing a resin composition and having a thickness of 15 μm or less,
The resin composition comprises (A) an epoxy resin, (B) an aromatic hydrocarbon resin containing a monocyclic or condensed ring having two or more hydroxyl groups, and (C) an inorganic material having an average particle size of 100 nm or less. A resin composition layer containing a filler. A resin composition layer containing a resin composition and having a thickness of 15 μm or less,
The resin composition is (A) an epoxy resin, (B) an aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring having two or more hydroxyl groups, and (C) a specific surface area of 15 m ² / g or more. A resin composition layer comprising an inorganic filler. The resin composition layer according to claim 1 or 2, wherein the component (B) is represented by the following formula (1) or formula (2).

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

(In Formula (2), R ^{1 to} R ⁴ each independently represents a hydrogen atom or a monovalent hydrocarbon group.) The resin composition layer according to any one of claims 1 to 3, wherein the component (B) is represented by the following formula (3) or formula (4).

(In Formula (3), n2 represents the integer of 0-6.)

(In Formula (4), R ^{1 to} R ⁴ each independently represents a hydrogen atom or a monovalent hydrocarbon group.)   (B) The resin composition layer as described in any one of Claims 1-4 whose quantity of a component is 5 mass%-50 mass% with respect to 100 mass% of resin components in a resin composition.   (C) The resin composition layer as described in any one of Claims 1-5 whose quantity of a component is 50 mass% or more with respect to 100 mass% of non-volatile components in a resin composition.   The resin composition layer according to claim 1, which is for forming an insulating layer for forming a conductor layer.   The resin composition layer according to claim 1, which is used for forming an interlayer insulating layer of a printed wiring board.   The resin composition layer according to claim 1, which is for forming an insulating layer having a via hole having a top diameter of 35 μm or less. A support;
The resin sheet containing the resin composition layer as described in any one of Claims 1-9 provided on the support body.   The printed wiring board containing the insulating layer formed with the hardened | cured material of the resin composition layer as described in any one of Claims 1-9. A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
The insulating layer has a thickness of 15 μm or less;
The insulating layer has a via hole with a top diameter of 35 μm or less,
The taper ratio of the via hole is 80% or more,
The haloing distance from the bottom edge of the via hole is 5 μm or less,
The printed wiring board whose haloing ratio with respect to the bottom radius of this via hole is 35% or less.   The printed wiring board according to claim 12, wherein a haloing ratio with respect to a bottom radius of the via hole is 5% or more.   The semiconductor device containing the printed wiring board as described in any one of Claims 11-13.

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