TWI786106B - resin composition layer - Google Patents

Abstract

The subject of this invention is to provide the resin composition layer which can suppress the haloing phenomenon (haloing phenomenon) even if thickness is thin, and can form the insulating layer of the via-hole of a favorable shape. The solution of the present invention is a resin composition layer comprising a resin composition layer having a thickness of 15 μm or less, wherein the resin composition comprises: (A) epoxy resin, (B) containing as having 2 Aromatic hydrocarbon resin having a monocyclic or condensed ring aromatic ring with more than one hydroxyl group, 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.

Description

resin composition layer

The present invention relates to a resin composition layer. Furthermore, the present invention relates to a resin sheet including the resin composition layer; and a printed wiring board and a semiconductor device including an insulating layer formed of a cured product of the resin composition layer.

In recent years, in order to achieve miniaturization of electronic equipment, further thinning of printed wiring boards has been developed. Along with this, the miniaturization of the wiring circuit of the inner layer substrate is progressing. For example, Patent Document 1 describes a resin sheet (adhesive film) that can correspond to fine wiring including a support body and a resin composition layer. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2014-36051

[Problem to be Solved by the Invention]

The inventors of the present invention have studied to reduce the thickness of the resin composition layer of the resin sheet in order to achieve further miniaturization and thinning of electronic equipment. As a result of investigation, the present inventors have found that when a thin resin composition layer is applied to an insulating layer, a halo phenomenon occurs after the formation of via holes. Here, the halo phenomenon refers to the discoloration phenomenon of the resin of the insulating layer around the via hole. Such a halo phenomenon is usually caused by deterioration of the resin around the through hole. Furthermore, it was found that if the roughening treatment is performed on the insulating layer where the halo phenomenon has occurred, the resin in the portion of the insulating layer where the halo phenomenon has occurred (hereinafter, sometimes referred to as "halo portion") will It will be corroded, and delamination will occur between the insulating layer and the inner substrate.

Furthermore, the present inventors have found that when a thin resin composition layer is applied to an insulating layer, it becomes difficult to control the shape of the via hole, and it is difficult to obtain a via hole with a good shape. Here, the "good" shape of the through hole means that the taper ratio of the through hole is close to 1. Also, the taper ratio of the through hole refers to the ratio of the bottom diameter of the through hole to the top diameter.

The above-mentioned problems are all caused by reducing the thickness of the resin composition layer, which is a novel problem that has not been known in the past. A solution to these problems is desired from the viewpoint of improving the conduction reliability between layers of a printed wiring board.

The present invention was made in view of the foregoing problems, and its object is to provide a resin composition layer capable of obtaining an insulating layer capable of suppressing the halo phenomenon and forming well-shaped through holes even if the thickness is thin; including the foregoing A resin sheet of a resin composition layer; a printed wiring board including a thin insulating layer capable of suppressing the halo phenomenon and forming well-shaped through holes; and a semiconductor device including the aforementioned printed wiring board. [Means to solve the problem]

As a result of diligent research by the present inventors in order to solve the aforementioned problems, it was found that by combining (A) an epoxy resin, (B) an aromatic hydrocarbon containing an aromatic ring as a monocyclic or condensed ring having two or more hydroxyl groups The resin and (C) a resin composition of 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 can solve the above-mentioned problems, thus completing the present invention. That is, the present invention includes the following contents.

(於式(1)中，R⁰ 各自獨立表示2價之烴基，n1表示0~6之整數)，

(於式(2)中，R¹ ~R⁴ 各自獨立表示氫原子或1價之烴基)。 　　[4]如[1]~[3]中任一項之樹脂組成物層，其中，(B)成分為以下述式(3)或式(4)所表示：

(於式(3)中，n2表示0~6之整數)，

(於式(4)中，R¹ ~R⁴ 各自獨立表示氫原子或1價之烴基)。 　　[5]如[1]~[4]中任一項之樹脂組成物層，其中，相對於樹脂組成物中之樹脂成分100質量%而言，(B)成分之量為5質量%~50質量%。 　　[6]如[1]~[5]中任一項之樹脂組成物層，其中，相對於樹脂組成物中之非揮發性成分100質量%而言，(C)成分之量為50質量%以上。 　　[7]如[1]~[6]中任一項之樹脂組成物層，其係用以形成導體層之絕緣層形成用。 　　[8]如[1]~[7]中任一項之樹脂組成物層，其係印刷配線板之層間絕緣層形成用。 　　[9]如[1]~[8]中任一項之樹脂組成物層，其係具有頂徑35μm以下之通孔的絕緣層形成用。 　　[10]一種樹脂薄片，其係包含支撐體，與 　　設置於支撐體上之如[1]~[9]中任一項之樹脂組成物層。 　　[11]一種印刷配線板，其係包含以如[1]~[9]中任一項之樹脂組成物層的硬化物所形成之絕緣層。 　　[12]一種印刷配線板，其係包含第1導體層、第2導體層、以及形成於第1導體層與第2導體層之間的絕緣層之印刷配線板， 　　絕緣層之厚度為15μm以下， 　　絕緣層具有頂徑35μm以下的通孔， 　　該通孔之漸縮比為80%以上， 　　該通孔之底部的邊緣起之暈輪距離為5μm以下， 　　相對於該通孔的底部半徑之暈輪比(halo ratio)為35%以下。 　　[13]如[12]之印刷配線板，其中，相對於該通孔的底部半徑之暈輪比為5%以上。 　　[14]一種半導體裝置，其係包含如[11]~[13]中任一項之印刷配線板。 [發明效果][1] A resin composition layer comprising a resin composition layer having a thickness of 15 μm or less, the resin composition comprising: (A) an epoxy resin, (B) a monocyclic compound having two or more hydroxyl groups Aromatic hydrocarbon resins with aromatic rings or condensed rings, and (C) inorganic fillers with an average particle diameter of 100 nm or less. [2] A resin composition layer comprising a resin composition layer having a thickness of 15 μm or less, the resin composition comprising: (A) an epoxy resin, (B) a monocyclic compound having two or more hydroxyl groups Or an aromatic hydrocarbon resin having an aromatic ring with condensed rings, and (C) an inorganic filler having a specific surface area of 15 m ² /g or more. [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 independently represents a divalent hydrocarbon group, and n represents an integer of 0 to 6),

(In formula (2), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group). [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 an integer from 0 to 6),

(In formula (4), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group). [5] The resin composition layer according to any one of [1] to [4], wherein the amount of component (B) is 5% by mass to 50% by mass relative to 100% by mass of the resin component in the resin composition. quality%. [6] The resin composition layer according to any one of [1] to [5], wherein the amount of component (C) is 50% by mass relative to 100% by mass of non-volatile components in the resin composition above. [7] The resin composition layer according to any one of [1] to [6], which is used 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 used 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 used for forming an insulating layer having a through-hole having a top diameter of 35 μm or less. [10] A resin sheet comprising a support, and a resin composition layer according to any one of [1] to [9] provided on the support. [11] A printed wiring board comprising an insulating layer formed of a cured resin composition layer according to any one of [1] to [9]. [12] A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, wherein the thickness of the insulating layer is 15 μm or less , the insulating layer has a through hole with a top diameter of 35 μm or less, the tapering ratio of the through hole is more than 80%, the halo distance from the edge of the bottom of the through hole is less than 5 μm, and the halo relative to the radius of the bottom of the through hole Wheel ratio (halo ratio) is 35% or less. [13] The printed wiring board according to [12], wherein the halo ratio with respect to the radius of the bottom of the through hole is 5% or more. [14] A semiconductor device comprising the printed wiring board according to any one of [11] to [13]. [Invention effect]

According to the present invention, there can be provided a resin composition layer capable of obtaining an insulating layer capable of suppressing the halo phenomenon and forming well-shaped through holes even if the thickness is thin; a resin sheet comprising the aforementioned resin composition layer; comprising A printed wiring board with a thin insulating layer capable of suppressing the halo phenomenon and forming well-shaped through holes; and a semiconductor device including the aforementioned printed wiring board.

Hereinafter, embodiments and examples are shown, and the present invention will be described in detail. However, the present invention is not limited to the embodiments and examples listed below, and can be implemented with arbitrarily changed within a range that does not depart from the gist of the present invention and within a range of equality.

In the following description, the "resin component" of the resin composition means 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 not more than a specific value. Also, the resin composition contained in the resin composition layer of the present invention includes: (A) epoxy resin, (B) 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. Therefore, any one of the following first resin composition and second resin composition may be included in the resin composition contained in the resin composition layer of the present invention.

The first resin composition includes: (A) epoxy resin, (B) aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring having two or more hydroxyl groups, and (C) an epoxy resin having an average particle diameter of 100 nm or less. Inorganic filler.

The second resin composition includes: (A) epoxy resin, (B) aromatic hydrocarbon resin containing an aromatic ring which is a monocyclic or condensed ring having two or more hydroxyl groups, and (C) a specific surface area of 15 m ² /g The above inorganic fillers.

By using such a resin composition layer, a thin insulating layer can be obtained. In addition, the desired effect of the present invention can be obtained in that a via hole of a good shape can be formed while suppressing the halo phenomenon in the obtained insulating layer.

[2. (A) Component: Epoxy Resin] As the epoxy resin of (A) component, for example: bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin , bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, triphenol 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 Oxygen resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin , Epoxy resins containing spiro rings, cyclohexane epoxy resins, cyclohexanedimethanol epoxy resins, naphthyl ether epoxy resins, trimethylol epoxy resins, tetraphenylethane Type epoxy resin, etc. Epoxy resins may be used alone or in combination of two or more.

The resin composition is preferably an epoxy resin containing two or more epoxy groups in one molecule as (A) epoxy resin. From the viewpoint of remarkably obtaining the desired effect of the present invention, an epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile components of the (A) epoxy resin The ratio is preferably at least 50% by mass, more preferably at least 60% by mass, and most preferably at least 70% by mass.

In the epoxy resin, there are epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins"), and epoxy resins that are solid at a temperature of 20°C (sometimes called "liquid epoxy resins"). "solid epoxy resin"). The resin composition may contain only liquid epoxy resin or only solid epoxy resin as (A) epoxy resin, but it is preferable to contain liquid epoxy resin and solid epoxy resin in combination. By using a combination of a liquid epoxy resin and a solid epoxy resin as (A) epoxy resin, the flexibility of the resin composition layer can be improved, or the breaking strength of the cured product of the resin composition layer can be improved.

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule shaped epoxy resin. Here, the "aromatic" epoxy resin means an epoxy resin having an aromatic ring in its molecule.

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, Glycidylamine-type epoxy resin, phenol novolac-type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, epoxypropylene Amino-based epoxy resins and epoxy resins with a butadiene structure, more preferably bisphenol A epoxy resins, bisphenol F epoxy resins and cyclohexane epoxy resins.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", " 825", "Epikote 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac epoxy resin) manufactured by Mitsubishi Chemical Corporation varnish type epoxy resin); "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A type epoxy resin) manufactured by Nippon Steel Sumikin Chemical Co. Bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "CELLOXIDE 2021P" (alicyclic resin with ester skeleton) manufactured by DAICEL type epoxy resin); "PB-3600" (epoxy resin with butadiene structure) manufactured by DAICEL; "ZX1658" and "ZX1658GS" (liquid 1,4-cyclo Oxypropyl cyclohexane type epoxy resin), etc. These systems may be used alone or in combination of two or more.

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

As the solid epoxy resin, bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, and dicyclopentadiene-type epoxy resins are preferable. Resin, triphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type Epoxy resin, tetraphenylethane type epoxy resin, more preferably bixylenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF type epoxy resin, and naphthyl ether type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; resin); DIC Corporation's "N-690" (cresol novolak type epoxy resin); DIC Corporation's "N-695" (cresol novolak type epoxy resin); DIC Corporation's "HP- 7200" (dicyclopentadiene epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC Corporation ", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Corporation; manufactured by Nippon Kayaku Corporation "NC7000L" (naphthol novolak type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V" (naphthalene-type epoxy resin); "ESN485" (naphthol novolak-type epoxy resin) made by Nippon Steel & Sumikin Chemical Co., Ltd.; "YX4000H", "YX4000" and "YL6121" made by Mitsubishi Chemical Corporation " (biphenyl type epoxy resin); "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; manufactured by Osaka Gas Chemicals "PG-100" and "CG-500" manufactured by Mitsubishi Chemical Corporation; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These systems may be used alone or in combination of two or more.

In the case of using liquid epoxy resin and solid epoxy resin in combination as (A) epoxy resin, the amount ratio (liquid epoxy resin: solid epoxy resin) is preferably in terms of mass ratio 1:1~1:20, more preferably 1:2~1:15, especially 1:5~1:13. When the amount ratio of 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, when used in the form of a resin sheet, moderate adhesiveness can be obtained normally. Also, when used in the form of a resin sheet, sufficient flexibility can be obtained to improve handleability. Furthermore, a cured product having sufficient breaking strength is usually obtained.

(A) The epoxy equivalent of the epoxy resin is preferably 50-5000, more preferably 50-3000, more preferably 80-2000, and still more preferably 110-1000. By setting it as this range, the crosslink density of the hardened|cured material of a resin composition layer becomes sufficient, and the insulating layer with a small surface roughness can be obtained. The epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy group. This epoxy equivalent can be measured based on JISK7236.

(A) The weight-average molecular weight (Mw) of the epoxy resin is preferably 100-5000, more preferably 250-3000, and even more preferably 400-1500 from the viewpoint of significantly 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 (A) epoxy resin in the resin composition is preferably from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, relative to 100% by mass of the resin component in the resin composition It is 10 mass % or more, more preferably 20 mass % or more, still more preferably 30 mass % or more. The upper limit of the epoxy resin content is preferably at most 90% by mass, more preferably at most 85% by mass, particularly preferably at most 80% by mass, from the viewpoint of remarkably obtaining the desired effect of the present invention.

[3. (B) Component: Aromatic hydrocarbon resin containing an aromatic ring which is a monocyclic 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 (B) component. Usually, (B) component can react with (A) epoxy resin by the hydroxyl group which an aromatic ring has, Therefore, (B) component can function as a hardening|curing agent for hardening a resin composition. And, by the action of this (B) component, the halo phenomenon can be suppressed.

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

As an example of an aromatic ring, a benzene ring, a naphthalene ring, an anthracene ring, etc. are mentioned. Moreover, the type of aromatic ring contained in 1 molecule of aromatic hydrocarbon resin may be 1 type, and may be 2 or more types.

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

(B) The number of aromatic rings having two or more hydroxyl groups per molecule of the component is usually one or more, preferably two or more, more preferably from the viewpoint of significantly obtaining the desired effect of the present invention 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 improving reactivity with epoxy resins.

As an example of a suitable (B) component, the aromatic hydrocarbon resin represented by following formula (1), and the aromatic hydrocarbon resin represented by following formula (2) are mentioned.

In formula (1), R ⁰ each independently represents a divalent hydrocarbon group. The divalent hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in the divalent hydrocarbon group is usually 1 or more, and 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 above-mentioned 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 the integer of 0-6. Among these, n1 is preferably 1 or more, more preferably 2 or more, and preferably 4 or less, more preferably 3 or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

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

In formula (2), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group. The monovalent hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Among them, an aliphatic hydrocarbon group is preferable, a saturated aliphatic hydrocarbon group is more preferable, and a chain saturated aliphatic hydrocarbon group is particularly preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. The number of carbon atoms in the monovalent hydrocarbon group is usually 1 or more, 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: hydrogen atoms; alkyl groups such as methyl, ethyl, propyl, butyl, and hexyl. When the aromatic hydrocarbon resin represented by the formula (2) is used, peeling of the halo portion due to erosion during roughening treatment can be effectively suppressed particularly.

Among them, the aromatic hydrocarbon resin represented by the following formula (3) and the aromatic hydrocarbon resin represented by the following formula (4) are mentioned as a particularly preferable aromatic hydrocarbon resin whose (B) component is. In formula (3), n2 represents an integer having the same definition as n1 in formula (1), and the preferred range is also the same. Also, in formula (4), R ¹ to R ⁴ are synonymous with R ¹ to R ⁴ in formula (2).

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

As the aromatic hydrocarbon resin of the (B) component, one type may be used alone, or two or more types may be used in combination.

The hydroxyl equivalent of the component (B) is preferably 50 g/eq or more from the viewpoint of increasing the crosslink density of the insulating layer which is a cured product of the resin composition layer, and from the viewpoint of remarkably obtaining the desired effect of the present invention. , more preferably at least 60 g/eq, more preferably at least 70 g/eq, and more preferably at most 200 g/eq, more preferably at most 150 g/eq, most preferably at most 120 g/eq. The hydroxyl equivalent is the mass of resin containing 1 equivalent of hydroxyl.

The amount of component (B) in the resin composition is preferably at least 5% by mass, more preferably at least 7% by mass, particularly preferably at least 9% by mass, relative to 100% by mass of the resin component in the resin composition , and preferably less than 50% by mass, more preferably less than 40% by mass, less than 30% by mass or less than 20% by mass. When the quantity of (B) component is the said range, halo phenomenon can be suppressed effectively.

The amount of component (B) relative to 100% by mass of (A) epoxy resin is preferably at least 5% by mass, more preferably at least 8% by mass, particularly preferably at least 10% by mass, and more preferably 100% by mass At most, more preferably at most 50% by mass, particularly preferably at most 30% by mass. When the quantity of (B) component is the said range, halo phenomenon can be suppressed effectively.

When the number of epoxy groups in (A) epoxy resin is 1, the number of hydroxyl groups in component (B) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and more preferably 2 or less, more preferably not more than 1.5, still more preferably not more than 1, and most preferably not more than 0.5. Here, "the number of epoxy groups in (A) epoxy resin" means the total value obtained by dividing the mass of non-volatile components of (A) component present in the resin composition by the epoxy equivalent. Moreover, "the number of hydroxyl groups of (B) component" means the value which divided the mass of the non-volatile component of (B) component which exists in a resin composition, and the value of the hydroxyl equivalent. When the number of epoxy groups of (A) epoxy resin is 1, the number of hydroxyl groups of (B) component is the said range, and halo phenomenon can be suppressed effectively.

[4. Component (C): Inorganic Filler Having At Least One of an Average Particle Size 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 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 which is (C)component has at least one of the average particle diameter of 100 nm or less and the specific surface area of 15 m< ² >/g or more. An insulating layer capable of forming a via hole with a good shape can be realized by using the component (C) and the component (B) in combination as an inorganic filler having at least one of the average particle diameter and the specific surface area in such a range .

As the material of the inorganic filler, an inorganic compound is used. Examples of materials for inorganic fillers include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and gibbsite , aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanic acid Bismuth, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphotungstate, etc. Among them, silicon dioxide is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as silica, spherical silica is preferable. The inorganic fillers may be used alone or in combination of two or more.

The average particle size of the component (C) is usually 100nm or less, preferably 90nm or less, more preferably 80nm from the viewpoint of reducing the thickness of the insulating layer and controlling the shape of the through hole to achieve a good shape. the following. The lower limit of the average particle diameter is not particularly limited, but is preferably 50 nm or more, 60 nm or more, or 70 nm or more. As a commercial item of the inorganic filler which has such an average particle diameter, "UFP-30" by Denki Kagaku Kogyo Co., Ltd., "UFP-40", etc. are mentioned, for example.

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

(C) The specific surface area of the component is usually at least 15m ² /g, preferably at least 20m ² /g, and most preferably at least 30m ² /g, from the viewpoint of making it easy to control the shape of the through hole to achieve a good shape. more than g. In addition, the component (C) having such a large specific surface area generally has a small particle diameter, so that the insulating layer can be thinned. The upper limit is not particularly limited, but is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area 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 surface treatment agents include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, and organosilazane compounds. , Titanate coupling agent, etc. Moreover, a surface treatment agent may be used individually by 1 type, and may use it in combination of 2 or more types arbitrarily.

Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyl Trimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) oxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM- 4803" (long-chain epoxy-type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The degree of surface treatment with a surface treatment agent preferably falls within a specific range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, for 100 parts by mass of the inorganic filler, the surface treatment is preferably performed with 0.2 to 5 parts by mass of a surface treatment agent, preferably 0.2 to 3 parts by mass of surface treatment agent, preferably 0.3 parts by mass Parts by mass to 2 parts by mass for surface treatment.

The degree of surface treatment with a surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and still more preferably 0.2 mg from the viewpoint of improving the dispersibility of the inorganic filler / ^m2 or more. On the other hand, from the viewpoint of suppressing the increase of the melt viscosity of the resin varnish and the melt viscosity in the form of flakes, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, still more preferably 0.5 mg / ^m2 or less.

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

The amount of component (C) in the resin composition is preferably at least 30% by mass relative to 100% by mass of the non-volatile components in the resin composition from the viewpoint of reducing the dielectric tangent of the insulating layer. More preferably, it is at least 35% by mass, and still more preferably at least 40% by mass. Also, in the past, when the layer of the resin composition containing such a large amount of inorganic filler is thin, it is difficult to make the shape of the through hole good. When the non-volatile component is 100% by mass and 50% by mass or more, it is particularly difficult to form through-holes with a good shape. Therefore, from the viewpoint of effectively utilizing the advantage of the present invention that it is possible to form a through hole of such a good shape that has been particularly difficult in the past, the amount of the component (C) is relatively low relative to 100% by mass of the non-volatile components in the resin composition. Preferably it is at least 50% by mass, and particularly preferably at least 54% by mass. The upper limit of the amount of the component (C) is preferably at most 90% by mass, more preferably at most 85% by mass, from the viewpoint of improving the mechanical strength of the insulating layer with respect to 100% by mass of the non-volatile components in the resin composition. , more preferably 80% by mass or less, or 75% by mass or less.

[5. (D) Component: Thermoplastic Resin] The resin composition may further contain (D) a thermoplastic resin as an optional component in addition to the above-mentioned components.

Examples of the thermoplastic resin of component (D) include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, and polyether resins. Imide resin, polyresin, polyether resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, etc. Among them, phenoxy resin is preferred from the viewpoint of remarkably obtaining the desired effect of the present invention and obtaining an insulating layer having particularly excellent adhesion to a conductive layer having a small surface roughness. Moreover, a thermoplastic resin type can be used individually by 1 type, or can use it in combination of 2 or more types.

As the phenoxy resin, for example, a resin having a structure selected from bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fennel skeleton, dicyclopentan A phenoxy resin having one or more skeletons selected from the group consisting of a diene skeleton, a norcamphene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin can also be any functional group such as phenolic hydroxyl group or epoxy group.

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

Examples of the polyvinyl acetal resin include polyvinyl formaldehyde resin and polyvinyl butyral resin, preferably polyvinyl butyral resin. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", and "Denka Butyral 6000-EP" manufactured by Denki Kagaku Kogyo Co., Ltd. ; S-LEC BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series, etc. manufactured by Sekisui Chemical Industry Co., Ltd.

Specific examples of the polyimide resin include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Chemical Co., Ltd. Specific examples of polyimide resins include linear polyimides obtained by reacting difunctional hydroxyl-terminated polybutadiene, diisocyanate compounds, and tetrabasic acid anhydrides (Japanese Patent Application Laid-Open No. 2006-37083 Polyimides described in the publication), polyimides containing a polysiloxane skeleton (polyimides described in Japanese Patent Application Publication No. 2002-12667 and Japanese Patent Application Publication No. 2000-319386), etc. imide.

Specific examples of the polyamideimide resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Corporation. Specific examples of polyamideimide resins include denatured polyamideimide resins such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd. imine.

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

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

Specific examples of the polycarbonate resin include polycarbonate "P1700" and "P3500" manufactured by Solvay Advanced Polymers, Inc., and the like.

(D) The weight average molecular weight (Mw) of the thermoplastic resin is preferably at least 8,000, more preferably at least 10,000, particularly preferably at least 20,000, and is more preferably Less than 70,000, more preferably less than 60,000, most preferably less than 50,000.

In the case of using (D) thermoplastic resin, the amount of (D) thermoplastic resin in the resin composition is relative to 100 wt. %, preferably at least 0.1% by mass, more preferably at least 0.5% by mass, more preferably at least 1% by mass, more preferably at most 15% by mass, more preferably at most 12% by mass, and more preferably at least 12% by mass. 10% by mass or less.

[6. Component (E): 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 above-mentioned components.

嗪系硬化劑、氰酸酯系硬化劑、及碳二醯亞胺系硬化劑等。又，硬化劑係可單獨使用1種，或者亦可併用2種以上。其中，就顯著得到本發明之所期望的效果之觀點而言，較佳為活性酯系硬化劑。As the hardening agent of (E) component, what has the action which hardens (A) component can be used. Examples of (E) curing agents include active ester-based curing agents, phenol-based curing agents, naphthol-based curing agents, benzo

Azine-based hardeners, cyanate-based hardeners, carbodiimide-based hardeners, etc. Moreover, as a hardening|curing agent system, 1 type may be used individually, or 2 or more types may be used together. Among these, active ester-based hardeners are preferred from the viewpoint of remarkably obtaining the desired effects of the present invention.

As the active ester-based curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, as active ester-based hardeners, esters having two or more highly reactive esters in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds, are preferred. base compound. The active ester-based hardener is preferably obtained through the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, active ester-based hardeners obtained from carboxylic acid compounds and hydroxy compounds are preferred, and active ester-based hardeners obtained from carboxylic acid compounds and phenolic compounds and/or naphthol compounds are more preferred. hardener.

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

Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methyl Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-bis Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglycerol, glucinol, dicyclopentadiene-type diphenol compounds , Phenolic novolac, etc. Here, the "dicyclopentadiene-type diphenol compound" means the diphenol compound obtained by condensing 1 molecule of dicyclopentadiene and 2 molecules of phenol.

Preferable examples of active ester-based hardeners include: active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, and active ester compounds containing acetylated phenol novolaks . Active ester compounds comprising benzoyl compounds of phenolic novolaks. Among them, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" means a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

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

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

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

嗪系硬化劑之具體例，可列舉：昭和高分子公司製之「HFB2006M」、四國化成工業公司製之「P-d」、「F-a」。as benzo

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

Examples of cyanate-based hardeners include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4' -Methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1, 3-bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl)sulfide, and bis(4-cyanate phenyl)ether, etc. Bifunctional cyanate resins; multifunctional cyanate resins derived from phenol novolaks and cresol novolacs; prepolymers in which part of these cyanate resins has been triazinated, etc. Specific examples of cyanate-based hardeners include "PT30" and "PT60" (phenol novolac type multifunctional cyanate resins), "ULL-950S" (multifunctional cyanate resins) manufactured by Lonza Japan Co., Ltd. Resin), "BA230", "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazinated to form a trimer), etc.

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

In the case of using the (E) curing agent, the amount of the (E) curing agent in the resin composition is relative to 100% by mass of the resin component in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. For example, it is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, more preferably at least 1% by mass, and preferably at most 20% by mass, more preferably at most 15% by mass, and more preferably at least 12% by mass. Mass% or less.

In addition, when using (E) curing agent, the amount of (E) curing agent in the resin composition is relative to 100% by mass of (B) component from the viewpoint of remarkably obtaining the desired effect of the present invention. In other words, preferably at least 40% by mass, more preferably at least 50% by mass, particularly preferably at least 60% by mass, and preferably at most 120% by mass, more preferably at most 100% by mass, most preferably at most 90% by mass .

Furthermore, when the epoxy group number of the (A) epoxy resin is set to 1, the active group number of the component (E) is preferably 0.1 or more, more preferably 0.2 or more, and preferably 2 or less, more preferably 1.5 or less, more preferably 1 or less, particularly preferably 0.5 or less. Here, "the active group number of (E) component" means the value which divided the mass of the non-volatile component of (E) component which exists in a resin composition by the active group equivalent value and the total sum. When the number of epoxy groups of (A) epoxy resin is 1, the active group number of (E) component falls within the said range, and the insulating layer excellent in mechanical strength can be obtained especially.

[7. Component (F): Hardening Accelerator] The resin composition may further contain (F) a hardening accelerator as an optional component in addition to the above-mentioned components.

Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among them, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferable, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are more preferable. The hardening accelerator system may be used alone or in combination of two or more.

Examples of phosphorus-based hardening accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine and tetrabutylphosphonium Decanoate.

Examples of amine-based hardening accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,- ginseng(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-bis Azabicyclo(5,4,0)-undecene.

Examples of imidazole-based hardening accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methanol Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole , 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4 -Methylimidazole, 1-cyanoethyl-2-phenylimellitic acid, imidazolium salt of 1-cyanoethyl-2-undecyl trimellitic acid, 1-cyanoethyl-2-phenyl trimellitic acid Imidazolium salt, 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-dimethylolimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3 -Dihydroxy-1H-pyrrole[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzyl imidazolium chloride, 2-methylimidazoline, 2-phenyl An imidazole compound such as imidazoline and an adduct of an imidazole compound and an epoxy resin are preferably 2-ethyl-4-methylimidazole or 1-benzyl-2-phenylimidazole.

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

基)胍、二甲基胍、二苯基胍、三甲基胍、四甲基胍、五甲基胍、1,5,7-三氮雜雙環[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮雜雙環[4.4.0]癸-5-烯、1-甲基雙胍、1-乙基雙胍、1-n-丁基雙胍、1-n-十八烷基雙胍、1,1-二甲基雙胍、1,1-二乙基雙胍、1-環己基雙胍、1-烯丙基雙胍、1-苯基雙胍、1-(o-

基)雙胍等，較佳為二氰二胺、1,5,7-三氮雜雙環[4.4.0]癸-5-烯。As the guanidine hardening accelerator, for example: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-

base) 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]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n- Octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-

base) biguanide, etc., preferably dicyandiamine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, and organocopper complexes such as copper(II) acetylacetonate , organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, manganese acetylacetonate (II) Organic manganese complexes, etc. Examples of organic metal salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

In the case of using the (F) hardening accelerator, the amount of the (F) hardening accelerator in the resin composition is relative to 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 at least 0.01% by mass, more preferably at least 0.05% by mass, more preferably at least 0.1% by mass, and preferably at most 3% by mass, more preferably at most 2% by mass, and more preferably at least 2% by mass. 1.5% by mass or less.

[8. (G) Component: Optional Additives] The resin composition may further contain arbitrary additives as optional components in addition to the above-mentioned components. Examples of such additives include: organic fillers; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; flame retardants, thickeners, defoamers, leveling agents, and adhesion imparting agents. Resin additives such as additives, colorants, etc. 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-mentioned resin composition, and has a thickness of not more than a specified value. The specific thickness of the resin composition layer is usually 15 μm or less, preferably 14 μm or less, more preferably 12 μm or less. Conventionally, the thickness of the resin composition layer for forming the insulating layer of a printed wiring board is generally thick. In contrast, the present inventors thinned the resin composition layer of a general composition as described above, and found that the halo phenomenon and the shape control of the via hole occurred in such a thin resin composition layer. Difficulty of the previously unknown subject. From the viewpoint of thinning the printed wiring board to solve such a novel problem, the resin composition layer of the present invention is provided thinner as described above. The lower limit of the thickness of the resin composition layer is arbitrary, for example, it can be 1 micrometer or more, 3 micrometers 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 resin composition layer can be obtained. In this insulating layer, well-shaped via holes can be formed. Also, when a via hole is formed in the insulating layer, the halo 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 and an inner substrate 200 obtained by curing the resin composition layer according to the first embodiment of the present invention. In this first figure, a cross section of the insulating layer 100 is shown 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 hardening the resin composition layer formed on the inner layer substrate 200 including the conductor layer 210, and the resin composition layer composed of hardened matter. In addition, a via hole 110 is formed in the insulating layer 100 . The through hole 110 is generally formed in a forward tapered shape with a larger diameter closer to the surface 100U of the insulating layer 100 on the opposite side to the conductive layer 210, and a smaller diameter closer to the conductive layer 210. Ideally, it is formed in a The insulating layer 100 has a columnar shape with a certain diameter in the thickness direction. This via hole 110 is usually formed by irradiating laser light on the surface 100U of the insulating layer 100 opposite to the conductive layer 210 to remove a part of the insulating layer 100 .

The bottom of the above-mentioned via hole 110 on the side of the conductor layer 210 is appropriately called "hole bottom", and is indicated by a symbol 120 . And, the diameter of this hole bottom 120 is called a bottom diameter Lb. Also, the opening formed on the side opposite to the conductor layer 210 of the via hole 110 is appropriately referred to as a "hole top", and is indicated by a symbol 130 . And, the diameter of this hole top 130 is called a top diameter Lt. Usually, the planar shape of the hole bottom 120 and the hole top 130 viewed from the thickness direction of the insulating layer 100 is circular, but they may also be elliptical. When the planar shape of the hole bottom 120 and the hole top 130 is an ellipse, the bottom diameter Lb and the top diameter Lt represent the major diameters of the aforementioned ellipse, respectively.

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

For example, heat the resin composition layer at 100°C for 30 minutes, and then heat at 180°C for 30 minutes to harden the insulating layer 100 obtained by shooting with a mask diameter of 1mm, pulse width of 16μs, and energy of 0.2mJ/shot. Number 2. Under the conditions of collision mode (10kHz), _CO2 laser light is irradiated to form a through hole 110 with a top diameter Lt of 30 μm±2 μm. In this case, the tapered ratio Lb/Lt of the through hole 110 can be It is preferably set at 60%~100%, more preferably at 70%~100%, and particularly preferably at 80%~100%.

The taper ratio Lb/Lt of the through hole 110 can be calculated from the bottom diameter Lb and the top diameter Lt of the through hole 110 . In addition, the bottom diameter Lb and the top diameter Lt of the through hole 110 can be obtained by using FIB (focused ion beam) to make the insulating layer 100 parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the hole bottom 120. After cutting out so that the cross section appeared, the cross section was observed and measured with an electron microscope.

FIG. 2 schematically shows a top view of the surface 100U of the insulating layer 100 obtained by curing the resin composition layer according to the first embodiment of the present invention, which is opposite to the conductor layer 210 (not shown in FIG. 2 ). As shown in FIG. 2 , if the insulating layer 100 formed with the through hole 110 is observed, a halo portion 140 where the insulating layer 100 is discolored is observed around the through hole 110 . The halo portion 140 is formed due to the halo phenomenon when the through hole 110 is formed, and is usually formed continuously from the through hole 110 . Also, in many cases, the halo portion 140 becomes a whitened portion.

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

The edge 150 of the hole top 130 corresponds to the inner peripheral edge of the halo portion 140 . The halo distance Wt from the edge 150 of the hole top 130 represents the distance from the edge 150 of the hole top 130 to the edge 160 on the outer peripheral side of the halo portion 140 . The smaller the halo distance Wt from the edge 150 of the hole top 130, the smaller the halo phenomenon can be evaluated.

For example, heat the resin composition layer at 100°C for 30 minutes, and then heat at 180°C for 30 minutes to harden the insulating layer 100 obtained by shooting with a mask diameter of 1mm, pulse width of 16μs, and energy of 0.2mJ/shot. Number 2. Under the condition of collision mode (10kHz), _CO2 laser light is irradiated to form a through hole 110 with a top diameter Lt of 30 μm±2 μm. In this case, a halo can be formed from the edge 150 of the hole top 130 The distance Wt is preferably 6 μm or less, more preferably 5 μm or less.

The halo distance Wt from the edge 150 of the hole top 130 can be determined by observation with an optical microscope.

In addition, according to the research of the present inventors, it is known that the larger the diameter of the through hole 110 is, the larger the size of the halo portion 140 tends to be. Therefore, the degree of suppression of the halo phenomenon can be evaluated by the ratio of the size of the halo portion 140 to the diameter of the through hole 110 . For example, it can be evaluated by the halo ratio Ht relative to the top radius Lt/2 of the via hole 110 . Here, the top radius Lt/2 of the through hole 110 refers to the radius of the top 130 of the through hole 110 . Also, the halo ratio Ht with respect to the top radius Lt/2 of the through hole 110 refers to a ratio obtained by dividing the halo distance Wt from the edge 150 of the hole top 130 by the top radius Lt/2 of the through hole 110 . The smaller the halo ratio Ht relative to the top radius Lt/2 of the through hole 110, the smaller the halo phenomenon can be effectively suppressed.

For example, heat the resin composition layer at 100°C for 30 minutes, and then heat at 180°C for 30 minutes to harden the insulating layer 100 obtained by shooting with a mask diameter of 1mm, pulse width of 16μs, and energy of 0.2mJ/shot. Equation 2. Under the condition of collision mode (10kHz), _CO2 laser light is irradiated to form a through hole 110 with a top diameter Lt of 30 μm±2 μm. In this case, the hole radius Lt/2 relative to the through hole 110 can be The halo ratio Ht is preferably set to be 45% or less, more preferably 40% or less, still more preferably 35% or less.

The halo ratio Ht relative to the top radius Lt/2 of the through hole 110 can be calculated from the top diameter Lt of the through hole 110 and the halo distance Wt from the edge 150 of the top 130 of the through hole 110 .

FIG. 3 is a cross-sectional view schematically showing the roughened insulating layer 100 and inner substrate 200 obtained by curing the resin composition layer according to the first embodiment of the present invention. FIG. 3 shows a cross section of the insulating layer 100 on 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. 3, if the roughening treatment is performed on the insulating layer 100 formed with the through hole 110, the insulating layer 100 of the halo portion 140 will be peeled off from the conductive layer 210 to form a Continuous gap portion 180 . The gap portion 180 is usually formed by erosion of the halo portion 140 during the roughening process.

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

The edge 170 of the hole bottom 120 corresponds to the inner peripheral edge of the gap portion 180 . Therefore, the distance Wb from the edge 170 of the hole bottom 120 to the end portion 190 on the outer peripheral side of the gap portion 180 (that is, the end portion away from the center 120C of the hole bottom 120 ) is equivalent to the in-plane distance of the gap portion 180. The dimension of the direction. Here, the in-plane direction refers to a direction perpendicular to the thickness direction of the insulating layer 100 . Also, in the following description, the aforementioned distance Wb is sometimes referred to as the halo distance Wb from the edge 170 of the bottom 120 of the through hole 110 .

The degree of inhibition of the formation of the gap portion 180 can be evaluated by the halo distance Wb from the edge 170 of the hole bottom 120 . Specifically, the smaller the halo distance Wb from the edge 170 of the hole bottom 120, the smaller the formation of the gap portion 180 can be evaluated.

Moreover, the gap portion 180 is formed by peeling off the insulating layer 100 of the halo portion 140 , so its size is related to the size of the halo phenomenon 140 . Therefore, the smaller the halo distance Wb from the edge 170 of the hole bottom 120 is, it can be evaluated that the halo phenomenon can be effectively suppressed.

For example, heat the resin composition layer at 100°C for 30 minutes, and then heat at 180°C for 30 minutes to harden the insulating layer 100 obtained by shooting with a mask diameter of 1mm, pulse width of 16μs, and energy of 0.2mJ/shot. Equation 2. Under the condition of collision mode (10kHz), CO ₂ laser light is irradiated to form a through hole 110 with a top diameter Lt of 30 μm±2 μm. Thereafter, it was immersed in a swelling solution at 60°C for 10 minutes, then immersed in an oxidizing agent solution at 80°C for 20 minutes, then immersed in a neutralizing solution at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. When such a roughening treatment is performed, the halo distance Wb from the edge 170 of the hole bottom 120 can be set to preferably 60 μm or less, more preferably 50 μm or less, most preferably 40 μm or less.

The halo distance Wb from the edge 170 of the hole bottom 120 can be displayed by using FIB (focused ion beam) to make the insulating layer 100 parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the hole bottom 120. After cutting out in the manner of , the cross-section was observed and measured with an electron microscope.

Furthermore, according to the research of the present inventors, it is known that the larger the diameter of the through hole 110 is, the larger the size of the halo portion 140 is likely to be. Therefore, the size of the gap portion 180 tends to be larger. Therefore, according to the ratio of the size of the gap portion 180 to the diameter of the through hole 110 , the degree of suppression of the halo phenomenon, and even the suppression degree of the formation of the gap portion 180 can be evaluated. For example, it can be evaluated by the halo ratio Hb relative to the bottom radius Lb/2 of the via hole 110 . Here, the bottom radius Lb/2 of the through hole 110 refers to the radius of the bottom 120 of the through hole 110 . Also, the halo ratio Hb to the bottom radius Lb/2 of the through hole 110 refers to a ratio obtained by dividing the halo distance Wb from the edge 170 of the hole bottom 120 by the bottom radius Lt/2 of the through hole 110 . The smaller the halo ratio Hb relative to the bottom radius Lb/2 of the through hole 110, the smaller the formation of the gap portion 180 can be effectively suppressed.

For example, heat the resin composition layer at 100°C for 30 minutes, and then heat at 180°C for 30 minutes to harden the insulating layer 100 obtained by shooting with a mask diameter of 1mm, pulse width of 16μs, and energy of 0.2mJ/shot. Equation 2. Under the condition of collision mode (10kHz), CO ₂ laser light is irradiated to form a through hole 110 with a top diameter Lt of 30 μm±2 μm. Thereafter, it was immersed in a swelling solution at 60°C for 10 minutes, then immersed in an oxidizing agent solution at 80°C for 20 minutes, then immersed in a neutralizing solution at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. In the case of performing such a roughening treatment, the halo ratio Hb relative to the bottom radius Lb/2 of the through hole 110 can be preferably set to be 60% or less, more preferably 50% or less, and more preferably 40%. %the following.

The halo ratio Hb relative to the bottom radius Lb/2 of the through hole 110 can be calculated from the bottom diameter Lb of the through hole 110 and the halo distance Wb from the edge 170 of the bottom 120 of the through hole 110 .

In the manufacturing process of the printed wiring board, the through hole 110 is usually formed on the surface 100U of the insulating layer 100 opposite to the conductor layer 210 without another conductor layer (not shown). Therefore, if the manufacturing process of the printed wiring board is known, the structure in which the hole bottom 120 is provided on the conductor layer 210 side and the hole top 130 is opened on the side opposite to the conductor layer 210 can be clearly recognized. However, in a completed printed wiring board, conductor layers may be provided on both sides of the insulating layer 100 . In this case, it may be difficult to distinguish the hole bottom 120 from the hole top 130 due to the positional relationship with the conductor layer. However, usually the top diameter Lt of the hole top 130 is greater than the bottom diameter Lb of the hole bottom 120 . Therefore, in the aforementioned situation, the hole bottom 120 and the hole top 130 can be distinguished by the diameter.

The inventors of the present invention presume that the resin composition layer of the present invention can obtain the above-mentioned effect structure as follows. However, the technical scope of the present invention is not limited by the structures described below.

Usually, when forming the via hole 110 , energy such as heat or light is applied to a portion of the via hole 110 where the insulating layer 100 is to be formed. Part of the energy applied at this time may be transferred to the periphery of the portion where the via hole 110 is to be formed, thereby causing oxidation of the resin. When such oxidation occurs, the resin deteriorates and appears as a halo phenomenon. However, since the component (B) is 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 of the aforementioned hydroxyl groups. Therefore, in the insulating layer 100 obtained by using the resin composition layer of the present invention, the halo phenomenon can be suppressed.

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 applied to the insulating layer 100 can be favorably transmitted to the thickness direction of the insulating layer 100 . For example, when heat energy or light energy is applied to the surface 100U of the insulating layer 100 , the energy can be transmitted to the thickness direction without significant attenuation. Therefore, the through hole 110 having a large taper ratio can be easily formed, and thus the shape of the through hole 110 can be made good.

[11. Use of resin composition layer] The resin composition layer of the present invention can be suitably used as a resin composition layer for insulation. Specifically, the resin composition layer of the present invention can be suitably used as a resin composition layer for forming an insulating layer of a printed wiring board (resin composition layer for forming an insulating layer of a printed wiring board), and furthermore, can be more suitable A resin composition layer for forming an interlayer insulating layer of a printed wiring board (resin composition layer for forming an interlayer insulating layer of a printed wiring board) was used. Also, the resin composition layer of the present invention can be suitably used as a resin composition layer for forming a conductor layer (including a rewiring layer) on an insulating layer (insulating layer forming layer for forming a conductor layer). layer with a resin composition).

In particular, the aforementioned resin composition layer is suitable as a resin composition layer for forming an insulating layer having a through hole from the viewpoint of effectively utilizing the advantage of suppressing the halo phenomenon and forming a well-shaped through hole. (Resin composition layer for forming an insulating layer having a through hole) Among them, it is particularly suitable as a resin composition layer for forming an insulating layer having a through hole having a top diameter of 35 μm or less.

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

Examples of the support include films, metal foils, and release paper made of plastic materials, preferably films and metal foils made of plastic materials.

In the case of using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate ( Acrylic polymers such as polyesters such as polycarbonate (hereinafter sometimes referred to as "PC"), polymethyl methacrylate (hereinafter sometimes referred to as "PMMA"), Cyclic polyolefin, triacetyl cellulose (hereinafter sometimes abbreviated as "TAC"), polyether sulfide (hereinafter sometimes abbreviated as "PES"), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and low-priced polyethylene terephthalate is particularly preferred.

When using a metal foil as a support body, as a metal foil, copper foil, an aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil composed of a single metal of copper can be used, and a foil composed of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can also be used .

The support may also be subjected to matte treatment, corona treatment, antistatic treatment, etc. on the surface to be bonded to the resin composition layer.

Moreover, as a support body, the support body with a release layer which has a release layer on the surface bonded to a resin composition layer can also be used. Examples of the release agent used for the release layer of the support body with release layer include those selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. More than one type of release agent. A commercially available product can also be used as the supporting body with a release layer, and examples thereof include "SK-1" and "AL -5", "AL-7"; "LUMIRROR T60" manufactured by Toray Corporation; "PUREX" manufactured by Teijin Corporation; "Unipeel" manufactured by Unitika Corporation, etc.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Moreover, 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, a resin sheet may contain arbitrary layers other than a support body and a resin composition layer as needed. As such an arbitrary layer, for example, a protective film as a 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), and the like. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. Adhesion or damage of dust and the like to the surface of the resin composition layer can be suppressed by the protective film.

The resin sheet, for example, can be prepared by preparing a resin varnish containing an organic solvent and a resin composition, and coating the resin varnish on a support using a coating device such as a die coater, and drying it to form a resin sheet. Composition layer, and manufacture.

Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, celuxoacetate, propylene glycol monomethyl ether acetate, and carbene Acetate solvents such as alcohol acetate; carbitol solvents such as celuso and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide Amide solvents such as amine (DMAc), N-methylpyrrolidone, etc. An organic solvent may be used individually by 1 type, and may use it in combination of 2 or more types.

Drying can be carried out by methods such as heating and hot air blowing. The drying conditions are not particularly limited, but 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. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, in the case of using a resin varnish containing an organic solvent of 30% by mass to 60% by mass, it can be heated at 50°C to 150°C for 3 minutes to 10 minutes. dried to form a resin composition layer.

Resin sheets can be stored by rolling them into rolls. In the case where the resin sheet has a protective film, it is usually in a usable state by peeling off the protective film.

[13. Printed Wiring Board] The printed wiring board of the present invention includes an insulating layer formed of a cured product of the thin resin composition layer as described above. In addition, this insulating layer suppresses the halo phenomenon when forming a via hole, and can form a via hole with a good shape. Therefore, by using the resin composition layer of this invention, reduction of the thickness of a printed wiring board can be achieved, suppressing the fall of the performance by a halo phenomenon or the deterioration of the shape of a via hole.

A via hole is usually provided to conduct conduction between the conductor layers provided on both sides of the insulating layer having the via hole. Therefore, the printed wiring board of the present invention generally includes a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer. In addition, a via hole is formed in the insulating layer, and the first conductive layer and the second conductive layer can be conducted through the via hole.

By utilizing the advantages of the resin composition layer that can suppress the halo phenomenon and form well-shaped through holes, it is possible to realize a specific printed wiring board that was difficult to achieve in the past. This 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, and satisfies all of the following requirements (i)~(v ). (i) The thickness of the insulating layer is 15 μm or less. (ii) The insulating layer has a through hole with a top diameter of 35 μm or less. (iii) The taper ratio of the through hole is 80% or more. (iv) The halo distance from the edge of the bottom of the through hole is 5 μm or less. (v) The halo ratio relative to the bottom radius of the through hole is 35% or less.

Hereinafter, drawings are shown, and a specific printed wiring board is demonstrated. Fig. 4 is a schematic sectional view of a printed wiring board 300 according to a second embodiment of the present invention. FIG. 4 shows a cross section of the printed wiring board 300 on a plane passing through the center 120C of the bottom 120 of the through hole 110 and parallel to the thickness direction of the insulating layer 100 . In addition, in Fig. 4, parts corresponding to the elements described in Fig. 1 to Fig. 3 are marked with the same symbols as those used in Fig. 1 to Fig. 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 a layer formed between the first conductor layer 210 and the second conductor layer 220 . The insulating layer 100 between them. A via hole 110 is formed in the insulating layer 100 . Also, usually, the second conductor layer 220 is provided after the via hole 110 is formed. Therefore, the second conductor layer 220 is usually not only formed on the surface 100U of the insulating layer 100, but also formed in the through hole 110, and the first conductor layer 210 and the second conductor layer 220 are connected through the through hole 110.

The thickness T of the insulating layer 100 included in the specific printed wiring board 300 is usually not more than 15 μm, preferably not more than 12 μm, more preferably not more than 10 μm, and most preferably not more than 5 μm. Since the specific printed wiring board 300 has such a thin insulating layer 100, it is possible to achieve thinning of the specific printed wiring board 300 itself. The lower limit of the thickness T of the insulating layer 100 is preferably at least 1 μm, more preferably at least 2 μm, particularly preferably at least 3 μm, from the viewpoint of improving the insulating performance of the insulating layer 100 . Here, the thickness T of the insulating layer 100 represents the size of the insulating layer 100 between the first conductive layer 210 and the second conductive layer 220, and does not represent the insulating layer at a position where the first conductive layer 210 or the second conductive layer 220 is absent. 100 in size. The thickness T of the insulating layer 100 is generally consistent with the distance between the main surface 210U of the first conductive layer 210 and the main surface 220D of the second conductive layer 220 facing each other across the insulating layer 100, and is the same as the depth of the through hole 110. unanimous.

The top diameter Lt of the through 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, 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, miniaturization of wiring including the first conductor layer 210 and the second conductor layer 220 can be promoted. The lower limit of the top diameter Lt of the via hole 110 is preferably at least 3 μm, more preferably at least 10 μm, and particularly preferably at least 15 μm, from the viewpoint of facilitating the formation of the via hole 110 .

The tapering ratio Lb/Lt(%) of the through hole 110 included in the insulating layer 100 included in the specific printed wiring board 300 is usually 80%~100%. The specific printed wiring board 300 includes the insulating layer 100 having the through-hole 110 having a good shape with a taper ratio Lb/Lt high in this way. Therefore, the reliability of conduction between the first conductor layer 210 and the second conductor layer 220 can generally be improved for a specific printed wiring board 300 .

The halo distance Wb from the edge 170 of the bottom 120 of the through 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 halo distance Wb from the edge 170 of the hole bottom 120 is so small that the peeling of the insulating layer 100 from the first conductor layer 210 is small. Therefore, the reliability of conduction between the first conductor layer 210 and the second conductor layer 220 can generally be improved for a specific printed wiring board 300 .

The halo ratio Hb of the insulating layer 100 included in the specific printed wiring board 300 relative to the bottom radius Lb/2 of the through hole 110 is usually 35% or less, preferably 33% or less, more preferably 31% or less . In the specific printed wiring board 300 , since the halo ratio Hb with respect to the bottom radius Lb/2 is so small, the peeling of the insulating layer 100 from the first conductor layer 210 is small. The specific printed wiring board 300 including the insulating layer 100 having such a small halo ratio Hb can generally 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 to the bottom radius Lb/2 is ideally zero, but usually 5% or more.

The number of through 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 through 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). Also, for example, it is preferable that the via holes 110 at five locations 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 from a cured product of the resin composition layer of the present invention. At this time, although the planar shapes of the hole bottom 120 and the hole top 130 of the through hole 110 formed in the insulating layer 100 are arbitrary, they are usually circular or elliptical, preferably circular.

Printed wiring boards, such as a specific printed wiring board, can be manufactured by performing the manufacturing method including the following process (I) - process (III) using a resin sheet, for example. (I) A step of laminating a resin sheet on the inner substrate so that the resin composition layer is bonded to the inner 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 substrate" used in the step (I) refers to a member that becomes a substrate of a printed wiring board. Examples of the inner layer substrate include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. Usually, it is used as an inner layer substrate with a conductive layer on one or both sides. Then, an insulating layer is formed on the conductive layer. This conductive layer may be patterned, for example, in order to function as a circuit. An inner layer substrate in which a conductor layer is formed as a circuit on one or both sides of the substrate is sometimes referred to as an "inner layer circuit board". In addition, when manufacturing a printed wiring board, an intermediate product for further forming an insulating layer and/or a conductive layer is also included in the "inner layer substrate". When the printed wiring board is a circuit board with built-in parts, an inner layer board with built-in parts can also be used.

The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by bonding the resin sheet to the inner layer substrate by heat and pressure from the support side, and bonding the resin composition layer to the inner layer substrate. As a member for thermocompression-bonding a resin sheet to an inner layer substrate (hereinafter, sometimes referred to as "thermocompression bonding member"), for example, a heated metal plate (SUS mirror plate, etc.) or a metal roll (SUS roll), etc. . In addition, it is preferable not to directly press the resin sheet with a thermocompression bonding member, but to press through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner substrate.

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

Lamination can be performed by a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum press laminator manufactured by Meiki Seisakusho Co., Ltd., a Vacuum Applicator manufactured by Nikko-Materials, and a batch-type vacuum press laminator.

After lamination, smoothing treatment of the laminated resin sheet can also be performed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressure conditions for the smoothing treatment can be set to the same conditions as the above-mentioned thermocompression bonding conditions for lamination. The smoothing process can be performed with a commercially available lamination machine. In addition, the lamination and smoothing treatment can also be performed continuously using the above-mentioned commercially available vacuum laminator.

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

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

Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before thermally curing the resin composition layer, the resin can be heated at a temperature of usually 50°C to 120°C (preferably 60°C to 115°C, more preferably 70°C to 110°C). The composition layer is usually preheated for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and more preferably 15 minutes to 100 minutes).

In step (III), via holes are formed in the insulating layer. As a method of forming a through hole, irradiation of laser light, etching, mechanical drilling, etc. are mentioned. Among them, the irradiation of laser light is generally prone to produce halo phenomenon. Therefore, from the viewpoint of effectively utilizing the effect of suppressing the halo phenomenon, irradiation with laser light is preferable.

Irradiation of this laser light 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. Examples of laser processing machines that can be used include CO ₂ laser processing machine "LC-2k212/2C" manufactured by Via Mechanics, 605GTWIII(-P) manufactured by Mitsubishi Electric Corporation, and lasers manufactured by Panasonic Welding Systems. Shot processing machines, etc.

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

In addition, the support body may be removed between step (I) and step (II), may also be removed between step (II) and step (III), or may be removed after step (III). Among them, from the viewpoint of further suppressing the occurrence of the gouged portion, it is preferably removed after the step (III) of forming the through hole in the insulating layer. For example, if the support body is peeled off after forming a via hole in an insulating layer by irradiation of laser light, it becomes easy to form a via hole of a favorable shape.

The manufacturing method of a printed wiring board may further include (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer. These steps (IV) and (V) can also be implemented according to various methods used in the manufacture of printed wiring boards. In addition, when the support is removed after step (III), the removal of the support can be carried out between step (III) and step (IV), or between step (IV) and step (V). time to implement.

Step (IV) is a step of roughening the insulating layer. The program and conditions of the roughening process are not specifically limited, Arbitrary programs and conditions used when forming the insulating layer of a printed wiring board can be employ|adopted. For example, the insulating layer may be roughened by sequentially performing swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution.

Although it does not specifically limit as a swelling liquid, For example, an alkali solution, a surfactant solution, etc. are mentioned, Preferably it is an alkali solution. As the alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. As a commercially available swelling liquid, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan Co., Ltd., etc. are mentioned, for example. In addition, one type of swelling liquid system may be used alone, or two or more types may be used in combination at an arbitrary ratio. The swelling treatment with a swelling solution is not particularly limited, for example, it can be performed by immersing the insulating layer in a swelling solution at 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution 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 dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. Moreover, the oxidizing agent system may be used individually by 1 type, and may use it in combination of 2 or more types by arbitrary ratios. Roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing solution heated to 60°C to 80°C for 10 minutes to 30 minutes. Also, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. As a commercially available oxidizing agent, the alkali permanganate solution, such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan Co., Ltd., are mentioned, for example.

The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction solution Securiganth P" manufactured by Atotech Japan. Moreover, the neutralization liquid system may be used individually by 1 type, and may use it in combination of 2 or more types by arbitrary ratios. The treatment with the neutralizing solution can be carried out by immersing the treated surface after the roughening treatment with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 minutes to 30 minutes. In terms of workability, etc., the method of immersing the object roughened 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 in the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer includes one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium the above metals. The conductor layer system can be a single metal layer or an alloy layer. The alloy layer includes, for example, a layer formed of an alloy of two or more metals selected from the above-mentioned group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper is preferred from the viewpoints of the versatility of the formation of the conductor layer, cost, and ease of patterning; Or the alloy layer of nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy. Furthermore, it is more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; or an alloy layer of nickel-chromium alloy, and particularly preferably a single metal layer of copper.

The conductor layer system can be a single-layer structure, or a multi-layer structure including two or more single metal layers or alloy layers composed 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.

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

The conductor layer can also be formed by plating. For example: semi-additive method, full-additive method, etc., can be used to plate the surface of the insulating layer to form a conductor layer with a desired wiring pattern. Among these, formation by the semi-additive method is preferable from the viewpoint of the simplicity of production.

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

Firstly, the formation of the insulating layer and the conductor layer performed in steps (I) to (V) can also be repeatedly implemented as required to manufacture a multilayer printed wiring board.

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

Examples of semiconductor devices include various semiconductor devices supplied to electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as locomotives, automobiles, trains, ships, and aircraft).

A semiconductor device can be manufactured, for example, by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conduction part" is "the part where the electrical signal is transmitted on the printed wiring board", and this place may be either the surface or the buried part. In addition, the semiconductor chip can use any circuit element using a semiconductor as a material.

There is no particular limitation on the mounting method of the semiconductor wafer in the manufacture of the semiconductor device as long as the semiconductor wafer can effectively function. Examples of mounting methods include: wire bonding mounting method, flip chip mounting method, flangeless build-up layer (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, ) installation method, etc. Here, the "mounting method of bumpless build-up layer (BBUL)" refers to "a mounting method in which a semiconductor chip is directly buried in a recess of a printed wiring board, and the semiconductor chip is connected to wiring on the printed wiring board." [Example]

Hereinafter, the present invention will be specifically described with examples shown. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" indicating amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, the operations described below were carried out under normal temperature and normal pressure unless otherwise stated.

[Description of inorganic filler] <Measuring method of average particle diameter of inorganic filler> Weigh 100 mg of inorganic filler, 0.1 g of dispersant ("SN9228" manufactured by San Nopco Co., Ltd.), and 10 g of methyl ethyl ketone in a medicine In the bottle, disperse with ultrasound for 20 minutes. The particle size distribution of the inorganic filler was measured on a volume basis using a laser diffraction particle size distribution measuring device (“SALD-2200” manufactured by Shimadzu Corporation) in a batch unit system. Next, from the obtained particle diameter distribution, the average particle diameter of the inorganic filler was calculated as the median diameter.

<Measurement method of the specific surface area of the inorganic filler> The specific surface area of the inorganic filler was measured using a BET automatic specific surface area measuring device ("Macsorb HM-1210" manufactured by Mountech).

<Types of inorganic fillers> Inorganic filler 1: For 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), the N- 2 parts of phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573) were used for surface treatment.

Inorganic filler ² : N-phenyl-3-aminopropyltrimethoxy One part of silane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573) was used for surface treatment.

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

[Example 2. Preparation of Resin Composition 2] Except for changing the type and amount of the reagent used as shown in Table 1, the same operation as in Example 1 was carried out to prepare a resin composition 2. The specific changes from Example 1 are as follows. Instead of 2 parts of cyclohexane-type epoxy resin ("ZX1658GS" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 135), bisphenol-type epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent about 169. 4 parts of bisphenol A type and bisphenol F type 1:1 mixture), and naphthyl ether type epoxy resin ("EXA-7311-G4" manufactured by DIC Corporation, epoxy equivalent about 213) 2 parts . Also, 2 parts of substituted phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of cyclohexanone: methyl ethyl ketone (MEK) with 30% by mass of non-volatile components, Mw=35000), and 2 parts of phenoxy resin ("YL7500BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of cyclohexanone: methyl ethyl ketone (MEK) of 30 mass % of non-volatile components, Mw=44000) was used. Furthermore, as (B) component substituted naphthol-based curing agent ("SN395" manufactured by Nippon Steel Sumitomo Chemical Co., Ltd., hydroxyl equivalent 107) 5 parts, a phenolic curing agent (aromatic resin represented by formula (4) Hydrocarbon resin: 4 parts of "GRA13H" produced by Qunyei Chemical Industry Co., Ltd., hydroxyl equivalent weight about 75).

[Comparative Example 1. Preparation of Resin Composition 3] Except for changing the type and amount of the reagent used as shown in Table 1, the same operation as in Example 1 was carried out to prepare a resin composition 3. The specific changes from Example 1 are as follows. Instead of 2 parts of cyclohexane-type epoxy resin ("ZX1658GS" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 135), bisphenol-type epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent about 169. 4 parts of bisphenol A type and bisphenol F type 1:1 mixture), and naphthyl ether type epoxy resin ("EXA-7311-G4" manufactured by DIC Corporation, epoxy equivalent about 213) 2 parts . Also, 2 parts of substituted phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of cyclohexanone: methyl ethyl ketone (MEK) with 30% by mass of non-volatile components, Mw=35000), and 2 parts of phenoxy resin ("YL7500BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of cyclohexanone: methyl ethyl ketone (MEK) of 30 mass % of non-volatile components, Mw=44000) was used. Furthermore, instead of 5 parts of the naphthol-based hardener ("SN395" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., hydroxyl equivalent 107), a cresol novolak-based hardener (DIC Co. "LA-3018-50P", 10 parts of 2-methoxy propanol solution with hydroxyl equivalent weight about 151 and 50% non-volatile components).

[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 the reagents used were changed as shown in Table 1. The specific changes from Example 1 are as follows. Instead of 5 parts of naphthol-based hardener ("SN395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 107), a triazine-skeleton-containing cresol novolak-based hardener ("SN395" manufactured by DIC Corporation) was used as component (E). LA-3018-50P", 4 parts of 2-methoxy propanol solution with hydroxyl equivalent weight about 151 and 50% non-volatile components. Furthermore, instead of 150 parts of inorganic fillers, 280 parts of inorganic fillers 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 the reagents used were changed as shown in Table 1. The specific changes from Example 1 are as follows. Instead of 5 parts of naphthol-based hardener ("SN395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 107), a naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Hydroxyl equivalent weight about 215) 4 parts, and triazine skeleton-containing cresol novolac hardener ("LA-3018-50P" manufactured by DIC Corporation, 2-methoxyl group with hydroxyl equivalent weight about 151, non-volatile content 50%) Propanol solution) 4 parts.

[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 the reagents used were changed as shown in Table 1. The specific changes from Example 1 are as follows. As a curing agent, a combination of 5 parts of naphthol curing agent ("SN395" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., with a hydroxyl equivalent weight of 107) and an active ester type curing agent ("EXB-8000L-65TM" manufactured by DIC Corporation, with an active group equivalent weight of approx. 220. 6 parts of toluene with 65% by mass of non-volatile components: 1:1 solution of MEK) 6 parts, and further, use a triazine skeleton-containing cresol novolac hardener (manufactured by DIC Corporation "LA- 3018-50P", 4 parts of 2-methoxypropanol solution with hydroxyl equivalent weight about 151 and 50% non-volatile components. Also, instead of 150 parts of inorganic fillers, 280 parts of inorganic fillers were used.

[Composition of Resin Composition] Components used in the preparation of resin compositions 1 to 6 and their blending amounts (parts by mass of non-volatile components) are shown in Table 1 below. The abbreviations in the following tables are as follows. Curing agent content: The content of the hardening agent relative to 100% by mass of the resin component in the resin composition. Active ester-based hardener content: The content of active ester-based hardener relative to 100% by mass of the resin component in the resin composition. Content of inorganic filler: The content of inorganic filler relative to 100% by mass of non-volatile components in the resin composition.

[Manufacture of resin sheet] A polyethylene terephthalate film ("LUMIRROR R80" manufactured by Toray Corporation) subjected to release treatment with an alkyd resin-based release agent ("AL-5" manufactured by LINTEC Corporation) was prepared as a support system. , Thickness 38μm, softening point 130℃).

Resin compositions 1 to 6 were uniformly coated on the support with a die coater so that the thickness of the dried resin composition layer became 10 μm, and dried from 70°C to 95°C for 2 minutes. Here, a resin composition layer is 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) was attached as a protective film to the surface of the resin composition layer that was 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 is obtained.

[Method for Measuring Thickness] The thickness of layers such as the resin composition layer was measured using a contact film thickness gauge ("MCD-25MJ" manufactured by Mitutoyo Corporation).

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

<Preparation of samples for evaluation> (1) Preparation of the inner substrate: As the inner substrate, a glass cloth base material with copper foil layers on both sides is prepared, and an epoxy resin double-sided copper laminated board is prepared (the thickness of the copper foil is 3 μm, and the thickness of the substrate is 0.15 mm, "HL832NSF LCA" manufactured by Mitsubishi Gas Chemical Co., Ltd., size 255×340 mm).

(2) Lamination of resin sheets: The protective film is peeled off from the resin sheet A to expose the resin composition layer. Using a batch-type vacuum pressure laminator (Nikko-Materials, two-stage build-up laminator "CVP700"), lamination is performed on both sides of the inner substrate so that the resin composition layer is in contact with the inner substrate. Floor. Lamination was carried out by pressure-bonding at 130° C. and a pressure of 0.74 MPa for 45 seconds after adjusting the air pressure to 13 hPa or less by depressurizing for 30 seconds. Next, hot pressing was performed at 120° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermal hardening of the resin composition layer: After that, put the inner layer substrate laminated with the resin sheet into an oven at 100°C for 30 minutes to heat, and then move to an oven at 180°C for 30 minutes to heat to make the resin composition The material layer is thermally hardened to form an insulating layer. The thickness of the insulating layer was 10 μm. Thereby, the hardened board|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 is obtained.

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

(5) Roughening treatment: After the through holes are formed in the insulating layer, the support body is peeled off to obtain a drilled substrate A having an insulating layer, an inner layer substrate and an insulating layer in this order. Thereafter, the desmearing process is performed on the drilled substrate A as a roughening process. As the desmearing treatment, the following wet desmearing treatment was implemented.

(Wet desmearing treatment) The drilled substrate A was immersed in a swelling solution ("Swelling Dip Securiganth P" manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 10 Minutes, followed by immersion in an oxidizing agent solution ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., an aqueous solution with a concentration of potassium permanganate of about 6% and a concentration of sodium hydroxide of about 4%) at 80°C for 20 minutes, and then at 40°C After being immersed in a neutralizing solution ("Reduction solution Securiganth P" manufactured by Atotech Japan, sulfuric acid aqueous solution) for 5 minutes, drying was performed at 80° C. for 15 minutes. The drilled substrate A subjected to the wet desmear treatment is referred to as a roughened substrate A.

<Measurement of dimensions of through-holes before roughening treatment> A drilled substrate A before roughening treatment was prepared as a sample. With respect to this drilled substrate A, a cross-sectional observation was performed using a FIB-SEM composite device ("SMI3050SE" manufactured by SII Nano Technology Co., Ltd.). Specifically, the insulating layer was chipped using FIB (focused ion beam) so that a cross section parallel to the thickness direction of the insulating layer and passing through the center of the bottom of the via hole appeared. The cross section was observed by SEM (scanning electron microscope), and the top diameter and bottom diameter of the through hole were measured from the observed image.

The aforementioned measurement was carried out in through-holes at 5 locations selected at random. And, the average of the measured values of the top diameters of the through-holes at five measured locations was adopted as the top diameter Lt1 of the through-holes of the sample. In addition, the average of the measured values of the bottom diameters of the through-holes at five locations measured was adopted as the bottom diameter Lb1 of the through-holes of the sample.

<Measurement of dimensions of through-holes after roughening treatment> Instead of the drilled substrate A, a roughened substrate A was used as a sample. Except for the above matters, the same operation as the aforementioned <measurement of the size of the via hole before roughening treatment> was performed, and the top diameter Lt2 and the bottom diameter Lb2 of the via hole after the roughening treatment were measured.

<Measurement of halo distance before roughening treatment> The drilled substrate A before the roughening treatment was observed with an optical microscope ("KH8700" manufactured by Hirox Corporation). Specifically, the insulating layer around the through hole was observed from the upper portion of the drilled substrate A using an optical microscope (CCD). This observation was performed by focusing an optical microscope on the through hole. As a result of the observation, around the via hole, a donut-shaped halo portion continued from the edge of the hole top of the via hole, and the insulating layer became white. Therefore, from the observed image, measure the radius r1 of the top of the through hole (equivalent to the radius of the inner circumference of the halo portion) r1, and the radius r2 of the outer circumference of the halo portion, and calculate the difference between the radius r1 and the radius r2 r2- r1 was calculated as the halo distance from the edge of the top of the hole at the measurement point.

The above-mentioned measurement was carried out with through-holes at 5 locations selected at random. And, the average value of the measured values of the halo distances of the through-holes measured at five locations was adopted as the halo distance Wt from the edge of the hole top of the sample.

<Dimensional Measurement of Halo Distance After Roughening Treatment> For the roughened substrate A, cross-sectional observation was performed using a FIB-SEM composite device ("SMI3050SE" manufactured by SII NanoTechnology Co., Ltd.). Specifically, the insulating layer was chipped using FIB (focused ion beam) so that a cross section parallel to the thickness direction of the insulating layer and passing through the center of the bottom of the via hole appeared. This 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 bottom of the hole. From the observed image, measure the distance from the center of the hole bottom to the edge of the hole bottom (equivalent to the inner circumference radius of the halo part) r3, and the distance from the center of the hole bottom to the end of the side away from the aforementioned gap ( Corresponding to the halo portion outer peripheral radius) r4, the difference r4-r3 between the distance r3 and the distance r4 is calculated as the halo distance from the edge of the hole bottom at the measurement point.

The above-mentioned measurement was carried out with through-holes at 5 locations selected at random. And, the average value of the measured values of the halo distances of the through-holes measured at five locations was adopted as the halo distance Wb from the edge of the hole bottom of the sample.

[Results] The evaluation results of the aforementioned Examples and Comparative Examples are shown in Table 2 below. In Table 2, the tapering ratio represents the ratio "Lb1/Lt1" of the top diameter Lt1 to the bottom diameter Lb1 of the via hole before the roughening treatment. If the tapering ratio Lb1/Lt1 is 75% or more, the drilling workability is judged as "good", and if the tapering ratio Lb1/Lt1 is less than 75%, the drilling workability is judged as "poor" .

In Table 2, the halo ratio Ht before the roughening treatment represents the halo distance Wt from the edge of the top of the hole before the roughening treatment, and the radius of the top of the via hole before the roughening treatment (Lt1/2) The ratio "Wt/(Lt1/2)". If the halo ratio Ht is less than 35%, the halo evaluation is judged as "good", and if the halo ratio Ht is greater than 35%, the halo evaluation is judged as "bad".

In Table 2, the halo ratio Hb after roughening represents the halo distance Wb from the edge of the bottom of the hole after roughening, and the radius of the bottom of the through hole after roughening (Lb2/2) The ratio "Wb/(Lb2/2)". If the halo ratio Hb is less than 35%, the halo evaluation is judged as "good", and if the halo ratio Ht is greater than 35%, the halo evaluation is judged as "bad".

[Discussion] As can be seen from Table 2, in Examples, since the insulating layer was formed using a thin resin composition layer with a thickness of 10 μm, a via hole with a large tapering ratio could be formed in the insulating layer. From these results, it was confirmed that the resin composition layer of the present invention can realize an insulating layer in which a via hole of a good shape can be formed even if the thickness is thin.

Also, as can be seen from Table 2, in Examples, the insulating layer was formed using a thin resin composition layer with a thickness of 10 μm, and the halo ratio of the halo portion generated with the formation of the via hole was small. From these results, it was confirmed that the resin composition layer of the present invention can realize an insulating layer capable of suppressing the halo phenomenon even if the thickness is thin.

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

In Examples 1 to 2, although the specific results of the formation of the conductive layer on the insulating layer of the roughened substrate A are not shown, if the results of the above-mentioned examples are observed, it is found that by roughening the insulating layer of the substrate A The fact that the formation of the conductor layer can obtain a specific printed wiring board that satisfies the requirements (i) to (v) is clearly understood by the supplier. Also, in Examples 1 to 2, it was confirmed that even in the case of not containing (D) component to (F) component, although there was a difference in degree, the same result as in the above-mentioned examples was also returned.

100‧‧‧Insulating layer 100U‧‧‧The surface of the insulating layer opposite to the conductor layer 110‧‧‧Through hole 120‧‧‧The bottom of the hole 120C‧‧‧The center of the bottom of the hole 130‧‧‧The top of the hole 140‧‧‧ Halo part 150‧‧‧Edge of the top of the through hole 160‧‧‧Edge of the outer peripheral side of the halo part 170‧‧‧Edge of the bottom of the through hole 180‧‧‧Gap 190‧‧‧Gap Outer peripheral end 200‧‧‧inner substrate 210‧‧‧conductor layer (first conductor layer) 220‧‧‧second conductor layer 300‧‧‧printed wiring board Lb‧‧‧bottom diameter Lt of through hole ‧‧‧Top diameter T‧‧‧Thickness of insulating layer Wt‧‧‧Halo distance from edge of hole top Wb‧‧‧Halo distance from edge of hole bottom

[Fig. 1] Fig. 1 is a cross-sectional view schematically showing an insulating layer and an inner substrate obtained by curing the resin composition layer according to the first embodiment of the present invention. [Fig. 2] Fig. 2 is a plan view schematically showing the surface opposite to the conductor layer of the insulating layer obtained by curing the resin composition layer according to the first embodiment of the present invention. [Fig. 3] Fig. 3 schematically shows a cross-sectional view of an insulating layer and an inner substrate after roughening treatment obtained by hardening the resin composition layer according to the first embodiment of the present invention. [Fig. 4] Fig. 4 is a schematic sectional view of a printed wiring board according to a second embodiment of the present invention.

100‧‧‧Insulation layer

100U‧‧‧The surface of the insulating layer opposite to the conductor layer

110‧‧‧through hole

120‧‧‧hole bottom

120C‧‧‧Center of hole bottom

130‧‧‧hole top

140‧‧‧Halo department

150‧‧‧edge of hole top

200‧‧‧Inner substrate

210‧‧‧conductor layer (first conductor layer)

Lb‧‧‧Bottom diameter of through hole

Lt‧‧‧Top diameter of through hole

Wt‧‧‧halo distance from the edge of the hole top

Claims (13)

A resin composition layer comprising a resin composition layer having a thickness of 15 μm or less, the resin composition comprising: (A) an epoxy resin, (B) an aromatic ring containing an aromatic ring as a single ring or a condensed ring Hydrocarbon resins, (C) inorganic fillers with an average particle size of 100 nm or less, and (E) hardeners other than component (B) containing active ester-based hardeners; the aforementioned aromatic rings have two or more aromatic rings The amount of the hydroxyl group in the resin composition is 50 mass % or more with respect to 100 mass % of non-volatile components in the resin composition. A resin composition layer comprising a resin composition layer having a thickness of 15 μm or less, the resin composition comprising: (A) an epoxy resin, (B) an aromatic ring containing an aromatic ring as a single ring or a condensed ring Hydrocarbon resins, (C) inorganic fillers with a specific surface area of 15 m ² /g or more, and (E) hardeners other than component (B) containing active ester-based hardeners; the aforementioned aromatic rings have 2 The number of hydroxyl groups is more than 50 mass % with respect to 100 mass % of non-volatile components in a resin composition, and the quantity of (C) component is 50 mass % or more. The resin composition layer as claimed in claim 1 or 2, wherein the component (B) is represented by the following formula (1) or formula (2):

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

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

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

(In formula (4), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group). The resin composition layer according to claim 1 or 2, wherein the amount of component (B) is 5% by mass to 50% by mass relative to 100% by mass of the resin component in the resin composition. The resin composition layer according to Claim 1 or 2, which is used for forming an insulating layer for forming a conductor layer. The resin composition layer according to Claim 1 or 2, which is used for forming an interlayer insulating layer of a printed wiring board. The resin composition layer according to claim 1 or 2, which is used for forming an insulating layer having a through hole with a top diameter of 35 μm or less. A resin sheet comprising A support body, and the resin composition layer according to any one of claims 1 to 8 arranged on the support body. A printed wiring board comprising an insulating layer formed of a hardened resin composition layer according to any one of claims 1 to 8. A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, the thickness of the insulating layer being 15 μm or less, the insulating layer A through hole with a top diameter of 35 μm or less, a taper ratio of the through hole of 80% or more, a halo distance from the edge of the bottom of the through hole of 5 μm or less, and a halo ratio relative to the radius of the bottom of the through hole ( halo ratio) is below 35%. The printed wiring board according to claim 11, wherein the halo ratio with respect to the bottom radius of the through hole is 5% or more. A semiconductor device comprising the printed wiring board according to any one of Claims 10-12.

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