JP2017019970A - Resin composition - Google Patents

Abstract

Provided is a resin composition capable of achieving an insulating layer exhibiting a high peel strength with respect to a conductor layer and exhibiting a low dielectric loss tangent even when the roughness is low. A resin composition comprising (A) an epoxy resin and (B) an active ester compound containing a triazine structure. [Selection figure] None

Description

  The present invention relates to a resin composition. Furthermore, the present invention relates to an adhesive film, a prepreg, a printed wiring board, and a semiconductor device.

  As a technique for manufacturing a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method by the build-up method, the insulating layer is generally formed by curing a resin composition. As a resin composition for forming such an insulating layer, for example, a resin composition containing an epoxy resin, an active ester compound, a phenol resin having a triazine structure, a maleimide compound, and a phenoxy resin is known (Patent Literature). 1).

JP 2013-234328 A

According to the resin composition described in Patent Document 1, it is possible to provide an insulating layer exhibiting high adhesion (peel strength) to the conductor layer even if the roughness is low, but further enhancement of performance is possible. It is desired.
The problem to be solved by the present invention is to provide a resin composition that exhibits a high peel strength with respect to a conductor layer even when the roughness is low and can achieve an insulating layer having a low dielectric loss tangent.

  As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by combining (A) an epoxy resin and (B) an active ester compound containing a triazine structure. It came to be completed.

（式中、Ｘ^１及びＸ^２は、それぞれ独立に、−Ｏ−又は−ＮＨ−を表し、
Ｒ^１は、アミノ基、アルキル基、アリール基、アルコキシ基、水素原子、又はハロゲン原子を表し、Ｒ^２は、１価の芳香族基、１価の脂肪族基、又は１価の脂環式基を表し、
Ａｒ^１及びＡｒ^２は、それぞれ独立に、置換基を有していてもよい３価の芳香族基を表し、ｊ及びｋは、それぞれ正の数を表し、ｌは０以上の数を表す）
［５］ （Ｃ）無機充填材を含む［１］〜［４］のいずれかに記載の樹脂組成物。
［６］ （Ｃ）無機充填材の含有量が、樹脂組成物中の不揮発成分を１００質量％としたとき、５０質量％以上である［５］に記載の樹脂組成物。
［７］ 熱硬化により形成される絶縁層の誘電正接が０．００８以下である〔１〕〜〔６〕のいずれかに記載の樹脂組成物。
［８］ 支持体と、該支持体上に設けられた［１］〜［７］のいずれかに記載の樹脂組成物を含む樹脂組成物層と、を有する接着フィルム。
［９］ ［１］〜［７］のいずれかに記載の樹脂組成物がシート状繊維基材中に含浸されたプリプレグ。
［１０］ ［１］〜［７］のいずれかに記載の樹脂組成物の硬化物により形成された絶縁層を含むプリント配線板。
［１１］ ［１０］に記載のプリント配線板を含む、半導体装置。 That is, the present invention includes the following contents.
[1] A resin composition comprising (A) an epoxy resin and (B) an active ester compound containing a triazine structure.
[2] The resin composition according to [1], in which the content of the (A) epoxy resin is 0.1% by mass to 30% by mass when the nonvolatile component in the resin composition is 100% by mass.
[3] (B) The content of the active ester compound containing a triazine structure is 0.1% by mass to 30% by mass when the nonvolatile component in the resin composition is 100% by mass [1] or [ 2].
[4] The resin composition according to any one of [1] to [3], wherein (B) the active ester compound having a triazine structure is represented by the following formula (1).

(Wherein, X ¹ and X ² each independently represent —O— or —NH—,
R ¹ represents an amino group, an alkyl group, an aryl group, an alkoxy group, a hydrogen atom, or a halogen atom, and R ² represents a monovalent aromatic group, a monovalent aliphatic group, or a monovalent alicyclic group. Represents a group,
Ar ¹ and Ar ² each independently represents a trivalent aromatic group which may have a substituent, j and k each represents a positive number, and l represents a number of 0 or more)
[5] The resin composition according to any one of [1] to [4], comprising (C) an inorganic filler.
[6] The resin composition according to [5], wherein the content of (C) the inorganic filler is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass.
[7] The resin composition according to any one of [1] to [6], wherein a dielectric loss tangent of an insulating layer formed by thermosetting is 0.008 or less.
[8] An adhesive film having a support and a resin composition layer comprising the resin composition according to any one of [1] to [7] provided on the support.
[9] A prepreg in which the resin composition according to any one of [1] to [7] is impregnated in a sheet-like fiber base material.
[10] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [7].
[11] A semiconductor device including the printed wiring board according to [10].

  ADVANTAGE OF THE INVENTION According to this invention, even if roughness is low, the resin composition which can achieve the insulating layer which shows high peel strength with respect to a conductor layer, and shows a low dielectric loss tangent can be provided.

  Hereinafter, the resin composition, adhesive film, prepreg, printed wiring board, and semiconductor device of the present invention will be described.

[Resin composition]
The resin composition of the present invention contains (A) an epoxy resin and (B) an active ester compound containing a triazine structure. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

<(A) Epoxy resin>
The resin composition of the present invention contains (A) an epoxy resin (hereinafter also referred to as “component (A)”).

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, Phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type Epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring Epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it has two or more epoxy groups in one molecule, and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule, It is preferable to contain a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the cured product of the resin composition is also improved.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, phenol novolac type epoxy resins, and alicyclic epoxy resins having an ester skeleton. And epoxy resins having a butadiene structure are preferred, and bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins and naphthalene type epoxy resins are more preferred. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “828US”, “jER828EL” (bisphenol A) manufactured by Mitsubishi Chemical Corporation. Type epoxy resin), “jER807” (bisphenol F type epoxy resin), “jER152” (phenol novolac type epoxy resin), “YL7760” (bisphenol AF type epoxy resin), “ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ( Bisphenol A type epoxy resin and bisphenol F type epoxy resin mixture), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, “Celoxide 2021P” (ester structure) manufactured by Daicel Corporation Alicyclic Epoxy with Resin), "PB-3600" (epoxy resin having a butadiene structure) and the like. These may be used alone or in combination of two or more.

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” manufactured by DIC Corporation. "(Cresol novolac type epoxy resin)", "N-695" (Cresol novolac type epoxy resin), "HP-7200" (Dicyclopentadiene type epoxy resin), "HP-7200HH", "EXA7311", "EXA7311-G3 ”,“ EXA7311-G4 ”,“ EXA7311-G4S ”,“ HP6000 ”(naphthylene ether type epoxy resin),“ EPPN-502H ”(trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.,“ NC7000L ” (Naphthol novolac type epoxy resin), “NC3000 ”,“ NC3000 ”,“ NC3000L ”,“ NC3100 ”(biphenyl type epoxy resin),“ ESN475V ”(naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.,“ ESN485 ”(naphthol novolak type epoxy resin), Mitsubishi “YX4000H”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin) manufactured by Kagaku Co., Ltd., “ “PG-100”, “CG-500”, “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “jER1010” (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “jER1031S” (Tetraphenylethane type epoxy resin) And the like.

Epoxy resin, if it contains solid epoxy resin and a liquid epoxy resin, the ratio of the mass M _S of a solid epoxy resin to the weight M _L of the liquid epoxy resin (M S _{/ M L)} is not less than 0.1 Preferably, it is 0.3 or more, 0.5 or more, 1 or more, or 1.5 or more. The upper limit of the M _S / _{M L} is preferably 10 or less, 8 or less, 6 or less, 5 or less, or more preferably 4 or less. The M S _/ M _L, With such a range, i) moderate tackiness is brought when used in the form of adhesive film, ii) sufficient flexibility when used in the form of an adhesive film Is obtained, the handleability is improved, and iii) a cured product having sufficient breaking strength can be obtained.

The content of the component (A) in the resin composition is preferably 0.1% by mass or more, more preferably 5% by mass or more, and still more preferably from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. Is 10% by mass or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 22 mass% or less.
Therefore, the content of the component (A) in the resin composition is preferably 0.1 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 10 to 22% by mass.

  In addition, in this invention, content of each component in a resin composition is a value when the non-volatile component in a resin composition is 100 mass% unless there is separate description.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and it can bring about an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  The weight average molecular weight of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

<(B) Active ester compound containing triazine structure>
The resin composition of the present invention contains (B) an active ester compound containing a triazine structure (hereinafter also referred to as “triazine structure-containing active ester compound”, “component (B)”).

  The component (B) is a compound containing a triazine structure and an active ester group. The component (B) is a component that acts as a curing agent for the component (A), and can promote the curing action by the active ester group by the catalytic action of the triazine structure. The component (B) is preferably a compound in which at least a part of the phenolic hydroxyl group is acylated in a resin containing a triazine structure and a phenolic hydroxyl group. From the viewpoint of obtaining an insulating layer having a high peel strength and a low dielectric loss tangent even when the roughness is low, when the total amount of phenolic hydroxyl groups is 100 mol%, the phenolic hydroxyl groups are preferably 80 mol%. More preferably, 90 mol% or more, more preferably 95 mol% or more, 97 mol% or more, or 99 mol% or more is acylated, and substantially all phenolic hydroxyl groups are acylated. It is particularly preferred that In such preferred compounds, the active ester group results from acylation of the phenolic hydroxyl group. In the component (B), the active ester group is preferably at least one ester group selected from the group consisting of an aromatic ester group, an aliphatic ester group, and an alicyclic ester group. Particularly preferred. Examples of the aromatic ester group include an aryl ester group and a heteroaryl ester group, and an aryl ester group is preferable. The number of carbon atoms of the aryl ester group is preferably 7-15, more preferably 7-11. The number of carbon atoms of the heteroaryl ester group is preferably 3 to 14, more preferably 3 to 10. As the aliphatic ester group, an alkyl ester group is preferable, and the number of carbon atoms thereof is preferably 2 to 7, more preferably 2 to 5, and further preferably 2 or 3. As the alicyclic ester group, a cycloalkyl ester group is preferable, and the number of carbon atoms thereof is preferably 4 to 7.

  The component (B) can be prepared, for example, by a condensation reaction (acylation reaction) between a resin containing a triazine structure and a phenolic hydroxyl group and a carboxylic acid compound. The resin containing a triazine structure and a phenolic hydroxyl group may be prepared by a known method. For example, a resin containing a triazine structure, a compound containing a phenolic hydroxyl group, and an aldehyde compound may be prepared. Examples of the compound containing a triazine structure include melamine; guanamine derivatives such as acetoguanamine and benzoguanamine; cyanuric acid; cyanuric acid derivatives such as methyl cyanurate, ethyl cyanurate, acetyl cyanurate, and cyanuric chloride. Among them, melamine Acetguanamine, benzoguanamine and cyanuric acid are preferred. As the compound containing a phenolic hydroxyl group, a phenol compound is preferable, for example, phenol, cresol, xylenol; alkylphenols such as ethylphenol, butylphenol, nonylphenol, octylphenol; many such as bisphenol A, bisphenol F, bisphenol S, resorcin, and catechol Hydric phenols; halogenated phenols, phenylphenols, aminophenols and the like. As the aldehyde compound, formaldehyde is preferable. Preferable examples of the resin containing a triazine structure and a phenolic hydroxyl group include a triazine structure-containing phenol novolak resin, a triazine structure-containing cresol novolak resin, a triazine structure-containing naphthol novolak resin, and the like. Is preferred.

  The carboxylic acid compound used in the acylation reaction of a resin containing a triazine structure and a phenolic hydroxyl group is one or more carboxylic acids selected from the group consisting of aromatic carboxylic acids, aliphatic carboxylic acids, and alicyclic carboxylic acids. Of these, aromatic carboxylic acids are preferred. Examples of the aromatic carboxylic acid include aryl carboxylic acids and heteroaryl carboxylic acids, and aryl carboxylic acids are preferable. The number of carbon atoms of the arylcarboxylic acid is preferably 7-15, more preferably 7-11. The number of carbon atoms of the heteroaryl carboxylic acid is preferably 3 to 14, more preferably 3 to 10. As the aliphatic carboxylic acid, an alkyl carboxylic acid is preferable, and the number of carbon atoms thereof is preferably 2 to 7, more preferably 2 to 5, and further preferably 2 or 3. As the alicyclic carboxylic acid, a cycloalkyl carboxylic acid is preferable, and the number of carbon atoms thereof is preferably 4 to 7. Preferable examples of the carboxylic acid compound include benzoic acid, naphthalene carboxylic acid, anthracene carboxylic acid, acetic acid, propionic acid and the like. Of these, benzoic acid is particularly preferred.

  (B) As a suitable example of a component, the compound represented by Formula (1) is mentioned.

（式中、 Ｘ^１及びＸ^２は、それぞれ独立に、−Ｏ−又は−ＮＨ−を表し、
Ｒ^１は、アミノ基、アルキル基、アリール基、アルコキシ基、水素原子、又はハロゲン原子を表し、Ｒ^２は、１価の芳香族基、１価の脂肪族基、又は１価の脂環式基を表し、
Ａｒ^１及びＡｒ^２は、それぞれ独立に、置換基を有していてもよい３価の芳香族基を表し、ｊ及びｋは、それぞれ正の数を表し、ｌは０以上の数を表す）

(Wherein, X ¹ and X ² each independently represent —O— or —NH—,
R ¹ represents an amino group, an alkyl group, an aryl group, an alkoxy group, a hydrogen atom, or a halogen atom, and R ² represents a monovalent aromatic group, a monovalent aliphatic group, or a monovalent alicyclic group. Represents a group,
Ar ¹ and Ar ² each independently represents a trivalent aromatic group which may have a substituent, j and k each represents a positive number, and l represents a number of 0 or more)

  In the formula (1), the structural unit to which the subscript j is attached, the structural unit to which the subscript k is attached, and the structural unit to which the subscript l is attached may be combined in a block shape, and randomly. May be bonded to.

The number of carbon atoms of the alkyl group or alkoxy group represented by R ¹ is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 or 2. The number of carbon atoms of the aryl group represented by R ¹ is preferably 6 to 14, more preferably 6 to 10. Examples of the halogen atom represented by R ¹ include a fluorine atom, a chlorine atom, and a bromine atom.

Examples of the monovalent aromatic group represented by R ² include an aryl group and a heteroaryl group, and an aryl group is preferable. The number of carbon atoms of the aryl group is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms in the heteroaryl group is preferably 2 to 13, more preferably 2 to 9. The monovalent aliphatic group represented by R ² is preferably an alkyl group, and the number of carbon atoms thereof is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 or 2. The monovalent alicyclic group represented by R ² is preferably a cycloalkyl group, and the number of carbon atoms thereof is preferably 3-6. Among these, R ² is preferably a monovalent aromatic group from the viewpoint of improving heat resistance.

As the trivalent aromatic group represented by Ar ¹ and Ar ² , an aryltriyl group is preferable, and the number of carbon atoms is preferably 6 to 14, more preferably 6 to 10, and still more preferably 6 (that is, Benzenetriyl group). The trivalent aromatic group represented by Ar ¹ and Ar ² may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and a halogen atom. The number of carbon atoms of the alkyl group or alkoxy group used as a substituent is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3. The number of carbon atoms of the aryl group or aryloxy group used as a substituent is preferably 6 to 14, more preferably 6 to 10, and still more preferably 6. As a halogen atom used as a substituent, a chlorine atom is preferable.

j, k, and l are preferably in the range of 120 to 500, more preferably 150 to 400, in terms of the active ester group (R ² —C (═O) —O— group) equivalent of the compound represented by formula (1). And a number that is more preferably in the range of 180 to 300. Here, the ratio of k to the sum of k and l, that is, k / (k + 1) is preferably 0.8 or more, more preferably 0.9 or more, still more preferably 0.95 or more, 0.97 or more, Or it is 0.99 or more, and it is especially suitable that it is substantially 1.

  Specific examples of the active ester compound containing a triazine structure include “EXB9510” and “EXB9511” manufactured by DIC Corporation.

The content of the component (B) in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 5% from the viewpoint of obtaining an insulating layer having high peel strength and a low dielectric loss tangent. It is at least mass%. Although the upper limit of content of (B) component is not specifically limited as long as the effect of this invention is show | played, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less. .
Therefore, the content of the component (B) in the resin composition is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and still more preferably 5 to 20% by mass.

<Curing agent other than component (B)>
The resin composition of the present invention may contain a curing agent other than the component (B) together with the component (B).
The curing agent other than the component (B) is not particularly limited as long as it has a function of curing the epoxy resin. For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, and a cyanate. Examples thereof include ester-based curing agents and carbodiimide-based curing agents. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

  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 to the conductor layer (circuit wiring), a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. . Among these, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion (peel strength) to the conductor layer, it is preferable to use a triazine skeleton-containing phenol novolac resin or a triazine skeleton-containing naphthol novolak resin as a curing agent.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN375”, “SN395” manufactured by Toto Kasei Co., Ltd. "LA7052", "LA7054", "LA3018", etc. manufactured by DIC Corporation.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester 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 curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester 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, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadienyl diphenol, phenol novolac and the like.

  Specifically, an active ester compound containing a dicyclopentadienyl diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of a phenol novolak, and an active ester compound containing a benzoylated product of a phenol novolak are preferred. Of these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadienyl diphenol structure are more preferred.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (DIC Corporation) as active ester compounds containing a dicyclopentadienyl diphenol structure. Manufactured product), "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, Examples of the active ester compound containing a benzoylated compound include “YLH1026” (manufactured by Mitsubishi Chemical Corporation).

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

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylene bis (2,6-dimethylphenyl cyanate), 4, 4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), 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; Phenol novolac and Polyfunctional cyanate resin derived from resol novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolak polyfunctional cyanate ester resins) and “BA230” (part or all of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. And the like, and the like, and the like.

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

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

<(C) Inorganic filler>
The resin composition of the present invention may contain (C) an inorganic filler (hereinafter also referred to as “component (C)”).
The material of the inorganic filler is not particularly limited. 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 zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly preferred. Moreover, spherical silica is preferable as the silica. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of commercially available inorganic fillers include “SO-C2” and “SO-C1” manufactured by Admatechs Corporation.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 4 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less from the viewpoint of obtaining an insulating layer having a small surface roughness and improving the fine wiring formability. More preferably, it is 1 μm or less, 0.7 μm or less, 0.5 μm or less, 0.4 μm or less, or 0.3 μm or less. On the other hand, from the viewpoint of obtaining a resin varnish having an appropriate viscosity and good handleability when forming a resin varnish using the resin composition, the average particle size of the inorganic filler is preferably 0.01 μm or more, 0.03 μm or more is more preferable, 0.05 μm or more, 0.07 μm or more, or 0.1 μm or more is more preferable.

  The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring apparatus, “LA-500” manufactured by Horiba, Ltd. or the like can be used.

  Inorganic fillers are aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents from the viewpoint of improving moisture resistance and dispersibility. It is preferable that it is processed with 1 or more types of surface treating agents. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (hexamethyldisilazane) manufactured by KK, "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type) Silane coupling agent).

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, 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 more preferable from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the sheet form. 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 the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount 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. can be used.

  Although content of (C) component in a resin composition is not specifically limited, From a viewpoint of obtaining an insulating layer with a low coefficient of thermal expansion, Preferably it is 50 mass% or more, More preferably, it is 60 mass% or more or 65 mass% or more. is there. The upper limit of the content of the inorganic filler in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less.

  The resin composition of the present invention may contain additives such as thermoplastic resins, curing accelerators, flame retardants, and rubber particles in addition to the curing agents other than the components (A) to (C) and (B). .

-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 thereof include thermoplastic resins such as ether ketone resins and polyester resins, and among these, phenoxy resins are preferred. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  The polystyrene equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. 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” (manufactured by Mitsubishi Chemical Corporation). In addition, “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YL6954BH30”, “YX7553”, “YL7769BH30” manufactured by Mitsubishi Chemical Co., Ltd., “YL6794”, “YL7213”, “YL7290”, “YL7482” and the like.

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, and “Electrical butyral 6000-EP” manufactured by Denki Kagaku Kogyo Co., Ltd. Sekisui Chemical Co., Ltd.'s S-REC BH series, BX series, KS series, BL series, BM series and the like.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

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

  Among these, phenoxy resin and polyvinyl acetal resin are preferable as the thermoplastic resin from the viewpoint of obtaining an insulating layer having a lower surface roughness and superior adhesion to the conductor layer in combination with other components. Therefore, in one suitable embodiment, (D) component contains 1 or more types selected from the group which consists of a phenoxy resin and polyvinyl acetal resin.

  The content of the thermoplastic resin in the resin composition is not particularly limited, but is preferably 0% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, and even more preferably 1% by mass to 5% by mass. %.

-Curing accelerator-
Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, phosphorus-based curing accelerators, amine-based curing accelerators, and imidazole-based accelerators. A curing accelerator is preferable, and an amine-based curing accelerator and an imidazole-based curing accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl Examples include imidazole compounds such as 3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2-phenyl. Imidazole is preferred.

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

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

  Although content of the hardening accelerator in a resin composition is not specifically limited, It is preferable to use in 0.05 mass%-3 mass%.

-Flame retardant-
The resin composition of the present invention may 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. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

  Commercially available products may be used as the flame retardant, and examples thereof include “HCA-HQ” manufactured by Sanko Co., Ltd.

  The content of the flame retardant in the resin composition is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and even more preferably 1.5% by mass to 10% by mass. % Is more preferable.

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

  A commercially available product may be used as the rubber particles, and examples thereof include “AC3816N” manufactured by Aika Industry Co., Ltd.

  The content of the organic filler in the resin composition is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 10% by mass.

  The resin composition may further contain other additives other than the flame retardant and the organic filler, if necessary. Examples of such other additives include an organic copper compound, an organic zinc compound, and Examples thereof include organic metal compounds such as organic cobalt compounds, and resin additives such as organic fillers, thickeners, antifoaming agents, leveling agents, adhesion imparting agents, and coloring agents.

[Adhesive film]
The adhesive film of this invention has a support body and the resin composition layer provided on this support body containing the resin composition of this invention.

  The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and even more preferably 50 μm or less, or 40 μm or less from the viewpoint of thinning the insulating layer. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it may be 1 micrometer or more, 5 micrometers or more, 10 micrometers or more, etc.

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

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). It may be used.

  The support may be subjected to mat treatment or corona treatment on the surface to be bonded to the resin composition layer.

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. , “AL-5”, “AL-7” and the like.

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

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

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

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

  A protective film according to the support can be further laminated on the surface of the adhesive film that is not joined to the support of the resin composition layer (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can be stored in a roll. When an adhesive film has a protective film, it can be used by peeling off the protective film.

  The adhesive film of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (a printed wiring board). For the interlayer insulating layer).

[Prepreg]
The prepreg of the present invention is characterized in that the resin composition of the present invention is impregnated in a sheet-like fiber base material.

  The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of thinning the insulating layer, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and even more preferably 20 μm or less. Although the minimum of the thickness of a sheet-like fiber base material is not specifically limited, Usually, it is 10 micrometers or more.

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

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

  The prepreg of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). (For interlayer insulating layers).

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

For example, the printed wiring board of the present invention can be produced 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 step (I) is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one or both surfaces of the substrate. A circuit board on which a patterned conductor layer (circuit) is formed. Further, when the printed wiring board is manufactured, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is further formed is also included in the “inner layer board” in the present invention. When the printed wiring board is a component built-in circuit board, an inner layer board with built-in components may be used.

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

  Lamination of the inner layer substrate and the adhesive film may be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

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

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

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

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

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

  For example, although the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, 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 in the range of 170 ° C to 200 ° C.) and 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 formed at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

  The dielectric loss tangent of the insulating layer formed by thermosetting the resin composition (layer) is preferably 0.008 or less, more preferably 0.007 or less, and further preferably 0.006 or less. Although a lower limit is not specifically limited, It will be 0.001 or more, 0.003 or more, etc.

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

  The printed wiring board of this invention can be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as when an adhesive film is used.

  Step (III) is a step of making a hole in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, 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 for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd. The neutralizing solution is preferably an acidic aqueous solution. Examples of commercially available products include “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  The arithmetic average roughness Ra (roughness) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, still more preferably 300 nm or less, 250 nm or less, 200 nm or less, or 150 nm or less. Although a lower limit is not specifically limited, It will be 10 nm or more, 50 nm or more, etc. The arithmetic average roughness (Ra) of the insulating layer surface can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Becoins Instruments is cited.

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

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

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

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

  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. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

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

  The insulating layer formed using the resin composition of the present invention exhibits high peel strength with respect to the conductor layer. The peel strength is preferably 0.40 kgf / cm or more, more preferably 0.45 kgf / cm or more. The upper limit value of the peel strength is not particularly limited, but is 1.2 kgf / cm or less, 0.90 kgf / cm or less, and the like. In the present invention, although the arithmetic average roughness Ra (roughness) of the surface of the insulating layer after the roughening treatment is small, an insulating layer exhibiting such a high peel strength can be formed. It contributes significantly to miniaturization. In the present invention, the peel strength between the insulating layer and the conductor layer refers to a peel strength (90-degree peel strength) when the conductor layer is peeled off in a direction perpendicular to the insulating layer (90-degree direction). The peel strength when the layer is peeled in the direction perpendicular to the insulating layer (90-degree direction) can be determined by measuring with a tensile tester. Examples of the tensile tester include “AC-50C-SL” manufactured by TSE Corporation.

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

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

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conduction location” is a “location where an electrical signal is transmitted on a printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

(Example 1)
15 parts of liquid bisphenol A type epoxy resin (Mitsubishi Chemical Corporation "828US", epoxy equivalent 190) and biphenyl aralkyl type epoxy resin (epoxy equivalent 291; Nippon Kayaku Co., Ltd. "NC3000H") Was dissolved in 5 parts of methyl ethyl ketone (hereinafter abbreviated as “MEK”) and 5 parts of cyclohexanone with stirring. Thereto, 25 parts of a solution in which a triazine structure-containing active ester compound (“EXB9510” manufactured by DIC Corporation, active ester equivalent 214) was dissolved in MEK so as to have a nonvolatile content of 60%, a curing accelerator (Guangei Chemical Industry Co., Ltd.) Co., Ltd., “4-dimethylaminopyridine”) 0.1 part, spherical silica (average particle size 0.5 μm, phenylaminosilane-treated “SO-C2”, manufactured by Admatechs, carbon per unit weight 100 parts of 0.18%) and 15 parts of phenoxy resin (YX6954BH30, 30% by weight solid MEK and cyclohexanone solution, weight average molecular weight 35000) are mixed and uniformly dispersed with a high-speed rotating mixer to produce a resin varnish. did. Next, the resin varnish was applied onto polyethylene terephthalate (thickness 38 μm, hereinafter abbreviated as “PET”) with a die coater so that the resin thickness after drying was 40 μm, and 80 to 120 ° C. (average (100 ° C.) for 6 minutes to obtain a sheet-like adhesive film.

(Example 2)
The triazine structure-containing active ester compound of Example 1 (“EXB9510” manufactured by DIC Corporation, MEK solution having an active ester equivalent of 214 and a nonvolatile content of 60%) was converted into the triazine structure-containing active ester compound (“EXB9511” manufactured by DIC Corporation). A resin varnish was prepared in the same manner as in Example 1 except that the active ester equivalent 240) was changed to a solution in MEK so that the nonvolatile content was 60%, and an adhesive film was obtained.

Example 3
15 parts of liquid bisphenol A type epoxy resin (“828US” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190) in Example 1 is changed to 10 parts of naphthalene type epoxy resin (“EXA4032SS” manufactured by DIC Corporation, epoxy equivalent 143) In addition, 15 parts of biphenyl aralkyl type epoxy resin (“NC3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 291) is added to 15 parts of naphthol aralkyl type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 331). A resin varnish was prepared in the same manner as in Example 1 except that the adhesive film was changed to an adhesive film.

Example 4
15 parts of liquid bisphenol A type epoxy resin (“828US” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190) of Example 2 was changed to 10 parts of naphthalene type epoxy resin (“EXA4032SS” manufactured by DIC Corporation, epoxy equivalent 143) In addition, 15 parts of biphenyl aralkyl type epoxy resin (“NC3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 291) is added to 15 parts of naphthol aralkyl type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 331). A resin varnish was produced in the same manner as in Example 2 except that the adhesive film was changed to an adhesive film.

(Comparative Example 1)
The triazine structure-containing active ester compound (“EXB-9510” manufactured by DIC Corporation, active ester equivalent 214) of Example 3 was used as the active ester compound containing no triazine structure (“HPC-8000-65T” manufactured by DIC Corporation). Resin varnish was prepared in the same manner as in Example 3 except that it was changed to 20 parts of a toluene solution having an active ester equivalent of 223 and a non-volatile content of 65% to obtain an adhesive film.

(Comparative Example 2)
The triazine structure-containing active ester compound of Example 3 (DIC Corporation "EXB-9510", active ester equivalent 214) was converted to a triazine structure-containing phenol novolak compound (DIC Corporation "LA7052", phenolic hydroxyl group equivalent 120). The MEK solution having a non-volatile content of 60% was changed to 15 parts, and the addition amount of “SO-C2” with phenylaminosilane treatment (manufactured by Admatechs Co., Ltd., carbon amount 0.18% per unit weight) was 65 parts. Except for the above, a resin varnish was prepared in the same manner as in Example 3 to obtain an adhesive film.

(Comparative Example 3)
The triazine structure-containing active ester compound of Example 3 (DIC Corporation "EXB-9510", active ester equivalent 214) was converted to a triazine structure-containing phenol novolak compound (DIC Corporation "LA7052", phenolic hydroxyl group equivalent 120). 10 parts of a MEK solution having a nonvolatile content of 60%) and 5 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, active ester equivalent 223, toluene solution having a nonvolatile content of 65%) containing no triazine structure. In the same manner as in Example 3 except that the number of added parts of “SO-C2” with phenylaminosilane treatment, manufactured by Admatechs Co., Ltd., carbon amount 0.18% per unit weight) was changed to 65 parts. A resin varnish was prepared to obtain an adhesive film.

(Evaluation test)
Hereinafter, measurement methods and evaluation methods in each evaluation test will be described.

1. Measurement of peel strength (peel strength) of plating conductor layer and measurement of arithmetic average roughness (roughness) (1) Base treatment of laminated board Glass cloth base epoxy resin double-sided copper-clad laminate with inner layer circuit formed (Copper foil thickness 18 μm, residual copper ratio 60%, substrate thickness 0.3 mm, R5715ES manufactured by Matsushita Electric Works Co., Ltd.) Both surfaces were immersed in CZ8100 manufactured by MEC Co., Ltd. to roughen the copper surface.

(2) Lamination of adhesive film The adhesive film prepared in each example and each comparative example was subjected to both sides of a laminate using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Seisakusho Co., Ltd.). Laminated. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.

(3) Curing of resin composition The PET film was peeled from the laminated adhesive film, and the resin composition was cured under curing conditions at 170 ° C for 30 minutes.

(4) Roughening treatment The laminated plate is immersed in a swelling dip secu-ligand P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. for 10 minutes at 60 ° C., and then used as a roughening solution. Soaked in Concentrate Compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally as a neutralizing solution, Atotech Japan Co., Ltd. It was immersed in securigant P at 40 ° C. for 5 minutes. The laminate after the roughening treatment was designated as sample A.

(5) Plating formation by semi-additive method In order to form a circuit on the surface of the insulating layer, the laminate was immersed in an electroless plating solution containing PdCl ₂ and then immersed in an electroless copper plating solution. After annealing for 30 minutes at 150 ° C., an etching resist was formed. After pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing was performed at 180 ° C. for 60 minutes. This laminate was designated as Sample B.

(6) Measurement of arithmetic average roughness (roughness) For sample A, using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Beeco Instruments), the measurement range is 121 μm × 92 μm with a 50 × lens. As a result, the arithmetic average roughness (roughness) was obtained. And it was set as the measured value by calculating | requiring the average value of 10 each, and was shown in Table 1.

(7) Measurement of peel strength (peel strength) of the plated conductor layer Cut the conductor layer of sample B into a 10 mm wide and 100 mm long part, peel off one end, S.E., Autocom type tester AC-50C-SL), measured the load (kgf / cm) when peeling 35mm vertically at a speed of 50mm / min at room temperature. It was shown in 1.

2. Measurement of dielectric loss tangent The adhesive films obtained in each Example and each Comparative Example were thermally cured at 190 ° C. for 90 minutes, and the PET film was peeled off to obtain a sheet-like cured product. The cured product was cut into a test piece having a width of 2 mm and a length of 80 mm, and a cavity resonator perturbation method dielectric constant measuring device CP521 manufactured by Kanto Applied Electronics Development Co., Ltd. and a network analyzer E8362B manufactured by Agilent Technology Co., Ltd. were used. The dielectric loss tangent (tan δ) was measured by the cavity resonance method at a measurement frequency of 5.8 GHz. Two test pieces were measured, and the average value was calculated and shown in Table 1.

  In addition, in Table 1, the material used when producing the resin composition of each Example and each comparative example and the ratio (mass part) were shown with the result of the evaluation test.

Claims (11)

  A resin composition comprising (A) an epoxy resin and (B) an active ester compound containing a triazine structure.   The resin composition according to claim 1, wherein the content of (A) the epoxy resin is 0.1% by mass to 30% by mass when the nonvolatile component in the resin composition is 100% by mass.   (B) Content of the active ester compound containing a triazine structure is 0.1 mass%-30 mass% when the non-volatile component in a resin composition is 100 mass%. Resin composition. (B) The resin composition of any one of Claims 1-3 whose active ester compound which has a triazine structure is following formula (1).

(Wherein, X ¹ and X ² each independently represent —O— or —NH—,
R ¹ represents an amino group, an alkyl group, an aryl group, an alkoxy group, a hydrogen atom, or a halogen atom, and R ² represents a monovalent aromatic group, a monovalent aliphatic group, or a monovalent alicyclic group. Represents a group,
Ar ¹ and Ar ² each independently represents a trivalent aromatic group which may have a substituent, j and k each represents a positive number, and l represents a number of 0 or more)   (C) The resin composition of any one of Claims 1-4 containing an inorganic filler.   The resin composition according to claim 5, wherein the content of (C) the inorganic filler is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass.   The resin composition according to any one of claims 1 to 6, wherein a dielectric loss tangent of an insulating layer formed by thermosetting is 0.008 or less.   The adhesive film which has a support body and the resin composition layer containing the resin composition of any one of Claims 1-7 provided on this support body.   A prepreg in which the resin composition according to any one of claims 1 to 7 is impregnated in a sheet-like fiber base material.   The printed wiring board containing the insulating layer formed with the hardened | cured material of the resin composition of any one of Claims 1-7.   A semiconductor device comprising the printed wiring board according to claim 10.