JP6911806B2 - Resin composition, sheet-like laminated material, printed wiring board and semiconductor device - Google Patents

Description

The present invention relates to resin compositions. Furthermore, the present invention relates to a sheet-like laminated material, a printed wiring board, and a semiconductor device using the resin composition.

As a manufacturing technique for a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately stacked on an inner layer substrate is known. In the build-up manufacturing method, the insulating layer is generally formed by curing the resin composition. For example, Patent Document 1 describes a resin composition containing (A) a radically polymerizable compound, (B) an epoxy resin, (C) a curing agent, and (D) a roughening component. ..

Japanese Unexamined Patent Publication No. 2014-304580

In recent years, there has been an increasing demand for a resin composition capable of forming an insulating layer having a low dielectric loss tangent. Further, the miniaturization and high performance of electronic devices are advancing, and in printed wiring boards, the build-up layer is multi-layered, and there is a demand for miniaturization and high density of wiring.

In order to achieve further miniaturization and high density of wiring, a resin composition having a low dielectric loss tangent and good plating adhesion and substrate adhesion is required, but all of these have not been sufficiently satisfied. is the current situation.

An object of the present invention is to provide a resin composition having a low dielectric loss tangent and good plating adhesion and substrate adhesion.

As a result of diligent studies on the above-mentioned problems, the present inventors have found that in a resin composition containing (A) an epoxy resin and (B) a curing agent, (C) a resin having a radically polymerizable unsaturated group and (D) a fat. It has been found that the above-mentioned problems can be realized by blending with a group phosphine compound in combination, and the present invention has been completed.

（式中、
Ｒ^ｄ１及びＲ^ｄ２は、それぞれ独立に、水素原子又は式：−（Ｒ−Ｏ）_ｌ−Ｒ’で表される１価の基を表し、ここで、ｌは０〜５の整数を表し、Ｒは置換基を有していてもよい２価の芳香族基、又は置換基を有していてもよい２価の脂肪族基を表し、Ｒ’は置換基を有していてもよい１価の芳香族基、又は置換基を有していてもよい１価の脂肪族基を表し、Ｒが複数存在する場合、それらは互いに同じでも異なっていてもよく、
Ｒ^ｄ３は、式：−（Ｒ’’−Ｏ）_ｍ−Ｒ’’’で表される１価の基を表し、ここで、ｍは０〜５の整数を表し、Ｒ’’は置換基を有していてもよい２価の脂肪族基を表し、Ｒ’’’は置換基を有していてもよい１価の脂肪族基を表し、Ｒ’’が複数存在する場合、それらは互いに同じでも異なっていてもよい。）

（式中、
Ｒ^ｄ１及びＲ^ｄ２は上記と同義であり、
Ｌは、式：−（Ｒ’’−Ｏ）_ｎ−Ｒ’’−で表される２価の基を表し、ここで、ｎは０〜５の整数を表し、Ｒ’’は上記と同義であり、Ｒ’’が複数存在する場合、それらは互いに同じでも異なっていてもよく、
Ｒ^ｄ４及びＲ^ｄ５は、それぞれ独立に、水素原子、式：−（Ｒ−Ｏ）_ｌ−Ｒ’で表される１価の基又は式：−Ｌ−Ｐ（−Ｒ^ｄ１）（−Ｒ^ｄ２）で表される１価の基を表し、ここで、ｌ、Ｒ、Ｒ’、Ｌ、Ｒ^ｄ１及びＲ^ｄ２は上記と同義である。）
［６］ （Ｄ）成分が、下記式の何れか１つで表される化合物を含む、［１］〜［５］の何れかに記載の樹脂組成物。

［７］ 樹脂成分を１００質量％とした場合、（Ｄ）成分の含有量が、０．００１質量％〜１０質量％である、［１］〜［６］の何れかに記載の樹脂組成物。
［８］ （Ａ）成分が、ビフェニル型エポキシ樹脂を含む、［１］〜［７］の何れかに記載の樹脂組成物。
［９］ （Ｂ）成分が、活性エステル系硬化剤を含む、［１］〜［８］の何れかに記載の樹脂組成物。
［１０］ （Ｃ）成分が、炭素−炭素二重結合を有する、［１］〜［９］の何れかに記載の樹脂組成物。
［１１］ （Ｃ）成分が、アクリル基、メタクリル基、スチリル基、アリル基、ビニル基、プロペニル基及びマレイミド基からなる群から選択される１以上の基を有する、［１］〜［１０］の何れかに記載の樹脂組成物。
［１２］ さらに（Ｅ）無機充填材を含む、［１］〜［１１］の何れかに記載の樹脂組成物。
［１３］ 樹脂組成物中の不揮発成分を１００質量％とした場合、（Ｅ）無機充填材の含有量が５０質量％以上である、［１２］に記載の樹脂組成物。
［１４］ 導体層を形成するための絶縁層用である、［１］〜［１３］の何れかに記載の樹脂組成物。
［１５］ ［１］〜［１４］の何れかに記載の樹脂組成物を含有する、シート状積層材料。
［１６］ ［１］〜［１４］の何れかに記載の樹脂組成物の硬化物からなる絶縁層を含む、プリント配線板。
［１７］ ［１］〜［１４］の何れかに記載の樹脂組成物の硬化物を含む、半導体装置。 That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a resin having a radically polymerizable unsaturated group, and (D) an aliphatic phosphine compound.
[2] The resin composition according to [1], wherein the component (D) has a phosphorus atom to which an aliphatic carbon atom is directly bonded.
[3] The resin composition according to [1] or [2], wherein the component (D) has 1 to 4 phosphorus atoms to which an aliphatic carbon atom is directly bonded in one molecule.
[4] The resin composition according to any one of [1] to [3], wherein the component (D) has 2 to 40 aliphatic carbon atoms in one molecule.
[5] The resin composition according to any one of [1] to [4], wherein the component (D) is a compound represented by the formula (D1) or the formula (D2).

(During the ceremony,
R ^d1 and R ^d2 each independently represent a hydrogen atom or a monovalent group represented by the formula:-(RO) _l- R', where l represents an integer of 0-5. R represents a divalent aromatic group which may have a substituent or a divalent aliphatic group which may have a substituent, and R'may have a substituent 1 Represents a valent aromatic group or a monovalent aliphatic group which may have a substituent, and when a plurality of Rs are present, they may be the same or different from each other.
R ^d3 represents a monovalent group represented by the formula:-(R''-O) _m- R'''where m represents an integer of 0-5 and R'' represents a substituent. Represents a divalent aliphatic group which may have a substituent, R'''represents a monovalent aliphatic group which may have a substituent, and if there are a plurality of R'', they represent They may be the same or different from each other. )

(During the ceremony,
R ^d1 and R ^d2 are synonymous with the above.
L represents a divalent group represented by the formula: − (R''− O) _n −R''−, where n represents an integer from 0 to 5, and R'' is synonymous with the above. And if there are multiple R''s, they may be the same or different from each other.
R ^d4 and R ^d5 are independently hydrogen atoms, a monovalent group represented by _{the formula:-(RO) l} ^{-R'or the formula: -LP (-R d1} ) ( ^{-R d2).} ) Represents a monovalent group, where l, R, R', L, R ^d1 and R ^d2 are synonymous with the above. )
[6] The resin composition according to any one of [1] to [5], wherein the component (D) contains a compound represented by any one of the following formulas.

[7] The resin composition according to any one of [1] to [6], wherein the content of the component (D) is 0.001% by mass to 10% by mass when the resin component is 100% by mass. ..
[8] The resin composition according to any one of [1] to [7], wherein the component (A) contains a biphenyl type epoxy resin.
[9] The resin composition according to any one of [1] to [8], wherein the component (B) contains an active ester-based curing agent.
[10] The resin composition according to any one of [1] to [9], wherein the component (C) has a carbon-carbon double bond.
[11] The component (C) has one or more groups selected from the group consisting of an acrylic group, a methacryl group, a styryl group, an allyl group, a vinyl group, a propenyl group and a maleimide group, [1] to [10]. The resin composition according to any one of.
[12] The resin composition according to any one of [1] to [11], further comprising (E) an inorganic filler.
[13] The resin composition according to [12], wherein the content of the (E) inorganic filler is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[14] The resin composition according to any one of [1] to [13], which is used for an insulating layer for forming a conductor layer.
[15] A sheet-like laminated material containing the resin composition according to any one of [1] to [14].
[16] A printed wiring board including an insulating layer made of a cured product of the resin composition according to any one of [1] to [14].
[17] A semiconductor device comprising a cured product of the resin composition according to any one of [1] to [14].

According to the present invention, it is possible to provide a resin composition having a low dielectric loss tangent and good plating adhesion and substrate adhesion.

<Explanation of terms>
As used herein, the term "aliphatic phosphine-based compound" means a compound in which at least one of the organic groups bonded to a phosphorus atom is an aliphatic group among the organic phosphine compounds. In the present specification, the aliphatic group broadly means a non-aromatic organic group, and in addition to a non-aromatic hydrocarbon group, a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom, a boron atom and a silicon atom. Also includes non-aromatic organic groups containing. When the aliphatic group is a non-aromatic organic group containing a hetero atom, the carbon atom of the organic group is bonded to the phosphorus atom. Therefore, the "aliphatic phosphine compound" in the present invention is characterized by containing a phosphorus atom to which an aliphatic carbon atom is directly bonded.

In the present specification, the term "may have a substituent" attached immediately before a group refers to the case where the hydrogen atom of the group is not substituted with a substituent and the hydrogen atom of the group. It means both when a part or all of is substituted with a substituent.

As used herein, the term "substituent" refers to a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy, unless otherwise specified. Group means monovalent heterocyclic group, alkylidene group, amino group, silyl group, phosphino group, mercapto group, formyl group, acyl group, acyloxy group, carboxy group, cyano group, nitro group, hydroxy group and oxo group. ..

Examples of the halogen atom used as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group used as the substituent may be either linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The number of carbon atoms of the cycloalkyl group used as the substituent is preferably 3 to 12, more preferably 3 to 6. The alkoxy group used as the substituent may be either linear or branched. The number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 6. The number of carbon atoms of the cycloalkyloxy group used as the substituent is preferably 3 to 12, more preferably 3 to 6. The number of carbon atoms of the aryl group used as the substituent is preferably 6 to 14, more preferably 6 to 10. The aryloxy group used as the substituent has preferably 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. The arylalkyl group used as the substituent has preferably 7 to 15 carbon atoms, more preferably 7 to 11 carbon atoms. The arylalkoxy group used as the substituent has preferably 7 to 15 carbon atoms, more preferably 7 to 11 carbon atoms. The monovalent heterocyclic group used as a substituent means a group obtained by removing one hydrogen atom from the heterocycle of a heterocyclic compound. The monovalent heterocyclic group has preferably 3 to 15 carbon atoms, more preferably 3 to 9 carbon atoms. The monovalent heterocyclic group also includes a monovalent aromatic heterocyclic group (heteroaryl group). The alkylidene group used as a substituent is a group obtained by removing two hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms of the alkylidene group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. The amino group, silyl group, phosphino group, and mercapto group used as substituents are _{a group represented by the formula: -NH 2} , a group represented by the formula: -SiH ₃ , and a formula: -PH ₂ , respectively. Group represented and formula: means a group represented by -SH. Acyl group used as a substituent of the formula: -C (= O) (wherein, ^{R S} is alkyl or aryl group) -R ^S group represented by means a. The ^{alkyl group represented by RS} may be linear or branched. The number of carbon atoms of the acyl group is preferably 2 to 13, and more preferably 2 to 7. Acyloxy group used as a substituent of the formula: (wherein, ^{R S} is as defined above) -O-C (= O) -R S group represented by a. The number of carbon atoms of the acyloxy group is preferably 2 to 13, more preferably 2 to 7. The above-mentioned substituent may further have a substituent (sometimes referred to as a "secondary substituent"). Unless otherwise specified, the secondary substituent may be the same as the above-mentioned substituent. Examples of the substituent having a secondary substituent include a dimethylamino group.

Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof.

[Resin composition]
The resin composition of the present invention is characterized by containing (A) an epoxy resin, (B) a curing agent, (C) a resin having a radically polymerizable unsaturated group, and (D) an aliphatic phosphine compound.

A resin composition containing (A) an epoxy resin and (B) a curing agent, wherein (C) a resin having a radically polymerizable unsaturated group and (D) an aliphatic phosphine compound are combined and blended. Can provide a cured product having a low dielectric loss tangent and good plating adhesion (adhesion to the plating conductor layer) and base adhesion (adhesion to the base conductor layer).

<(A) Epoxy resin>
The resin composition of the present invention contains an epoxy resin as the component (A). Examples of the epoxy resin include bisphenol type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, and naphthalene type epoxy resin. , Naftor 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 with butadiene structure, alicyclic Examples thereof include a type epoxy resin, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, and a tetraphenylethane type epoxy resin. .. The epoxy resin may be used alone or in combination of two or more. The bisphenol type epoxy resin refers to an epoxy resin having a bisphenol structure, and examples thereof include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, and a bisphenol AF type epoxy resin. The biphenyl type epoxy resin refers to an epoxy resin having a biphenyl structure, wherein the biphenyl structure may have a substituent such as an alkyl group, an alkoxy group, or an aryl group. Therefore, the biphenyl type epoxy resin and the biphenyl aralkyl type epoxy resin are also included in the biphenyl type epoxy resin.

As the epoxy resin, an aromatic epoxy resin is preferable. Here, the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule. The aromatic ring includes not only a monocyclic structure such as a benzene ring but also a polycyclic aromatic structure such as a naphthalene ring and an aromatic heterocyclic structure. Above all, from the viewpoint of realizing excellent plating adhesion and substrate adhesion in combination with the component (C) and the component (D), the component (A) is a bisphenol type epoxy resin, a biphenyl type epoxy resin, or a naphthylene ether type. One or more selected from the group consisting of epoxy resin, naphthalene type tetrafunctional epoxy resin and naphthol type epoxy resin is preferable, and one or more selected from the group consisting of bisphenol type epoxy resin and biphenyl type epoxy resin is more preferable. Epoxy resins are even more preferred. In one preferred embodiment, component (A) comprises a biphenyl type epoxy resin.

The epoxy resin preferably has two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70. It is mass% or more.

Epoxy resins include a liquid epoxy resin at a temperature of 20 ° C. (hereinafter, also referred to as “liquid epoxy resin”) and a solid epoxy resin at a temperature of 20 ° C. (hereinafter, also referred to as “solid epoxy resin”). .. The resin composition of the present invention may contain the liquid epoxy resin alone or the solid epoxy resin alone as the component (A), and may be a combination of the liquid epoxy resin and the solid epoxy resin. May be included. Above all, the resin composition of the present invention preferably contains a solid epoxy resin as the component (A), and contains the solid epoxy resin alone or in combination with the solid epoxy resin and the liquid epoxy resin. Is preferable.

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 biphenyl 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 type epoxy resin, tetraphenylethane type epoxy resin are preferable, bixilenol type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, naphthalene type A tetrafunctional epoxy resin and a naphthol type epoxy resin are more preferable, and a bixilenol type epoxy resin is further 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" (dicyclopentadiene type epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (HP6000) manufactured by DIC. Naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayaku Co., Ltd .; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl aralkyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; "ESN485" (naphthol) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Novorak type epoxy resin); Mitsubishi Chemical's "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin); Mitsubishi Chemical's "YX4000HK" (bixilenol type epoxy resin); "YX8800" (anthracene type epoxy resin); "PG-100" and "CG-500" (bisphenol AF type epoxy resin) manufactured by Osaka Gas Chemical Co., Ltd .; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. Mitsubishi Chemical's "YL7800" (fluorene type epoxy resin); Mitsubishi Chemical's "jER1010" (solid bisphenol A type epoxy resin); Mitsubishi Chemical's "jER1031S" (tetraphenylethane type epoxy resin) ; Can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical Co., Ltd. , "Epicoat 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "630" and "630LSD" manufactured by Mitsubishi Chemical Co., Ltd. (glycidylamine type epoxy resin); "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX Corporation "EX-721" (glycidyl ester type epoxy resin); "Selokiside 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Co., Ltd .; "PB-3600" (epoxy having a butadiene structure) manufactured by Daicel Co., Ltd. Resin); "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation; and the like. 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 epoxy resin, their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.1 to 1:15, more preferably. It is 1: 0.5 to 1:10, particularly preferably 1: 1 to 1: 8. By setting the mass ratio of the liquid epoxy resin to the solid epoxy resin in the above range and setting the amount ratio of the liquid epoxy resin to the solid epoxy resin in such a range, i) the form of the sheet-shaped laminated material. When used in the form of a sheet-like laminated material, sufficient flexibility is obtained and handleability is improved, and ii) has sufficient breaking strength. Effects such as being able to obtain an insulating layer can be obtained.

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

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. The weight average molecular weight of a resin such as an epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The content of the component (A) in the resin composition is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 8 from the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability. It is mass% or more. The upper limit of the content of the component (A) is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less or 20. It is mass% or less.

In the present invention, the content of each component constituting the resin composition is a value when the total of the non-volatile components in the resin composition is 100% by mass.

<(B) Hardener>
The resin composition of the present invention contains a curing agent as the component (B). The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and for example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, and a carbodiimide. A system curing agent can be mentioned. The curing agent may be used alone or in combination of two or more.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion strength (peel strength) with the conductor layer, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. .. Of these, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength with the conductor layer. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", manufactured by Nippon Steel & Sumitomo Metal Corporation, "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-1356", "TD2090" manufactured by DIC Co., Ltd. , Etc. can be mentioned.

The active ester-based curing agent is not particularly limited, but generally contains an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more esters is preferably used. 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.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. 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 structural unit composed of phenylene-dicyclopentalene-phenylene.

Commercially available active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (manufactured by DIC Co., Ltd.) as active ester compounds containing a dicyclopentadiene-type diphenol structure. ), "EXB9416-70BK" (manufactured by DIC Co., Ltd.) as an active ester compound containing a naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing an acetylated product of phenol novolac, benzoyl of phenol novolac. Examples of the active ester compound containing a compound include "YLH1026" (manufactured by Mitsubishi Chemical Corporation).

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

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate (oligo (3-methylene-1,5-phenylencyanate)), 4,4'-methylenebis (2,6-dimethylphenylcyanate), 4, 4'-Etilidendidiphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-) Bifunctional cyanate resins such as dimethylphenyl) 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 novolak and the like, and 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) and "BA230" (part or all of bisphenol A disicanate) manufactured by Lonza Japan Co., Ltd. Is a prepolymer that has been triadinated to form a trimer) and the like.

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

From the viewpoint of obtaining a cured product having excellent heat resistance, and from the viewpoint of achieving good plating adhesion and substrate adhesion in combination with the components (C) and (D), the component (B) is an active ester-based curing agent. It is preferable to include it.

The amount ratio of (A) epoxy resin and (B) curing agent is the ratio of [total number of epoxy groups in epoxy resin]: [total number of reactive groups in curing agent], 1: 0.2 to 1: The range of 2 is preferable, 1: 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1.2 is further preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and differs depending on the type of the curing agent. The total number of epoxy groups in the epoxy resin is the total number of all epoxy resins obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and the total number of reactive groups in the curing agent is The value obtained by dividing the solid content mass of each curing agent by the reaction group equivalent is the total value for all curing agents. By setting the amount ratio of the epoxy resin and the curing agent within such a range, the heat resistance of the obtained insulating layer is further improved.

<(C) Resin having radically polymerizable unsaturated group>
The resin composition of the present invention contains a resin having a radically polymerizable unsaturated group (also referred to as an ethylenically or acetylene unsaturated group) as the component (C). In the following description, the "resin having a radically polymerizable unsaturated group" as the component (C) may be referred to as an "unsaturated resin". Only one carbon-carbon unsaturated bond (ethylenic or acetylene unsaturated bond) having radical polymerizable property may be contained in one molecule of (C) unsaturated resin, and a plurality of carbon-carbon unsaturated bonds may be contained. You may. The cured product of the resin composition containing the (C) unsaturated resin usually contains a molecular structure site formed by the reaction of the unsaturated binding site of the (C) unsaturated resin. As a result, the polarity of the cured product is reduced, and the value of the dielectric loss tangent can be reduced. The component (C) may be used alone or in combination of two or more.

The radically polymerizable unsaturated group contained in the (C) unsaturated resin is preferably an ethylenically unsaturated group having a carbon-carbon double bond. Therefore, in one embodiment, component (C) has a carbon-carbon double bond. In a more preferred embodiment, the radically polymerizable unsaturated group is preferably one or more groups selected from the group consisting of an acrylic group, a methacryl group, a styryl group, an olefin group and a maleimide group. Preferred examples of the olefin group include an allyl group, a vinyl group and a propenyl group. Thus, in a preferred embodiment, component (C) has one or more groups selected from the group consisting of acrylic, methacryl, styryl, allyl, vinyl, propenyl and maleimide groups.

The unsaturated resin (C) is preferably a resin having a cyclic ether structure of 5 members or more (hereinafter, also referred to as “cyclic ether structure-containing unsaturated resin”). Since the cyclic ether structure-containing unsaturated resin usually has restricted molecular movement, the dielectric loss tangent can be effectively lowered.

The cyclic ether structure-containing unsaturated resin may contain only one cyclic ether structure, or may contain a plurality of cyclic ether structures.

The cyclic ether structure may have a monocyclic structure containing only one ring, a polycyclic structure containing two or more rings, and a condensed ring structure including a condensed ring. You may.

The number of oxygen atoms contained in one cyclic ether structure is preferably 1 or more, more preferably 2 or more, preferably 5 or less, more preferably 4 or less, from the viewpoint of remarkably obtaining the desired effect of the present invention. More preferably, it is 3 or less.

The cyclic ether structure is preferably a 5- to 10-membered ring, more preferably a 5- to 8-membered ring, and even more preferably a 5- to 6-membered ring. Specific examples of the cyclic ether structure having five or more membered rings include a furan structure, a tetrahydrofuran structure, a dioxolane structure, a pyran structure, a dihydropyran structure, a tetrahydropyran structure, and a dioxane structure. Above all, the dioxane structure is preferable from the viewpoint of improving the compatibility of the resin composition. The dioxane structure includes a 1,2-dioxane structure, a 1,3-dioxane structure and a 1,4-dioxane structure, and a 1,3-dioxane structure is preferable.

The cyclic ether structure may have a substituent. The type of the substituent is not particularly limited, and may be any of the above-mentioned substituents, and examples thereof include an alkyl group and an alkoxy group. The number of carbon atoms of such a substituent is as described above, but is preferably 1 to 6, more preferably 1 to 3.

Among the unsaturated resins containing a cyclic ether structure, a resin having a vinyl group is preferable. A cyclic ether structure-containing unsaturated resin having a vinyl group (that is, a resin having a vinyl group as a radically polymerizable unsaturated group and having a cyclic ether structure having a 5-membered ring or more) is used as the (C) unsaturated resin. Therefore, the desired effect of the present invention can be remarkably obtained. Further, usually, the dielectric loss tangent of the resin composition can be effectively lowered.

Preferred examples of the unsaturated resin (C) include a compound represented by the following formula (C1), a compound represented by the following formula (C6), a compound represented by the following formula (C7), and a compound represented by the following formula (C9). ), And the compound represented by the following formula (C10). Among them, the compound represented by the formula (C7) is a cyclic ether structure-containing unsaturated resin, which is particularly preferable.

In the formula (C1), R ^{1 to} R ⁶ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. In the formula (C1), A represents a divalent group represented by the following formula (C2) or the following formula (C3).

In the formula (C2), B represents a divalent group represented by the following formula (C2-1), (C2-2) or (C2-3).

In the formula (C2-1), R ^{15 to} R ¹⁸ independently represent a hydrogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms, and preferably a hydrogen atom or a methyl group.
In the formula (C2-2), R ^{19 to} R ²⁶ independently represent a hydrogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms, and preferably a hydrogen atom or a methyl group.
In the formula (C2-3), R ^{27 to} R ³⁴ independently represent a hydrogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms, and preferably a hydrogen atom or a methyl group. Further, in the formula (C2-3), E represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

In the formula (C3), D represents a divalent group represented by the following formula (C4).

In the formula (C4), R ^{7 to} R ¹⁴ independently represent a hydrogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms, and preferably a hydrogen atom or a methyl group. In particular, R ⁷ , R ⁸ , R ¹³ and R ¹⁴ more preferably represent a methyl group. In formula (C4), a and b are integers of 0 or more and 100 or less, at least one of which is not 0. In the formula (C4), B represents a divalent group represented by the above formula (C2-1), (C2-2) or (C2-3).

The compound represented by the formula (C1) is preferably a compound represented by the following formula (C5).

In the formula (C5), R ^{1 to} R ^{6 are synonymous with R 1 to} R ⁶ in the formula (C1), B is synonymous with B in the formula (C2), and a and b are synonymous. , Synonymous with a and b in the above formula (C4).

In formula (C7), ring F represents a divalent group having a cyclic ether structure of 5 or more members. The range of the cyclic ether structure is as described above. Further, the cyclic ether structure may have a substituent as described above.

Examples of the divalent group having a cyclic ether structure having a 5-membered ring or more include a furan-2,5-diyl group, a tetrahydrofuran-2,5-diyl group, a dioxolan-2,5-diyl group, and a pyran-2. 5-Diyl group, dihydropyran-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,2-dioxane-3,6-diyl group, 1,3-dioxane-2,5-diyl group , 1,4-Dioxane-2,5-diyl group, 5-ethyl-1,3-dioxane-2,5-diyl group. Of these, 5-ethyl-1,3-dioxane-2,5-diyl groups are preferable.

In formula (C7), B ¹ and B ² each independently represent a single bond or a divalent linking group. B ¹ and B ² are preferably divalent linking groups. Examples of the divalent linking group include an alkylene group which may have a substituent, an alkenylene group which may have a substituent, an alkynylene group which may have a substituent, and a substituent. An arylene group which may have a substituent, a heteroarylene group which may have a substituent, a group represented by -COO-, a group represented by -CO-, a group represented by -CONH-, a group represented by -NHCONH. Group represented by-, group represented by -NHCOO-, group represented by -C (= O)-, group represented by -S-, group represented by -SO-, group represented by -NH- Examples thereof include a group represented by and a group in which a plurality of these groups are combined.

Among these, B ¹ and B ² are an alkylene group which may have a substituent, an alkenylene group which may have a substituent, an alkynylene group which may have a substituent, and -COO-. It is preferable that two or more groups are selected and combined from the group consisting of the group represented by and the group represented by −O−. In particular, B ¹ and B ² are more preferably a group in which two or more groups are selected and combined from the group consisting of an alkylene group which may have a substituent and a group represented by −COO−. ..

In formula (C7), C ¹ and C ² each independently represent a functional group. Examples of the functional group include a vinyl group, a methacryl group, an acrylic group, an allyl group, a styryl group, a propenyl group and an epoxy group. In one preferred embodiment, C ¹ and C ² are vinyl groups.

Specific examples of the compound represented by the formula (C7) include a compound represented by the following formula (C8).

In formula (C10), n represents 1-5.

Examples of the unsaturated resin include "OPE-2St 1200" manufactured by Mitsubishi Gas Chemicals, Inc. (styrene-modified polyphenylene ether resin, number average molecular weight 1200, equivalent to the above formula (C5)), and "YL7776" manufactured by Mitsubishi Chemicals (C5). Bixyleneol diallyl ether resin, number average molecular weight 331, equivalent to the above formula (C6)), "A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (dioxane acrylic monomer glycol diacrylate, number average molecular weight 326, equivalent to the above formula (C8)) , Nippon Kayaku Co., Ltd. "KAYARAD R-604" (corresponding to the above formula (C8)), Shin-Nakamura Chemical Industry Co., Ltd. "A-DCP" (tricyclodecanedimethanol diacrylate, number average molecular weight 304, the above formula (C9) ) Equivalent), "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., and the above formula (C10) equivalent). Further, the unsaturated resin (C) may be used alone or in combination of two or more.

The number average molecular weight of the unsaturated resin (C) is preferably 100 or more, more preferably 200 or more, preferably 10,000 or less, and more preferably 3000 or less. (C) When the number average molecular weight of the unsaturated resin is in the above range, it is possible to suppress volatilization of the resin varnish during drying and to prevent the melt viscosity of the resin composition from becoming excessive. The number average molecular weight can be measured by a gel permeation chromatography (GPC) method in terms of polystyrene. For the measurement of the number average molecular weight by the GPC method, for example, "LC-9A / RID-6A" manufactured by Shimadzu Corporation is used as a measuring device, and "Shodex K-800P / K-804L / K-804L" manufactured by Showa Denko Corporation is used as a column. ], Using chloroform as the mobile phase, can be measured at a column temperature of 40 ° C.

The content of the component (C) in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, or 5% by mass or more from the viewpoint of obtaining a cured product having a low dielectric loss tangent. be. The upper limit of the content of the component (C) is preferably 20% by mass or less, more preferably 15% by mass or less, or 10% by mass or less from the viewpoint of improving the compatibility of the resin composition.

<(D) Aliphatic phosphine compound>
The resin composition of the present invention contains an aliphatic phosphine compound as the component (D). By blending the component (D) and the component (C) described above in combination, it is possible to obtain a resin composition that provides a cured product having a low dielectric loss tangent and excellent plating adhesion and substrate adhesion.

As described above, by blending the component (C), the dielectric loss tangent of the cured product of the resin composition can be lowered. However, on the other hand, the present inventors have found that the result is a cured product having poor plating adhesion and substrate adhesion. As a result of diligent studies on such issues, the present inventors have stated that the dielectric loss tangent of the cured product of the resin composition can be lowered by blending the component (D) in combination with the component (C) (C). ), While maintaining the characteristics of using the components, we have achieved a resin composition that provides a cured product with excellent plating adhesion and substrate adhesion.

As described above, the component (D) is characterized by containing a phosphorus atom to which an aliphatic carbon atom is directly bonded. In this respect, it is the present invention that an organic phosphine compound that does not have a phosphorus atom to which an aliphatic carbon atom is directly bonded cannot achieve the desired effect in combination with the component (C). Have confirmed (Comparative Example 2 described later). Since the aliphatic carbon atom exhibiting electron donating property is directly bonded to the phosphorus atom, the phosphorus atom becomes an electron-rich state, and the electron-rich phosphorus atom is the component (A) and the component (C). It is considered that the cured product composition that contributes to the adhesion to the conductor is reproduced by promoting the reaction of. From the viewpoint of achieving a resin composition that provides a cured product with better plating adhesion and substrate adhesion, the component (D) may contain a phosphorus atom in which both an aliphatic carbon atom and an aromatic carbon atom are directly bonded. preferable.

The number of phosphorus atoms to which the aliphatic carbon atom is directly bonded is not particularly limited, but is usually 1 to 10, preferably 1 to 8, and more preferably 1 to 6 per molecule of the component (D). , 1-4 or 1-3, more preferably 1 or 2. As long as the aliphatic carbon atom contains a phosphorus atom to which the aliphatic carbon atom is directly bonded, the component (D) may contain a phosphorus atom to which the aliphatic carbon atom is not directly bonded.

The number of aliphatic carbon atoms contained in one molecule of the component (D) is not particularly limited, but is preferably 2 or more, more preferably 3 or more or 4 or more. Here, the number of aliphatic carbon atoms is the total number of carbon atoms other than the aromatic carbon atoms contained in the component (D). For example, when the component (D) has two phenyl groups and one cyclohexyl group in one molecule, the number of aliphatic carbon atoms thereof is six. When the component (D) contains one phenyl group and two cyclooctyl groups in one molecule, the number of aliphatic carbon atoms thereof is 16. The upper limit of the number of aliphatic carbon atoms contained in one molecule of the component (D) is not particularly limited, but is usually 100 or less, preferably 80 or less, more preferably 60 or less, still more preferably 40 or less. 20 or less, 12 or less, or 8 or less.

In one embodiment, the component (D) is a compound represented by the following formula (D1) or formula (D2).

（式（Ｄ１）中、
Ｒ^ｄ１及びＲ^ｄ２は、それぞれ独立に、水素原子又は式：−（Ｒ−Ｏ）_ｌ−Ｒ’で表される１価の基を表し、ここで、ｌは０〜５の整数を表し、Ｒは置換基を有していてもよい２価の芳香族基、又は置換基を有していてもよい２価の脂肪族基を表し、Ｒ’は置換基を有していてもよい１価の芳香族基、又は置換基を有していてもよい１価の脂肪族基を表し、Ｒが複数存在する場合、それらは互いに同じでも異なっていてもよく、
Ｒ^ｄ３は、式：−（Ｒ’’−Ｏ）_ｍ−Ｒ’’’で表される１価の基を表し、ここで、ｍは０〜５の整数を表し、Ｒ’’は置換基を有していてもよい２価の脂肪族基を表し、Ｒ’’’は置換基を有していてもよい１価の脂肪族基を表し、Ｒ’’が複数存在する場合、それらは互いに同じでも異なっていてもよい。）

（式（Ｄ２）中、
Ｒ^ｄ１及びＲ^ｄ２は上記と同義であり、
Ｌは、式：−（Ｒ’’−Ｏ）_ｎ−Ｒ’’−で表される２価の基を表し、ここで、ｎは０〜５の整数を表し、Ｒ’’は上記と同義であり、Ｒ’’が複数存在する場合、それらは互いに同じでも異なっていてもよく、
Ｒ^ｄ４及びＲ^ｄ５は、それぞれ独立に、水素原子、式：−（Ｒ−Ｏ）_ｌ−Ｒ’で表される１価の基又は式：−Ｌ−Ｐ（−Ｒ^ｄ１）（−Ｒ^ｄ２）で表される１価の基を表し、ここで、ｌ、Ｒ、Ｒ’、Ｌ、Ｒ^ｄ１及びＲ^ｄ２は上記と同義である。）

(In equation (D1),
R ^d1 and R ^d2 each independently represent a hydrogen atom or a monovalent group represented by the formula:-(RO) _l- R', where l represents an integer of 0-5. R represents a divalent aromatic group which may have a substituent or a divalent aliphatic group which may have a substituent, and R'may have a substituent 1 Represents a valent aromatic group or a monovalent aliphatic group which may have a substituent, and when a plurality of Rs are present, they may be the same or different from each other.
R ^d3 represents a monovalent group represented by the formula:-(R''-O) _m- R'''where m represents an integer of 0-5 and R'' represents a substituent. Represents a divalent aliphatic group which may have a substituent, R'''represents a monovalent aliphatic group which may have a substituent, and if there are a plurality of R'', they represent They may be the same or different from each other. )

(In equation (D2),
R ^d1 and R ^d2 are synonymous with the above.
L represents a divalent group represented by the formula: − (R''− O) _n −R''−, where n represents an integer from 0 to 5, and R'' is synonymous with the above. And if there are multiple R''s, they may be the same or different from each other.
R ^d4 and R ^d5 are independently hydrogen atoms, a monovalent group represented by _{the formula:-(RO) l} ^{-R'or the formula: -LP (-R d1} ) ( ^{-R d2).} ) Represents a monovalent group, where l, R, R', L, R ^d1 and R ^d2 are synonymous with the above. )

In formula (D1), R ^d1 and R ^d2 each independently represent a hydrogen atom or a monovalent group represented by the formula:-(RO) _l-R'. l represents an integer from 0 to 5, R represents a divalent aromatic group which may have a substituent, or R'represents a divalent aliphatic group which may have a substituent. It represents a monovalent aromatic group which may have a substituent or a monovalent aliphatic group which may have a substituent, and when there are a plurality of Rs, they are the same or different from each other. May be good. In one preferred embodiment, ^{at least one of R d1} and R ^d2 represents a monovalent group represented by the formula:-(RO) _l -R'and is directly attached to the phosphorus atom. In the case of 1 to 5) and R'(in the case of l = 0), a divalent aromatic group which may have a substituent and a monovalent aromatic group which may have a substituent are used. show.

As used herein, the term "divalent aromatic group" refers to a group obtained by removing two hydrogen atoms from the aromatic ring of an aromatic compound. In one preferred embodiment, the divalent aromatic group comprises an arylene group, a heteroarylene group. The heteroarylene group is a group obtained by removing two hydrogen atoms from the heterocycle of an aromatic heterocyclic compound. The heterocycle means a ring containing not only a carbon atom but also a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a boron atom and a silicon atom as atoms constituting the ring. Further, in the present specification, the "monovalent aromatic group" refers to a group obtained by removing one hydrogen atom from the aromatic ring of an aromatic compound, and in a preferred embodiment, an aryl group or a heteroaryl group is used. include. The heteroaryl group refers to a group obtained by removing one hydrogen atom from the heterocycle of an aromatic heterocyclic compound, and is the same as the heteroarylene group except that one hydrogen atom is removed from the heterocycle.

As used herein, the term "divalent aliphatic group" refers to a group obtained by removing two hydrogen atoms from an aliphatic compound. Here, the aliphatic compound may be a saturated aliphatic compound or an unsaturated aliphatic compound. In one preferred embodiment, the divalent aliphatic group comprises an alkylene group, an alkaneylene group, a cycloalkylene group, a cycloalkenylene group, a heterocycloalkylene group, a heterocycloalkenylene group. The heterocycloalkylene group is a group obtained by removing two hydrogen atoms from the heterocycle (that is, the saturated heterocycle) of the saturated aliphatic heterocyclic compound, and the heterocycloalkenylene group has a carbon-carbon double bond. It refers to a group obtained by removing two hydrogen atoms from the heterocycle of an unsaturated aliphatic heterocyclic compound having a carbon-carbon double bond (that is, an unsaturated heterocycle having a carbon-carbon double bond). The hetero atom contained in the heterocycle is the same as above. Further, in the present specification, the "monovalent aliphatic group" means a group obtained by removing one hydrogen atom from an aliphatic compound. In one preferred embodiment, the monovalent aliphatic group comprises an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a heterocycloalkyl group, a heterocycloalkenyl group. The heterocycloalkyl group refers to a group obtained by removing one hydrogen atom from the heterocycle of a saturated aliphatic heterocyclic compound, and is the same as the heterocycloalkylene group except that one hydrogen atom is removed from the heterocycle. Is. The heterocycloalkenyl group refers to a group obtained by removing one carbon atom from the heterocycle of an unsaturated aliphatic heterocyclic compound having a carbon-carbon double bond, and one hydrogen atom removed from the heterocycle. It is the same as the heterocycloalkenylene group except that.

l is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, and even more preferably 0.

In a preferred embodiment, R comprises an arylene group which may have a substituent, a heteroarylene group which may have a substituent, an alkylene group which may have a substituent, and a substituent. An alkenylene group which may have a substituent, a cycloalkylene group which may have a substituent, a cycloalkenylene group which may have a substituent, a heterocycloalkylene group which may have a substituent, or Represents a heterocycloalkenylene group which may have a substituent.

The number of carbon atoms of the arylene group in R is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. Specific examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

The number of carbon atoms of the heteroarylene group in R is preferably 3 to 21, more preferably 3 to 15, still more preferably 3 to 9, and even more preferably 3 to 6. Specific examples of the heteroarylene group include a pyridiyl group, a pyrroldiyl group, a frangyl group, a thiophendiyl group, a pyridinediyl group, a pyridazinediyl group, a pyrimidinediyl group, a pyrazinediyl group, a triazinediyl group, a pyrolindiyl group and a piperidinediyl group. , Triazolediyl group, purindiyl group, anthraquinonediyl group, carbazolediyl group, fluorangeyl group, quinolinediyl group, and isoquinolindiyl group.

The alkylene group in R may be linear or branched, and the number of carbon atoms thereof is preferably 1 to 12, more preferably 1 to 9, and even more preferably 1 to 6 or 1 to 4. .. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group and a dodecylene group.

The alkenylene group in R may be linear or branched, and the number of carbon atoms thereof is preferably 2 to 12, more preferably 2 to 9, and even more preferably 2 to 6 or 2 to 4. .. Specific examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, a noneneylene group, a desenylene group, an undecenylene group and a dodecenylene group.

The number of carbon atoms of the cycloalkylene group in R is preferably 3 to 12, more preferably 3 to 10, 3 to 8 or 3 to 6. Specific examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a decahydronaphthanylene group, a norbornanylene group, and an adamantanylene group.

The number of carbon atoms of the cycloalkenylene group in R is preferably 3 to 10, more preferably 3 to 6. Specific examples of the cycloalkenylene group include a cyclopropenylene group, a cyclobutenylene group, a cyclopentenylene group, a cyclohexenylene group, and a norbornenylene group.

The number of carbon atoms of the heterocycloalkylene group in R is preferably 2 to 21, more preferably 2 to 15, and even more preferably 2 to 9, 2 to 6 or 2 to 5. The hetero atom constituting the heterocycloalkylene group preferably contains at least one selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a boron atom and a silicon atom, and preferably contains an oxygen atom, a sulfur atom and a sulfur atom. It is more preferable to contain one or more selected from the group consisting of nitrogen atoms. Specific examples of the heterocycloalkylene group include an oxylangidiyl group, an aziridinediyl group, an azetidinediyl group, an oxetanediyl group, a thietandiyl group, a pyrrolidinediyl group, a dihydrofurandiyl group, and a tetrahydrofurandiyl group.

The number of carbon atoms of the heterocycloalkenylene group in R is preferably 2 to 21, more preferably 2 to 15, and even more preferably 2 to 9, 2 to 6 or 2 to 5. Suitable heteroatoms are the same as described for heterocycloalkylene groups. Specific examples of the heterocycloalkenylene group include an oxylenidyl group and an oxetendyl group.

The substituents that the divalent group in R may have are as described above. When the divalent group in R has a plurality of substituents, they may be the same or different.

In a preferred embodiment, R'is an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkyl group which may have a substituent, a substituent. An alkenyl group which may have a substituent, a cycloalkyl group which may have a substituent, a cycloalkenyl group which may have a substituent, a heterocycloalkyl group which may have a substituent, Alternatively, it represents a heterocycloalkenyl group which may have a substituent.

Suitable carbon atoms of the aryl group, heteroaryl group, alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, heterocycloalkyl group, and heterocycloalkenyl group in R'are the arylene group and hetero in R, respectively. It is the same as the suitable number of carbon atoms described for the arylene group, the alkylene group, the alkenylene group, the cycloalkylene group, the cycloalkenylene group, the heterocycloalkylene group, and the heterocycloalkenylene group.

In formula (D1), R ^d3 represents a monovalent group represented by the formula:-(R''-O) _m- R''', where m represents an integer from 0 to 5. R ″ represents a divalent aliphatic group which may have a substituent, R ′ ″ represents a monovalent aliphatic group which may have a substituent, and R'' represents a plurality of. If present, they may be the same or different from each other.

m is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, and even more preferably 0.

In a preferred embodiment, R ″ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, a cycloalkylene group which may have a substituent, a substituent. It represents a cycloalkenylene group which may have a group, a heterocycloalkylene group which may have a substituent, or a heterocycloalkenylene group which may have a substituent.

In a preferred embodiment, R'''is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkyl group which may have a substituent, and the like. Represents a cycloalkenyl group which may have a substituent, a heterocycloalkyl group which may have a substituent, or a heterocycloalkenyl group which may have a substituent.

Suitable carbon atoms of the alkylene group, alkaneylene group, cycloalkylene group, cycloalkenylene group, heterocycloalkylene group, and heterocycloalkenylene group in R'' are the alkylene group, alkenylene group, cycloalkylene group, respectively, in R. It is the same as the suitable number of carbon atoms described for the cycloalkaneylene group, the heterocycloalkylene group, and the heterocycloalkenylene group. Further, the preferable number of carbon atoms of the alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, heterocycloalkyl group and heterocycloalkenyl group in R'' is the alkylene group, alkaneylene group and cyclo in R, respectively. It is the same as the suitable number of carbon atoms described for the alkylene group, the cycloalkenylene group, the heterocycloalkylene group, and the heterocycloalkenylene group.

When R'' is a heterocycloalkylene group (or heterocycloalkenylene group) which may have a substituent, the carbon atom constituting the heterocycloalkylene group (or heterocycloalkenylene group) is bonded to the phosphorus atom. .. When m is 0 and R ′ ″ is a heterocycloalkyl group (or heterocycloalkenyl group) which may have a substituent, it constitutes a heterocycloalkyl group (or heterocycloalkenyl group). The carbon atom is bonded to the phosphorus atom.

In one embodiment, in formula (D1),
i) Both R ^d1 and R ^d2 represent a monovalent group represented by the formula:-(RO) _l- R', where l is 0, even though R'has a substituent. A good aryl group,
ii) R ^d3 represents a monovalent group represented by the formula:-(R''-O) _m- R''', m is an integer from 0 to 2, and R'' has a substituent. It is an alkylene group which may have a substituent or a cycloalkylene group which may have a substituent, and R'''is an alkyl group which may have a substituent and an alkenyl which may have a substituent. It is a cycloalkyl group which may have a group or a substituent.

In one preferred embodiment, in formula (D1),
i) Both R ^d1 and R ^d2 represent a monovalent group represented by the formula:-(RO) _l- R', where l is 0, even though R'has a substituent. It is a good phenyl group and
ii) R ^d3 represents a monovalent group represented by the formula:-(R''-O) _m- R'', m is 0, and R'''has a substituent. It is also a good cycloalkyl group.

In another embodiment, in formula (D1),
i) R ^d1 represents a monovalent group represented by the formula:-(RO) _l- R', l is 0, and R'is an aryl group which may have a substituent. ,
ii) R ^d2 represents a monovalent group represented by the formula:-(RO) _l- R', l is 0, and R'is an alkyl group or substitution that may have a substituent. An alkenyl group that may have a group,
iii) R ^d3 represents a monovalent group represented by the formula:-(R''-O) _m- R''', m is an integer from 0 to 2, and R'' has a substituent. It is an alkylene group which may have a substituent or a cycloalkylene group which may have a substituent, and R'''is an alkyl group which may have a substituent and an alkenyl which may have a substituent. It is a cycloalkyl group which may have a group or a substituent.

In another preferred embodiment, in formula (D1),
i) R ^d1 represents a monovalent group represented by the formula:-(RO) _l- R', l is 0, and R'is a phenyl group which may have a substituent. ,
ii) R ^d1 represents a monovalent group represented by the formula:-(RO) _l- R', l is 0, and R'is an alkyl group which may have a substituent. ,
iii) R ^d3 represents a monovalent group represented by the formula:-(R''-O) _m- R'', m is 0, and R'''has a substituent. Is also a good alkyl group.

In the formula (D2), R ^d1 and R ^d2 are synonymous with the above, that is, they are synonymous with ^{R d1} and R ^{d2 in the formula (D1).}

In formula (D2), L represents a divalent group represented by the formula:-(R''-O) _{n-R "-.} n represents an integer from 0 to 5, and R'' is synonymous with the above, that is, synonymous with ^{R'' described for R d3} in equation (D1), and if there are multiple R''s, they are synonymous. They may be the same or different from each other.

n is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, and even more preferably 0.

In formula (D2), R ^d4 and R ^d5 are independently hydrogen atoms, _{a monovalent group represented by the formula:-(RO) l} -R'or the formula: -LP (-R). ^d1 ) represents a monovalent group represented by (-R ^d2 ), where l, R, R', L, R ^d1 and R ^d2 are synonymous with the above.

In one embodiment, in formula (D2),
i) Both R ^d1 and R ^d2 represent a monovalent group represented by the formula:-(RO) _l- R', where l is 0, even though R'has a substituent. A good aryl group,
ii) L represents a divalent group represented by the formula:-(R''-O) _n- R "-, n is an integer of 0 to 2, and R" has a substituent. An alkylene group which may have an alkylene group or a cycloalkylene group which may have a substituent and may have a substituent.
iii) Both R ^d4 and R ^d5 represent a monovalent group represented by the formula:-(RO) _l- R', where l is 0, even if R'has a substituent. A good aryl group.

In one preferred embodiment, in formula (D2),
i) Both R ^d1 and R ^d2 represent a monovalent group represented by the formula:-(RO) _l- R', where l is 0, even though R'has a substituent. It is a good phenyl group and
ii) L represents a divalent group represented by the formula: − (R''− O) _n −R''−, n is 0, and R'' may have a substituent. It is an alkylene group
iii) Both R ^d4 and R ^d5 represent a monovalent group represented by the formula:-(RO) _l- R', where l is 0, even if R'has a substituent. A good phenyl group.

In one embodiment, the component (D) comprises a compound represented by any one of the following formulas.

Examples of the component (D) include "DPPE" (1,3-bisdiphenylphosphinoetan), "DPPP" (1,3-bisdiphenylphosphinopropane), and "DPPPB" (1,3-bisdiphenylphosphinoetan) manufactured by Hokuko Kagaku Co., Ltd. 3-Bisdiphenylphosphinobtan), "DPCP" (diphenylcyclohexylphosphine), "TCHP" (tricyclohexylphosphine), "Amphos" ([4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine) ).

When the total of the resin components in the resin composition is 100% by mass, even if the content of the component (D) is as low as 0.001% by mass, the dielectric loss tangent is formed in combination with the component (C). It is possible to realize a resin composition that provides a cured product that is low and has excellent plating adhesion and substrate adhesion. The content of the component (D) in the resin composition is determined in the resin composition from the viewpoint of realizing a resin composition that, when combined with the component (C), provides a cured product having remarkably excellent plating adhesion and substrate adhesion. When the total of the resin components of the above is 100% by mass, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, and 0.2% by mass. % Or more, 0.3% by mass or more, or 0.5% by mass or more. The "resin component" refers to a component of the non-volatile components constituting the resin composition, excluding the (E) inorganic filler described later.

As described above, the component (D) has a phosphorus atom in which an aliphatic carbon atom is directly bonded, and such an electron-rich phosphorus atom promotes the reaction between the component (A) and the component (C). Therefore, it is considered that the cured product composition that contributes to the adhesion to the conductor is reproduced. Due to its high reaction promoting effect, when the component (D) is added, the melt viscosity of the resin composition may increase with time, and the storage time from the preparation of the resin composition to the use is long. Depending on the mode of use, thickening of the resin composition may become apparent. In this respect, when the total of the resin components in the resin composition is 100% by mass, the thickening can be effectively suppressed by setting the content of the component (D) to 10% by mass or less. The upper limit of the content of the component (D) is preferably 10% by mass or less, more preferably 8% by mass or less, 6% by mass or less, and 5% by mass or less from the viewpoint of obtaining a resin composition having a good pot life. , Or 3% by mass or less.

The resin composition of the present invention contains, if necessary, one or more additives selected from the group consisting of inorganic fillers, curing accelerators, indenkumaron resins, thermoplastic resins, flame retardants and organic fillers. It may be further contained.

-(E) Inorganic filler-
The resin composition of the present invention may further contain an inorganic filler as the component (E). By including the inorganic filler, a cured product having a lower linear thermal expansion coefficient and dielectric loss tangent can be realized.

The material of the inorganic filler is not particularly limited, but for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water. Aluminum oxide, 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 titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like, and 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. The inorganic filler may be used alone or in combination of two or more. Examples of commercially available spherical silica include "SO-C2" and "SO-C1" manufactured by Admatex Co., Ltd., "IMSIL A-8" and "IMSIL A-10" manufactured by Unimin.

The average particle size of the inorganic filler is preferably 4 μm or less, more preferably 3 μm or less, still more preferably 2.5 μm or less, even more preferably 2 μm or less, particularly preferably 1 μm or less, 0.7 μm or less, or 0.5 μm. It is as follows. The lower limit of the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.03 μm or more, still more preferably 0.05 μm or more, 0.07 μm or more, or 0.1 μm or more. The average particle size of the inorganic filler 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 type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction type particle size distribution measuring device, "LA-500", "LA-750", "LA-950", etc. manufactured by HORIBA, Ltd. can be used.

Inorganic fillers include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, alkoxysilane compounds, organosilazane compounds, titanate-based coupling agents, etc. from the viewpoint of enhancing moisture resistance and dispersibility. It is preferably treated with one or more surface treatment agents. Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and "KBM803" (3-mercaptopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. Examples thereof include "SZ-31" (hexamethyldisilazane) manufactured by Co., Ltd.

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 preventing 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.

From the viewpoint of obtaining a cured product having a low coefficient of linear thermal expansion and dielectric loss tangent, the content of the inorganic filler in the resin composition is preferably 50% by mass or more, more preferably 55% by mass or more, 60% by mass or more, 65. It is mass% or more, or 70 mass% or more. The upper limit of the content of the inorganic filler in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, from the viewpoint of the mechanical strength of the obtained cured product. ..

-(F) Curing accelerator-
The resin composition of the present invention may further contain a curing accelerator as the component (F). Examples of the curing accelerator include amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and peroxide-based curing accelerators. Of these, amine-based curing accelerators, imidazole-based curing accelerators, and peroxide-based curing accelerators are preferable. The curing accelerator may be used alone or in combination of two or more. When a curing accelerator is used, the content of the curing accelerator in the resin composition is preferably 0.005% by mass to 1% by mass, more preferably 0.01% by mass to 0.5% by mass.

-(G) Indenkumaron resin-
The resin composition of the present invention may further contain an indenkumaron resin as the component (G). By including the indenkumaron resin, the advantageous effect of the present invention due to the combination of the component (C) and the component (D) can be further enhanced. Examples of the indene mullon resin include copolymers of indene and kumaron, and copolymers of inden, kumaron and styrene. Specific examples of the indenkumaron resin include "H-100", "V-120S", and "V-120" manufactured by Nikko Kagaku Co., Ltd. The indenkumaron resin may be used alone or in combination of two or more. When an indenkumaron resin is used, the content of the indenkumaron resin in the resin composition is preferably 1 to 4% by mass, more preferably 2 to 3 from the viewpoint of obtaining a resin composition having good compatibility. It is 5.5% by mass.

-Thermoplastic resin-
The resin composition of the present invention may further contain a thermoplastic resin. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples include ether ketone resin and polyester resin. The thermoplastic resin may be used alone or in combination of two or more.

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

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

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "Electrified Butyral 4000-2", "Electrified Butyral 5000-A", "Electrified Butyral 6000-C", and "Electrified Butyral 6000-EP" manufactured by Denki Kagaku Kogyo Co., Ltd. , Eslek BH series, BX series, KS series, BL series, BM series, etc. manufactured by Sekisui Chemical Co., Ltd.

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

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

Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

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

When a thermoplastic resin is used, the content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, and further preferably 0. .3% by mass to 5% by mass.

-Flame retardant-
The resin composition of the present invention may further contain a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. The flame retardant may be used alone or in combination of two or more. When a flame retardant is used, the content of the flame retardant in the resin composition is not particularly limited, but is preferably 0.1% by mass to 15% by mass, and more preferably 0.5% by mass to 10% by mass. ..

-Organic filler-
The resin composition of the present invention may further contain an organic filler. As the organic filler, any organic filler that can be used when forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles, and rubber particles are preferable.

The rubber particles are not particularly limited as long as they are fine particles of a resin that is chemically crosslinked with a resin exhibiting rubber elasticity and is insoluble and insoluble in an organic solvent. For example, acrylonitrile butadiene rubber particles, butadiene rubber particles, and the like. Examples include acrylic rubber particles. Specific examples of the rubber particles include XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyroid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (manufactured by Aica Kogyo Co., Ltd.) Pararoid EXL2655. , EXL2602 (all manufactured by Kureha Chemical Industry Co., Ltd.) and the like.

The average particle size of the organic filler is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.2 μm to 0.6 μm. The average particle size of the organic filler can be measured using a dynamic light scattering method. For example, the organic filler is uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and the particle size distribution of the organic filler is measured by mass using a concentrated particle size analyzer (“FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.). It can be measured by creating a standard and using the median diameter as the average particle size. When an organic filler is used, the content of the organic filler in the resin composition is preferably 1% by mass to 10% by mass, more preferably 2 when the non-volatile component in the resin composition is 100% by mass. It is from mass% to 5% by mass.

The resin composition of the present invention may contain other components, if necessary. Such other components include, for example, organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds, and resin additions such as thickeners, defoamers, leveling agents, adhesion imparting agents and colorants. Agents and the like can be mentioned.

The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which a compounding component is mixed and dispersed using a rotary mixer or the like by adding a solvent or the like as necessary.

The resin composition of the present invention can provide a cured product having a low dielectric loss tangent. The dielectric loss tangent of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of Dissipation Factor> described later. Specifically, it can be measured at a frequency of 5.8 GHz and a measurement temperature of 23 ° C. by the cavity resonance perturbation method. From the viewpoint of preventing heat generation at high frequencies, reducing signal delay and signal noise, the dielectric loss tangent is preferably 0.010 or less, 0.009 or less, 0.008 or less, 0.007 or less, 0.006 or less, or 0. 005 or less is more preferable, and 0.004 or less, or 0.0035 or less is further preferable. The lower limit of the dielectric loss tangent is preferably as low as possible, but it can usually be 0.001 or more.

The resin composition of the present invention can provide a cured product having excellent adhesion to the plated conductor layer (plating adhesion) and adhesion to the base conductor layer (base adhesion). The plating adhesion of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of Plating Adhesion> described later. Further, the substrate adhesion of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of substrate adhesion> described later. The plating adhesion of the obtained cured product, that is, the adhesion strength (peeling strength) with the plated conductor layer is preferably more than 0.40 kgf / cm. The substrate adhesion of the obtained cured product, that is, the adhesion strength (peeling strength) with the substrate conductor layer is preferably more than 0.50 kgf / cm. The upper limit of the adhesion strength is not particularly limited, but usually, it may be 1.2 kgf / cm or less.

The resin composition of the present invention can provide a cured product having a low dielectric loss tangent and excellent plating adhesion and substrate adhesion. Therefore, the resin composition of the present invention is a resin composition for forming an insulating layer (including a rewiring layer) in which a conductor layer (including a rewiring layer) is formed in contact with the resin composition (resin for an insulating layer for forming a conductor layer). It can be suitably used as a composition). Further, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board. It can be more preferably used as a resin composition (resin composition for forming an interlayer insulating layer of a printed wiring board). Further, the resin composition of the present invention can be suitably used as a resin composition (resin composition for embedding parts) for embedding semiconductor parts in a semiconductor package or embedding parts in a circuit board with built-in parts. .. The resin composition of the present invention can also be used in a wide range of applications in which a resin composition is required, such as an adhesive film, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, and a hole filling resin.

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

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

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

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

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

When a film made of a plastic material is used as the support, the plastic material includes, for example, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and acrylic such as polycarbonate (PC) and polymethylmethacrylate (PMMA). , Cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. 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 on the side to be joined with the resin composition layer may be matted or corona-treated. Further, as the support, a support with a release layer having a release layer on the surface on the side to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, olefin resin, urethane resin, and silicone resin. .. Examples of commercially available release agents include "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, which are alkyd resin-based release agents.

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 the support is a support with a release layer, the thickness of the entire support with a release layer is preferably in the above range.

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

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like. Examples thereof include carbitols, aromatic hydrocarbons such as toluene and xylene, and 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.

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

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

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

The prepreg can be produced by a known method such as a hot melt method or a solvent method.

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

In the sheet-like laminated material, the minimum melt viscosity of the resin composition layer is determined by the specific design of the printed wiring board (circuit thickness of the inner layer board, line / space ratio, and for accommodating parts when manufacturing the circuit board with built-in parts. Optimal values for achieving good circuit embedding property and component embedding property differ depending on the cavity size, etc.). Therefore, in producing the sheet-shaped laminated material, the resin composition layer is designed so as to exhibit the desired minimum melt viscosity. However, with respect to a sheet-like laminated material using a conventional resin composition containing a curing accelerator, the resin composition may gradually cure during storage and the viscosity may increase, and when used in the production of a printed wiring board. In some cases showed a minimum melt viscosity significantly higher than the expected value.

On the other hand, the resin composition of the present invention in which the component (C) and the component (D) are blended in combination can not only realize a cured product having a low dielectric loss tangent and excellent plating adhesion and substrate adhesion. , The progress of curing of the resin composition during storage is suppressed, and the desired minimum melt viscosity can be advantageously maintained. In one embodiment, the sheet-shaped laminated material of the present invention has a resin composition having a minimum melt viscosity of the resin composition layer immediately after its production of V ₁ (poise) and stored at room temperature (25 ° C.) for 24 hours. When the minimum melt viscosity of the layer is V ₂ (poise), _{the ratio of V 2} / V ₁ (hereinafter, also referred to as “thickening ratio”) is preferably 2 or less, more preferably 1.8 or less, and further. It is preferably 1.6 or less, even more preferably 1.5 or less, and particularly preferably 1.4 or less, 1.3 or less, 1.2 or less or 1.1 or less. The lower limit of the thickening ratio is preferably 1.

Here, the "minimum melt viscosity" of the resin composition layer means the lowest viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. Specifically, when the resin composition layer is heated at a constant temperature rise rate to melt the resin, the melt viscosity decreases as the temperature rises in the initial stage, and then, when the temperature exceeds a certain temperature, the melt viscosity increases as the temperature rises. Rise. The "minimum melt viscosity" means the melt viscosity of such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by the method described in <Measurement of minimum melt viscosity> described later. Specifically, the minimum melt viscosity of the resin composition layer can be obtained by performing dynamic viscoelasticity measurement under the conditions of a measurement start temperature of 60 ° C., a heating rate of 5 ° C./min, a frequency of 1 Hz, and a strain of 1 deg. can. Examples of the dynamic viscoelasticity measuring device include "Rheosol-G3000" manufactured by UBM Co., Ltd.

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

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

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

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

The inner layer substrate and the adhesive film may be laminated by a vacuum laminating method. In the vacuum laminating method, the heat 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 the commercially available vacuum laminator include a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., and the like.

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

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

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

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

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

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

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

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

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

Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions 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 is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, and an alkaline solution is preferable, and the alkaline solution is more preferably a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Security SBU" and "Swelling Dip Security SBU" manufactured by Atotech Japan Co., Ltd. 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 cured product in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. The oxidizing agent 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 80 ° 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 Co., Ltd. The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Security P" manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing liquid can be carried out by immersing the treated surface that has been roughened with the oxidizing agent in the neutralizing liquid at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 to 20 minutes is preferable.

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

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). A layer formed of 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 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.

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

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

When a printed wiring board is manufactured using the resin composition of the present invention containing a specific component (C) and component (D) in combination, an insulating layer having a low dielectric loss tangent and excellent plating adhesion and substrate adhesion. Can be realized.

[Semiconductor package]
The semiconductor package of the present invention includes a circuit board, a semiconductor component mounted on the circuit board, and a sealing material for embedding (sealing) the semiconductor component, and the sealing material is the resin composition of the present invention. It is characterized by being formed from the cured product of. Here, the structure and type of the circuit board and the semiconductor component constituting the semiconductor package of the present invention are not particularly limited, and any circuit board and the semiconductor component usually used when forming the semiconductor package may be used.

The semiconductor package of the present invention can be manufactured by embedding (sealing) a semiconductor component with the resin composition of the present invention. The conditions for sealing the semiconductor are not particularly limited, and any sealing conditions usually used in manufacturing a semiconductor package may be adopted.

[Semiconductor device]
The semiconductor device of the present invention includes a cured product of the resin composition of the present invention. The semiconductor device of the present invention can be manufactured by using the printed wiring board or the semiconductor package of the present invention.

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

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

First, the measurement / evaluation method in the physical property evaluation in the present specification will be described.

<Preparation of sample for evaluation of cured physical properties>
The adhesive films obtained in Examples and Comparative Examples were heat-cured at 200 ° C. for 90 minutes, and the support was peeled off to prepare a sheet-shaped sample for evaluation of a cured product.

<Measurement of dielectric loss tangent>
A test piece having a width of 2 mm and a length of 80 mm was cut out from the sample for evaluating the cured physical characteristics. The cut out test piece was measured for dielectric positive contact at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using a measuring device “HP8362B” manufactured by Agilent Technologies. When the dielectric loss tangent was 0.0035 or less, it was evaluated as "○" (good), when it was more than 0.0035 and 0.0040 or less, it was evaluated as "Δ" (possible), and when it was more than 0.0040, it was evaluated as "x" (defective).

<Preparation of evaluation board>
(1) Base treatment of inner layer circuit board Glass cloth base material with inner layer circuit Epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic Corporation “R1515A”) Both sides of the copper surface were dipped in a micro-etching agent (“CZ8101” manufactured by MEC Co., Ltd.) and etched by 1 μm to roughen the copper surface.

(2) Lamination of Adhesive Films The adhesive films produced in Examples and Comparative Examples are subjected to an inner layer circuit with a resin composition layer using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.). It was laminated on both sides of the inner layer circuit board so as to be bonded to the substrate. Lamination was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of Resin Composition Layer The laminated adhesive film was heat-cured at 200 ° C. for 90 minutes to form a cured product (insulating layer) on both sides of the inner layer circuit board. Then, the support was peeled off from the adhesive film.

(4) Roughening treatment The inner layer circuit board on which the insulating layer was formed was dipped in a swelling solution (Atotech Japan Co., Ltd. "Swelling Dip Securigant P", an aqueous solution of sodium hydroxide containing diethylene glycol monobutyl ether) at 60 ° C. for 10 minutes. Immerse in a roughening solution (Atotech Japan Co., Ltd. "Concentrate Compact P", an aqueous solution with a potassium permanganate concentration of 60 g / L and a sodium hydroxide concentration of 40 g / L) at 80 ° C. for 20 minutes, and finally. Was immersed in a neutralizing solution (Atotech Japan Co., Ltd. "Reduction Solution Securigant P", aqueous solution of hydroxylamine sulfate) at 40 ° C. for 5 minutes. Then, it was dried at 80 ° C. for 30 minutes. The obtained substrate is referred to as "evaluation substrate A".

(5) Formation of Plated Conductor Layer A plated conductor layer (second conductor layer) was formed on the surface of the evaluation substrate A according to the semi-additive method. Specifically, 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. The obtained evaluation substrate A was heated at 150 ° C. for 30 minutes for annealing, and then subjected to copper sulfate electrolytic plating to form a plated conductor layer having a thickness of 30 μm. The evaluation substrate A on which the plated conductor layer was formed was annealed at 190 ° C. for 60 minutes. The obtained substrate is referred to as "evaluation substrate B".

<Measurement of plating adhesion>
Make a notch in the plated conductor layer (second 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, grasp it with a gripper, and at room temperature (25 ° C.), 50 mm / min. The load (kgf / cm (N / cm)) when 35 mm was peeled off in the vertical direction was measured at the speed of. A tensile tester (“AC-50C-SL” manufactured by TSE Co., Ltd.) was used for the measurement. When the load was more than 0.4 kgf / cm, it was evaluated as “◯” (good), and when it was 0.4 kgf / cm or less, it was evaluated as “x” (poor).

<Measurement of substrate adhesion>
(1) Base treatment of copper foil The glossy surface of "3EC-III" (electric field copper foil, 35 μm) manufactured by Mitsui Mining & Smelting Co., Ltd. is immersed in a microetching agent ("CZ8101" manufactured by MEC Co., Ltd.) to form a copper surface. Was subjected to a roughening treatment (Ra value = 1 μm) and a rust preventive treatment (CL8300). This copper foil is called CZ copper foil. Further, it was heat-treated in an oven at 130 ° C. for 30 minutes.

(2) Lamination of Copper Foil and Formation of Insulation Layer A substrate from which the support was peeled off was prepared by performing the same operation as in "(2) Lamination of Adhesive Film" in <Preparation of Evaluation Substrate> above. On the resin composition layer, the treated surface of the CZ copper foil of "3EC-III" was laminated under the same conditions as "(2) Laminating of adhesive film" in <Preparation of evaluation substrate>. Then, a sample was prepared by curing the resin composition layer at 190 ° C. for 90 minutes to form an insulating layer.

(3) Measurement of Copper Foil Peeling Strength (Adhesion to Base) 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 grab it with a gripper (“AC-50C-SL” manufactured by TSE Co., Ltd.). The load when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min at room temperature was measured using an Instron universal tester in accordance with JIS C6481. When the load was more than 0.5 kgf / cm, it was evaluated as “◯” (good), and when it was 0.5 kgf / cm or less, it was evaluated as “x” (poor).

<Measurement of minimum melt viscosity>
The resin composition layer of the adhesive film produced in Examples and Comparative Examples was compressed with a mold to prepare pellets for measurement (diameter 18 mm, 1.2 to 1.3 g). The melt viscosity of the obtained measurement pellets was measured using a dynamic viscoelasticity measuring device (“Rheosol-G3000” manufactured by UBM Co., Ltd.). For the measurement pellets, a parallel plate with a diameter of 18 mm was used to raise the temperature from a starting temperature of 60 ° C. to 200 ° C. at a temperature rise rate of 5 ° C./min, with a measurement temperature interval of 2.5 ° C., a frequency of 1 Hz, and a strain of 1 deg. The dynamic viscoelasticity was measured under the above-mentioned measurement conditions, and the minimum melt viscosity (poise) was calculated. For each resin composition layer, the initial minimum melt viscosity V _{1 (poise) immediately after the preparation of the adhesive film and the minimum melt viscosity V 2} (poise) after storage at room temperature (25 ° C.) for 24 hours were obtained to increase the viscosity. The magnification (V ₂ / V ₁ ) was calculated.
When the thickening ratio exceeded 2, it was evaluated as “Δ”, and when it was 2 or less, it was evaluated as “◯”.

<Example 1>
30 parts of a bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) was heated and dissolved in 30 parts of solvent naphtha with stirring, and then cooled to room temperature. Spherical silica surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (“SO-C2” manufactured by Admatex Co., Ltd., average particle size 0.5 μm, carbon content per unit surface area 0.38 mg / m ² ) 250 parts were mixed and kneaded with 3 rolls to disperse. There, 53.8 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC Co., Ltd., a toluene solution having an active group equivalent of about 223 and a non-volatile content of 65%) and a resin having an acrylic group (Shin-Nakamura Chemical Co., Ltd.) 20 parts of "A-DOG" manufactured by Kogyo Co., Ltd., 10 parts of resin having a styryl group ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemicals Co., Ltd., toluene solution with 60% non-volatile content), indenkumaron resin (Nippon Kagaku (Nikko Kagaku) 5 parts of "H-100" manufactured by Nichiyu Co., Ltd., 2 parts of 5% MEK solution of 4-dimethylaminopyridine (DMAP) as a curing accelerator, and 0.13 of dicumyl peroxide ("Park Mill D" manufactured by Nichiyu Co., Ltd.) Parts, 1 part of 1,3-bisdiphenylphosphinopropane (“DPPP” manufactured by Hokuko Kagaku Co., Ltd.) were mixed and uniformly dispersed with a rotary mixer to prepare a resin varnish 1.

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

<Example 2>
The resin varnish 2 and the adhesive film 2 were prepared in the same manner as in Example 1 except that the blending amount of 1,3-bisdiphenylphosphinopropane (“DPPP” manufactured by Hokuko Chemical Co., Ltd.) was changed from 1 part to 0.5 part. Made.

<Example 3>
The resin varnish 3 and the adhesive film 3 were prepared in the same manner as in Example 1 except that the blending amount of 1,3-bisdiphenylphosphinopropane (“DPPP” manufactured by Hokuko Chemical Co., Ltd.) was changed from 1 part to 0.01 part. Made.

<Example 4>
Resin varnish 4 and adhesive film 4 were produced in the same manner as in Example 1 except that the blending amount of 1,3-bisdiphenylphosphinopropane (“DPPP” manufactured by Hokuko Chemical Co., Ltd.) was changed from 1 part to 10 parts. ..

<Example 5>
Resin varnish in the same manner as in Example 1 except that 1 part of 1,3-bisdiphenylphosphinopropane (“DPPP” manufactured by Hokuko Chemical Co., Ltd.) was changed to 1 part of diphenylcyclohexylphosphine (“DPCP” manufactured by Hokuko Chemical Co., Ltd.). 5 and the adhesive film 5 were produced.

<Example 6>
Example 1 except that one part of 1,3-bisdiphenylphosphinopropane (“DPPP” manufactured by Hokuko Chemical Co., Ltd.) was changed to one part of 1,3-bisdiphenylphosphinobtan (“DPBP” manufactured by Hokuko Chemical Co., Ltd.). The resin varnish 6 and the adhesive film 6 were produced in the same manner as in the above.

<Example 7>
1,3-Bisdiphenylphosphine propane (“DPPP” manufactured by Hokuko Chemical Co., Ltd.) 1 part [4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine (“Amphos” manufactured by Hokuko Chemical Co., Ltd.) 1 The resin varnish 7 and the adhesive film 7 were produced in the same manner as in Example 1 except that the parts were changed.

<Example 8>
Resin varnish 8 and adhesive film 8 were produced in the same manner as in Example 1 except that the blending amount of 1,3-bisdiphenylphosphinopropane (“DPPP” manufactured by Hokuko Chemical Co., Ltd.) was changed from 1 part to 15 parts. ..

<Comparative example 1>
A resin varnish 9 and an adhesive film 9 were prepared in the same manner as in Example 1 except that 1,3-bisdiphenylphosphinopropane (“DPPP” manufactured by Hokuko Chemical Co., Ltd.) was not blended.

<Comparative example 2>
Resin varnish in the same manner as in Example 1 except that 1 part of 1,3-bisdiphenylphosphinopropane (“DPPP” manufactured by Hokuko Chemical Co., Ltd.) was changed to 1 part of triphenylphosphine (“TPPP” manufactured by Hokuko Chemical Co., Ltd.). 10 and an adhesive film 10 were produced.

<Comparative example 3>
20 parts of resin with acrylic group ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.) and 10 parts of resin with styryl group ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, toluene solution with 60% non-volatile content) A resin varnish 11 and an adhesive film 11 were produced in the same manner as in Example 1 except that they were not blended.

Table 1 shows the evaluation results of Examples and Comparative Examples.

Even if the spherical silica "SO-C2" is not blended, the curing accelerator (dimethylaminopyridine (DMAP) and "Parkmill D") is not blended, or the indenkumaron resin "H-100" is not blended. Although there is a difference in the above, it has been confirmed that the result is similar to that of the above embodiment.

Claims (20)

A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a resin having a radically polymerizable unsaturated group, and (D) an aliphatic phosphine compound .
The component (C) has one or more groups selected from the group consisting of an acrylic group, a methacryl group, a styryl group, an olefin group and a maleimide group as radically polymerizable unsaturated groups, and has a number average molecular weight of 100 or more. It is less than 10,000 and
A resin composition in which the component (D) contains a phosphorus atom in which both an aliphatic carbon atom and an aromatic carbon atom are directly bonded. The component (C) is a compound represented by the formula (C5), a compound represented by the formula (C6), a compound represented by the formula (C7), a compound represented by the formula (C9), and a compound represented by the formula (C10). The resin composition according to claim 1, which is one or more selected from the group consisting of the compounds represented by.

(During the ceremony,
R ^{1 to} R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
a and b are integers of 0 or more and 100 or less, at least one of which is not 0.
B represents a divalent group represented by the formula (C2-1), the formula (C2-2) or the formula (C2-3).

In the formula (C2-1), R ^{15 to} R ¹⁸ independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
In the formula (C2-2), R ^{19 to} R ²⁶ independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.
In the formula (C2-3), R ^{27 to} R ³⁴ independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and E is a linear or branched group having 20 or less carbon atoms. Represents a morphic or cyclic divalent hydrocarbon group. )

(During the ceremony,
Ring F represents a divalent group having a cyclic ether structure of 5 or more members.
B ¹ and B ² are independently combined by selecting two or more groups from the group consisting of an alkylene group which may have a single bond or a substituent and a group represented by -COO-. Represents a group
C ¹ and C ² independently represent a vinyl group, a methacrylic group, an acrylic group or a styryl group, respectively. )

(During the ceremony,
n represents 1 to 5. ) The resin composition according to claim 1 or 2, wherein the component (D) has 1 to 4 phosphorus atoms to which an aliphatic carbon atom is directly bonded in one molecule. The resin composition according to any one of claims 1 to 3, wherein the component (D) has 2 to 40 aliphatic carbon atoms in one molecule. The resin composition according to any one of claims 1 to 4, wherein the component (D) is a compound represented by the formula (D1) or the formula (D2).

(During the ceremony,
R ^d1 and R ^d2 each independently represent a hydrogen atom or a monovalent group represented by the formula:-(RO) _l- R', where l represents an integer of 0-5. R represents a divalent aromatic group which may have a substituent or a divalent aliphatic group which may have a substituent, and R'may have a substituent 1 Represents a valent aromatic group or a monovalent aliphatic group which may have a substituent, and when a plurality of Rs are present, they may be the same or different from each other.
At ^{least one of R d1} and R ^d2 represents a monovalent group represented by the formula: − (RO) _l −R ′, and R (in the case of l = 1 to 5) directly bonded to the phosphorus atom. R'(in the case of l = 0) represents a divalent aromatic group which may have a substituent and a monovalent aromatic group which may have a substituent, respectively.
R ^d3 represents a monovalent group represented by the formula:-(R''-O) _m- R'''where m represents an integer of 0-5 and R'' represents a substituent. Represents a divalent aliphatic group which may have a substituent, R'''represents a monovalent aliphatic group which may have a substituent, and if there are a plurality of R'', they represent They may be the same or different from each other. )

(During the ceremony,
R ^d1 and R ^d2 are synonymous with the above.
L represents a divalent group represented by the formula: − (R''− O) _n −R''−, where n represents an integer from 0 to 5, and R'' is synonymous with the above. And if there are multiple R''s, they may be the same or different from each other.
R ^d4 and R ^d5 are independently hydrogen atoms, a monovalent group represented by _{the formula:-(RO) l} ^{-R'or the formula: -LP (-R d1} ) ( ^{-R d2).} ) Represents a monovalent group, where l, R, R', L, R ^d1 and R ^d2 are synonymous with the above. ) In equation (D1),
i) R ^d1 And R ^d2 Are both formulas:-(RO) _l Represents a monovalent group represented by −R ′, where l is 0 and R ′ is an aryl group which may have a substituent.
ii) R ^d3 Is the formula:-(R ″ -O) _m Represents a monovalent group represented by −R'', m is an integer from 0 to 2, and R'' may have an alkylene group or a substituent which may have a substituent. It is a good cycloalkylene group, and R'''is an alkyl group which may have a substituent, an alkenyl group which may have a substituent or a cycloalkyl group which may have a substituent. , The resin composition according to claim 5. In equation (D1),
i) R ^d1 Is the formula:-(RO) _l Represents a monovalent group represented by −R ′, where l is 0 and R ′ is an aryl group which may have a substituent.
ii) R ^d2 Is the formula:-(RO) _l Represents a monovalent group represented by −R ′, l is 0, and R ′ is an alkyl group which may have a substituent or an alkenyl group which may have a substituent.
iii) R ^d3 Is the formula:-(R ″ -O) _m Represents a monovalent group represented by −R'', m is an integer from 0 to 2, and R'' may have an alkylene group or a substituent which may have a substituent. It is a good cycloalkylene group, and R'''is an alkyl group which may have a substituent, an alkenyl group which may have a substituent or a cycloalkyl group which may have a substituent. , The resin composition according to claim 5. In equation (D2),
i) R ^d1 And R ^d2 Are both formulas:-(RO) _l Represents a monovalent group represented by −R ′, where l is 0 and R ′ is an aryl group which may have a substituent.
ii) L is the formula:-(R "-O) _n Represents a divalent group represented by −R''−, n is an integer of 0 to 2, and R'' may have an alkylene group or a substituent which may have a substituent. A good cycloalkylene group,
iii) R ^d4 And R ^d5 Are both formulas:-(RO) _l The resin composition according to claim 6, wherein the monovalent group represented by −R ′, l is 0, and R ′ is an aryl group which may have a substituent. The resin composition according to any one of claims 1 to 8 , wherein the component (D) contains a compound represented by any one of the following formulas.

The resin composition according to any one of claims 1 to 9, wherein the content of the component (C) is 1% by mass or more and 20% by mass or less when the non-volatile component in the resin composition is 100% by mass. thing. The resin composition according to any one of claims 1 to 10 , wherein the content of the component (D) is 0.001% by mass to 10% by mass when the resin component is 100% by mass. The resin composition according to any one of claims 1 to 11 , wherein the component (A) contains a biphenyl type epoxy resin. The resin composition according to any one of claims 1 to 12 , wherein the component (B) contains an active ester-based curing agent. Component (C), acryl group, having one or more groups selected from a methacrylic group and a styryl group or Ranaru group, resin composition according to any one of claims 1 to 13. The resin composition according to any one of claims 1 to 14 , further comprising (E) an inorganic filler. The resin composition according to claim 15 , wherein the content of the (E) inorganic filler is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 16 , which is used for an insulating layer for forming a conductor layer. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 17. A printed wiring board including an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 17. A semiconductor device comprising a cured product of the resin composition according to any one of claims 1 to 17.