TW202146574A - Resin composition - Google Patents

Abstract

The subject of the present invention is to provide a resin composition capable of controlling unevenness in lamination of the resin composition; a resin sheet containing the resin composition; a printed wiring board provided with an insulating layer formed using the resin composition, and semiconductor device. The solution of the present invention is a resin composition containing (A) an epoxy resin and (B) an active ester compound having at least one of the groups represented by the following formulae (1) to (3) . In the formula, * represents a bond bond. n represents an integer from 1 to 5.

Description

resin composition

The present invention relates to resin compositions. Furthermore, it is about the resin sheet, printed wiring board, and semiconductor device obtained using this resin composition.

As for the manufacturing technology of a printed wiring board, the manufacturing method by the assembling method of alternately stacking insulating layers and conductor layers is known.

As an insulating material of a printed wiring board used for such an insulating layer, for example, Patent Document 1 discloses a resin composition. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2018-199797

[The problem to be solved by the invention]

Generally, an insulating layer is formed by laminating|stacking a resin composition on a board|substrate, and making it thermally harden. The inventors of the present invention, as a result of their studies and examinations, found that when an insulating layer is formed by laminating a resin composition containing a conventional resin composition, the uniformity of the surface of the insulating layer is reduced, and unevenness is likely to occur (unevenness after lamination). ). If there is such unevenness on the surface of the insulating layer, the wiring formability of the insulating layer will be deteriorated.

An object of the present invention is to provide a resin composition capable of suppressing the occurrence of unevenness when a resin composition is laminated; a resin sheet comprising the resin composition; and a printed wiring board provided with an insulating layer formed using the resin composition, and semiconductor devices. [means to solve the problem]

As a result of diligently researching and examining the above-mentioned problem, the present inventors found that the above-mentioned problem can be solved by including an active ester compound having a specific group, and finally completed the present invention.

(式中，＊表示鍵結鍵。式(3)中，n表示1~5的整數。) [2]如[1]之樹脂組成物，其中 (B)成分為下述一般式(b-1)所示之活性酯系化合物。

(一般式(b-1)中， Ar¹¹ 各自獨立地表示式(1)所示之基、式(2)所示之基或式(3)所示之基、 Ar¹² 各自獨立地表示可具有取代基之2價的芳香族烴基、 Ar¹³ 各自獨立地表示可具有取代基之2價的芳香族烴基、可具有取代基之2價的脂肪族烴基、氧原子、硫原子、或此等的組合所成之2價的基。a表示1~6的整數、b表示0~10的整數。) [3]如[2]之樹脂組成物，其中 一般式(b-1)中的Ar¹³ 各自獨立地表示可具有取代基之2價的芳香族烴基及組合了氧原子之2價的基。 [4]如[1]~[3]中任一項之樹脂組成物，其中 (B)成分係下述一般式(b-3)所示之活性酯系化合物。

(一般式(b-3)中， Ar³¹ 各自獨立地表示式(1)所示之基、式(2)所示之基、或式(3)所示之基。a2表示1~6的整數、c2表示1~5的整數、d各自獨立地表示0~6的整數。) [5]如[1]~[4]中任一項之樹脂組成物，其中進一步含有(C)無機填充材。 [6]如[1]~[5]中任一項之樹脂組成物，其係絕緣層形成用。 [7]如[1]~[6]中任一項之樹脂組成物，其係用於形成導體層之絕緣層形成用。 [8]一種樹脂薄片，其係包含支持體與設於該支持體上包含如[1]~[7]中任一項之樹脂組成物的樹脂組成物層。 [9]一種印刷配線板，其係包含藉由如[1]~[7]中任一項之樹脂組成物之硬化物所形成的絕緣層。 [10]一種半導體裝置，其係包含如[9]之印刷配線板。 [發明之效果]That is, the present invention includes the following. [1] A resin composition comprising: (A) an epoxy resin, and (B) an active ester compound having at least one of groups represented by the following formulae (1) to (3).

(In the formula, * represents a bonding bond. In the formula (3), n represents an integer of 1 to 5.) [2] The resin composition according to [1], wherein the component (B) is the following general formula (b- 1) The active ester compound shown.

(In the general formula (b-1), Ar ¹¹ each independently represents a group represented by the formula (1), a group represented by the formula (2), or a group represented by the formula (3), and Ar ¹² each independently represents a possible A divalent aromatic hydrocarbon group having a substituent, Ar ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or the like A divalent group formed by a combination of . a represents an integer from 1 to 6, and b represents an integer from 0 to 10.) [3] The resin composition of [2], wherein Ar in the general formula (b-1) ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent and a divalent group in which an oxygen atom is combined. [4] The resin composition according to any one of [1] to [3], wherein the component (B) is an active ester compound represented by the following general formula (b-3).

(In general formula (b-3), Ar ³¹ each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3). a2 represents 1 to 6 Integer, c2 represents an integer of 1 to 5, and d each independently represents an integer of 0 to 6.) [5] The resin composition according to any one of [1] to [4], further comprising (C) an inorganic filler material. [6] The resin composition according to any one of [1] to [5], which is for forming an insulating layer. [7] The resin composition according to any one of [1] to [6], which is for forming an insulating layer for forming a conductor layer. [8] A resin sheet comprising a support and a resin composition layer provided on the support and including the resin composition according to any one of [1] to [7]. [9] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [7]. [10] A semiconductor device comprising the printed wiring board according to [9]. [Effect of invention]

According to the present invention, it is possible to provide a resin composition with unevenness after lamination that occurs when a resin composition is laminated; a resin sheet comprising the resin composition; and a printed wiring board provided with an insulating layer formed of a cured product of the resin composition , and semiconductor devices. [Form of implementing the invention]

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

(式中，＊表示鍵結鍵。式(3)中，n表示1~5的整數。)[Resin Composition] The resin composition of the present invention contains (A) an epoxy resin and (B) an active ester compound having at least one of groups represented by the following formulae (1) to (3). By containing the (B) component in the resin composition, post-lamination unevenness that occurs when laminating resin composition layers containing the resin composition can be suppressed. Moreover, in this invention, the hardened|cured material which is excellent in plating peeling strength, copper foil adhesion, and copper foil adhesion after HAST, and further has low dielectric property and low arithmetic mean roughness (Ra) can be obtained normally.

(In the formula, * represents a bonding bond. In the formula (3), n represents an integer of 1 to 5.)

The resin composition may further contain arbitrary components on the components (A) to (B) and combine them. In terms of optional components, (C) inorganic fillers, (D) curing agents, (E) curing accelerators, (F) other additives, and the like are mentioned, for example. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Epoxy resin> The resin composition system contains the (A) epoxy resin as the (A) component. In the aspect of (A) component, for example, bis-xylenol 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, ginseng type epoxy resin, naphthol novolac type epoxy resin, phenol novolak type epoxy resin, tert-butyl-quinol type epoxy resin, naphthalene type ring Oxygen resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, thread aliphatic epoxy resins, epoxy resins with butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro-containing epoxy resins, cyclohexane-type epoxy resins, cyclohexanediol Methanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

It is preferable that the resin composition contains an epoxy resin having two or more epoxy groups in one molecule as the (A) epoxy resin. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the nonvolatile content of the epoxy resin (A) is preferably 50 mass % or more, more preferably 60 mass % or more, particularly preferably 70 mass % or more.

Among the epoxy resins, there are epoxy resins that are liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter referred to as "solid epoxy resins"). ). The resin composition may contain only a liquid epoxy resin or only a solid epoxy resin in terms of the component (A), or may be a combination of a liquid epoxy resin and a solid epoxy resin, but the present invention is remarkably obtained from From the viewpoint of the desired effect, it is preferable to contain only solid epoxy resin.

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

In terms of solid epoxy resins, bis-xylenol epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, and dicyclopentadiene-type epoxy resins are used. , Phenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin Resin and tetraphenylethane type epoxy resin are preferable, and naphthol type epoxy resin is more preferable.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation. resin); "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-Novolak type epoxy resin" manufactured by DIC Corporation 7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC Corporation ", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (Shenphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" manufactured by Nippon Kayaku Co., Ltd. ” (naphthol novolac type epoxy resin); “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; manufactured by Nippon Steel Chemical & Materials Co., Ltd. "ESN475V" (naphthol type epoxy resin); "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "YX4000H", "YX4000", "YL6121" manufactured by Mitsubishi Chemical Corporation "(biphenyl type epoxy resin); "YX4000HK" (bis-xylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Osaka Gas Chemical Co., Ltd. "PG-100" and "CG-500" manufactured by Mitsubishi Chemical Corporation; "YL7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (Fine-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "jER1010" (solid bisphenol A type epoxy resin) manufactured by the company; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

Liquid epoxy resins are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidylamine type epoxy resin and Epoxy resins having a butadiene structure are preferred, and naphthalene type epoxy resins are more preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", " 825", "EPIKOTE 828EL" (bisphenol A epoxy resin); "jER807", "1750" (bisphenol F epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac) manufactured by Mitsubishi Chemical Corporation Varnish type epoxy resin); "630", "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" manufactured by Nippon Steel Chemical & Materials Phenol F type epoxy resin mixture); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex; "CELLOXIDE2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel Corporation ; "PB-3600" (epoxy resin with a butadiene structure) manufactured by Daicel; epoxy resin) etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

(A) In terms of components, when the liquid epoxy resin and the solid epoxy resin are used in combination, the amount ratio (liquid epoxy resin: solid epoxy resin) is based on the mass ratio, preferably 1: 1~1:20, more preferably 1:1.5~1:15, particularly preferably 1:2~1:10. By making the quantitative ratio of the liquid epoxy resin and the solid epoxy resin within this range, the desired effect of the present invention can be obtained remarkably. In addition, when it is generally used in the form of a resin sheet, moderate adhesiveness can be brought about. In addition, when it is generally used in the form of a resin sheet, sufficient flexibility can be obtained, and the pick-up property can be improved. Furthermore, a hardened product having sufficient breaking strength can usually be obtained.

The epoxy equivalent of the component (A) is preferably 50g/eq.~5000g/eq., more preferably 50g/eq.~3000g/eq., still more preferably 80g/eq.~2000g/eq. Preferably, it is 110g/eq.~1000g/eq.. Within this range, the crosslinking density of the cured product of the resin composition layer is sufficient, and an insulating layer with small surface roughness can be obtained. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the component (A) is preferably 100-5000, more preferably 200-3000, still more preferably 250-1500, from the viewpoint of significantly obtaining the desired effect of the present invention. The weight average molecular weight of the resin was measured as a value in terms of polystyrene by a colloid permeation chromatography (GPC) method.

The content of the component (A) is preferably 1 mass % or more when the non-volatile content in the resin composition is 100 mass %, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. , more preferably 5 mass % or more, still more preferably 10 mass % or more. The upper limit of the content of the epoxy resin is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less, from the viewpoint of remarkably obtaining the desired effect of the present invention. In addition, in this invention, unless otherwise specified, the content of each component in a resin composition is a value when the non-volatile matter in a resin composition becomes 100 mass %.

<(B) Active ester compound having at least one of the groups represented by the following formulae (1) to (3)> The resin composition contains, as the component (B), an active ester compound having at least one of the groups represented by the following formulae (1) to (3). The occurrence of unevenness after lamination can be suppressed by containing the (B) component in the resin composition. In addition, by containing the (B) component in the resin composition, it is generally possible to obtain excellent plating peeling strength, copper foil adhesion, and copper foil adhesion after HAST, as well as low dielectric properties and arithmetic mean roughness. (Ra) low hardened material.

(式中，＊表示鍵結鍵。式(3)中，n表示1~5的整數。)

(In the formula, * represents a bonding bond. In the formula (3), n represents an integer of 1 to 5.)

The (B) component has at least one of the groups represented by the formulae (1) to (3), and a compound having an active ester moiety reactive with the (A) component can be used. In the aspect of the component (B), it is preferable that the terminal has at least one of the groups represented by the formulae (1) to (3). As for the component (B), the groups at both ends may be different, or the groups at both ends may be the same.

The group represented by the formula (1) may be a group derived from cresol shown below. The methyl group in the group represented by the formula (1) is preferably bonded to any one of the ortho position, the meta position, and the para position with respect to the oxygen atom, and it is more preferably bonded to the ortho position.

The group represented by the formula (2) may be a group derived from phenylphenol shown below. The phenyl group in the base represented by the formula (2) is preferably any one of ortho, meta and para positions for the oxygen atom bonded to the p-phenol position, and it is more preferable to bond in the ortho position. good.

The group represented by the formula (3) may be a group derived from styrenated phenol shown below. The styrene moiety in the base represented by the formula (3) is preferably any one of ortho, meta and para positions to the oxygen atom bonded to the p-phenol moiety, and the one bonded in the ortho position is preferred. better.

(式中，n1係與式(3)中的n相同。) (B)成分係以下述一般式(b-1)所示之化合物為佳。

(一般式(b-1)中，Ar¹¹ 各自獨立地表示式(1)所示之基、式(2)所示之基或式(3)所示之基、Ar¹² 各自獨立地表示可具有取代基之2價的芳香族烴基、Ar¹³ 各自獨立地表示可具有取代基之2價的芳香族烴基、可具有取代基之2價的脂肪族烴基、氧原子、硫原子、或此等的組合所成之2價的基。a表示1~6的整數、b表示0~10的整數。)In formula (3), n represents an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.

(In the formula, n1 is the same as n in the formula (3).) The component (B) is preferably a compound represented by the following general formula (b-1).

(In general formula (b-1), Ar ¹¹ each independently represents a group represented by formula (1), a group represented by formula (2) or a group represented by formula (3), and Ar ¹² each independently represents a possible A divalent aromatic hydrocarbon group having a substituent, Ar ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or the like A divalent base formed by a combination of . a represents an integer from 1 to 6, and b represents an integer from 0 to 10.)

In general formula (b-1), Ar ¹¹ each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3). The groups represented by the formulae (1) to (3) are as described above. Among them, the group represented by the formula (1) and the group represented by the formula (2) are preferable.

In the general formula (b-1), Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent. As a divalent aromatic hydrocarbon group, an aryl group, an aralkyl group, etc. are mentioned, and an aryl group is preferable. In terms of the aryl group, the aryl group with 6-30 carbon atoms is preferable, the aryl group with 6-20 carbon atoms is more preferable, and the aryl group with 6-10 carbon atoms is even more preferable. As such an aryl-extended group, for example, a phenyl-extended group, a naphthyl-extended group, an anthracenyl-extended group, and a bi-extended phenyl group can be mentioned. In terms of the aralkyl group, an aralkyl group with a carbon number of 7 to 30 is preferred, an aralkyl group with a carbon number of 7 to 20 is more preferred, and an aralkyl group with a carbon number of 7 to 15 is even more preferred. . Among them, a phenylene group is more preferable.

In the general formula (b-1), Ar ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a combination thereof The bivalent basis formed by these combinations is preferably a bivalent basis. The divalent aromatic hydrocarbon group is the same as the divalent aromatic hydrocarbon group represented by ^{Ar 12 .}

As for the divalent aliphatic hydrocarbon group, a divalent saturated aliphatic hydrocarbon group is more preferable, an alkylene group and a cycloalkylene group are more preferable, and a cycloalkylene group is more preferable.

In terms of alkylene, the alkylene with 1-10 carbon atoms is preferred, the alkylene with 1-6 carbon atoms is more preferred, and the alkylene with 1-3 carbon atoms is even more preferred. In the aspect of alkylene, for example, methylene, ethylidene, propylidene, 1-methylmethylene, 1,1-dimethylmethylene, 1-methylethylidene, 1,1 -Dimethylidene, 1,2-dimethylethylidene, butylene, 1-methylpropylidene, 2-methylpropylidene, pentylene, hexylene, etc.

In terms of the cycloalkylene group, a cycloextended alkyl group having 3 to 20 carbon atoms is preferable, a cycloextended alkyl group of 3 to 15 is more preferable, and a cycloextended alkyl group of 5 to 10 is even more preferable. In the case of a cyclo-alkylene group, for example, a cyclo-propylene group, a cyclo-butylene group, a cyclo-pentylene group, a cyclo-hexylene group, a cyclo-pentylene group, a cyclo-heptide group, etc. are mentioned.

The divalent group formed by the combination of these is preferably a divalent aromatic hydrocarbon group which may have a substituent and a divalent group combined with an oxygen atom, and a divalent group which may have one or more substituents. An aromatic hydrocarbon group and a divalent group in which one or more oxygen atoms are alternately combined are more preferable, and a naphthyl group which may have one or more substituents and a divalent group in which one or more oxygen atoms are alternately combined are more preferable. Therefore, naphthyloxy which may have a substituent is more preferable.

The ^{divalent aromatic hydrocarbon group represented by Ar 12} , the divalent aromatic hydrocarbon group represented by Ar ¹³ , and the divalent aliphatic hydrocarbon group may have a substituent. The substituent may be one or plural. The substituents include, for example, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, and the like. The substituents may be contained alone or in combination of two or more.

The aryl group having 6 to 20 carbon atoms includes, for example, a benzyl group, a phenyl group, a naphthyl group, an anthracenyl group, a tolyl group, and a xylyl group, and a benzyl group is preferred.

The alkyl group having 1 to 10 carbon atoms includes, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl , isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, n-nonyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , cycloheptyl, cyclooctyl, cyclononyl.

As the alkoxy group having 1 to 10 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and a 2-ethylhexyl group are mentioned. oxy, octyloxy, nonyloxy, etc.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned. The above-mentioned substituent may further have a substituent (hereinafter referred to as a "secondary substituent"). Regarding the secondary substituent, unless otherwise specified, the same ones as those described above can be used.

In the general formula (b-1), a represents an integer of 1 to 6, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3. In addition, when the compound represented by general formula (b-1) is an oligomer or a polymer, a represents the average value.

In the general formula (b-1), b represents an integer from 0 to 10, preferably an integer from 0 to 5, more preferably an integer from 0 to 3, and even more preferably 0. In addition, when the compound represented by general formula (b-1) is an oligomer or a polymer, b represents the average value.

(一般式(b-2)中，Ar²¹ 各自獨立地表示式(1)所示之基、式(2)所示之基或式(3)所示之基、Ar²² 各自獨立地表示可具有取代基之2價的芳香族烴基、Ar²³ 各自獨立地表示可具有取代基之2價的芳香族烴基。a1表示1~6的整數、c1表示1~5的整數。)The component (B) is preferably a compound represented by the general formula (b-2).

(In general formula (b-2), Ar ²¹ each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3), and Ar ²² each independently represents a possible The divalent aromatic hydrocarbon group having a substituent and Ar ²³ each independently represent a divalent aromatic hydrocarbon group which may have a substituent. a1 represents an integer of 1 to 6, and c1 represents an integer of 1 to 5.)

Ar ²¹ each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3). The groups represented by the formulae (1) to (3) are as described above. Among them, the base represented by the formula (1) and the base represented by the formula (2) are more preferable.

Ar ²² each independently represents a divalent aromatic hydrocarbon group which may have a substituent. Ar ²² is the same as ^{Ar 12} in the general formula (b-1).

Ar ²³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent. Ar ²³ is the same as the divalent aromatic hydrocarbon group which may have a substituent ^{of Ar 13 in} the general formula (b-1).

In the general formula (b-2), a1 represents an integer of 1 to 6. a1 is the same as a in the general formula (b-1).

In the general formula (b-2), c1 represents an integer of 1 to 5. c1 is preferably an integer representing 1 to 4, more preferably an integer representing 1 to 3.

(一般式(b-3)中，Ar³¹ 各自獨立地表示式(1)所示之基、式(2)所示之基、或式(3)所示之基。a2表示1~6的整數、c2表示1~5的整數、d各自獨立地表示0~6的整數。)The component (B) is preferably a compound represented by the general formula (b-3).

(In general formula (b-3), Ar ³¹ each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3). a2 represents 1 to 6 Integer, c2 represents an integer from 1 to 5, and d represents an integer from 0 to 6 independently.)

Ar ³¹ each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3). The groups represented by the formulae (1) to (3) are as described above. Among them, the group represented by the formula (1) and the group represented by the formula (2) are more preferable.

In the general formula (b-3), a2 represents an integer of 1 to 6. a2 is the same as a in the general formula (b-1).

In the general formula (b-3), c2 represents an integer of 1 to 5. c2 is the same as c1 in the general formula (b-2).

In the general formula (b-3), d each independently represents an integer of 0 to 6. d preferably represents an integer from 1 to 5, and more preferably represents an integer from 1 to 4.

The component (B) can be synthesized by a known method, for example, it can be synthesized by the method described in the following examples. The synthesis of the component (B) can be carried out, for example, by the method described in International Publication No. 2018/235424 or International Publication No. 2018/235425.

The weight average molecular weight of the component (B) is preferably 150 or more, more preferably 200 or more, still more preferably 250 or more, more preferably 4000 or less, from the viewpoint that the effect of the present invention can be remarkably obtained. Preferably it is 3000 or less, More preferably, it is 2500 or less. The weight average molecular weight of the component (B) is the weight average molecular weight in terms of polystyrene measured by a colloid permeation chromatography (GPC) method.

The active ester equivalent (equivalent of unsaturated bond) of the component (B) is preferably 50 g/eq. or more, more preferably 100 g/eq. or more, from the viewpoint that the effects of the present invention can be remarkably obtained, and even more preferably 150 g/eq., preferably 2000 g/eq. or less, more preferably 1000 g/eq. or less, still more preferably 500 g/eq. or less. The active ester equivalent is the mass of the component (B) containing 1 equivalent of unsaturated bond.

The quantitative ratio of (A) component and (B) component is calculated as the ratio of [total number of epoxy groups of (A) component]: [total number of active ester groups of (B) component], 1:0.01~1 The range of :20 is better, 1:0.1~1:10 is better, and 1:0.5~1:5 is better. Here, "the total number of epoxy groups of the component (A)" means the total value of the mass of the nonvolatile components of the component (A) present in the resin composition divided by the epoxy equivalent. In addition, "the total number of active ester groups of (B) component" means the total value of all the non-volatile components of (B) component present in the resin composition divided by the active ester group equivalent. The effect of this invention can be remarkably acquired by making the quantitative ratio of (A) component and (B) component into this range.

The content of the component (B) is preferably 5% by mass or more, more preferably 10% by mass or more, relative to 100% by mass of the nonvolatile content in the resin composition, from the viewpoint of suppressing the occurrence of unevenness after lamination, More preferably, it is 15 mass % or more, preferably 30 mass % or less, more preferably 25 mass % or less, and more preferably 20 mass % or less.

<(C) Inorganic fillers> In addition to the above-mentioned components, the resin composition may further contain an inorganic filler as the component (C) in terms of optional components. By using the (C) inorganic filler, the dielectric properties and insulating properties of the cured product of the resin composition can be improved.

As the material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silica, alumina, glass, lapis lazuli, silicate, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, hydrogen Alumina, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron oxide, aluminum oxide, manganese oxide, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, Zirconium acid, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, etc. Among them, silicon oxide is particularly suitable. As for the silicon oxide, for example, amorphous silicon oxide, molten silicon oxide, crystalline silicon oxide, synthetic silicon oxide, hollow silicon oxide, and the like can be mentioned. In addition, in terms of silicon oxide, spherical silicon oxide is preferred. (C) Inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

As for the commercial products of the component (C), for example, "UFP-30" manufactured by Denka Corporation; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Corporation; "YC100C" manufactured by Admatechs Corporation , "YA050C", "YA050C-MJE", "YA010C"; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by TOKUYAMA; "SC2500SQ", "SO" manufactured by Admatechs -C4", "SO-C2", "SO-C1"; etc.

The specific surface area of the component (C) is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, and particularly ^{preferably 3 m 2} /g or more. The upper limit is not particularly limited, but is preferably not more than 60 m ² /g, not more than 50 m ² /g, or not more than 40 m ² /g. The specific surface area was obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mounttech) according to the BET method, and calculating the specific surface area by the BET multipoint method.

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

The average particle diameter of the component (C) can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis with a laser diffraction scattering particle size distribution analyzer, and the median diameter can be measured as an average particle size. As a measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed into a small glass vial and dispersed with ultrasonic waves for 10 minutes. Using a laser diffraction particle size distribution analyzer for the measurement sample, the wavelength of the light source used is divided into blue and red, the volume-based particle size distribution of the component (C) is measured by a flow cell method, and the obtained particle size distribution is calculated. The average particle diameter was taken as the median diameter. As a laser diffraction particle size distribution measuring apparatus, "LA-960" manufactured by HORIBA, Ltd., etc. is mentioned, for example.

The component (C) is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. In terms of surface treatment agents, for example, vinylsilane-based coupling agents, (meth)acrylic-based coupling agents, fluorine-containing silane-based coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, Silane-based coupling agents, alkoxysilanes, organosilazane compounds, titanate-based coupling agents, etc. Among them, vinylsilane-based coupling agents, (meth)acrylic-based coupling agents, and aminosilane-based coupling agents are preferable from the viewpoint of remarkably obtaining the effects of the present invention. In addition, a surface treatment agent may be used individually by 1 type, and may combine 2 or more types arbitrarily.

Commercially available surface treatment agents include "KBM1003" (vinyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM503" (3-methacryloyloxypropyl triethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Ethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxytrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Kogyo Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy silane) manufactured by Shin-Etsu Chemical Co., Ltd. coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably kept within a predetermined range. Specifically, 100 parts by mass of inorganic fillers are preferably those treated with a surface treatment agent of 0.2 to 5 parts by mass, preferably 0.2 parts by mass to 3 parts by mass, and more preferably 0.3 parts by mass. ~2 parts by mass of the surface-treated ones are even better.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The carbon content per unit surface area of the inorganic filler, from the viewpoint of improving the dispersibility of the inorganic filler, is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and 0.2 mg/m ² or more. better. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in a 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 still more preferable. better.

The carbon content per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, as a solvent, a sufficient amount of MEK was added to the inorganic filler surface-treated with a surface-treating 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 inorganic filler can be measured using a carbon analyzer. For the carbon analyzer, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd., etc. can be used.

The content of the inorganic filler is preferably 50% by mass or more, more preferably 60% by mass or more, when the nonvolatile content in the resin composition is 100% by mass, from the viewpoint of obtaining the effect of the present invention significantly, More preferably, it is 70 mass % or more, more preferably 90 mass % or less, more preferably 80 mass % or less, and still more preferably 75 mass % or less.

<(D) Hardener> In addition to the above-mentioned components, the resin composition may further contain a curing agent as a component (D) in terms of optional components. However, those equivalent to component (B) are excluded.

(D) As a curing agent, a compound capable of curing the resin composition with the component (A) can be used, and examples thereof include active ester-based curing agents, phenol-based curing agents, and benzoxazine-based curing agents that do not correspond to the (B) component. Hardeners, carbodiimide hardeners, acid anhydride hardeners, amine hardeners, cyanate ester hardeners, maleimide hardeners, polyphenylene ether hardeners (styrene hardeners) )Wait. Among them, any one of a phenol-based hardener, a carbodiimide-based hardener, a maleimide-based hardener, and a polyphenylene ether-based hardener is used from the viewpoint of significantly obtaining the effects of the present invention. better.

As an active ester type hardening|curing agent, the hardening|curing agent which has one or more active ester groups in 1 molecule is mentioned. Among them, in terms of active ester-based curing agents, phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. have two or more ester groups with high reactivity in one molecule. Compounds are preferred. The active ester-based hardener is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based hardener obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable .

The carboxylic acid compound includes, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like.

As a phenol compound or a naphthol compound, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthaloline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, diphenol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxyl Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, 1,3,5-phloroglucinol, 1,2,4-phloroglucinol, bicyclic Pentadiene-type diphenol compounds, phenol novolacs, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing 1 molecule of dicyclopentadiene with 2 molecules of phenol.

Preferable specific examples of the active ester-based curing agent include active ester compounds containing dicyclopentadiene-type diphenol structures, active ester compounds containing naphthalene structures, and active esters of phenol novolac-containing acetyl compounds. Compounds, active ester compounds of phenol novolac-containing benzyl compounds. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a bivalent structure composed of phenylene-dicyclopentadiene-phenylene.

Commercially available active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC- 8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", (manufactured by DIC Corporation); "HPC-8150- 62T", "EXB-8100L-65T", "EXB-8150L-65T", "EXB9416-70BK", "HPC-8900-70BK" (manufactured by DIC Corporation); active ester of acetoxylated phenol novolak Examples of compounds include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester compounds of phenol novolak-containing benzyl compounds include "YLH1026" (manufactured by Mitsubishi Chemical Corporation); Examples of the active ester-based hardener include "DC808" (manufactured by Mitsubishi Chemical Corporation); "YLH1026" (manufactured by Mitsubishi Chemical Corporation) and "YLH1030" as active ester-based curing agents of benzyl-based phenol novolacs (Mitsubishi Chemical Corporation), "YLH1048" (Mitsubishi Chemical Corporation); etc.

As a phenol-based curing agent, a curing agent having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring (a benzene ring, a naphthalene ring, etc.) in one molecule is exemplified. Among them, compounds having a hydroxyl group bonded to a benzene ring are preferred. Moreover, from the viewpoint of heat resistance and water resistance, a phenol-based hardener having a novolak structure is preferable. Furthermore, from the viewpoint of adhesiveness, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. In particular, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, it is preferable that the triazine skeleton contains a phenol novolak hardener.

Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd.; Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH" manufactured by the company; "SN-170", "SN-180", "SN-190", "SN-475", "SN- 485", "SN-495", "SN-495V", "SN-375", "SN-395"; "TD-2090", "TD-2090-60M", "LA-7052" manufactured by DIC Corporation , "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163" , "KA-1165"; "GDP-6115L", "GDP-6115H", "ELPC75" manufactured by Qunrong Chemical Co., Ltd.

Specific examples of benzoxazine-based curing agents include "HFB2006M" manufactured by Showa Polymer Co., Ltd., "Pd", "Fa", and "ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd., and manufactured by JFE Chemical Co., Ltd. "ODA-BOZ".

Specific examples of the carbodiimide-based curing agent include "V-03", "V-05", and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.; Stabaxol® (registered trademark) manufactured by LAN-CHEMI Co., Ltd. )P et al.

As an acid anhydride type hardening agent, the hardening agent which has one or more acid anhydride groups in 1 molecule is mentioned. Specific examples of the acid anhydride-based curing agent include anhydrous phthalic acid, tetrahydroanhydrophthalic acid, hexahydroanhydrophthalic acid, methyltetrahydroanhydrophthalic acid, and 4-methylhexahydroanhydrophthalic acid , Methylhexahydrophthalic acid anhydrous, Methylnadic acid anhydride, Hydrogenated methylnadic acid anhydride, Trialkyltetrahydrophthalic acid anhydrous, Dodecenyl anhydrous succinic acid, 5-(2,5-two side Oxytetrahydro-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, anhydrous trimellitic acid, anhydrous pyromellitic acid, benzophenone tetracarboxylic acid Anhydrate, Biphenyltetracarboxylic acid dihydrate, Naphthalenetetracarboxylic acid dihydrate, Oxydiphthalic acid dihydrate, 3,3'-4,4'-Diphenyltetracarboxylic acid dianhydrous compound, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxy-3-yl)-naphtho[1,2-C]furan-1 , 3-dione, ethylene glycol bis (trimellitic anhydride ester), styrene and maleic acid copolymerization of styrene-maleic acid resin and other polymer anhydrides. As an acid anhydride type hardening|curing agent, a commercial item can also be used, For example, "MH-700" by Nippon Chemical Co., Ltd., etc. are mentioned.

As an amine-based hardener, hardeners having one or more amine groups in one molecule are mentioned, and examples thereof include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, and the like, among which, From the viewpoint of achieving the desired effects of the present invention, aromatic amines are preferred. The amine-based hardener is preferably a first-grade amine or a second-grade amine, more preferably a first-grade amine. Specific examples of the amine-based curing agent include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminodiphenyl, and 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl, 3,3'-diaminodiphenyl, m-phenylenediamine, m-xylenediamine, diethyltoluenediamine, 4 ,4'-Diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diamino Biphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4 ,4-Diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3 -Bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'- Bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)bis(4-(3-aminophenoxy)phenyl)bis(4-(3-aminophenoxy)phenyl), Wait. Commercially available amine-based hardeners may be used, for example, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., "Epicure W" manufactured by a chemical company, etc.

As a cyanate-based hardener, for example, bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4' - Methylene bis(2,6-dimethylphenylcyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,1 3-bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl) sulfide and bis(4-cyanate phenyl) ether, etc. bifunctional cyanate resins; polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs, etc.; partially triazinated prepolymers of these cyanate resins; and the like. Specific examples of cyanate-based hardeners include "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate resins) manufactured by Lonza Japan; "ULL-950S" (polyfunctional cyanate resin) ester resin); "BA230", "BA230S75" (part or all of bisphenol A dicyanate is triazineized to form a triazine prepolymer); etc.

The maleimide-based curing agent is a compound containing a maleimide group represented by the following formula (D-1) in the molecule. The maleimide-based curing agent may be used alone or in combination of two or more.

The number of maleimide groups per molecule of the maleimide-based hardener is preferably 1 or more, more preferably 2 or more, from the viewpoint of significantly obtaining the desired effect of the present invention. More preferably, it is 3 or more, more preferably 10 or less, still more preferably 6 or less, particularly preferably 3 or less.

The maleimide-based curing agent preferably has either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably has an aliphatic hydrocarbon group and an aromatic hydrocarbon group, from the viewpoint of remarkably obtaining the desired effect of the present invention.

In terms of the aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group is preferable, a bivalent saturated aliphatic hydrocarbon group is more preferable, and an alkylene group is even more preferable. In terms of alkylene, the alkylene with 1 to 10 carbon atoms is preferred, the alkylene with 1 to 6 carbon atoms is better, the alkylene with 1 to 3 carbon atoms is even better, and methylene is particularly preferred. good.

As for the aromatic hydrocarbon group, monovalent and divalent aromatic hydrocarbon groups are preferable, and aryl groups and aryl-extended groups are more preferable. In terms of the extended aryl group, the extended aryl group with the carbon number of 6-30 is preferred, the extended aryl group with the carbon number of 6-20 is more preferable, and the extended aryl group with the carbon number of 6-10 is even more preferable. Such arylidene groups include, for example, phenylene groups, naphthyl groups, anthracenyl groups, aralkyl groups, biphenylene groups, biphenylene aralkyl groups, etc. Biphenyl group and biphenyl aralkyl group are preferable, and phenylene group, aralkyl group and biphenyl group are more preferable. In terms of aryl groups, aryl groups with 6 to 30 carbon atoms are preferred, aryl groups with 6 to 20 carbon atoms are more preferred, aryl groups with 6 to 10 carbon atoms are even more preferred, and phenyl groups are particularly preferred.

Among the maleimide-based curing agents, it is preferable that the nitrogen atom of the maleimide group is directly bonded to a monovalent or divalent aromatic hydrocarbon group from the viewpoint of remarkably obtaining the desired effect of the present invention. Here, "directly" means that there is no other group between the nitrogen atom of the maleimide group and the aromatic hydrocarbon group.

式(D-2)中，R³¹ 及R³⁶ 表示馬來醯亞胺基，R³² 、R³³ 、R³⁴ 及R³⁵ 各自獨立地表示氫原子、烷基或芳基，D各自獨立地表示2價的芳香族基。m1及m2各自獨立地表示1~10的整數、a表示1~100的整數。The maleimide-based curing agent preferably has a structure represented by, for example, the following formula (D-2).

In formula (D-2), R ³¹ and R ³⁶ represent a maleimide group, R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group, and D each independently represents a A divalent aromatic group. m1 and m2 each independently represent an integer of 1 to 10, and a represents an integer of 1 to 100.

^{R 32} , R ³³ , R ³⁴ and R ^{35 in} formula (D-2) each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom.

In terms of the alkyl group, an alkyl group with 1 to 10 carbon atoms is preferable, an alkyl group with 1 to 6 carbon atoms is more preferable, and an alkyl group with 1 to 3 carbon atoms is even more preferable. Alkyl groups can be straight chain, branched or cyclic. As such an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, etc. are mentioned, for example.

The aryl group is preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 15 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms. The aryl group may be a monocyclic ring or a condensed ring. As such an aryl group, a phenyl group, a naphthyl group, an anthracenyl group, etc. are mentioned, for example.

The alkyl group and the aryl group may have a substituent. As for the substituent, for example, halogen atom, -OH, -OC _1-6 alkyl group, -N(C _1-10 alkyl group) ₂ , C _1-10 alkyl group, C _6-10 aryl group, -NH ₂ , -CN, -C(O)OC _1-10 alkyl, -COOH, -C(O)H, -NO _2, etc. Here, the term "C _pq " (p and q are positive integers and satisfy p<q) means that the number of carbon atoms of the organic group described after the term is p to q. For example, _{the expression "C 1-10} alkyl group" means an alkyl group having 1 to 10 carbon atoms. These substituents may also be bonded to each other to form a ring, and the ring structure includes a spiro ring or a condensed ring.

D in formula (D-2) represents a divalent aromatic group. For the divalent aromatic group, for example, a phenylene group, a naphthylene group, an anthracenyl group, an aralkyl group, a biphenylene group, a biphenylene aralkyl group, etc. are mentioned. Aralkyl is preferred, and biphenyl is more preferred. The divalent aromatic group may have a substituent. The substituents are the same as those that the alkyl group represented by ^{R 32 in the} general formula (D-2) may have.

m1 and m2 each independently represent an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 3, still more preferably 1 to 2, and still more preferably 1.

a represents an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 20, still more preferably 1 to 5.

式(D-3)中，R³⁷ 及R³⁸ 表示馬來醯亞胺基。a1表示1~100的整數。The maleimide-based curing agent is preferably a resin represented by the formula (D-3).

In formula (D-3), R ³⁷ and R ³⁸ represent a maleimide group. a1 represents an integer from 1 to 100.

a1 is the same as a in formula (D-2), and the preferable range is also the same.

As such a maleimide-based curing agent, a commercial item can be used. As a commercial item, "MIR-3000-70MT" by Nippon Kayaku Co., Ltd., etc. is mentioned, for example.

Moreover, in another embodiment of the maleimide-based curing agent, it is a compound having at least one maleimide group in the molecule.

In this maleimide-based curing agent, the aliphatic group having 5 or more carbon atoms is preferably one directly bonded to the nitrogen atom of the maleimide group. The aliphatic group having 5 or more carbon atoms includes, for example, an alkyl group, an alkylene group, an alkenylene group, and the like.

The number of maleimide groups per molecule of the maleimide-based hardener can be 1, preferably 2 or more, preferably 10 or less, still more preferably 6 or less, especially Preferably it is 3 or less. The effect of the present invention can be remarkably obtained by using a maleimide-based hardener having two or more maleimide groups per molecule.

一般式(D-4)中，M表示可具有取代基之碳原子數為5以上2價的脂肪族基，L表示單鍵或2價的連結基。The maleimide-based curing agent is preferably represented by the following general formula (D-4).

In general formula (D-4), M represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

M represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. The number of carbon atoms of the divalent aliphatic 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 divalent aliphatic group includes, for example, an alkylene group, an alkenylene group, and the like. ^{The substituent of M is the same as that of the alkyl group represented by R 32 in the} general formula (D-2), and the substituent is preferably an alkyl group having 5 or more carbon atoms.

L represents a single bond or a divalent linking group. For the divalent linking group, alkylene, alkenylene, alkynylene, arylidene, -C(=O)-, -C(=O)-O-, -NR ⁰ -(R are exemplified ⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms), an oxygen atom, a sulfur atom, C(=O)NR ⁰ -, a divalent group derived from phthalimide, a group derived from pyromellitic acid A divalent group of diimide, a group formed by combining two or more of these divalent groups, and the like. Alkylene group, alkenylene group, alkynylene group, arylidene group, divalent group derived from phthalimide, divalent group derived from pyromellitic acid diimide, and two or more A group formed by a combination of divalent groups may have an alkyl group having 5 or more carbon atoms as a substituent. The divalent group derived from phthalimide means a divalent group derived from phthalimide, and specifically, it is a group represented by general formula (D-5). The divalent group derived from pyromellitic acid diimide means a divalent group derived from pyromellitic acid diimide, specifically, a group represented by general formula (D-6) . In the formula, "*" represents a bond bond.

The alkylene group used as a divalent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, and an alkylene group having 1 to 40 carbon atoms. The base is particularly good. The alkylene group may be any of linear, branched and cyclic. As such an alkylene group, for example, methyl ethylidene, cyclohexenyl, pentylene, hexylene, heptyl, octyl, nonyl, decyl, undecyl, Dodecylidene, tridecylidene, heptadecylidene, hexadecanetridecyl, base with octyl-cyclohexene structure, with octyl-cyclohexene-octylidene structure base, base with propylidene-cyclohexene-octylidene structure, etc.

The alkenylene group used as a divalent linking group in L is preferably an alkenylene group having 2 to 20 carbon atoms, more preferably an alkenylene group having 2 to 15 carbon atoms, and an alkenylene group having 2 to 10 carbon atoms. The base is particularly good. The alkenylene group may be any of linear, branched and cyclic. Such an alkenylene group includes, for example, a methyl vinylene group, a cyclohexenylene group, a pentenylene group, a hexenylene group, a heptenene group, an octenylene group, and the like.

The alkynylene group used as a divalent linking group in L is preferably an alkynylene group with 2 to 20 carbon atoms, more preferably an alkynylene group with 2 to 15 carbon atoms, and an alkynylene group with 2 to 10 carbon atoms. The base is particularly good. The alkynylene group may be any of linear, branched and cyclic. As such an alkynylene group, for example, a methylethynylene group, a cyclohexylene group, a pentynyl group, a hexylene group, a heptynylene group, a cyclooctynyl group, and the like are mentioned.

The aryl extended group used as a divalent linking group in L is preferably an extended aryl group with a carbon number of 6 to 24, an extended aryl group with a carbon number of 6 to 18, and an extended aryl group with a carbon number of 6 to 14. The base is even more preferable, and the aryl group having 6 to 10 carbon atoms is even more preferable. In the case of an arylidene group, for example, a phenylene group, a naphthyl group, an anthracenyl group, and the like can be mentioned.

The alkylene group, the alkenylene group, the alkynylene group, and the arylidene group which are the divalent linking groups in L may have a substituent. The substituent is the same as that of the alkyl group represented by ^{R 32 in the} general formula (D-2), preferably an alkyl group having 5 or more carbon atoms.

The group formed by the combination of two or more divalent groups in L includes, for example, an alkylene group, a divalent group derived from phthalimide, and a divalent group formed by a combination with an oxygen atom. group; a divalent group derived from the combination of a divalent group of phthalimide, an oxygen atom, an arylidene group and an alkylene group; an alkylene group and a group derived from pyromellitic acid diimide A bivalent basis formed by a combination of bivalent basis; etc. A group consisting of a combination of two or more divalent groups can form a ring such as a condensed ring by the combination of the respective groups. In addition, the group formed by combining two or more divalent groups may be a repeating unit whose number of repeating units is 1 to 10.

Wherein, in the aspect of L in the general formula (D-4), it is an oxygen atom, an aryl group with 6 to 24 carbon atoms which may have a substituent, and an extension with 1 to 50 carbon atoms which may have a substituent. An alkyl group, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, or 2 or more of these groups The combination of 2-valent basis is better. Wherein, L is an alkylene group; a bivalent one having the structure of an alkylene group-a divalent group derived from phthalimide-oxygen atom-a divalent group derived from phthalimide Radical; with alkylene group-divalent group derived from phthalimide-oxygen atom-arylidene-alkylene-arylidene-oxygen atom-divalent group derived from phthalimide The divalent group of the structure of the group; the divalent group having the structure of the divalent group derived from the alkylene-pyromellitic acid diimide is more preferable.

一般式(D-7)中，M¹ 各自獨立地表示可具有取代基之碳原子數為5以上的2價的脂肪族基、Z各自獨立地表示可具有取代基之碳原子數為5以上的伸烷基或可具有取代基之具芳香環之2價的基。t表示1~10的整數。The maleimide-based curing agent represented by the general formula (D-4) is preferably represented by the general formula (D-7).

In the general formula (D-7), M ¹ each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and Z each independently represents a carbon number which may have a substituent having 5 or more carbon atoms. The alkylene group or the divalent group with an aromatic ring which may have a substituent. t represents an integer from 1 to 10.

M ¹ each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M ¹ is the same as M in the general formula (D-4), and represents an alkylene group or an alkenylene group.

Z each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent or a divalent group having an aromatic ring which may have a substituent. In the aspect of the Z middle alkylene group, any of chain-like, branched-chain, and cyclic, and among them, a cyclic alkylene group having 5 or more carbon atoms and having a substituent is more preferable. The number of carbon atoms of the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, and still more preferably 40 or less. As such an alkylene group, for example, a group having an octene-cyclohexene structure, a group having an octene-cyclohexene-octene structure, a propylidene-cyclohexene-octene-octyl group can be mentioned. The basis of construction, etc.

As for the aromatic ring in the divalent group having an aromatic ring represented by Z, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic acid diimide ring, an aromatic ring can be mentioned. Heterocycles, etc., are preferably benzene ring, phthalimide ring and pyromellitic acid diimide ring. That is, as a 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, A divalent group having a diimide ring of pyromellitic acid which may have a substituent is preferred. The divalent group having an aromatic ring includes, for example, a divalent group derived from phthalimide and a group formed by combining with an oxygen atom; a divalent group derived from phthalimide, A group formed by the combination of an oxygen atom, an arylidene group and an alkylene group; a group formed by a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; derived from pyromellitic acid diimide A divalent group of amine; a group formed by a combination of a divalent group derived from phthalimide and an alkylene group; and the like. The above-mentioned arylidene group and alkylene group are the same as the arylidene group and the alkylene group in the divalent linking group represented by L in the general formula (F-4).

The alkylene group represented by Z and the divalent group having an aromatic ring may have a substituent. The substituents are the same as those of the alkyl group represented by ^{R 32 in the} general formula (D-2).

Specific examples of the base represented by Z include the following bases. In the formula, "*" represents a bond bond.

一般式(D-8)中，M² 及M³ 各自獨立地表示可具有取代基之碳原子數為5以上的2價的脂肪族基，R⁴⁰ 各自獨立地表示氧原子、伸芳基、伸烷基、或此等之基的2以上的組合所成之2價的基。t1表示1~10的整數。 一般式(D-9)中，M⁴ 、M⁶ 及M⁷ 各自獨立地表示可具有取代基之碳原子數為5以上的2價的脂肪族基、M⁵ 各自獨立地表示可具有取代基之具芳香環之2價的基、R⁴¹ 及R⁴² 各自獨立地表示碳原子數為5以上的烷基。t2表示0~10的整數、u1及u2各自獨立地表示0~4的整數。Maleimide-based hardeners represented by general formula (D-4) are maleimide-based hardeners represented by general formula (D-8) and maleimide-based hardeners represented by general formula (D-9) Any one of the maleimide-based hardeners is preferred.

In the general formula (D-8), M ² and M ³ each independently represent a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and R ⁴⁰ each independently represents an oxygen atom, an aryl group, A divalent group consisting of an alkylene group or a combination of two or more of these groups. t1 represents an integer from 1 to 10. In the general formula (D-9), M ⁴ , M ⁶ and M ⁷ each independently represent a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and M ⁵ each independently represents an optionally substituted group. The divalent group having an aromatic ring, R ⁴¹ and R ⁴² each independently represent an alkyl group having 5 or more carbon atoms. t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.

M ² and M ³ each independently represent a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M ² and M ³ are the same as the divalent aliphatic group with 5 or more carbon atoms represented by M in the general formula (D-4). , Hexatricosyl is preferred.

R ⁴⁰ each independently represents an oxygen atom, an aryl group, an alkyl group, or a group formed by combining two or more divalent groups thereof. The arylidene group and the alkylene group are the same as the arylidene group and the alkylene group in the divalent linking group represented by L in the general formula (F-4). R ⁴⁰ is preferably a group formed by combining two or more divalent groups or an oxygen atom.

In R ⁴⁰ , as a group formed by a combination of two or more divalent groups, an oxygen atom, a combination of an arylidene group, and an alkylene group can be mentioned. As a specific example of a group formed by combining two or more divalent groups, the following groups are exemplified. In the formula, "*" represents a bond bond.

M ⁴ , M ⁶ and M ⁷ each independently represent a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M ⁴ , M ⁶ and M ⁷ are the same as the divalent aliphatic group represented by M in the general formula (D-4) and may have a substituent with 5 or more carbon atoms, and represent an alkylene group or an alkenylene group, Hexyl, heptyl, octyl, nonyl and decyl are preferred, and octyl is more preferred.

M ⁵ each independently represents a divalent group having an aromatic ring which may have a substituent. M ⁵ is the same as the divalent group having an aromatic ring which may have a substituent represented by Z in the general formula (D-7), and is an alkylene group and a divalent group derived from pyromellitic acid diimide. The base formed by the combination of radicals; the base formed by the combination of the divalent radical from phthalimide and the alkylene group is preferably, the alkylene radical and the divalent radical from pyromellitic acid diimide The base formed by the combination of the bases is better. The above-mentioned arylidene group and alkylene group are the same as the arylidene group and the alkylene group in the divalent linking group represented by L in the general formula (D-4).

Specific examples of the group represented by M ⁵ include, for example, the following groups. In the formula, "*" represents a bond bond.

R ⁴¹ and R ⁴² each independently represent an alkyl group having 5 or more carbon atoms. R ⁴¹ and R ⁴² are the same as the above-mentioned alkyl groups having 5 or more carbon atoms, preferably hexyl, heptyl, octyl, nonyl and decyl, more preferably hexyl and octyl.

u1 and u2 each independently represent an integer of 1 to 15, preferably an integer of 1 to 10.

Specific examples of the maleimide-based curing agent include the following compounds (D1) to (D3). However, the maleimide-based curing agent is not limited to these specific examples. In the formula, v represents an integer from 1 to 10.

Specific examples of the maleimide-based curing agent include "BMI1500" (the compound of the formula (D1)), "BMI1700" (the compound of the formula (D2)), "BMI689" (the compound of the formula ( D3) compound), etc.

The maleimide group equivalent of the maleimide-based hardener is preferably 50 g/eq. to 2000 g/eq., more preferably 100 g/eq. ~1000g/eq., more preferably 150g/eq.~500g/eq.. The maleimide group equivalent is the mass of the maleimide-based hardener containing 1 equivalent of the maleimide group.

(＊表示鍵結鍵。)The polyphenylene ether-based hardener is a hardener with vinyl phenyl. The vinyl phenyl group is a group having the structure shown below.

(* indicates a bond key.)

From the viewpoint of obtaining a cured product with low dielectric loss, the polyphenylene ether-based curing agent preferably has two or more vinylphenyl groups per molecule.

The polyphenylene ether-based curing agent preferably has a ring structure from the viewpoint of obtaining a cured product with low dielectric loss. In terms of the cyclic structure, a divalent cyclic group is preferable. The divalent cyclic group is any of an alicyclic structure-containing cyclic group and an aromatic ring structure-containing cyclic group. In addition, a plurality of divalent cyclic groups may be present.

The bivalent cyclic group, from the viewpoint of significantly obtaining the desired effect of the present invention, is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, more preferably a 5-membered ring or more, and preferably a 20-membered ring. ring or less, more preferably less than 15-member ring, still more preferably less than 10-member ring. Moreover, a monocyclic structure may be sufficient as a bivalent cyclic group, and a polycyclic structure may be sufficient as it.

In the ring of the divalent cyclic group, the skeleton of the ring may be constituted by a hetero atom other than the carbon atom. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example, Oxygen atom is preferable. The heteroatom has one or two or more in the aforementioned ring.

(2價的基(i)、(ii)中，R⁵¹ 、R⁵² 、R⁵⁵ 、R⁵⁶ 、R⁵⁷ 、R⁶¹ 及R⁶² 各自獨立地表示鹵素原子、碳原子數為6以下的烷基、或苯基，R⁵³ 、R⁵⁴ 、R⁵⁸ 、R⁵⁹ 及R⁶⁰ 各自獨立地表示氫原子、鹵素原子、碳原子數6以下的烷基、或苯基。)Specific examples of the divalent cyclic group include the following divalent group (i) or (ii).

(In the divalent groups (i) and (ii), R ⁵¹ , R ⁵² , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁶¹ and R ⁶² each independently represent a halogen atom or an alkyl group having 6 or less carbon atoms , or a phenyl group, R ⁵³ , R ⁵⁴ , R ⁵⁸ , R ⁵⁹ and R ⁶⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As the alkyl group having 6 or less carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc. may be mentioned, and a methyl group is preferable. R ⁵¹ , R ⁵² , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁶¹ and R ⁶² preferably represent a methyl group. R ⁵³ , R ⁵⁴ , R ⁵⁸ , R ⁵⁹ and R ⁶⁰ are preferably hydrogen atoms or methyl groups.

(式(D4)中，R⁷¹ 、R⁷² 、R⁷⁵ 、R⁷⁶ 、R⁷⁷ 、R⁸¹ 、R⁸² 、R⁸⁵ 及R⁸⁶ 各自獨立地表示鹵素原子、碳原子數為6以下的烷基、或苯基，R⁷³ 、R⁷⁴ 、R⁷⁸ 、R⁷⁹ 、R⁸⁰ 、R⁸³ 及R⁸⁴ 各自獨立地表示氫原子、鹵素原子、碳原子數6以下的烷基、或苯基。d1及d2表示0~300的整數。但是，排除d1及d2之一為0的情況。)In addition, the divalent cyclic group may be a combination of plural divalent cyclic groups. As a specific example when a divalent cyclic group is combined, a divalent cyclic group represented by the following formula (D4) can be mentioned.

(In formula (D4), R ⁷¹ , R ⁷² , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁸¹ , R ⁸² , R ⁸⁵ and R ⁸⁶ each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, R ⁷³ , R ⁷⁴ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. d1 and d2 Indicates an integer from 0 to 300. However, the case where one of d1 and d2 is 0 is excluded.)

R ⁷¹ , R ⁷² , R ⁸⁵ and R ⁸⁶ are the same as ^{R 51} in formula (i). R ⁷³ , R ⁷⁴ , R ⁸³ and R ⁸⁴ are the same as ^{R 53} in formula (i). R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁸¹ and R ⁸² are the same as ^{R 55} in formula (ii). R ⁷⁸ , R ⁷⁹ and R ⁸⁰ are the same as ^{R 58} in formula (ii).

d1 and d2 represent integers from 0 to 300. However, the case where one of d1 and d2 is 0 is excluded. In terms of d1 and d2, an integer representing 1-100 is preferable, an integer representing 1-50 is more preferable, and an integer representing 1-10 is more preferable. d1 and d2 may be the same or different.

The divalent cyclic group may have a substituent. As the substituent, for example, halogen atom, alkyl group, alkoxy group, aryl group, arylalkyl group, silyl group, acyl group, acyloxy group, carboxyl group, sulfonic acid group, cyano group, nitro group, hydroxyl group, Sulfhydryl, pendant oxy, etc., preferably alkyl.

The vinylphenyl group may be directly bonded to a divalent cyclic group, or may be bonded via a bivalent linking group. For the divalent linking group, for example, an alkylene group, an alkenylene group, an arylidene group, a heteroarylidene group, -C(=O)O-, -O-, -NHC(=O)-, -NC may be mentioned. (=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc., and it is also possible to combine these bases in plural. In terms of alkylene, the alkylene with 1 to 10 carbon atoms is preferred, the alkylene with 1 to 6 carbon atoms is more preferred, the alkylene with 1 to 5 carbon atoms, or the alkylene with 1 to 5 carbon atoms, or the alkylene with 1 to 5 carbon atoms. The alkylene group of 4 is even more preferred. The alkylene group may be any of linear, branched and cyclic. Such alkylene groups include, for example, methylene, ethylidene, propylidene, butylene, pentylene, hexylene, 1,1-dimethylethylidene, and the like. Ethylene and 1,1-dimethyl ethylidene are preferred. In terms of the alkenylene group, the alkenylene group with 2-10 carbon atoms is preferable, the alkenylene group with 2-6 carbon atoms is more preferable, and the alkenylene group with 2-5 carbon atoms is even more preferable. In terms of aryl extended group and hetero extended aryl group, it is preferably an extended aryl group or a hetero extended aryl group with a carbon number of 6-20, and more preferably a extended aryl group or a hetero extended aryl group with a carbon number of 6-10. In terms of the divalent linking group, an alkylene group is preferable, and a methylene group is more preferable among them.

(式(D-10)中，R⁹¹ 及R⁹² 各自獨立地表示2價的連結基。環B1表示2價的環狀基。)The polyphenylene ether-based curing agent is preferably represented by the following formula (D-10).

(In formula (D-10), R ⁹¹ and R ⁹² each independently represent a divalent linking group. Ring B1 represents a divalent cyclic group.)

R ⁹¹ and R ⁹² each independently represent a divalent linking group. The divalent linking group is the same as the above-mentioned bivalent linking group.

Ring B1 represents a divalent cyclic group. Ring B1 is the same as the above-mentioned divalent cyclic group.

Ring B1 may have a substituent. The substituent is the same as the substituent which the above-mentioned divalent cyclic group may have.

(q1係與式(D4)中的d1相同，q1係與式(D4)中的d2相同。)Although the specific example of a polyphenylene ether type hardening|curing agent is shown below, this invention is not limited to this.

(q1 is the same as d1 in formula (D4), and q1 is the same as d2 in formula (D4).)

As a polyphenylene ether type hardening|curing agent system, a commercial item can be used, For example, "OPE-2St" by Mitsubishi Gas Chemical Co., Ltd., etc. are mentioned. The polyphenylene ether-based curing agent may be used alone or in combination of two or more.

The number average molecular weight of the polyphenylene ether-based hardener is preferably 3,000 or less, more preferably 2,500 or less, still more preferably 2,000 or less, and 1,500 or less, from the viewpoint of remarkably obtaining the desired effect of the present invention. The lower limit is preferably 100 or more, more preferably 300 or more, still more preferably 500 or more, and 1000 or more. The number average molecular weight is the number average molecular weight in terms of polystyrene measured using colloidal permeation chromatography (GPC).

The content of the hardener (D) is preferably 1% by mass or more, more preferably 5% by mass, when the nonvolatile content in the resin composition is 100% by mass, from the viewpoint of remarkably obtaining the effects of the present invention. Above, more preferably 10 mass % or more, more preferably 25 mass % or less, more preferably 20 mass % or less, still more preferably 15 mass % or less.

When the number of epoxy groups of the component (A) is 1, the number of active groups of the hardener (D) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, preferably 2 or less, more preferably 1.8 or less, more preferably 1.6 or less, particularly preferably 1.4 or less. Here, "(D) the number of active bases of the hardener" is the total value obtained by dividing the mass of the nonvolatile content of the (D) hardener present in the resin composition by the equivalent of the active group. When the number of epoxy groups of the component (A) is 1, the number of active groups of the hardener (D) when the number of epoxy groups is 1 is within the aforementioned range, and the desired effect of the present invention can be obtained remarkably.

<(E) Hardening accelerator> In addition to the above-mentioned components, the resin composition may further contain a curing accelerator as the component (E) in terms of optional components.

As for the component (E), for example, a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, and a metal-based curing accelerator can be mentioned. (E) A component may be used individually by 1 type, and may be used in combination of 2 or more types.

Phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, ( 4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., with triphenylphosphine, tetrabutylphosphonium Caprates are preferred.

Amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-paraffin (dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., 4-dimethylaminopyridine, 1,8-diazabicyclo (5,4,0)-undecene is preferred.

As an imidazole-based hardening accelerator, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2- Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino -6-[2'-Undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methyl Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazinetri Polycyanic acid adduct, 2-phenylimidazole cyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazole, 2,3-Dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazole As for imidazole compounds such as oxoline, 2-phenylimidazoline, and adducts between imidazole compounds and epoxy resins, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

As an imidazole type hardening accelerator, a commercial item can also be used, for example, "P200-H50" by Mitsubishi Chemical Corporation, etc. are mentioned.

As the guanidine-based curing accelerator, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, and dimethylguanidine can be mentioned. guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1 ,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-Dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc. Cyanamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

As a metal-based hardening accelerator, for example, metal organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin are exemplified. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetone acetone, cobalt (III) acetylacetone acetone, and copper (II) acetylacetone acetone. Organo-copper complexes such as acetone, organozinc complexes such as zinc (II) acetylacetone acetone, organo-iron complexes such as iron (III) acetylacetone acetone, nickel (II) Organo-nickel complexes such as acetylacetone acetone, etc., and organic manganese complexes such as manganese (II) acetylacetone acetone, etc. As an organometallic salt, zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. are mentioned, for example.

The content of the component (E) is preferably 0.01 mass % or more, more preferably 0.02 mass % or more, when the non-volatile content in the resin composition is 100 mass % from the viewpoint of remarkably obtaining the desired effect of the present invention. , more preferably 0.03 mass % or more, preferably 1 mass % or less, more preferably 0.5 mass % or less, still more preferably 0.1 mass % or less.

<(F) Other additives> In addition to the above-mentioned components, the resin composition may further contain other additives in terms of optional components. As such additives, resin additives such as thermoplastic resins, flame retardants, tackifiers, defoaming agents, leveling agents, and adhesiveness imparting agents can be mentioned, for example. These additives may be used alone or in combination of two or more. The respective contents can be appropriately set by those skilled in the field.

Although the preparation method of the resin composition of this invention is not specifically limited, For example, the method of adding a solvent etc. as needed by blending components, and mixing and dispersing using a rotary stirrer etc. is mentioned.

<Physical properties and applications of resin composition> The resin composition contains (A) component and (B) component. Thereby, the generation|occurrence|production of unevenness which arises when laminating|stacking the resin composition layer containing a resin composition can be suppressed. In addition, in the present invention, generally, a cured product having excellent plating peeling strength, copper foil adhesion, and copper foil adhesion after HAST, low dielectric properties, and low arithmetic mean roughness (Ra) can be obtained.

The resin composition exhibits the property of suppressing the occurrence of unevenness when laminating resin composition layers containing the resin composition. Specifically, it was carried out according to the method described in the following examples. In this case, the unevenness is usually not observed at all, and it is a completely uniform surface. The details of the evaluation of unevenness after lamination can be measured according to the method described in the examples described later.

The resin composition is thermally hardened at 130° C. for 30 minutes and then at 170° C. for 30 minutes, and the roughened surface after roughening the surface of the hardened product thus obtained generally exhibits a low arithmetic mean roughness (Ra). Therefore, the aforementioned hardened product results in an insulating layer having a low arithmetic mean roughness. The arithmetic mean roughness is preferably 300 nm or less, more preferably 250 nm or less, and still more preferably 200 nm or less. On the other hand, the lower limit value of the arithmetic mean roughness may be 30 nm or more. The evaluation of arithmetic mean roughness (Ra) can be measured according to the method described in the Example mentioned later.

A cured product obtained by thermally curing the resin composition at 190° C. for 90 minutes generally exhibits low dielectric properties (dielectric loss). Therefore, the aforementioned cured product has an insulating layer with low dielectric loss. The dielectric loss is preferably 0.005 or less, more preferably 0.004 or less, and still more preferably 0.003 or less. The lower limit value of the dielectric loss may be 0.0001 or more. The dielectric loss can be measured according to the method described in the following examples.

When the resin composition is thermally cured at 130°C for 30 minutes, then at 170°C for 30 minutes, and then at 200°C for 90 minutes, there is usually a gap between the resin composition and the conductor layer (plated conductor layer) formed by plating. The characteristics of excellent peeling strength. Therefore, the said hardened|cured material has the insulating layer which is excellent in the peeling strength from the plated conductor layer. The peeling strength is preferably 0.3 kgf/cm or more, more preferably 0.35 kgf/cm or more, and still more preferably 0.4 kgf/cm or more. The upper limit of the peeling strength may be 10 kgf/cm or less. The peeling strength of the plated conductor layer can be measured according to the method described in the examples described later.

The resin composition is thermally cured at 130°C for 30 minutes, then at 170°C for 30 minutes, and then at 200°C for 90 minutes, and usually shows excellent peeling strength (copper foil adhesion) with copper foil. characteristic. Therefore, the said hardened|cured material has the insulating layer excellent in the peeling strength from the copper foil. The peeling strength is preferably 0.3 kgf/cm or more, more preferably 0.4 kgf/cm or more, and still more preferably 0.5 kgf/cm or more. The upper limit of the peeling strength may be 10 kgf/cm or less. The measurement of copper foil adhesiveness can be measured according to the method described in the Example mentioned later.

The cured product, which is thermally cured at 130°C for 30 minutes and then at 170°C for 30 minutes, usually shows the peeling strength ( Copper foil adhesion after HAST) excellent characteristics. Therefore, the said hardened|cured material has the insulating layer which is excellent in the peeling strength after HAST with the copper foil. The copper foil adhesion after HAST is preferably 0.15 kgf/cm or more, more preferably 0.2 kgf/cm or more, and even more preferably 0.25 kgf/cm or more. The upper limit value of the copper foil adhesion after HAST may be 10 kgf/cm or less. The measurement of the copper foil adhesiveness after HAST can be measured according to the method described in the Example mentioned later.

The resin composition of the present invention can suppress the occurrence of unevenness during lamination of resin composition layers containing the resin composition. Therefore, the resin composition of the present invention is suitable for use as a resin composition for insulating purposes. Specifically, it is suitable for use as a resin composition for forming a conductor layer (including a rewiring layer) on an insulating layer for forming the insulating layer (resin composition for forming an insulating layer for forming a conductor layer).

Further, in the multilayer printed wiring board described later, a resin composition for forming an insulating layer of a multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board), a resin composition for forming an insulating layer of a printed wiring board, and an interlayer insulation for forming a printed wiring board are suitably used. The resin composition of the layer (the resin composition for forming the interlayer insulating layer between the printed wiring boards).

Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is suitable for use as a resin composition for a rewiring formation layer as an insulating layer for forming a rewiring layer (resin composition for rewiring formation layer formation), and resin composition for sealing semiconductor wafers (resin composition for sealing semiconductor wafer). When a semiconductor chip package can be manufactured, a rewiring layer can also be further formed on the sealing layer. (1) The step of laminating the temporary fixing film on the substrate, (2) the step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) the step of forming a sealing layer on the semiconductor wafer, (4) the step of peeling the base material and the temporary fixing film from the semiconductor wafer, (5) The step of forming a rewiring formation layer as an insulating layer on the surface of the substrate and the temporary fixing film from which the semiconductor wafer is peeled off, and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

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

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm from the viewpoint of providing a cured product with excellent insulating properties even if the thickness of the printed wiring board is reduced and the cured product of the resin composition is a thin film. Hereinafter, it is more preferably 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and it is usually 5 μm or more.

As for the support, for example, a film made of a plastic material, a metal foil, and a release paper can be mentioned, and a film and a metal foil made of a plastic material are preferable.

When a film made of a plastic material is used as the support, as the plastic material, for example, polyethylene terephthalate (hereinafter referred to as "PET"), polyethylene naphthalene dicarboxylic acid (hereinafter referred to as "PEN") Polyester such as polyester, polycarbonate (hereinafter referred to as "PC"), acrylate such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyetherketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalene dicarboxylic acid are more preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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

The support system can be subjected to matting treatment, corona treatment and antistatic treatment on the surface that is joined to the resin composition layer.

Moreover, the support body can also be used as a support body with a release layer having a release layer on the surface to be joined to the resin composition layer. The release agent used in the release layer of the support with the release layer can be, for example, at least one selected from the group consisting of alkyd resin, polyolefin resin, urethane resin and polysiloxane resin release agent. Commercially available products can also be used for the support with a release layer, for example, a PET film having a release layer mainly composed of an alkyd resin-based release agent, such as "SK-1", "AL" manufactured by LINTEC -5", "AL-7", "Lumirror T60" manufactured by Toray Corporation, "Purex" manufactured by Teijin Corporation, "unipeel" manufactured by UNITIKA Corporation, etc.

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

In one embodiment, the resin sheet may contain any layer as needed. The optional layer includes, for example, a protective film or the like provided on the surface not joined to the support of the resin composition layer (that is, the surface opposite to the support). Although the thickness of the protective film is not particularly limited, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust or the like to the surface of the resin composition layer and scratches can be suppressed.

The resin sheet can be produced, for example, by dissolving a resin composition in an organic solvent to prepare a resin varnish, applying the resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer.

In terms of organic solvents, for example, ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; Acetates such as acetates and carbitol acetates; carbitols such as celusol and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, Amide-based solvents such as dimethylacetamide (DMAc) and N-methylpyrrolidone, etc. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

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

The resin sheet can be rolled into a roll and stored. When the resin sheet has a protective film, the protective film can be removed and used.

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

A printed wiring board can be manufactured, for example, by a method including the steps of the following (I) and (II) after using the above-mentioned resin sheet. (1) Step of laminating on the inner layer substrate in such a way that the resin composition layer of the resin sheet is bonded to the inner layer substrate (II) Step of thermosetting the resin composition layer to form an insulating layer

The "inner layer substrate" used in the step (1) is a member that becomes the substrate of the printed wiring board, such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermal Hardened polyphenylene ether substrates, etc. In addition, the substrate may have a conductor layer on one side or both sides thereof, and the conductor layer may be patterned. An inner-layer substrate in which a conductor layer (circuit) is formed on one or both sides of the substrate may be referred to as an "inner-layer circuit substrate". Moreover, when manufacturing a printed wiring board, the intermediate product in which an insulating layer and/or a conductor layer should be formed is further included in the "inner layer substrate" referred to in the present invention. When the printed wiring board is a circuit board with built-in components, an inner-layer substrate with built-in components can be used.

The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermally pressing the resin sheet onto the inner layer substrate from the support side. As for the member (hereinafter referred to as "heat-bonding member") for heating and pressing the resin sheet to the inner layer substrate, for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller) can be mentioned. In addition, instead of pressing the thermocompression member directly on the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate.

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

The lamination system can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, the vacuum pressurization laminator by Meiki Seisakusho Co., Ltd., the vacuum applicator by Nikko Materials Co., Ltd., the batch vacuum pressurization laminator, etc. are mentioned, for example.

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

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

In step (II), the insulating layer is formed by thermosetting the resin composition layer. The thermosetting conditions of the resin composition layer are not particularly limited, and generally used conditions may be used when forming the insulating layer of the printed wiring board.

For example, although the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C °C. The hardening time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 minutes.

Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before thermosetting the resin composition layer, the resin composition layer is preheated at a temperature of not less than 50°C and not more than 120°C (preferably not less than 60°C and not more than 115°C, more preferably not less than 70°C and not more than 110°C). 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and still more preferably 15 minutes to 100 minutes).

When manufacturing a printed wiring board, (III) the step of opening a hole in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming the conductor layer may be further carried out. These steps (III) to (V) can also be implemented according to various methods well known to those skilled in the art used in the manufacture of printed wiring boards. In addition, when the support is removed after step (II), the removal of the support can also be performed between step (II) and step (III), between step (III) and step (IV), or between step ( IV) and step (V). Moreover, according to need, the formation of the insulating layer and the conductor layer of the steps (II) to (V) may be repeatedly performed to form a multilayer wiring board.

The step (III) is a step of opening holes in the insulating layer, thereby forming through holes such as via holes and through holes in the insulating layer. The step (III) can also be implemented using, for example, drilling, laser, plasma, etc., depending on the composition of the resin composition used in the formation of the insulating layer, and the like. The size and shape of the through hole can be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually in this step (IV), stain removal is also performed. The procedures and conditions of the roughening treatment are not particularly limited, and well-known procedures and conditions generally used when forming an insulating layer of a printed wiring board can be employed. For example, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid are sequentially performed to roughen the insulating layer. The swelling liquid used in the roughening treatment is not particularly limited, and examples thereof include an alkaline solution, a surfactant solution, and the like, and an alkaline solution is preferred, and a sodium hydroxide solution and a potassium hydroxide solution are more preferred as the alkaline solution. As a commercially available swelling liquid, "Swelling Dip Securiganth P", "Swelling Dip Securiganth SBU", and "Swelling Dip Securiganth P" manufactured by Atotech Japan can be mentioned, for example. The swelling treatment by the swelling liquid is not particularly limited, and for example, it can be performed 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 degree, it is preferable to immerse the insulating layer in a swelling liquid of 40° C. to 80° C. for 5 minutes to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, but an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide is exemplified. The roughening treatment by an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 minutes to 30 minutes. In addition, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Atotech Japan. In addition, an acidic aqueous solution is preferable in the neutralization liquid used for the roughening process, and "Reduction solution Securiganth P" by Atotech Japan is mentioned, for example as a commercial item. The treatment with the neutralizing liquid can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing liquid at 30° C. to 80° C. for 1 minute to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object to be subjected to the roughening treatment by the oxidizing agent in the neutralization solution at 40° C. to 70° C. for 5 minutes to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, and still more preferably 200 nm or less. The lower limit is not particularly limited, but is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, which is to form a conductor layer on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium . 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-mentioned group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). formed layer. Among them, from the viewpoints of versatility, cost, ease of patterning, etc. of conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or nickel・Alloy layer of chromium alloy, copper-nickel alloy, copper-titanium alloy is preferred, single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or alloy layer of nickel-chromium alloy is more preferable Preferably, a single metal layer of copper is preferred.

The conductor layer may have a single-layer structure, or may have a multiple-layer structure in which two or more layers of a single metal layer or an alloy layer composed of different kinds of metals or alloys are laminated. When the conductor layer has a multiple-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 a nickel-chromium alloy.

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

In one embodiment, the conductor layer can be formed by plating. For example, by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method, a conductor layer having a desired wiring pattern can be formed, from the viewpoint of simplicity of manufacture. See, the one formed by the semi-additive method is better. Hereinafter, an example in which the conductor layer is formed by the semi-additive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed by exposing a part of the plating seed layer corresponding to a desired wiring pattern on the formed plating seed layer. After the metal layer is formed 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.

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

The semiconductor device includes various semiconductor devices supplied to electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and rides (for example, motorcycles, motorcycles, trains, ships, and aircraft, etc.).

The semiconductor device of the present invention is manufactured by mounting a component (semiconductor chip) at the conductive portion of the printed wiring board. The so-called "conduction place" is "the place where the electrical signal in the printed wiring board is transmitted", which can be the surface or the embedded place. In addition, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

The mounting method of a semiconductor chip in the manufacture of a semiconductor device is not particularly limited as long as the semiconductor chip can operate effectively. Specifically, a wire bonding mounting method, a flip chip mounting method, a bumpless mounting method, Mounting method for assembly layer (BBUL), mounting method for anisotropic conductive film (ACF), mounting method for non-conductive film (NCF), etc. Here, the so-called "mounting method by bumpless build layer (BBUL)" refers to "mounting method in which the semiconductor chip is directly embedded in the concave portion of the printed wiring board, and the semiconductor chip is connected to the wiring on the printed wiring board" .

[Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples. In addition, in the following description, unless otherwise expressly stated, "part" and "%" represent "mass part" and "mass %", respectively.

<Synthesis Example 1: Synthesis of Active Ester Compound (B-1)> In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 320 g (2.0 moles) of 2,7-dihydroxynaphthalene, 184 g (1.7 moles) of benzyl alcohol, p-toluenesulfonic acid were placed・5.0 g of 1 water mixture was stirred at room temperature while blowing nitrogen gas. Then, it heated up to 150 degreeC, and it stirred for 4 hours, distilling the produced|generated water out of the system. After completion of the reaction, 900 g of methyl isobutyl ketone and 5.4 g of a 20% aqueous sodium hydroxide solution were added for neutralization, and then the aqueous layer was removed by liquid separation, and washed three times with 280 g of water to remove methyl alcohol under reduced pressure. isobutyl ketone to obtain 460 g of benzyl-modified naphthalene compound (A-1). The obtained benzyl-modified naphthalene compound (A-1) was a black solid, and the hydroxyl group equivalent was 180 g/equivalent.

In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 203.0 g of isophthalic acid chloride (molar number of acid chloride base: 2.0 mol) and 1400 g of toluene were put into the flask. In the reaction system, nitrogen substitution under reduced pressure was performed and dissolved. Next, 72.4 g (0.67 mol) of o-cresol and 240 g of the benzyl-modified naphthalene compound (A-1) (molar number of phenolic hydroxyl group: 1.33 mol) were placed, and the reaction system was substituted with nitrogen under reduced pressure. and dissolve it. Then, 0.70 g of tetrabutylammonium bromide was dissolved, and the inside of the reaction system was controlled to be 60° C. or lower while purging with nitrogen gas, and 400 g of a 20% aqueous sodium hydroxide solution was dropped over 3 hours. Next, stirring was continued under these conditions for 1.0 hour. After the reaction was completed, the solution was left to stand for separation and the aqueous layer was removed. In addition, the reactant was dissolved, put into water in the toluene layer, stirred and mixed for 15 minutes, and left to stand for liquid separation, and then the water layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Then, water was removed by dehydration with a decanter to obtain an active ester compound (B-1) in the state of a toluene solution with a nonvolatile content of 65% by mass. The active ester equivalent of the obtained active ester compound (B-1) was 238 g/eq.

<Synthesis example 2: Synthesis of active ester compound (B-2)> In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 203.0 g of isophthalic acid chloride (molar number of acid chloride base: 2.0 mol) and 1400 g of toluene were placed, and The inside of the reaction system was substituted with nitrogen under reduced pressure and dissolved. Next, 113.9 g (0.67 mol) of o-phenylphenol and 240 g of the benzyl-modified naphthalene compound (A-1) (the number of moles of phenolic hydroxyl groups: 1.33 mol) were placed, and the reaction system was depressurized. Nitrogen replaces and dissolves it. Then, 0.70 g of tetrabutylammonium bromide was dissolved, and the inside of the reaction system was controlled to be 60° C. or lower while purging with nitrogen gas, and 400 g of a 20% aqueous sodium hydroxide solution was dropped over 3 hours. Next, stirring was continued under these conditions for 1.0 hour. After the reaction was completed, the solution was left to stand for separation and the aqueous layer was removed. In addition, the reactant was dissolved, put into water in the toluene layer, stirred and mixed for 15 minutes, and left to stand for liquid separation, and then the water layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Then, water was removed by dehydration with a decanter to obtain an active ester compound (B-2) in the state of a toluene solution of 65% by mass of nonvolatile content. The active ester equivalent of the obtained active ester compound (B-2) was 206 g/eq.

<Synthesis Example 3: Synthesis of Active Ester Compound (B-3)> In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 203.0 g of isophthalic acid chloride (molar number of acid chloride base: 2.0 mol) and 1400 g of toluene were placed, and The inside of the reaction system was substituted with nitrogen under reduced pressure and dissolved. Next, 132.7 g (0.67 mol) of styrenated phenol phenol and 240 g of the benzyl-modified naphthalene compound (A-1) (molar number of phenolic hydroxyl groups: 1.33 mol) were added to the reaction system, and the reaction system was subjected to reduced pressure nitrogen. replace and dissolve. Then, 0.70 g of tetrabutylammonium bromide was dissolved, and the inside of the reaction system was controlled to be 60° C. or lower while purging with nitrogen gas, and 400 g of a 20% aqueous sodium hydroxide solution was dropped over 3 hours. Next, stirring was continued under these conditions for 1.0 hour. After the reaction was completed, the solution was left to stand for separation and the aqueous layer was removed. In addition, the reactant was dissolved, put into water in the toluene layer, stirred and mixed for 15 minutes, and left to stand for liquid separation, and then the water layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Then, water was removed by dehydration with a decanter to obtain an active ester compound (B-3) in the state of a toluene solution with a nonvolatile content of 65% by mass. The active ester equivalent of the obtained active ester compound (B-3) was 259 g/eq.

The identification of the active ester compound (B-1) to the active ester compound (B-3) was carried out as follows. As a result of the identification, it is known that the active ester compound (B-1) is of the general formula (b-3) where Ar ³¹ has a group represented by the formula (1), and the active ester compound (B-2) is of the general formula (b- ^{Ar 31 in} 3) has a group represented by formula (2), and the active ester compound (B-3) is a general formula (b-3) Ar ³¹ has a group represented by formula (3) (n=1~ 5).

<Example 1: Preparation of resin composition 1> 3 parts of epoxy resin "ESN475V" (manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent: about 330 g/eq.) as the component (A) and ( A) 7 parts of epoxy resin "HP-4032-SS" (manufactured by DIC Corporation, epoxy equivalent: about 144 g/eq.) of component A was dissolved in 10 parts of methyl ethyl ketone (MEK) to obtain epoxy resin solution A . To the epoxy resin solution A, 25 parts of active ester compound (B-1) as component (B) and an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) as component (C) were added to the surface 65 parts of treated spherical silica (average particle size: 0.77 μm, “SO-C2” manufactured by Admatechs) (hereinafter also referred to as “inorganic filler A”), imidazole compound “1B2PZ” (Shikoku) as component (E) 0.2 part of Kasei Co., Ltd.) was uniformly dispersed with a high-speed rotary mixer to prepare Resin Paint A. The average particle diameter of the inorganic filler A was 0.5 μm, and the specific surface area was 5.9 m ² /g.

<Example 2: Preparation of resin composition 2> In Example 1, 25 parts of active ester compounds (B-1) were changed to 25 parts of active ester compounds (B-2). Except for the above matters, the resin composition 2 was prepared in the same manner as in Example 1.

<Example 3: Preparation of resin composition 3> In Example 1, 25 parts of active ester compounds (B-1) were changed to 25 parts of active ester compounds (B-3). Except for the above matters, the resin composition 3 was prepared in the same manner as in Example 1.

<Example 4: Preparation of resin composition 4> In Example 1, the system will The amount of active ester compound (B-1) was changed from 25 parts to 22 parts, The amount of imidazole compound (1B2PZ manufactured by Shikoku Chemical Industry Co., Ltd.) was changed from 0.2 part to 0.02 part, In addition, 2 parts of triazine-containing cresol novolak resin ("LA-3018-50P" manufactured by DIC, a methoxypropanol solution with a solid content of 50% by mass) and a carbodiimide resin (manufactured by Nisshinbo Chemical Co., Ltd.) were used. "V-03", an active group equivalent of about 216, a toluene solution with a solid content of 50% by mass) 1 part. Resin composition 4 was prepared in the same manner as in Example 1 except for the above matters.

<Example 5: Preparation of resin composition 5> In Example 2, the system will be The amount of active ester compound (B-2) was changed from 25 parts to 22 parts, The amount of imidazole compound (1B2PZ manufactured by Shikoku Chemical Industry Co., Ltd.) was changed from 0.2 part to 0.02 part, In addition, 2 parts of triazine-containing cresol novolak resin ("LA-3018-50P" manufactured by DIC, a methoxypropanol solution with a solid content of 50% by mass) and a carbodiimide resin (manufactured by Nisshinbo Chemical Co., Ltd.) were used. "V-03", an active group equivalent of about 216, a toluene solution with a solid content of 50% by mass) 1 part. Resin composition 5 was prepared in the same manner as in Example 2 except for the above.

<Example 6: Preparation of resin composition 6> In Example 3, the system will be The amount of active ester compound (B-3) was changed from 25 parts to 22 parts, The amount of imidazole compound (1B2PZ manufactured by Shikoku Chemical Industry Co., Ltd.) was changed from 0.2 part to 0.02 part, In addition, 2 parts of triazine-containing cresol novolak resin ("LA-3018-50P" manufactured by DIC, a methoxypropanol solution with a solid content of 50% by mass) and a carbodiimide resin (manufactured by Nisshinbo Chemical Co., Ltd.) were used. "V-03", an active group equivalent of about 216, a toluene solution with a solid content of 50% by mass) 1 part. Except for the above matters, the resin composition 6 was prepared in the same manner as in Example 3.

<Example 7: Preparation of resin composition 7> In Example 1, the system will The amount of active ester compound (B-1) was changed from 25 parts to 22 parts, The amount of imidazole compound (1B2PZ manufactured by Shikoku Chemical Industry Co., Ltd.) was changed from 0.2 part to 0.02 part, In addition, 2 parts of triazine-containing cresol novolak resin (“LA-3018-50P” manufactured by DIC, a methoxypropanol solution with a solid content of 50% by mass) was used, and 2 parts of vinylbenzyl resin ("OPE-2St" by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a solid content of 65% by mass) was used. Except for the above matters, the resin composition 7 was prepared in the same manner as in Example 1.

<Example 8: Preparation of resin composition 8> In Example 7, the system Changed 2 parts of vinylbenzyl resin ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with a solid content of 65% by mass) to maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. 2 parts of toluene and MEK solution with a solid content of 70% by mass. Resin composition 8 was prepared in the same manner as in Example 7 except for the above matters.

<Example 9: Preparation of resin composition 9> In Example 7, the system 2 parts of vinylbenzyl resin ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with a solid content of 65% by mass) was changed to 1 part of maleimide resin ("BMI-689" manufactured by DMI Corporation). Resin composition 9 was prepared in the same manner as in Example 7 except for the above-mentioned matters.

<Example 10: Preparation of resin composition 10> In Example 7, the system 2 parts of vinylbenzyl resin ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with a solid content of 65% by mass) was changed to 1 part of maleimide resin ("BMI-1500" manufactured by DMI Corporation) . Except for the above matters, the resin composition 10 was prepared in the same manner as in Example 7.

<Comparative Example 1: Preparation of Resin Composition 11> In Example 1, 25 parts of active ester compounds (B-1) were changed to 25 parts of other hardeners (active ester-based hardeners, manufactured by DIC Corporation, "HPC8150-62T", toluene solution with a solid content of 62%) . Except for the above matters, the resin composition 11 was prepared in the same manner as in Example 1.

<Comparative example 2: Preparation of resin composition 12> In Example 1, 25 parts of active ester compounds (B-1) were changed to 23 parts of other hardeners (active ester-based hardeners, manufactured by DIC Corporation, "HPC8000-65T", toluene solution with a solid content of 65%) . Except for the above matters, the resin composition 12 was prepared in the same manner as in Example 1.

<Comparative example 3: Preparation of resin composition 13> In Example 4, 22 parts of active ester compounds (B-1) were changed to another hardener (active ester type hardener, manufactured by DIC Corporation, "HPC8150-62T", 22 parts of a toluene solution with a solid content of 62%. Except for the above matters, the resin composition 13 was prepared in the same manner as in Example 4.

<Comparative example 4: Preparation of resin composition 14> In Example 3, 22 parts of active ester compounds (B-2) were changed to 21 parts of other hardeners (active ester-based hardeners, manufactured by DIC Corporation, "HPC8000-65T", toluene solution with a solid content of 65%) . Except for the above matters, the resin composition 14 was prepared in the same manner as in Example 3.

<Evaluation of unevenness after lamination, arithmetic mean roughness, and measurement of peeling strength of plated conductor layer> (1) Preparation of the resin sheet A whose thickness of the resin composition layer is 40 μm As a support, a polyethylene terephthalate film ("AL5" manufactured by LINTEC, thickness 38 μm) provided with a release layer was prepared. On the release layer of this support, the resin compositions obtained in Examples and Comparative Examples were uniformly applied so that the thickness of the resin composition layer after drying was 40 μm. Then, the resin composition was dried at 80° C. to 100° C. (average 90° C.) for 4 minutes to obtain a resin sheet A including a support and a resin composition layer.

(2) Preparation of inner layer substrate A glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, "R1515A" manufactured by Panasonic Corporation) on which the inner layer circuit is formed was coated with a microetchant ("R1515A" manufactured by MEC Corporation) on both sides. CZ8101") was etched at 1 μm to roughen the copper surface.

(3) Lamination of resin sheet A Using a batch-type vacuum pressure laminator (Nikko-Materials, 2-stage assembly laminator "CVP700"), the resin composition layer was laminated on both sides of the inner-layer substrate so that the resin composition layer was in contact with the inner-layer substrate. The lamination was performed by reducing the pressure for 30 seconds and adjusting the air pressure to 13 hPa or less, and then pressing at 120° C. and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed for 60 seconds at 100° C. and a pressure of 0.5 MPa.

(4) Thermosetting of the resin composition layer Then, the inner layer substrate laminated with the resin sheet A was put into a 130°C oven and heated for 30 minutes, and then moved to a 170°C oven and heated for 30 minutes to thermally harden the resin composition layer to form an insulating layer. Then, the support body was peeled off, and the cured board|substrate A which has an insulating layer, an inner-layer board|substrate, and an insulating layer in this order was obtained.

(5) Evaluation of unevenness after lamination On both surfaces of the hardened substrate A, the surface uniformity of the part where the resin sheet A is laminated (the surface on the opposite side to the laminated board) was visually observed and evaluated as follows. ○: No unevenness was observed at all, and a completely uniform surface was exhibited. ×: A non-uniform part was observed in the part where the resin sheet was laminated.

(6) Coarsening treatment An electroless copper plating process as a roughening process is performed on the hardened board|substrate A. As for the electroless copper plating treatment, the following wet electroless copper plating treatment was performed.

(Wet electroless copper plating) The cured substrate A was immersed in a swelling solution (“Concentrate Compact P” manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60° C. for 5 minutes, and then immersed in an oxidizing agent solution (Atotech Japan). "Concentrate Compact CP", an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) was immersed at 80°C for 20 minutes. Next, it was immersed at 40 degreeC for 5 minutes in a neutralizing liquid ("Reduction solution Securiganth P", sulfuric acid aqueous solution by Atotech Japan company), and it dried at 80 degreeC for 15 minutes.

(7) Determination of the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening treatment The arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment was obtained by using a non-contact surface roughness meter (WYKO NT3300, manufactured by Bruker Corporation) with a measurement range of 121 μm×92 μm by a VSI mode and a 50-fold lens. value to obtain. Measured by taking the average value of each 10 points.

(8) Formation of conductor layer According to the semi-additive method, the conductor layer was formed on the roughened surface of the insulating layer. That is, the roughened substrate was immersed in an _{electroless plating solution containing PdCl 2} at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. Next, after annealing treatment by heating at 150° C. for 30 minutes, an etching resist was formed, and a pattern was formed by etching. Then, copper sulfate electroplating was performed to form a conductor layer with a thickness of 25 μm, and annealing treatment was performed at 190° C. for 60 minutes. The obtained board|substrate is called "evaluation board|substrate B".

(9) Determination of peeling strength of plated conductor layer The measurement of the peeling strength of the insulating layer and the conductor layer is carried out according to the Japanese Industrial Standard (JIS C6481). Specifically, in the conductor layer of the evaluation substrate B, a 10 mm wide and 100 mm long incision was made, and the end was peeled off with a clamp, and the measurement was carried out at room temperature at a speed of 50 mm/min and peeled off in the vertical direction. The load (kgf/cm) at 35 mm was used to obtain the peel strength. For the measurement, a tensile tester (“AC-50C-SL” manufactured by TSE) was used.

<Evaluation of Dielectric Properties> The evaluation of the dielectric properties was carried out by measuring the value of the dielectric loss (Df). Specifically, as follows, the cured product B for evaluation was produced, and the dielectric loss (Df) was measured.

The resin sheets A obtained in Examples and Comparative Examples were cured in an oven at 190° C. for 90 minutes. By peeling off the support from the resin sheet A taken out from the oven, a cured product of the resin composition layer was obtained. This cured product was cut out to a length of 80 mm and a width of 2 mm as a cured product B for evaluation.

For each cured product B for evaluation, "HP8362B" manufactured by Agilent Technologies was used, and the value of dielectric loss (Df value) was measured by the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. The measurement was performed on two test pieces, and the average was calculated.

<Measurement of Copper Foil Adhesion (Peeling Strength)> (1) Fabrication of a substrate for adhesion evaluation For the inner layer substrate, a glass cloth base epoxy resin double-sided copper-clad laminate with copper foil on the surface was prepared (copper foil thickness 18 μm, substrate thickness 0.8 mm, “R1515A” manufactured by Panasonic Corporation). All the copper foils on the surface of the inner layer substrate are removed by etching. Then, it dried at 190 degreeC for 30 minutes.

Using a batch-type vacuum pressure laminator (Nikko-Materials, Inc., 2-stage assembly laminator "CVP700"), the above-mentioned implementation was carried out on both areas of the inner-layer substrate by bonding the resin composition layer to the inner-layer substrate. The resin sheet A obtained in Example and Comparative Example. After this lamination was decompressed for 30 seconds to reduce the air pressure to 13 hPa or less, it was carried out by pressing at a temperature of 100° C. and a pressure of 0.74 MPa for 30 seconds.

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

Moreover, the copper foil (thickness 35 micrometers, "3EC-III" by Mitsui Metals Corporation) which has a glossy surface was prepared. The glossy surface of this copper foil was etched with a copper etching amount of 1 μm using a microetchant (“CZ8101” manufactured by MEC Corporation), and a roughening process was performed. The copper foil thus obtained is called "roughened copper foil".

This roughened copper foil is laminated on both surfaces of the intermediate clad body 1 so that the surface of the roughened copper foil subjected to the roughening treatment and the resin composition layer of the intermediate cladding body 1 are bonded. This lamination was performed under the same conditions as the above-mentioned lamination of the resin sheet on the inner layer substrate. Thereby, the "intermediate cladding body II" comprising the roughened copper foil, the resin composition layer, the inner layer substrate, the resin composition layer, and the roughened copper foil in this order can be obtained.

This intermediate cladding body II was put into an oven at 100° C. and heated for 30 minutes, and then moved to an oven at 170° C. and heated for 30 minutes. Then, after taking out the intermediate cladding body II from the oven to a room temperature atmosphere, it was further put into a 200° C. oven for additional heating for 90 minutes. Thereby, the thermal curing of the resin composition layer can be performed to obtain the insulating layer including the roughened copper foil, the cured product of the resin composition layer, the inner layer substrate, the insulating layer of the cured product of the resin composition layer, and "Evaluation substrate C" of roughened copper foil. In this evaluation board|substrate C, the roughened copper foil corresponds to a conductor layer.

(2) Measurement of copper foil adhesion (strength of peeling off) Using the aforementioned evaluation substrate C, the measurement of the peeling strength between the roughened copper foil and the insulating layer was performed. The measurement of the peeling strength was carried out in accordance with JIS C6481. Specifically, the peeling strength was measured by the following operation.

For the roughened copper foil of the evaluation board C, an incision was made into a rectangular portion having a width of 10 mm and a length of 100 mm. One end of this rectangular part was peeled off, and it clamped with a clamp (TSE Corporation make, Autocom type testing machine "AC-50C-SL"). The range of the length of 35 mm of the said rectangular part was peeled in the vertical direction, and the load (kgf/cm) at the time of this peeling was measured as peeling strength. The aforementioned peeling was performed at a speed of 50 mm/min at room temperature. In addition, after the HAST test (130 degreeC, humidity 85%RH, 100 hours), the copper foil adhesiveness (peeling strength) was measured again.

In Examples 1 to 10, even when the components (C) to (E) were not contained, there were differences in degrees, but it was confirmed that the same results as those of the above-mentioned Examples were summarized.

Claims (10)

A resin composition comprising: (A) an epoxy resin, and (B) an active ester compound having at least one of the groups represented by the following formulae (1) to (3),

(In the formula, * represents a bonding bond; in the formula (3), n represents an integer of 1 to 5). The resin composition of claim 1, wherein the component (B) is an active ester compound represented by the following general formula (b-1),

(In the general formula (b-1), Ar ¹¹ each independently represents a group represented by the formula (1), a group represented by the formula (2), or a group represented by the formula (3), and Ar ¹² each independently represents a possible A divalent aromatic hydrocarbon group having a substituent, Ar ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or the like The 2-valent base formed by the combination of ; a represents an integer from 1 to 6, and b represents an integer from 0 to 10). The resin composition according to claim 2, wherein Ar ¹³ in the general formula (b-1) each independently represents a divalent aromatic hydrocarbon group which may have a substituent and a divalent group in which an oxygen atom is combined. The resin composition of claim 1, wherein the component (B) is an active ester compound represented by the following general formula (b-3),

(In general formula (b-3), Ar ³¹ each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3); a2 represents 1 to 6 Integer, c2 represents an integer of 1 to 5, and d each independently represents an integer of 0 to 6). The resin composition according to claim 1, which further contains (C) an inorganic filler. The resin composition according to claim 1 is for forming an insulating layer. The resin composition according to claim 1, which is used for forming an insulating layer for forming a conductor layer. A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of Claims 1 to 7. A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 7. A semiconductor device comprising the printed wiring board as claimed in claim 9.