JP6992333B2 - Resin composition - Google Patents

Description

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

As a manufacturing technique for a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked is known.

As an insulating material for a printed wiring board used for such an insulating layer, for example, Patent Document 1 describes a maleimide compound (A), an epoxy compound (B), and a cyanate ester compound (C) having a melting point of 40 ° C. or lower. And a thermosetting resin composition containing an inorganic filler (D) are disclosed.

Japanese Unexamined Patent Publication No. 2016-010964

From the viewpoint of enabling the formation of wiring with a fine pattern, the viewpoint of enhancing the mounting reliability of the printed wiring board, and the viewpoint of enhancing the connection reliability of the printed wiring board, it is desirable that the insulating layer has high adhesion to the conductor layer. Therefore, in recent years, as the performance of the insulating layer, it is required to have high adhesion to the conductor layer. Further, in order to improve the long-term reliability of the printed wiring board, it is desirable that the insulating layer has high adhesion to the conductor layer even after the ultra-accelerated high temperature and high humidity life test (HAST test). It is also required to keep the melt viscosity low and improve the wiring embedding property.

As described above, it is disclosed in Patent Document 1 that maleimide is contained in the resin composition used for the insulating layer of the printed wiring board. However, Patent Document 1 does not study any adhesion and wiring embedding property after the HAST test. The present inventors have found that by using a predetermined maleimide compound in a resin composition, the adhesion between the conductor layer and the insulating layer can be maintained even after the HAST test. It was also found that the use of a predetermined maleimide compound in the resin composition is excellent in wiring embedding property. As far as the present inventors know, the technical idea of obtaining an insulating layer capable of maintaining high adhesion after the HAST test by containing a predetermined maleimide compound in the resin composition as described above has not been conventionally used. It can be said that it was not proposed.

The subject of the present invention is a resin composition capable of obtaining an insulating layer having high adhesion to a conductor layer after a HAST test and having a low melt viscosity; a resin sheet containing the resin composition; the resin composition. It is an object of the present invention to provide a printed wiring board provided with an insulating layer formed by using the above, and a semiconductor device.

As a result of diligent studies to achieve the object of the present invention, the present inventors can maintain the adhesion between the conductor layer and the insulating layer even after the HAST test by containing a predetermined maleimide compound. I found. Further, they have found that in addition to the above-mentioned adhesiveness, they are excellent in smear removing property and the melt viscosity of the resin composition is low, which has led to the completion of the present invention.

一般式（Ｂ－１）中、Ｒはそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基を表し、Ｌは単結合又は２価の連結基を表す。
［３］ （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、０．１質量％以上１０質量％以下である、［１］又は［２］に記載の樹脂組成物。
［４］ 更に、（Ｃ）活性エステル化合物を含む、［１］～［３］のいずれかに記載の樹脂組成物。
［５］ （Ｃ）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、５質量％以上である、［４］に記載の樹脂組成物。
［６］ 更に、（Ｄ）無機充填材を含む、［１］～［５］のいずれかに記載の樹脂組成物。
［７］ （Ｄ）成分の含有量が、５０質量％以上である、［６］に記載の樹脂組成物。
［８］ 一般式（Ｂ－１）中、Ｌは、酸素原子、置換基を有していてもよい炭素原子数６～２４のアリーレン基、置換基を有していてもよい炭素原子数が１～５０のアルキレン基、炭素原子数が５以上のアルキル基、フタルイミド由来の２価の基、ピロメリット酸ジイミド由来の２価の基、又はこれらの基の２以上の組み合わせからなる２価の基である、［１］～［７］のいずれかに記載の樹脂組成物。
［９］ （Ｂ）成分が、下記一般式（Ｂ－２）で表される、［１］～［８］のいずれかに記載の樹脂組成物。

一般式（Ｂ－２）中、Ｒ’はそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基を表し、Ａはそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基又は置換基を有していてもよい芳香環を有する２価の基を表す。ｎは１～１０の整数を表す。
［１０］ 一般式（Ｂ－２）中、Ａはそれぞれ独立に、置換基を有していてもよい炭素原子数が５以上の環状のアルキレン基；置換基を有していてもよいベンゼン環を有する２価の基；置換基を有していてもよいフタルイミド環を有する２価の基；又は置換基を有していてもよいピロメリット酸ジイミド環を有する２価の基を表す、［９］に記載の樹脂組成物。
［１１］ プリント配線板の絶縁層形成用である、［１］～［１０］のいずれかに記載の樹脂組成物。
［１２］ プリント配線板の層間絶縁層形成用である、［１］～［１１］のいずれかに記載の樹脂組成物。
［１３］ 支持体と、該支持体上に設けられた［１］～［１２］のいずれかに記載の樹脂組成物で形成された樹脂組成物層とを含む、樹脂シート。
［１４］ 樹脂組成物層の厚みが２５μｍ以下である、［１３］に記載の樹脂シート。
［１５］ 第１の導体層、第２の導体層、及び、第１の導体層と第２の導体層との間に形成された絶縁層を含むプリント配線板であって、
該絶縁層は、［１］～［１２］のいずれかに記載の樹脂組成物の硬化物である、プリント配線板。
［１６］ ［１５］に記載のプリント配線板を含む、半導体装置。 That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin and (B) a maleimide compound.
(B) A resin composition comprising at least one of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms as a component (B).
[2] The resin composition according to [1], wherein the component (B) is represented by the following general formula (B-1).

In the general formula (B-1), R represents an alkylene group having 5 or more carbon atoms which may independently have a substituent, and L represents a single bond or a divalent linking group.
[3] The content of the component (B) is 0.1% by mass or more and 10% by mass or less when the non-volatile component in the resin composition is 100% by mass, according to [1] or [2]. Resin composition.
[4] The resin composition according to any one of [1] to [3], further comprising (C) an active ester compound.
[5] The resin composition according to [4], wherein the content of the component (C) is 5% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[6] The resin composition according to any one of [1] to [5], further comprising (D) an inorganic filler.
[7] The resin composition according to [6], wherein the content of the component (D) is 50% by mass or more.
[8] In the general formula (B-1), L has an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have a substituent, and a carbon atom which may have a substituent. A divalent group consisting of 1 to 50 alkylene groups, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from diimide pyromellitic acid, or a combination of 2 or more of these groups. The resin composition according to any one of [1] to [7], which is a group.
[9] The resin composition according to any one of [1] to [8], wherein the component (B) is represented by the following general formula (B-2).

In the general formula (B-2), R'represents an alkylene group having 5 or more carbon atoms which may independently have a substituent, and A may have an independent substituent. Represents a divalent group having an aromatic ring which may have an alkylene group or a substituent having 5 or more carbon atoms. n represents an integer from 1 to 10.
[10] In the general formula (B-2), each A independently may have a substituent and may have a cyclic alkylene group having 5 or more carbon atoms; a benzene ring which may have a substituent. A divalent group having a substituent; a divalent group having a phthalimide ring which may have a substituent; or a divalent group having a diimide ring of pyromellitic acid which may have a substituent, [ 9] The resin composition according to.
[11] The resin composition according to any one of [1] to [10], which is used for forming an insulating layer of a printed wiring board.
[12] The resin composition according to any one of [1] to [11], which is used for forming an interlayer insulating layer of a printed wiring board.
[13] A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of [1] to [12] provided on the support.
[14] The resin sheet according to [13], wherein the thickness of the resin composition layer is 25 μm or less.
[15] A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer.
The insulating layer is a printed wiring board which is a cured product of the resin composition according to any one of [1] to [12].
[16] A semiconductor device including the printed wiring board according to [15].

According to the present invention, an insulating layer having high adhesion to a conductor layer can be obtained after a HAST test, and a resin composition having a low melt viscosity; a resin sheet containing the resin composition; the resin composition. It is possible to provide a printed wiring board provided with an insulating layer formed by using the above, and a semiconductor device.

FIG. 1 is a partial cross-sectional view schematically showing an example of a printed wiring board.

Hereinafter, the resin composition, the resin sheet, the printed wiring board, and the semiconductor device of the present invention will be described in detail.

[Resin composition]
The resin composition of the present invention contains (A) an epoxy resin and (B) a maleimide compound, and the component (B) is at least an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms. Including either.

By incorporating a maleimide compound containing at least one of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms in the resin composition, the maleimide compound is contained between the resin composition and the conductor layer even after the HAST test. It becomes possible to obtain a cured product that can maintain adhesion and is also excellent in smear removal property. Further, by incorporating the maleimide compound in the resin composition, it becomes possible to obtain a resin composition having a low melt viscosity. And, usually, a cured product that can maintain high adhesion even after the HAST test can exhibit high adhesion for a long period of time.

In addition to the components (A) to (B), the resin composition comprises (C) an active ester compound, (D) an inorganic filler, (E) a curing agent, (F) a curing accelerator, and (G). ) It may contain a thermoplastic resin and (H) any additive. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

<(A) Epoxy resin>
The resin composition contains (A) an epoxy resin. Examples of the epoxy resin include bixilenol 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, and trisphenol type. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , Cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane Examples thereof include a dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, and a tetraphenylethane type epoxy resin. The epoxy resin may be used alone or in combination of two or more.

The epoxy resin (A) preferably has two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, the resin composition is a combination of a liquid epoxy resin at a temperature of 20 ° C. (hereinafter, also referred to as “liquid epoxy resin”) and a solid epoxy resin at a temperature of 20 ° C. (also referred to as “solid epoxy resin”). It is preferable to include it. As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable, and an aromatic liquid epoxy resin having two or more epoxy groups in one molecule is more preferable. As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. The alicyclic epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure are preferable, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, "828US", "jER828EL", "825" and "Epicoat" manufactured by Mitsubishi Chemical Co., Ltd. 828EL "(bisphenol A type epoxy resin)," jER807 "," 1750 "(bisphenol F type epoxy resin)," jER152 "(phenol novolac type epoxy resin)," 630 "," 630LSD "(glycidylamine type epoxy resin) , "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" manufactured by Nagase Chemtex Co., Ltd. (glycidyl ester type epoxy resin), manufactured by Daicel Co., Ltd. "Selokiside 2021P" (alicyclic epoxy resin with an ester skeleton), "PB-3600" (epoxy resin with a butadiene structure), "ZX1658", "ZX1658GS" (liquid 1,4-glycidyl) manufactured by Nippon Steel & Sumitomo Metal Corporation. Cyclohexane type epoxy resin), "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., and the like. These may be used alone or in combination of two or more.

Examples of the solid epoxy resin include bixilenol 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, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and naphthalene type epoxy resin is more preferable. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalen type tetrafunctional epoxy resin), and "N-690" manufactured by DIC. Cresol novolak type epoxy resin), "N-695" (cresol novolak type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA-7311" , "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" manufactured by Nippon Kayakusha ( Trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. ( Naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. , "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "YL7800" (Fluoren Type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "jER1031S" (tetraphenylethane type epoxy resin) and the like can be mentioned. These may be used alone or in combination of two or more.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (A), the amount ratio (liquid epoxy resin: solid epoxy resin) thereof is in the range of 1: 1 to 1:20 in terms of mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range, i) when used in the form of a resin sheet, appropriate adhesiveness is obtained, and ii) when used in the form of a resin sheet. Sufficient flexibility can be obtained, handleability is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the quantitative ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more in the range of 1: 1 to 1:15 in terms of mass ratio. The range of 1: 1 to 1:10 is preferable, and the range of 1: 1 to 1:10 is more preferable.

The content of the component (A) in the resin composition is preferably 5% by mass when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. % Or more, more preferably 10% by mass or more, still more preferably 15% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less.
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.

The epoxy equivalent of the component (A) is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. Within this range, the crosslink density of the cured product becomes sufficient, and an insulating layer having a small surface roughness can be obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

The weight average molecular weight of the component (A) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

<(B) Maleimide compound>
The resin composition contains a maleimide compound containing at least one of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms. (B) The maleimide compound is a compound containing a maleimide group represented by the following formula (1) in its molecule.

(B) The maleimide compound contains at least one of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms. Further, a maleimide compound containing at least one of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms has a flexible molecular structure due to the action of its long carbon chain. Therefore, it is possible to achieve a lower minimum melt viscosity as compared with a maleimide compound containing an arylene group in its main composition. Further, since the maleimide group is easily dissolved in an alkaline solution, it is usually possible to obtain a cured product having excellent smear removing property. Alkyl groups having 5 or more carbon atoms and alkylene groups having 5 or more carbon atoms show hydrophobicity because they have a long carbon chain. Therefore, the maleimide compound (B) is less likely to deteriorate in a high temperature and high humidity environment, and can suppress delamination accompanied by destruction of the insulating layer even after the HAST test. As a result, it becomes possible to obtain an insulating layer having high adhesion to the conductor layer after the HAST test.

The number of carbon atoms of an alkyl group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. The alkyl group may be linear, branched or cyclic, and the linear group is preferable. Examples of such an alkyl group include a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and the like. The alkyl group having 5 or more carbon atoms may have as a substituent of the alkylene group having 5 or more carbon atoms.

The number of carbon atoms of the alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. The alkylene group may be linear, branched or cyclic, and the linear group is preferable. Here, the cyclic alkylene group is a concept including a case where it is composed of only a cyclic alkylene group and a case where it contains both a linear alkylene group and a cyclic alkylene group. Examples of such an alkylene group include a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, a hexatriacontylene group and an octylene-cyclohexylene. Examples thereof include a group having a structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like.

(B) In the maleimide compound, the alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms are preferably directly bonded to the nitrogen atom of the maleimide group. Here, "directly" means that there is no other group between the nitrogen atom of the maleimide group and the alkyl group or the alkylene group. As a result, the adhesion and the minimum melt viscosity after the HAST test can be made particularly good.

(B) The maleimide compound contains both an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms from the viewpoint of obtaining an insulating layer having high adhesion to the conductor layer after the HAST test. It is preferable to include it.

Alkyl groups having 5 or more carbon atoms and alkylene groups having 5 or more carbon atoms may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a fused ring. Examples of the ring formed by bonding with each other include a cyclohexane ring and the like.

The alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms preferably do not have a substituent, but may have a substituent. The substituent is not particularly limited, and is, for example, a halogen atom, -OH, -OC _1-6 alkyl group, -N (C _1-10 alkyl group) ₂ , C _1-10 alkyl group, C _6- . Examples thereof include a ₁₀ aryl group, -NH ₂ , -CN, -C (O) OC _1-10 alkyl group, -COOH, -C (O) H, -NO ₂ and the like. Here, the term "C _p-q " (p and q are positive integers and satisfy p <q) is described immediately after this term in that the number of carbon atoms of the organic group is p to q. Represents that there is. For example, the expression "C _1-10 alkyl group" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring.

The above-mentioned substituent may further have a substituent (hereinafter, may be referred to as a "secondary substituent"). Unless otherwise specified, the same as the above-mentioned substituent may be used as the secondary substituent.

(B) The number of maleimide groups per molecule of the maleimide compound may be 1, but is preferably 2 or more, preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less. .. By using the (B) maleimide compound having two or more maleimide groups per molecule, it is possible to obtain an insulating layer having higher adhesion to the conductor layer after the HAST test.

(B) The maleimide compound may be used alone or in combination of two or more.

一般式（Ｂ－１）中、Ｒはそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基を表し、Ｌは単結合又は２価の連結基を表す。 (B) The maleimide compound may contain at least one of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms, but has higher adhesion to the conductor layer after the HAST test. From the viewpoint of obtaining an insulating layer having properties, a maleimide compound represented by the following general formula (B-1) is preferable.

In the general formula (B-1), R represents an alkylene group having 5 or more carbon atoms which may independently have a substituent, and L represents a single bond or a divalent linking group.

R represents an alkylene group having 5 or more carbon atoms, each of which may have a substituent independently. R has the same meaning as the above-mentioned alkylene group having 5 or more carbon atoms, and the preferred range is also the same.

L represents a single bond or a divalent linking group. The divalent linking group includes an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C (= O)-, -C (= O) -O-, and -NR ^0- (R ⁰ is a hydrogen atom and carbon. Alkyl group with 1 to 3 atoms), oxygen atom, sulfur atom, C (= O) NR ^0- , divalent group derived from phthalimide, divalent group derived from diimide pyromellitic acid, and 2 of these groups Examples thereof include a divalent group composed of the above combinations. The phthalimide-derived divalent group represents a divalent group derived from phthalimide, and specifically, is a group represented by the general formula (2). The divalent group derived from diimide pyromellitic acid represents a divalent group derived from diimide pyromellitic acid, and specifically, is a group represented by the general formula (3). In the formula, "*" represents a bond.

As the alkylene group, an alkylene group having 1 to 50 carbon atoms is preferable, an alkylene group having 1 to 45 carbon atoms is more preferable, and an alkylene group having 1 to 40 carbon atoms is particularly preferable. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylethylene group, a cyclohexylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group and a hexatria. Examples thereof include a contylene group, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure and the like.

As the alkenylene group, an alkenylene group having 2 to 20 carbon atoms is preferable, an alkenylene group having 2 to 15 carbon atoms is more preferable, and an alkenylene group having 2 to 10 carbon atoms is particularly preferable. The alkenylene group may be linear, branched or cyclic. Examples of such an alkenylene group include a methylethylenylene group, a cyclohexenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group and the like.

As the alkynylene group, an alkynylene group having 2 to 20 carbon atoms is preferable, an alkynylene group having 2 to 15 carbon atoms is more preferable, and an alkynylene group having 2 to 10 carbon atoms is particularly preferable. The alkynylene group may be linear, branched or cyclic. Examples of such an alkynylene group include a methylethynylene group, a cyclohexynylene group, a pentynylene group, a hexynylene group, a heptinylene group, an octynylene group and the like.

As the arylene group, an arylene group having 6 to 24 carbon atoms is preferable, an arylene group having 6 to 18 carbon atoms is more preferable, an arylene group having 6 to 14 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. The arylene group is even more preferred. Examples of the arylene group include a phenylene group, a naphthylene group, an anthrasenylene group and the like.

The divalent linking group alkylene group, alkenylene group, alkynylene group, and arylene group may have a substituent. The substituent is the same as the substituent which may be possessed by the alkyl group having 5 or more carbon atoms represented by R in the general formula (B-1), and preferably the alkyl having 5 or more carbon atoms. It is a group.

Examples of the divalent group consisting of two or more combinations of these groups include an alkylene group, a divalent group derived from phthalimide, and a divalent group consisting of a combination with an oxygen atom; a divalent group derived from phthalimide. Examples thereof include a divalent group consisting of a combination of an oxygen atom, an arylene group and an alkylene group; a divalent group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; and the like. A divalent group consisting of two or more combinations of these groups may form a ring such as a fused ring by the combination of the respective groups. Further, the divalent group consisting of two or more combinations of these groups may be a repeating unit having 1 to 10 repeating units.

Among them, L in the general formula (B-1) includes an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have a substituent, and a carbon atom which may have a substituent. A divalent group consisting of 1 to 50 alkylene groups, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from diimide pyromellitic acid, or a combination of 2 or more of these groups. It is preferably a group. Among them, L is an alkylene group; an alkylene group-a divalent group derived from phthalimide-an oxygen atom-a divalent group having a structure of a divalent group derived from phthalimide; an alkylene group-a divalent group derived from phthalimide- Oxygen atom-allylen group-alkylene group-allylen group-oxygen atom-divalent group having a divalent group structure derived from phthalimide; divalent group having a divalent group structure derived from alkylene-pyramellitic acid diimide Groups are more preferred.

一般式（Ｂ－２）中、Ｒ’はそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基を表し、Ａはそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基又は置換基を有していてもよい芳香環を有する２価の基を表す。ｎは１～１０の整数を表す。 The maleimide compound represented by the general formula (B-1) is preferably represented by the general formula (B-2).

In the general formula (B-2), R'represents an alkylene group having 5 or more carbon atoms which may independently have a substituent, and A may have an independent substituent. Represents a divalent group having an aromatic ring which may have an alkylene group or a substituent having 5 or more carbon atoms. n represents an integer from 1 to 10.

R'represents an alkylene group having 5 or more carbon atoms, each of which may have a substituent independently. R'is the same as R in the general formula (B-1).

A represents an alkylene group having 5 or more carbon atoms which may independently have a substituent or a divalent group having an aromatic ring which may have a substituent. However, when A represents an alkylene group, the case where it consists only of a linear alkylene group is excluded. When A represents an alkylene group, it may be branched chain or cyclic, and among them, a cyclic, that is, a cyclic alkylene group having 5 or more carbon atoms which may have a substituent is preferable. The number of carbon atoms is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. Examples of such an alkylene group include a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like.

Examples of the aromatic ring in the divalent group having an aromatic ring which may have a substituent include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a diimide ring of pyromellitic acid, an aromatic heterocycle and the like. Therefore, a benzene ring, a phthalimide ring, and a diimide ring of pyromellitic acid are preferable. That is, as the divalent group having an aromatic ring, a divalent group having a benzene ring which may have a substituent, a divalent group having a phthalimide ring which may have a substituent, and a substitution group. A divalent group having a diimide ring of pyromellitic acid, which may have a group, is preferable. The divalent group having an aromatic ring is, for example, a group composed of a combination of a divalent group derived from phthalimide and an oxygen atom; a divalent group derived from phthalimide, an oxygen atom, an arylene group and an alkylene group. Group; a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; a divalent group derived from diimide pyromellitic acid; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group; etc. Can be mentioned. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (B-1), and the preferable range is also the same.

The divalent group having an alkylene group and an aromatic ring represented by A may have a substituent. The substituent is the same as the substituent which may be contained in the alkyl group having 5 or more carbon atoms represented by R in the general formula (B-1).

Specific examples of the group represented by A include the following groups. In the formula, "*" represents a bond.

一般式（Ｂ－３）中、Ｒ^１はそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基を表し、Ｒ^２はそれぞれ独立に、酸素原子、アリーレン基、アルキレン基、又はこれらの基の２以上の組み合わせからなる２価の基を表す。ｎ１は１～１５の整数を表す。
一般式（Ｂ－４）中、Ｒ^３はそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基を表し、Ｒ^４はそれぞれ独立に置換基を有していてもよい芳香環を有する２価の基を表し、Ｒ^５はそれぞれ独立に炭素原子数が５以上のアルキル基を表す。ｎ２は０～１０の整数を表し、ｍはそれぞれ独立に０～４の整数を表す。 The maleimide compound represented by the general formula (B-1) may be either a maleimide compound represented by the general formula (B-3) or a maleimide compound represented by the general formula (B-4). preferable.

In the general formula (B-3), R ¹ represents an alkylene group having 5 or more carbon atoms which may independently have a substituent, and R ² independently represents an oxygen atom, an arylene group and an alkylene. Represents a divalent group consisting of a group or a combination of two or more of these groups. n1 represents an integer of 1 to 15.
In the general formula (B-4), R ³ represents an alkylene group having 5 or more carbon atoms which may independently have a substituent, and R ⁴ may have an independent substituent. It represents a divalent group with a good aromatic ring, and each R ⁵ independently represents an alkyl group having 5 or more carbon atoms. n2 represents an integer of 0 to 10, and m represents an integer of 0 to 4 independently.

R ¹ represents an alkylene group having 5 or more carbon atoms which may independently have a substituent. R ¹ is the same as the alkylene group having 5 or more carbon atoms represented by R in the general formula (B-1), and a hexatriacontylene group is preferable.

R ² independently represents a divalent group consisting of an oxygen atom, an arylene group, an alkylene group, or a combination of two or more of these groups. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (B-1), and the preferable range is also the same. ^R2 is preferably a divalent group or an oxygen atom consisting of two or more combinations of these groups.

Examples of the divalent group consisting of two or more combinations of these groups include a combination of an oxygen atom, an arylene group, and an alkylene group. Specific examples of a divalent group consisting of two or more combinations of these groups include the following groups. In the formula, "*" represents a bond.

R ³ represents an alkylene group having 5 or more carbon atoms, each of which may have a substituent independently. R ³ is the same as the alkylene group having 5 or more carbon atoms represented by R in the general formula (B-1), preferably a hexylene group, a heptylene group, an octylene group, a nonylene group, or a decylene group, and the octylene group is preferable. More preferred.

R ⁴ represents a divalent group having an aromatic ring, each of which may independently have a substituent. ^R4 is the same as the divalent group having an aromatic ring represented by A in the general formula (B-2), and is a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; derived from phthalimide. A group consisting of a combination of a divalent group and an alkylene group is preferable, and a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide is more preferable. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (B-1), and the preferable range is also the same.

Specific examples of the group represented by R ⁴ include the following groups. In the formula, "*" represents a bond.

R ⁵ independently represents an alkyl group having 5 or more carbon atoms. R ⁵ is the same as the above-mentioned alkyl group having 5 or more carbon atoms, preferably a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group, and more preferably a hexyl group and an octyl group.

m represents an integer of 0 to 4, preferably an integer of 1 to 3, and more preferably 2.

Specific examples of the (B) maleimide compound include the following compounds (4) to (7). However, the (B) maleimide compound is not limited to these specific examples. In the formula, n represents an integer from 1 to 10.

Specific examples of the maleimide compound (B) include "BMI1500" (compound of formula (4)), "BMI1700" (compound of formula (5)), and "BMI3000J" (formula (6)) manufactured by Designer Molecule's. ), “BMI689” (compound of formula (7)), and the like.

The molecular weight of the maleimide compound (B) is preferably 200 or more, more preferably 300 or more, still more preferably 400 or more, preferably 100,000 or less, from the viewpoint of improving the adhesion to the conductor layer after the HAST test. It is more preferably 80,000 or less, still more preferably 60,000 or less.

The content of the maleimide compound (B) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1% by mass when the non-volatile component in the resin composition is 100% by mass. That is all. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less or 3% by mass or less. By keeping the content of the component (B) within such a range, the increase in the minimum melt viscosity of the resin composition is further suppressed, and the adhesion between the insulating layer and the conductor layer after the HAST test and the smear removal property are improved. It is possible to obtain an excellent cured product.

<(C) Active ester compound>
In one embodiment, the resin composition may contain (C) the active ester compound. It is known that the use of an active ester compound usually results in poor smear removal. However, since the resin composition of the present invention contains the (B) maleimide compound, the cured product of the resin composition is excellent in smear removing property. Therefore, even if the active ester compound is used, the smear removing property is not inferior.

The active ester compound is not particularly limited, but generally, an ester group having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds is contained in one molecule. A compound having two or more is preferably used. The active ester compound is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester compound 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, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, 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, dihydroxybenzophenol, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compound, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available products of the active ester compound include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-65TM" as active ester compounds containing a dicyclopentadiene type diphenol structure. , "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC), "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure, an active ester containing an acetylated product of phenol novolac. "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as a compound, "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated product of phenol novolac, and "DC808" (Mitsubishi Chemical Co., Ltd.) as an active ester compound which is an acetylated product of phenol novolac. (Manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.), etc. ..

When the resin composition contains (C) the active ester compound, the amount ratio of the epoxy resin to the active ester compound is [total number of epoxy groups in the epoxy resin]: [total number of reactive groups in the active ester compound]. The ratio is preferably in the range of 1: 0.01 to 1: 5, more preferably 1: 0.05 to 1: 3, and even more preferably 1: 0.1 to 1: 1.5. Here, the reactive group of the active ester compound is an active ester group. The total number of epoxy groups in the epoxy resin is the total number of all epoxy resins obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and is the total number of reactive groups in the active ester compound. , The value obtained by dividing the solid content mass of each active ester compound by the reaction group equivalent is the total value for all the active ester compounds. By setting the quantitative ratio of the epoxy resin and the active ester compound within such a range, the heat resistance of the cured product of the resin composition is further improved.

When the resin composition contains the (C) active ester compound, the content of the component (C) is preferably 1% by mass or more, more preferably 3 when the non-volatile component in the resin composition is 100% by mass. By mass or more, more preferably 5% by mass or more. 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 (C) within such a range, the peel strength before and after the HAST test can be improved.

<(D) Inorganic filler>
In one embodiment, the resin composition may contain (D) an inorganic filler. (D) The material of the inorganic filler is not particularly limited as long as it is an inorganic compound, but for example, 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, titanic acid Examples thereof include magnesium, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like. Of these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

(D) Commercially available inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials; "YC100C", "YA050C" and "YA050C-MJE" manufactured by Admatex. , "YA010C"; "UFP-30" manufactured by Denka; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama; "SC2500SQ" manufactured by Admatex. Examples thereof include "SO-C4", "SO-C2", "SO-C1"; and the like.

Usually, (D) the inorganic filler is contained in the resin composition in the form of particles. (D) The average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferably 5.0 μm or less, more preferably 2.0 μm or less, still more preferably 1.0 μm or less. Further, when the average particle size of the (D) inorganic filler is within the above range, it is usually possible to improve the circuit embedding property of the resin composition layer and reduce the surface roughness of the insulating layer.

(D) The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating the particle size distribution of (D) the inorganic filler on a volume basis by a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, (D) an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd., "SALD-2200" manufactured by Shimadzu Corporation, or the like can be used.

(D) The inorganic filler may be surface-treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of the surface treatment agent include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, organosilazane compounds, titanate-based coupling agents, and the like. .. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-" manufactured by Shin-Etsu Chemical Co., Ltd. 7103 ”(3,3,3-trifluoropropyltrimethoxysilane) and the like. The surface treatment agent may be used alone or in combination of two or more.

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

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

(D) The content of the inorganic filler is preferably 50% by mass or more, more preferably 55% by mass or more, when the non-volatile component in the resin composition is 100% by mass from the viewpoint of lowering the thermal expansion rate. More preferably, it is 60% by mass or more or 65% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less. It is known that when a large amount of inorganic filler is blended, the adhesion is reduced, but in the present invention, even if a large amount of (D) inorganic filler is blended, the decrease in adhesion can be effectively suppressed.

<(E) Curing agent>
In one embodiment, the resin composition may contain (E) a curing agent. However, the (C) active ester compound is not included in the (E) curing agent. The (E) curing agent is not particularly limited as long as it has a function of curing the component (A), and for example, a phenol-based curing agent, a naphthol-based curing agent, a benzoxazine-based curing agent, and a cyanate ester-based curing agent. Examples thereof include agents and carbodiimide-based curing agents. Above all, from the viewpoint of improving insulation reliability, the (E) curing agent is preferably one or more 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 contain a phenolic curing agent. The curing agent may be used alone or in combination of two or more.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. 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 the naphthol-based curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" manufactured by Nippon Steel & Sumitomo Metal Corporation , DIC Corporation "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" and the like.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa High Polymer Co., Ltd., "Pd" and "FA" manufactured by Shikoku Chemicals Corporation.

Examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylencyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidendiphenyl disyanate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol. Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), and "BA230" manufactured by Ronza Japan. , "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazined to form a trimer) and the like.

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

When the resin composition contains (E) a curing agent, the amount ratio of the epoxy resin to the curing agent is the ratio of [total number of epoxy groups in the epoxy resin]: [total number of reactive groups in the curing agent]. , 1: 0.01 to 1: 2, more preferably 1: 0.01 to 1: 3, and even more preferably 1: 0.01 to 1: 1.5. Here, the reactive group of the curing agent is an active hydroxyl group or the like, and differs depending on the type of the curing agent. The total number of epoxy groups in the epoxy resin is the total number of all epoxy resins obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and the total number of reactive groups in the curing agent is The value obtained by dividing the solid content mass of each curing agent by the reaction group equivalent is the total value for all the curing agents. By setting the amount ratio of the epoxy resin and the curing agent within such a range, the heat resistance of the cured product of the resin composition is further improved.

When the resin composition contains (C) active ester compound and (E) curing agent, the amount ratio of the epoxy resin to the active ester compound is [total number of epoxy groups in the epoxy resin]: [(C) and ( E) The ratio of [total number of reactive groups of the components] is preferably in the range of 1: 0.01 to 1: 5, more preferably 1: 0.01 to 1: 3, and 1: 0.01 to 1: 1. .5 is more preferable. By setting the amount ratio of the epoxy resin to the component (C) and the component (E) within 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 0.1% by mass, when the non-volatile component in the resin composition is 100% by mass. It is preferably 0.3% by mass or more, more preferably 0.5% by 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. (E) By keeping the content of the curing agent within such a range, the adhesion to the conductor layer after the HAST test can be improved.

<(F) Curing accelerator>
In one embodiment, the resin composition may contain (F) a curing accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like, and phosphorus-based curing accelerators and amine-based curing agents. Curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators are more preferable. The curing accelerator may be used alone or in combination of two or more.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and the like. 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'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline Examples thereof include imidazole compounds such as 2-phenylimidazolin and adducts of the imidazole compound and an epoxy resin, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

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

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, and trimethylguanidine. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylviguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned, with dicyandiamide and 1,5,7-triazabicyclo [4.4.0] deca-5-ene being 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 organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples thereof include an organic zinc complex such as iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate. 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 (F) a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.01% by mass, when the non-volatile component in the resin composition is 100% by mass. Is 0.05% by mass or more, more preferably 0.1% by mass or more. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less. By setting the content of the curing accelerator within such a range, a cured product having excellent adhesion after the HAST test can be obtained even if an inorganic filler having a small average particle size is used.

<(G) Thermoplastic resin>
In one embodiment, the resin composition may contain (G) a thermoplastic resin. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, and polycarbonate resin. , Polyether ether ketone resin, polyester resin and the like, and phenoxy resin is preferable. The thermoplastic resin may be used alone or in combination of two or more.

The polystyrene-equivalent weight average molecular weight of the (G) thermoplastic resin is preferably 38,000 or more, more preferably 40,000 or more, still more preferably 42,000 or more. The upper limit is preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less. (G) The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of (G) thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L manufactured by Showa Denko Corporation as a column. / K-804L can be calculated by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase and using a standard polystyrene calibration curve.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpene. Examples thereof include phenoxy resins having one or more skeletons selected from the group consisting of skeletons and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resin), "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" (bisphenol acetophenone) manufactured by Mitsubishi Chemical Corporation. (Skeletal-containing phenoxy resin), and also "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Corporation, "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30" manufactured by Mitsubishi Chemical Corporation. , "YL6794", "YL7213", "YL7290", "YL7482" and the like.

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, "Electrified Butyral 4000-2", "Electrified Butyral 5000-A", "Electrified Butyral 6000-C", "Electrified Butyral 6000-EP", Sekisui Chemical Co., Ltd. Examples thereof include Eslek BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Chemical Industry Co., Ltd.

Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by NEW JAPAN CHEMICAL CO., LTD. Specific examples of the polyimide resin include a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), and a polysiloxane skeleton. Examples thereof include modified polyimides such as contained polyimides (polyimides described in JP-A-2002-12667 and JP-A-2000-31386).

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

Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of the polyphenylene ether resin include oligophenylene ether / styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company.

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

Among them, as the (G) thermoplastic resin, a phenoxy resin and a polyvinyl acetal resin are preferable. Thus, in one preferred embodiment, the thermoplastic resin comprises one or more selected from the group consisting of phenoxy resins and polyvinyl acetal resins. Among them, as the thermoplastic resin, a phenoxy resin is preferable, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferable.

When the resin composition contains (G) a thermoplastic resin, the content of the (G) thermoplastic resin is preferably 0.1% by mass or more when the non-volatile component in the resin composition is 100% by mass. It is more preferably 0.2% by mass or more, still more preferably 0.3% by 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 (G) thermoplastic resin within such a range, a cured product having excellent adhesion after the HAST test can be obtained even if an inorganic filler having a small average particle size is used.

<(H) Arbitrary additive>
In one embodiment, the resin composition may further contain other additives, if desired, such other additives include, for example, flame retardants, organic fillers, organocopper compounds, organics. Examples thereof include organometallic compounds such as zinc compounds and organocobalt compounds, and resin additives such as thickeners, defoaming agents, leveling agents, adhesion-imparting agents, and colorants.

Examples of the flame retardant include a phosphazene compound, an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, a metal hydroxide and the like. Specific examples of the phosphazene compound include, for example, "SPH-100", "SPS-100", "SPB-100" and "SPE-100" manufactured by Otsuka Chemical Co., Ltd., and "FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd. Examples thereof include "FP-110", "FP-300", "FP-400", etc. As a flame retardant other than the phosphazene compound, a commercially available product may be used, for example, "HCA-HQ" manufactured by Sanko Co., Ltd. , "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. and the like.

As the organic filler, any organic filler that can be used for forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles. As the rubber particles, commercially available products may be used, and examples thereof include "EXL2655" manufactured by Dow Chemical Japan Co., Ltd., "AC3401N" and "AC3816N" manufactured by Aica Kogyo Co., Ltd.

<Physical characteristics and uses of resin composition>
A cured product obtained by thermally curing the resin composition at 100 ° C. for 30 minutes, 170 ° C. for 30 minutes, and then at 200 ° C. for 90 minutes has the characteristic of being excellent in copper foil peeling strength (peeling strength) before the HAST test. show. That is, it provides an insulating layer having excellent adhesion before the HAST test. The peel strength before the HAST test is preferably 0.4 kgf / cm or more, more preferably 0.5 kgf / cm or more, and further preferably 0.6 kgf / cm or more. The upper limit is not particularly limited, but may be 10 kgf / cm or less. The copper foil peeling strength before the HAST test can be measured by the method described in Examples described later.

A cured product obtained by thermally curing the resin composition at 100 ° C. for 30 minutes, 170 ° C. for 30 minutes, and then at 200 ° C. for 90 minutes has the characteristic of being excellent in copper foil peeling strength (peel strength) after the HAST test. show. That is, it provides an insulating layer that has excellent adhesion after the HAST test and can exhibit high adhesion over a long period of time. The peel strength after the HAST test is preferably 0.15 kgf / cm or more, more preferably 0.2 kgf / cm or more, and further preferably 0.3 kgf / cm or more. The upper limit is not particularly limited, but may be 10 kgf / cm or less. The peel strength after the HAST test can be measured by the method described in Examples described later.

A cured product obtained by thermally curing the resin composition at 100 ° C. for 30 minutes and then at 170 ° C. for 30 minutes usually exhibits excellent smear removing property. That is, even if a via hole is formed in the cured product, an insulating layer having a maximum smear length of 5 μm or less at the bottom of the via hole is provided. The smear removability can be measured by the method described in Examples described later.

The resin composition of the present invention indicates that the minimum melt viscosity at 60 to 200 ° C. is low. That is, it provides a resin composition having excellent wiring embedding property. The minimum melt viscosity of the resin composition at 60 to 200 ° C. is preferably 5000 poise or less, more preferably 4500 poise or less, still more preferably 4000 poise or less. The lower limit of the minimum melt viscosity is preferably 100 poise or more, and more preferably 1000 poise or more, from the viewpoint of stably maintaining the thickness even if the resin composition layer is thin. The minimum melt viscosity can be measured by the dynamic viscoelastic method, for example, according to the method described in Examples described later.

The resin composition of the present invention can provide an insulating layer having excellent thin film insulating properties and capable of maintaining adhesion with the conductor layer after the HAST test. Therefore, the resin composition of the present invention can be suitably used as a resin composition (resin composition for an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board, and can be suitably used between layers of the printed wiring board. It can be more preferably used as a resin composition for forming an insulating layer (resin composition for an interlayer insulating layer of a printed wiring board). Further, since the resin composition of the present invention provides an insulating layer having good component embedding property, it can be suitably used even when the printed wiring board is a component built-in circuit board.

[Resin sheet]
The resin sheet of the present invention includes 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 25 μm or less, more preferably 20 μm or less, still more preferably 20 μm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product having excellent insulating properties even if it is a thin film. It is 15 μm or less, or 10 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

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, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) And other polyesters, polycarbonate (hereinafter abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyimides. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, and the like, and 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.) may be used. You may use it.

The support may be matted, corona-treated, or antistatic-treated on the surface to be joined to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be joined to the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based mold release agent as a main component. Examples include "AL-5", "AL-7", "Lumilar T60" manufactured by Toray Industries, "Purex" manufactured by Teijin Ltd., and "Unipee" manufactured by Unitika Ltd.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

In one embodiment, the resin sheet may further contain other layers, if necessary. Examples of such other layers include a protective film similar to the support provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Be done. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion and scratches of dust and the like on the surface of the resin composition layer.

For the resin sheet, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied onto a support using a die coater or the like and further dried to form a resin composition layer. It can be manufactured by.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol and the like. Carbitols; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

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

The resin sheet can be rolled up and stored. If 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, a first conductor layer, and a second conductor layer formed by a cured product of the resin composition of the present invention. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer and the second conductor layer (the conductor layer is a wiring layer). be).

The insulating layer is formed of a cured product of the resin composition of the present invention. The thickness of the insulating layer between the first and second conductor layers is preferably 6 μm or less, more preferably 5.5 μm or less, still more preferably 5 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more. The distance between the first conductor layer and the second conductor layer (thickness of the insulating layer between the first and second conductor layers) is the main surface of the first conductor layer 1 as shown in FIG. 1 as an example. It refers to the thickness t1 of the insulating layer 3 between the main surface 21 of the 11 and the second conductor layer 2. The first and second conductor layers are adjacent conductor layers via an insulating layer, and the main surface 11 and the main surface 21 face each other.

The thickness t2 of the entire insulating layer is preferably 15 μm or less, more preferably 13 μm or less, and further preferably 10 μm or less. The lower limit is not particularly limited, but may be usually 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

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

The "inner layer substrate" used in the step (I) is a member that becomes a substrate of a printed wiring board, and is, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. And so on. Further, the substrate may have a conductor layer on one side or both sides thereof, and the conductor layer may be patterned. An inner layer board in which a conductor layer (circuit) is formed on one side or both sides of the board may be referred to as an "inner layer circuit board". Further, an intermediate product in which an insulating layer and / or a conductor layer should be formed when the printed wiring board is manufactured is also included in the "inner layer substrate" in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

The inner layer substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressing the resin sheet to the inner layer substrate (hereinafter, also referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). It is preferable not to press the heat-bonded member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

The inner layer substrate and the resin sheet may be laminated by a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and the heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions with a pressure of 26.7 hPa or less.

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

After laminating, the laminated resin sheet may be smoothed by pressing under normal pressure (under atmospheric pressure), for example, from the support side. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The smoothing process can be performed by a commercially available laminator. The laminating and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

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

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

The thermosetting conditions of the resin composition layer are not particularly limited, and the conditions usually adopted when forming the insulating layer of the printed wiring board may be used.

For example, the thermosetting conditions of the resin composition layer differ 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., still more 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 even more preferably 15 minutes to 90 minutes.

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

In manufacturing the printed wiring board, (III) a step of drilling a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing a printed wiring board. When the support is removed after the step (II), the support may be removed between the steps (II) and the step (III), between the steps (III) and the step (IV), or the step ( It may be carried out between IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board. In this case, the thickness of the insulating layer between the respective conductor layers (t1 in FIG. 1) is preferably within the above range.

The step (III) is a step of drilling 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 by 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 dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions usually used for forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling solution used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution, and the alkaline solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. preferable. Examples of commercially available swelling liquids include "Swelling Dip Security Guns P" and "Swelling Dip Security Guns SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C to 80 ° C for 5 to 15 minutes. The oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C to 80 ° C for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dozing Solution Security P" manufactured by Atotech Japan. The neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Security Gant P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be performed by immersing the treated surface that has been roughened with the oxidizing agent in the neutralizing solution at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with an oxidizing agent in a neutralizing solution at 40 ° C to 70 ° C for 5 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, still more preferably 300 nm or less. The lower limit is not particularly limited, but may be preferably 0.5 nm or more, more preferably 1 nm or more, and the like. 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 further preferably 300 nm or less. The lower limit is not particularly limited, but may be preferably 0.5 nm or more, more preferably 1 nm or more, and the like. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer. When the conductor layer is not formed on the inner layer substrate, the step (V) is a step of forming the first conductor layer, and when the conductor layer is formed on the inner layer substrate, the conductor layer is the first conductor layer. The step (V) is a step of forming the second conductor layer.

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). Examples include layers formed from nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility, cost, ease of patterning, etc. for forming a conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. A nickel alloy, a copper-titanium alloy alloy layer is preferable, a chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layer, or a nickel-chromium alloy alloy layer is more preferable, and a copper single metal layer is preferable. A metal layer is more preferred.

The conductor layer may have a single-layer structure, a single metal layer made of different types of metals or alloys, or a multi-layer structure in which two or more alloy layers are laminated. When the conductor layer has a multi-layer 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 depends on the design of the desired printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full additive method, and the semi-additive can be manufactured from the viewpoint of ease of manufacture. It is preferably formed by the method. Hereinafter, an example of forming the conductor layer by the semi-additive method will be shown.

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

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

The printed wiring board manufactured by using the resin sheet of the present invention has an embodiment including 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. May be 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 by using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conduction point" is a "place for transmitting an electric signal in the printed wiring board", and the place may be a surface or an embedded place. Further, 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 in manufacturing a 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, and a bumpless build-up layer. Examples thereof include a mounting method using (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the "mounting method using the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.

Hereinafter, the present invention will be specifically described with reference to Examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, 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 169), and naphthol type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. " , Epoxy equivalent of about 330) was dissolved by heating in 40 parts of Solvent Nafsa with stirring. This was cooled to room temperature to prepare a dissolution composition of (A) epoxy resin.

This (A) epoxy resin dissolution composition is a phenolic compound having 5 parts of a phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass), a triazine skeleton and a novolak structure. 5 parts of curing agent ("LA-3018-50P" manufactured by DIC, active group equivalent of about 151, 2-methoxypropanol solution having 50% solid content), active ester-based curing agent ("HPC-8000-65T" manufactured by DIC) , Active group equivalent of about 223, solid content 65% by mass of toluene solution) 50 parts, curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), solid content of 10% by mass MEK solution), amine-based alkoxy 250 parts of spherical silica (average particle size 0.77 μm, "SO-C2" manufactured by Admatex) surface-treated with a silane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and a maleimide compound (Designer Molecule's Co., Ltd.) 25 parts of a 40 mass% toluene solution manufactured by "BMI3000J") was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 μm) having a release layer was prepared. The resin varnish was uniformly applied onto the release layer of the support so that the thickness of the resin composition layer after drying was 25 μm. Then, the resin varnish was dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 4 minutes to obtain a resin sheet containing a support and a resin composition layer.

[Example 2]
In Example 1, 25 parts of a 40% by mass toluene solution of a maleimide compound (“BMI3000J” manufactured by Designer Molecule) was added to 25 parts of a 40% by mass toluene solution of a maleimide compound (“BMI1700” manufactured by Designer Molecule). changed. Except for the above items, a resin varnish and a resin sheet were manufactured in the same manner as in Example 1.

[Example 3]
In Example 1, 25 parts of a 40% by mass toluene solution of a maleimide compound (“BMI3000J” manufactured by Designer Molecule) was added to 25 parts of a 40% by mass toluene solution of a maleimide compound (“BMI1500” manufactured by Designer Molecule). changed. Except for the above items, a resin varnish and a resin sheet were manufactured in the same manner as in Example 1.

[Example 4]
In Example 1, 25 parts of a 40% by mass toluene solution of a maleimide compound (“BMI3000J” manufactured by Designer Molecule) was added to 25 parts of a 40% by mass toluene solution of a maleimide compound (“BMI689” manufactured by Designer Molecule). changed. Except for the above items, a resin varnish and a resin sheet were manufactured in the same manner as in Example 1.

式中、Ｍｅはメチル基を表し、Ｅｔはエチル基を表す。 [Comparative Example 1]
In Example 1, 25 parts of a 40 mass% toluene solution of a maleimide compound (“BMI3000J” manufactured by Designer Molecule's Co., Ltd.) is divided into 40 mass% of a maleimide compound (“BMI70” manufactured by Keiai Kasei Co., Ltd.) represented by the following structural formula. It was changed to 25 parts of% MEK solution. Except for the above items, a resin varnish and a resin sheet were manufactured in the same manner as in Example 1.

In the formula, Me represents a methyl group and Et represents an ethyl group.

[Comparative Example 2]
In Example 2, the amount of spherical silica (average particle size 0.77 μm, “SO-C2” manufactured by Admatex) surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was 250 parts. The number was changed from 240 parts to 240 parts, and no maleimide compound (“BMI3000J” manufactured by Designer Molecule's Co., Ltd.) was used. Except for the above items, a resin varnish and a resin sheet were manufactured in the same manner as in Example 2.

[Evaluation methods]
The resin sheets obtained in the above-mentioned Examples and Comparative Examples were evaluated by the following methods.

[Measuring method of peel strength]
<Making a substrate for adhesion evaluation>
(1) Base treatment of interior board:
As the inner layer substrate, a glass cloth base material epoxy resin double-sided copper-clad laminate having a copper foil on the surface (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic “R1515A”) was prepared. All the copper foil on the surface of this inner layer substrate was removed by etching. Then, it dried at 190 degreeC for 30 minutes.

(2) Lamination of resin sheets:
The resin sheets obtained in the above-mentioned Examples and Comparative Examples were subjected to a batch type vacuum pressurizing laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), and the resin composition layer was used with the above-mentioned inner layer substrate. It was laminated on both sides of the inner layer substrate so as to be joined. This laminating was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at a temperature of 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

Next, the laminated resin sheet was heat-pressed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure to smooth it. Then, the support was peeled off to obtain an "intermediate multilayer body I" containing the resin composition layer, the inner layer substrate and the resin composition layer in this order.

On the other hand, a copper foil having a glossy surface (thickness 35 μm, “3EC-III” manufactured by Mitsui Mining & Smelting Co., Ltd.) was prepared. The glossy surface of the copper foil was etched with a micro-etching agent (“CZ8101” manufactured by MEC) with a copper etching amount of 1 μm to perform a roughening treatment. The copper foil thus obtained is called "roughened copper foil".

This roughened copper foil was laminated on both sides of the intermediate multilayer body I so that the surface of the roughened copper foil subjected to the roughening treatment was bonded to the resin composition layer of the intermediate multilayer body I. This laminating was performed under the same conditions as the laminating of the resin sheet on the inner layer substrate described above. As a result, an "intermediate multilayer body II" containing the roughened copper foil, the resin composition layer, the inner layer substrate, the resin composition layer and the roughened copper foil in this order was obtained.

The intermediate multilayer II was placed in an oven at 100 ° C. and heated for 30 minutes, then transferred to an oven at 170 ° C. and heated for 30 minutes. Then, the intermediate multilayer body II was taken out from the oven under a room temperature atmosphere, and then put into an oven at 200 ° C. for additional heating for 90 minutes. As a result, the resin composition layer is thermally cured, and the roughened copper foil, the insulating layer as a cured product of the resin composition layer, the inner layer substrate, the insulating layer as a cured product of the resin composition layer, and the rough An "evaluation substrate A" containing a copperized copper foil in this order was obtained. In this evaluation base material A, the roughened copper foil corresponds to the conductor layer.

<Measurement of peel strength before HAST test>
Using the evaluation substrate A, the peel strength between the roughened copper foil and the insulating layer was measured. This peel strength measurement was performed in accordance with JIS C6481. Specifically, the peel strength was measured by the following operation.

A notch surrounding a rectangular portion having a width of 10 mm and a length of 100 mm was made in the roughened copper foil of the evaluation substrate A. One end of this rectangular portion was peeled off and grasped with a gripping tool (autocom type testing machine "AC-50C-SL" manufactured by TSE). A range of 35 mm in length of the rectangular portion was peeled off in the vertical direction, and the load (kgf / cm) at the time of this peeling was measured as the peel strength. The peeling was performed at a rate of 50 mm / min at room temperature.

<Measurement of peel strength after HAST test>
Then, the evaluation substrate A was subjected to a HAST test in which the evaluation substrate A was placed in an environment of a temperature of 130 ° C. and a humidity of 85% RH for 100 hours. After this HAST test, the peel strength between the roughened copper foil of the evaluation substrate A and the insulating layer was measured by the same method as before the HAST test.

[Evaluation of smear removal property]
(1) Base treatment of interior board:
As the inner layer substrate, a glass cloth base material epoxy resin double-sided copper-clad laminate having a copper foil on the surface (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic “R1515A”) was prepared. The copper foil on the surface of this inner layer substrate was etched with a micro-etching agent (“CZ8101” manufactured by MEC) at a copper etching amount of 1 μm to perform a roughening treatment. Then, it dried at 190 degreeC for 30 minutes.

(2) Laminating and curing of resin sheets:
The resin sheets obtained in the above-mentioned Examples and Comparative Examples were subjected to a batch type vacuum pressurizing laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), and the resin composition layer was used with the above-mentioned inner layer substrate. It was laminated on both sides of the inner layer substrate so as to be joined. This laminating was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at a temperature of 100 ° C. and a pressure of 0.74 MPa for 30 seconds.
Next, the laminated resin sheet was heat-pressed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure to smooth it. Further, this 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.

(3) Via hole formation:
Using a CO ₂ laser machine (LK-2K212 / 2C) manufactured by Via Mechanics, the insulating layer is machined on the surface of the insulating layer under the conditions of a pulse width of 3 μsec, an output of 0.95 W, and a number of shots of 3 at a frequency of 2000 Hz. A via hole having a top diameter (diameter) of 50 μm and a diameter of 50 μm on the bottom surface of the insulating layer was formed. After that, the support was peeled off to obtain a circuit board.

(4) Roughening treatment The surface of the insulating layer of the circuit board was immersed in a swollen liquid, Swelling Dip Securigant P of Atotech Japan Co., Ltd., at 60 ° C. for 10 minutes. Next, the surface of the insulating layer of the circuit board was immersed in Atotech Japan's Concentrate Compact P (an aqueous solution of KMnO ₄ : 60 g / L, NaOH: 40 g / L), which is a roughening liquid, at 80 ° C. for 25 minutes. Finally, the surface of the insulating layer of the circuit board was immersed in Atotech Japan's Reduction Solution Security P, which is a neutralizing solution, at 40 ° C. for 5 minutes.

(5) Evaluation of residue on the bottom of the via hole The circumference 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 is less than 5 μm ×: Maximum smear length is 5 μm or more

[Measurement of minimum melt viscosity]
The melt viscosity of the resin composition layer in the resin sheets produced in Examples and Comparative Examples was measured using a dynamic viscoelasticity measuring device (“Rheosol-G3000” manufactured by UBM). This measurement was performed on a 1 g sample taken from the resin composition layer using a parallel plate with a diameter of 18 mm. The measurement conditions were a starting temperature of 60 ° C. to 200 ° C., a heating rate of 5 ° C./min, a measurement temperature interval of 2.5 ° C., and a vibration of 1 Hz / deg. The minimum melt viscosity was determined from the obtained measured values of melt viscosity.

[result]
The results of the above-mentioned Examples and Comparative Examples are shown in the table below. In the table below, the amount of each component represents the non-volatile component equivalent amount. In the table below, the meanings of the abbreviations are as follows.
ESN475V: Naphthol type epoxy resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent about 330
ZX1059: Bisphenol type epoxy resin, manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169
BMI3000J: Maleimide compound, Designer Molecule's BMI1700: Maleimide compound, Designer Molecule's BMI1500: Maleimide compound, Designer Molecule's BMI689: Maleimide compound, Designer Molecule's BMI70: Maleimide compound, Kay HPC-8000-65T manufactured by Ai Kasei Co., Ltd .: active ester-based curing agent, manufactured by DIC Co., Ltd., toluene solution having an active group equivalent of about 223 and a solid content of 65% by mass SO-C2: amine-based alkoxysilane compound (manufactured by Shinetsu Chemical Industry Co., Ltd.) Spherical silica surface-treated with "KBM573"), average particle size 0.5 μm, LA-3018-50P manufactured by Admatex: phenolic curing agent having triazine skeleton and novolak structure, manufactured by DIC, active group equivalent of about 151 , 2-methoxypropanol solution with 50% solid content YX7553BH30: Phenoxy resin, manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of MEK and cyclohexanone with 30% by mass solid content 1B2PZ: Curing accelerator, 1-benzyl-2-phenylimidazole, MEK solution with 10% by mass of solid content

In Examples 1 to 4, it has been confirmed that even when the components (C) to (G) are not contained, the same results as those in the above-mentioned Examples are obtained, although the degree is different.

1 First conductor layer 11 Main surface of the first conductor layer 2 Second conductor layer 21 Main surface of the second conductor layer 3 Insulation layer t1 Spacing between the first conductor layer and the second conductor layer (first) And the thickness of the insulating layer between the second conductor layers)
t2 Thickness of the entire insulating layer

Claims (14)

Contains (A) epoxy resin, (B) maleimide compound and (C) active ester compound.
The component (B) is a maleimide compound represented by the following general formula (B-4).
The content of the component (C) is 3% by mass or more and 30% by mass or less when the non-volatile component in the resin composition is 100% by mass. Excluding resin compositions containing substrates).

In the general formula (B-4),
R ³ represents an alkylene group having 5 or more carbon atoms which may have a substituent.
^R4 represents a divalent group having an aromatic ring which may have a substituent.
R ⁵ independently represents an alkyl group having 5 or more carbon atoms.
n2 is 0
m represents an integer of 1 to 3. Contains (A) epoxy resin, (B) maleimide compound and (C) active ester compound.
The component (B) contains at least one of an alkyl group having 5 or more carbon atoms and an alkylene group having 5 or more carbon atoms.
The component (C) is from an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoyl compound of phenol novolac. It is an active ester compound derived from a carboxylic acid compound, which is one or more selected from the above group.
The content of the component (B) is 0.1% by mass or more and 10% by mass or less when the non-volatile component in the resin composition is 100% by mass.
The content of the component (C) is 3% by mass or more and 30% by mass or less when the non-volatile component in the resin composition is 100% by mass. Excluding resin compositions containing substrates). The resin composition according to claim 2, wherein the component (B) is represented by the following general formula (B-1).

In the general formula (B-1), R represents an alkylene group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group. The resin composition according to claim 1, wherein the content of the component (B) is 0.1% by mass or more and 10% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 4, wherein the content of the component (C) is 5% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 5, further comprising (D) an inorganic filler. The resin composition according to claim 6, wherein the content of the component (D) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. In the general formula (B-1), L has an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have a substituent, and 1 to 50 carbon atoms which may have a substituent. Alkylene group, divalent group derived from phthalimide, divalent group derived from diimide pyromellitic acid, or a divalent group consisting of two or more combinations of these groups, any of claims 3 , 5 to 7. The resin composition according to item 1. The resin composition according to any one of claims 2 , 3, 5 to 8, wherein the component (B) is represented by the following general formula (B-2).

In the general formula (B-2), R'represents an alkylene group having 5 or more carbon atoms which may independently have a substituent, and A may have an independent substituent. Represents a divalent group having an aromatic ring which may have an alkylene group or a substituent having 5 or more carbon atoms. n represents an integer from 1 to 10. In the general formula (B-2), each of A independently has a cyclic alkylene group having 5 or more carbon atoms which may have a substituent; and has a benzene ring which may have a substituent 2 Claim 9 represents a valent group; a divalent group having a phthalimide ring which may have a substituent; or a divalent group having a diimide ring of pyromellitic acid which may have a substituent. The resin composition described. A resin sheet (excluding a prepreg) comprising a support and a resin composition layer formed on the resin composition according to any one of claims 1 to 10 provided on the support. The resin sheet according to claim 11, wherein the thickness of the resin composition layer is 25 μm or less. A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer.
The insulating layer is a printed wiring board which is a cured product of the resin composition according to any one of claims 1 to 10. A semiconductor device including the printed wiring board according to claim 13.

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