JP2018044040A - Resin composition - Google Patents

Abstract

To provide a resin composition capable of obtaining a cured product having a high glass transition temperature, good adhesion to a conductor layer, and low dielectric loss tangent.
A resin composition containing (A) an epoxy resin, (B) an active ester compound having a carbon-carbon unsaturated bond, and (C) a resin having an unsaturated hydrocarbon group.
[Selection figure] None

Description

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

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

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

  Patent Document 2 discloses a resin composition comprising (A) a radical polymerizable compound, (B) an epoxy resin, (C) a curing agent, and (D) a roughening component. .

  As described above, many proposals for an epoxy resin composition suitable for forming an insulating layer of an inner circuit board have been made, but it has a good balance of characteristics such as low dielectric loss tangent and excellent heat resistance and adhesion. There is a growing demand for resin compositions capable of forming insulating layers.

JP 2014-47318 A JP 2014-34580 A

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

As a result of intensive studies on the above problems, the present inventor includes a combination of (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 present inventors have found that the above problems can be solved by using a resin composition, and have completed the present invention.
That is, the present invention includes the following contents.

（前記一般式（１）中、ｍは１〜６の整数を表し、ｎは１〜２０の整数を表す。）
〔８〕前記（Ｃ）成分が、アクリル基、メタクリル基、スチリル基、又はオレフィン基を有する樹脂である上記〔１〕〜〔７〕のいずれかに記載の樹脂組成物。
〔９〕プリント配線板の絶縁層形成用である上記〔１〕〜〔８〕のいずれかに記載の樹脂組成物。
〔１０〕上記〔１〕〜〔９〕のいずれかに記載の樹脂組成物を含む、シート状積層材料。
〔１１〕上記〔１〕〜〔９〕のいずれかに記載の樹脂組成物の硬化物により形成された絶縁層を含む、プリント配線板。
〔１２〕上記〔１１〕に記載のプリント配線板を含む、半導体装置。 [1] (A) Epoxy resin (hereinafter also referred to as “component (A)” in this specification), (B) Active ester compound having a carbon-carbon unsaturated bond (hereinafter referred to as “(B)” in this specification) And a resin composition containing (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 [1], wherein the content of the component (B) is 10 to 60% by mass when the resin component is 100% by mass.
[3] When the content of the component (A) is 10 to 50% by mass when the resin component is 100% by mass, and the content of the (C) component is 100% by mass of the resin component The resin composition according to [1] or [2], which is 3 to 30% by mass.
[4] The resin composition according to any one of [1] to [3], wherein the component (B) is an active ester compound having a carbon-carbon double bond.
[5] The resin composition according to [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 [5], wherein the component (B) is an active ester compound having a styryl group.
[7] The resin composition according to [6], wherein the component (B) includes 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 [1] to [7], wherein the component (C) is a resin having an acryl group, a methacryl group, a styryl group, or an olefin group.
[9] The resin composition according to any one of [1] to [8], which is used for forming an insulating layer of a printed wiring board.
[10] A sheet-like laminate material comprising the resin composition according to any one of [1] to [9].
[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].
[12] A semiconductor device including the printed wiring board according to [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 loss tangent; a sheet-like laminated material containing the resin composition; A printed wiring board and a semiconductor device including 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 exemplifications, and can be implemented with any modifications without departing from the scope of the claims of the present invention and the equivalents thereof.

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

[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 is a molecular structure site formed by the reaction of the unsaturated bond site of component (B) with the unsaturated hydrocarbon group of component (C). including. This molecular structure site has a small polarity due to the action of the unsaturated bond site of component (B) and the unsaturated hydrocarbon group of component (C). Therefore, the polarity of the cured product is reduced, and the value of dielectric loss tangent can be reduced.
Further, the cured product formed by curing the resin composition of the present invention is a molecular structure site formed by a reaction between the unsaturated bond site of the component (B) and the unsaturated hydrocarbon group of the component (C). In addition, it includes a molecular structure site formed by the reaction of the active ester site of the component (B) with 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. Furthermore, since the crosslink density is increased, 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.

Thus, since the resin composition of this invention has the reaction site | part which (B) component can react with (A) component and (C) component in a compound, (A) component and (C) component are included. The cured | curing material which show | plays simultaneously the effect which can be expressed when each is used independently can be formed.
Furthermore, when 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 separately used and when the component (B) is used, (A ) Component, (B) component, and (C) component can be improved in miscibility. Therefore, since the uniformity of the composition in the cured product can be improved, the above effect can be obtained at a higher level.

[2. (A) Epoxy resin]
The resin composition of this invention contains (A) component. When the cured product has a molecular structure site formed by the reaction of the active ester site of the component (A) and the component (B), the structure becomes dense, the glass transition temperature of the cured product is high, and the adhesiveness is excellent. It will be a thing.
Examples of the component (A) include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol type epoxies. 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, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, Cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic ring Epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin, and halogenated epoxy resins.

  Among these, as component (A), from the viewpoint of improving adhesion, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether Type epoxy resin, glycidyl ester type epoxy resin and 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 coefficient. 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 epoxy resins are preferable, and one or more epoxy resins selected from the group consisting of bisphenol A type epoxy resins, biphenyl type epoxy resins, and naphthalene type epoxy resins are more preferable.

  Moreover, it is preferable that a resin composition contains the epoxy resin which has a 2 or more epoxy group in 1 molecule as (A) component. The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 100% by mass of the nonvolatile component (A). 70% by mass or more. Among them, the resin composition has three or more epoxy groups in one molecule as the component (A) and is sometimes referred to as a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. ) Is preferably included.

  (A) A component may be used individually by 1 type and may be used combining 2 or more types by arbitrary ratios. Therefore, the resin composition may contain only a solid epoxy resin as the component (A), or may contain a combination of a solid epoxy resin and another epoxy resin. Among them, the resin composition has, as component (A), a solid epoxy resin and two or more epoxy groups in one molecule, and is a liquid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “liquid epoxy resin”). May be included in combination. As the component (A), by using a combination of a liquid epoxy resin and a solid epoxy resin, the flexibility of the resin composition may be improved, or the breaking strength of the cured product of the resin composition may be improved. it can.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. Preferred are cycloaliphatic epoxy resins, cyclohexanedimethanol type epoxy resins, glycidylamine type epoxy resins, and epoxy resins having a butadiene structure. Glycidylamine type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF Type epoxy resin and naphthalene type epoxy resin are more preferable.

  Examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC; “YL980”, “828US”, “jER828EL”, “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 Corporation; "jER152" manufactured by Mitsubishi Chemical Corporation ( Phenol novolac type epoxy resin); “630” and “630LSD” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) Product); Nagase Chemte "EX-721" (glycidyl ester type epoxy resin) manufactured by Susu; "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel; "PB-3600" (butadiene structure manufactured by Daicel) Epoxy resin having a resin composition; “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd. These may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

  Solid epoxy resins 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, naphthylene. Ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, tetraphenylethane type epoxy resins, and bixylenol type epoxy resins are preferred. Naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, naphthol type epoxy resins, and bixylenol 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 Kayaku Co., Ltd. “EPPN-502H” (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. “NC7000L” (naphtho Lunovolak type epoxy resin); “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin) manufactured by Nippon Kayaku; “ESN475V” (naphthol naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical; "YX4000H", "YX4000", "YX4000HK" manufactured by Mitsubishi Chemical (Bixylenol type epoxy resin); "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Company; "YL7760" (bisphenol manufactured by Mitsubishi Chemical Corporation) AF type epoxy resin); Mitsubishi Chemical "YL7800" of manufacturing (fluorene epoxy resin); "jER1010" of Mitsubishi Chemical Corporation (solid bisphenol A epoxy resin); manufactured by Mitsubishi Chemical Corporation "jER1031S" (tetraphenyl ethane epoxy resin) and the like. These may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

When the liquid epoxy resin and the 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. The ratio is preferably 1: 0.5 to 1:10, particularly preferably 1: 1 to 1: 8.
When the mass ratio of the liquid epoxy resin is within such a range, sufficient flexibility is obtained when used in the form of an adhesive film, handling is improved, and sufficient fluidity is obtained during lamination. be able to.
When the mass ratio of the solid epoxy resin is within such a range, the viscosity of the epoxy resin is reduced, and when used in the form of an adhesive film, the deaeration during vacuum lamination can be improved. Moreover, the peelability of the protective film and the support film can be improved during vacuum lamination, 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 within the above range, the crosslinked density of the cured product of the resin composition becomes sufficient, and an insulating layer having a small surface roughness can be obtained.
The 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 still more preferably 400 to 1500 from the viewpoint of remarkably obtaining the desired effect of the present invention.
The weight average molecular weight of component (A) can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC). For example, the weight average molecular weight of the resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column, chloroform, etc. as a mobile phase. Can be calculated at a column temperature of 40 ° C. 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 having a high glass transition temperature and high adhesion. More preferably, it is 10 mass% or more, More preferably, it is 20 mass% or more. The upper limit of the amount of component (A) is arbitrary as long as the effect of the present invention is exhibited, 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 below mass%.

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

Conventionally, when two resins having different reactivities are used in combination, the miscibility of each resin is poor, and a cured product is hardly formed uniformly. Therefore, it has been 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 reactivities in the same compound. Therefore, (B) component can connect each resin, can form hardened | cured material, and can form uniform hardened | cured material. Therefore, the above characteristics can be expressed simultaneously at a high level, and the desired effect of the present invention can be achieved.
Furthermore, when the component (B) is used, the miscibility of the component (A), the component (B) and the component (C) can be improved. Therefore, since the uniformity of the composition in the cured product can be improved, 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. Among these, a carbon-carbon double bond is preferable. Examples of the carbon-carbon double bond include a vinyl group, a methacryl group, an acrylic group, an allyl group, a styryl group, and a propenyl group. Among 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。 (B) As a component, it is preferable that the compound represented by following General formula (1) is included.

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

  In general formula (1), m is preferably an integer of 1 to 6, more preferably an integer of 1 to 3. 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. By being in such a numerical range, the component (B) reacts 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 values of m and n of the compound represented by the general formula (1). In the case of a mixture, as long as the component (B) includes a compound represented by the general formula (1), a compound in which n is 0 in the general formula (1) (a compound represented by the following formula (0-1)) Or n is an integer of 1-20 and m may contain the compound (compound represented by the following general formula (0-2)) which is 0.
The total proportion of the compound represented by the formula (0-1) and the compound represented by the general formula (0-2) is preferably 10% by mass or less with respect to 100% by mass of the component (B). More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less, Most preferably, it is 1 mass% or less, 0 mass%. By being within such a range, the component (B) reacts with the component (C) at an appropriate ratio, and a decrease in dielectric loss tangent can be realized.

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

  A commercially available product or a synthetic product may be used as the compound represented by the general formula (1). As a commercial item, a brand name "PC1300-02-65MA" (made by Air Water) is mentioned, for example.

  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 having a low dielectric loss tangent, a high glass transition temperature, and high adhesion. It is at least 10% by mass, more preferably at least 10% by mass, and even more preferably at least 20% by mass. The upper limit of the amount of 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 an unsaturated hydrocarbon group]
The resin composition of this invention contains (C) component. When the cured product has a molecular structure site formed by the reaction of the unsaturated bond sites of the component (C) and the component (B), the polarity of the cured product is reduced and the value of the dielectric loss tangent can be reduced. .
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 methacryl group, a styryl group, or an olefin group. Among these, 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 are 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 general formula (2), R < ¹ > -R < ⁶ > represents a hydrogen atom or a C1-C4 alkyl group each independently, Preferably it is a hydrogen atom. A represents the structure represented by the following general formula (3) or the following general formula (4).

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

In general formula (3), B represents the 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 general formula (4), D represents the 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 General Formula (5), R ^{7 to} R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and preferably a hydrogen atom or a methyl group. In particular, R ⁷ , R ⁸ , R ¹³ and R ¹⁴ are more preferably a methyl group. a and b are integers of 0 to 100, at least one of which is not 0. B represents a structure represented by the following general formula (B-1), (B-2) or (B-3).

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

In the general formula ^{(B-1), R 15} ~R 18 are independently a hydrogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms, preferably a hydrogen atom or a methyl group.
In General Formula (B-2), R ^{19 to} R ²⁶ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and preferably a hydrogen atom or a methyl group.
In general formula (B-3), R < ²⁷ > -R < ³⁴ > represents a hydrogen atom, a C6 or less alkyl group, or a phenyl group each independently, Preferably they are 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 styrene-modified polyphenylene ether resin ("OPE-2St 1200 (number average molecular weight 1200)" manufactured by Mitsubishi Gas Chemical Co., Ltd., equivalent to general formula (6)), bixylenol diallyl ether resin. ("YL7776 (number average molecular weight 331)" manufactured by Mitsubishi Chemical Corporation, equivalent to formula (7)), dioxane acrylic monomer glycol diacrylate ("A-DOG (number average molecular weight 326)" manufactured by Shin-Nakamura Chemical Co., Ltd.), 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 excessively increasing. It is in the range of ~ 3000. In addition, the number average molecular weight in this invention is measured by the 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, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column, and mobile phase It can be measured using chloroform or the like at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.

  The amount of 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. It is at least 10% by mass, more preferably at least 10% by mass. The upper limit of the amount of component (C) is arbitrary as long as the 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. Curing agent]
Unless the effect of this invention is impaired, the resin composition may contain the hardening | curing agent different from (B) component. The curing agent is not particularly limited, and examples thereof include a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester curing agent, and a carbodiimide curing agent. It is done. Among these, an active ester curing agent is preferable from the viewpoint of obtaining an insulating layer having excellent adhesion to the conductor layer. In addition, a hardening | curing agent may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

  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. Of these, a triazine skeleton-containing phenol novolak curing agent or a triazine skeleton-containing naphthol novolak curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer.

  Examples of the phenol-based curing agent and naphthol-based curing agent include “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., “NHN”, “CBN” manufactured by Nippon Kayaku Co., Ltd. , “GPH”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485”, “SN-495”, “SN-375” manufactured by Nippon Steel & Sumikin Co., Ltd. ”,“ SN-395 ”,“ TD-2090 ”,“ LA-7052 ”,“ LA-7054 ”,“ LA-1356 ”,“ LA-3018-50P ”manufactured by DIC.

  The active ester curing agent is not particularly limited. For example, compounds having two or more ester groups with high reaction 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 curing agent is preferably obtained by a condensation reaction between at least one of a carboxylic acid compound and a thiocarboxylic acid compound and at least one of a hydroxy compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester 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, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  The active ester type curing agent includes an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac. The active ester compound containing a naphthalene structure and the active ester compound containing a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

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

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

  The cyanate ester curing agent is not particularly limited. For example, novolak type cyanate ester type curing agents such as phenol novolak type and alkylphenol novolak type; dicyclopentadiene type cyanate ester type curing agent; bisphenol type cyanate ester type curing such as bisphenol A type, bisphenol F type and bisphenol S type Agents, and prepolymers in which these are partially triazines. Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), 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 Novolac and K Polyfunctional cyanate resin derived from tetrazole novolac; and, these cyanate resins Some triazine of prepolymer. Commercially available products include “PT30”, “PT60” (both phenol novolac-type polyfunctional cyanate ester resins) and “BA230” (partially or all of bisphenol A dicyanate, trimerized by Lonza Japan Co., Ltd.) A prepolymer).

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

  The curing agent is preferably at least one selected from a phenolic curing agent, a naphthol curing agent, an active ester curing agent, and a carbodiimide curing agent, and at least any of a phenol curing agent and an active ester curing agent More preferably.

When the number of epoxy groups in the component (A) is 1, from the viewpoint of obtaining an insulating layer with good mechanical strength, the lower limit of the number of reactive groups of the curing agent is preferably 0.1 or more, more preferably 0.2 or more. More preferably, it is 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, and 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 varies depending on the type of the curing agent. Further, “the number of epoxy groups of component (A)” is a value obtained by totaling the values obtained by dividing the solid content mass of each epoxy resin in the resin composition by the epoxy equivalent for all epoxy resins. Furthermore, “the number of reactive groups of the curing agent” is a value obtained by totaling the values obtained by dividing the solid content mass of each curing agent present in the resin composition by the reactive group equivalent for all the curing agents. (A) By making the quantity ratio of an epoxy resin and a hardening | curing agent into such a range, the heat resistance of the hardened | cured material of a resin composition can be improved more.

  The content of the curing agent in the resin composition is not particularly limited. For example, the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, particularly preferably 18% by mass or less, with respect to 100% by mass of the resin component in the resin composition. It is 15 mass% or less. The lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, further 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 that is more excellent in the linear thermal expansion coefficient, dielectric loss tangent, and adhesion with the conductor layer of the resin composition can be formed.

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

  The material of the component (D) is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, titanium Bismuth oxide, titanium oxide, zirconium oxide, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is preferable, amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica are more preferable. From the viewpoint of reducing the surface roughness of the insulating layer, fused silica, spherical Silica is more preferred, and spherical fused silica is particularly preferred. (D) A component may be used individually by 1 type and may be used combining 2 or more types by arbitrary ratios.

  Usually, the component (D) is contained in the resin composition in the form of particles. The average particle size of the component (D) particles is preferably 5 μm or less, more preferably 3 μm or less, even more preferably 2 μm or less, particularly preferably from the viewpoint of improving the 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, or 0.4 μm or less. The lower limit of the average particle diameter is preferably 0.01 μm or more, more preferably 0.03 μm or more, from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from being lowered when the resin varnish is used. Preferably they are 0.05 micrometer or more, Most preferably, they are 0.07 micrometer or more and 0.1 micrometer or more.

  As a commercial item of (D) component which has the above average particle diameters, for example, "SP60-05", "SP507-05" by Nippon Steel & Sumikin Materials Co., Ltd .; "YC100C", "YA050C" by Admatechs “YA050C-MJE”, “YA010C”; “UFP-30” manufactured by Denka; “Silfil NSS-3N”, “Silfil NSS-4N”, “Silfil NSS-5N” manufactured by Tokuyama; “SC2500SQ manufactured by Admatechs” , "SO-C4", "SO-C2", "SO-C1".

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

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

  Examples of commercially available surface treatment agents include “KBM-22” (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu. “KBM-803” (3-mercaptopropyltrimethoxysilane) manufactured by Chemical Industry 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. "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by KK Moreover, a surface treating agent may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

The degree of the 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 the melt viscosity of the resin composition and the increase in melt viscosity in the form of a sheet, the amount of carbon is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, 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 surface treatment (D) component is washed with a solvent (for example, methyl ethyl ketone (hereinafter sometimes abbreviated as “MEK”)). . For example, a sufficient amount of methyl ethyl ketone and the component (D) surface-treated with the surface treatment agent are mixed and ultrasonically cleaned at 25 ° C. for 5 minutes. Then, after removing a supernatant liquid and drying solid content, the carbon amount per unit surface area of (D) component can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. may be used.

  From the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion, the lower limit of the amount of component (D) in the resin composition is preferably 100 parts by mass or more, more preferably relative to 100 parts by mass of the resin component in the resin composition. 200 parts by mass or more, more preferably 250 parts by mass or more. The upper limit is preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and still more 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) as necessary. By using the component (E), curing can be accelerated when the resin composition is cured.

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

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

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

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2- Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6 -[2 -Methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s -Triazine 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 Imidazole compounds of 2-phenyl imidazoline and imidazole compounds and adducts with epoxy resins. Of these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

  Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl), and the biguanide. Of these, dicyandiamide and 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate; organocopper 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 curing accelerator include cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydro Examples thereof include peroxide, cumene hydroperoxide, and tert-butyl hydroperoxide.

  A commercially available product may be used as the peroxide curing accelerator, 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 polyresin. Examples include ether ether ketone resins, polyester resins, and indene coumarone resins. Among these, indene coumarone resin is preferable from the viewpoint of improving compatibility. In addition, (F) component may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

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

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

  Examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resins) manufactured by Mitsubishi Chemical Corporation; “YX8100” (bisphenol S skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation; “YX6954” (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. “FX280” and “FX293”; Mitsubishi Chemical Corporation “YX6954BH30”, “YX7553”, “YX7553BH30”, “YL7769BH30” YL6794 "," YL7213 "," YL7290 "," YL7891BH30 "," YL7482 ", etc. are mentioned.

  Examples of indene coumarone resins include “H-100”, “WS-100G”, “WS-100H”, “WS-120V”, “WS-100GC” manufactured by Nikko Chemical Co., Ltd .; manufactured by Novales Rutgers “C10”, “C30”, and “CA80”.

  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 with respect to 100% by mass of the resin component in the resin composition. Moreover, the upper limit becomes like this. Preferably it is 10 mass% or less, More preferably, it is 5 mass% or less. By being in such a range, the effect of improving the film forming 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 reduced.

[9. Optional ingredients]
The resin composition of the present invention may contain an optional component in addition to the components described above. Examples of such optional components include flame retardants; organic fillers; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; thickeners; antifoaming agents; leveling 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. Commercially available products may be used as the flame retardant, such as “HCA-HQ”, “HCA-HQ-HS” manufactured by Sanko Co., Ltd., and “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd. In addition, a flame retardant may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

  The amount of the flame retardant in the resin composition is preferably in the range of 0.5 to 20% by mass with respect to 100% by mass of the resin component in the resin composition 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 more preferable.

<Organic filler>
Since the resin composition of this invention can improve the softness | flexibility of the hardened | cured material of a resin composition by using an organic filler, it can improve the extensibility of an insulating layer.
As the organic filler, any organic filler that can be used in forming the insulating layer of the printed wiring board can be used. Examples thereof include rubber particles, polyamide particles, and silicone particles. Moreover, as a rubber particle, you may use a commercial item, for example, "EXL-2655" by Dow Chemical Japan, and "AC3816N" by Aika Industry. In addition, an organic filler may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

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

  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 mass% is more preferable, the range of 0.3 to 5 mass% is more preferable, and the range of 0.5 to 3 mass% is particularly preferable.

[10. Production 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 the compounding components are mixed and dispersed using a rotary mixer or the like after adding a solvent or the like as necessary.

  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, it can be measured at a load of 1 g and a heating rate of 5 ° C./min by performing a thermomechanical analysis by a tensile load method. The cured product of the resin composition of the present invention can preferably exhibit a glass transition temperature of 158 ° C. or higher, more preferably 160 ° C. or higher, and still 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 can usually be 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 (resin composition for an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board, It can use more suitably as a resin composition (resin composition for interlayer insulation layers of a printed wiring board) for forming an insulating layer. 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 sealing material, a hole-filling resin, and a component-filling resin. Can be used in a wide range of applications.

[11. Sheet-like laminated material]
The resin composition of the present invention can be used by being applied in a varnish state, but industrially, it is generally preferable to use it in the form of a sheet-like laminate 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 includes 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 is usually 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more.

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

  When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA). Cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil. Among 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.). It may be used.

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

  The thickness of a support body is not specifically limited, The range of 5-75 micrometers is preferable and the range of 10-60 micrometers is more preferable. In addition, when a support body is a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  For the adhesive film, for example, a resin varnish obtained by dissolving a resin composition 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. Can be manufactured.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol, etc. And aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

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

  In the adhesive film, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). The thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can be stored in a roll. When an 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 the sheet-like fiber base material with the resin composition of the present invention.

  The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The minimum of the thickness of a sheet-like fiber base material is not specifically 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 adhesive film described above.

  In the present invention using the resin composition containing the 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-shaped laminated material that is extremely useful in the production of a printed wiring board, resulting in a cured product.

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

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

In one Embodiment, the printed wiring board of this invention can be manufactured by the method including the process of following (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 step (I) is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one or both surfaces of the substrate. A circuit board on which a patterned conductor layer (circuit) is formed. Moreover, when manufacturing a printed wiring board, an inner layer circuit board of an intermediate product in which at least one of an insulating layer and a conductor layer is to be formed is also included in the “inner layer board” in the present invention. When the printed wiring board is a component built-in circuit board, an inner layer board with built-in components may be used.

  Lamination | stacking of an inner layer board | substrate and an adhesive film can be performed by heat-pressing an adhesive film to an inner layer board | substrate from the support body side, for example. Examples of the member that heat-presses the adhesive film to the inner layer substrate (hereinafter also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll). In addition, it is preferable not to press the thermocompression bonding member directly on 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.

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

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and the like.

  After lamination, the laminated adhesive film may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

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

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

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

  For example, the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition. 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 formed 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 more (preferably 5 to 150 minutes, more preferably 15 to 120 minutes).

  When manufacturing a printed wiring board, (III) a step of drilling an 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 may be further performed. Good. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used in the production of printed wiring boards. In addition, when removing a support body after process (II), removal of this support body is performed between process (II) and process (III), between process (III) and process (IV), or process ( 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.

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

  Step (IV) is a step of roughening the insulating layer. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a 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 Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited. For example, it can be performed 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 body in a swelling liquid at 40 to 80 ° C. for 5 to 15 minutes.

  The oxidizing agent is not particularly limited. For example, an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide can be mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 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 oxidizers include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan. As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, for example, “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. can be mentioned.

  The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment 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 an object subjected to roughening treatment 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. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper / An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.

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

  Although the thickness of a conductor layer is based on the design of a desired printed wiring board, generally it is 3-35 micrometers, Preferably it is 5-30 micrometers.

  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 a metal foil. When forming a conductor layer using metal foil, it is suitable to implement process (V) between process (I) and process (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. Lamination of the resin composition layer and the metal foil may be performed by a vacuum laminating method. The conditions for stacking may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed 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 electrolytic method or a rolling method. Examples of commercially available metal foil include HLP foil manufactured by JX Nippon Mining & Metals, JXUT-III foil, 3EC-III foil, TP-III foil manufactured by Mitsui Metal Mining.

  When producing a printed wiring board using the resin composition of the present invention comprising a combination of the component (A), the component (B), and the component (C), a conductor layer is formed by plating or a metal foil is used. Regardless of whether it is formed, 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 the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  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 location” is a “location where an electrical signal is transmitted on a printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for 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 mounting method using a bumpless buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF) can be mentioned. Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

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

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

  The resin varnish 1 is placed on the release surface of a polyethylene terephthalate film with an alkyd release treatment (“AL-5” manufactured by Lintec Corporation, thickness 38 μm) so that the thickness of the resin composition layer after drying is 40 μm. It apply | coated uniformly with the die-coater, and it dried for 5 minutes at 80-110 degreeC (average 95 degreeC), and produced the adhesive film 1. FIG.

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

<Example 3>
In Example 1, 5 parts of 25 parts of a xylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185) having a vinyl group (“OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Co., Inc., nonvolatile content) (60% toluene solution) 8.3 parts. Except for the above, a resin varnish 3 and an adhesive film 3 were produced in the same manner as in Example 1.

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

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

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

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

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

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

<Measurement of dielectric loss tangent>
A test piece having a width of 2 mm and a length of 80 mm was cut from the cured physical property evaluation sample. The cut specimen was measured for dielectric loss tangent 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.
The case of 0.0035 or less was evaluated as “excellent”, the case of 0.0037 or less was evaluated as “good”, and the case of exceeding 0.0037 was evaluated as “bad”.

<Measurement of glass transition temperature>
A sample for evaluation of cured properties is cut into a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis is performed by a tensile load method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). went. Specifically, after the test piece was mounted on the thermomechanical analyzer, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. In the second measurement, the glass transition temperature (Tg; ° C) was calculated.
In addition, the case where it exceeded 138 degreeC was evaluated as "good", and the case where it was 138 degrees C or less was evaluated as "bad".

<Measurement of adhesion>
(1) Substrate treatment of copper foil The glossy surface of “3EC-III” (electrolytic copper foil, 35 μm) manufactured by Mitsui Kinzoku Mining Co., Ltd. is immersed in Mec etch bond “CZ-8101” manufactured by Mec Co., Ltd. to roughen the copper surface. (Ra value = 1 μm) was performed, and rust prevention treatment (CL8300) was performed. This copper foil is called CZ copper foil. Furthermore, it heat-processed for 30 minutes in 130 degreeC oven.

(2) Lamination of copper foil and formation of insulating layer The adhesive film produced in Examples and Comparative Examples was prepared by using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Co., Ltd.), and the resin composition layer was the inner layer. Lamination was performed on both sides of the inner circuit board so as to be bonded to the circuit board. The laminating process was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. The PET film as a support was peeled from the laminated adhesive film. On the resin composition layer, the treated surface of “3EC-III” CZ copper foil was laminated under the same conditions as described above. And the sample was produced by hardening | curing a resin composition layer on 190 degreeC and the hardening conditions for 90 minutes, and forming an insulating layer.

(3) Measurement of copper foil peeling strength (adhesion) The prepared sample was cut into small pieces of 150 x 30 mm. Cut the copper foil part of the small piece into a 10 mm wide and 100 mm long part using a cutter, peel off one end of the copper foil and make a gripping tool (manufactured by TS E Corp., Autocom testing machine, AC-50C-SL "), and using an Instron universal testing machine, measure the load when peeling 35 mm vertically at a speed of 50 mm / min in accordance with JIS C6481 at room temperature. "Adhesion".
In addition, the case where it exceeded 0.3 kgf / cm was evaluated as "good", and the case where it was 0.3 kgf / cm or less was evaluated as "bad".

<Result>
The results of the above-described examples and comparative examples are shown in the following table. In the following table, 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: an active ester-based curing agent having a vinyl group ("PC1300-02-65MA" manufactured by Air Water)
HPC-8000: Active ester curing agent (“HPC-8000-65T” manufactured by DIC)
EXB-8000L: Active ester curing agent (“EXB-8000L-65TM” manufactured by DIC)
EXB-9416: Active ester curing agent (“EXB-9416L-70BK” manufactured by DIC)
OPE-2St 1200: Resin having a vinyl group ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company)
A-DOG: Dioxane acrylic monomer (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.)
H-100: Indencoumarone resin (“H-100” manufactured by Nikkiso Chemical)
SOC2: Spherical silica ("SO-C2" manufactured by Admatechs)
Park Mill D: Dicumyl Peroxide (Nippon “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 an active ester curing agent are inferior in glass transition temperature and adhesion. In particular, the active ester curing agent containing a naphthalene structure used in Comparative Example 3 was slightly inferior in dielectric loss tangent.
On the other hand, Examples 1-4 using (B) component made the glass transition temperature high, and showed favorable adhesiveness, keeping the value of 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 It was confirmed that the resin composition which can obtain an insulating layer with favorable adhesiveness with a layer is realizable.

Claims (12)

  A resin composition comprising (A) an epoxy resin, (B) an active ester compound having a carbon-carbon unsaturated bond, and (C) a resin having an unsaturated hydrocarbon group.   2. The resin composition according to claim 1, wherein the content of the component (B) is 10 to 60 mass% when the resin component is 100 mass%. The content of the component (A) is 10 to 50% by mass when the resin component is 100% by mass,
The resin composition according to claim 1 or 2, wherein the content of the component (C) is 3 to 30% by mass when the resin component is 100% by mass.   The resin composition according to any one of claims 1 to 3, wherein the component (B) is an active ester compound having a carbon-carbon double bond.   The resin composition according to claim 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.   The resin composition according to claim 5, wherein the component (B) is an active ester compound having a styryl group. The resin composition according to claim 6, wherein the component (B) includes 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 7, wherein the component (C) is a resin having an acryl group, a methacryl group, a styryl group, or an olefin group.   The resin composition according to claim 1, which is used for forming an insulating layer of a printed wiring board.   A sheet-like laminate material comprising the resin composition according to claim 1.   The printed wiring board containing the insulating layer formed with the hardened | cured material of the resin composition of any one of Claims 1-9.   A semiconductor device comprising the printed wiring board according to claim 11.