JP7180657B2 - resin composition - Google Patents

Description

The present invention relates to resin compositions. Furthermore, it relates to a sheet-like laminate material containing the resin composition, a printed wiring board including an insulating layer formed of a cured product of the resin composition, and a semiconductor device.

As a technique for manufacturing a printed wiring board, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked on an inner layer substrate is known. An insulating layer is generally formed by curing a resin composition.

For example, Patent Document 1 describes an active compound containing the naphthalene structure when the non-volatile component in the resin composition containing at least an epoxy resin (A) and an active ester compound (B) containing a naphthalene structure is 100% by mass. A thermosetting epoxy resin composition is disclosed in which the content of the ester compound (B) is 0.1 to 30% by mass.

Further, Patent Document 2 discloses a resin composition characterized by containing (A) a radically polymerizable compound, (B) an epoxy resin, (C) a curing agent, and (D) a roughening component. .

As described above, many proposals have been made for epoxy resin compositions suitable for forming insulating layers of inner layer circuit boards. There is a growing demand for a resin composition that can form an insulating layer with a higher thickness.

JP 2014-47318 A JP 2014-34580 A

An object of the present invention is to provide a resin composition capable of forming an insulating layer having a low dielectric loss tangent, a high glass transition temperature, and high adhesion.

As a result of intensive studies on the above problems, the present inventors have found that (A) an epoxy resin, (B) an active ester compound having a carbon-carbon unsaturated bond, and (C) a resin having an unsaturated hydrocarbon group are combined. The inventors have found that the above problems can be solved by a resin composition, and have completed the present invention.
That is, the present invention includes the following contents.

（前記一般式（１）中、ｍは１～６の整数を表し、ｎは１～２０の整数を表す。）
〔８〕前記（Ｃ）成分が、アクリル基、メタクリル基、スチリル基、又はオレフィン基を有する樹脂である上記〔１〕～〔７〕のいずれかに記載の樹脂組成物。
〔９〕プリント配線板の絶縁層形成用である上記〔１〕～〔８〕のいずれかに記載の樹脂組成物。
〔１０〕上記〔１〕～〔９〕のいずれかに記載の樹脂組成物を含む、シート状積層材料。
〔１１〕上記〔１〕～〔９〕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。
〔１２〕上記〔１１〕に記載のプリント配線板を含む、半導体装置。 [1] (A) epoxy resin (hereinafter also referred to as "(A) component" in this specification), (B) an active ester compound having a carbon-carbon unsaturated bond (hereinafter referred to as "(B) component”), and (C) a resin having an unsaturated hydrocarbon group (hereinafter also referred to as “component (C)” in this specification).
[2] The resin composition according to [1] above, wherein the content of component (B) is 10 to 60% by mass based on 100% by mass of the resin component.
[3] When the content of the component (A) is 10 to 50% by mass when the resin component is 100% by mass, and the content of the component (C) is 100% by mass when the resin component is 100% by mass , 3 to 30% by mass of the resin composition according to [1] or [2] above.
[4] The resin composition according to any one of [1] to [3] above, wherein the component (B) is an active ester compound having a carbon-carbon double bond.
[5] The resin composition as described in [4] above, wherein the component (B) is an active ester compound having a vinyl group, a methacrylic group, an acrylic group, an allyl group, a styryl group, or a propenyl group.
[6] The resin composition as described in [5] above, wherein the component (B) is an active ester compound having a styryl group.
[7] The resin composition according to [6] above, wherein the component (B) contains a compound represented by the following general formula (1).

(In the general formula (1), m represents an integer of 1 to 6, and n represents an integer of 1 to 20.)
[8] The resin composition as described in any one of [1] to [7] above, wherein the component (C) is a resin having an acrylic group, a methacrylic group, a styryl group, or an olefin group.
[9] The resin composition according to any one of [1] to [8], which is used for forming an insulating layer of a printed wiring board.
[10] A sheet-like laminate material comprising the resin composition according to any one of [1] to [9] above.
[11] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [9] above.
[12] A semiconductor device comprising the printed wiring board according to [11] above.

According to the present invention, a resin composition having a high glass transition temperature, good adhesion to a conductor layer, and capable of obtaining a cured product having a low dielectric loss tangent; a sheet-like laminate material containing the resin composition; , a printed wiring board and a semiconductor device containing a cured product of the resin composition can be provided.

Hereinafter, the present invention will be described in detail by showing embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

In the following description, the amount of each component in the resin composition is a value based on 100% by mass of the resin component in the resin composition, unless otherwise specified.
In the following description, unless otherwise specified, the term “resin component” refers to (D) inorganic filler (hereinafter referred to as “(D) component” in this specification) among the non-volatile components contained in the resin composition. (Also called).

[1. Overview of resin composition]
The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester compound having a carbon-carbon unsaturated bond, and (C) a resin having an unsaturated hydrocarbon group. The cured product formed by curing the resin composition of the present invention is a molecular structure site formed by reacting the unsaturated bond site of component (B) with the unsaturated hydrocarbon group of component (C). including. This molecular structure site has a small polarity due to the action of the unsaturated bond site of component (B) and the unsaturated hydrocarbon group of component (C). Therefore, the polarity of the cured product is reduced, and the value of the dielectric loss tangent can be reduced.
In addition, the cured product formed by curing the resin composition of the present invention is a molecular structural site formed by the reaction between the unsaturated bond site of component (B) and the unsaturated hydrocarbon group of component (C). In addition, the active ester site of the component (B) and the component (A) react to form a molecular structure site. Therefore, the crosslink density becomes dense (that is, the structure becomes dense), and the glass transition temperature of the cured product becomes high. Furthermore, since the cross-linking density is high, the mechanical strength of the cured product is improved, and peeling accompanied by destruction of the cured product is less likely to occur, resulting in excellent adhesion between the cured product and the conductor layer.

As described above, in the resin composition of the present invention, the component (B) has a reaction site capable of reacting with the component (A) and the component (C). It is possible to form a cured product that simultaneously exhibits the effects that can be exhibited when each is used alone.
Furthermore, when comparing the case where the ester compound that can react with the component (A) and the compound having an unsaturated bond that can react with the component (C) are used separately and the case where the component (B) is used, (A ) component, (B) component and (C) component can be improved in miscibility. Therefore, the uniformity of the composition in the cured product can be improved, and the above effects can be obtained at a higher level.

[2. (A) Epoxy resin]
The resin composition of the present invention contains component (A). Since the cured product has a molecular structure site formed by the reaction of the active ester site of the component (A) and the component (B), the structure becomes dense, the glass transition temperature of the cured product is high, and the adhesion is excellent. become a thing.
Component (A) includes, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin. resins, naphthol novolak-type epoxy resins, phenol novolak-type epoxy resins, tert-butyl-catechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, Naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, and halogenated epoxy resins can be mentioned.

Among these, from the viewpoint of improving adhesion, component (A) includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, and naphthylene ether. type epoxy resins, glycidyl ester type epoxy resins and anthracene type epoxy resins are preferred, and epoxy resins containing an aromatic skeleton are preferred from the viewpoint of lowering the average coefficient of linear thermal expansion. Here, the aromatic skeleton is a concept including polycyclic aromatics and aromatic heterocycles. The epoxy resin containing an aromatic skeleton is selected from the group consisting of bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, naphthalene-type epoxy resins, biphenyl-type epoxy resins, dicyclopentadiene-type epoxy resins, and naphthol-type epoxy resins. and more preferably one or more epoxy resins selected from the group consisting of bisphenol A type epoxy resins, biphenyl type epoxy resins, and naphthalene type epoxy resins.

Moreover, it is preferable that the resin composition contains an epoxy resin having two or more epoxy groups in one molecule as the component (A). The ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably It is 70% by mass or more. Among them, the resin composition has, as the component (A), an epoxy resin that has three or more epoxy groups in one molecule and is solid at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resin”). ) is preferably included.

Component (A) may be used singly or in combination of two or more at any ratio. Therefore, the resin composition may contain only the solid epoxy resin as the component (A), or may contain a combination of the solid epoxy resin and other epoxy resins. Among them, the resin composition has, as the component (A), a solid epoxy resin and an epoxy resin that has two or more epoxy groups in one molecule and is liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin"). ) in combination. By using a combination of a liquid epoxy resin and a solid epoxy resin as component (A), the flexibility of the resin composition can be improved, and the breaking strength of the cured product of the resin composition can be improved. can.

Examples of liquid epoxy resins 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, glycidyl amine type epoxy resin, phenol novolak type epoxy resin, ester skeleton. An alicyclic epoxy resin having a type epoxy resins and naphthalene type epoxy resins are more preferred.

Examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "YL980", "828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation. , "Epikote 828EL" (bisphenol A type epoxy resin); "jER806H", "jER807", "YL983U", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" manufactured by Mitsubishi Chemical Corporation ( Phenol novolac type epoxy resin); "630" and "630LSD" manufactured by Mitsubishi Chemical Corporation (glycidylamine type epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. product); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celoxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by Daicel (epoxy resin having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd.; These may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

Solid epoxy resins include naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, and naphthylene. Ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, tetraphenylethane-type epoxy resin, bixylenol-type epoxy resin are preferred, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, naphthol-type epoxy resin, bixylenol. type epoxy resins and biphenyl type epoxy resins are more preferred.

Solid epoxy resins include, for example, DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin); DIC's "N-690", "N-695" (cresol novolac type epoxy resin); "HP-7200", "HP-7200HH", "HP-7200H" manufactured by DIC (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolak type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3100" (biphenyl type epoxy resin); Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V" (naphtholnaphthalene type epoxy resin); Nippon Steel & Sumikin Chemical Co., Ltd. "ESN485" (naphthol novolac type epoxy resin); YL6121" (biphenyl-type epoxy resin); "YX4000H", "YX4000", "YX4000HK" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Osaka Gas "PG-100" and "CG-500" manufactured by Chemical Company; "YL7760" manufactured by Mitsubishi Chemical Corporation (bisphenol AF type epoxy resin); "YL7800" manufactured by Mitsubishi Chemical Corporation (fluorene type epoxy resin); "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

When a combination of a liquid epoxy resin and a solid epoxy resin is used as component (A), the mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:15, and more. It is preferably 1:0.5 to 1:10, particularly preferably 1:1 to 1:8.
When the mass ratio of the liquid epoxy resin is within this range, sufficient flexibility is obtained when used in the form of an adhesive film, handling is improved, and sufficient fluidity is obtained during lamination. be able to.
When the mass ratio of the solid epoxy resin is within this range, the viscosity of the epoxy resin can be reduced, and when used in the form of an adhesive film, the degassing property during vacuum lamination can be improved. In addition, it is possible to improve the releasability of the protective film and the support film during vacuum lamination, and to improve the heat resistance after curing.

The epoxy equivalent of component (A) is preferably 50 to 5,000, more preferably 50 to 3,000, even more preferably 80 to 2,000, and particularly preferably 110 to 1,000. When the epoxy equivalent of component (A) is within the above range, the crosslink density of the cured product of the resin composition is sufficient, and an insulating layer with a small surface roughness can be obtained.
An epoxy equivalent is the mass of a resin containing one equivalent of epoxy groups, and can be measured according to JIS K7236.

The weight average molecular weight of component (A) is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500 from the viewpoint of significantly obtaining the desired effects of the present invention.
The weight average molecular weight of component (A) can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC). For example, the weight-average molecular weight of the resin is measured by LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd. as a column, and chloroform as a mobile phase. can be measured at a column temperature of 40° C. and calculated using a standard polystyrene calibration curve.

From the viewpoint of obtaining an insulating layer exhibiting a high glass transition temperature and high adhesion, the amount of component (A) in the resin composition is preferably 5% by mass or more with respect to 100% by mass of the resin component in the resin composition. More preferably 10% by mass or more, still more preferably 20% by mass or more. The upper limit of the amount of component (A) is arbitrary as long as the effect of the present invention is exhibited, and is preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass. % by mass or less.

[3. (B) an active ester compound having a carbon-carbon unsaturated bond]
The resin composition of the present invention contains component (B). By using component (B), it reacts with both component (A) and component (C) to form a cured product.
The cured product has a molecular structure site formed by the reaction between the unsaturated bond site of the component (B) and the component (C), thereby reducing the polarity of the cured product and reducing the value of the dielectric loss tangent. be able to.
In addition, since the cured product has a molecular structure site formed by the reaction between the active ester site of the component (B) and the component (A), the structure becomes dense and the glass transition temperature of the cured product is high. It becomes a thing excellent in adhesiveness.

Conventionally, when two resins having different reactivities are used together, the miscibility of each resin is poor, and it is difficult to form a uniform cured product. Therefore, it was difficult to express the above effects at a high level at the same time.
On the other hand, in the resin composition of the present invention, the component (B) has sites in the same compound that can react with resins having two different reactivities. Therefore, the component (B) connects each resin to form a cured product, and a uniform cured product can be formed. Therefore, the above characteristics can be exhibited at a high level at the same time, and the desired effects of the present invention can be achieved.
Furthermore, the miscibility of the (A) component, the (B) component and the (C) component can be improved by using the (B) component. Therefore, the uniformity of the composition in the cured product can be improved, and the above effect can be obtained at a higher level.

Carbon-carbon unsaturated bonds include, for example, carbon-carbon double bonds and carbon-carbon triple bonds. Among them, a carbon-carbon double bond is preferred. Carbon-carbon double bonds include, for example, vinyl groups, methacryl groups, acryl groups, allyl groups, styryl groups, and propenyl groups. Among them, a styryl group is particularly preferable from the viewpoint of excellent heat resistance.

一般式（１）中、ｍは１～６の整数を表し、ｎは１～２０の整数を表す。 Component (B) preferably contains a compound represented by the following general formula (1).

In general formula (1), m represents an integer of 1-6, and n represents an integer of 1-20.

In general formula (1), m is preferably an integer of 1-6, more preferably an integer of 1-3. Also, n is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3. With such a numerical range, the component (B) reacts with the component (C) in an appropriate proportion, and the dielectric loss tangent can be lowered.

一般式（０－２）中、ｎは１～２０の整数を表す。 The component (B) may be a mixture of compounds represented by the general formula (1) having different m and n values. In the case of a mixture, the component (B) is a compound represented by the general formula (1) where n is 0 (compound represented by the following formula (0-1)), as long as it contains the compound represented by the general formula (1). and compounds in which n is an integer of 1 to 20 and m is 0 (compounds represented by the following general formula (0-2)).
The total ratio of the compound represented by the formula (0-1) and the compound represented by the general formula (0-2) to 100% by mass of the component (B) is preferably 10% by mass or less, It is more preferably 5% by mass or less, still more preferably 3% by mass or less, particularly preferably 1% by mass or less, and 0% by mass. Within this range, the component (B) reacts with the component (C) in an appropriate proportion, and the dielectric loss tangent can be lowered.

In general formula (0-2), n represents an integer of 1-20.

A commercially available product or a synthetic product may be used as the compound represented by the general formula (1). Commercially available products include, for example, the trade name “PC1300-02-65MA” (manufactured by Air Water).

The amount of component (B) in the resin composition is preferably 5% with respect to 100% by mass of the resin component in the resin composition, from the viewpoint of obtaining an insulating layer exhibiting a low dielectric loss tangent, a high glass transition temperature, and high adhesion. % by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more. The upper limit of the amount of component (B) is arbitrary as long as the effects of the present invention are exhibited, and is preferably 70% by mass or less, more preferably 65% by mass or less, and still more preferably 60% by mass or less.

[4. (C) Resin having an unsaturated hydrocarbon group]
The resin composition of the present invention contains component (C). When the cured product has a molecular structure site formed by the reaction of the unsaturated bond sites of the component (C) and the component (B), the polarity of the cured product is reduced, and the value of the dielectric loss tangent can be reduced. .
Component (C) is not particularly limited as long as it has an unsaturated hydrocarbon group. By using the unsaturated hydrocarbon group, the dielectric loss tangent of the cured product can be lowered. Preferred unsaturated hydrocarbons are acryl groups, methacryl groups, styryl groups, and olefin groups. Among them, it is more preferable to have a styryl group from the viewpoint of excellent heat resistance.
As used herein, the term "olefin group" refers to an aliphatic hydrocarbon group having a carbon-carbon double bond in its molecule. Examples include allyl, vinyl and propenyl groups.

As component (C), compounds represented by the following general formula (2) are preferred.

一般式（２）中、Ｒ^１～Ｒ^６は、それぞれ独立に、水素原子又は炭素数１～４のアルキル基を表し、好ましくは水素原子である。Ａは、下記一般式（３）又は下記一般式（４）で表される構造を表す。

In general formula (2), R ¹ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. A represents a structure represented by the following general formula (3) or the following general formula (4).

一般式（３）中、Ｂは、下記一般式（Ｂ－１）、（Ｂ－２）又は（Ｂ－３）で表される構造を表す。

In general formula (3), B represents a structure represented by general formula (B-1), (B-2) or (B-3) below.

一般式（４）中、Ｄは、下記一般式（５）で表される構造を表す。

In general formula (4), D represents a structure represented by general formula (5) below.

一般式（５）中、Ｒ^７～Ｒ^１４は、それぞれ独立に、水素原子、炭素数６以下のアルキル基又はフェニル基を表し、好ましくは水素原子又はメチル基である。特にＲ^７、Ｒ^８、Ｒ^１３、Ｒ^１４は、より好ましくはメチル基である。ａ、ｂは、少なくとも一方が０でない０～１００の整数である。Ｂは、下記一般式（Ｂ－１）、（Ｂ－２）又は（Ｂ－３）で表される構造を表す。

In general formula (5), R ⁷ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, preferably a hydrogen atom or a methyl group. In particular, R ⁷ , R ⁸ , R ¹³ and R ¹⁴ are more preferably methyl groups. a and b are integers from 0 to 100, at least one of which is not 0; B represents a structure represented by the following general formula (B-1), (B-2) or (B-3).

一般式（Ｂ－１）中、Ｒ^１５～Ｒ^１８は、それぞれ独立に、水素原子、炭素数６以下のアルキル基又はフェニル基を表し、好ましくは水素原子又はメチル基である。
一般式（Ｂ－２）中、Ｒ^１９～Ｒ^２６は、それぞれ独立に、水素原子、炭素数６以下のアルキル基又はフェニル基を表し、好ましくは水素原子又はメチル基である。
一般式（Ｂ－３）中、Ｒ^２７～Ｒ^３４は、それぞれ独立に、水素原子、炭素数６以下のアルキル基又はフェニル基を表し、好ましくは水素原子又はメチル基である。Ｅは、炭素数２０以下の直鎖状、分岐状又は環状の２価の炭化水素基を表す。

In general formula (B-1), R ¹⁵ to R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, preferably a hydrogen atom or a methyl group.
In general formula (B-2), R ¹⁹ to R ²⁶ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, preferably a hydrogen atom or a methyl group.
In general formula (B-3), R ²⁷ to R ³⁴ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, preferably a hydrogen atom or a methyl group. E represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

Component (C) is more preferably a compound represented by the following general formula (6), formula (7) or formula (8) below.

一般式（６）中、Ｒ^１～Ｒ^６は、一般式（２）中のＲ^１～Ｒ^６と同義であり、Ｂは、一般式（３）中のＢと同義であり、ａ、ｂは、一般式（５）中のａ、ｂと同義である。

In general formula (6), R ¹ to R ⁶ have the same definitions as R ¹ to R ⁶ in general formula (2), B has the same meaning as B in general formula (3), and a, b is synonymous with a and b in general formula (5).

Commercially available component (C) includes, for example, styrene-modified polyphenylene ether resin (“OPE-2St 1200 (number average molecular weight: 1200)” manufactured by Mitsubishi Gas Chemical Co., Ltd., equivalent to general formula (6)), bixylenol diallyl ether resin. ("YL7776 (number average molecular weight 331)" manufactured by Mitsubishi Chemical Corporation, equivalent to formula (7)), dioxane acrylic monomer glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. "A-DOG (number average molecular weight 326)", formula (8 ) equivalent).

The number average molecular weight of component (C) is preferably in the range of 100 to 10,000, more preferably 200, from the viewpoint of preventing volatilization during drying of the resin varnish and preventing excessive increase in melt viscosity of the resin composition. ~3000. The number average molecular weight in the present invention is measured by a gel permeation chromatography (GPC) method (converted to polystyrene). As the number average molecular weight by GPC method, for example, LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Co., Ltd. as a column, and a mobile phase. It can be measured using chloroform or the like at a column temperature of 40° C. and calculated using a standard polystyrene calibration curve.

The amount of component (C) in the resin composition is preferably 3% by mass or more, more preferably 5% by mass, based on 100% by mass of the resin component in the resin composition, from the viewpoint of reducing the dielectric loss tangent value of the cured product. It is at least 10% by mass, more preferably at least 10% by mass. The upper limit of the amount of component (C) is arbitrary as long as the effects of the present invention are exhibited, and is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

[5. Curing agent]
The resin composition may contain a curing agent different from component (B) as long as the effects of the present invention are not impaired. The curing agent is not particularly limited, and examples thereof include phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents. be done. Among them, an active ester curing agent is preferable from the viewpoint of obtaining an insulating layer having excellent adhesion to the conductor layer. The curing agent may be used singly or in combination of two or more at any ratio.

As the phenol-based curing agent or naphthol-based curing agent, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenolic curing agent or a nitrogen-containing naphthol curing agent is preferable, and a triazine skeleton-containing phenolic curing agent or a triazine skeleton-containing naphthol curing agent is more preferable. Among them, a triazine skeleton-containing phenol novolac curing agent or a triazine skeleton-containing naphthol novolak curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer.

Examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" and "CBN" manufactured by Nippon Kayaku Co., Ltd. , “GPH”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485”, “SN-495”, “SN-375” manufactured by Nippon Steel & Sumikin Co., Ltd. ", "SN-395", DIC's "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P" and the like.

The active ester curing agent is not particularly limited. For example, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, can be used. The active ester curing agent is preferably obtained by a condensation reaction of at least one of a carboxylic acid compound and a thiocarboxylic acid compound and at least one of a hydroxy compound and 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 preferred.

Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Active ester curing agents include active ester compounds containing a dicyclopentadiene type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing acetylated phenol novolacs, and active ester compounds containing benzoylated phenol novolacs. is preferred, and an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferred. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Examples of commercially available active ester curing agents include DIC's "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "EXB-8000L-65TM", and "HPC-8000H- 65M” (an active ester compound containing a dicyclopentadiene type diphenol structure), DIC’s “EXB-9416L-70BK” (an active ester compound containing a naphthalene structure), Mitsubishi Chemical Corp.’s “DC808” (phenol novolac active ester compound containing acetylated product), Mitsubishi Chemical's "YLH1026" (active ester compound containing benzoylated phenol novolac), DIC's "EXB-9050L-62M" (phosphorus atom-containing active ester compound), etc. is mentioned.

Examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Kobunshi Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Kasei Kogyo Co., Ltd.

The cyanate ester curing agent is not particularly limited. For example, novolac type cyanate ester curing agents such as phenol novolak type and alkylphenol novolak type; dicyclopentadiene type cyanate ester type curing agents; bisphenol type cyanate ester curing agents such as bisphenol A type, bisphenol F type and bisphenol S type. agents; and prepolymers in which these are partially triazined. Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate, oligo(3-methylene-1,5-phenylenecyanate), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4 '-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethyl Bifunctional cyanate resins such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether; phenol polyfunctional cyanate resins derived from novolacs, cresol novolaks, etc.; and prepolymers obtained by partially triazinizing these cyanate resins. Commercially available products include "PT30" and "PT60" (both of which are phenol novolak type polyfunctional cyanate ester resins) and "BA230" (part or all of bisphenol A dicyanate is triazined and trimerized by Lonza Japan). prepolymer).

Carbodiimide-based curing agents include, for example, “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

The curing agent is preferably one or more selected from phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents and carbodiimide-based curing agents. It is more preferable that

When the number of epoxy groups in component (A) is 1, the lower limit of the number of reactive groups of the curing agent is preferably 0.1 or more, more preferably 0.2 or more, from the viewpoint of obtaining an insulating layer with good mechanical strength. More preferably 0.3 or more, particularly preferably 0.4 or more. The upper limit is preferably 2 or less, more preferably 1.5 or less, and even more preferably 1 or less.
Here, the "reactive group of the curing agent" is an active hydroxyl group, an active ester group, or the like, and varies depending on the type of curing agent. The "number of epoxy groups in component (A)" is the sum of the values obtained by dividing the mass of the solid content of each epoxy resin in the resin composition by the epoxy equivalent for all the epoxy resins. Furthermore, the "reactive group number of the curing agent" is the sum of the values obtained by dividing the solid content mass of each curing agent present in the resin composition by the reactive group equivalent for all curing agents. (A) By setting the ratio between the epoxy resin and the curing agent within such a range, the heat resistance of the cured product of the resin composition can be further improved.

The content of the curing agent in the resin composition is not particularly limited. For example, the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, and particularly preferably 18% by mass or less, relative to 100% by mass of the resin component in the resin composition. It is 15% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and particularly preferably 7% by mass or more and 10% by mass or more. By setting the content of the curing agent within this range, it is possible to form a cured product that is more excellent in the linear thermal expansion coefficient, dielectric loss tangent, and adhesion to the conductor layer of the resin composition.

[6. (D) Inorganic filler]
The resin composition usually contains component (D). By using the component (D), the thermal expansion coefficient of the cured product of the resin composition can be reduced, so that reflow warping of the insulating layer can be suppressed.

The material of component (D) is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, titanium Bismuth oxide, titanium oxide, zirconium oxide, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is preferred, and amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica and spherical silica are more preferred. From the viewpoint of reducing the surface roughness of the insulating layer, fused silica and spherical silica are preferred. Silica is more preferred, and spherical fused silica is particularly preferred. Component (D) may be used singly or in combination of two or more at any ratio.

The component (D) is usually contained in the resin composition in the form of particles. The average particle diameter of the particles of component (D) is preferably 5 μm or less, more preferably 3 μm or less, even more preferably 2 μm or less, and particularly preferably from the viewpoint of improving circuit embedding properties and obtaining an insulating layer with a small surface roughness. is 1 μm or less, 0.8 μm or less, 0.6 μm or less, or 0.4 μm or less. The lower limit of the average particle size is preferably 0.01 μm or more, more preferably 0.03 μm or more, and further preferably 0.03 μm or more, from the viewpoint of preventing the viscosity of the varnish from increasing and the handleability from decreasing when it is made into a resin varnish. It is preferably 0.05 μm or more, particularly preferably 0.07 μm or more and 0.1 μm or more.

Commercially available products of the component (D) having the above average particle size include, for example, Nippon Steel & Sumikin Materials Co., Ltd. “SP60-05” and “SP507-05”; Admatechs Co., Ltd. “YC100C” and “YA050C”. , "YA050C-MJE", "YA010C"; Denka "UFP-30"; Tokuyama "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N"; ”, “SO—C4”, “SO—C2”, and “SO—C1”.

The average particle size of the particles of component (D) can be measured by a laser diffraction/scattering method based on Mie scattering theory. For example, it is possible to measure the particle size distribution of particles on a volume basis with a laser diffraction scattering type particle size distribution analyzer, and measure the average particle size as the median size from the particle size distribution. As the measurement sample, particles dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution analyzer, "LA-500" manufactured by Horiba Ltd. can be used.

The component (D) may be surface-treated with any surface treatment agent. Examples of surface treatment agents include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. By surface-treating component (D) with these surface-treating agents, the moisture resistance and dispersibility of component (D) can be enhanced.

Examples of commercially available surface treatment agents include "KBM-22" (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry Co., Ltd. "KBM-803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE-903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-573" ( N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM-103" (phenyltrimethoxysilane), Shin-Etsu Chemical "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by K.K. The surface treatment agents may be used singly or in combination of two or more at any ratio.

The degree of surface treatment with a surface treatment agent can be evaluated by the amount of carbon per unit surface area of component (D). From the viewpoint of improving dispersibility of component (D), the amount of carbon per unit surface area of component (D) is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and particularly preferably 0. .2 mg/m2 or ^more . On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition and the melt viscosity in the form of a sheet, the amount of carbon is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and particularly preferably is less than or equal to 0.5 mg/ ^m2 .

The amount of carbon per unit surface area of the component (D) can be measured after the surface-treated component (D) is washed with a solvent (for example, methyl ethyl ketone (hereinafter sometimes abbreviated as “MEK”)). . For example, a sufficient amount of methyl ethyl ketone and component (D) surface-treated with a surface treatment agent are mixed, and ultrasonically cleaned at 25° C. for 5 minutes. Then, after removing the supernatant liquid and drying the solid content, the amount of carbon per unit surface area of component (D) can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

From the viewpoint of obtaining an insulating layer with a low coefficient of thermal expansion, the lower limit of the amount of component (D) in the resin composition is preferably 100 parts by mass or more, more preferably 100 parts by mass or more, with respect to 100 parts by mass of the resin component in the resin composition. 200 parts by mass or more, more preferably 250 parts by mass or more. The upper limit is preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and even more preferably 350 parts by mass or less, from the viewpoint of mechanical strength, particularly elongation, of the insulating layer.

[7. (E) Curing accelerator]
The resin composition of the present invention may further contain (E) a curing accelerator (hereinafter also referred to as "component (E)" in this specification), if necessary. By using the component (E), curing can be accelerated when the resin composition is cured.

Examples of component (E) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and peroxide-based curing accelerators. . Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, peroxide-based curing accelerators or metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators, peroxide A physical curing accelerator or a metallic curing accelerator is more preferable.
In addition, (E) component may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. Among them, triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo [5,4,0]-undecene can be mentioned. Among them, 4-dimethylaminopyridine and 1,8-diazabicyclo[5,4,0]-undecene are preferred.

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2- Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6 -[2′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-undecylimidazolyl-(1′)]-ethyl-s-triazine, 2, 4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-methylimidazolyl-(1′)] -ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 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 imidazole compounds and imidazole compounds and epoxy resins Adduct bodies are mentioned. Among them, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are 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.

Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide. Among them, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Examples of organic metal complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate; organic copper complexes such as copper (II) acetylacetonate; and zinc (II) acetylacetonate and the like. organic zinc complexes; organic iron 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 organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate and zinc stearate.

Examples of peroxide-based curing accelerators include cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, and diisopropylbenzene hydrochloride. Peroxide, cumene hydroperoxide, tert-butyl hydroperoxide.

As the peroxide-based curing accelerator, a commercially available product may be used.

The amount of component (E) in the resin composition is preferably in the range of 0.01 to 3% by mass with respect to 100% by mass of the resin component in the resin composition from the viewpoint of significantly obtaining the desired effects of the present invention. .

[8. (F) Thermoplastic resin]
The resin composition of the present invention may further contain (F) a thermoplastic resin (hereinafter also referred to as “(F) component” in the specification). Examples of component (F) include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, poly Ether ether ketone resins, polyester resins, and indene cumarone resins can be mentioned. Among them, an indene cumarone resin is preferable from the viewpoint of improving compatibility. In addition, (F) component may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

The polystyrene equivalent weight average molecular weight of component (F) is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. .
(F) The polystyrene equivalent weight average molecular weight of the component is measured by a gel permeation chromatography (GPC) method. For example, the polystyrene-equivalent weight average molecular weight of the component (F) is measured by Shimadzu Corporation's LC-9A/RID-6A as a measuring device, and Showa Denko's Shodex K-800P/K-804L/K-804L as a column. , using chloroform or the like as a mobile phase, measuring at a column temperature of 40° C., and calculating using a standard polystyrene calibration curve.

Examples of phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, and terpene. and a phenoxy resin having one or more skeletons selected from the group consisting of 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 resins may be used singly or in combination of two or more at any ratio.

Examples of phenoxy resins include Mitsubishi Chemical's "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins); Mitsubishi Chemical's "YX8100" (bisphenol S skeleton-containing phenoxy resin); "YX6954" (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "FX280" and "FX293"; YL6794", "YL7213", "YL7290", "YL7891BH30" and "YL7482".

Examples of indene cumarone resins include "H-100", "WS-100G", "WS-100H", "WS-120V", and "WS-100GC" manufactured by Nichinuri Chemical Co.; "C10", "C30", and "CA80" of

The lower limit of the amount of component (F) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to 100% by mass of the resin component in the resin composition. Moreover, the upper limit thereof is preferably 10% by mass or less, more preferably 5% by mass or less. Within this range, the effect of improving the film moldability and mechanical strength can be exhibited, and furthermore, the melt viscosity can be increased and the surface roughness of the insulating layer after the wet roughening process can be reduced.

[9. Optional component]
The resin composition of the present invention may contain optional components in addition to the components described above. Examples of such optional components include flame retardants; organic fillers; organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; thickeners; Resin additives such as colorants are included.

<Flame retardant>
The resin composition of the present invention can further improve the glass transition temperature of the cured product of the resin composition by using a flame retardant.
Examples of flame retardants include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. As the flame retardant, commercially available products may be used, and examples thereof include “HCA-HQ” and “HCA-HQ-HS” manufactured by Sanko Co., Ltd., and “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd. In addition, a flame retardant may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

From the viewpoint of imparting heat resistance, the amount of the flame retardant in the resin composition is preferably in the range of 0.5 to 20% by mass with respect to 100% by mass of the resin component in the resin composition, and 0.5% by mass to A range of 15 mass % is more preferred, and a range of 0.5 to 10 mass % is even more preferred.

<Organic filler>
By using an organic filler, the resin composition of the present invention can improve the flexibility of the cured product of the resin composition, so that the elongation of the insulating layer can be improved.
As the organic filler, any organic filler that can be used in forming the insulating layer of a printed wiring board can be used. Examples include rubber particles, polyamide particles, and silicone particles. As the rubber particles, commercially available products may be used, and examples thereof include "EXL-2655" manufactured by Dow Chemical Japan Co., Ltd. and "AC3816N" manufactured by Aica Kogyo Co., Ltd. In addition, an organic filler may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

The average particle size of the organic filler particles is preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less, from the viewpoint of excellent dispersibility in the resin composition. The lower limit of the average particle size of the organic filler is preferably 0.05 μm or more, more preferably 0.08 μm or more, and particularly preferably 0.10 μm or more.

From the viewpoint of adjusting the mechanical properties of the cured product of the resin composition to an appropriate range, the amount of the organic filler in the resin composition is 0.1 to 20% with respect to 100% by mass of the resin component in the resin composition. A range of 0.2 to 10% by mass is preferred, a range of 0.3 to 5% by mass is even more preferred, and a range of 0.5 to 3% by mass is particularly preferred.

[10. Production method and properties of the resin composition]
The method of 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 ingredients, if necessary, and mixing and dispersing using a rotary mixer or the like.

The resin composition of the present invention can provide a cured product with a high glass transition temperature. The glass transition temperature of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of glass transition temperature> below. Specifically, by performing thermomechanical analysis by a tensile loading method, measurement can be performed with a load of 1 g and a heating rate of 5° C./min. A cured product of the resin composition of the present invention can exhibit a glass transition temperature of preferably 158° C. or higher, more preferably 160° C. or higher, and even more preferably 162° C. or higher. The upper limit of the glass transition temperature is not particularly limited, and is usually 250° C. or lower.

The resin composition of the present invention can provide a cured product with a low dielectric loss tangent. The dielectric loss tangent of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of dielectric loss tangent> below. Specifically, it can be measured at a frequency of 5.8 GHz and a measurement temperature of 23° C. by the cavity resonator perturbation method. The dielectric loss tangent value is preferably 0.0037 or less, more preferably 0.0035 or less, from the viewpoints of preventing heat generation at high frequencies and reducing signal delay and signal noise. The lower limit of the value of the dielectric loss tangent is preferably as low as possible, and can usually be 0.0001 or more.

The resin composition of the present invention can provide a cured product having high adhesion to the conductor layer. The adhesion of the cured product of the resin composition of the present invention can be evaluated by the method described in <Measurement of Adhesion> below. The resulting adhesion between the conductor layer and the insulating layer is preferably 0.60 kgf/cm or more, more preferably 0.70 kgf/cm or more. The upper limit of the adhesion is not particularly limited, and can be usually 1.2 kgf/cm or less.

The resin composition of the present invention can provide a cured product having a high glass transition temperature, a low dielectric loss tangent, and good adhesion to a conductor layer. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board). It can be used more preferably as a resin composition for forming an insulating layer (a resin composition for an interlayer insulating layer of a printed wiring board). The resin composition of the present invention also includes adhesive films, sheet laminate materials such as prepreg, solder resists, underfill materials, die bonding materials, semiconductor sealing materials, hole-filling resins, component-embedding resins, and the like. Can be used for a wide range of applications.

[11. Sheet laminated material]
Although the resin composition of the present invention can be applied in the form of a varnish, it is industrially preferably used in the form of a sheet-like laminated material containing the resin composition.

Adhesive films and prepregs shown below are preferable as the sheet-like laminate material.

In one embodiment, the adhesive film comprises a support and a resin composition layer (adhesive layer) bonded to the support, wherein the resin composition layer (adhesive layer) is the resin composition of the present invention. formed from

The thickness of the resin composition layer is preferably 100 µm or less, more preferably 80 µm or less, still more preferably 60 µm or less, and particularly preferably 50 µm or less and 40 µm or less, from the viewpoint of thinning the printed wiring board. The lower limit of the thickness of the resin composition layer is not particularly limited, and is usually 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more.

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA); ; cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among them, 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. Among them, 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 other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

The support may be subjected to matte treatment or corona treatment on the surface thereof to be bonded to the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface of the side bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, olefin resins, urethane resins, and silicone resins. . Examples of commercially available releasing agents include “SK-1”, “AL-5” and “AL-7” manufactured by Lintec Co., Ltd., which are alkyd resin releasing agents.

The thickness of the support is not particularly limited, and is preferably in the range of 5-75 μm, more preferably in the range of 10-60 μm. When the support is a release layer-attached support, the thickness of the release layer-attached support as a whole is preferably within the above range.

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

Examples of organic solvents 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; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used singly or in combination of two or more at any ratio.

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

In the adhesive film, a protective film conforming to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 to 40 μm. By laminating the protective film, it is possible to prevent dust from adhering to the surface of the resin composition layer and scratches on the surface of the resin composition layer. The adhesive film can be wound into a roll and stored. When the adhesive film has a protective film, it can be used by peeling off the protective film.

In one embodiment, a prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited. Usually, it is 10 μm or more.

A prepreg can be manufactured by a known method such as a hot melt method or a solvent method.

The thickness of the prepreg can be in the same range as the resin composition layer in the adhesive film described above.

In the present invention using a resin composition containing a combination of components (A), (B), and (C), the glass transition temperature is high, the dielectric loss tangent is low, and the adhesion to the conductor layer is good. A sheet-like laminate material that yields a cured product and is extremely useful in the production of printed wiring boards can be realized.

The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). for interlayer insulating layers of wiring boards).

[12. Printed wiring board]
The printed wiring board of the present invention includes an insulating layer obtained by thermosetting the resin composition of the present invention or the sheet-like laminate material of the present invention.

In one embodiment, the printed wiring board of the present invention can be produced by a method including the following steps (I) and (II) using the adhesive film described above.
(I) Step of laminating an adhesive film on the inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate (II) Step of thermosetting the resin composition layer to form an insulating layer

The "inner layer substrate" used in step (I) mainly means a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or a substrate having A circuit board on which a patterned conductor layer (circuit) is formed. Further, an inner layer circuit board, which is an intermediate product on which at least one of an insulating layer and a conductor layer is further formed when manufacturing a printed wiring board, is also included in the "inner layer board" of the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer board containing components may be used.

The lamination of the inner layer substrate and the adhesive film can be performed, for example, by thermocompression bonding the adhesive film to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the adhesive film to the inner layer substrate (hereinafter also referred to as “thermocompression member”) include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of directly pressing the thermocompression member onto the adhesive film, it is preferable to press the adhesive film through an elastic material such as heat-resistant rubber so that the adhesive film can sufficiently follow the unevenness of the surface of the inner layer substrate.

Lamination of the inner layer substrate and the adhesive film may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably 60 to 160°C, more preferably 80 to 140°C. The thermocompression pressure is preferably in the range of 0.098-1.77 MPa, more preferably 0.29-1.47 MPa. The thermocompression bonding time is preferably 20 to 400 seconds, more preferably 30 to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and the like.

After lamination, the laminated adhesive film may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned commercially available vacuum laminator.

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

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

The thermosetting conditions for the resin composition layer are not particularly limited, and conditions that are commonly used for forming insulating layers of printed wiring boards may be used.

For example, the thermosetting conditions for the resin composition layer differ depending on the type of the resin composition. For example, the curing temperature is in the range of 120-240°C (preferably in the range of 150-220°C, more preferably in the range of 170-200°C). Curing times range from 5 to 120 minutes (preferably 10 to 100 minutes, more preferably 15 to 90 minutes).

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

When manufacturing a printed wiring board, (III) the step of drilling holes in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer on the surface of the insulating layer may be further carried out. good. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or step ( It may be carried out between IV) and step (V).

In another embodiment, the printed wiring board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as in the case of using an adhesive film.

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

Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards can be employed. 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 neutralizing treatment with a neutralizing liquid in this order.

The swelling liquid is not particularly limited. Examples include alkaline solutions and surfactant solutions. An alkaline solution is preferable, and sodium hydroxide solution and potassium hydroxide solution are more preferable as the alkaline solution. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited. For example, the insulating layer can be immersed in a swelling liquid of 30 to 90° C. for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40 to 80° C. for 5 to 15 minutes.

The oxidizing agent is not particularly limited. For example, an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide can be used. 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 to 80° C. for 10 to 30 minutes. Further, the permanganate concentration in the alkaline permanganate solution is preferably 5 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. Moreover, as a neutralizing liquid, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. can be mentioned.

The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30 to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40 to 70° C. for 5 to 20 minutes is preferable.

Step (V) is a step of forming a conductor layer.

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains 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, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred. A metal layer is more preferred.

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

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method.

In other embodiments, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, step (V) is preferably performed between step (I) and step (II). For example, after step (I), the support is removed and a metal foil is laminated on the exposed surface of the resin composition layer. Lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Then, step (II) is performed to form an insulating layer. After that, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventional known techniques such as the subtractive method and the modified semi-additive method.

A metal foil can be manufactured by a known method such as an electrolysis method or a rolling method. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Mining Co., Ltd., and the like.

When producing a printed wiring board using the resin composition of the present invention containing a combination of components (A), (B), and (C), the conductor layer is formed by plating or a metal foil is used. Adhesion between the conductor layer and the insulating layer can be remarkably improved regardless of whether or not the layer is formed through the contact.

[13. semiconductor device]
A semiconductor device of the present invention includes the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, 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. A "conducting part" is a "part where an electric signal is transmitted on a printed wiring board", and the place may be a surface or an embedded part. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. For example, there are a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, "a mounting method using a build-up layer without bumps (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected." is.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples shown below. In the following description, "parts" and "%" representing amounts are based on mass unless otherwise specified.

<Example 1>
25 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) and 10 parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180) are stirred into 25 parts of solvent naphtha. The solution was dissolved by heating while stirring, and then cooled to room temperature. 315 parts of an inorganic filler (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm, carbon amount per unit surface area 0.38 mg/m ² ) was mixed and kneaded and dispersed with a triple roll. Then, 69.2 parts of an active ester curing agent having a vinyl group ("PC1300-02-65MA" manufactured by Air Water Co., Ltd., a methyl amyl ketone solution having an active group equivalent of about 199 and a non-volatile content of 65%) and a vinyl group were added. Resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a nonvolatile content of 60%) 25 parts, indene cumarone resin (manufactured by Nihon Chemical "H-100") 15 parts, 4 as a curing accelerator 2 parts of a 5% MEK solution of dimethylaminopyridine (DMAP) and 0.13 parts of dicumyl peroxide ("Percumyl D" manufactured by NOF Corporation) are mixed and uniformly dispersed in a rotating mixer to obtain resin varnish 1. made.

Resin varnish 1 is applied on the release surface of a polyethylene terephthalate film with alkyd release treatment (“AL-5” manufactured by Lintec, thickness 38 μm) so that the thickness of the resin composition layer after drying is 40 μm. The adhesive film 1 was prepared by uniformly coating with a die coater and drying at 80 to 110° C. (average 95° C.) for 5 minutes.

<Example 2>
In Example 1, 30 out of 69.2 parts of an active ester curing agent having a vinyl group (“PC1300-02-65MA” manufactured by Air Water Co., Ltd., a methyl amyl ketone solution with an active group equivalent weight of about 199 and a non-volatile content of 65%) 8 parts was replaced with 30.8 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC, a toluene solution with an active group equivalent weight of about 223 and a non-volatile content of 65%). A resin varnish 2 and an adhesive film 2 were produced in the same manner as in Example 1 except for the above matters.

<Example 3>
In Example 1, 5 parts out of 25 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., epoxy equivalent of about 185) was added to resin having a vinyl group ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., non-volatile 60% toluene solution) to 8.3 parts. A resin varnish 3 and an adhesive film 3 were produced in the same manner as in Example 1 except for the above matters.

<Example 4>
In Example 1, a resin having a vinyl group ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a nonvolatile content of 60%) was added to 25 parts of a dioxane acrylic monomer ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.). Changed to 15 copies. A resin varnish 4 and an adhesive film 4 were produced in the same manner as in Example 1 except for the above matters.

<Comparative Example 1>
In Example 1, an active ester curing agent having a vinyl group (“PC1300-02-65MA” manufactured by Air Water, a methyl amyl ketone solution having an active group equivalent of about 199 and a non-volatile content of 65%) was added as an active ester curing agent. ("HPC-8000-65T" manufactured by DIC, a toluene solution with an active group equivalent of about 223 and a non-volatile content of 65%). A resin varnish 5 and an adhesive film 5 were produced in the same manner as in Example 1 except for the above matters.

<Comparative Example 2>
In Example 1, an active ester curing agent having a vinyl group (“PC1300-02-65MA” manufactured by Air Water, a methyl amyl ketone solution having an active group equivalent of about 199 and a non-volatile content of 65%) was added as an active ester curing agent. ("EXB-8000L-65TM" manufactured by DIC, a toluene solution with an active group equivalent of about 220 and a non-volatile content of 65%). A resin varnish 6 and an adhesive film 6 were produced in the same manner as in Example 1 except for the above matters.

<Comparative Example 3>
In Example 1, 69.2 parts of an active ester curing agent having a vinyl group (“PC1300-02-65MA” manufactured by Air Water Co., Ltd., a methyl amyl ketone solution with an active group equivalent of about 199 and a non-volatile content of 65%) was activated. The ester curing agent (“EXB-9416L-70BK” manufactured by DIC, a toluene solution with an active group equivalent of about 330 and a non-volatile content of 70%) was changed to 64.3 parts. A resin varnish 7 and an adhesive film 7 were produced in the same manner as in Example 1 except for the above matters.

[Evaluation method]
The adhesive films obtained in the above Examples and Comparative Examples were evaluated by the following methods.

<Preparation of sample for evaluation of cured physical properties>
The adhesive films obtained in Examples and Comparative Examples were thermally cured at 190° C. for 90 minutes, and the PET support was peeled off to prepare a sheet-like cured product evaluation sample.

<Measurement of dielectric loss tangent>
A test piece having a width of 2 mm and a length of 80 mm was cut from the cured physical property evaluation sample. The dielectric loss tangent of the cut test piece was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by a cavity resonance perturbation method using a measuring device "HP8362B" manufactured by Agilent Technologies.
A value of 0.0035 or less was evaluated as "excellent", a value of 0.0037 or less was evaluated as "good", and a value of more than 0.0037 was evaluated as "bad".

<Measurement of glass transition temperature>
A sample for evaluation of cured physical properties is cut into a test piece having a width of about 5 mm and a length of about 15 mm, and a thermomechanical analysis device ("Thermo Plus TMA8310" manufactured by Rigaku Co., Ltd.) is used to perform thermomechanical analysis by a tensile load method. gone. Specifically, after mounting the test piece on the thermomechanical analyzer, the measurement was performed twice continuously under the measurement conditions of a load of 1 g and a temperature increase rate of 5° C./min. Then, in the second measurement, the glass transition temperature (Tg; °C) was calculated.
In addition, the case of exceeding 138° C. was evaluated as “good”, and the case of 138° C. or lower was evaluated as “poor”.

<Measurement of adhesion>
(1) Surface treatment of copper foil The glossy surface of “3EC-III” (electrolytic copper foil, 35 μm) manufactured by Mitsui Kinzoku Mining Co., Ltd. is immersed in MEC Etch Bond “CZ-8101” manufactured by MEC Co., Ltd. to roughen the copper surface. (Ra value = 1 µm), and an antirust treatment (CL8300) was applied. This copper foil is called CZ copper foil. Further, heat treatment was performed in an oven at 130° C. for 30 minutes.

(2) Lamination of copper foil and formation of an insulating layer The adhesive films prepared in Examples and Comparative Examples are laminated using a batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Co., Ltd.), and the resin composition layer is the inner layer. Both sides of the inner layer circuit board were laminated so as to be bonded to the circuit board. The lamination process was carried out by pressure bonding for 30 seconds at 100° C. and pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds. The PET film as the support was peeled off from the laminated adhesive film. The treated surface of the "3EC-III" CZ copper foil was laminated on the resin composition layer under the same conditions as above. Then, a sample was produced by curing the resin composition layer under curing conditions of 190° C. for 90 minutes to form an insulating layer.

(3) Measurement of Copper Foil Peeling Strength (Adhesion) The prepared sample was cut into small pieces of 150×30 mm. Using a cutter, cut the copper foil portion of the small piece with a width of 10 mm and a length of 100 mm. AC-50C-SL"), and using an Instron universal testing machine, at room temperature, measure the load when peeling off 35 mm in the vertical direction at a speed of 50 mm / min in accordance with JIS C6481. , "adhesion".
In addition, the case of exceeding 0.3 kgf/cm was evaluated as "good", and the case of 0.3 kgf/cm or less was evaluated as "poor".

<Results>
The results of the examples and comparative examples described above are shown in the table below. In the table below, the abbreviations have the following meanings.
YX4000HK: bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation)
828US: Bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation)
PC1300-02: Active ester curing agent having a vinyl group ("PC1300-02-65MA" manufactured by Air Water)
HPC-8000: Active ester curing agent ("HPC-8000-65T" manufactured by DIC)
EXB-8000L: Active ester curing agent (manufactured by DIC "EXB-8000L-65TM")
EXB-9416: Active ester curing agent (manufactured by DIC "EXB-9416L-70BK")
OPE-2St 1200: resin having a vinyl group (“OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Co., Ltd.)
A-DOG: dioxane acrylic monomer (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.)
H-100: Indene cumarone resin ("H-100" manufactured by Nichinori Chemical)
SOC2: Spherical silica ("SO-C2" manufactured by Admatechs)
Parkmil D: dicumyl peroxide (NOF Corporation "Parkmil D")
DMAP: 4-dimethylaminopyridine In addition, in the table, the compounding amount is a solid content conversion value.

[examination]
Comparative Examples 1 to 3 using an active ester curing agent are inferior in glass transition temperature and adhesiveness. In particular, the active ester curing agent containing a naphthalene structure used in Comparative Example 3 was slightly inferior in dielectric loss tangent.
On the other hand, Examples 1 to 4 using the component (B) increased the glass transition temperature while maintaining a low dielectric loss tangent value, and exhibited good adhesion. Therefore, from the results of Examples 1 to 4 and Comparative Examples 1 to 3, by combining the (A) component, (B) component, and (C) component, the dielectric loss tangent is low, the glass transition temperature is high, and the conductive It was confirmed that a resin composition capable of obtaining an insulating layer having good adhesion to a layer can be realized.

Claims (10)

(A) an epoxy resin, (B) an active ester compound having a carbon-carbon unsaturated bond, and (C) a resin having an unsaturated hydrocarbon group,
The content of the component (A) is 10 to 50% by mass when the resin component is 100% by mass,
the component (B) is an active ester compound having a styryl group,
A resin composition in which the component (C) is either a compound represented by the general formula (2) or a compound represented by the general formula (8).

In general formula (2), R ¹ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A is represented by general formula (3) or general formula (4) below. represents a structure that is

In general formula (3), B represents a structure represented by general formula (B-1), (B-2) or (B-3) below.

In general formula (4), D represents a structure represented by general formula (5) below.

In general formula (5), R ⁷ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and at least one of a and b is an integer of 0 to 100 and not 0. be. B represents a structure represented by the following general formula (B-1), (B-2) or (B-3).

In general formula (B-1), R ¹⁵ to R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
In general formula (B-2), R ¹⁹ to R ²⁶ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
In general formula (B-3), R ²⁷ to R ³⁴ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. E represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

2. The resin composition according to claim 1, wherein the content of component (B) is 10 to 60% by mass based on 100% by mass of the resin component. 3. The resin composition according to claim 1, wherein the content of the component (C) is 3 to 30% by mass when the resin component is 100% by mass. The resin composition according to any one of claims 1 to 3, wherein the component (B) contains a compound represented by the following general formula (1).

(In the general formula (1), m represents an integer of 1 to 6, and n represents an integer of 1 to 20.) 5. The resin composition according to any one of claims 1 to 4, wherein the component (C) is a resin having an acrylic group , a styryl group, or an allyl group. The resin composition according to any one of claims 1 to 5, which is used for forming an insulating layer of a printed wiring board. 7. The resin composition according to any one of claims 1 to 6, wherein component (C) is a compound represented by the following general formula (6), formula (7) or formula (8) below.

In general formula (6), R ¹ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and B is the following general formula (B-1), (B-2) or Represents the structure represented by (B-3), in which at least one of a and b is an integer of 0 to 100 and not 0.

In general formula (B-1), R ¹⁵ to R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
In general formula (B-2), R ¹⁹ to R ²⁶ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
In general formula (B-3), R ²⁷ to R ³⁴ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group, and E is a linear or branched chain having 20 or less carbon atoms. or represents a cyclic divalent hydrocarbon group. A sheet-like laminate material comprising the resin composition according to any one of claims 1 to 7 . A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 7 . A semiconductor device comprising the printed wiring board according to claim 9 .