JP6776749B2 - Resin composition - Google Patents

Description

The present invention relates to resin compositions. Further, the present invention relates to a sheet-like laminated 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 manufacturing technique for a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately stacked on an inner layer substrate is known. The insulating layer is generally formed by curing the resin composition.

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

Further, Patent Document 2 discloses a resin composition 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 an insulating layer of an inner circuit board, but they have well-balanced characteristics of low dielectric loss tangent and excellent heat resistance and adhesion. There is an increasing demand for a resin composition capable of forming an insulating layer.

Japanese Unexamined Patent Publication No. 2014-47318 Japanese Unexamined Patent Publication No. 2014-34580

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

As a result of diligent studies on the above issues, the present inventor includes (A) an epoxy resin, (B) an active ester compound having a carbon-carbon unsaturated bond, and (C) a resin having an unsaturated hydrocarbon group in combination. It has been found that the resin composition can solve the above-mentioned problems, and the present invention has been completed.
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 the present specification), (B) Active ester compound having a carbon-carbon unsaturated bond (hereinafter, “(B)) in the present specification. A resin composition containing (also referred to as “component”) and (C) a resin having an unsaturated hydrocarbon group (hereinafter, also referred to as “component (C)” in the present specification).
[2] The resin composition according to the above [1], wherein the content of the component (B) is 10 to 60% by mass when the resin component is 100% by mass.
[3] 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. The resin composition according to the above [1] or [2], which is 3 to 30% by mass.
[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 according to the above [4], wherein the component (B) is an active ester compound having a vinyl group, a methacryl group, an acrylic group, an allyl group, a styryl group or a propenyl group.
[6] The resin composition according to the above [5], wherein the component (B) is an active ester compound having a styryl group.
[7] The resin composition according to the above [6], 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 according to any one of the above [1] to [7], 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 the above [1] to [8], which is used for forming an insulating layer of a printed wiring board.
[10] A sheet-like laminated material containing the resin composition according to any one of the above [1] to [9].
[11] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [9] above.
[12] A semiconductor device including the printed wiring board according to the above [11].

According to the present invention, a resin composition capable of obtaining a cured product having a high glass transition temperature, good adhesion to a conductor layer, and low dielectric adjacency; a sheet-like laminated 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 with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.

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

[1. Outline 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 has a molecular structure site formed by the reaction of the unsaturated bond site of the component (B) and the unsaturated hydrocarbon group of the component (C). including. This molecular structure site has a small polarity due to the action of the unsaturated bond site of the component (B) and the unsaturated hydrocarbon group of the component (C). Therefore, the polarity of the cured product becomes small, and the value of the dielectric loss tangent can be reduced.
Further, the cured product formed by curing the resin composition of the present invention has a molecular structure site formed by the reaction between the unsaturated bond site of the component (B) and the unsaturated hydrocarbon group of the component (C). In addition, it contains a molecular structure site formed by the reaction of the active ester moiety of the component (B) and the component (A). Therefore, the crosslink density becomes dense (that is, the structure becomes dense), and the glass transition temperature of the cured product becomes high. Further, when the crosslink density becomes dense, the mechanical strength of the cured product is improved, and peeling accompanied by destruction of the cured product is less likely to occur, so that the adhesion between the cured product and the conductor layer is excellent.

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

[2. (A) Epoxy resin]
The resin composition of the present invention contains the component (A). Since the cured product has a molecular structure portion formed by reacting the active ester moiety of the component (A) and the active ester moiety of the component (B), the structure becomes dense, the glass transition temperature of the cured product is high, and the adhesion is excellent. It becomes a thing.
Examples of the component (A) include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type epoxy. Resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, Cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, Examples thereof include naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, and halogenated epoxy resin.

Among these, the 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 from the viewpoint of improving adhesion. A type epoxy resin, a glycidyl ester type epoxy resin, and an anthracene type epoxy resin are preferable, and an epoxy resin containing an aromatic skeleton is preferable from the viewpoint of reducing the average linear thermal expansion rate. 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 resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, and naphthol type epoxy resin. One or more kinds of epoxy resins are preferable, and one or more kinds of epoxy resins selected from the group consisting of bisphenol A type epoxy resin, biphenyl type epoxy resin, and naphthalene type epoxy resin are more preferable.

Further, the resin composition preferably 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 to 100% by mass of the non-volatile component of the component (A) 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 may have three or more epoxy groups in one molecule as the component (A) and may be referred to as a solid epoxy resin at a temperature of 20 ° C. (hereinafter, referred to as "solid epoxy resin"). ) Is preferably included.

As the component (A), one type may be used alone, or two or more types may be used in combination at an arbitrary 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 a solid epoxy resin and two or more epoxy groups in one molecule as the component (A), and is a liquid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as "liquid epoxy resin"). In some cases), it is preferable to include in combination. By using a liquid epoxy resin and a solid epoxy resin in combination as the 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. it can.

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

Examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "YL980", "828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation. , "Epicoat 828EL" (bisphenol A type epoxy resin); "jER806H", "jER807", "YL983U", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER152" manufactured by Mitsubishi Chemical Co., Ltd. ( Phenol novolac type epoxy resin); Mitsubishi Chemical Co., Ltd. "630", "630LSD" (glycidylamine type epoxy resin); Nippon Steel & Sumitomo Metal Chemical Co., Ltd. "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) Product); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., Ltd .; "Selokiside 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Co., Ltd .; "PB-3600" manufactured by Daicel Co., Ltd. (Epoxy resin having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd. can be mentioned. These may be used alone or in combination of two or more at any ratio.

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

Examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; "N-690", "N-695" (cresol novolac type epoxy resin); "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin) manufactured by DIC; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC; Nippon Kayakusha "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayakusha; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayakusha; "NC3000H", "NC3000", "NC3000L" manufactured by Nippon Kayakusha, "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol naphthalene type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation; "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation; "YL6121" (biphenyl type epoxy resin); "YX4000H", "YX4000", "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX8800" (anthracen type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; Osaka Gas "PG-100" and "CG-500" manufactured by Chemical Co., Ltd .; "YL7760" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol AF type epoxy resin); "YL7800" manufactured by Mitsubishi Chemical Co., Ltd. (fluorene type epoxy resin); "JER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation can be mentioned. These may be used alone or in combination of two or more at any ratio.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (A), their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.1 to 1:15. It is preferably 1: 0.5 to 1:10, and particularly preferably 1: 1 to 1: 8.
When the mass ratio of the liquid epoxy resin is in such a range, sufficient flexibility is obtained when used in the form of an adhesive film, handleability is improved, and sufficient fluidity at the time of laminating is obtained. be able to.
When the mass ratio of the solid epoxy resin is in such a range, the viscosity of the epoxy resin can be reduced, and the degassing property at the time of vacuum lamination can be improved when used in the form of an adhesive film. In addition, the peelability of the protective film and the support film during vacuum lamination can be improved, and the heat resistance after curing can be improved.

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

The weight average molecular weight of the component (A) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500, from the viewpoint of remarkably obtaining the desired effect of the present invention.
The weight average molecular weight of the component (A) can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method. For example, the weight average molecular weight of the resin is such that LC-9A / RID-6A manufactured by Shimadzu Corporation is used as a measuring device, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Co., Ltd. is used as a column, and chloroform or the like is used as a mobile phase. Can be measured at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.

The amount of the 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 from the viewpoint of obtaining an insulating layer exhibiting a high glass transition temperature and high adhesion. It is more preferably 10% by mass or more, still more preferably 20% by mass or more. The upper limit of the amount of the 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. It is mass% or less.

[3. (B) Active ester compound having a carbon-carbon unsaturated bond]
The resin composition of the present invention contains the component (B). By using the component (B), it reacts with both the components (A) and (C) to form a cured product.
Since the cured product has a molecular structure site formed by the reaction of the unsaturated bond site of the component (B) and the component (C), the polarity of the cured product is reduced and the value of dielectric loss tangent is reduced. be able to.
Further, since the cured product has a molecular structure portion formed by the reaction of the active ester moiety of the component (B) and the component (A), the structure becomes dense and the glass transition temperature of the cured product is high. It has excellent adhesion.

Conventionally, when two resins having different reactivity are used in combination, the miscibility of each resin is poor, and it is difficult to form a cured product uniformly. Therefore, it was difficult to simultaneously express the above effects at a high level.
On the other hand, in the resin composition of the present invention, the component (B) has a site capable of reacting with two resins having different reactivity in the same compound. Therefore, the component (B) can connect the resins to form a cured product, and a uniform cured product can be formed. Therefore, the above-mentioned characteristics can be simultaneously expressed at a high level, and the desired effect of the present invention can be obtained.
Furthermore, when the component (B) is used, the miscibility of the component (A), the component (B) and the component (C) can be improved. Therefore, the uniformity of the composition in the cured product can be improved, and the above effect can be obtained at a higher level.

Examples of the carbon-carbon unsaturated bond include a carbon-carbon double bond and a carbon-carbon triple bond. Of these, a carbon-carbon double bond is preferable. Examples of the carbon-carbon double bond include a vinyl group, a methacrylic group, an acrylic group, an allyl group, a styryl group, and a propenyl group. Of these, 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。 The component (B) preferably 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.

In the general formula (1), m is preferably an integer of 1 to 6, and more preferably an integer of 1 to 3. Further, 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. Within such a numerical range, the component (B) can react with the component (C) at an appropriate ratio, and a decrease in dielectric loss tangent can be realized.

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 having different m and n values of the compound represented by the general formula (1). In the case of a mixture, the component (B) contains a compound represented by the general formula (1), and a compound in which n is 0 in the general formula (1) (a compound represented by the following formula (0-1)). Alternatively, it may contain a compound in which n is an integer of 1 to 20 and m is 0 (a compound 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, further preferably 3% by mass or less, and particularly preferably 1% by mass or less and 0% by mass. Within such a range, the component (B) can react with the component (C) at an appropriate ratio, and a decrease in dielectric loss tangent can be realized.

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

As the compound represented by the general formula (1), a commercially available product may be used, or a synthetic product may be used. Examples of commercially available products include the trade name "PC1300-02-65MA" (manufactured by Air Water Inc.).

The amount of the 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 low dielectric loss tangent, high glass transition temperature, and high adhesion. By mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more. The upper limit of the amount of the component (B) 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, and further preferably 60% by mass or less.

[4. (C) Resin having unsaturated hydrocarbon group]
The resin composition of the present invention contains the component (C). Since 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 can be reduced and the value of dielectric loss tangent can be reduced. ..
The component (C) is not particularly limited as long as it has an unsaturated hydrocarbon group. By using an unsaturated hydrocarbon group, the dielectric loss tangent of the cured product can be reduced. The unsaturated hydrocarbon is preferably an acrylic group, a methacrylic group, a styryl group, or an olefin group. Above all, it is more preferable to have a styryl group from the viewpoint of excellent heat resistance.
Here, the "olefin group" refers to an aliphatic hydrocarbon group having a carbon-carbon double bond in the molecule. For example, an allyl group, a vinyl group, and a propenyl group can be mentioned.

As the component (C), a compound represented by the following general formula (2) is preferable.

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 the general formula (2), R ^{1 to} R ⁶ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and are preferably hydrogen atoms. 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 the general formula (3), B represents a structure represented by the following general formula (B-1), (B-2) or (B-3).

一般式（４）中、Ｄは、下記一般式（５）で表される構造を表す。

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

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 the general formula (5), R ^{7 to} R ¹⁴ independently represent a hydrogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms, and are 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 of 0 to 100 in which at least one of them 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 the general formula (B-1), R ^{15 to} R ¹⁸ independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and are preferably a hydrogen atom or a methyl group.
In the general formula (B-2), R ^{19 to} R ²⁶ independently represent a hydrogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms, and are preferably a hydrogen atom or a methyl group.
In the general formula (B-3), R ^{27 to} R ³⁴ independently represent a hydrogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms, and are preferably a hydrogen atom or a methyl group. E represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

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

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 the general formula ^(6), R 1 to R ⁶ in general formula (2) has the same meaning as ^R 1 to R ⁶ of the, B has the same meaning as the general formula (3) in B, a, b Is synonymous with a and b in the general formula (5).

Examples of the commercially available component (C) include a styrene-modified polyphenylene ether resin (“OPE-2St 1200 (number average molecular weight 1200)” manufactured by Mitsubishi Gas Chemicals, Inc., equivalent to the general formula (6)), and a bixilenol diallyl ether resin. (Mitsubishi Chemical Co., Ltd. "YL7776 (number average molecular weight 331)", equivalent to formula (7)), Dioxane acrylic monomer glycol diacrylate (Shin-Nakamura Chemical Co., Ltd. "A-DOG (number average molecular weight 326)", formula (8) ) Equivalent).

The number average molecular weight of the 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 the melt viscosity of the resin composition from increasing too much. It is in the range of ~ 3000. The number average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (polystyrene conversion). As the number average molecular weight by the GPC method, for example, LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Corporation as a column are used as mobile phases. It can be measured at a column temperature of 40 ° C. using chloroform or the like, and calculated using a standard polystyrene calibration curve.

The amount of the component (C) in the resin composition is preferably 3% by mass or more, more preferably 5 with respect to 100% by mass of the resin component in the resin composition, from the viewpoint of reducing the value of the dielectric loss tangent of the cured product. By mass or more, more preferably 10% by mass or more. The upper limit of the amount of the component (C) is arbitrary as long as the effect of the present invention is exhibited, and is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

[5. Hardener]
The resin composition may contain a curing agent different from the 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 a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent. Be done. Above all, an active ester-based 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 alone or in combination of two or more at an arbitrary ratio.

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

Examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "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 & Sumitomo Metal Corporation , "SN-395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P" manufactured by DIC, and the like.

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

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

Examples of the active ester-based curing agent include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoyl product of phenol novolac. Is preferable, and an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Examples of commercially available active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "EXB-8000L-65TM", and "HPC-8000H-" manufactured by DIC. "65M" (active ester compound containing dicyclopentadiene type diphenol structure), "EXB-9416L-70BK" manufactured by DIC (active ester compound containing naphthalene structure), "DC808" manufactured by Mitsubishi Chemical Co., Ltd. (phenol novolac) Active ester compound containing acetylated product), "YLH1026" manufactured by Mitsubishi Chemical Corporation (active ester compound containing benzoylated product of phenol novolac), "EXB-9050L-62M" manufactured by DIC (phosphorus atom-containing active ester compound), etc. Can be mentioned.

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

The cyanate ester-based curing agent is not particularly limited. For example, novolak type cyanate ester type curing agent such as phenol novolac type and alkylphenol novolak type; dicyclopentadiene type cyanate ester type curing agent; bisphenol type cyanate ester type curing agent such as bisphenol A type, bisphenol F type and bisphenol S type. Agents; and prepolymers in which these are partially triazined. Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidene diphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; phenol Examples thereof include polyfunctional cyanate resins derived from novolak, cresol novolak, and the like; and prepolymers in which these cyanate resins are partially triazined. Commercially available products include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins) manufactured by Ronza Japan Co., Ltd., and "BA230" (part or all of bisphenol A disicanate is triazined to form a trimer. Prepolymer).

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

The curing agent is preferably one or more selected from a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a carbodiimide-based curing agent, and at least one of the phenol-based curing agent and the active ester-based curing agent. It is more preferable that

When the number of epoxy groups of the component (A) is 1, the lower limit of the number of reaction 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 having good mechanical strength. It is more preferably 0.3 or more, and particularly preferably 0.4 or more. The upper limit is preferably 2 or less, more preferably 1.5 or less, still 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 differs depending on the type of the curing agent. The "number of epoxy groups of the component (A)" is a value obtained by dividing the solid content mass of each epoxy resin in the resin composition by the epoxy equivalent and the total value for all the epoxy resins. Further, the "number of reactive groups of the curing agent" is a value obtained by dividing the solid content mass of each curing agent present in the resin composition by the reactive group equivalent and the total value for all the curing agents. (A) By setting the amount ratio of the epoxy resin and the curing agent within such a range, the heat resistance of the cured product of the resin composition can be further improved.

The content of the curing agent in the resin composition is not particularly limited. For example, with respect to 100% by mass of the resin component in the resin composition, 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. 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 in such a range, a cured product having more excellent linear thermal expansion coefficient, dielectric loss tangent, and adhesion to the conductor layer of the resin composition can be formed.

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

The material of the component (D) is not particularly limited, but for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, etc. 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 Examples thereof include bismuth acid acid, titanium oxide, zirconate oxide, barium titanate titanate, barium zirconate titanate, calcium zirconate, zirconate zirconate, and zirconate titnate tantistate. Among these, silica is preferable, amorphous silica, crushed silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica are more preferable, and fused silica and spherical silica are used from the viewpoint of reducing the surface roughness of the insulating layer. Silica is more preferable, and spherical fused silica is particularly preferable. As the component (D), one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

Usually, the component (D) is contained in the resin composition in the form of particles. The average particle size of the particles of the component (D) is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 2 μm or less, particularly preferably, from the viewpoint of improving circuit embedding property and obtaining an insulating layer having a small surface roughness. Is 1 μm or less, 0.8 μm or less, 0.6 μm or less, 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, from the viewpoint of preventing the viscosity of the varnish from increasing and the handleability from decreasing when the resin varnish is used. It is preferably 0.05 μm or more, particularly preferably 0.07 μm or more, and 0.1 μm or more.

Examples of commercially available products of the component (D) having an average particle size as described above include "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; "YC100C" and "YA050C" manufactured by Admatex Co., Ltd. , "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama; "SC2500SQ" manufactured by Admatex , "SO-C4", "SO-C2", "SO-C1".

The average particle size of the particles such as the component (D) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. For example, a laser diffraction / scattering type particle size distribution measuring device can measure the particle size distribution of particles on a volume basis, and the average particle size can be measured as the median diameter from the particle size distribution. As the measurement sample, those in which the particles are dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd. or the like can be used.

The component (D) may be surface-treated with any surface treatment agent. Examples of the surface treatment agent include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, alkoxysilane compounds, organosilazane compounds, titanate-based coupling agents, and the like. By surface-treating the component (D) with these surface treatment agents, the moisture resistance and dispersibility of the 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., and Shin-Etsu Chemical Co., Ltd. "KBM-803" (3-mercaptopropyltrimethoxysilane) manufactured by Kagaku Kogyo Co., Ltd., "KBE-903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd. ( N-phenyl-3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. Examples thereof include "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by the company. Further, the surface treatment agent may be used alone or in combination of two or more at an arbitrary ratio.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the component (D). (D) a carbon amount per unit surface area of the component, from the viewpoint of improving dispersibility of the component (D), preferably 0.02 mg / ^{m 2} or more, more preferably 0.1 mg / ^{m 2} or more, particularly preferably 0 .2 mg / m ² 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 sheet form, the amount of carbon is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, particularly preferably. Is 0.5 mg / m ² or less.

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

The lower limit of the amount of the component (D) in the resin composition is preferably 100 parts by mass or more, more preferably 100 parts by mass or more, based on 100 parts by mass of the resin component in the resin composition from the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion. It is 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 further preferably 350 parts by mass or less from the viewpoint of mechanical strength of the insulating layer, particularly elongation.

[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 the present specification), if necessary. By using the component (E), curing can be promoted when the resin composition is cured.

Examples of the component (E) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, peroxide-based curing accelerators, and the like. .. Of these, 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, and peroxides are preferred. A physical curing accelerator or a metal curing accelerator is more preferable.
The component (E) may be used alone or in combination of two or more at an arbitrary ratio.

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

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. [5,4,0] -Undesen can be mentioned. Of these, 4-dimethylaminopyridine and 1,8-diazabicyclo [5,4,0] -undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 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-undecyl imidazolium trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 2,4-diamino-6 -[2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2, 4-Diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')] -ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')] -Ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3- Dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline imidazole compound and imidazole compound and epoxy resin Adduct body can be mentioned. Of these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

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

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

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

Examples of the peroxide-based curing accelerator include cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, and diisopropylbenzene hydro. Examples thereof include peroxide, cumene hydroperoxide, and tert-butyl hydroperoxide.

As the peroxide-based curing accelerator, a commercially available product may be used, and examples thereof include "Park Mill D" manufactured by NOF CORPORATION.

The amount of the 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 remarkably obtaining the desired effect 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 “component (F)” in the present specification). Examples of the component (F) include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and poly. Examples thereof include ether ether ketone resin, polyester resin, and indenkumaron resin. Of these, the indene marron resin is preferable from the viewpoint of improving compatibility. The component (F) may be used alone or in combination of two or more at an arbitrary ratio.

The polystyrene-equivalent weight average molecular weight of the 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. ..
The polystyrene-equivalent weight average molecular weight of the component (F) is measured by a gel permeation chromatography (GPC) method. For example, the polystyrene-equivalent weight average molecular weight of component (F) is determined by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Co., Ltd. as a column. , Chloroform or the like is used as the mobile phase, the measurement can be performed at a column temperature of 40 ° C., and the calculation can be performed using a standard polystyrene calibration curve.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpen. Examples thereof include phenoxy resins having one or more skeletons selected from the group consisting of skeletons and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more at any ratio.

Examples of the phenoxy resin include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are bisphenol A skeleton-containing phenoxy resins); "YX8100" manufactured by Mitsubishi Chemical Corporation (bisphenol S skeleton-containing phenoxy resin); "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin); "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Corporation; "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL7769BH30" manufactured by Mitsubishi Chemical Corporation. Examples thereof include "YL6794", "YL7213", "YL7290", "YL7891BH30" and "YL7482".

Examples of the indene marron resin include "H-100", "WS-100G", "WS-100H", "WS-120V", and "WS-100GC" manufactured by Nikko Kagaku Co., Ltd .; manufactured by Novales Lutgers. "C10", "C30", "CA80" can be mentioned.

The lower limit of the amount of the component (F) in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on 100% by mass of the resin component in the resin composition. The upper limit thereof is preferably 10% by mass or less, more preferably 5% by mass or less. Within such a range, the effect of improving the film molding ability and the mechanical strength can be exhibited, and further, the melt viscosity can be increased and the roughness of the surface of the insulating layer after the wet roughening step can be lowered.

[9. Optional ingredient]
The resin composition of the present invention may contain an arbitrary component in addition to the above-mentioned components. Such optional components include, for example, flame retardants; organic fillers; organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; thickeners; defoaming agents; leveling agents; adhesion-imparting agents; Examples thereof include resin additives such as colorants.

<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 the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. As the flame retardant, a commercially available product 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. The flame retardant may be used alone or in combination of two or more at any ratio.

The amount of the flame retardant in the resin composition is preferably in the range of 0.5 to 20% by mass, preferably 0.5% by mass to 100% by mass, based on 100% by mass of the resin component in the resin composition from the viewpoint of imparting heat resistance. The range of 15% by mass is more preferable, and the range of 0.5 to 10% by mass is further preferable.

<Organic filler>
In the resin composition of the present invention, the flexibility of the cured product of the resin composition can be improved by using the organic filler, so that the extensibility of the insulating layer can be improved.
As the organic filler, any organic filler that can be used when forming the insulating layer of the printed wiring board can be used. For example, rubber particles, polyamide particles, and silicone particles can be mentioned. 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. The organic filler may be used alone or in combination of two or more at any ratio.

The average particle size of the particles of the organic filler is preferably 5 μm or less, more preferably 4 μm or less, still 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.

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 from the viewpoint of adjusting the mechanical properties of the cured product of the resin composition to an appropriate range. The range of mass% is preferable, the range of 0.2 to 10% by mass is more preferable, the range of 0.3 to 5% by mass is further preferable, and the range of 0.5 to 3% by mass is particularly preferable.

[10. Manufacturing method and characteristics of resin composition]
The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which a compounding component is added with a solvent or the like as necessary and mixed and dispersed using a rotary mixer or the like.

The resin composition of the present invention can provide a cured product having 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> described later. Specifically, by performing thermomechanical analysis by the tensile weighting method, it is possible to measure at a load of 1 g and a heating rate of 5 ° C./min. The 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 having 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> described later. 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 value of the dielectric loss tangent is preferably 0.0037 or less, more preferably 0.0035 or less, from the viewpoint of preventing heat generation at high frequencies, 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> described later. The adhesion between the obtained 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 adhesiveness is not particularly limited, and may 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 the 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), and can be used between layers of the printed wiring board. It can be more preferably used as a resin composition for forming an insulating layer (resin composition for an interlayer insulating layer of a printed wiring board). The resin composition of the present invention also requires a resin composition such as an adhesive film, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, and a component embedding resin. Can be used in a wide range of applications.

[11. Sheet-shaped laminated material]
The resin composition of the present invention can be applied and used in a varnished state, but industrially, it is generally preferable to use the resin composition in the form of a sheet-like laminated material containing the resin composition.

As the sheet-like laminated material, the following adhesive films and prepregs are preferable.

In one embodiment, the adhesive film comprises a support and a resin composition layer (adhesive layer) bonded to the support, and 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, particularly preferably 50 μm or less, 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 may be usually 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more, and the like.

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

When a film made of a plastic material is used as the support, the plastic material includes, for example, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); acrylic such as polycarbonate (PC) and polymethylmethacrylate (PMMA). Cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

The surface of the support on the side to be joined with the resin composition layer may be matted or corona-treated. Further, as the support, a support with a release layer having a release layer on the surface on the side to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, olefin resin, urethane resin, and silicone resin. .. Examples of commercially available release agents include "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, which are alkyd resin-based mold release agents.

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

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

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

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, and the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30 to 60% by mass of an organic solvent is used, 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 similar 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 and the like from adhering to the surface of the resin composition layer and scratches. The adhesive film can be rolled up and stored. If the adhesive film has a protective film, it can be used by peeling off the protective film.

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

The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for the prepreg such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-shaped 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-shaped fiber base material is not particularly limited. Usually, it is 10 μm or more.

The prepreg can be produced 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 above-mentioned adhesive film.

In the present invention using a resin composition containing a combination of the component (A), the component (B), and the component (C), the glass transition temperature is high, the dielectric loss tangent is low, and the adhesion to the conductor layer is good. It is possible to realize a sheet-like laminated material which is extremely useful in the production of a printed wiring board, which brings about a cured product.

The sheet-shaped 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 (printed). It can be more preferably used for the interlayer insulating layer of the wiring board).

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

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

The "inner layer substrate" used in the step (I) is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate or the like, or one or both sides of the substrate. A circuit board on which a patterned conductor layer (circuit) is formed. Further, the "inner layer substrate" of the present invention also includes an inner layer circuit board of an intermediate product in which at least one of an insulating layer and a conductor layer should be formed when the printed wiring board is manufactured. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components may be used.

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

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

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

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

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

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

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

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

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

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

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 when an adhesive film is used.

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

Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

The swelling liquid is not particularly limited. For example, an alkaline solution and a surfactant solution can be mentioned. An alkaline solution is preferable, and as the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Dip Security SBU" and "Swelling Dip Security SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited. For example, it can be carried out by immersing the insulating layer in a swelling liquid at 30 to 90 ° C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured product in a swelling solution 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 mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in the oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate 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. Further, the neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan.

The treatment with the neutralizing solution can be carried out by immersing the treated surface that has been roughened with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with an oxidizing agent in a neutralizing solution at 40 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 is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). A layer formed from a nickel alloy and a copper / titanium alloy) can be mentioned. Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. An alloy layer of a nickel alloy or a copper-titanium alloy is preferable, and a monometal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single copper is preferable. A metal layer is more preferred.

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

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

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

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

The metal foil can be produced by a known method such as an electrolysis method or a rolling method. Examples of commercially available metal foils include HLP foils and JXUT-III foils manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foils and TP-III foils manufactured by Mitsui Mining & Smelting Co., Ltd.

When a printed wiring board is manufactured using the resin composition of the present invention containing a combination of the component (A), the component (B), and the component (C), the conductor layer is formed by plating or a metal foil is used. Regardless of whether it is formed or not, the adhesion between the conductor layer and the insulating layer can be remarkably improved.

[13. Semiconductor device]
The 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 electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.).

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

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

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

<Example 1>
Stir 25 parts of bixilenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent about 185) and 10 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. "828US", epoxy equivalent about 180) to 25 parts of solvent naphtha. While heating and dissolving, it was then cooled to room temperature. 315 parts of an inorganic filler (“SO-C2” manufactured by Admatex Co., Ltd., average particle size 0.5 μm, carbon amount 0.38 mg / m ² per unit surface area) was mixed, and kneaded and dispersed by three rolls. There, 69.2 parts of an active ester-based curing agent having a vinyl group (“PC1300-02-65MA” manufactured by Air Water Co., Ltd., a methylamylketone solution having an active group equivalent of about 199 and a non-volatile content of 65%) and a vinyl group were added. 25 parts of resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemicals Co., Ltd., toluene solution with 60% non-volatile content), 15 parts of indenkumaron resin ("H-100" manufactured by Nikko Chemical Co., Ltd.), 4-as a curing accelerator Mix 2 parts of a 5% MEK solution of dimethylaminopyridine (DMAP) and 0.13 part of dicumyl peroxide (“Park Mill D” manufactured by Nichiyu Co., Ltd.) and uniformly disperse with a rotary mixer to obtain resin varnish 1. Made.

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

<Example 2>
In Example 1, an active ester-based curing agent having a vinyl group (“PC1300-02-65MA” manufactured by Air Water Co., Ltd., a methylamylketone solution having an active group equivalent of about 199 and a non-volatile content of 65%) in 69.2 parts was 30 parts. .8 parts was changed to 30.8 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC, a toluene solution having an active group equivalent 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 items.

<Example 3>
In Example 1, a resin having a vinyl group ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Inc.) in which 5 out of 25 parts of a bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) is a non-volatile component. 60% toluene solution) 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 items.

<Example 4>
In Example 1, 25 parts of a resin having a vinyl group (“OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Company, a toluene solution having a non-volatile content of 60%) was added to 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 items.

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

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

<Comparative example 3>
In Example 1, 69.2 parts of an active ester-based curing agent having a vinyl group (“PC1300-02-65MA” manufactured by Air Water Co., Ltd., a methylamylketone solution having an active group equivalent of about 199 and a non-volatile content of 65%) was activated. The ester-based curing agent (“EXB-9416L-70BK” manufactured by DIC, a toluene solution having 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 items.

[Evaluation methods]
The adhesive films obtained in the above-mentioned 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 heat-cured at 190 ° C. for 90 minutes, and the PET of the support was peeled off to prepare a sheet-shaped sample for evaluation of the cured product.

<Measurement of dielectric loss tangent>
A test piece having a width of 2 mm and a length of 80 mm was cut out from the sample for evaluation of cured physical properties. The cut out test piece was measured for dielectric positive contact 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 case of 0.0035 or less was evaluated as "excellent", a case of 0.0037 or less was evaluated as "good", and a case of more than 0.0037 was evaluated as "poor".

<Measurement of glass transition temperature>
A sample for evaluation of cured physical properties is cut into test pieces having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis is performed by a tensile weighting method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). went. Specifically, after the test piece was attached to the thermomechanical analyzer, measurements were taken twice in succession under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. Then, in the second measurement, the glass transition temperature (Tg; ° C.) was calculated.
When the temperature was higher than 138 ° C, it was evaluated as “good”, and when it was lower than 138 ° C, it was evaluated as “bad”.

<Measurement of adhesion>
(1) Base treatment of copper foil The glossy surface of "3EC-III" (electric field copper foil, 35 μm) manufactured by Mitsui Metal Mining Co., Ltd. is immersed in Mech Etch Bond "CZ-8101" manufactured by Mech Co., Ltd. to roughen the copper surface. (Ra value = 1 μm) was performed, and a rust preventive treatment (CL8300) was applied. This copper foil is called CZ copper foil. Further, it was heat-treated in an oven at 130 ° C. for 30 minutes.

(2) Lamination of Copper Foil and Formation of Insulation Layer The adhesive film produced in Examples and Comparative Examples is subjected to a resin composition layer as an inner layer using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Co., Ltd.). Both sides of the inner layer circuit board were laminated so as to be bonded to the circuit board. The laminating treatment was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. The PET film as a support was peeled off from the laminated adhesive film. The treated surface of the CZ copper foil of "3EC-III" was laminated on the resin composition layer under the same conditions as described above. Then, a sample was prepared 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. Use a cutter to make a notch in a small piece of copper foil with a width of 10 mm and a length of 100 mm, peel off one end of the copper foil, and use a gripper (manufactured by JIS, Autocom type testing machine, " AC-50C-SL "), and using an Instron universal tester, measure the load when 35 mm is peeled off vertically at a speed of 50 mm / min at room temperature in accordance with JIS C6481. , "Adhesion".
The case of more than 0.3 kgf / cm was evaluated as "good", and the case of less than 0.3 kgf / cm was evaluated as "poor".

<Result>
The results of the above-mentioned Examples and Comparative Examples are shown in the table below. In the table below, the meanings of the abbreviations are as follows.
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-based curing agent having a vinyl group (“PC1300-02-65MA” manufactured by Air Water Inc.)
HPC-8000: Active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation)
EXB-8000L: Active ester-based curing agent ("EXB-8000L-65TM" manufactured by DIC Corporation)
EXB-9416: Active ester-based curing agent ("EXB-9416L-70BK" manufactured by DIC Corporation)
OPE-2St 1200: Resin having a vinyl group ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Inc.)
A-DOG: Dioxane acrylic monomer ("A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
H-100: Indenkumaron resin (Nippon Kagaku "H-100")
SOC2: Spherical silica ("SO-C2" manufactured by Admatex)
Park Mill D: Dikmil Peroxide (NOF Corporation "Park Mill D")
DMAP: 4-Dimethylaminopyridine In the table, the blending amount is a solid content conversion value.

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

Claims (8)

It 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 content of the component (A) is 10 to 50% by mass when the resin component is 100% by mass.
The content of the component (C) is 3 to 30% by mass when the resin component is 100% by mass.
A resin composition in which the component (B) is an active ester compound having a styryl group. The resin composition according to claim 1, wherein the content of the component (B) is 10 to 60% by mass when the resin component is 100% by mass. The resin composition according to claim 1 or 2 , 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.) The resin composition according to any one of claims 1 to 3 , wherein the component (C) is a resin having an acrylic group, a methacrylic group, a styryl group, or an olefin group. The resin composition according to any one of claims 1 to 4 , which is used for forming an insulating layer of a printed wiring board. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 5 . A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 5 . A semiconductor device including the printed wiring board according to claim 7 .