JP2021014546A - Resin composition - Google Patents

Abstract

To provide a resin composition that gives a cured product having excellent peel strength with a conductor layer formed by plating and copper foil adhesion; a resin sheet containing the resin composition; and a printed wiring board and a semiconductor device having an insulating layer formed using the resin composition.SOLUTION: A resin composition contains (A) a phenoxy resin containing a perfluoroalkyl group, (B) an epoxy resin, and (C) a curing agent.SELECTED DRAWING: None

Description

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

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

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

JP-A-2019-53092

In recent years, further improvement of adhesion including peel strength and copper foil peeling strength (copper foil adhesion) with a conductor layer formed by plating has been required.

An object of the present invention is a resin composition capable of obtaining a cured product having excellent peel strength and copper foil adhesion with a conductor layer formed by plating; a resin sheet containing the resin composition; the resin composition. It is an object of the present invention to provide a printed wiring board provided with an insulating layer formed by using the above, and a semiconductor device.

As a result of diligent studies on the above problems, the present inventors have found that the above problems can be solved by containing a phenoxy resin containing a perfluoroalkyl group, and have completed the present invention.

（一般式（Ａ−１）中、Ｒ^１１は、置換基を有していてもよい、１以上のパーフルオロアルキル基を含む２価の脂肪族炭化水素基を表し、Ｒ^１２及びＲ^１３はそれぞれ独立に置換基を表す。ｎ１及びｎ２はそれぞれ独立に０〜４の整数を表し、＊は結合手を表す。）
［３］ （Ａ）成分が、さらに、以下の一般式（Ａ−２）で表される構造を含む、［２］に記載の樹脂組成物。

（一般式（Ａ−２）中、Ｒ^２１は、単結合又は置換基を有していてもよい２価の脂肪族炭化水素基を表し、Ｒ^２２及びＲ^２３はそれぞれ独立に置換基を表す。ｍ１及びｍ２はそれぞれ独立に０〜４の整数を表し、＊は結合手を表す。）
［４］ （Ａ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、０．１質量％以上５質量％以下である、［１］〜［３］のいずれかに記載の樹脂組成物。
［５］ さらに、（Ｄ）無機充填材を含有する、［１］〜［４］のいずれかに記載の樹脂組成物。
［６］ 絶縁層形成用である、［１］〜［５］のいずれかに記載の樹脂組成物。
［７］ 導体層を形成するための絶縁層形成用である、［１］〜［６］のいずれかに記載の樹脂組成物。
［８］ 支持体と、該支持体上に設けられた、［１］〜［７］のいずれかに記載の樹脂組成物を含む樹脂組成物層とを含む、樹脂シート。
［９］ ［１］〜［７］のいずれかに記載の樹脂組成物の硬化物により形成された絶縁層を含む、プリント配線板。
［１０］ ［９］に記載のプリント配線板を含む、半導体装置。 That is, the present invention includes the following contents.
[1] (A) Phenoxy resin containing a perfluoroalkyl group,
A resin composition containing (B) an epoxy resin and (C) a curing agent.
[2] The resin composition according to [1], wherein the component (A) contains a structure represented by the following general formula (A-1).

(In the general formula (A-1), R ¹¹ represents a divalent aliphatic hydrocarbon group containing one or more perfluoroalkyl groups which may have a substituent, and R ¹² and R ¹³ are. Each independently represents a substituent. N1 and n2 each independently represent an integer of 0 to 4, and * represents a bond.)
[3] The resin composition according to [2], wherein the component (A) further comprises a structure represented by the following general formula (A-2).

(In the general formula (A-2), R ²¹ represents a divalent aliphatic hydrocarbon group which may have a single bond or a substituent, and R ²² and R ²³ each independently represent a substituent. . M1 and m2 each independently represent an integer from 0 to 4, and * represents a bond.)
[4] Any of [1] to [3], wherein the content of the component (A) is 0.1% by mass or more and 5% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to.
[5] The resin composition according to any one of [1] to [4], which further contains (D) an inorganic filler.
[6] The resin composition according to any one of [1] to [5], which is used for forming an insulating layer.
[7] The resin composition according to any one of [1] to [6], which is used for forming an insulating layer for forming a conductor layer.
[8] A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [7].
[9] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [7].
[10] A semiconductor device including the printed wiring board according to [9].

According to the present invention, a resin composition capable of obtaining a cured product having excellent peel strength and copper foil adhesion with a conductor layer formed by plating; a resin sheet containing the resin composition; the resin composition. It is possible to provide a printed wiring board provided with an insulating layer formed by using the above, and a semiconductor device.

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

[Resin composition]
The resin composition of the present invention contains (A) a phenoxy resin containing a perfluoroalkyl group, (B) an epoxy resin, and (C) a curing agent. In the present invention, by containing the component (A), a cured product having excellent peel strength and copper foil adhesion with the conductor layer formed by plating can be obtained. Further, in the present invention, it is possible to obtain a cured product which is usually excellent in adhesion to copper foil after a reliability test, has a low coefficient of linear thermal expansion (CTE), and can suppress warpage.

The resin composition may further contain any component in combination with the components (A) to (C). Examples of the optional component include (D) an inorganic filler, (E) a curing accelerator, (F) a flame retardant, and (G) other additives. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Phenoxy resin containing a perfluoroalkyl group>
The resin composition contains (A) a phenoxy resin containing a perfluoroalkyl group as a component (A). By incorporating the component (A) in the resin composition, it is possible to obtain a cured product having excellent peel strength and copper foil adhesion.

Examples of the phenoxy resin include bisphenol AF skeleton, bisphenol TMC skeleton, biphenylene skeleton, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton. , Naphthalene skeleton, anthracene skeleton, adamantan skeleton, terpen skeleton, and trimethylcyclohexane skeleton, and phenoxy resin having one or more kinds of skeletons selected from the group. Among them, as the component (A), a phenoxy resin having one or more skeletons selected from the group consisting of a bisphenol AF skeleton, a bisphenol TMC skeleton, and a biphenylene skeleton is preferable, and a phenoxy resin having a bisphenol AF skeleton is more preferable. The biphenylene skeletons, those hydrogen atoms from biphenyl group which two removed, i.e. _{-C 6 H 4 -C 6 H 4} - is a skeleton represented by.

The component (A) contains a perfluoroalkyl group. The perfluoroalkyl group is a group having a structure in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms, and is preferably provided as a substituent of the skeleton constituting the phenoxy resin.

The perfluoroalkyl group may be linear, branched or cyclic, and linear is preferable. As the perfluoroalkyl group, a perfluoroalkyl group having 1 to 10 carbon atoms is preferable, a perfluoroalkyl group having 1 to 6 carbon atoms is more preferable, and a perfluoroalkyl group having 1 to 3 carbon atoms is further preferable. ..

Examples of the perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group and the like, and among them, a trifluoromethyl group is preferable.

The terminal of the component (A) is preferably a functional group such as a phenolic hydroxyl group or an epoxy group from the viewpoint of remarkably obtaining the effect of the present invention.

The component (A) may have a substituent in the skeleton constituting the phenoxy resin. Examples of the substituent include a perfluoro (C _1-10 alkyl) group, a halogen atom, -OH, an -OC _1-6 alkyl group, -N (C _1-10 alkyl group) ₂ , and C _1-10. Alkyl groups, C _6-10 aryl groups, -NH ₂ , -CN, -C (O) O-C _1-10 alkyl groups, -COOH, -C (O) H, -NO _{2 and the} like can be mentioned. Here, the term "C _p-q " (p and q are positive integers and satisfy p <q) is described immediately after this term and the number of carbon atoms of the organic group is p to q. Indicates that there is. For example, the expression "C _1-10 alkyl group" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring.

The above-mentioned substituent may further have a substituent (hereinafter, may be referred to as a "secondary substituent"). Unless otherwise specified, the same as the above-mentioned substituent may be used as the secondary substituent.

（一般式（Ａ−１）中、Ｒ^１１は、置換基を有していてもよい、１以上のパーフルオロアルキル基を含む２価の脂肪族炭化水素基を表し、Ｒ^１２及びＲ^１３はそれぞれ独立に置換基を表す。ｎ１及びｎ２はそれぞれ独立に０〜４の整数を表し、＊は結合手を表す。） The component (A) preferably contains a structure represented by the general formula (A-1).

(In the general formula (A-1), R ¹¹ represents a divalent aliphatic hydrocarbon group containing one or more perfluoroalkyl groups which may have a substituent, and R ¹² and R ¹³ are. Each independently represents a substituent. N1 and n2 each independently represent an integer of 0 to 4, and * represents a bond.)

R ¹¹ represents a divalent aliphatic hydrocarbon group having one or more perfluoroalkyl groups as substituents. As the divalent aliphatic hydrocarbon group, a divalent saturated aliphatic hydrocarbon group is preferable, an alkylene group and a cycloalkylene group are more preferable, and an alkylene group is further preferable.

As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is further preferable. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group and a 1,2-dimethylethylene group. Examples thereof include a group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, a hexylene group and the like, and a methylene group is preferable.

As the cycloalkylene group, a cycloalkylene group having 3 to 20 carbon atoms is preferable, a cycloalkylene group having 3 to 15 carbon atoms is more preferable, and a cycloalkylene group having 5 to 10 carbon atoms is further preferable. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a 1,1-cyclohexylene group, a cyclopentylene group, a cycloheptylene group and the like.

The divalent aliphatic hydrocarbon group represented by R ¹¹ has one or more perfluoroalkyl groups as substituents. The perfluoroalkyl group is as described above, and a trifluoromethyl group is preferable. The perfluoroalkyl group preferably has 1 or more, more preferably 2 or more, preferably 5 or less, and more preferably 3 or less, with respect to the structure represented by the general formula (A-1). It is more preferable to have two perfluoroalkyl groups as substituents.

The divalent aliphatic hydrocarbon group represented by R ¹¹ may have a substituent other than the perfluoroalkyl group. The substituents are the same as the substituents that the skeleton constituting the phenoxy resin may have.

R ¹² and R ¹³ each independently represent a substituent. The substituents are the same as the substituents that the skeleton constituting the phenoxy resin may have.

n1 and n2 each independently represent an integer of 0 to 4, and 0 is preferable.

（式（ｉ）中、ｎ及びｍはそれぞれ独立に１以上の整数を表し、好ましくは１である。） Specific examples of the structure represented by the general formula (A-1) include the following structure (i). In the formula, "*" represents a bond.

(In formula (i), n and m each independently represent an integer of 1 or more, and is preferably 1.)

（一般式（Ａ−２）中、Ｒ^２１は、単結合又は置換基を有していてもよい２価の脂肪族炭化水素基を表し、Ｒ^２２及びＲ^２３はそれぞれ独立に置換基を表す。ｍ１及びｍ２はそれぞれ独立に０〜４の整数を表し、＊は結合手を表す。） The component (A) may have a structure represented by the general formula (A-2) in addition to the structure represented by the general formula (A-1).

(In the general formula (A-2), R ²¹ represents a divalent aliphatic hydrocarbon group which may have a single bond or a substituent, and R ²² and R ²³ each independently represent a substituent. . M1 and m2 each independently represent an integer from 0 to 4, and * represents a bond.)

R ²¹ represents a divalent aliphatic hydrocarbon group which may have a single bond or a substituent. As the divalent aliphatic hydrocarbon group, a divalent saturated aliphatic hydrocarbon group is preferable, an alkylene group and a cycloalkylene group are more preferable, and a cycloalkylene group is even more preferable.

As the cycloalkylene group, a cycloalkylene group having 3 to 20 carbon atoms is preferable, a cycloalkylene group having 3 to 15 carbon atoms is more preferable, and a cycloalkylene group having 5 to 10 carbon atoms is further preferable. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a 1,1-cyclohexylene group, a cyclopentylene group, a cycloheptylene group and the like, and 1,1-cyclohexylene group. A silene group is preferred.

As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is further preferable. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group and a 1,2-dimethylethylene group. Examples thereof include a group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group and a hexylene group.

The divalent aliphatic hydrocarbon group represented by R ²¹ may have a substituent. The substituents are the same as the substituents that the skeleton constituting the phenoxy resin may have.

（式中、Ｒ^２１０は置換基を表し、ｓは０〜５の整数を表す。） Specific examples of the divalent aliphatic hydrocarbon group represented by R ²¹ include the following group (a). In the formula, "*" represents a bond.

(In the formula, R ²¹⁰ represents a substituent and s represents an integer from 0 to 5.)

The substituent represented by R ²¹⁰ is the same as the substituent that the skeleton constituting the phenoxy resin may have, and a methyl group is preferable. s is preferably 1 to 5, more preferably 2 to 4, and even more preferably 3.

R ²² and R ²³ each independently represent a substituent. The substituents are the same as the substituents that the skeleton constituting the phenoxy resin may have.

m1 and m2 each independently represent an integer of 0 to 4, and an integer of 0 to 2 is preferable.

Specific examples of the structure represented by the general formula (A-2) include the following structures (ii) to (iii). In the formula, "*" represents a bond.

The component (A) preferably has one or both of the structure represented by the general formula (A-1) and the structure represented by the general formula (A-2) as a repeating unit.

The weight average molecular weight of the component (A) is preferably 10,000 or more, more preferably 15,000 or more, and further preferably 20,000 or more. The upper limit is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 60,000 or less. The polystyrene-equivalent weight average molecular weight of the component (A) is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the component (A) is determined by using Shimadzu LC-9A / RID-6A as a measuring device and Showa Denko Shodex K-800P / K-804L / K as a column. -804 L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase.

The content of the component (A) is preferably 0.1% by mass or more when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining a cured product having excellent peel strength and copper foil adhesion. It is more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less. In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

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

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the component (B). From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass with respect to 100% by mass of the non-volatile component of the component (B). As mentioned above, it is more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

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

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

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

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

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

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

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

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

The epoxy equivalent of the component (B) is preferably 50 g / eq. ~ 5000 g / eq. , More preferably 50 g / eq. ~ 3000 g / eq. , More preferably 80 g / eq. ~ 2000g / eq. , Even more preferably 110 g / eq. ~ 1000 g / eq. Is. Within this range, the crosslink density of the cured product of the resin composition layer becomes sufficient, and an insulating layer having a small surface roughness can be provided. Epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of an epoxy group. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the component (B) is preferably 100 to 5000, more preferably 250 to 3000, still more preferably 400 to 1500, from the viewpoint of significantly obtaining the desired effect of the present invention.
The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The content of the component (B) is preferably 1% by mass or more when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. It is preferably 5% by mass or more, and more preferably 10% by mass or more. The upper limit of the content of the epoxy resin is preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

When the content (parts by mass) of the component (A) in the resin composition is a and the content (parts by mass) of the component (B) in the resin composition is b, (a / (a + b)) × 100 is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. By adjusting the contents of the component (A) and the component (B) so that a / (a + b) is within such a range, the desired effect of the present invention can be remarkably obtained.

<(C) Hardener>
The resin composition contains a curing agent as the component (C). The curing agent (C) usually has a function of reacting with the component (B) to cure the resin composition. (C) One type of curing agent may be used alone, or two or more types may be used in combination at an arbitrary ratio.

As the (C) curing agent, a compound capable of reacting with the (B) epoxy resin to cure the resin composition can be used. For example, an acid anhydride-based curing agent, an amine-based curing agent, and a phenol-based curing agent can be used. Examples thereof include agents, active ester-based curing agents, cyanate ester-based curing agents, benzoxazine-based curing agents, and carbodiimide-based curing agents. Of these, an acid anhydride-based curing agent is preferable from the viewpoint of remarkably obtaining the effect of the present invention.

Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylnagic. Acid anhydride, methylnadic hydride anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-Dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3 , 3'-4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-franyl) -naphtho [ 1,2-C] Fran-1,3-dione, ethylene glycol bis (anhydrotrimeritate), polymer-type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized. Be done. A commercially available product may be used as the acid anhydride-based curing agent, and examples thereof include "MH-700" manufactured by New Japan Chemical Co., Ltd.

Examples of amine-based curing agents include curing agents having one or more amino groups in one molecule, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Among them, aromatic amines are preferable from the viewpoint of achieving the desired effect of the present invention. As the amine-based curing agent, a primary amine or a secondary amine is preferable, and a primary amine is more preferable. Specific examples of amine-based curing agents include 4,4'-methylenebis (2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'. -Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl- 4,4'-Diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane Diamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3- Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, Examples thereof include bis (4- (3-aminophenoxy) phenyl) sulfone. Commercially available products may be used as the amine-based curing agent. For example, "KAYABOND C-200S", "KAYABOND C-100", "Kayahard A-A", "Kayahard AB", "Kayahard AB" manufactured by Nippon Kayaku Corporation. Examples include "Kayahard AS" and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

Examples of the phenolic curing agent include a curing agent having one or more, preferably two or more hydroxyl groups bonded to an aromatic ring (benzene ring, naphthalene ring, etc.) in one molecule. Of these, a compound having a hydroxyl group bonded to a benzene ring is preferable. Further, from the viewpoint of heat resistance and water resistance, a phenolic curing agent having a novolak structure is preferable. Further, from the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. In particular, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion.

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

Examples of the active ester-based curing agent include curing agents having one or more active ester groups in one molecule. Among them, as the active ester-based curing agent, two or more ester groups having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are contained in one molecule. The compound having is preferable. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. ..

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

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

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

Commercially available active ester-based curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", and "" HPC-8000-65T ”,“ HPC-8000H-65TM ”,“ EXB-8000L ”,“ EXB-8000L-65TM ”,“ EXB-8150-65T ”(manufactured by DIC); as an active ester compound containing a naphthalene structure "EXB-8100L-65T", "EXB-8150L-65T", "EXB9416-70BK" (manufactured by DIC); "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing the benzoylated product of "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent which is an acetylated product of phenol novolac; activity which is a benzoylated product of phenol novolac. Examples of the ester-based curing agent include "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.); and the like.

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

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

Specific examples of the carbodiimide-based curing agent include "V-03", "V-05", and "V-07" manufactured by Nisshinbo Chemical Co., Ltd .; Stavaxol (registered trademark) P manufactured by Rheinchemy Co., Ltd. and the like.

The content of the curing agent (C) is preferably 1% by mass or more, more preferably 3% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of remarkably obtaining the effect of the present invention. It is more preferably 5% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.

When the number of epoxy groups of the component (B) is 1, the number of active groups of the curing agent (C) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and preferably 0.3 or more. It is 2 or less, more preferably 1.8 or less, still more preferably 1.6 or less, and particularly preferably 1.4 or less. Here, the "number of epoxy groups of the component (B)" is a total value obtained by dividing the mass of the non-volatile component of the component (B) present in the resin composition by the epoxy equivalent. The "(C) number of active groups of the curing agent" is a total value obtained by dividing the mass of the non-volatile component of the (C) curing agent present in the resin composition by the active group equivalent. When the number of active groups of the (C) curing agent is in the above range when the number of epoxy groups of the component (B) is 1, the desired effect of the present invention can be remarkably obtained.

The content (parts by mass) of the component (A) in the resin composition is a, the content (parts by mass) of the component (B) in the resin composition is b, and the content of the component (C) in the resin composition is b. When the content (part by mass) is c, b / (a + b + c) is preferably 30 or more, more preferably 40 or more, still more preferably 50 or more, preferably 80 or less, more preferably 70 or less, and further. It is preferably 60 or less. By adjusting the contents of the component (A), the component (B) and the component (C) so that (b / (a + b + c)) × 100 is within such a range, the desired effect of the present invention can be remarkably obtained. It becomes possible to obtain.

<(D) Inorganic filler>
In addition to the above-mentioned components, the resin composition may contain an inorganic filler as an arbitrary component and further as a component (D).

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

Examples of commercially available components (D) include "UFP-20" and "UFP-30" manufactured by Denka Corporation; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; Admatex Co., Ltd. "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Tokuyama Corporation; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama Corporation; Examples thereof include "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1";

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

The average particle size of the component (D) is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and preferably 0.1 μm or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. It is 5 μm or less, more preferably 2 μm or less, still more preferably 1 μm or less.

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

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

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

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

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

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. or the like can be used.

The content of the component (D) is preferably 60% by mass or more, more preferably 63% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of remarkably obtaining the effect of the present invention. It is more preferably 65% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less.

<(E) Curing accelerator>
In addition to the above-mentioned components, the resin composition may contain a curing accelerator as an arbitrary component and further as a component (E).

Examples of the component (E) include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, and a metal-based curing accelerator. The component (E) may be used alone or in combination of two or more.

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

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

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

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

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

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

The content of the component (E) is preferably 0.01% by mass or more, more preferably 0, when the non-volatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. It is 0.03% by mass or more, more preferably 0.05% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less.

<(F) Flame Retardant>
In addition to the above-mentioned components, the resin composition may contain a flame retardant as an arbitrary component and further as a component (F).

Examples of the flame retardant (F) include a phosphazene compound, an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, a metal hydroxide and the like, and a phosphazene compound is preferable. The flame retardant may be used alone or in combination of two or more.

The phosphazene compound is not particularly limited as long as it is a cyclic compound containing nitrogen and phosphorus as constituent elements, but the phosphazene compound is preferably a phosphazene compound having a phenolic hydroxyl group.

Specific examples of the phosphazene compound include, for example, "SPH-100", "SPS-100", "SPB-100" and "SPE-100" manufactured by Otsuka Chemical Co., Ltd., and "FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd. Examples thereof include "FP-110", "FP-300", "FP-400", and "SPH-100" manufactured by Otsuka Chemical Co., Ltd. is preferable.

As the flame retardant other than the phosphazene compound, a commercially available product may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. As the flame retardant, one that is hard to hydrolyze is preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

The content of the flame retardant (F) is preferably 0.1% by mass or more, more preferably 0% by mass, when the non-volatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the effect of the present invention. It is 3% by mass or more, more preferably 0.5% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.

<(G) Other additives>
In addition to the above-mentioned components, the resin composition may further contain other additives as arbitrary components. Examples of such an additive include a thermoplastic resin such as a phenoxy resin other than the component (A), a resin additive such as a thickener, a defoaming agent, a leveling agent, and an adhesion imparting agent. These additives may be used alone or in combination of two or more. Each content can be appropriately set by those skilled in the art.

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

<Physical characteristics and uses of resin composition>
Since the resin composition contains the component (A), a cured product having excellent peel strength and copper foil adhesion between the resin composition and the conductor layer formed by plating can be obtained. Further, the resin composition usually has excellent adhesion to the copper foil after the reliability test, has a low coefficient of linear thermal expansion, and can obtain a cured product capable of suppressing warpage.

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

The cured product obtained by thermally curing the resin composition at 190 ° C. for 90 minutes exhibits a characteristic of excellent copper foil adhesion. Therefore, the cured product provides an insulating layer having excellent copper foil adhesion. The copper foil adhesion is preferably 0.3 kgf / cm or more, more preferably 0.5 kgf / cm or more, still more preferably 0.6 kgf / cm or more. The upper limit of the copper foil adhesion may be 10 kgf / cm or less. The copper foil adhesion can be measured according to the method described in Examples described later.

The cured product obtained by thermosetting the resin composition at 190 ° C. for 90 minutes exhibits a characteristic of excellent copper foil adhesion after a reliability test under high temperature and high humidity conditions. Therefore, the cured product provides an insulating layer having excellent copper foil adhesion after the reliability test. The adhesion of the copper foil after the reliability test is preferably more than 0.4 kgf / cm, more preferably 0.42 kgf / cm or more, still more preferably 0.44 kgf / cm or more. The upper limit of the copper foil adhesion after the reliability test may be 10 kgf / cm or less. The copper foil adhesion after the reliability test can be measured according to the method described in Examples described later.

A cured product obtained by thermosetting the resin composition at 190 ° C. for 90 minutes usually exhibits a characteristic that the amount of warpage is reduced. Therefore, the cured product provides an insulating layer with a reduced amount of warpage. The amount of warpage is preferably less than 3 cm, more preferably less than 1 cm. The lower limit is not particularly limited, but may be 0.001 cm or more. The amount of warpage can be measured according to the method described in Examples described later.

A cured product obtained by thermosetting the resin composition at 190 ° C. for 90 minutes usually exhibits a characteristic of having a low coefficient of linear thermal expansion. Therefore, the cured product provides an insulating layer having a low coefficient of linear thermal expansion. The coefficient of linear thermal expansion is preferably 30 ppm or less, more preferably 25 ppm or less, still more preferably 22 ppm or less. On the other hand, the lower limit of the coefficient of linear thermal expansion can be 1 ppm or more. The coefficient of linear thermal expansion can be measured according to the method described in Examples described later.

With the resin composition of the present invention, it is possible to obtain a cured product having excellent peel strength and copper foil adhesion with the conductor layer formed by plating. Further, the resin composition usually has excellent adhesion to the copper foil after the reliability test, has a low coefficient of linear thermal expansion, and can obtain a cured product capable of suppressing warpage. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating applications. Specifically, a resin composition for forming the insulating layer for forming the conductor layer (including the rewiring layer) formed on the insulating layer (resin for forming the insulating layer for forming the conductor layer). It can be suitably used as a composition).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The step (V) is a step of forming the conductor layer, and forms the conductor layer on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). A layer formed from a nickel alloy and a copper / titanium alloy) can be mentioned. Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. An alloy layer of a nickel alloy or a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single copper layer is preferable. A metal layer is more preferred.

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

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

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

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

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

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

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

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

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

<Synthesis of phenoxy resin (phenoxy resin A) having a bisphenol AF type structure and a trimethyldiphenylcyclohexane structure>
In the reaction vessel, 250 g of bisphenol AF type epoxy resin (“YX7760” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 240 g / eq.), 1,3,3-trimethyl-5,5-diparahydroxyphenylcyclohexane (phenolic hydroxyl group equivalent of about) 105 g / eq.) 105 g and 150 g of cyclohexanone were added and stirred to dissolve. Then, 0.5 g of a tetramethylammonium chloride solution was added dropwise, and the reaction was carried out at 180 ° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was filtered using a filter cloth and diluted with a solvent to obtain phenoxy resin A, which is a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass. The epoxy equivalent of phenoxy resin A is 13000 g / eq. The weight average molecular weight of the phenoxy resin A was 55,000. The phenoxy resin A had the following structure. In the following formula, "*" represents a bond.

<Synthesis of phenoxy resin (phenoxy resin B) having a bisphenol AF type structure>
In the reaction vessel, 125 g of bisphenol AF type epoxy resin (“YX7760” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 240 g / eq.), 80 g of bisphenol AF type phenol (phenolic hydroxyl group equivalent of about 160 g / eq.), And 150 g of cyclohexanone are placed. , Stirred to dissolve. Then, 0.5 g of a tetramethylammonium chloride solution was added dropwise, and the reaction was carried out at 180 ° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was filtered using a filter cloth and diluted with a solvent to obtain a phenoxy resin B which is a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass. The epoxy equivalent of phenoxy resin B is 5300 g / eq. The weight average molecular weight of the phenoxy resin B was 25,000. The phenoxy resin B had the following structure. In the following formula, "*" represents a bond.

<Synthesis of phenoxy resin (phenoxy resin C) having a tetramethylbiphenyl structure and a bisphenol AF type structure>
In the reaction vessel, 100 g of bixylenol type epoxy resin (“YX4000H” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 190 g / eq.), 80 g of bisphenol AF type phenol (phenolic hydroxyl group equivalent of 160 g / eq.), And 150 g of cyclohexanone were placed. It was stirred and dissolved. Then, 0.5 g of a tetramethylammonium chloride solution was added dropwise, and the reaction was carried out at 180 ° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was filtered using a filter cloth and diluted with a solvent to obtain a phenoxy resin C which is a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass. The epoxy equivalent of phenoxy resin C is 12000 g / eq. The weight average molecular weight of the phenoxy resin C was 35,000. The phenoxy resin C had the following structure. In the following formula, "*" represents a bond.

<Example 1: Preparation of resin composition 1>
13 parts (solid content 30%) of phenoxy resin A synthesized in Synthesis Example 1, 20 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation "828US", epoxy equivalent about 180 g / eq.), Bisphenol AF type epoxy resin ( "NC-3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 271 g / eq.) 20 parts, and bisphenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy equivalent of about 190 g / eq.), 20 parts, flame retardant ("HCA-HQ" manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 3 parts MEK60 It was dissolved by heating while stirring in the part.

After cooling to room temperature, 70 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC, an active group equivalent of about 223 g / eq., A toluene solution having a solid content of 65% by mass), a phenol-based curing agent ( "LA-7054" manufactured by DIC, active group equivalent of about 125 g / eq., 5 parts of 2-methoxypropanol solution having a solid content of 60%, curing accelerator (4-dimethylaminopyridine (DMAP), solid content of 5% by mass) MEK solution) 6 parts, spherical silica surface-treated with N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., molecular weight 325.2) ("SC2050-SXF" manufactured by Admatex Co., Ltd., specific surface area) 260 parts (surface area 5.9 m ² / g, average particle size 0.77 μm) were mixed, uniformly dispersed with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP020” manufactured by ROKITECHNO) to form a resin composition 1. Was produced.

<Example 2: Preparation of resin composition 2>
In Example 1,
1) Change the amount of phenoxy resin A from 13 parts to 26 parts,
2) Flame retardant ("HCA-HQ" manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphazenanthrene-10-oxide, average particle size 2 μm) Change 3 parts to 3 parts of phosphazene flame retardant ("FP-100" manufactured by Fushimi Seisakusho Co., Ltd.)
3) Spherical silica (“SC2050-SXF” manufactured by Admatex Co., Ltd., specific surface area 5.9 m ² ) surface-treated with N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., molecular weight 325.2). / G, average particle size 0.77 μm) 260 parts surface-treated with N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., molecular weight 325.2) Spherical silica (manufactured by Denka Co., Ltd. "UFP" -20 ”, specific surface area 22 m ² / g, average particle size 1.5 μm) 210 parts. A resin composition 2 was produced in the same manner as in Example 1 except for the above items.

<Example 3: Preparation of resin composition 3>
In Example 1,
1) Change the amount of phenoxy resin A from 13 parts to 10 parts,
2) Spherical silica (“SC2050-SXF” manufactured by Admatex Co., Ltd., specific surface area 5.9 m ² ) surface-treated with N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 325.2). / G, average particle size 0.77 μm) was changed from 260 parts to 210 parts.
3) 70 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC, an active group equivalent of about 223 g / eq., A toluene solution having a solid content of 65% by mass) was added to a phenol-based curing agent (Nippon Steel & Sumitomo Metal Chemical Corporation). Made by "SN-485", phenol equivalent about 205 g / eq.) 12 parts,
4) The amount of the phenolic curing agent (“LA-7054” manufactured by DIC Corporation, active group equivalent of about 125 g / eq., 2-methoxypropanol solution having a solid content of 60%) was changed from 5 parts to 20 parts.
A resin composition 3 was prepared in the same manner as in Example 1 except for the above items.

<Example 4: Preparation of resin composition 4>
In Example 1,
1) Change the amount of phenoxy resin A from 13 parts to 20 parts,
2) Flame retardant ("HCA-HQ" manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphazenanthrene-10-oxide, average particle size 2 μm) Change 3 parts to 3 parts of phosphazene flame retardant ("FP-100" manufactured by Fushimi Seisakusho Co., Ltd.)
3) Spherical silica (“SC2050-SXF” manufactured by Admatex Co., Ltd., specific surface area 5.9 m ² ) surface-treated with N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., molecular weight 325.2). / G, average particle size 0.77 μm) 260 parts surface-treated with N-phenyl-8-aminooctyl-trimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., molecular weight 325.2) Spherical silica (manufactured by Denka Co., Ltd. UFP-20 ”, specific surface area 22 m ² / g, average particle size 1.5 μm) 160 parts,
4) 70 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC, an active group equivalent of about 223 g / eq., A toluene solution having a solid content of 65% by mass) was added to a phenol-based curing agent (Nippon Steel & Sumitomo Metal Chemical Corporation). Made by "SN-485", phenol equivalent about 205 g / eq.) 12 parts,
5) 5 parts of a phenolic curing agent (“LA-7054” manufactured by DIC Corporation, an active group equivalent of about 125 g / eq., A 2-methoxypropanol solution having a solid content of 60%) was changed to 20 parts.
A resin composition 4 was prepared in the same manner as in Example 1 except for the above items.

<Example 5: Preparation of resin composition 5>
In Example 1, 10 parts of the phenoxy resin A was changed to 13 parts of the phenoxy resin B synthesized in Synthesis Example 2 (solid content: 30%). A resin composition 5 was prepared in the same manner as in Example 1 except for the above items.

<Example 6: Preparation of resin composition 6>
In Example 1, 13 parts of the phenoxy resin A was changed to 13 parts of the phenoxy resin C synthesized in Synthesis Example 3 (solid content: 30%). A resin composition 6 was prepared in the same manner as in Example 1 except for the above items.

<Comparative Example 1: Preparation of Comparative Resin Composition 1>
In Example 1, 13 parts of phenoxy resin A was changed to 13 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass). A comparative resin composition 1 was prepared in the same manner as in Example 1 except for the above items.

<Comparative Example 2: Preparation of Comparative Resin Composition 2>
In Example 2, 26 parts of phenoxy resin A was changed to 27 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass). A comparative resin composition 2 was prepared in the same manner as in Example 2 except for the above items.

<Comparative Example 3: Preparation of Comparative Resin Composition 3>
In Example 3, 10 parts of phenoxy resin A was changed to 10 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass). A comparative resin composition 3 was prepared in the same manner as in Example 3 except for the above items.

<Comparative Example 4: Preparation of Comparative Resin Composition 4>
In Example 4, 20 parts of phenoxy resin A was changed to 20 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass). A comparative resin composition 4 was prepared in the same manner as in Example 4 except for the above items.

<Measurement of average particle size of inorganic filler>
100 mg of an inorganic filler, 0.1 g of a dispersant (“SN9228” manufactured by San Nopco Co., Ltd.), and 10 g of methyl ethyl ketone were weighed in a vial and dispersed by ultrasonic waves for 20 minutes. Using a laser diffraction type particle size distribution measuring device (“SALD-2200” manufactured by Shimadzu Corporation), the particle size distribution was measured by a batch cell method, and the average particle size based on the median diameter was calculated.

<Making a resin sheet>
As a support, a PET film ("Lumilar R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., hereinafter "Release PET") treated with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Corporation). There are times when.) Was prepared.

Each resin composition is uniformly applied on the release PET with a die coater so that the thickness of the resin composition layer after drying is 25 μm, and dried at 80 ° C. for 1 minute on the release PET. A resin composition layer was obtained. Next, a rough surface of a polypropylene film (“Alfan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) as a protective film is bonded to the resin composition layer on the surface that is not bonded to the support of the resin composition layer. Laminated so as to. As a result, a resin sheet composed of a release PET (support), a resin composition layer, and a protective film was obtained.

<Measurement of peel strength between the conductor layer formed by plating>
(Preparation of measurement sample)
(1) Base treatment of inner layer circuit board Both sides of the glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic R1515A) on which the inner layer circuit is formed are manufactured by MEC. The copper surface was roughened by etching with "CZ8101" by 1 μm.

(2) Laminating of resin sheet with support Peel off the protective film from each produced resin sheet, and use a batch type vacuum pressure laminator (2-stage build-up laminator manufactured by Nikko Materials, CVP700) to make an inner layer circuit board. Laminated on both sides of. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and crimping at 130 ° C. and a pressure of 0.74 MPa for 45 seconds. Then, heat pressing was performed at 120 ° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Curing of Resin Composition The laminated resin sheet was cured at 130 ° C. for 30 minutes, and then at 170 ° C. for 30 minutes to cure the resin composition to form an insulating layer.

(4) Roughening treatment 60 of the inner layer circuit board on which the insulating layer was formed was added to a swelling liquid, a swirling dip securigant P (glycol ethers, aqueous solution of sodium hydroxide) containing diethylene glycol monobutyl ether manufactured by Atotech Japan. Soak at ° C for 10 minutes, then as a roughening solution, soak in Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) manufactured by Attec Japan at 80 ° C for 20 minutes, and finally. As a neutralizing solution, it was immersed in Reduction Shorusin Securigant P (aqueous solution of sulfuric acid) manufactured by Attec Japan Co., Ltd. at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 30 minutes. This substrate was designated as "evaluation substrate A".

(5) Plating by Semi-Additive Method The evaluation substrate A was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. After heating at 150 ° C. for 30 minutes to perform annealing treatment, an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 20 μm. Next, the annealing treatment was performed at 200 ° C. for 60 minutes. This substrate was designated as "evaluation substrate B".

(Measurement of peel strength)
Make a notch in the conductor layer of the evaluation substrate B with a width of 10 mm and a length of 100 mm, peel off one end of the notch, and grab it with a gripper (TSE Co., Ltd., Autocom type testing machine AC-50C-SL). The load (kgf / cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min was measured at room temperature.

<Measurement of copper foil adhesion and copper foil adhesion after its insulation reliability test>
(Preparation of measurement sample)
(1) Base treatment of copper foil The glossy surface of the copper foil "3EC-III (thickness 35 μm)" manufactured by Mitsui Mining & Smelting Co., Ltd. is immersed in a microetching agent (CZ8101 manufactured by MEC) to roughen the copper surface (Ra value). = 1 μm), and rust preventive treatment was performed using a rust preventive agent (CL8300 manufactured by MEC). This copper foil is called CZ copper foil. Further, it was heat-treated in an oven at 130 ° C. for 30 minutes.

(2) Lamination of copper foil and formation of insulating layer The protective film was peeled off from the resin sheets produced in Examples and Comparative Examples, and a batch type vacuum pressure laminator (2-stage build-up laminator manufactured by Nikko Materials Co., Ltd., CVP700) was used. In use, both sides of the inner layer circuit board were laminated so that the resin composition layer was bonded to the inner layer circuit board. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and crimping at 130 ° C. and a pressure of 0.74 MPa for 45 seconds. Then, heat pressing was performed at 120 ° C. and a pressure of 0.5 MPa for 75 seconds. The PET film, which is a support, was peeled off from the laminated resin sheet. The treated surface of the CZ copper foil of "3EC-III" was laminated on the resin composition layer under the same conditions as described above. Then, a sample was prepared by curing the resin composition layer under curing conditions of 190 ° C. for 90 minutes to form an insulating layer.

(Measurement of copper foil adhesion)
The prepared sample was cut into small pieces of 150 × 30 mm. Use a cutter to make a notch in the small piece of copper foil with a width of 10 mm and a length of 100 mm, peel off one end of the copper foil, and use a gripper (manufactured by JIS, Autocom type testing machine "AC". -50C-SL "), and using an Instron universal tester, measure the load when 35 mm is peeled off vertically at a speed of 50 mm / min at room temperature in accordance with JIS C6481. It was evaluated according to the following criteria.
◯: Copper foil adhesion exceeds 0.6 kgf / cm.
X: Copper foil adhesion is 0.6 kgf / cm or less.

(Measurement of copper foil adhesion after reliability test)
The prepared sample was allowed to elapse for 200 hours under the conditions of 130 ° C., 85% relative humidity and 3.3 V DC voltage application using a highly accelerated life test device (“PM422” manufactured by ETAC). After that, one end of the copper foil is peeled off and grasped with a gripping tool (manufactured by JIS, Autocom type testing machine "AC-50C-SL"), and using an Instron universal testing machine, at room temperature. The load when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min was measured according to JIS C6481 and evaluated according to the following criteria.
◯: The copper foil adhesion after the reliability test exceeds 0.4 kgf / cm.
X: The copper foil adhesion after the reliability test is 0.4 kgf / cm or less.

<Evaluation of warpage>
(1) Laminating of resin sheets The resin sheets produced in Examples and Comparative Examples were cut into a size of 9.5 cm square, and a batch type vacuum pressurizing laminator (2-stage build-up laminator manufactured by Nikko Materials Co., Ltd., CVP700) was used. It was laminated on the roughened surface of a copper foil "3EC-III (thickness 35 μm)" manufactured by Mitsui Mining & Smelting Co., Ltd., which was cut into 10 cm squares. The laminate was decompressed for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then pressure-bonded at 120 ° C. for 30 seconds at a pressure of 0.74 MPa to prepare a metal foil with a resin composition layer, and then PET as a support. The film was peeled off.

(2) Curing of Resin Composition Layer The four sides of the metal leaf with the resin composition layer obtained in (1) above are attached to a SUS plate having a thickness of 1 mm so that the resin composition layer is on the upper surface with polyimide tape. The resin composition layer was cured under the curing conditions of 190 ° C. and 90 minutes.

(3) Measurement of warpage Of the four sides of the metal leaf with the resin composition layer obtained in (2) above, the polyimide tape on three sides is peeled off, and the height of the highest point is obtained from the SUS plate to obtain the height of the warp. The value was calculated and evaluated according to the following criteria.
◯: The amount of warpage is less than 1 cm.
Δ: The size of the warp is 1 cm or more and less than 3 cm.
X: The size of the warp is 3 cm or more.

<Measurement of coefficient of linear thermal expansion>
The resin sheets obtained in Examples and Comparative Examples were heat-cured by heating at 190 ° C. for 90 minutes, and peeled from the PET film as a support to obtain a sheet-like cured product. The cured product was cut into test pieces having a width of 5 mm, a length of 15 mm, and a thickness of 30 mm, and thermomechanical analysis was performed by a tensile weight method using a thermomechanical analyzer (Thermo Plus TMA8310 manufactured by Rigaku Corporation). .. After the test piece was attached to the apparatus, 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. The average coefficient of linear thermal expansion (ppm) from 25 ° C to 150 ° C in the second measurement was calculated.

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

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

It has been confirmed that in Examples 1 to 6, even when the components (D) to (F) are not contained, the same result as in the above-mentioned Examples is obtained, although the degree is different.

Claims (10)

(A) Phenoxy resin containing a perfluoroalkyl group,
A resin composition containing (B) an epoxy resin and (C) a curing agent. The resin composition according to claim 1, wherein the component (A) contains a structure represented by the following general formula (A-1).

(In the general formula (A-1), R ¹¹ represents a divalent aliphatic hydrocarbon group containing one or more perfluoroalkyl groups which may have a substituent, and R ¹² and R ¹³ are. Each independently represents a substituent. N1 and n2 each independently represent an integer of 0 to 4, and * represents a bond.) The resin composition according to claim 2, wherein the component (A) further comprises a structure represented by the following general formula (A-2).

(In the general formula (A-2), R ²¹ represents a divalent aliphatic hydrocarbon group which may have a single bond or a substituent, and R ²² and R ²³ each independently represent a substituent. . M1 and m2 each independently represent an integer from 0 to 4, and * represents a bond.) The item according to any one of claims 1 to 3, wherein the content of the component (A) is 0.1% by mass or more and 5% by mass or less when the non-volatile component in the resin composition is 100% by mass. Resin composition. The resin composition according to any one of claims 1 to 4, further comprising (D) an inorganic filler. The resin composition according to any one of claims 1 to 5, which is used for forming an insulating layer. The resin composition according to any one of claims 1 to 6, which is used for forming an insulating layer for forming a conductor layer. A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of claims 1 to 7. A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 7. A semiconductor device including the printed wiring board according to claim 9.