JP2019119819A - Resin composition - Google Patents

Abstract

To provide a resin composition capable of providing a cured article low in dielectric loss tangent and excellent in smear removal property, a resin sheet having a resin composition layer containing the resin composition, a printed wiring board containing an insulation layer formed by a cured article of the resin composition, and a semiconductor device containing the cured article of the resin composition.SOLUTION: There is provided a resin composition containing (A) an aromatic hydrocarbon resin containing an aromatic ring as a single ring or a condensed ring, and having 2 or more groups containing an oxygen atom bound to the aromatic ring per 1 aromatic ring, and (B) an active ester-based curing agent.SELECTED DRAWING: None

Description

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

  In recent years, miniaturization and higher performance of electronic devices progress, and in multilayer printed wiring boards, build-up layers are multilayered, and miniaturization and densification of wiring are required, and dielectric loss is required to reduce transmission loss. There is a need for insulating materials with low tangent.

  For example, Patent Document 1 shows a resin composition containing (A) epoxy resin, (B) active ester compound, and (C) smear suppressing component, and the non-volatile component of the resin composition is 100% by mass. In some cases, the resin composition in which the (C) smear suppression component is 0.001 to 10% by mass is described.

JP, 2014-5464, A

  When the insulating layer of the multilayer printed wiring board is drilled, smear (resin residue) is generated in the via hole, and it is required to remove the smear in the roughening treatment step. However, according to the findings of the present inventors, when a multilayer printed wiring board was manufactured using a low dielectric loss tangent resin composition containing an active ester compound, the inside of the via hole is roughened after the hole drilling processing of the insulating layer. However, it has been found that the removal of smear (resin residue) in the via hole may be insufficient, and the smaller the via hole, the harder it becomes.

  Therefore, the problem to be solved by the present invention is a resin composition capable of obtaining a cured product having a low dielectric loss tangent and excellent smear removability; a resin sheet having a resin composition layer containing the above resin composition It is an object of the present invention to provide a printed wiring board including an insulating layer formed of a cured product of the above resin composition; and a semiconductor device including the cured product of the above resin composition.

As a result of intensive studies to solve the above problems, the present inventor (A) contains an aromatic ring as a single ring or a fused ring, and contains an oxygen atom bonded to the aromatic ring per aromatic ring. The inventors have found that the above-mentioned problems can be solved by a resin composition containing an aromatic hydrocarbon resin having two or more groups and an (B) active ester-based curing agent in combination, and the present invention has been completed.
That is, the present invention includes the following contents.

（式（１）中、Ｒ^１１はそれぞれ独立に１価の基を表す。）
［３］ （Ａ）成分が、下記式（２）で表される構造を有する、［１］又は［２］に記載の樹脂組成物。

（式（２）中、Ｒ^２１は、それぞれ独立に１価の基を表す。）
［４］ （Ａ）成分が、下記式（３）で表される、［１］又は［２］に記載の樹脂組成物。

（式（３）中、Ｒ^３１は、それぞれ独立に１価の基を表し、Ｒ^３２はそれぞれ独立に２価の炭化水素基を表す。ｎ３は、０〜１０の整数を表す。）
［５］ （Ａ）成分が、下記式（６）で表される、［１］〜［４］のいずれかに記載の樹脂組成物。

（式（６）中、Ｒ^６１は、それぞれ独立に１価の基を表す。ｎ６は０〜１０の整数を表す。）
［６］ 芳香環に結合する酸素原子を含有する基が、エポキシアルキレンオキシ基、アルコキシ基、又は水酸基である、［１］〜［５］のいずれかに記載の樹脂組成物。
［７］ さらに、（Ｃ）エポキシ樹脂を含有する、［１］〜［６］のいずれかに記載の樹脂組成物。
［８］ （Ａ）成分の含有量が、（Ａ）成分及び（Ｃ）成分の合計含有量を１００質量％とした場合、５質量％以上５０質量％以下である、［７］に記載の樹脂組成物。
［９］ （Ｂ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、１質量％以上３０質量％以下である、［１］〜［８］のいずれかに記載の樹脂組成物。
［１０］ さらに、（Ｄ）無機充填材を含有する、［１］〜［９］のいずれかに記載の樹脂組成物。
［１１］ （Ｄ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、５０質量％以上である、［１０］に記載の樹脂組成物。
［１２］ 多層プリント配線板の絶縁層形成用の樹脂組成物である、［１］〜［１１］のいずれかに記載の樹脂組成物。
［１３］ トップ径が３５μｍ以下のビアホールを有する絶縁層形成用の樹脂組成物である、［１］〜［１２］のいずれかに記載の樹脂組成物。
［１４］ 絶縁層の厚み（μｍ）とトップ径（μｍ）とのアスペクト比（絶縁層の厚み／トップ径）が０．５以上のビアホールを有する絶縁層形成用の樹脂組成物である、［１］〜［１３］のいずれかに記載の樹脂組成物。
［１５］ 支持体と、該支持体上に設けられた、［１］〜［１４］のいずれかに記載の樹脂組成物を含む樹脂組成物層とを含む、樹脂シート。
［１６］ 樹脂組成物層の厚みが、２０μｍ以下である、［１５］に記載の樹脂シート。
［１７］ ［１］〜［１４］のいずれかに記載の樹脂組成物の硬化物により形成された絶縁層を含む、プリント配線板。
［１８］ ［１７］に記載のプリント配線板を含む、半導体装置。 [1] (A) An aromatic hydrocarbon resin containing an aromatic ring as a single ring or a fused ring, and having two or more groups containing an oxygen atom bonded to the aromatic ring per one aromatic ring, and (B) A resin composition containing an active ester curing agent.
[2] The resin composition according to [1], wherein the component (A) has a structure represented by the following formula (1).

(In formula (1), each R ¹¹ independently represents a monovalent group.)
[3] The resin composition according to [1] or [2], wherein the component (A) has a structure represented by the following formula (2).

(In formula (2), each R ²¹ independently represents a monovalent group.)
[4] The resin composition according to [1] or [2], wherein the component (A) is represented by the following formula (3).

(In formula (3), R ³¹ each independently represents a monovalent group, R ³² each independently represents a divalent hydrocarbon group. N 3 represents an integer of 0 to 10.)
[5] The resin composition according to any one of [1] to [4], wherein the component (A) is represented by the following formula (6).

(In formula (6), each R ⁶¹ independently represents a monovalent group. N 6 represents an integer of 0 to 10.)
[6] The resin composition according to any one of [1] to [5], wherein the group containing an oxygen atom bonded to an aromatic ring is an epoxy alkyleneoxy group, an alkoxy group, or a hydroxyl group.
[7] The resin composition according to any one of [1] to [6], further comprising (C) an epoxy resin.
[8] The component according to [7], wherein the content of component (A) is 5% by mass or more and 50% by mass or less, when the total content of component (A) and component (C) is 100% by mass. Resin composition.
[9] The content of the component (B) according to any one of [1] to [8], which is 1% by mass or more and 30% by mass or less when the nonvolatile component in the resin composition is 100% by mass. Resin composition.
[10] The resin composition according to any one of [1] to [9], further comprising (D) an inorganic filler.
[11] The resin composition according to [10], wherein the content of the component (D) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass.
[12] The resin composition according to any one of [1] to [11], which is a resin composition for forming an insulating layer of a multilayer printed wiring board.
[13] The resin composition according to any one of [1] to [12], which is a resin composition for forming an insulating layer having a via hole having a top diameter of 35 μm or less.
[14] A resin composition for forming an insulating layer having a via hole having an aspect ratio (thickness of insulating layer / top diameter) of thickness (μm) of insulating layer to top diameter (μm) of 0.5 or more [ The resin composition in any one of [1]-[13].
[15] A resin sheet, comprising: a support; and a resin composition layer provided on the support and including the resin composition according to any one of [1] to [14].
[16] The resin sheet according to [15], wherein the thickness of the resin composition layer is 20 μm or less.
[17] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [14].
[18] A semiconductor device comprising the printed wiring board according to [17].

  According to the present invention, a resin composition capable of obtaining a cured product having a low dielectric loss tangent and excellent smear removability; a resin sheet having a resin composition layer containing the above resin composition; the above resin composition A printed wiring board including an insulating layer formed of the cured product of the above; and a semiconductor device including the cured product of the resin composition described above.

  Hereinafter, the present invention will be described in detail by way of embodiments and exemplifications. However, the present invention is not limited to the embodiments and exemplifications listed below, and can be implemented with arbitrary modifications without departing from the scope of the claims of the present invention and the equivalents thereof.

[Resin composition]
The resin composition of the present invention contains (A) an aromatic ring as a single ring or a fused ring, and an aromatic group having two or more groups containing an oxygen atom bonded to the aromatic ring per one aromatic ring. It contains a hydrocarbon resin and (B) an active ester-based curing agent. By using such a resin composition layer, it is possible to obtain the desired effect of the present invention that a cured product having a low dielectric loss tangent and excellent smear removability can be obtained. Therefore, the hardened | cured material of this resin composition can be preferably used as an insulating layer of a multilayer printed wiring board taking advantage of the outstanding characteristic.

  Moreover, the said resin composition may be combined with the (A)-(B) component, and may further contain arbitrary components. Optional components include, for example, (C) epoxy resin, (D) inorganic filler, (E) curing agent, (F) thermoplastic resin, (G) curing accelerator, and (H) other additives, etc. Can be mentioned. Hereinafter, each component contained in the resin composition of this invention is demonstrated in detail.

<(A) An aromatic hydrocarbon resin containing an aromatic ring as a single ring or a fused ring, and having two or more groups containing an oxygen atom bonded to the aromatic ring per one aromatic ring>
An aromatic hydrocarbon resin containing (A) an aromatic ring as a single ring or a condensed ring, and having two or more groups containing an oxygen atom bonded to the aromatic ring per one aromatic ring. Contains The aromatic ring is easily oxidized by donating an oxygen atom in a group containing an oxygen atom bonded to the aromatic ring. Moreover, since this group is contained 2 or more per aromatic ring, the aromatic ring is more easily oxidized. Therefore, since the component (A) is easily oxidized, the smear removability of the cured product of the resin composition can be improved.

  Here, the term "aromatic ring" includes both an aromatic ring as a single ring such as a benzene ring and an aromatic ring as a fused ring such as a naphthalene ring. The number of carbon atoms per aromatic ring contained in the component (A) is preferably 6 or more, preferably 10 or more, from the viewpoint of achieving the desired effects of the present invention. Is 20 or less, more preferably 14 or less.

  Examples of the aromatic ring include a single ring such as a benzene ring and a biphenyl ring; a fused ring such as a naphthalene ring and an anthracene ring; and the like, and a fused ring is preferable from the viewpoint of improving smear removability. Further, the number of types of aromatic rings contained in one aromatic hydrocarbon resin molecule may be one, or two or more.

  At least one of the aromatic rings contained in the aromatic hydrocarbon resin as the component (A) has two or more groups each containing an oxygen atom bonded to the aromatic ring. The number of groups containing an oxygen atom bonded to an aromatic ring per aromatic ring is preferably 4 or less, more preferably 3 or less, particularly preferably from the viewpoint of achieving the desired effects of the present invention. There are two.

  The number of aromatic rings having a group containing an oxygen atom bonded to two or more of the above aromatic rings per molecule of component (A) is usually one or more, and the desired effect of the present invention is remarkable. From the viewpoint of obtaining, it is preferably 2 or more, more preferably 3 or more. Although the upper limit is not particularly limited, it is preferably 6 or less, more preferably 5 or less from the viewpoint of suppressing steric hindrance and enhancing the reactivity with the epoxy resin.

  As an example of the group containing the oxygen atom couple | bonded with an aromatic ring, an epoxy alkylene oxy group, an alkoxy group, a hydroxyl group etc. are mentioned. The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and most preferably an alkoxy group having 1 to 3 carbon atoms from the viewpoint of obtaining the desired effects of the present invention. A group is more preferable, and an alkoxy group having 1 carbon atom (methoxy group) is particularly preferable. The alkylene group in the epoxy alkyleneoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms, from the viewpoint of achieving the desired effects of the present invention. And 1 carbon atom (glycidyl ether group) is particularly preferable.

（式（１）中、Ｒ^１１はそれぞれ独立に１価の基を表す。） As the component (A), for example, an aromatic hydrocarbon resin having a structure represented by the following formula (1) is preferable.

(In formula (1), each R ¹¹ independently represents a monovalent group.)

In formula (1), each R ¹¹ independently represents a monovalent group. A group containing an oxygen atom bonded to an aromatic ring is “—OR ¹¹ ” in formula (1). Examples of the monovalent group include hydrogen atoms; and monovalent organic groups such as an epoxy alkyl group and an alkyl group which may be substituted. The number of carbon atoms of the alkyl group and the alkyl group in the epoxyalkyl group is the same as the number of carbon atoms of the alkoxy group described above. As a substituent of an alkyl group, a halogen atom, a hydroxyl group, an epoxy group etc. are mentioned, for example. Also, two or more substituents may combine to form a ring. Among them, from the viewpoint of improving smear removability, R ¹¹ is preferably an epoxyalkyl group or a hydrogen atom, more preferably an epoxyalkyl group, and still more preferably a glycidyl group.

（式（２）中、Ｒ^２１は、それぞれ独立に１価の基を表す。） The structure represented by Formula (1) is preferably represented by the following Formula (2).

(In formula (2), each R ²¹ independently represents a monovalent group.)

In Formula (2), R ²¹ represents a monovalent group, and R ²¹ has the same meaning as R ¹¹ in Formula (1). As in the case of Formula (2), when a group containing an oxygen atom bonded to an aromatic ring is bonded to the 1- and 6-positions of the naphthalene ring, it is possible to further improve the smear removability.

（式（３）中、Ｒ^３１は、それぞれ独立に１価の基を表し、Ｒ^３２はそれぞれ独立に２価の炭化水素基を表す。ｎ３は、０〜１０の整数を表す。） As the component (A), for example, an aromatic hydrocarbon resin represented by the following formula (3) is preferable.

(In formula (3), R ³¹ each independently represents a monovalent group, R ³² each independently represents a divalent hydrocarbon group. N 3 represents an integer of 0 to 10.)

In Formula (3), R ³¹ represents a monovalent group, and R ³¹ has the same meaning as R ¹¹ in Formula (1).

In Formula (3), R ³² represents a divalent hydrocarbon group. The divalent hydrocarbon group may be an aliphatic hydrocarbon group, may be an aromatic hydrocarbon group, or may be a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. . The carbon atom number of the divalent hydrocarbon group is usually 1 or more, and preferably 3 or more, more preferably 5 or more, and still more preferably 7 or more from the viewpoint of obtaining the desired effects of the present invention remarkably. The upper limit of the number of carbon atoms may be preferably 20 or less, 15 or less, or 10 or less from the viewpoint of obtaining the desired effects of the present invention remarkably.

Specific examples of R ³² include the following divalent hydrocarbon groups.

  In Formula (3), n3 represents the integer of 0-10. From the viewpoint of obtaining the desired effects of the present invention remarkably, n3 is preferably 0 or more, more preferably 2 or more, still more preferably 3 or more, preferably 10 or less, more preferably 5 or less.

（式（４）中、Ｒ^４１は、それぞれ独立に１価の基を表し、Ｒ^４２はそれぞれ独立にアルキレン基を表す。ｎ４は０〜１０の整数を表す。） The aromatic hydrocarbon resin represented by the formula (3) is preferably an aromatic hydrocarbon resin represented by the following formula (4).

(In formula (4), R ⁴¹ each independently represents a monovalent group, and R ⁴² each independently represents an alkylene group. N 4 represents an integer of 0 to 10.)

In Formula (4), R ⁴¹ represents a monovalent group, and R ⁴¹ has the same meaning as R ¹¹ in Formula (1).

In formula (4), R ⁴² represents an alkylene group. The number of carbon atoms of the alkylene group is preferably 10 or less, more preferably 6 or less, still more preferably 3 or less, and the lower limit may be 1 or more. Among them, a methylene group and a dimethylethylene group are preferable from the viewpoint of obtaining the desired effects of the present invention remarkably.

  In Formula (4), n4 represents an integer of 0 to 10, and n4 has the same meaning as n3 in Formula (3).

A phenylene group in the formula (4) is preferably combined with an alkylene group represented by two R ⁴² in 1 and 4 positions.

（式（５）中、Ｒ^５１は、それぞれ独立に１価の基を表し、Ｒ^５２はそれぞれ独立にアルキレン基を表す。ｎ５は０〜１０の整数を表す。） The aromatic hydrocarbon resin represented by the formula (4) is preferably an aromatic hydrocarbon resin represented by the following formula (5).

(In formula (5), R ⁵¹ each independently represents a monovalent group, and R ⁵² each independently represents an alkylene group. N 5 represents an integer of 0 to 10.)

In Formula (5), R ⁵¹ represents a monovalent group, and R ⁵¹ has the same meaning as R ¹¹ in Formula (1).

In formula (5), R ⁵² represents an alkylene group. R ⁵² has the same meaning as R ⁴² in formula (4).

  In Formula (5), n5 represents the integer of 0-10, n5 is synonymous with n3 in Formula (3).

（式（６）中、Ｒ^６１は、それぞれ独立に１価の基を表す。ｎ６は０〜１０の整数を表す。） Among them, the component (A) is preferably an aromatic hydrocarbon resin represented by the following formula (6).

(In formula (6), each R ⁶¹ independently represents a monovalent group. N 6 represents an integer of 0 to 10.)

In Formula (6), R ⁶¹ represents a monovalent group, and R ⁶¹ has the same meaning as R ¹¹ in Formula (1).

  In Formula (6), n6 represents an integer of 0 to 10, and n6 has the same meaning as n3 in Formula (3).

  Examples of commercial products of the component (A) include “ESN 375” and “SN 395” manufactured by Nippon Steel Sumikin Chemical Co., Ltd., “HP 4032” and “HP 4032 D” manufactured by DIC, “HP 4032 SS”, “HP 4032 H” and “HP 4700”. Examples include "HP 4710" and "NC 3500" manufactured by Nippon Kayaku Co., Ltd.

  The aromatic hydrocarbon resin as the component (A) may be used alone or in combination of two or more.

  When the group containing an oxygen atom bonded to the aromatic ring of the component (A) contains an epoxy group, the epoxy equivalent of the component (A) is preferably 50 to 5000 g from the viewpoint of significantly achieving the desired effect of the present invention / Eq, more preferably 50 to 3000 g / eq, still more preferably 80 to 2000 g / eq, still more preferably 90 to 1000 g / eq. Epoxy equivalent is the mass of resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

  When the group containing an oxygen atom bonded to the aromatic ring of the component (A) contains a hydroxyl group, the hydroxyl equivalent of the component (A) increases the crosslink density of the insulating layer as a cured product of the resin composition layer, Or 50 g / eq or more, more preferably 60 g / eq or more, still more preferably 70 g / eq or more, and preferably 250 g / eq or less, more preferably, from the viewpoint of obtaining the desired effects of the present invention remarkably. Is 150 g / eq or less, particularly preferably 120 g / eq or less. The hydroxyl equivalent is the mass of the resin containing one equivalent of hydroxyl group.

  When the group containing an oxygen atom bonded to the aromatic ring of component (A) contains a hydroxyl group, the oxygen atom bonded to the aromatic ring of component (A), assuming that the number of epoxy groups of epoxy resin (C) is 1. The number of groups containing is preferably 1 or more, more preferably 5 or more, still more preferably 10 or more, preferably 30 or less, more preferably 25 or less, from the viewpoint of obtaining a cured product which is more excellent in smear removability. Is less than 20. Here, "the number of epoxy groups of (C) epoxy resin" is a value obtained by totaling all values obtained by dividing the mass of the nonvolatile component of the (C) component present in the resin composition by the epoxy equivalent. Further, “the number of groups containing an oxygen atom bonded to the aromatic ring of the component (A)” means that the mass of the non-volatile component of the component (A) present in the resin composition is an oxygen atom bonded to the aromatic ring It is the value which totaled all the values divided by the equivalent of the group to be carried out.

The content of the component (A) is preferably 0.5% by mass or more, and more preferably 0.8% by mass, from the viewpoint of obtaining a cured product excellent in smear removability, with 100% by mass of nonvolatile components in the resin composition. The content is preferably at least 1 mass%, more preferably at most 15 mass%, more preferably at most 10 mass%, still more preferably at most 8 mass% or at most 5 mass%.
In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass unless otherwise specified.

  Further, the content of the component (A) is preferably 2 when the total content of the component (A) and the epoxy resin (C) described later is 100% by mass from the viewpoint of obtaining a cured product excellent in smear removability. The content is preferably 5% by mass or more, more preferably 15% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

<(B) Active ester curing agent>
The resin composition contains (B) an active ester-based curing agent. The use of an active ester-based curing agent can usually lower the dielectric loss tangent while having poor smear removability. However, since the resin composition of the present invention contains the component (A), the dielectric loss tangent can be lowered, and a resin composition capable of obtaining a cured product excellent in smear removability can be obtained.

  (B) As an active ester curing agent, an ester group having high reaction activity such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound is generally contained in one molecule in one molecule. Compounds having one or more are preferably used. The active ester curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. As a phenol compound or naphthol compound, for example, hydroquinone, resorcine, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compounds, phenol novolac and the like can be mentioned. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensation of two molecules of phenol with one molecule of dicyclopentadiene.

  Specifically, dicyclopentadiene type active ester type curing agent, active ester type curing agent containing naphthalene structure, active ester type curing agent containing acetylated compound of phenol novolac, active ester type curing agent containing benzoylated compound of phenol novolac Among them, active ester-based curing agents having a naphthalene structure and dicyclopentadiene-type active ester-based curing agents are more preferable, and dicyclopentadiene-type active ester-based curing agents are more preferable. As the dicyclopentadiene type active ester curing agent, an active ester curing agent containing a dicyclopentadiene type diphenol structure is preferable. The "dicyclopentadiene type diphenol structure" represents a bivalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

  (B) As a commercial item of the active ester type curing agent, “EXB9451”, “EXB 9460”, “EXB 9460S”, “HPC-8000-65T” as an active ester type curing agent containing a dicyclopentadiene type diphenol structure, “HPC-8000H-65TM”, “EXB8000L-65TM” (manufactured by DIC), “EXB 8150-60T” as an active ester curing agent containing a naphthalene structure, “EXB9416-70BK” (manufactured by DIC), acetyl of phenol novolac Active ester-based curing agent containing “PVC” (Mitsubishi Chemical Co., Ltd.), active ester-based curing agent containing benzo novolak of phenol novolak “YLH1026” (Mitsubishi Chemical Co., Ltd.), acetylated product of phenol novolac Beauty treatment "Dc 808" (Mitsubishi Chemical Co., Ltd.) as a curing agent, "YLH 1026" (Mitsubishi Chemical Co., Ltd.), an activated ester curing agent that is a benzoyl compound of phenol novolak, "YLH 1030" (Mitsubishi Chemical), "YLH 1048" (Mitsubishi Chemical Co., Ltd.) and the like.

  The amount ratio of the (B) active ester type curing agent to the (A) and (C) components is [total number of epoxy groups of the (A) and (C) components]: [the reactive group of the active ester type curing agent The ratio of the total number is preferably in the range of 1: 0.01 to 1: 5, more preferably 1: 0.05 to 1: 2, and still more preferably 1: 0.1 to 1: 1.8. Here, the reactive group of the active ester-based curing agent is an active ester group. The total number of epoxy groups of components (A) and (C) is a value obtained by totaling all values obtained by dividing the solid content mass of each component by the epoxy equivalent, and the total of the reactive groups of the active ester curing agent The number is a value obtained by totaling the value obtained by dividing the solid content mass of each active ester curing agent by the reactive group equivalent for all active ester curing agents. The heat resistance of the hardened | cured material of a resin composition improves more by making quantity ratio of an epoxy resin and an active ester type hardening | curing agent into such a range.

  The content of the active ester-based curing agent (B) is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. It is. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less. By setting the content of the component (B) in such a range, it is possible to obtain a cured product excellent in smear removability.

<(C) Epoxy resin>
The resin composition may contain (C) an epoxy resin. However, the thing applicable to (A) component is remove | excluded from (C) component.

  (C) As an epoxy resin, 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, trisphenol type Epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin Cresol novolac epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin Heterocyclic epoxy resins, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. The epoxy resin may be used alone or in combination of two or more.

  The resin composition preferably contains, as the (C) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of obtaining the desired effects of the present invention remarkably, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% with respect to 100% by mass of the nonvolatile component (C) epoxy resin. % Or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more.

  The epoxy resin includes an epoxy resin which is liquid at a temperature of 20 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) and an epoxy resin which is solid at a temperature of 20 ° C. (hereinafter, referred to as “solid epoxy resin”). And there. The resin composition may contain only the liquid epoxy resin as the (C) epoxy resin, or may contain only the solid epoxy resin, but includes the liquid epoxy resin and the solid epoxy resin in combination. Is preferred. (C) By using a liquid epoxy resin and a solid epoxy resin in combination as the 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. it can.

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

  As 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, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, ester skeleton Preferred are cycloaliphatic epoxy resin, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having butadiene structure, and bisphenol A type epoxy resin, bisphenol F type epoxy resin and cyclohexane type epoxy Resin is more preferred.

  Specific examples of the liquid epoxy resin include “828US”, “jER 828 EL”, “825”, and “Epikote 828 EL” (bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; “jER 807” and “1750” manufactured by Mitsubishi Chemical Co. (Bisphenol F type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "630", "630LSD" (glycidyl amine type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. “ZX1059” (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd. “Celoxide 2021 P” manufactured by Daicel (ester skeleton Cycloaliphatic epoxy resin Resin); "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel; "ZX1658" manufactured by Nippon Steel Sumikin Chemical Co., Ltd., "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin), etc. . These 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, and more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule.

  As solid epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl Type epoxy resin, naphthalene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin is preferable, and bixylenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF Type epoxy resin, and naphthalene ether type epoxy resin are more preferable.

  Specific examples of the solid epoxy resin include “N-690” (cresol novolac epoxy resin) manufactured by DIC; “N-695” manufactured by DIC (cresol novolac epoxy resin); “HP manufactured by DIC -7200 "," HP-7200HH "," HP-7200H "(dicyclopentadiene type epoxy resin);" EXA-7311 "," EXA-7311-G3 "," EXA-7311-G4 "manufactured by DIC Corporation, “EXA-7311-G4S”, “HP6000” (naphthylene ether type epoxy resin); “EPPN-502H” (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; “NC7000L” (Naphthol manufactured by Nippon Kayaku Co., Ltd.) Novolak type epoxy resin); “NC3000H”, “NC3000”, “NC300” manufactured by Nippon Kayaku Co., Ltd. L "," NC3100 "(biphenyl type epoxy resin);" ESN 475 V "(naphthol type epoxy resin) manufactured by Nippon Steel Sumikin Chemical Co., Ltd .;" ESN 485 "(naphthol novolac type epoxy resin) manufactured by Nippon Steel Sumikin Chemical Co., Ltd .; “YX4000H”, “YX4000”, “YL6121” (biphenyl epoxy resin); “YX4000HK” (bixylenol epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; “YX8800” (anthracene epoxy resin) manufactured by Mitsubishi Chemical Co .; Osaka Gas Chemical's "PG-100", "CG-500"; Mitsubishi Chemical's "YL 7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical's "YL 7800" (fluorene type epoxy resin); Mitsubishi Chemical company's "jER10 0 "(solid bisphenol A epoxy resin); Mitsubishi Chemical Co." jER1031S "(tetraphenyl ethane epoxy resin) and the like. These may be used alone or in combination of two or more.

  (C) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio (liquid epoxy resin: solid epoxy resin) is preferably 1: 1 to 1:20 by mass ratio. More preferably, it is 1: 1-1: 15, Especially preferably, it is 1: 1-1: 10. When the ratio of the liquid epoxy resin to the solid epoxy resin is in such a range, the desired effect of the present invention can be remarkably obtained. Furthermore, usually, when used in the form of a resin sheet, adequate tackiness is provided. In addition, usually, when used in the form of a resin sheet, sufficient flexibility is obtained, and the handleability is improved. Furthermore, usually, a cured product having sufficient breaking strength can be obtained.

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

The weight average molecular weight (Mw) of the epoxy resin (C) is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500, from the viewpoint of obtaining the desired effects of the present invention remarkably.
The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

  When the resin composition contains (C) an epoxy resin, the content of the (C) epoxy resin is preferably 100 of the non-volatile components in the resin composition from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. When it is referred to as mass%, it is preferably 1 mass% or more, more preferably 3 mass% or more, and still more preferably 5 mass% or more. The upper limit of the content of the epoxy resin is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less from the viewpoint of obtaining the desired effects of the present invention remarkably.

<(D) Inorganic filler>
The resin composition may contain (D) an inorganic filler. An inorganic compound is used as a material of the inorganic filler. Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide And barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Moreover, as silica, spherical silica is preferable. The inorganic filler (D) may be used alone or in combination of two or more.

  (D) As a commercial item of the inorganic filler, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; "YC100C", "YA050C" and "YA050C-MJE" manufactured by Admatechs Co., Ltd. "YAFO C"; "UFP-30" manufactured by Denka; "Sylfil NSS-3N" manufactured by Tokuyama, "Sylfil NSS-4N", "Sylfil NSS-5N"; "SC2500 SQ" manufactured by Admatex Co., Ltd. "SO-C4", "SO-C2", "SO-C1"; etc. are mentioned.

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

  (D) The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle diameter distribution of the inorganic filler can be created on a volume basis by a laser diffraction scattering type particle size distribution measuring device, and the median diameter can be measured as an average particle diameter. As a measurement sample, 100 mg of an inorganic filler, 0.1 g of a dispersant ("SN 9228" manufactured by San Nopco), and 10 g of methyl ethyl ketone can be weighed in a vial and dispersed by ultrasonic waves for 20 minutes. The particle size distribution of the measurement sample was measured by a batch cell method using a laser diffraction type particle size distribution measuring apparatus ("SALD-2200" manufactured by Shimadzu Corporation), and the average particle size was calculated as a median diameter.

The specific surface area of the inorganic filler (D) is preferably 1 m ² / g or more, more preferably 2 m ² / g or more, particularly preferably 5 m, from the viewpoint of facilitating control of the shape of the via hole to realize a good shape. ² / g or more. The upper limit is not particularly limited, but 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 (D) inorganic filler is preferably treated with a surface treatment agent from the viewpoint of enhancing the moisture resistance and the dispersibility. As the surface treatment agent, for example, fluorine-containing silane coupling agent, aminosilane type coupling agent, epoxysilane type coupling agent, mercaptosilane type coupling agent, silane type coupling agent, alkoxysilane, alkoxysilane, organosilazane compound, titanate type Coupling agents etc. may be mentioned. Moreover, a surface treatment agent may be used individually by 1 type, and may be used combining 2 or more types arbitrarily.

  Examples of commercially available surface treatment agents include "KBM 403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM 803" (3-mercaptopropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry Co., Ltd. "KBE 903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" ( Hexamethyldisilazane), Shin-Etsu Chemical "KBM 103" (phenyltrimethoxysilane), Shin-Etsu Chemical "KBM-4803" (long-chain epoxy type silane coupling agent), Shin-Etsu Chemical "KBM- 7103 "(3,3,3-trifluoropropyltrimethoxysilane) and the like.

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

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

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

  When the resin composition contains (D) an inorganic filler, the content of the (D) inorganic filler is from 100% by mass of nonvolatile components in the resin composition from the viewpoint of lowering the dielectric loss tangent of the insulating layer. Preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less .

<(E) Hardening agent>
The resin composition may contain (E) a curing agent. However, the (B) active ester-based curing agent is not included in the (E) curing agent. Examples of the curing agent (E) include phenol-based curing agents, naphthol-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents. Among them, from the viewpoint of improving insulation reliability, the (E) curing agent is preferably at least one of a phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent. It is more preferable to include a phenolic curing agent. A hardening agent may be used individually by 1 type, or may use 2 or more types together.

  From the viewpoints of heat resistance and water resistance, as the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure is preferable. Further, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.

  Specific examples of the phenol-based curing agent and naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7851” manufactured by Meiwa Kasei Co., “NHN” manufactured by Nippon Kayaku Co., Ltd. "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. And “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500” and the like manufactured by DIC Corporation.

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

  As a cyanate ester-based curing agent, for example, bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylene bis (2,6-dimethylphenyl cyanate), 4,4 '-Ethylidene diphenyl dicyanate, hexafluoro bisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1, 1-bis (4- cyanate phenyl methane), bis (4- cyanate 3,5- dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatophenyl-1- (methylethylidene)) benzene, bis (4-cyanatophenyl) thioether, and bis (4-cyanatophenyl) ether, phenol Novolak and Ku Polyfunctional cyanate resin derived from tetrazole novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (phenol novolac-type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), "BA230" manufactured by Lonza Japan Co., Ltd. And “BA 230 S 75” (a prepolymer in which part or all of bisphenol A dicyanate is triazinated to form a trimer), and the like.

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

  When the resin composition contains (E) a curing agent, the quantitative ratio of the (A) and (C) components to the (E) curing agent is [the total number of epoxy groups of the (A) and (C) components The ratio of [total number of reactive groups of curing agent] is preferably in the range of 1: 0.01 to 1: 2, more preferably 1: 0.01 to 1: 1, and 1: 0.03 to 1. 0.5 is more preferable. Here, the reactive group of the curing agent is an active hydroxyl group or the like, which differs depending on the type of curing agent. The total number of reactive groups of the curing agent is the value obtained by dividing the mass of the solid content of each curing agent by the equivalent of the reactive group for all curing agents. By setting the ratio of the components (A) and (C) to the curing agent in such a range, the heat resistance of the cured product of the resin composition is further improved.

  When the resin composition contains (B) an active ester-based curing agent and (E) a curing agent, the quantitative ratio of (A) and (C) components to (B) active ester-based curing agent and (E) curing agent Is a ratio of [total number of epoxy groups of components (A) and (C)]: [total number of reactive groups of components (B) and (E)], in the range of 1: 0.01 to 1: 5. Is preferable, 1: 0.05 to 1: 2 is more preferable, and 1: 0.1 to 1: 1 is more preferable. By setting the ratio in such a range, the heat resistance of the cured product of the resin composition is further improved.

  When the resin composition contains (E) a curing agent, the content of the (E) curing agent is preferably 0.1% by mass or more, more preferably 100% by mass of the non-volatile component in the resin composition. Preferably it is 0.3 mass% or more, More preferably, it is 0.5 mass% or more. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less. By setting the content of the curing agent (E) in such a range, the heat resistance of the cured product of the resin composition is further improved.

<(F) Thermoplastic resin>
The resin composition may contain (F) a thermoplastic resin. As the thermoplastic resin as the component (F), for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin And polycarbonate resins, polyether ether ketone resins, polyester resins and the like. Among them, phenoxy resins are preferable from the viewpoint of obtaining the desired effects of the present invention remarkably and from the viewpoint of obtaining an insulating layer which is small in surface roughness and particularly excellent in adhesion to a conductor layer. The thermoplastic resins may be used alone or in combination of two or more.

  As the phenoxy resin, for example, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene The phenoxy resin which has frame | skeleton and one or more types of frame | skeleton selected from the group which consists of trimethyl cyclohexane frame | skeleton is mentioned. The terminal of the phenoxy resin may be any functional group such as phenolic hydroxyl group and epoxy group.

  As a specific example of phenoxy resin, "1256" and "4250" (all are bisphenol A frame | skeleton containing phenoxy resin) by Mitsubishi Chemical Co., Ltd .; "YX8100" (bisphenol S frame | skeleton containing phenoxy resin) by Mitsubishi Chemical Co., Ltd .; Company's "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin); "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; “YL 7769 BH30”, “YL 6794”, “YL 7213”, “YL 7290” and “YL 748 2”;

  As polyvinyl acetal resin, polyvinyl formal resin, polyvinyl butyral resin is mentioned, for example, Polyvinyl butyral resin is preferable. As a specific example of polyvinyl acetal resin, "Electric charge butyral 4000-2", "electric charge butyral 5000-A", "electric charge butyral 6000-C", "electric charge butyral 6000-EP" made by Denki Kagaku Kogyo Co., Ltd .; Sekisui Chemical Co., Ltd. Elek BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series;

  As a specific example of a polyimide resin, "Rika coat SN20" and "Rika coat PN20" by Shin Nippon Rika Co., Ltd. are mentioned. Specific examples of the polyimide resin also include a linear polyimide (polyimide described in JP-A-2006-37083) obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride, and a polysiloxane skeleton Modified polyimides such as contained polyimides (polyimides described in JP-A-2002-12667 and JP-A-2000-319386) can be mentioned.

  As a specific example of polyamide imide resin, Toyobo Co., Ltd. "Viromax HR11NN" and "Viromax HR16NN" are mentioned. Specific examples of the polyamideimide resin also include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.

  As a specific example of polyether sulfone resin, Sumitomo Chemical Co., Ltd. "PES5003P" etc. are mentioned.

  As a specific example of polyphenylene ether resin, oligo phenylene ether styrene resin "OPE-2St 1200" made by Mitsubishi Gas Chemical Co., Ltd., etc. may be mentioned.

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

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

  When the resin composition contains (F) a thermoplastic resin, the content of the (F) thermoplastic resin is 100% by mass of non-volatile components in the resin composition from the viewpoint of obtaining the desired effect of the present invention remarkably. If it is, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, preferably 1.5% by mass or less, more preferably 1% by mass The following content is more preferably 0.5% by mass or less.

<(G) Hardening accelerator>
The resin composition may contain (G) a curing accelerator. Examples of the (G) 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 curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are more preferable. The curing accelerator may be used alone or in combination of two or more.

  As a phosphorus-based curing accelerator, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate Tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate and the like, and triphenyl phosphine and tetrabutyl phosphonium decanoate are preferable.

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

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

  A commercial item may be used as an imidazole series hardening accelerator, for example, "P200-H50" by Mitsubishi Chemical Corporation etc. is mentioned.

  As the guanidine-based curing accelerator, for example, dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, dimethyl guanidine, diphenyl guanidine, trimethyl guanidine, 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-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1-( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  Examples of the metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, zinc (II) acetylacetonate Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, organic manganese complexes such as manganese (II) acetylacetonate, and the like. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

  When the resin composition contains (G) a curing accelerator, the content of the (G) curing accelerator is 100% by mass of non-volatile components in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. If it is, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less More preferably, it is 1.5 mass% or less.

<(H) Optional additive>
The resin composition may further contain optional additives as optional components in addition to the components described above. As such additives, for example, organic fillers; organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds; flame retardants, thickeners, antifoaming agents, leveling agents, adhesion imparting agents, Resin additives such as coloring agents; and the like. These additives may be used alone or in combination of two or more.

<Physical Properties of Resin Composition, Applications>
A cured product obtained by heat curing the resin composition at 100 ° C. for 30 minutes and then at 170 ° C. for 30 minutes usually exhibits the property of excellent smear removability. Therefore, even if a via hole is formed in the cured product, an insulating layer is obtained in which the maximum smear length at the bottom of the via hole is less than 5 μm. The smear removability can be measured by the method described in the examples described later.

  The cured product obtained by heat curing the resin composition at 200 ° C. for 90 minutes exhibits the property of low dielectric loss tangent. Thus, an insulating layer with a low dielectric loss tangent is provided. The dielectric loss tangent is preferably 0.01 or less, more preferably 0.008 or less, and still more preferably 0.005 or less. The lower limit is not particularly limited, but may be 0.0001 or more. The dielectric loss tangent can be measured by the method described in the examples described later.

  The resin composition of the present invention can provide an insulating layer having a low dielectric loss tangent and excellent smear removability. Therefore, the resin composition of the present invention can be suitably used as a resin composition (resin composition for insulating layer of multilayer printed wiring board) for forming insulating layer of multilayer printed wiring board, and printed wiring board It can use more suitably as a resin composition (resin composition for interlayer insulation layers of a printed wiring board) for forming an interlayer insulation layer of the above. Further, the resin composition of the present invention can be suitably used even when the printed wiring board is a component-embedded circuit board because the resin composition of the present invention provides a good insulating layer for the component embedding property.

  In particular, since the resin composition of the present invention can provide an insulating layer having a low dielectric loss tangent and excellent smear removability, it becomes possible to form an insulating layer having a small via hole diameter. Therefore, the above-mentioned resin composition is suitable as a resin composition for forming an insulating layer having a via hole (resin composition for forming an insulating layer having a via hole), and in particular, has a via hole with a top diameter of 35 μm or less Resin composition for forming an insulating layer, resin for forming an insulating layer having a via hole having an aspect ratio (thickness of insulating layer / top diameter) of thickness (μm) of insulating layer to top diameter (μm) of 0.5 or more It is particularly suitable as a composition. Here, the term "top diameter" refers to the maximum diameter of the opening formed on the side opposite to the substrate of the via hole when the via hole is formed in the insulating layer on the substrate, and "thickness of the insulating layer" means It represents the thickness of the entire insulating layer, ie, the depth of the via.

  The aspect ratio (thickness of insulating layer / top diameter) between the thickness (μm) of the insulating layer and the top diameter (μm) is preferably 0.5 or more from the viewpoint of downsizing of the electronic device and improvement of performance. Preferably it is 0.6 or more, More preferably, it is 0.7 or more, Preferably it is 3 or less, More preferably, it is 2 or less, More preferably, it is 1 or less.

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

  The thickness of the resin composition layer is preferably 40 μm or less, more preferably 35 μm or less, and still more preferably from the viewpoint of thinning the printed wiring board and providing a cured product having excellent insulation properties even if it is a thin film. 25 μm or less, 20 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may usually be 3 μm or more, 5 μm or more, 7 μm or more.

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

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) Polyester, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Ketone, polyimide and the like can be mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

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

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. As the release agent used for the release layer of the support with release layer, for example, one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin can be mentioned. . The release layer-provided support may be a commercially available product. For example, “SK-1” manufactured by Lintec Co., Ltd., which is a PET film having a release layer containing an alkyd resin-based release agent as a main component AL-5 "," AL-7 "," Lumirror T60 "manufactured by Toray Industries," Purex "manufactured by Teijin," Uni-Pel "manufactured by Unitika, and the like.

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

  In one embodiment, the resin sheet may further contain other layers as needed. As such other layers, there may be mentioned, for example, a protective film according to a support, etc. provided on the side of the resin composition layer not bonded to the support (that is, the side opposite to the support). Be Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to suppress adhesion of dust and the like to the surface of the resin composition layer and scratches.

  For example, a resin sheet is prepared by dissolving a resin composition in an organic solvent, and the resin varnish is applied onto a support using a die coater or the like, and then dried to form a resin composition layer. Can be manufactured by

  Organic solvents include, for example, ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, acetates such as propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol etc. And aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used singly or in combination of two or more.

  Drying may be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it changes also with the boiling points of the organic solvent in a resin varnish, when using the resin varnish containing 30 mass%-60 mass% organic solvent, for example, resin composition by making it dry at 50 degreeC-150 degreeC for 3 minutes-10 minutes Object layer can be formed.

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

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

The printed wiring board can be manufactured, for example, by the method including the following steps (I) and (II) using the above-mentioned resin sheet.
(I) Step of laminating the resin composition layer of the resin sheet so as to bond with the inner layer substrate on the inner layer substrate (II) Step of thermally curing the resin composition layer to form an insulating layer

  The "inner layer substrate" used in step (I) is a member to be a substrate of a printed wiring board, and for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate Etc. The substrate may have a conductor layer on one side or both sides, and the conductor layer may be patterned. The inner layer substrate in which a conductor layer (circuit) is formed on one side or both sides of the substrate may be referred to as "inner layer circuit board". Further, an intermediate product on which an insulating layer and / or a conductor layer is to be formed is further included in the “inner layer substrate” in the present invention when producing a printed wiring board. When the printed wiring board is a component built-in circuit board, an inner layer substrate containing components can be used.

  The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet from the support side to the inner layer substrate. Examples of the member (hereinafter, also referred to as “heat-pressing member”) for heat-pressing the resin sheet to the inner layer substrate include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). In addition, it is preferable to press via an elastic material such as heat resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate, instead of directly pressing the heat pressure-bonding member on the resin sheet.

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

  Lamination can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressure type laminator manufactured by Nikkiso Co., Ltd., a vacuum applicator manufactured by Nikko Materials, a batch type vacuum pressure laminator, etc. may be mentioned.

  After lamination, the laminated resin sheet may be subjected to a smoothing treatment by normal pressure (atmospheric pressure), for example, by pressing the heat pressure-bonding member from the support side. The pressing conditions for the smoothing treatment can be the same as the heating and pressing conditions for the above-mentioned lamination. The smoothing treatment can be performed by a commercially available laminator. In addition, you may perform lamination | stacking and smoothing processing continuously using said commercially available vacuum laminator.

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

  In the step (II), the resin composition layer is thermally cured to form an insulating layer.

  The heat curing conditions of the resin composition layer are not particularly limited, and conditions generally employed for forming an insulating layer of a printed wiring board may be used.

  For example, the heat curing conditions of the resin composition layer vary depending on the type of the resin composition and the like, but the curing temperature is preferably 120 ° C. to 240 ° C., more preferably 150 ° C. to 220 ° C., further preferably 170 ° C. to 200 ° C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still 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, prior to heat curing of the resin composition layer, the resin composition layer is heated at a temperature of 50.degree. C. or more and less than 120.degree. C. (preferably 60.degree. C. or more and 115.degree. C. or less, more preferably 70.degree. C. or more and 110.degree. C. or less). It may be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes).

  When producing a printed wiring board, the steps of: (III) drilling holes in the insulating layer; (IV) roughening the insulating layer; and (V) forming the conductor layer may be further performed. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used for producing a printed wiring board. When the support is removed after the step (II), the removal of the support may be performed between the step (II) and the step (III), between the step (III) and the step (IV), or It may be carried out between IV) and step (V). In addition, if necessary, the formation of the insulating layer and the conductor layer in the steps (II) to (V) may be repeated to form a multilayer wiring board.

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

  The top diameter of the via hole is preferably 70 μm or less, more preferably 60 μm or less, still more preferably 55 μm or less, or 35 μm or less from the viewpoint of downsizing and high performance of the electronic device. The lower limit is not particularly limited, but may be 10 μm or more. The top diameter of the via hole can be measured, for example, using a SEM.

  Step (IV) is a step of roughening the insulating layer. Usually, removal of smear is also performed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions generally used in forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling process with a swelling solution, a roughening process with an oxidizing agent, and a neutralization process with a neutralizing solution in this order. The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution, a surfactant solution and the like, preferably an alkaline solution, and examples of the alkaline solution include sodium hydroxide solution and potassium hydroxide solution. preferable. As a swelling liquid marketed, "Swelling dip security G" and "Swelling dip security SBU" by Atotech Japan Ltd., etc. are mentioned, for example. Although the swelling process by a swelling liquid is not specifically limited, For example, it can carry out by immersing an insulating layer in the swelling liquid of 30 degreeC-90 degreeC for 1 minute-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 for 5 minutes to 15 minutes in a swelling liquid at 40 ° C to 80 ° C. The oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof include alkaline permanganic acid solutions in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in the oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 minutes to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan Co., Ltd. Moreover, as a neutralization liquid used for roughening treatment, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Security G" manufactured by Atotech Japan Co., Ltd. may be mentioned. The treatment with the neutralization solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralization solution at 30 ° C. to 80 ° C. for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the target subjected to the roughening treatment with the oxidizing agent in a neutralization solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited, but preferably 0.5 nm or more, more preferably 1 nm or more. Further, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited, but preferably 0.5 nm or more, more preferably 1 nm or more. Arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a noncontact surface roughness meter.

  Process (V) is a process of forming a conductor layer, and forms a conductor layer on an insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and as the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, And layers formed of nickel alloy and copper-titanium alloy). Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layer, nickel-chromium alloy, copper, from the viewpoint of versatility of conductor layer formation, cost, easiness of patterning, etc. An alloy layer of nickel alloy, copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is more preferable, single copper Metal layers are more preferred.

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

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

  In one embodiment, the conductor layer may be formed by plating. For example, the conductor layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method, and from the viewpoint of manufacturing simplicity, semi-additive It is preferable to form by a method. Hereinafter, the example which forms a conductor layer by a semiadditive method is shown.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, on the formed plating seed layer, a mask pattern is formed to expose a part of the plating seed layer corresponding to the desired wiring pattern. 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 can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

  The resin sheet of the present invention can also be suitably used when the printed wiring board is a component-embedded circuit board because the resin sheet of the present invention also provides an insulating layer having good component embedding properties. The component built-in circuit board can be manufactured by a known manufacturing method.

  The printed wiring board manufactured using the resin sheet of the present invention is an aspect provided with an insulating layer which is a cured product of the resin composition layer of the resin sheet, and an embedded wiring layer embedded in the insulating layer, It is also good.

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

  Examples of the semiconductor device include various semiconductor devices provided for electric products (for example, computers, mobile phones, digital cameras, televisions and the like) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft and the like) and the like.

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) at a conductive portion of a printed wiring board. The "conductive location" is a "location for transmitting an electrical signal in a printed wiring board", and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The mounting method of the semiconductor chip at the time of manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, a bumpless buildup layer The mounting method by (BBUL), the mounting method by an anisotropic conductive film (ACF), the mounting method by a nonconductive film (NCF), etc. are mentioned. Here, "the mounting method using a bumpless build-up layer (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board to connect the semiconductor chip and the wiring on the printed wiring board". It is.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass" unless otherwise specified. Moreover, the operation described below was performed in an environment of normal temperature and normal pressure unless otherwise specified.

Example 1
10 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent of 169), and naphthol type epoxy resin (“ESN 475 V” manufactured by Nippon Steel Sumikin Chemical Co., Ltd.) Thirty parts of an epoxy equivalent weight of about 330 was heated and dissolved in 40 parts of solvent naphtha while stirring. The mixture was cooled to room temperature to prepare a solution composition of epoxy resin (X). In addition, 10 parts of an aromatic hydrocarbon resin ("NSN 375" manufactured by Nippon Steel Sumikin Chemical Co., Ltd .; epoxy equivalent weight: about 171) having a structure shown below is heated and dissolved in 10 parts of MEK while stirring and cooled to room temperature. A solution of aromatic hydrocarbon resin (Y) was prepared.

（ｎは、１〜１０の整数を表す。）

(N represents an integer of 1 to 10)

  In the dissolution composition of this epoxy resin (X), 5 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK having a solid content of 30% by mass), a phenol type having a triazine skeleton and a novolac structure 5 parts of a curing agent ("LA-3018-50P" manufactured by DIC, an active group equivalent weight of about 151, 50% solid content in 2-methoxypropanol solution), an active ester curing agent ("HPC-8000-65T" manufactured by DIC) 50 parts of active group equivalent of about 223, solid content of 65 mass% in toluene, 5 parts of curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), 10 mass% of solid MEK solution), amine alkoxy Spherical silica (average particle size 0.77 μm, surface treated with silane compound (“KBM 573” manufactured by Shin-Etsu Chemical Co., Ltd.), De Admatechs Co. "SO-C2") 220 parts, and mixing the solution 20 parts of an aromatic hydrocarbon resin (Y), and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish.

  As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, 38 μm thick, PET film) provided with a release layer was prepared. The resin varnish was uniformly coated on the release layer of the support so that the thickness of the resin composition layer after drying was 15 μm. Thereafter, the resin varnish was dried at 80 ° C. to 100 ° C. (average 90 ° C.) for 3 minutes to prepare a resin sheet including a support and a resin composition layer.

Example 2
In Example 1, 50 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC, an active group equivalent weight of about 223, a toluene solution with a solid content of 65% by mass) is added It changed into 50 parts of "EXB8000L-65TM", the active group equivalent 220, and the toluene * MEK mixed solution of solid content 65%. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

[Example 3]
In Example 1, 50 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC, an active group equivalent weight of about 223, a toluene solution with a solid content of 65% by mass) is added It changed into 55 parts of "EXB 8150-60T", the active group equivalent 230, and the toluene solution of 60% of solid content). A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

Example 4
10 parts of bisphenol type epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), and naphthol type epoxy resin ("ESN 475V" manufactured by Nippon Steel Sumikin Chemical Co., Ltd.) And 20 parts of epoxy equivalent weight were heated and dissolved in 40 parts of solvent naphtha while stirring. The mixture was cooled to room temperature to prepare a solution composition of epoxy resin (X2). In addition, 20 parts of an aromatic hydrocarbon resin ("ESN 375, manufactured by Nippon Steel Sumikin Chemical Co., Ltd., epoxy equivalent weight: about 171) is dissolved by heating in 20 parts of MEK with stirring, and this is further cooled to room temperature to obtain an aromatic hydrocarbon resin ( A solution of Y2) was prepared.

  A solution of this epoxy resin (X2), 5 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., a solution of 30% by mass of MEK and cyclohexanone in solid content, 5 parts), active ester curing agent (manufactured by DIC) "EXB 8150-60T", active group equivalent 230, solid solution 60% in toluene solution 80 parts, curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), solid content 10% by weight in MEK solution) 5 parts, 250 parts of spherical silica (average particle diameter 0.77 μm, “SO-C2” manufactured by Admatex Co., Ltd.) surface-treated with an amine alkoxysilane compound (“KBM 573” manufactured by Shin-Etsu Chemical Co., Ltd.), and an aromatic hydrocarbon resin Forty parts of the solution (Y2) were mixed and uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish. Furthermore, in the same manner as in Example 1, a resin sheet was produced.

[Example 5]
In Example 3,
1) Change the amount of 20 parts of aromatic hydrocarbon resin ("ESN 375" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent weight: about 171) from 20 parts to 5 parts,
2) Change the amount of naphthol type epoxy resin ("ESN 475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent weight: about 330) from 30 parts to 40 parts,
3) The amount of spherical silica (average particle diameter 0.77 μm, "SO-C2" manufactured by Admatex Co., Ltd.) surface-treated with an amine alkoxysilane compound ("KBM 573" manufactured by Shin-Etsu Chemical Co., Ltd.) is 220 to 230 parts Changed to
A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

[Example 6]
10 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent of 169), and naphthol type epoxy resin (“ESN 475 V” manufactured by Nippon Steel Sumikin Chemical Co., Ltd.) 50 parts of epoxy equivalent weight was heated and dissolved in 40 parts of solvent naphtha while stirring. The mixture was cooled to room temperature to prepare a solution composition of epoxy resin (X3). In addition, 3 parts of an aromatic hydrocarbon resin ("SN 395-50 M" manufactured by Nippon Steel Sumikin Chemical Co., Ltd., used as a MEK solution having an active group equivalent of 107 and a solid content of 50%) having a structure shown below, and an aromatic hydrocarbon resin ( Five parts of “ESN 375” (manufactured by Nippon Steel Sumikin Chemical Co., Ltd., epoxy equivalent weight: about 171) was heated and dissolved in 10 parts of MEK with stirring, and further cooled to room temperature to prepare a solution of aromatic hydrocarbon resin (Y3).

（ｎは１〜１０の整数を表す。）

(N represents an integer of 1 to 10)

  In the dissolution composition of this epoxy resin (X3), 5 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK having a solid content of 30% by mass), a phenol type having triazine skeleton and novolac structure 2 parts of a curing agent ("LA-3018-50P" manufactured by DIC, an active group equivalent weight of about 151, 50% solid content in 2-methoxypropanol solution), active ester curing agent ("EXB 8150-60T" manufactured by DIC), activity Group equivalent: 230, solid solution 60% in toluene solution 55 parts, curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), solid content 10% by mass in MEK solution) 5 parts, amine alkoxysilane compound (Shin-Ekoshi) Spherical silica (average particle size 0.77 μm, Adma) surface-treated with “KBM 573” manufactured by Chemical Industry Co., Ltd. Box manufactured "SO-C2") 240 parts, and mixing the solution 13 parts of an aromatic hydrocarbon resin (Y3), and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish. Furthermore, in the same manner as in Example 1, a resin sheet was produced.

Comparative Example 1
In Example 1,
1) 220 to 240 parts of spherical silica (average particle diameter 0.77 μm, "SO-C2" manufactured by Admatechs Co., Ltd.) surface-treated with an amine alkoxysilane compound ("KBM 573" manufactured by Shin-Etsu Chemical Co., Ltd.) Change to
2) Change the amount of naphthol type epoxy resin ("ESN 475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent weight: about 330) from 40 parts to 50 parts,
3) 10 parts of aromatic hydrocarbon resin ("ESN 375", manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent weight: about 171) was not used.
A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

Comparative Example 2
In Example 2,
1) 220 to 240 parts of spherical silica (average particle diameter 0.77 μm, "SO-C2" manufactured by Admatechs Co., Ltd.) surface-treated with an amine alkoxysilane compound ("KBM 573" manufactured by Shin-Etsu Chemical Co., Ltd.) Change to
2) Change the amount of naphthol type epoxy resin ("ESN 475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent weight: about 330) from 40 parts to 50 parts,
3) 10 parts of aromatic hydrocarbon resin ("ESN 375", manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent weight: about 171) was not used.
A resin varnish and a resin sheet were produced in the same manner as in Example 2 except for the above matters.

Comparative Example 3
In Example 3,
1) 220 to 240 parts of spherical silica (average particle diameter 0.77 μm, "SO-C2" manufactured by Admatechs Co., Ltd.) surface-treated with an amine alkoxysilane compound ("KBM 573" manufactured by Shin-Etsu Chemical Co., Ltd.) Change to
2) Change the amount of naphthol type epoxy resin ("ESN 475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent weight: about 330) from 40 parts to 50 parts,
3) 10 parts of aromatic hydrocarbon resin ("ESN 375", manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent weight: about 171) was not used.
A resin varnish and a resin sheet were produced in the same manner as in Example 3 except for the above matters.

<Evaluation of smear removability>
(1) Base treatment of interior substrate Glass cloth base epoxy resin double-sided copper-clad laminate with copper foil on the surface as inner layer substrate (18 μm thickness of copper foil, 0.8 mm thickness of substrate, manufactured by Panasonic "R1515A ") Prepared. The copper foil on the surface of the inner layer substrate was roughened by etching using a microetching agent ("CZ 8101" manufactured by MEC) at a copper etching amount of 1 μm. Thereafter, drying was performed at 190 ° C. for 30 minutes.

(2) Lamination and curing of resin sheets The resin sheets obtained in the above-described Examples and Comparative Examples were treated using a batch-type vacuum pressure laminator (a two-stage build-up laminator "CVP 700" manufactured by Nikko Materials Co., Ltd.). The inner layer substrate was laminated on both sides so that the composition layer was bonded to the inner layer substrate. This laminate was carried out by pressure-reducing for 30 seconds to a pressure of 13 hPa or less, and pressure bonding for 30 seconds at a temperature of 100 ° C. and a pressure of 0.74 MPa.
Then, the laminated resin sheet was heat-pressed for 60 seconds at 100 ° C. under a pressure of 0.5 MPa under atmospheric pressure for smoothing. Furthermore, it was put into an oven at 100 ° C. and heated for 30 minutes, then transferred to an oven at 170 ° C. and heated for 30 minutes to form an insulating layer.

(3) Via hole formation:
The insulating layer is processed under the conditions of a frequency of 2000 Hz, a pulse width of 6 μs, an output of 0.24 mJ and a shot number of 3 using a CO ₂ laser processing machine (LK-2K212 / 2C) manufactured by Via Mechanics Co., Ltd. Via holes having a top diameter (diameter) of 25 μm and a diameter of 19 μm at the bottom of the insulating layer were formed. Thereafter, the PET film of the support was peeled off.

(4) Roughening treatment The inner layer substrate was immersed for 5 minutes at 60 ° C. in a swelling dip sealing D made by Atotech Japan Co., Ltd., which is a swelling solution. Next, it was immersed for 20 minutes at 80 ° C. in a concentrate compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) manufactured by Atotech Japan Co., Ltd., which is a roughening solution. Finally, it was immersed for 5 minutes at 40 ° C. in a reduction solution Securitygant P manufactured by Atotech Japan Co., Ltd., which is a neutralizing solution.

(5) Evaluation of residue on bottom of via hole The periphery of the bottom of the via hole was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via hole was measured from the obtained image and evaluated according to the following criteria.
○: Maximum smear length less than 5 μm ×: Maximum smear length 5 μm or more

<Measurement of dielectric loss tangent>
The resin sheet obtained in each Example and each Comparative Example was thermally cured at 200 ° C. for 90 minutes to peel off the PET film to obtain a sheet-like cured product. The cured product is cut into a test piece of 2 mm in width and 80 mm in length, and a cavity resonator perturbation method dielectric constant measuring apparatus “CP 521” manufactured by Kanto Applied Electronic Development Co., Ltd. and “Network Analyzer E8362 B” manufactured by Agilent Technologies, Inc. are used. Then, the dielectric loss tangent (tan δ) was measured at a measurement frequency of 5.8 GHz by the cavity resonance method. The measurement was performed on two test pieces, and the average value was calculated.

表中、「（Ａ）成分の含有量（質量％）」は、（Ａ）成分及び（Ｃ）成分の合計含有量を１００質量部とした場合の（Ａ）成分の含有量を表し、「（Ｄ）成分の含有量（質量％）」は、樹脂組成物中の不揮発成分を１００質量％とした場合の（Ｄ）成分の含有量を表す。

In the table, "content of component (A) (mass%)" represents the content of component (A) when the total content of components (A) and (C) is 100 parts by mass, " The content (% by mass) of the component (D) represents the content of the component (D) when the nonvolatile component in the resin composition is 100% by mass.

  In Examples 1 to 6, even when the components (C) to (G) were not contained, it was confirmed that the results were similar to those of the above-mentioned examples, although the degree was different.

Claims (18)

(A) an aromatic hydrocarbon resin containing an aromatic ring as a single ring or a fused ring, and having two or more groups containing an oxygen atom bonded to the aromatic ring per one aromatic ring, and (B) A resin composition containing an active ester curing agent. The resin composition according to claim 1, wherein the component (A) has a structure represented by the following formula (1).

(In formula (1), each R ¹¹ independently represents a monovalent group.) The resin composition of Claim 1 or 2 in which (A) component has a structure represented by following formula (2).

(In formula (2), each R ²¹ independently represents a monovalent group.) The resin composition according to claim 1, wherein the component (A) is represented by the following formula (3).

(In formula (3), R ³¹ each independently represents a monovalent group, R ³² each independently represents a divalent hydrocarbon group. N 3 represents an integer of 0 to 10.) The resin composition according to any one of claims 1 to 4, wherein the component (A) is represented by the following formula (6).

(In formula (6), each R ⁶¹ independently represents a monovalent group. N 6 represents an integer of 0 to 10.)   The resin composition according to any one of claims 1 to 5, wherein the group containing an oxygen atom bonded to the aromatic ring is an epoxy alkyleneoxy group, an alkoxy group, or a hydroxyl group.   Furthermore, the resin composition of any one of Claims 1-6 containing (C) epoxy resin.   The resin composition according to claim 7, wherein the content of the component (A) is 5% by mass or more and 50% by mass or less when the total content of the components (A) and (C) is 100% by mass. .   The resin composition according to any one of claims 1 to 8, wherein the content of the component (B) is 1% by mass or more and 30% by mass or less when the nonvolatile component in the resin composition is 100% by mass. object.   The resin composition according to any one of claims 1 to 9, further comprising (D) an inorganic filler.   The resin composition according to claim 10, wherein the content of the component (D) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass.   The resin composition according to any one of claims 1 to 11, which is a resin composition for forming an insulating layer of a multilayer printed wiring board.   The resin composition according to any one of claims 1 to 12, which is a resin composition for forming an insulating layer having a via hole having a top diameter of 35 μm or less.   The resin composition for forming an insulating layer having a via hole having an aspect ratio (thickness of insulating layer / top diameter) of thickness (μm) of insulating layer to top diameter (μm) is 0.5 or more. 13. The resin composition according to any one of 13.   The resin sheet containing a support body and the resin composition layer containing the resin composition of any one of Claims 1-14 provided on this support body.   The resin sheet according to claim 15, wherein the thickness of the resin composition layer is 20 μm or less.   The printed wiring board containing the insulating layer formed of the hardened | cured material of the resin composition of any one of Claims 1-14.   A semiconductor device comprising the printed wiring board according to claim 17.