JP2021014545A - Resin composition - Google Patents

Abstract

To provide a resin composition that can suppress the unevenness occurring in a curing substrate and gives a cured product with excellent dielectric properties.SOLUTION: A resin composition contains (A) an epoxy resin, (B) an active ester curing agent having a specific constitutional unit, and (C) an inorganic filler. The (B) component content is 30 mass% or less when a nonvolatile content in the resin composition is 100 mass%. The (C) component content is 60 mass% or less when the nonvolatile content in the resin composition is 100 mass%.SELECTED DRAWING: None

Description

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

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

As an insulating material for a printed wiring board used for such an insulating layer, for example, Patent Document 1 discloses a resin composition.

JP-A-2019-6869

In recent years, further improvement of dielectric properties such as dielectric constant and dielectric loss tangent of an insulating layer has been required. Therefore, it is conceivable to increase the content of the inorganic filler.

However, as a result of diligent studies by the present inventors, when an insulating layer is formed on a substrate having irregularities using a resin composition having a high content of an inorganic filler, the surface of the insulating layer opposite to the substrate becomes a substrate. It was found that the flatness of the insulating layer deteriorates following the unevenness of the above, and unevenness (unevenness on the surface of the insulating layer) tends to occur on the cured substrate. If the cured substrate is uneven, the composition of the insulating layer becomes non-uniform, and the wiring formability may be inferior.

An object of the present invention is a resin composition capable of suppressing unevenness occurring in a cured substrate and obtaining a cured product having excellent dielectric properties; a resin sheet containing the resin composition; insulation formed by using the resin composition. It is an object of the present invention to provide a printed wiring board provided with a layer and a semiconductor device.

As a result of diligent studies on the above problems, the present inventors have found that the above problems can be solved by containing a predetermined active ester-based curing agent, and have completed the present invention.

（一般式（１）中、Ｒ^１１は、それぞれ独立に置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表し、Ｚは、置換基を有していてもよいイソフタロイル基、又は置換基を有していてもよいナフタレンジカルボニル基を表す。ｎ１は０又は１〜３の整数を表す。
一般式（２）中、Ｒ^１２は、それぞれ独立に置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表す。ｎ２は０又は１〜３の整数を表す。）
［２］ 一般式（１）中のＲ^１１及び一般式（２）中のＲ^１２が、それぞれ独立に置換基を有していてもよい脂肪族炭化水素基を表す、［１］に記載の樹脂組成物。
［３］ 脂肪族炭化水素基が、分岐構造を有するアルキル基を表す、［１］又は［２］に記載の樹脂組成物。
［４］ 樹脂組成物中の不揮発成分を１００質量％とした場合の（Ｂ）成分の含有量をｂとし、樹脂組成物中の不揮発成分を１００質量％とした場合の（Ｃ）成分の含有量をｃとしたとき、ｂ／ｃが、０．０１以上３以下である、［１］〜［３］のいずれかに記載の樹脂組成物。
［５］ さらに、（Ｆ）硬化剤を含有する、［１］〜［４］のいずれかに記載の樹脂組成物。
［６］ 絶縁層形成用である、［１］〜［５］のいずれかに記載の樹脂組成物。
［７］ 導体層を形成するための絶縁層形成用である、［１］〜［６］のいずれかに記載の樹脂組成物。
［８］ 支持体と、該支持体上に設けられた、［１］〜［７］のいずれかに記載の樹脂組成物を含む樹脂組成物層とを含む、樹脂シート。
［９］ ［１］〜［７］のいずれかに記載の樹脂組成物の硬化物により形成された絶縁層を含む、プリント配線板。
［１０］ ［９］に記載のプリント配線板を含む、半導体装置。 That is, the present invention includes the following contents.
[1] (A) Epoxy resin,
(B) A resin composition containing an active ester-based curing agent having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), and (C) an inorganic filler. And
The content of the component (B) is 30% by mass or less when the non-volatile component in the resin composition is 100% by mass.
A resin composition in which the content of the component (C) is 60% by mass or more when the non-volatile component in the resin composition is 100% by mass.

(In the general formula (1), R ¹¹ has an aliphatic hydrocarbon group which may independently have a substituent, an aryl group which may have a substituent, or a substituent. May represent an aralkyl group, where Z represents an isophthaloyl group which may have a substituent or a naphthalenedicarbonyl group which may have a substituent. N1 represents an integer of 0 or 1-3. ..
In the general formula (2), R ¹² may have an aliphatic hydrocarbon group which may independently have a substituent, an aryl group which may have a substituent, or a substituent. Represents a good aralkyl group. n2 represents an integer of 0 or 1-3. )
[2] The above-described in [1], wherein R ¹¹ in the general formula (1) and R ¹² in the general formula (2) represent an aliphatic hydrocarbon group which may independently have a substituent. Resin composition.
[3] The resin composition according to [1] or [2], wherein the aliphatic hydrocarbon group represents an alkyl group having a branched structure.
[4] The content of the component (B) when the non-volatile component in the resin composition is 100% by mass is b, and the content of the component (C) when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of [1] to [3], wherein b / c is 0.01 or more and 3 or less when the amount is c.
[5] The resin composition according to any one of [1] to [4], which further contains (F) a curing agent.
[6] The resin composition according to any one of [1] to [5], which is used for forming an insulating layer.
[7] The resin composition according to any one of [1] to [6], which is used 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 containing 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 including the printed wiring board according to [9].

According to the present invention, a resin composition capable of suppressing unevenness occurring in a cured substrate and obtaining a cured product having excellent dielectric properties; a resin sheet containing the resin composition; insulation formed by using the resin composition. A printed wiring board having a layer and a semiconductor device can be provided.

FIG. 1 is a schematic side view showing an example of two test tubes used for determining a liquid, semi-solid, and solid state of a thermosetting resin.

Hereinafter, the present invention will be described in detail according to its preferred embodiment. However, the present invention is not limited to the following embodiments and examples, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.

（一般式（１）中、Ｒ^１１は、それぞれ独立に置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表し、Ｚは、置換基を有していてもよいイソフタロイル基、又は置換基を有していてもよいナフタレンジカルボニル基を表す。ｎ１は０又は１〜３の整数を表す。
一般式（２）中、Ｒ^１２は、それぞれ独立に置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表す。ｎ２は０又は１〜３の整数を表す。） [Resin composition]
The resin composition of the present invention comprises (A) an epoxy resin, (B) an active ester-based curing agent having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). A resin composition containing (C) and an inorganic filler, wherein the content of the component (B) is 30% by mass or less when the non-volatile component in the resin composition is 100% by mass. C) The content of the component is 60% by mass or more when the non-volatile component in the resin composition is 100% by mass. In the present invention, by containing a predetermined amount of the component (B) and a predetermined amount of the component (C), unevenness occurring in the cured substrate can be suppressed, and a cured product having excellent dielectric properties can be obtained. Further, in the present invention, it is usually possible to obtain a cured product having excellent peel strength.

(In the general formula (1), R ¹¹ has an aliphatic hydrocarbon group which may independently have a substituent, an aryl group which may have a substituent, or a substituent. May represent an aralkyl group, where Z represents an isophthaloyl group which may have a substituent or a naphthalenedicarbonyl group which may have a substituent. N1 represents an integer of 0 or 1-3. ..
In the general formula (2), R ¹² may have an aliphatic hydrocarbon group which may independently have a substituent, an aryl group which may have a substituent, or a substituent. Represents a good aralkyl group. n2 represents an integer of 0 or 1-3. )

The resin composition may further contain any component in combination with the components (A) to (C). Optional components include, for example, (D) curing accelerator, (E) thermoplastic resin, (F) curing agent, and (G) other additives. Hereinafter, each component contained in the resin composition will be described in detail.

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

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the component (A). 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 is preferably 50% by mass with respect to 100% by mass of the non-volatile component of the component (A). As mentioned above, it is more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

The epoxy resin may be a liquid epoxy resin at a temperature of 20 ° C. (hereinafter sometimes referred to as "liquid epoxy resin") or a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as "solid epoxy resin"). ). The resin composition may contain only the liquid epoxy resin as the component (A), may contain only the solid epoxy resin, or may contain a combination of the liquid epoxy resin and the solid epoxy resin. Although good, it is preferable to contain only the solid epoxy resin from the viewpoint of remarkably obtaining the desired effect of the present invention.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

Examples of the solid epoxy resin include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and naphthalene type epoxy resin is more preferable.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690" (cresol novolac type epoxy resin); DIC "N-695" (cresol novolac type epoxy resin); DIC "HP-7200", "HP-7200HH", "HP" -7200H "(dicyclopentadiene type epoxy resin);" EXA-7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(made by DIC) Naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayakusha; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayakusha; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation; "ESN485" (naphthol novolac) manufactured by Nippon Steel & Sumitomo Metal Corporation Type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX8800" (anthracene type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd .; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YL7800" manufactured by Mitsubishi Chemical Co., Ltd. (Fluorene type epoxy resin); "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. and the like can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are more preferable.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828EL", "825", and "Epicoat" manufactured by Mitsubishi Chemical Co., Ltd. 828EL (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "jER152" (phenol novolac type epoxy resin); Mitsubishi Chemical's "630", "630LSD" (glycidylamine type epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Corporation (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX" manufactured by Nagase ChemteX. -721 "(glycidyl ester type epoxy resin);" seroxide 2021P "manufactured by Daicel Co., Ltd. (alicyclic epoxy resin having an ester skeleton);" PB-3600 "manufactured by Daicel Co., Ltd. (epoxy resin having a butadiene structure); Examples thereof include "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Sumikin Chemical Co., Ltd. These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (A), their quantity ratio (liquid epoxy resin: solid epoxy resin) is preferably 1: 1 to 1:20 in terms of mass ratio. It is more preferably 1: 1.5 to 1:15, and particularly preferably 1: 2 to 1:10. When the amount ratio of the liquid epoxy resin to the solid epoxy resin is within such a range, the desired effect of the present invention can be remarkably obtained. Furthermore, usually, when used in the form of a resin sheet, moderate adhesiveness is provided. In addition, when used in the form of a resin sheet, sufficient flexibility is usually obtained and handleability is improved. Further, usually, a cured product having sufficient breaking strength can be obtained.

The epoxy equivalent of the component (A) is preferably 50 g / eq. ~ 5000 g / eq. , More preferably 50 g / eq. ~ 3000 g / eq. , More preferably 80 g / eq. ~ 2000g / eq. , Even more preferably 110 g / eq. ~ 1000 g / eq. Is. Within this range, the crosslink density of the cured product of the resin composition layer becomes sufficient, and an insulating layer having a small surface roughness can be provided. Epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of an 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 to 5000, more preferably 250 to 3000, still more preferably 400 to 1500, from the viewpoint of significantly obtaining the desired effect of the present invention.
The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The content of the component (A) is preferably 1% by mass or more when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. It is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit of the content of the epoxy resin is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less, from the viewpoint of remarkably obtaining the desired effect of the present invention. In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

<(B) Active ester-based curing agent having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2)>
The resin composition contains an active ester-based curing agent having a structural unit represented by the general formula (1) and a structural unit represented by the following general formula (2) as the component (B). By incorporating a predetermined amount of the component (B) in the resin composition, it is possible to obtain a cured product having excellent dielectric properties.

（一般式（１）中、Ｒ^１１は、それぞれ独立に置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表し、Ｚは、置換基を有していてもよいイソフタロイル基、又は置換基を有していてもよいナフタレンジカルボニル基を表す。ｎ１は０又は１〜３の整数を表す。
一般式（２）中、Ｒ^１２は、それぞれ独立に置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表す。ｎ２は０又は１〜３の整数を表す。）

(In the general formula (1), R ¹¹ has an aliphatic hydrocarbon group which may independently have a substituent, an aryl group which may have a substituent, or a substituent. May represent an aralkyl group, where Z represents an isophthaloyl group which may have a substituent or a naphthalenedicarbonyl group which may have a substituent. N1 represents an integer of 0 or 1-3. ..
In the general formula (2), R ¹² may have an aliphatic hydrocarbon group which may independently have a substituent, an aryl group which may have a substituent, or a substituent. Represents a good aralkyl group. n2 represents an integer of 0 or 1-3. )

Examples of the aliphatic hydrocarbon group which may have a substituent represented by R ¹¹ in the general formula (1) include an alkyl group and an alkenyl group, and an alkyl group is preferable. The aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 10 carbon atoms or 1 to 8 or 1 to 5 carbon atoms. The aliphatic hydrocarbon group preferably has a branched structure, and more preferably an alkyl group having a branched structure and an alkenyl group having a branched structure.

Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group and t-. Pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, t-octyl group, n-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclo Examples thereof include octyl group and cyclononyl group. Among them, alkyl groups having a branched structure such as isopropyl group, s-butyl group, isobutyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group and t-octyl group. Is preferable.

Examples of the alkenyl group include vinyl group, allyl group, propenyl group, isopropenyl group, 1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-hexenyl group and 2-hexenyl group. Examples thereof include 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-octenyl group, 2-octenyl group and 1-undecenyl group.

As the aryl group which may have the substituent represented by R ¹¹ in the general formula (1), an aryl group having 6 to 30 carbon atoms is preferable, and an aryl group having 6 to 20 carbon atoms is more preferable. Aryl groups having 6 to 10 carbon atoms are more preferable. Examples of such an aryl group include a phenyl group, a tolyl group, a furanyl group, a pyrrolyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a pyridinyl group, a pyrimidinyl group and a pyridadinyl group. A monocyclic aromatic compound such as a group, a pyrazinyl group, or a triazinyl group from which one hydrogen atom has been removed; a naphthyl group, an anthracenyl group, a phenalenyl group, a phenanthrenyl group, a quinolinyl group, an isoquinolinyl group, a quinazolyl group, a phthalazinyl group, a pteridinyl group. A condensed ring aromatic compound such as a group, a coumarinyl group, an indol group, a benzoimidazolyl group, a benzofuranyl group, or an acridinyl group from which one hydrogen atom has been removed; and the like can be mentioned.

As the aralkyl group which may have the substituent represented by R ¹¹ in the general formula (1), an aralkyl group having 7 to 30 carbon atoms is preferable, and an aralkyl group having 7 to 20 carbon atoms is more preferable. An aralkyl group having 7 to 10 carbon atoms is more preferable. Examples of such an aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group and the like.

The aliphatic hydrocarbon group, aryl group, and aralkyl group represented by R ¹¹ in the general formula (1) may have a substituent. Examples of the substituent include a 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, _and-. Examples thereof include NH ₂ , -CN, -C (O) O-C _1-10 alkyl group, -COOH, -C (O) H, -NO ₂ . Here, the term "C _p-q " (p and q are positive integers and satisfy p <q) is described immediately after this term and the number of carbon atoms of the organic group is p to q. Indicates that there is. For example, the expression "C _1-10 alkyl group" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring.

As R ¹¹ in the general formula (1), an aliphatic hydrocarbon group which may have a substituent is preferable, an alkyl group is more preferable, and an alkyl group having a branched structure is further preferable.

Z in the general formula (1) represents an isophthaloyl group which may have a substituent or a naphthalenedicarbonyl group which may have a substituent, and an isophthaloyl group is preferable. The isophthaloyl group and the naphthalene dicarbonyl group represented by Z in the general formula (1) may have a substituent. The substituent is the same as the substituent that the aliphatic hydrocarbon group represented by R ¹¹ may have. The isophthaloyl group is a structure represented by the formula (α), and the naphthalene carbonyl group is a group in which two carbonyl groups are bonded to a naphthalene ring, and is a structure represented by the formula (β). .. In the following formula, "*" represents a bond.

N1 in the general formula (1) represents an integer of 0 or 1-3, preferably 1 or 2, and more preferably 1. In the general formula (1), it is preferable that R ¹¹ is bonded to the para position with respect to "-OZ-" in the general formula (1).

R ¹² in the general formula (2) is the same as R ¹¹ in the general formula (1). Further, n2 in the general formula (2) is the same as n1 in the general formula (1). In the general formula (2), it is preferable that R ¹² is bonded to the para position with respect to "-O-" in the general formula (2).

The structural unit represented by the general formula (1) has three bonds. Further, the structural unit represented by the general formula (2) has three bonds. The bond represented by * in the structural unit represented by the general formula (1) is preferably combined with the bond represented by * in the structural unit represented by the general formula (2).

（一般式（１−１）中、Ｒ^１３及びＲ^１４は、それぞれ独立に置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表し、Ｚ^１は、置換基を有していてもよいイソフタロイル基、又は置換基を有していてもよいナフタレンジカルボニル基を表す。ｎ３及びｎ４はそれぞれ独立に、０又は１〜３の整数を表す。＊は結合手を表す。） The component (B) preferably has a structure represented by the following general formula (1-1).

(In the general formula (1-1), R ¹³ and R ¹⁴ are an aliphatic hydrocarbon group which may have a substituent independently, an aryl group which may have a substituent, or a substituent. Represents an aralkyl group which may have a substituent, Z ¹ represents an isophthaloyl group which may have a substituent, or a naphthalenedicarbonyl group which may have a substituent. N3 and n4 represent, respectively. Independently, it represents an integer of 0 or 1-3. * Represents a bond.)

R ¹³ and R ¹⁴ in the general formula (1-1) are the same as R ¹¹ in the general formula (1), and Z ¹ in the general formula (1-1) is in the general formula (1). Same as Z. N3 and n4 in the general formula (1-1) are the same as n1 in the general formula (1).

（式（１−２）中、Ｒ^１５は、一般式（１）中のＲ^１１と同様であり、Ｚ^２は、一般式（１）中のＺと同様である。ｎ５は、一般式（１）中のｎ１と同様であり、＊は結合手を表す。） The terminal of the component (B) has a structure formed by reacting a phenolic hydroxyl group-containing compound having an aliphatic hydrocarbon group, an aryl group, or an aralkyl group with an aromatic polycarboxylic acid or an acid halide thereof. obtain. Specifically, the component (B) preferably has the following structure (1-2) at the end.

(In the formula (1-2), R ¹⁵ is the same as R ¹¹ in the general formula (1), Z ² is the same as Z in the general formula (1), and n 5 is the general formula (1). 1) Same as n1 in, * represents a bonder.)

（一般式（３）中、Ｒ^１は、それぞれ独立に置換基を有していてもよい脂肪族炭化水素基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表し、Ｚ^３は、置換基を有していてもよいフェニレン基又は置換基を有していてもよいナフチレン基を表す。ｎはそれぞれ独立に、０又は１〜５の整数を表す。） The component (B) is an active ester-based curing agent having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2), and an active ester represented by the following general formula (3). It may be a mixture with a system curing agent.

(In the general formula (3), R ¹ has an aliphatic hydrocarbon group which may independently have a substituent, an aryl group which may have a substituent, or a substituent. May represent an aralkyl group, where Z ³ represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. N is an independently integer of 0 or 1-5, respectively. Represents.)

R ¹ in the general formula (3) is the same as R ¹¹ in the general formula (1), and Z ³ in the general formula (3) is the same as Z in the general formula (1). N in the general formula (3) is the same as n1 in the general formula (1).

When the component (B) contains an active ester-based curing agent represented by the general formula (3), the content thereof is based on 100% of the component (B) from the viewpoint of remarkably obtaining the effect of the present invention. It is preferably less than 40%, more preferably 35% or less, still more preferably 30% or less. The lower limit is not particularly limited, but may be 0.5% or more.

When the component (B) contains an active ester-based curing agent represented by the general formula (3), it has a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2). The content of the active ester-based curing agent is preferably more than 60%, more preferably 65% or more, still more preferably 70% with respect to 100% of the component (B) from the viewpoint of remarkably obtaining the effect of the present invention. That is all. The lower limit is not particularly limited, but may be 99.5% or less.

As the component (B), one synthesized by a known method may be used. For example, a phenolic hydroxyl group-containing compound having an aliphatic hydrocarbon group, an aryl group, or an aralkyl group, and a phenol compound having one or more aliphatic hydrocarbon groups, an aryl group, or an aralkyl group on the aromatic ring. A phenol resin having a molecular structure knotted with a methylene group and an aromatic polycarboxylic acid or an acid halide thereof can be synthesized as a reaction raw material. The specific synthesis of the component (B) can be carried out, for example, by the method described in International Publication No. 2018/008412 and International Publication No. 2018/008415.

As the component (B), a commercially available product may be used. Examples of commercially available products include "EXB8500-65T" manufactured by DIC Corporation.

The amount ratio of the component (A) to the component (B) is a ratio of [total number of epoxy groups of the component (A)]: [total number of reactive groups of the component (B)] from 1: 0.01 to The range of 1:20 is preferable, 1: 0.1 to 1:10 is more preferable, and 1: 0.5 to 1: 5 is even more preferable. Here, the "number of epoxy groups of the component (A)" is a total value obtained by dividing the mass of the non-volatile component of the component (A) present in the resin composition by the epoxy equivalent. The "number of active groups of the component (B)" is a total value obtained by dividing the mass of the non-volatile component of the component (B) present in the resin composition by the active group equivalent. By setting the quantitative ratio of the component (A) to the component (B) within such a range, a cured product having more excellent dielectric properties can be obtained.

The content of the component (B) is 30% by mass or less, preferably 28% by mass or less, more preferably 28% by mass or less, based on 100% by mass of the non-volatile component in the resin composition, from the viewpoint of suppressing unevenness of the cured substrate. It is 25% by mass or less. The content of the component (B) is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, from the viewpoint of obtaining a cured product having excellent dielectric properties.

<(C) Inorganic filler>
The resin composition contains an inorganic filler as the component (C). By using the inorganic filler, the dielectric properties and insulating performance of the cured product of the resin composition can be improved.

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

Commercially available products of the component (C) include, for example, "UFP-30" manufactured by Denka Corporation; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; "YC100C" manufactured by Admatex Corporation. "YA050C", "YA050C-MJE", "YA010C"; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO" manufactured by Admatex -C4 "," SO-C2 "," SO-C1 "; and the like.

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 60 m ² / g or less, 50 m ² / g or less, or 40 m ² / g or less. The specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method. ..

The average particle size 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, and preferably 0.1 μm or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. It is 5 μm or less, more preferably 2 μm or less, still more preferably 1 μm or less.

The average particle size of the component (C) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, 100 mg of an inorganic filler and 10 g of methyl ethyl ketone can be weighed in a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device, the wavelengths of the light sources used were blue and red, and the volume-based particle size distribution of component (C) was measured by the flow cell method, and the obtained particle size distribution was obtained. The average particle size can be calculated as the median diameter from. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by HORIBA, Ltd.

The component (C) is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of the surface treatment agent include vinylsilane-based coupling agents, (meth) acrylic-based coupling agents, fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, and mercaptosilane-based coupling agents. Examples thereof include silane-based coupling agents, alkoxysilanes, organosilazane compounds, and titanate-based coupling agents. Of these, 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, one type of surface treatment agent may be used alone, or two or more types may be used in any combination.

Examples of commercially available surface treatment agents include "KBM1003" (vinyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM503" (3-methacryloxypropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. , "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyl) manufactured by Shin-Etsu Chemical Co., Ltd. (Trimethoxysilane), "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type silane coupling agent), "KBM-7103" manufactured by Shin-Etsu Chemical Co., Ltd. (3,3,3-trifluoropropyltrimethoxysilane) And so on.

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

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

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed 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. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. or the like can be used.

By including a predetermined amount of the component (B) in the resin composition, unevenness of the cured substrate can be suppressed even if a large amount of the component (C) is contained. In the present invention, there is technical significance in that unevenness of the cured substrate is suppressed even if the content of the component (C) is large, and the dielectric properties are further improved. The content of the component (C) is 60% by mass or more, preferably 61% by mass or more, more preferably 62% by mass or more, preferably 62% by mass or more, when the non-volatile component in the resin composition is 100% by mass. It is 95% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less.

When the non-volatile component in the resin composition is 100% by mass, the content of the component (B) is b, and when the non-volatile component in the resin composition is 100% by mass, the content of the component (C) is c. When, b / c is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or 0.2 or more, preferably 3 or less, more preferably 1 or less, and further. It is preferably 0.5 or less. By adjusting b / c so as to be within such a range, unevenness occurring in the cured substrate can be suppressed, and a cured product having excellent dielectric properties can be obtained.

<(D) Curing accelerator>
In addition to the above-mentioned components, the resin composition may contain a curing accelerator as an arbitrary component and further as a component (D). By containing the component (D), it becomes possible to further promote polymerization by heat.

Examples of the component (D) include 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. The component (D) may be used alone or in combination of two or more.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-cyanoethyl- 2-Phenylimidazolium trimerite, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Phenylimidazoline and other imidazole compounds and adducts of the imidazole compound and an epoxy resin are mentioned, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

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

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and the like. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned, with dicyandiamide and 1,5,7-triazabicyclo [4.4.0] deca-5-ene being preferred.

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

The content of the component (D) is preferably 0.01% by mass or more, more preferably 0, when the non-volatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. It is 0.02% by mass or more, more preferably 0.03% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less.

<(E) Thermoplastic resin>
The resin composition may contain (E) a thermoplastic resin as an arbitrary component. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyester resin and the like. The phenoxy resin is preferable. The thermoplastic resin may be used alone or in combination of two or more.

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

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpen Examples thereof include a phenoxy resin having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resin), "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" (bisphenol acetophenone) manufactured by Mitsubishi Chemical Corporation. (Skeletal-containing phenoxy resin), and also "FX280" and "FX293" manufactured by Nittetsu Chemical & Materials Co., Ltd., [YX7200B35], "YL7500BH30", "YX6954BH30", "YX7553" manufactured by Mitsubishi Chemical Co., Ltd., Examples thereof include "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482".

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

Specific examples of the polyimide resin include "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd. Specific examples of the polyimide resin include a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), and a polysiloxane skeleton. Examples thereof include modified polyimides such as contained polyimides (polyimides described in JP-A-2002-12667 and JP-A-2000-319386).

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

Specific examples of the polyetheretherketone resin include "Sumiproi K" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of the polyetherimide resin include "Ultem" manufactured by GE.

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

Examples of the polyolefin resin include ethylene-based copolymers such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer. Resin: Polyolefin-based elastomers such as polypropylene and ethylene-propylene block copolymers can be mentioned.

Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethyl terephthalate resin and the like.

Among them, the phenoxy resin is preferable as the (E) thermoplastic resin. Therefore, as a suitable thermoplastic resin, a phenoxy resin is preferable, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferable.

The content of the thermoplastic resin (E) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0% by mass, when the non-volatile component in the resin composition is 100% by mass. It is 5% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.

<(F) Hardener>
The resin composition may contain (F) a curing agent as an arbitrary component. However, as for the component (F), those corresponding to the component (B) are excluded. By including the curing agent (F) in the resin composition, unevenness of the cured substrate can be further suppressed.

Examples of the (F) curing agent include phenol-based curing agents, naphthol-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, amine-based curing agents, acid anhydride-based curing agents, and maleimide. Examples thereof include a system-based curing agent, a (meth) acrylic-based curing agent, a polyphenylene ether-based curing agent (styrene-based curing agent), an allyl-based curing agent, and an active ester-based curing agent other than the component (B). (F) One type of curing agent may be used alone, or two or more types may be used in combination.

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

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

Specific examples of the benzoxazine-based curing agent include "ODA-BOZ" manufactured by JFE Chemical Co., Ltd., "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "FA" manufactured by Shikoku Chemicals Corporation. Can be mentioned.

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

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

Examples of amine-based curing agents include curing agents having one or more amino groups in one molecule, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Among them, aromatic amines are preferable from the viewpoint of achieving the desired effect of the present invention. As the amine-based curing agent, a primary amine or a secondary amine is preferable, and a primary amine is more preferable. Specific examples of amine-based curing agents include 4,4'-methylenebis (2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'. -Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl- 4,4'-Diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane Diamine, 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) sulfone, Examples thereof include bis (4- (3-aminophenoxy) phenyl) sulfone. Commercially available products may be used as the amine-based curing agent. For example, "KAYABOND C-200S", "KAYABOND C-100", "Kayahard A-A", "Kayahard AB", "Kayahard AB" manufactured by Nippon Kayaku Corporation. Examples include "Kayahard AS" and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, and methylnadic hydride. Anhydride, trialkyltetrahydrophthalic anhydride, succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trihydride Merit acid, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'- Diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-franyl) -naphtho [1,2-C] furan-1 , 3-Dione, ethylene glycol bis (anhydrotrimeritate), polymer-type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized, and the like.

The maleimide-based curing agent is a compound containing a maleimide group represented by the following formula (F-1) in the molecule. Maleimide-based curing agents include solid maleimide-based curing agents and liquid or semi-solid maleimide-based curing agents.

Here, the determination of liquid, semi-solid, and solid is performed in accordance with the attached second "Confirmation method of liquid" of the Ministerial Ordinance on Dangerous Goods Test and Properties (Ministerial Ordinance No. 1 of 1989). The specific determination method is as follows.

(1) Equipment constant temperature water tank:
Use a stirrer, heater, thermometer, and automatic temperature controller (those that can control the temperature at ± 0.1 ° C) with a depth of 150 mm or more.
In the determination of liquid, semi-solid, and solid, tap water of about 22 liters was used in combination with a low-temperature constant temperature water tank (model BU300) manufactured by Yamato Kagaku Co., Ltd. and a charging type constant temperature device Thermomate (model BF500). In a low temperature constant temperature water tank (model BU300), turn on the power of the thermomate (model BF500) attached to this, set the set temperature (20 ° C or 60 ° C), and set the water temperature to the set temperature ± 0.1 ° C. It can be fine-tuned with a thermomate (model BF500), but any device that can make similar adjustments can be used.

Test tube:
As shown in FIG. 1, the test tube is made of flat-bottomed cylindrical transparent glass having an inner diameter of 30 mm and a height of 120 mm, and marked lines 11A and 12B are attached at heights of 55 mm and 85 mm from the tube bottom, respectively. , A rubber stopper 13b having the same size as the liquid judgment test tube 10a in which the mouth of the test tube is sealed with a rubber stopper 13a, and having a hole in the center for inserting and supporting a thermometer. The test tube 10b for temperature measurement is used in which the mouth of the test tube is sealed and the thermometer 14 is inserted into the rubber stopper 13b. Hereinafter, the marked line having a height of 55 mm from the bottom of the pipe is referred to as "line A", and the marked line having a height of 85 mm from the bottom of the pipe is referred to as "line B".
As the thermometer 14, the one for freezing point measurement (SOP-58 scale range 0 to 100 ° C.) specified in JIS B7410 (1982) "Glass thermometer for petroleum test" is used, but the temperature is 0 to 100 ° C. Anything that can measure the range will do.

(2) Test implementation procedure Samples left for 24 hours or more under atmospheric pressure at a temperature of 60 ± 5 ° C. are subjected to a liquid determination test tube 10a shown in FIG. 1A and a temperature measurement test shown in FIG. 1B. Put up to 11A line in each tube 10b. The two test tubes 10a and 10b are placed upright in a low-temperature constant temperature water tank so that the 12B line is below the surface of the water. The thermometer should have its lower end 30 mm below the 11A line.
After the sample temperature reaches the set temperature ± 0.1 ° C, keep it as it is for 10 minutes. After 10 minutes, take out the liquid judgment test tube 10a from the low temperature constant temperature water tank, immediately lay it horizontally on a horizontal test table, and use a stopwatch to measure the time when the tip of the liquid level in the test tube moves from line 11A to line 12B. Measure and record.

Similarly, for a sample left at atmospheric pressure of 20 ± 5 ° C. for 24 hours or more, the test is carried out in the same manner as when it is left at atmospheric pressure of 60 ± 5 ° C. for 24 hours or more, and the liquid in the test tube is subjected to the same test. The time when the tip of the surface moves from the 11A line to the 12B line is measured and recorded with a stopwatch.

If the measured time is 90 seconds or less at 20 ° C., it is determined to be liquid.
Those having a measured time of more than 90 seconds at 20 ° C. and a measured time of 90 seconds or less at 60 ° C. are determined to be semi-solid.
If the measured time exceeds 90 seconds at 60 ° C., it is determined to be solid.

The number of maleimide groups per molecule of the solid maleimide-based curing agent is preferably 1 or more, more preferably 2 or more, and further preferably 3 from the viewpoint of significantly obtaining the desired effect of the present invention. It is more than that, preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less.

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

As the aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group is preferable, a divalent saturated aliphatic hydrocarbon group is more preferable, and an alkylene group is further preferable. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 3 carbon atoms is further preferable, and a methylene group is particularly preferable.

As the aromatic hydrocarbon group, monovalent and divalent aromatic hydrocarbon groups are preferable, and aryl groups and arylene groups are more preferable. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferable, an arylene group having 6 to 20 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is further preferable. Examples of such an arylene group include a phenylene group, a naphthylene group, an anthracenylene group, an aralkyl group, a biphenylene group, a biphenylaralkyl group and the like. Among them, a phenylene group, an aralkyl group, a biphenylene group and a biphenylaralkyl group are preferable. A phenylene group, an aralkyl group and a biphenylene group are more preferable. As the aryl group, an aryl group having 6 to 30 carbon atoms is preferable, an aryl group having 6 to 20 carbon atoms is more preferable, an aryl group having 6 to 10 carbon atoms is further preferable, and a phenyl group is particularly preferable.

In the solid maleimide-based curing agent, the nitrogen atom of the maleimide group is preferably 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（Ｆ−２）中、Ｒ^３１及びＲ^３６はマレイミド基を表し、Ｒ^３２、Ｒ^３３、Ｒ^３４及びＲ^３５は、それぞれ独立に水素原子、アルキル基、又はアリール基を表し、Ｄはそれぞれ独立に２価の芳香族基を表す。ｍ１及びｍ２はそれぞれ独立に１〜１０の整数を表し、ａは１〜１００の整数を表す。 The solid maleimide-based curing agent preferably has a structure represented by the following formula (F-2), for example.

In formula (F-2), R ³¹ and R ³⁶ represent maleimide groups, R ³² , R ³³ , R ³⁴ and R ³⁵ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and D is a respective group. Independently represents a divalent aromatic group. m1 and m2 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 the formula (F-2) independently represent a hydrogen atom, an alkyl group or an aryl group, and a hydrogen atom is preferable.

As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is further preferable. The alkyl group may be linear, branched or cyclic. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group and the like.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may be a monocyclic ring or a condensed ring. Examples of such an aryl group include a phenyl group, a naphthyl group, an anthracenyl group and the like.

The alkyl group and the aryl group may have a substituent. The substituent is the same as the substituent that the aliphatic hydrocarbon group represented by R ¹¹ in the general formula (1) may have.

D in the formula (F-2) represents a divalent aromatic group. Examples of the divalent aromatic group include a phenylene group, a naphthylene group, an anthracenylene group, an aralkyl group, a biphenylene group, a biphenylaralkyl group and the like. Among them, a biphenylene group and a biphenylaralkyl group are preferable, and a biphenylene group is more preferable. .. The divalent aromatic group may have a substituent. The substituent is the same as the substituent that the aliphatic hydrocarbon group represented by R ¹¹ in the general formula (1) 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 1 is even more preferable.

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

式（Ｆ−３）中、Ｒ^３７及びＲ^３８はマレイミド基を表す。ａ１は１〜１００の整数を表す。 As the solid maleimide-based curing agent, a resin represented by the formula (F-3) is preferable.

In formula (F-3), R ³⁷ and R ³⁸ represent maleimide groups. a1 represents an integer of 1 to 100.

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

As the solid maleimide-based curing agent, a commercially available product can be used. Examples of commercially available products include "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd.

A liquid or semi-solid maleimide-based curing agent is a compound having at least one maleimide group in the molecule.

In the maleimide-based curing agent, the alkyl group having 5 or more carbon atoms and the alkylene group having 5 or more carbon atoms are preferably directly bonded to the nitrogen atom of the maleimide group.

The number of maleimide groups per molecule of the maleimide-based curing agent may be 1, but is preferably 2 or more, preferably 10 or less, more preferably 6 or less, and particularly preferably 3 or less. By using a maleimide-based curing agent having two or more maleimide groups per molecule, the effect of the present invention can be remarkably obtained.

一般式（Ｆ−４）中、Ｍは置換基を有していてもよい炭素原子数が５以上のアルキレン基を表し、Ｌは単結合又は２価の連結基を表す。 The maleimide-based curing agent is preferably represented by the following general formula (F-4).

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

M represents an alkylene group having 5 or more carbon atoms which may have a substituent. The alkylene group of M is the same as the above-mentioned alkylene group having 5 or more carbon atoms. The substituent of M is the same as the substituent that the aliphatic hydrocarbon group represented by R ¹¹ in the general formula (1) may have, and the substituent preferably has 5 or more carbon atoms. It is an alkyl group.

L represents a single bond or a divalent linking group. The divalent linking group includes an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C (= O)-, -C (= O) -O-, and -NR ^0- (R ⁰ is a hydrogen atom and carbon. Alkyl group with 1-3 atoms), oxygen atom, sulfur atom, C (= O) NR ⁰ −, divalent group derived from phthalimide, divalent group derived from diimide pyromellitic acid, and two or more of these. Examples thereof include a group consisting of a combination of divalent groups. A group consisting of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent group derived from phthalimide, a divalent group derived from diimide pyromellitic acid, and a combination of two or more divalent groups has a carbon atom number. May have 5 or more alkyl groups as substituents. The divalent group derived from phthalimide represents a divalent group derived from phthalimide, and specifically, a group represented by the general formula (F-5). The divalent group derived from diimide pyromellitic acid represents a divalent group derived from diimide pyromellitic acid, and specifically, is a group represented by the general formula (F-6). In the formula, "*" represents a bond.

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

The alkenylene group as the 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 particularly preferably an alkenylene group having 2 to 10 carbon atoms. .. The alkenylene group may be linear, branched or cyclic. Examples of such an alkenylene group include a methylethyleneylene group, a cyclohexenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group and the like.

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

The arylene group as the divalent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, and even more preferably an arylene group having 6 to 14 carbon atoms. , An arylene group having 6 to 10 carbon atoms is even more preferable. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group and the like.

The divalent linking group in L, such as an alkylene group, an alkenylene group, an alkynylene group, and an arylene group, may have a substituent. The substituent is the same as the substituent that the aliphatic hydrocarbon group represented by R ¹¹ in the general formula (1) may have, and is preferably an alkyl group having 5 or more carbon atoms.

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

Among them, L in the general formula (F-4) includes an oxygen atom, an arylene group having 6 to 24 carbon atoms which may have a substituent, and a carbon atom which may have a substituent. A divalent group consisting of 1 to 50 alkylene groups, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from diimide pyromellitic acid, or a combination of 2 or more of these groups. It is preferably a group. Among them, L is an alkylene group; an alkylene group-a divalent group derived from phthalimide-an oxygen atom-a divalent group having a divalent group structure derived from phthalimide; an alkylene group-a divalent group derived from phthalimide- Oxygen atom-arylene group-alkylene group-arylene group-oxygen atom-divalent group having a divalent group structure derived from phthalimide; divalent group having a divalent group structure derived from alkylene-pyromellitic acid diimide Groups are more preferred.

一般式（Ｆ−７）中、Ｍ^１はそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基を表し、Ｚはそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基又は置換基を有していてもよい芳香環を有する２価の基を表す。ｔは１〜１０の整数を表す。 The maleimide-based curing agent represented by the general formula (F-4) is preferably represented by the general formula (F-7).

In the general formula (F-7), M ¹ may independently have a substituent and M ¹ represents an alkylene group having 5 or more carbon atoms, and Z may have an independent substituent. Represents a divalent group having an aromatic ring which may have an alkylene group or a substituent having 5 or more carbon atoms. t represents an integer of 1-10.

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

Z represents an alkylene group having 5 or more carbon atoms which may independently have a substituent or a divalent group having an aromatic ring which may have a substituent. The alkylene group in Z may be chain-shaped, branched-chain-shaped, or cyclic, and among them, a cyclic, that is, a cyclic alkylene group having 5 or more carbon atoms which may have a substituent is preferable. The number of carbon atoms of the alkylene group is preferably 6 or more, more preferably 8 or more, preferably 50 or less, more preferably 45 or less, still more preferably 40 or less. Examples of such an alkylene group include a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, a group having a propylene-cyclohexylene-octylene structure, and the like.

Examples of the aromatic ring in the divalent group having the aromatic ring represented by Z include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a diimide ring of pyromellitic acid, an aromatic heterocycle, and the like, and a benzene ring and a phthalimide ring. A ring and a diimide ring of pyromellitic acid are preferable. That is, as the divalent group having an aromatic ring, a divalent group having a benzene ring which may have a substituent, a divalent group having a phthalimide ring which may have a substituent, and a substituent are substituted. A divalent group having a diimide ring of pyromellitic acid, which may have a group, is preferable. The divalent group having an aromatic ring includes, for example, a group composed of a combination of a divalent group derived from phthalimide and an oxygen atom; a divalent group derived from phthalimide, an oxygen atom, an arylene group and an alkylene group. Group; a group consisting of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; a divalent group derived from diimide pyromellitic acid; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group; etc. Can be mentioned. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (F-4).

The divalent group represented by Z and having an alkylene group and an aromatic ring may have a substituent. The substituent is the same as the substituent that the aliphatic hydrocarbon group represented by R ¹¹ in the general formula (1) may have.

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

一般式（Ｆ−８）中、Ｍ^２及びＭ^３はそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基を表し、Ｒ^４０はそれぞれ独立に、酸素原子、アリーレン基、アルキレン基、又はこれらの基の２以上の組み合わせからなる２価の基を表す。ｔ１は１〜１０の整数を表す。
一般式（Ｆ−９）中、Ｍ^４、Ｍ^６及びＭ^７はそれぞれ独立に置換基を有していてもよい炭素原子数が５以上のアルキレン基を表し、Ｍ^５はそれぞれ独立に置換基を有していてもよい芳香環を有する２価の基を表し、Ｒ^４１及びＲ^４２はそれぞれ独立に炭素原子数が５以上のアルキル基を表す。ｔ２は０〜１０の整数を表し、ｕ１及びｕ２はそれぞれ独立に０〜４の整数を表す。 The maleimide-based curing agent represented by the general formula (F-4) is a maleimide-based curing agent represented by the general formula (F-8) and a maleimide-based curing agent represented by the general formula (F-9). It is preferably either.

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

M ² and M ³ each represent an alkylene group having 5 or more carbon atoms which may have a substituent independently. M ² and M ³ are the same as the alkylene group having 5 or more carbon atoms represented by M in the general formula (F-4), and a hexatriacontylene group is preferable.

Each R ⁴⁰ independently represents an oxygen atom, an arylene group, an alkylene group, or a group consisting of a combination of two or more divalent groups thereof. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (F-4). R ⁴⁰ is preferably a group consisting of a combination of two or more divalent groups or an oxygen atom.

Examples of the group consisting of a combination of two or more divalent group in R ^40, an oxygen atom, a combination of an arylene group and an alkylene group. Specific examples of a group composed of a combination of two or more divalent groups include the following groups. In the formula, "*" represents a bond.

M ⁴ , M ⁶ and M ⁷ each represent an alkylene group having 5 or more carbon atoms which may have a substituent independently. M ⁴ , M ⁶ and M ⁷ are the same as the alkylene group having 5 or more carbon atoms which may have a substituent represented by M in the general formula (F-4), and are a hexylene group and a heptylene group. , Octylene group, nonylene group, decylene group are preferable, and octylene group is more preferable.

M ⁵ represents a divalent group having an aromatic ring, each of which may independently have a substituent. M ⁵ is the same as a divalent group having an aromatic ring which may have a substituent represented by Z in the general formula (F-7), and is a divalent group derived from an alkylene group and diimide pyromellitic acid. Group consisting of a combination of groups; a group consisting of a combination of a divalent group derived from phthalimide and an alkylene group is preferable, and a group consisting of a combination of an alkylene group and a divalent group derived from diimide pyromellitic acid is more preferable. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (F-4).

Specific examples of the groups represented by M ⁵ include the following groups. In the formula, "*" represents a 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 group having 5 or more carbon atoms, preferably a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group, and more preferably a hexyl group and an octyl group.

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

Specific examples of the maleimide-based curing agent include the following compounds (F1) to (F3). However, the maleimide-based curing agent is not limited to these specific examples. In the formula, v represents an integer of 1-10.

Specific examples of the maleimide-based curing agent include "BMI1500" (compound of formula (F1)), "BMI1700" (compound of formula (F2)), and "BMI689" (formula (F3)) manufactured by Designer Moleculars. Compounds), etc.

The maleimide group equivalent of the maleimide-based curing agent is preferably 50 g / eq. From the viewpoint of significantly obtaining the desired effect of the present invention. ~ 2000g / eq. , More preferably 100 g / eq. ~ 1000 g / eq. , More preferably 150 g / eq. ~ 500 g / eq. Is. The maleimide group equivalent is the mass of the maleimide-based curing agent containing 1 equivalent of the maleimide group.

（＊は結合手を表す。） The polyphenylene ether-based curing agent is a curing agent having a vinyl phenyl group. The vinylphenyl group is a group having the following structure.

(* Indicates a bond.)

The polyphenylene ether-based curing agent preferably has two or more vinyl phenyl groups per molecule from the viewpoint of obtaining a cured product having a low dielectric loss tangent.

The polyphenylene ether-based curing agent preferably has a cyclic structure from the viewpoint of obtaining a cured product having a low dielectric loss tangent. As the cyclic structure, a divalent cyclic group is preferable. The divalent cyclic group may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Further, it may have a plurality of divalent cyclic groups.

The divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, still more preferably a 5-membered ring or more, and preferably a 20-membered ring, from the viewpoint of remarkably obtaining the desired effect of the present invention. Hereinafter, it is more preferably 15-membered ring or less, still more preferably 10-membered ring or less. Further, the divalent cyclic group may have a monocyclic structure or a polycyclic structure.

The ring skeleton of the divalent cyclic group may be composed of a hetero atom other than the carbon atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like, and an oxygen atom is preferable. The hetero atom may have one heteroatom in the ring, or may have two or more heteroatoms.

（２価の基（ｘｉｉ）、（ｘｉｉｉ）中、Ｒ^５１、Ｒ^５２、Ｒ^５５、Ｒ^５６、Ｒ^５７、Ｒ^６１、及びＲ^６２は、それぞれ独立にハロゲン原子、炭素原子数が６以下のアルキル基、又はフェニル基を表し、Ｒ^５３、Ｒ^５４、Ｒ^５８、Ｒ^５９、及びＲ^６０は、それぞれ独立に水素原子、ハロゲン原子、炭素原子数６以下のアルキル基、又はフェニル基を表す。） Specific examples of the divalent cyclic group include the following divalent groups (xii) or (xiii).

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

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 6 or less carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like, 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（Ｆ４）中、Ｒ^７１、Ｒ^７２、Ｒ^７５、Ｒ^７６、Ｒ^７７、Ｒ^８１、Ｒ^８２、Ｒ^８５及びＲ^８６は、それぞれ独立にハロゲン原子、炭素原子数が６以下のアルキル基、又はフェニル基を表し、Ｒ^７３、Ｒ^７４、Ｒ^７８、Ｒ^７９、Ｒ^８０、Ｒ^８３及びＲ^８４は、それぞれ独立に水素原子、ハロゲン原子、炭素原子数６以下のアルキル基、又はフェニル基を表す。ｄ１及びｄ２は、０〜３００の整数を表す。但し、ｄ１及びｄ２の一方は０である場合を除く。） Further, the divalent cyclic group may be a combination of a plurality of divalent cyclic groups. Specific examples of the combination of divalent cyclic groups include a divalent cyclic group represented by the following formula (F4) (divalent group (a)).

(In the formula (F4), R ⁷¹ , R ⁷² , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁸¹ , R ⁸² , R ⁸⁵ and R ⁸⁶ are independently halogen atoms and alkyl groups having 6 or less carbon atoms, respectively. , Or a phenyl group, and R ⁷³ , R ⁷⁴ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸³ and R ⁸⁴ are independent hydrogen atoms, halogen atoms, alkyl groups having 6 or less carbon atoms, or phenyl groups, respectively. Represents d1 and d2 are integers from 0 to 300, except when one of d1 and d2 is 0.)

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

d1 and d2 represent an integer from 0 to 300. However, this excludes the case where one of d1 and d2 is 0. As d1 and d2, it is preferable to represent an integer of 1 to 100, more preferably an integer of 1 to 50, and even more preferably an integer of 1 to 10. d1 and d2 may be the same or different.

The divalent cyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group and a mercapto group. Examples thereof include an oxo group, and an alkyl group is preferable.

The vinylphenyl group may be directly bonded to a divalent cyclic group or may be bonded via a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C (= O) O-, -O-, -NHC (= O)-, and -NC (= O). Examples thereof include N-, -NHC (= O) O-, -C (= O)-, -S-, -SO-, -NH-, and the like, and a group in which a plurality of these are combined may be used. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms. Is even more preferable. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a 1,1-dimethylethylene group and the like, and a methylene group, an ethylene group and 1,1 -Dimethylethylene groups are preferred. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferable, an alkenylene group having 2 to 6 carbon atoms is more preferable, and an alkenylene group having 2 to 5 carbon atoms is further preferable. As the arylene group and the heteroarylene group, an arylene group or a heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or a heteroarylene group having 6 to 10 carbon atoms is more preferable. As the divalent linking group, an alkylene group is preferable, and a methylene group is particularly preferable.

（式（Ｆ−１０）中、Ｒ^９１及びＲ^９２はそれぞれ独立に２価の連結基を表す。環Ｂ１は、２価の環状基を表す。） The polyphenylene ether-based curing agent is preferably represented by the following formula (F-10).

(In the formula (F-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 divalent linking group.

Ring B1 represents a divalent cyclic group. The ring B1 is the same as the above divalent cyclic group.

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

（ｑ１は、式（Ｆ４）中のｄ１と同じであり、ｑ１は、式（Ｆ４）中のｄ２と同じである。） Specific examples of the polyphenylene ether-based curing agent will be described below, but the present invention is not limited thereto.

(Q1 is the same as d1 in the equation (F4), and q1 is the same as d2 in the equation (F4).)

As the polyphenylene ether-based curing agent, a commercially available product may be used, and examples thereof include "OPE-2St" manufactured by Mitsubishi Gas Chemical Company. One type of polyphenylene ether-based curing agent may be used alone, or two or more types may be used in combination.

The number average molecular weight of the polyphenylene ether-based curing agent is preferably 3000 or less, more preferably 2500 or less, still more preferably 2000 or less and 1500 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, 1000 or more. The number average molecular weight is a polystyrene-equivalent number average molecular weight measured using gel permeation chromatography (GPC).

The (meth) acrylic curing agent is a compound containing acryloyl group, methacryloyl group, and a combination thereof. The (meth) acrylic curing agent preferably has two or more (meth) acryloyl groups per molecule from the viewpoint of remarkably obtaining the desired effect of the present invention. The term "(meth) acryloyl group" includes acryloyl and methacryloyl groups and combinations thereof.

The (meth) acrylic curing agent preferably has a cyclic structure from the viewpoint of remarkably obtaining the desired effect of the present invention. As the cyclic structure, a divalent cyclic group is preferable. The divalent cyclic group may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Above all, a cyclic group containing an alicyclic structure is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention.

The divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, still more preferably a 5-membered ring or more, and preferably a 20-membered ring, from the viewpoint of remarkably obtaining the desired effect of the present invention. Hereinafter, it is more preferably 15-membered ring or less, still more preferably 10-membered ring or less. Further, the divalent cyclic group may have a monocyclic structure or a polycyclic structure.

The ring skeleton of the divalent cyclic group may be composed of a hetero atom other than the carbon atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like, and an oxygen atom is preferable. The hetero atom may have one heteroatom in the ring, or may have two or more heteroatoms.

Specific examples of the divalent cyclic group include the following divalent groups (i) to (xi). Among them, (x) or (xi) is preferable as the divalent cyclic group.

The divalent cyclic group may have a substituent. Examples of such a substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group and a hydroxy group. Examples thereof include a mercapto group and an oxo group, and an alkyl group is preferable.

The (meth) acryloyl group may be directly attached to a divalent cyclic group or may be attached via a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, -C (= O) O-, -O-, -NHC (= O)-, and -NC (= O). Examples thereof include N-, -NHC (= O) O-, -C (= O)-, -S-, -SO-, -NH-, and the like, and a group in which a plurality of these are combined may be used. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 4 carbon atoms. Is even more preferable. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a 1,1-dimethylethylene group and the like, and a methylene group, an ethylene group and 1,1 -Dimethylethylene groups are preferred. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferable, an alkenylene group having 2 to 6 carbon atoms is more preferable, and an alkenylene group having 2 to 5 carbon atoms is further preferable. As the arylene group and the heteroarylene group, an arylene group or a heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or a heteroarylene group having 6 to 10 carbon atoms is more preferable. As the divalent linking group, an alkylene group is preferable, and a methylene group and a 1,1-dimethylethylene group are particularly preferable.

（式（Ｆ−１１）中、Ｒ^１０１及びＲ^１０４はそれぞれ独立にアクリロイル基又はメタクリロイル基を表し、Ｒ^１０２及びＲ^１０３はそれぞれ独立に２価の連結基を表す。環Ｂ２は、２価の環状基を表す。） The (meth) acrylic curing agent is preferably represented by the following formula (F-11).

(In formula (F-11), R ¹⁰¹ and R ¹⁰⁴ independently represent an acryloyl group or a methacryloyl group, respectively, and R ¹⁰² and R ¹⁰³ each independently represent a divalent linking group. Ring B2 is divalent. Represents a cyclic group.)

R ¹⁰¹ and R ¹⁰⁴ each independently represent an acryloyl group or a methacryloyl group, and an acryloyl group is preferable.

R ¹⁰² and R ¹⁰³ each independently represent a divalent linking group. The divalent linking group is the same as the divalent linking group to which the (meth) acryloyl group may be bonded.

Ring B2 represents a divalent cyclic group. The ring B2 is the same as the above divalent cyclic group. Ring B2 may have a substituent. The substituent is the same as the substituent that the above divalent cyclic group may have.

Specific examples of the (meth) acrylic curing agent include, but the present invention is not limited to this.

Commercially available products may be used as the (meth) acrylic curing agent. For example, "A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" manufactured by Kyoeisha Chemical Co., Ltd., and "NPDGA" manufactured by Nippon Kayaku Co., Ltd. , "FM-400", "R-687", "THE-330", "PET-30", "DPHA", "NK Ester DCP" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. and the like.

The (meth) acryloyl group equivalent of the (meth) acrylic curing agent is preferably 30 g / eq. From the viewpoint of remarkably obtaining the desired effect of the present invention. ~ 400 g / eq. , More preferably 50 g / eq. ~ 300 g / eq. , More preferably 75 g / eq. ~ 200 g / eq. Is. The (meth) acryloyl group equivalent is the mass of a (meth) acrylic curing agent containing 1 equivalent of the (meth) acryloyl group.

The allyl-based curing agent is a compound having at least one allyl group in the molecule. Here, a phenol-based curing agent, a naphthol-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, a carbodiimide-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent, a maleimide-based curing agent, (meth). Among the acrylic curing agent, the polyphenylene ether-based curing agent, and the styrene-based curing agent, those having an allyl group are allyl-based curing agents. The allyl-based curing agent is preferably in a liquid or semi-solid state. The determination of liquid, semi-solid, and solid is as described above.

The allyl-based curing agent preferably has one or more allyl groups per molecule, and more preferably has two or more allyl groups. The lower limit is not particularly limited, but may be preferably 10 or less, and more preferably 5 or less.

Further, the allyl-based curing agent has any of a benzoxazine ring, a phenol ring, an epoxy group, and a carboxylic acid derivative having a cyclic structure in addition to the allyl group from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferable, and it is more preferable to have a benzoxazine ring from the viewpoint of obtaining the desired effect of the present invention more remarkably.

In an allyl-based curing agent having a benzoxazine ring, the allyl group is bonded to either a nitrogen atom constituting the benzoxazine ring or a carbon atom constituting the benzoxazine ring from the viewpoint of significantly obtaining the desired effect of the present invention. It is more preferable that it is bonded to a carbon atom.

式（Ｆ−１２）中、Ｒ^２０、及びＲ^２１はアリル基を表し、Ｒ^２２はｙ価の基を表す。ｙは１〜４の整数を表し、ｘ１は０〜４の整数を表し、ｘ２は０〜２の整数を表す。 As the allyl-based curing agent having a benzoxazine ring, for example, an allyl-based curing agent having a benzoxazine ring represented by the following formula (F-12) is preferable.

In formula (F-12), R ²⁰ and R ²¹ represent an allyl group, and R ²² represents a y-valent group. y represents an integer of 1 to 4, x1 represents an integer of 0 to 4, and x2 represents an integer of 0 to 2.

The y-valent group represented by R ²² in the formula (F-12) is a y-valent group consisting of an allyl group, a y-valent aromatic hydrocarbon group, a y-valent aliphatic hydrocarbon group, an oxygen atom, or a combination thereof. Group is preferred. When R ²² has an allyl group, the allyl group may be a substituent of either a y-valent aromatic hydrocarbon group or a y-valent aliphatic hydrocarbon group. For example, when y is 2, R ²² is preferably a group consisting of an arylene group, an alkylene group, an oxygen atom, or a combination of these two or more divalent groups, and is preferably an arylene group or two or more divalent groups. A group consisting of a combination of two or more divalent groups is more preferable, and a group consisting of a combination of two or more divalent groups is further preferable.

As the arylene group in R ²² in the formula (F-12), an arylene group having 6 to 20 carbon atoms is preferable, an arylene group having 6 to 15 carbon atoms is more preferable, and an arylene group having 6 to 12 carbon atoms is more preferable. Is even more preferable. Specific examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group and the like, and a phenylene group is preferable.

As the alkylene group in R ²² in the formula (F-12), an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is more preferable. Is even more preferable. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group and the like, and a methylene group is preferable.

Examples of the group consisting of a combination of two or more divalent groups in R ²² in the formula (F-12) include a group in which one or more arylene groups and one or more oxygen atoms are bonded; for example, arylene-. A group in which one or more arylene groups such as a group having an alkylene-arylene structure and one or more alkylene groups are bonded; a group in which one or more alkylene groups and one or more oxygen atoms are bonded; one or more arylene groups and 1 Examples thereof include a group in which the above alkylene group and one or more oxygen atoms are bonded, and a group in which one or more arylene groups and one or more oxygen atoms are bonded, and one or more arylene groups and one or more alkylene groups. Bonded groups are preferred.

Y in the formula (F-12) represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.

X1 in the formula (F-12) represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 1. X2 in the formula (F-12) represents an integer of 0 to 2, represents 0 or 1, and 0 is preferable.

式（Ｆ−１３）中、Ｒ^２３、Ｒ^２４、及びＲ^２５はそれぞれ独立にアリル基を表し、ｓ１はそれぞれ独立に０〜４の整数を表し、ｓ２はそれぞれ独立に０〜３の整数を表し、ｒは０〜３の整数を表す。 Examples of the allyl-based curing agent having an allyl ring include a cresol resin containing an allyl group, a novolak-type phenol resin containing an allyl group, and a cresol novolak resin containing an allyl group. Among them, the allyl-based curing agent having a phenol ring is preferably an allyl-based curing agent having a phenol ring represented by the following formula (F-13).

In formula (F-13), R ²³ , R ²⁴ , and R ²⁵ each independently represent an allyl group, s1 each independently represents an integer 0-4, and s2 each independently represents an integer 0-3. Represents r represents an integer from 0 to 3.

R ^{23 to} R ²⁵ in the formula (F-13) each independently represent an allyl group. In the formula (B-2), the number of allyl groups is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 25 or less, more preferably 10 or less, still more preferably. 5 or less.

Each s1 in the formula (F-13) independently represents an integer of 0 to 4, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.

S2 in the formula (F-13) independently represents an integer of 0 to 3, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.

R in the formula (F-13) represents an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably an integer of 1 to 2.

The allyl-based curing agent having an epoxy group preferably contains two or more epoxy groups in one molecule. Further, the allyl-based curing agent having an epoxy group preferably has an aromatic structure, and when two or more kinds of allyl-based curing agents having an epoxy group are used, it is more preferable that at least one kind has an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles. The allyl-based curing agent having an epoxy group preferably has a bisphenol structure, and examples of the bisphenol structure include bisphenol A type, bisphenol F type, bisphenol AF type, etc. Among them, the effect of the present invention is remarkable. Bisphenol A type is preferable from the viewpoint of obtaining the above.

As the allyl-based curing agent having a carboxylic acid derivative having a cyclic structure, allyl carboxylate having a cyclic structure is preferable. The cyclic structure may be either a cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Further, the cyclic group may have a ring skeleton formed of a hetero atom other than the carbon atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like, and a nitrogen atom is preferable. The hetero atom may have one heteroatom in the ring, or may have two or more heteroatoms. The carboxylic acid derivative having a cyclic structure has a network structure having a cyclic structure, which improves the compatibility and dispersibility of the resin varnish, and as a result, it is possible to improve the laminate property, and a cured product having further excellent adhesion can be obtained. It becomes possible to obtain.

Examples of the carboxylic acid having a cyclic structure include isocyanuric acid, diphenic acid, phthalic acid, cyclohexanedicarboxylic acid and the like. Examples of the allyl-based curing agent having a carboxylic acid derivative having a cyclic structure include allyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, diallyl diphenate, allyl diphenate, orthodialyl phthalate, metadialyl phthalate, and paradialyl phthalate. Examples thereof include allyl cyclohexanedicarboxylic acid and diallyl cyclohexanedicarboxylic acid.

As the allyl-based curing agent, a commercially available product can be used. Examples of commercially available products include "MEH-8000H" and "MEH-8005" manufactured by Meiwa Kasei Co., Ltd. (allyl-based curing agent having a phenol ring); "RE-810NM" manufactured by Nihon Kasei Co., Ltd. (allyl-based having an epoxy group). Hardener); Shikoku Kasei Kogyo Co., Ltd. "ALP-d" (allyl-based hardener having a benzoxazine ring); Shikoku Kasei Kogyo Co., Ltd. "L-DAIC" (allyl-based hardener having an isocyanul ring); Nihon Kasei Co., Ltd. "TAIC" (allyl-based curing agent having an isocyanul ring (triallyl isocyanurate)); "MDAC" manufactured by Osaka Soda (allyl-based curing agent having a cyclohexanedicarboxylic acid derivative); "DAD" manufactured by Nihon Technofine Chemical Co., Ltd. (Diallyl diphenylate); Examples thereof include "Dai-sodap monomer" (orthodiallyl phthalate) manufactured by Osaka Soda Co., Ltd.

The allyl group equivalent of the allyl-based curing agent is preferably 20 g / eq. From the viewpoint of remarkably obtaining the desired effect of the present invention. ~ 1000 g / eq. , More preferably 50 g / eq. ~ 500 g / eq. , More preferably 100 g / eq. ~ 300 g / eq. Is. The allyl group equivalent is the mass of an allyl-based curing agent containing 1 equivalent of an allyl group.

As the active ester-based curing agent other than the component (B) (hereinafter, may be simply referred to as “active ester-based curing agent”), a compound having one or more active ester groups in one molecule can be used. .. Among them, as the active ester-based curing agent, two or more ester groups having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are contained in one molecule. The compound having is preferable. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. ..

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

Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Preferred specific examples of the active ester-based curing agent include an active ester-based curing agent containing a dicyclopentadiene-type diphenol structure, an active ester-based curing agent containing a naphthalene structure, and an active ester-based curing agent containing an acetylated product of phenol novolac. Examples thereof include active ester-based curing agents containing a benzoylated product of phenol novolac. Of these, an active ester-based curing agent containing a naphthalene structure and an active ester-based curing agent containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Commercially available active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC8000-65T", and "HPC8000H-65TM" as active ester-based curing agents containing a dicyclopentadiene-type diphenol structure. , "EXB8000L-65TM" (manufactured by DIC); "EXB-8100L-65T", "EXB-8150L-65T", "EXB8150-65T", "EXB9416-70BK" as active ester-based curing agents containing a naphthalene structure. (Manufactured by DIC); "DC808" as an active ester-based curing agent containing an acetylated product of phenol novolac (manufactured by Mitsubishi Chemical Co., Ltd.); ); "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent which is an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) and "YLH1030" as an active ester-based curing agent which is a benzoylated product of phenol novolac. "(Made by Mitsubishi Chemical Co., Ltd.)," YLH1048 "(manufactured by Mitsubishi Chemical Co., Ltd.); and the like.

The amount ratio of the component (A) to the component (F) is a ratio of [total number of epoxy groups of the component (A)]: [total number of reactive groups of the component (F)] from 1: 0.01 to The range of 1:10 is preferable, 1: 0.03 to 1: 5 is more preferable, and 1: 0.05 to 1: 1 is even more preferable. Here, the "number of epoxy groups of the component (A)" is a total value obtained by dividing the mass of the non-volatile component of the component (A) present in the resin composition by the epoxy equivalent. The "number of active groups of the component (F)" is a total value obtained by dividing the mass of the non-volatile component of the component (F) present in the resin composition by the active group equivalent. By setting the amount ratio of the component (A) to the component (F) within such a range, the occurrence of unevenness on the cured substrate can be further suppressed.

The content of the component (F) is preferably 0.1% by mass or more, more preferably 0% by mass, based on 100% by mass of the non-volatile component in the resin composition, from the viewpoint of remarkably obtaining the desired effect of the present invention. It is 3% by mass or more, more preferably 0.5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.

<(G) Other additives>
In addition to the above-mentioned components, the resin composition may further contain other additives as arbitrary components. Examples of such additives include resin additives such as thickeners, antifoaming agents, leveling agents, and adhesion imparting agents. These additives may be used alone or in combination of two or more. Each content can be appropriately set by those skilled in the art.

The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of adding a solvent or the like to the compounding components as necessary and mixing and dispersing them using a rotary mixer or the like.

<Physical characteristics and uses of resin composition>
The resin composition contains a component (A), a predetermined amount of the component (B), and a predetermined amount of the component (C). As a result, unevenness generated in the cured substrate can be suppressed, and a cured product having excellent dielectric properties can be obtained. Generally, when the content of (C) is increased, unevenness that occurs in the cured substrate tends to occur easily. However, by containing a predetermined amount of the component (B) in combination, it is possible to suppress the occurrence of unevenness occurring in the cured substrate even if the content of the component (C) is large. Further, it is possible to obtain a cured product which usually has excellent peel strength in addition to the dielectric property.

The resin composition exhibits a characteristic that unevenness occurring in the cured substrate can be suppressed. Specifically, after laminating the resin composition layer of the resin sheet on the glass cloth base material epoxy resin double-sided copper-clad laminate with a copper foil thickness of 18 μm, heat at 130 ° C. for 30 minutes and then at 170 ° C. for 30 minutes. It is cured to form an insulating layer. Visually observe the insulating layer of the portion where the resin sheet is laminated, and observe the surface uniformity of the surface opposite to the glass cloth base material epoxy resin double-sided copper-clad laminate. At this time, usually, the portion inside the portion 1 cm from the outer circumference of the portion on which the resin sheet is laminated has a uniform surface. Preferably, the entire surface of the insulating layer opposite to the laminated plate is a uniform surface. The details of the evaluation of the unevenness of the cured substrate can be measured according to the method described in Examples described later.

A cured product obtained by thermosetting the resin composition at 200 ° C. for 90 minutes exhibits a characteristic of low dielectric constant. Therefore, the cured product provides an insulating layer having a low dielectric constant. The dielectric constant is preferably 4 or less, more preferably 3.5 or less, still more preferably 3 or less. The lower limit of the dielectric constant may be 0.001 or more. The dielectric constant can be measured according to the method described in Examples described later.

A cured product obtained by thermosetting the resin composition at 200 ° C. for 90 minutes exhibits a characteristic of low dielectric loss tangent. Therefore, the cured product provides an insulating layer having a low dielectric loss tangent. The dielectric loss tangent is preferably 0.01 or less, more preferably 0.008 or less, still more preferably 0.005 or less. The lower limit of the dielectric loss tangent may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in Examples described later.

The cured product obtained by thermally curing the resin composition at 130 ° C. for 30 minutes and then at 170 ° C. for 30 minutes exhibits a characteristic of excellent peel strength between the resin composition and the conductor layer (plated conductor layer) formed by plating. .. Therefore, the cured product provides an insulating layer having excellent peel strength with the plated conductor layer. The peel strength is preferably 0.3 kgf / cm or more, more preferably 0.35 kgf / cm or more, still more preferably 0.4 kgf / cm or more. The upper limit of the peel strength may be 10 kgf / cm or less. The peel strength of the plated conductor layer can be measured according to the method described in Examples described later.

The resin composition of the present invention can suppress unevenness occurring in the cured substrate, and can provide an insulating layer having excellent dielectric properties and peel strength. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating applications. Specifically, a resin composition for forming the insulating layer for forming the conductor layer (including the rewiring layer) formed on the insulating layer (resin for forming the insulating layer for forming the conductor layer). It can be suitably used as a composition).

Further, in the multilayer printed wiring board described later, a resin composition for forming an insulating layer of the multilayer printed wiring board (resin composition for forming an insulating layer of the multilayer printed wiring board) and an interlayer insulating layer of the printed wiring board are formed. It can be suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board.

Further, for example, when the semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is for a rewiring forming layer as an insulating layer for forming the rewiring layer. Can also be suitably used as a resin composition (resin composition for forming a rewiring forming layer) and a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When the semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer.
(1) A process of laminating a temporary fixing film on a base material,
(2) A process of temporarily fixing a semiconductor chip on a temporary fixing film,
(3) Step of forming a sealing layer on a semiconductor chip,
(4) Step of peeling the base material and the temporary fixing film from the semiconductor chip,
(5) A step of forming a rewiring forming layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off, and (6) a rewiring layer as a conductor layer is formed on the rewiring forming layer. The process of forming

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

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

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

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

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

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

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

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

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

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

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

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

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

[Printed circuit 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.

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

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

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

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

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

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

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

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

For example, the thermosetting conditions of the resin composition layer differ depending on the type of the resin composition and the like, but the curing temperature is preferably 120 ° C. to 240 ° C., more preferably 150 ° C. to 220 ° C., still more preferably 170 ° C. to 210. ℃. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

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

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

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

Step (IV) is a step of roughening the insulating layer. Usually, smear removal is also performed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling solution used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution, and the alkaline solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P", "Swelling Dip Securigans SBU", and "Swelling Dip Securigant P" manufactured by Atotech Japan. Be done. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C. to 100 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan. Further, the neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be carried out by immersing the treated surface that has been roughened with the oxidizing agent in the neutralizing solution 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 roughened with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, 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 further preferably 50 nm or more. The arithmetic mean roughness (Ra) of the insulating layer surface can be measured using a non-contact surface roughness meter.

The step (V) is a step of forming the conductor layer, and forms the 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 is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). A layer formed from a nickel alloy and a copper / titanium alloy) can be mentioned. Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. An alloy layer of a nickel alloy or a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single copper layer is preferable. A metal layer is more preferred.

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

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

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

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

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

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

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

The mounting method of the semiconductor chip in manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up layer. Examples thereof include a mounting method using (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, the "mounting method using the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[Example 1. Preparation of Resin Composition 1]
10 parts of bixylenol type epoxy resin (Mitsubishi Chemical "YX4000H", epoxy equivalent about 185 g / eq.), 20 parts of fluorine-containing epoxy resin (Mitsubishi Chemical "YX7760", epoxy equivalent about 236 g / eq.) Intoluene It was dissolved by heating in 20 parts and 20 parts of MEK with stirring. After cooling the obtained solution to room temperature, an active ester-based curing agent represented by the general formula (B) (“EXB8500-65T” manufactured by DIC), an active group equivalent of 223 g / eq., And a solid content of 65% by mass. 50 parts of toluene solution, 4 parts of triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl equivalent of about 151 g / eq., 2-methoxypropanol solution having 50% solid content), phenoxy resin ( "YX7200B35" manufactured by Mitsubishi Chemical Co., Ltd., 10 parts of MEK solution with 35% by mass of solid content, 1 part of curing accelerator (MEK solution with 10% solid content of 4-dimethylaminopyridine (DMAP)), inorganic filler (amine-based) Mix 160 parts of spherical silica ("SO-C2" manufactured by Admatex, average particle size 0.5 μm) surface-treated with a silane coupling agent ("KBM573" manufactured by Shinetsu Chemical Industry Co., Ltd.) and use a high-speed rotating mixer. The resin composition 1 was obtained by uniformly dispersing.

[Example 2. Preparation of Resin Composition 2]
In Example 1, the amount of the active ester-based curing agent represented by the general formula (B) (“EXB8500-65T” manufactured by DIC, active group equivalent 223 g / eq., Toluene solution having a solid content of 65% by mass) was 50. Change from 10 parts to 100 parts, and add 4 parts of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151 g / eq., 2-methoxypropanol solution having a solid content of 50%) to carbodiimide. It was changed to 8 parts of a system resin (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution having an active group equivalent of about 216 and a solid content of 50% by mass). A resin composition 2 was obtained in the same manner as in Example 1 except for the above items.

[Example 3. Preparation of resin composition 3]
In Example 1,
1) Amount of spherical silica (“SO-C2” manufactured by Admatex, average particle size 0.5 μm) surface-treated with an inorganic filler (amine-based silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) From 160 copies to 120 copies,
2) Change the amount of phenoxy resin (Mitsubishi Chemical Corporation "YX7200B35", MEK solution with a solid content of 35% by mass) from 10 parts to 4 parts.
3) 4 parts of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151 g / eq., 2-methoxypropanol solution having a solid content of 50%) was added to an oligophenylene ether / styrene resin. ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemicals, Inc., a toluene solution with a solid content of 65%) was changed to 20 parts.
A resin composition 3 was obtained in the same manner as in Example 1 except for the above items.

[Example 4. Preparation of resin composition 4]
In Example 1, the amount of phenoxy resin (“YX7200B35” manufactured by Mitsubishi Chemical Chemical Co., Ltd., MEK solution having a solid content of 35% by mass) was changed from 10 parts to 4 parts, and a triazine skeleton-containing phenolic curing agent (“LA” manufactured by DIC Co., Ltd.) was changed. -3018-50P ", hydroxyl group equivalent about 151 g / eq., Solid content 50% 2-methoxypropanol solution) 4 parts, liquid bismaleimide ("BMI689" manufactured by Designer Moleculars, maleimide group equivalent 345 g / eq. ) Changed to 4 parts. A resin composition 4 was obtained in the same manner as in Example 1 except for the above items.

[Example 5. Preparation of Resin Composition 5]
In Example 1, spherical silica surface-treated with an inorganic filler (amine-based silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (“SO-C2” manufactured by Admatex Co., Ltd., average particle size 0.5 μm)). ) 160 parts of spherical silica (average particle size 0.3 μm, specific surface area 30.7 m ² / g, manufactured by Denka) surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shinetsu Chemical Industry Co., Ltd.) UFP-30 ") was changed to 120 copies. A resin composition 5 was obtained in the same manner as in Example 1 except for the above items.

[Example 6. Preparation of resin composition 6]
In Example 5, 4 parts of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151 g / eq., 2-methoxypropanol solution having a solid content of 50%) was used as a bifunctional acrylate. ((Meta) acrylic curing agent, "NK ester A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326) was changed to 10 parts. A resin composition 6 was obtained in the same manner as in Example 5 except for the above items.

[Example 7. Preparation of resin composition 7]
In Example 5, 4 parts of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC Corporation, a hydroxyl group equivalent of about 151 g / eq., A 2-methoxypropanol solution having a solid content of 50%) was benzoxazine-based. It was changed to 2 parts of a curing agent (“ODA-BOZ” manufactured by JFE Chemical Corporation). A resin composition 7 was obtained in the same manner as in Example 5 except for the above items.

[Example 8. Preparation of resin composition 8]
In Example 1, 4 parts of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC Corporation, a hydroxyl group equivalent of about 151 g / eq., A 2-methoxypropanol solution having a solid content of 50%) was not used. A resin composition 8 was obtained in the same manner as in Example 1 except for the above items.

[Example 9. Preparation of resin composition 9]
In Example 5, 4 parts of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC Corporation, a hydroxyl group equivalent of about 151 g / eq., A 2-methoxypropanol solution having a solid content of 50%) was not used. A resin composition 9 was obtained in the same manner as in Example 5 except for the above items.

[Comparative example 1. Preparation of Comparative Resin Composition 1]
In Example 1, 50 parts of an active ester-based curing agent represented by the general formula (B) (“EXB-8500-65T” manufactured by DIC, active group equivalent 223 g / eq., Toluene solution having a solid content of 65% by mass). Was changed to 46.4 parts of an active ester type curing agent containing a naphthalene structure (“EXB9416-70BK” manufactured by DIC, a methylisobutylketone solution having an active group equivalent of about 330 g / eq. And a non-volatile content of 70% by mass). A comparative resin composition 1 was obtained in the same manner as in Example 1 except for the above items.

[Comparative example 2. Preparation of Comparative Resin Composition 2]
In Example 1, the amount of the active ester-based curing agent represented by the general formula (B) (“EXB-8500-65T” manufactured by DIC, active group equivalent 223 g / eq., Toluene solution having a solid content of 65% by mass). Spherical silica ("SO-C2" manufactured by Admatex Co., Ltd., average particle size) surface-treated with an inorganic filler (amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.)) with 50 parts to 200 parts. The amount of 0.5 μm)) was changed from 160 parts to 250 parts. A comparative resin composition 2 was obtained in the same manner as in Example 1 except for the above items.

[Preparation of resin sheet]
As a support, a polyethylene terephthalate film ("Lumilar R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C.) subjected to mold release treatment with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Corporation) was prepared. ..

The resin compositions 1 to 9 and the comparative resin compositions 1 and 2 were uniformly applied on the supports with a die coater so that the thickness of the resin composition layer after drying was 30 μm, and the temperature was 70 ° C. to 95 ° C. A resin composition layer was formed on the support by drying at ° C. for 3 minutes. Next, a rough surface of a polypropylene film (“Alfan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) was attached as a protective film to the surface of the resin composition layer that was not bonded to the support. As a result, a resin sheet A having a support, a resin composition layer, and a protective film in this order was obtained.

[Evaluation of unevenness of cured substrate, measurement of peel strength of plated conductor layer]
(1) Preparation of inner layer substrate Both sides of the glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic “R1515A”) on which the inner layer circuit is formed are microscopic. The copper surface was roughened by etching 1 μm with an etching agent (“CZ8101” manufactured by MEC).

(2) Lamination of Resin Sheet The protective film was peeled off from the resin sheet A to expose the resin composition layer. Using a batch type vacuum pressurizing laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), the resin composition layer was laminated on both sides of the inner layer substrate so as to be in contact with the inner layer substrate. Lamination was carried out by reducing the pressure for 30 seconds, adjusting the atmospheric pressure to 13 hPa or less, and then crimping at 120 ° C. and a pressure of 0.74 MPa for 30 seconds. Then, heat pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Thermosetting of Resin Composition Layer After that, the inner layer substrate on which the resin sheet was laminated was put into an oven at 130 ° C. and heated for 30 minutes, then transferred to an oven at 170 ° C. and heated for 30 minutes. The resin composition layer was thermoset to form an insulating layer. Then, the support was peeled off to obtain a cured substrate A having an insulating layer, an inner layer substrate, and an insulating layer in this order.

<Evaluation of unevenness on the cured substrate>
On both sides of the cured substrate A, the surface uniformity of the portion where the resin sheet was laminated was visually observed and evaluated as follows.
⊚: No unevenness was observed, and the surface was completely uniform.
〇: Unevenness is observed only in the portion 1 cm from the outer circumference of the portion where the resin sheet is laminated, and the portion inside the portion has a completely uniform surface.
X: A non-uniform portion is observed in a portion inside 1 cm from the outer circumference of the portion on which the resin sheet is laminated.

(4) Roughing Treatment The cured substrate A was subjected to desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was carried out.
(Wet desmear treatment)
The cured substrate A is immersed in a swelling solution (“Swelling Dip Securiganto P” manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, and then an oxidizing agent solution (Atotech Japan). Immerse in "Concentrate Compact CP" manufactured by Atotech Japan, an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 ° C. for 15 minutes, and then a neutralizing solution (Atotech Japan's "Reduction". It was immersed in "Solution Security P", aqueous sulfuric acid solution) at 40 ° C. for 5 minutes and then dried at 80 ° C. for 15 minutes.

(5) Formation of Conductor Layer A conductor layer was formed on the roughened surface of the insulating layer according to the semi-additive method. 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. Then, after heating at 150 ° C. for 30 minutes to perform annealing treatment, an etching resist was formed and a pattern was formed by etching. Then, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 μm, and annealing treatment was performed at 200 ° C. for 60 minutes. The obtained substrate is referred to as "evaluation substrate B".

<Measurement of peel strength of plated conductor layer>
The peel strength of the insulating layer and the conductor layer was measured in accordance with the Japanese Industrial Standards (JIS C6481). Specifically, a notch having a width of 10 mm and a length of 100 mm is made in the conductor layer of the evaluation substrate B, one end of the notch is peeled off, and the conductor layer is grasped with a gripper. At room temperature, in the vertical direction at a speed of 50 mm / min. The load (kgf / cm) when the 35 mm was peeled off was measured, and the peeling strength was determined. A tensile tester (“AC-50C-SL” manufactured by TSE) was used for the measurement.

[Measurement of dielectric properties (dielectric constant, dielectric loss tangent)]
The protective film was peeled off from the resin sheets produced in Examples and Comparative Examples, and the resin composition layer was heat-cured by heating at 200 ° C. for 90 minutes, and then the support was peeled off. The obtained cured product is referred to as "evaluation cured product C". The cured product C for evaluation was cut into test pieces having a width of 2 mm and a length of 80 mm. With respect to the test piece, the dielectric constant and the dielectric loss tangent were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using "HP8362B" manufactured by Azilent Technologies. Measurements were made on the three test pieces, and the average value was calculated.

＊表中、「（Ａ）成分の含有量」は、樹脂組成物中の不揮発成分を１００質量％とした場合の（Ａ）成分の含有量を表し、「（Ｂ）成分の含有量」は、樹脂組成物中の不揮発成分を１００質量％とした場合の（Ｂ）成分の含有量を表し、「（Ｃ）成分の含有量」は、樹脂組成物中の不揮発成分を１００質量％とした場合の（Ａ）成分の含有量を表す。

* In the table, "content of component (A)" represents the content of component (A) when the non-volatile component in the resin composition is 100% by mass, and "content of component (B)" is Represents the content of the component (B) when the non-volatile component in the resin composition is 100% by mass, and the "content of the component (C)" is 100% by mass of the non-volatile component in the resin composition. The content of the component (A) in the case is represented.

In Examples 1 to 9, it has been confirmed that even when the components (D) to (F) are not contained, the same result as in the above-mentioned Examples is obtained, although the degree is different.

Claims (10)

(A) Epoxy resin,
(B) A resin composition containing an active ester-based curing agent having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), and (C) an inorganic filler. And
The content of the component (B) is 30% by mass or less when the non-volatile component in the resin composition is 100% by mass.
A resin composition in which the content of the component (C) is 60% by mass or more when the non-volatile component in the resin composition is 100% by mass.

(In the general formula (1), R ¹¹ has an aliphatic hydrocarbon group which may independently have a substituent, an aryl group which may have a substituent, or a substituent. May represent an aralkyl group, where Z represents an isophthaloyl group which may have a substituent or a naphthalenedicarbonyl group which may have a substituent. N1 represents an integer of 0 or 1-3. ..
In the general formula (2), R ¹² may have an aliphatic hydrocarbon group which may independently have a substituent, an aryl group which may have a substituent, or a substituent. Represents a good aralkyl group. n2 represents an integer of 0 or 1-3. ) The resin composition according to claim 1, wherein R ¹¹ in the general formula (1) and R ¹² in the general formula (2) represent an aliphatic hydrocarbon group which may independently have a substituent. .. The resin composition according to claim 1 or 2, wherein the aliphatic hydrocarbon group represents an alkyl group having a branched structure. When the non-volatile component in the resin composition is 100% by mass, the content of the component (B) is b, and when the non-volatile component in the resin composition is 100% by mass, the content of the component (C) is c. The resin composition according to any one of claims 1 to 3, wherein b / c is 0.01 or more and 3 or less. The resin composition according to any one of claims 1 to 4, further comprising (F) a curing agent. The resin composition according to any one of claims 1 to 5, which is used for forming an insulating layer. The resin composition according to any one of claims 1 to 6, 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 including the printed wiring board according to claim 9.

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