JP2018030981A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which provides a cured product that has low linear thermal expansion coefficient and dielectric loss tangent and has good adhesion to a conductor layer, and shows excellent flexibility and suppressed tackiness when it is uncured.SOLUTION: There is provided a resin composition which contains (A) a bi- or higher- functional epoxy compound which has viscosity at 25°C of 500 mPa s or less and contains a monovalent group represented by formula (1) (in the formula, X represents a methylene group or a single bond, Y represents an oxygen atom, a nitrogen atom, a carbon atom or an oxycarbonyl group, and m represents an integer of 1 to 3. When there are a plurality of pieces of X, X may be the same or different), and (B) an active ester compound. In the resin composition, a content of the component (A) is 0.5-8 mass% when a non-volatile component in the resin composition is 100 mass%.SELECTED DRAWING: None

Description

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

  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. For example, Patent Document 1 includes an epoxy resin, an active ester compound, a carbodiimide compound, a thermoplastic resin, and an inorganic filler, and the content of the inorganic filler is 100% by mass of the non-volatile component in the resin composition. The resin composition is 40% by mass or more. Patent Document 2 discloses a resin composition containing an epoxy resin having an ester skeleton.

JP 2016-27097 A JP 2014-177530 A

  The present invention provides a resin composition having a low coefficient of linear thermal expansion and a dielectric loss tangent, having a good adhesion with a conductor layer, and having excellent flexibility when uncured and suppressing tackiness.

  As a result of intensive studies on the above problems, the present inventors have (A) a bifunctional or higher functional epoxy compound containing a specific epoxy group-containing group having a viscosity at 25 ° C. of 500 mPa · s or less, and (B ) It has been found that a resin composition containing a combination of an active ester compound and the content of the component (A) in a predetermined range can realize the above-mentioned problems, and has completed the present invention.

（式中、Ｘはメチレン基又は単結合を表し、Ｙは酸素原子、窒素原子、炭素原子又はオキシカルボニル基を表し、ｍは１〜３の整数を表す。Ｘが複数個ある場合、それらは互いに同一でも異なっていてもよい。）
と、（Ｂ）活性エステル化合物とを含む樹脂組成物であって、
（Ａ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％としたとき、０．５質量％〜８質量％である、樹脂組成物。
［２］ 式（１）中、Ｘがメチレン基を表し、Ｙが酸素原子、窒素原子又はオキシカルボニル基を表す、［１］に記載の樹脂組成物。
［３］ （Ａ）成分が、シクロヘキサンジメタノール型エポキシ樹脂、トリメチロールプロパン型エポキシ樹脂、１，６−ヘキサンジオール型エポキシ樹脂、１，４−ブタンジオール型エポキシ樹脂、ベンゼンジメタノール型エポキシ樹脂、ビフェニルジメタノール型エポキシ樹脂、ジシクロペンタジエンジメタノール型エポキシ樹脂、ジエチレングリコール型エポキシ樹脂、及びｏ−トルイジン型エポキシ樹脂からなる群から選択される、［１］又は［２］に記載の樹脂組成物。
［４］ （Ａ）成分が、シクロヘキサンジメタノール型エポキシ樹脂、トリメチロールプロパン型エポキシ樹脂、１，６−ヘキサンジオール型エポキシ樹脂、及びｏ−トルイジン型エポキシ樹脂からなる群から選択される、［１］〜［３］の何れかに記載の樹脂組成物。
［５］ （Ａ）成分のエポキシ当量が、８０〜２５０である、［１］〜［４］の何れかに記載の樹脂組成物。
［６］ さらに（Ｃ）無機充填材を含む、［１］〜［５］の何れかに記載の樹脂組成物。
［７］ （Ｃ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％としたとき、４０質量％以上である、［６］に記載の樹脂組成物。
［８］ プリント配線板の絶縁層用である、［１］〜［７］の何れかに記載の樹脂組成物。
［９］ ［１］〜［８］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。
［１０］ ［１］〜［８］の何れかに記載の樹脂組成物又は［９］に記載のシート状積層材料を熱硬化して得られた絶縁層を含む、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) Bifunctional or higher functional epoxy compound containing a monovalent group represented by the following formula (1) having a viscosity at 25 ° C. of 500 mPa · s or less:

(In the formula, X represents a methylene group or a single bond, Y represents an oxygen atom, a nitrogen atom, a carbon atom or an oxycarbonyl group, m represents an integer of 1 to 3. When there are a plurality of X, they are They may be the same or different.
And (B) an active ester compound,
(A) The resin composition whose content of a component is 0.5 mass%-8 mass% when the non-volatile component in a resin composition is 100 mass%.
[2] The resin composition according to [1], wherein in formula (1), X represents a methylene group and Y represents an oxygen atom, a nitrogen atom or an oxycarbonyl group.
[3] The component (A) is a cyclohexanedimethanol type epoxy resin, trimethylolpropane type epoxy resin, 1,6-hexanediol type epoxy resin, 1,4-butanediol type epoxy resin, benzenedimethanol type epoxy resin, The resin composition according to [1] or [2], which is selected from the group consisting of biphenyldimethanol type epoxy resin, dicyclopentadiene dimethanol type epoxy resin, diethylene glycol type epoxy resin, and o-toluidine type epoxy resin.
[4] The component (A) is selected from the group consisting of cyclohexanedimethanol type epoxy resin, trimethylolpropane type epoxy resin, 1,6-hexanediol type epoxy resin, and o-toluidine type epoxy resin. ] The resin composition in any one of [3].
[5] The resin composition according to any one of [1] to [4], wherein the epoxy equivalent of the component (A) is 80 to 250.
[6] The resin composition according to any one of [1] to [5], further comprising (C) an inorganic filler.
[7] The resin composition according to [6], wherein the content of the component (C) is 40% by mass or more when the nonvolatile component in the resin composition is 100% by mass.
[8] The resin composition according to any one of [1] to [7], which is for an insulating layer of a printed wiring board.
[9] A sheet-like laminated material containing the resin composition according to any one of [1] to [8].
[10] A printed wiring board comprising an insulating layer obtained by thermosetting the resin composition according to any one of [1] to [8] or the sheet-like laminated material according to [9].
[11] A semiconductor device including the printed wiring board according to [10].

  According to the present invention, there is provided a resin composition having a low coefficient of linear thermal expansion and a dielectric loss tangent, providing a cured product having good adhesion with a conductor layer, having excellent flexibility when uncured, and suppressing tackiness. can do.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

[Resin composition]
The resin composition of the present invention comprises (A) a bifunctional or higher functional epoxy compound containing a monovalent group represented by the following formula (1) having a viscosity at 25 ° C. of 500 mPa · s or less, and (B ) An active ester compound, and the content of the component (A) is 0.5% by mass to 8% by mass when the nonvolatile component in the resin composition is 100% by mass.

（式中、Ｘはメチレン基又は単結合を表し、Ｙは酸素原子、窒素原子、炭素原子又はオキシカルボニル基を表し、ｍは１〜３の整数を表す。Ｘが複数個ある場合、それらは互いに同一でも異なっていてもよい。）

(In the formula, X represents a methylene group or a single bond, Y represents an oxygen atom, a nitrogen atom, a carbon atom or an oxycarbonyl group, m represents an integer of 1 to 3. When there are a plurality of X, they are They may be the same or different.

  In combination with the active ester compound, the viscosity at 25 ° C. is as low as 500 mPa · s or less and contains a monofunctional group represented by the above formula (1) (hereinafter referred to as “low viscosity”). The resin composition of the present invention containing a predetermined amount of “epoxy compound”) exhibits good flexibility and low tack when uncured, has a low linear thermal expansion coefficient and dielectric loss tangent, and is in close contact with the conductor layer. A cured product having good properties can be obtained.

<(A) Low viscosity epoxy compound>
The low viscosity epoxy compound (A) has a viscosity at 25 ° C. of 500 mPa · s or less.

  (B) Hardened | cured material which was further excellent in the viewpoint of obtaining the resin composition which shows further favorable softness | flexibility and low tack property in combination with the active ester compound mentioned later, a linear thermal expansion coefficient, a dielectric loss tangent, and a conductor layer In view of the above, the viscosity (25 ° C.) of the component (A) is preferably 400 mPa · s or less, more preferably 300 mPa · s or less, 250 mPa · s or less, 200 mPa · s or less, 150 mPa · s or less, 120 mPa · s. · S or less, 100 mPa · s or less, 80 mPa · s or less, 60 mPa · s or less, or 50 mPa · s or less. Although the minimum of this viscosity (25 degreeC) is not specifically limited, Usually, it can be set as 1 mPa * s or more, 2 mPa * s or more, 5 mPa * s or more. The viscosity (25 ° C.) of the low-viscosity epoxy compound can be measured according to the method described later in <Measurement of viscosity of epoxy compound (25 ° C.)>.

  The low-viscosity epoxy compound (A) is a bifunctional or higher functional epoxy compound containing a monovalent group represented by the above formula (1).

In formula (1), X represents a methylene group (—CH ₂ —) or a single bond. When there are a plurality of X in the formula (1), they may be the same as or different from each other. In one preferred embodiment, X represents a methylene group.

  In formula (1), Y represents an oxygen atom, a nitrogen atom, a carbon atom, or an oxycarbonyl group (—O—C (═O) —). When Y represents an oxygen atom or an oxycarbonyl group, m is 1. When Y represents a nitrogen atom, m is 2. M is 3 when Y represents a carbon atom. In one preferred embodiment, Y represents an oxygen atom, a nitrogen atom or an oxycarbonyl group.

  (B) Hardened | cured material which was further excellent in the viewpoint of obtaining the resin composition which shows further favorable softness | flexibility and low tack property in combination with the active ester compound mentioned later, a linear thermal expansion coefficient, a dielectric loss tangent, and a conductor layer In the formula (1), X represents a methylene group, and Y preferably represents an oxygen atom, a nitrogen atom or an oxycarbonyl group. Among them, in the formula (1), X represents a methylene group. It is more preferable that Y represents an oxygen atom or a nitrogen atom, and in formula (1), it is particularly preferable that X represents a methylene group and Y represents an oxygen atom.

  (A) The number of monovalent groups represented by the formula (1) contained per molecule is as long as the (A) component is bifunctional or more, that is, the (A) component is 2 or more. As long as it has an epoxy group, it is not particularly limited. When the component (A) contains two or more monovalent groups represented by the formula (1), they may be the same as or different from each other.

In a preferred embodiment, the component (A) is
(I) an epoxy compound containing two or more monovalent groups represented by formula (1) (wherein X represents a methylene group, Y represents an oxygen atom, and m represents 1);
(Ii) an epoxy compound containing one or more monovalent groups represented by formula (1) (wherein X represents a methylene group, Y represents a nitrogen atom, and m represents 2); or (iii) ) An epoxy compound containing two or more monovalent groups represented by formula (1) (wherein X represents a methylene group, Y represents an oxycarbonyl group, and m represents 1).

  The component (A) may or may not have another epoxy group-containing group as long as it contains the monovalent group represented by the above formula (1). Examples of such other epoxy group-containing groups include alicyclic epoxy groups having 4 to 10 carbon atoms.

  In one embodiment, an epoxy compound containing a monovalent group represented by formula (1) (wherein X represents a methylene group, Y represents an oxygen atom, and m represents 1), that is, glycidyl ether As the epoxy compound, a glycidyl etherified product of a polyol compound such as an aliphatic polyol or an aromatic polyol may be used. As long as a glycidyl ether-based epoxy compound having a viscosity at 25 ° C. of 500 mPa · s or less is obtained, the polyol compound as a raw material is not particularly limited and may be any of an alicyclic polyol, a chain polyol, and an aromatic polyol. Also good.

  In one embodiment, an epoxy compound containing a monovalent group represented by formula (1) (wherein X represents a methylene group, Y represents a nitrogen atom, and m represents 2), that is, glycidylamine As the epoxy compound, a glycidyl aminated product of an amine compound such as an aliphatic amine or an aromatic amine may be used. As long as a glycidylamine-based epoxy compound having a viscosity at 25 ° C. of 500 mPa · s or less is obtained, the starting amine compound is not particularly limited, and may be any of alicyclic amine, chain amine, and aromatic amine. These may be polyamine compounds.

  In one embodiment, an epoxy compound containing a monovalent group represented by formula (1) (wherein X represents a methylene group, Y represents an oxycarbonyl group, and m represents 1), that is, glycidyl. As the ester-based epoxy compound, a glycidyl esterified product of a polycarboxylic acid compound such as an aliphatic polycarboxylic acid or an aromatic polycarboxylic acid may be used. As long as a glycidyl ester epoxy compound having a viscosity at 25 ° C. of 500 mPa · s or less is obtained, the raw material polycarboxylic acid compound is not particularly limited, and alicyclic polycarboxylic acid, chain polycarboxylic acid, aromatic Any of polycarboxylic acids may be used.

  The number of epoxy functional groups in the component (A) may be two or more (two or more functions), and is not particularly limited as long as the desired viscosity characteristics are satisfied. The upper limit of the number of epoxy functional groups can usually be 6 or less, 4 or less, and the like.

  (B) From the viewpoint that the effects of the present invention can be more enjoyed in combination with the active ester compound, the component (A) is a polyol type epoxy resin or amine containing a monovalent group represented by the formula (1). Type epoxy resin is preferred. Here, the “polyol type epoxy resin” refers to an epoxy resin containing a structural unit derived from a polyol compound. The “structural unit derived from the polyol compound” refers to the remainder obtained by removing two or more hydroxy groups from the polyol compound. Examples of the polyol compound include aliphatic diols having 2 to 20 carbon atoms (preferably 3 to 16 or 3 to 14), aliphatic triols having 2 to 20 carbon atoms (preferably 3 to 16 or 3 to 14), and carbon. An aromatic diol having 6 to 30 atoms (preferably 6 to 20 or 6 to 16), an aromatic triol having 6 to 30 carbon atoms (preferably 6 to 20 or 6 to 16), and a condensate thereof. One or more selected from the group is preferred, cyclohexanedimethanol, trimethylolpropane, 1,6-hexanediol, 1,4-butanediol, benzenedimethanol, biphenyldimethanol, dicyclopentadienedimethanol, diethylene glycol, and One or more selected from the group consisting of these condensates is more preferred. The “amine type epoxy resin” means an epoxy resin containing a structural unit derived from an amine compound. The “structural unit derived from an amine compound” refers to the remainder obtained by removing one or more amino groups from an amine compound. As the amine compound, an aliphatic monoamine having 1 to 20 carbon atoms (preferably 2 to 16, 2 to 12 or 2 to 8), 1 to 20 carbon atoms (preferably 2 to 16, 2 to 12, or 2). -8) aliphatic diamines, aromatic monoamines having 6-30 carbon atoms (preferably 6-20, 6-16, 6-12 or 6-8), and 6-30 carbon atoms (preferably 6-6). 1 or more types selected from the group consisting of 20, 6-16, 6-12 or 6-8) aromatic diamines are preferred, and it has 6-30 carbon atoms (preferably 6-20, 6-16, 6-6). 12 or 6-8) alkylanilines are more preferred, and o-toluidine is more preferred. Therefore, in one preferred embodiment, the component (A) is a cyclohexanedimethanol type epoxy resin, trimethylolpropane type epoxy resin, or 1,6-hexane containing a monovalent group represented by the formula (1). Diol type epoxy resin, 1,4-butanediol type epoxy resin, benzenedimethanol type epoxy resin, biphenyldimethanol type epoxy resin, dicyclopentadiene dimethanol type epoxy resin, diethylene glycol type epoxy resin, and o-toluidine type epoxy resin A bifunctional or higher functional epoxy resin selected from the group consisting of In a particularly preferred embodiment, the component (A) is a cyclohexanedimethanol type epoxy resin, trimethylolpropane type epoxy resin, or 1,6-hexanediol containing a monovalent group represented by the formula (1). A bifunctional or higher functional epoxy resin selected from the group consisting of a type epoxy resin and an o-toluidine type epoxy resin.

  The epoxy equivalent of the component (A) is not particularly limited as long as the desired viscosity characteristics are satisfied. In one suitable embodiment, the epoxy equivalent of (A) component is 80-250. The lower limit of the epoxy equivalent of the component (A) is more preferably 90 or more, or 100 or more, and the upper limit of the epoxy equivalent is more preferably 240 or less, 220 or less, or 200 or less. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a compound containing 1 equivalent of an epoxy group.

  Specific examples of the component (A) include, for example, “ZX1658GS” (viscosity at 25 ° C., 34 mPa · s, epoxy equivalent 135, cyclohexanedimethanol type epoxy resin), “ZX1542” (25 Viscosity of 109 mPa · s at ℃, epoxy equivalent of 120, trimethylolpropane type epoxy resin), “Show Free CDMDG” manufactured by Showa Denko KK (viscosity at 25 ° C. of 34 mPa · s, epoxy equivalent of 138, cyclohexanedimethanol type) Epoxy resin), “Denacol EX212L” (viscosity at 25 ° C., epoxy equivalent 135, 1,6-hexanediol type epoxy resin) manufactured by Nagase ChemteX Corporation, “EP-” manufactured by ADEKA Corporation 3980S "(viscosity at 25 ° C. 31 mPa · s, epoxy equivalent 115, - toluidine type epoxy resin), "EP-4088S" (viscosity 213mPa · s at 25 ° C., epoxy equivalent 170, dicyclopentadiene methanol epoxy resin) and the like.

  Content of (A) component in a resin composition is 0.5 mass%-8 mass% when the non-volatile component in a resin composition is 100 mass%. The lower limit of the content of the component (A) is preferably 0.6% by mass or more, more preferably 0.8% by mass or more, and still more preferably 1. from the viewpoint of obtaining a resin composition exhibiting particularly excellent flexibility. They are 0 mass% or more, 1.2 mass% or more, 1.4 mass% or more, 1.6 mass% or more, or 1.8 mass% or more. The upper limit of the content of the component (A) is preferably 7.5 mass from the viewpoint of obtaining a resin composition in which tackiness is further suppressed, and from the viewpoint of realizing a cured product having a particularly low linear thermal expansion coefficient and dielectric loss tangent. % Or less, more preferably 7.0% by mass or less, 6.5% by mass or less, or 6.0% by mass or less.

-(A ') Other epoxy compounds-
The resin composition of the present invention may contain another epoxy compound different from the component (A) (hereinafter also referred to as “component (A ′)”) as long as the desired effect can be achieved. Good.

  Examples of the component (A ′) 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, and naphthol. Novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, linear aliphatic Epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthi N'eteru type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. Another epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The component (A ′) is preferably a bifunctional or higher functional epoxy compound. As the component (A ′), a solid epoxy resin (also referred to as “solid epoxy resin”) at a temperature of 25 ° C. alone or a solid epoxy resin and a liquid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 25 ° C. "Liquid epoxy resin") is preferably included in combination. Here, the liquid epoxy resin used as the component (A ′) has a viscosity at 25 ° C. higher than 500 mPa · s. As the solid epoxy resin, a trifunctional or higher functional solid epoxy resin is preferable, and a trifunctional or higher functional aromatic solid epoxy resin is more preferable. The liquid epoxy resin is preferably a bifunctional or higher liquid epoxy resin, and more preferably a bifunctional or higher aromatic liquid epoxy resin. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring in the molecule. When a solid epoxy resin and a liquid epoxy resin are used in combination as the component (A ′), the quantitative ratio thereof (solid epoxy resin: liquid epoxy resin) is 1: 0.001 to 1: 5 in mass ratio. The range is preferable, the range of 1: 0.01 to 1: 3 is more preferable, and the range of 1: 0.05 to 1: 2 is more preferable. Specific examples of the solid epoxy resin include “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690”, “N-695” (cresol novolak) manufactured by DIC Corporation. Type epoxy resin), “HP7200”, “HP7200H”, “HP7200HH” (dicyclopentadiene type epoxy resin), “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 novolak type epoxy resin), “NC3000H”, “NC3000”, “ NC3000L ”,“ NC3100 ”(Bifeni Type epoxy resin), "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "ESN485" (naphthol novolak type epoxy resin), "YX4000H", "YL6121" (biphenyl) manufactured by Mitsubishi Chemical Corporation Type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin), “PG-100”, “CG-500” manufactured by Osaka Gas Chemical Co., Ltd., Mitsubishi Chemical Corporation ) "YL7800" (fluorene type epoxy resin), Mitsubishi Chemical Corporation "jER1010" (solid bisphenol A type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), "jER1031S" (tetraphenyl) Ethane type epoxy resin). Specific examples of the liquid epoxy resin include “HP4032”, “HP4032H”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “828US” manufactured by Mitsubishi Chemical Corporation, “828EL” (bisphenol A type epoxy resin), “jER807” (bisphenol F type epoxy resin), “jER152” (phenol novolac type epoxy resin), “ZX1059” (bisphenol A type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. And bisphenol F type epoxy resin), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, “Celoxide 2021P” (manufactured by Daicel Corporation) (an alicyclic type having an ester skeleton) Epoxy resin), "PB-3600" (pig Epoxy resin) having an end structure.

  The content of the component (A ′) in the resin composition is preferably 1 when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining a cured product showing good mechanical strength and insulation reliability. It is at least 5% by mass, more preferably at least 3% by mass, even more preferably at least 5% by mass, or at least 10% by mass. 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 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less. It is 20 mass% or less.

<(B) Active ester compound>
Component (B) is an active ester compound, which is a compound having one or more active ester groups in one molecule. As the component (B), an active ester compound having two or more active ester groups in one molecule is preferable. For example, phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds An active ester compound having two or more ester groups with high reaction activity in one molecule is preferably used. (B) A component may be used individually by 1 type and may be used in combination of 2 or more type.

  In combination with the component (A), a carboxylic acid compound and / or a thiocarboxylic acid compound, a hydroxy compound and a compound having a linear thermal expansion coefficient, a dielectric loss tangent, and a cured product that is more excellent in adhesion to the conductor layer can be realized. An active ester compound obtained by a condensation reaction with a thiol compound is preferred. Among them, an active ester compound obtained by reacting a carboxylic acid compound with at least one selected from a phenol compound, a naphthol compound, and a thiol compound is more preferable, and a carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group Aromatic compounds having two or more active ester groups in one molecule, obtained by reacting a carboxylic acid compound having at least two or more carboxy groups in one molecule, and having a phenolic hydroxyl group An aromatic compound obtained by reacting with an aromatic compound, and more preferably an aromatic compound having two or more active ester groups in one molecule. The active ester compound may be linear or branched. Further, if the carboxylic acid compound having at least two or more carboxy groups in a molecule is a compound containing an aliphatic chain, the compatibility with other resin components constituting the resin composition can be increased. If it is a compound which has a ring, heat resistance can be made high.

  Examples of the carboxylic acid compound include an aliphatic carboxylic acid having 1 to 20 carbon atoms (preferably 2 to 10 and more preferably 2 to 8) and an aromatic having 7 to 20 carbon atoms (preferably 7 to 10). Carboxylic acid is mentioned. Examples of the aliphatic carboxylic acid include acetic acid, malonic acid, succinic acid, maleic acid, itaconic acid and the like. Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable from the viewpoint of suppressing the decrease in peel strength between the insulating layer and the circuit in a high-temperature and high-humidity environment due to HAST. More preferred are isophthalic acid and terephthalic acid.

  The thiocarboxylic acid compound is not particularly limited, and examples thereof include thioacetic acid and thiobenzoic acid.

  Examples of the phenol compound include phenol compounds having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 23, and further preferably 6 to 22). Specific examples include hydroquinone, Resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, tri Examples thereof include hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol and the like. As the phenol compound, a phenol novolak, a cresol novolak, or a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP2013-40270A may be used.

  Examples of the naphthol compound include naphthol compounds having 10 to 40 carbon atoms (preferably 10 to 30, more preferably 10 to 20), and specific examples include α-naphthol, β-naphthol, , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. A naphthol novolak may also be used as the naphthol compound.

  Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol, phenol novolak, cresol novolak, naphthol novolak, phosphorus atom-containing oligomer having phenolic hydroxyl group is preferable Catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphth Talen, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol, phenol novolak, cresol novolak, naphthol novolak, and phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferred. -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type diphenol, phenol novolac, cresol novolak, naphthol novolak, phenolic hydroxyl group More preferred are phosphorus atom-containing oligomers, Roxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene diphenol, phenol novolak, cresol novolak, naphthol novolak, phosphorus atom-containing oligomer having a phenolic hydroxyl group is even more preferred, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenol, phosphorus atom-containing oligomers having a phenolic hydroxyl group are particularly preferred, and dicyclopentadiene type diphenol is particularly preferred.

  The thiol compound is not particularly limited, and examples thereof include benzene dithiol and triazine dithiol.

  Preferred specific examples of the component (B) include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac. Active ester compounds containing, active ester compounds obtained by reacting aromatic carboxylic acids and phosphorus atom-containing oligomers having phenolic hydroxyl groups, among which active ester compounds containing dicyclopentadiene-type diphenol structures, naphthalene structures More preferred is an active ester compound containing, an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group. In the present invention, the “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

  As the component (B), active ester compounds disclosed in JP-A Nos. 2004-277460 and 2013-40270 may be used, and commercially available active ester compounds may also be used. Examples of commercially available products of component (B) include “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T”, “HPC-8000L-65M” (dicyclopentadiene type) manufactured by DIC Corporation. Active ester compound containing diphenol structure), “9416-70BK” (active ester compound containing naphthalene structure) manufactured by DIC Corporation, “DC808” manufactured by Mitsubishi Chemical Corporation (activity including acetylated product of phenol novolac) Ester compound), “YLH1026” (active ester compound containing a benzoylated phenol novolac) manufactured by Mitsubishi Chemical Corporation, and “EXB9050L-62M” (phosphorus atom-containing active ester compound) manufactured by DIC Corporation.

  In combination with the component (A), the content of the component (B) in the resin composition from the viewpoint of realizing a cured product that is more excellent in linear thermal expansion coefficient, dielectric loss tangent, and adhesion to the conductor layer, When the nonvolatile component in the resin composition is 100% by mass, 0.5% by mass or more is preferable, 1.0% by mass or more is more preferable, 1.5% by mass or more, 2.0% by mass or more. 5 mass% or more or 3.0 mass% or more is more preferable. (B) Although the upper limit of content of a component is not specifically limited, 30 mass% or less is preferable, 25 mass% or less is more preferable, 20 mass% or less, 15 mass% or less, 10 mass% or less, or 8 mass% is further. preferable.

  In addition, when the number of epoxy groups of the epoxy compound in the resin composition (that is, the component (A) and the component (A ′) when contained) is 1, from the viewpoint of obtaining an insulating layer with good mechanical strength, The number of reactive groups in component B) is preferably from 0.1 to 2, more preferably from 0.3 to 1.5, still more preferably from 0.5 to 1.2. Here, “the number of epoxy groups of the epoxy compound in the resin composition” means that the solid content mass of each of the epoxy compounds corresponding to the component (A) and the component (A ′) present in the resin composition is divided by the epoxy equivalent. This value is the sum of all the epoxy compounds. The “reactive group” as referred to for the component (B) means an active ester group, and the “number of reactive groups in the component (B)” means the active ester compound corresponding to the component (B) in the resin composition. This is the total value of the values obtained by dividing the solid content mass by the reactive group equivalent.

<(C) Inorganic filler>
The resin composition of the present invention may further contain an inorganic filler as the component (C). 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. 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, and silica is particularly suitable. That. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. 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 spherical silica include “SO-C2” and “SO-C1” manufactured by Admatechs 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, even 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 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 created on a volume basis by a laser diffraction particle size distribution measuring device, 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 type particle size distribution measuring device, “LA-500”, “LA-750”, “LA-950”, etc. manufactured by Horiba, Ltd. can be used.

  Inorganic fillers include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, titanate coupling agents and the like from the viewpoint of improving moisture resistance and dispersibility. It is preferable to treat with one or more surface treatment 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 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 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.

  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.

  From the viewpoint of obtaining a cured product having a low linear thermal expansion coefficient and dielectric loss tangent, the content of the inorganic filler in the resin composition is preferably 40% by mass or more when the nonvolatile component in the resin composition is 100% by mass. More preferably, it is 45 mass% or more, and still more preferably 50 mass% or more. In the prior art, when the content of the inorganic filler in the resin composition increases, the resin composition tends to become brittle and lose flexibility. On the other hand, in the resin composition of the present invention that includes the combination of the component (A) and the component (B) and the content of the component (A) is in a predetermined range, while suppressing the embrittlement of the resin composition. In addition, the content of the inorganic filler can be further increased. For example, the content of the inorganic filler in the resin composition can be increased to 55% by mass or more, 60% by mass or more, 65% by mass or more, or 70% by 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, and still more preferably 80% by mass or less, from the viewpoint of mechanical strength of the obtained cured product. .

<Other ingredients>
The resin composition of the present invention contains one or more additives selected from the group consisting of curing agents other than the component (B), thermoplastic resins, curing accelerators, flame retardants, and organic fillers as necessary. Furthermore, you may contain.

-Curing agents other than component (B)-
The resin composition of the present invention may further contain a curing agent other than the component (B), that is, a curing agent other than the active ester compound.

  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 phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, a benzoxazine-based curing agent, and A carbodiimide type hardening | curing agent is mentioned. A hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  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 (peel strength) to the conductor layer, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. . From the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength with the conductor layer, a triazine skeleton-containing phenol novolac-based curing agent and a triazine skeleton-containing naphthol novolak-based curing agent are preferable. 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”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "SN-495", "SN-375", "SN-395", "LA-7052," "LA-7054," "LA-3018," "LA-1356," "TD2090" manufactured by DIC Corporation Or the like.

  Although it does not specifically limit as a cyanate ester type hardening | curing agent, For example, novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening agent, dicyclopentadiene type cyanate ester type hardening agent, bisphenol type (bisphenol A type, And bisphenol F type, bisphenol S type, and the like) and cyanate ester-based curing agents, and prepolymers in which these are partially triazines. Specific examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidene diphenyl. Dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, Bifunctional cyanate resins such as 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol novolac and cresol novolac Invite from etc. Polyfunctional cyanate resin is, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30”, “PT30S” and “PT60” (all of which are phenol novolac polyfunctional cyanate ester resins) and “BADcy” (bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. , “BA230” (a prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified into a trimer), and the like.

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

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

  When a curing agent other than the component (B) is used, the content of the curing agent in the resin composition is preferably 0.5% by mass or more when the nonvolatile component in the resin composition is 100% by mass. More preferably, it is 1 mass% or more, More preferably, it is 1.5 mass% or more, or 2 mass% or more. The upper limit of the content is preferably 20% by mass or less, more preferably 15% by mass or less, or 10% by mass or less.

-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 resins and polyester resins. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  The weight average molecular weight in terms of polystyrene 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 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 measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used 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., “YX7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Corporation, “YL7290”, “YL7482” and the like can be mentioned.

  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 (described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (described in JP-A No. 2002-12667 and JP-A No. 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 polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” 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.

  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 100% by mass when the nonvolatile component in the resin composition is 100% by mass. Is 0.2% by mass to 10% by mass, more preferably 0.3% by mass to 5% by mass.

-Curing accelerator-
The resin composition of the present invention may contain a curing accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Of these, amine-based curing accelerators and imidazole-based curing accelerators are preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type. When using a curing accelerator, the content of the curing accelerator in the resin composition is preferably 0.005% by mass to 1% by mass, more preferably 100% by mass when the nonvolatile component in the resin composition is 100% by mass. Is 0.01% by mass to 0.5% 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. A flame retardant may be used individually by 1 type, or may be used in combination of 2 or more type. When using a flame retardant, the content of the flame retardant in the resin composition is not particularly limited, but preferably 0.1% by mass to 15% by mass when the nonvolatile component in the resin composition is 100% by mass. More preferably, it is 0.5 mass%-10 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 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.

  The rubber particle is not particularly limited as long as it is a fine particle of a resin that has been subjected to a chemical crosslinking treatment on a resin exhibiting rubber elasticity and is insoluble and infusible in an organic solvent. For example, acrylonitrile butadiene rubber particles, butadiene rubber particles, Examples include acrylic rubber particles. Specific examples of rubber particles include XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (above, manufactured by Aika Industry Co., Ltd.) Paraloid EXL2655. , EXL2602 (manufactured by Kureha Chemical Industry Co., Ltd.) and the like.

  The average particle diameter 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 diameter 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, etc., 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 setting the median diameter as the average particle diameter. When the 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 nonvolatile component in the resin composition is 100% by mass. It is 5 mass%-5 mass%.

  The resin composition of the present invention may contain other components as necessary. Examples of such other components include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and resin additions such as thickeners, antifoaming agents, leveling agents, adhesion imparting agents, and coloring agents. Agents and the like.

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

  The resin composition of the present invention can provide a cured product (insulating layer) having a low coefficient of linear thermal expansion. The linear thermal expansion coefficient of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of linear thermal expansion coefficient> described later. Specifically, the average linear thermal expansion coefficient in the plane direction in the range of 25 ° C. to 150 ° C. can be measured by performing thermomechanical analysis by a tensile load method. The cured product of the resin composition of the present invention is preferably at most 40 ppm / ° C., more preferably at most 35 ppm / ° C., further preferably at most 30 ppm / ° C., even more preferably at most 25 ppm / ° C., particularly preferably at most 24 ppm / ° C. Or a linear thermal expansion coefficient of 22 ppm / ° C. or less. Although the minimum of a linear thermal expansion coefficient is not specifically limited, Usually, it is 1 ppm / degrees C or more.

  The resin composition of the present invention can provide a cured product (insulating layer) having a low dielectric loss tangent. The dielectric loss tangent of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of dielectric loss tangent> described later. Specifically, it can be measured at a frequency of 5.8 GHz and a measurement temperature of 23 ° C. by the cavity resonator perturbation method. 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, more preferably 0.009 or less, 0.008 or less, 0.007 or less, 0.006 or less, Or 0.005 or less is still more preferable. The lower limit of the dielectric loss tangent is preferably as low as possible, but can usually be 0.001 or more.

  The resin composition of the present invention can provide a cured product (insulating layer) having high adhesion (peel strength) to the conductor layer. The peel strength of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of Adhesiveness (Peel Strength) with Conductor Layer> below. The peel strength between the obtained conductor layer and the insulating layer is preferably 0.40 kgf / cm or more, more preferably 0.45 kgf / cm or more, 0.50 kgf / cm or more, 0.55 kgf / cm or more, or 0.60 kgf. / Cm or more is more preferable. The upper limit of the peel strength is not particularly limited, but can be usually 1.2 kgf / cm or less.

  The resin composition of the present invention can provide a cured product having good flexibility and low tackiness when uncured, low linear thermal expansion coefficient and dielectric loss tangent, and good adhesion to the conductor layer. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and interlayer insulation of the printed wiring board. It can be more suitably used as a resin composition for forming a layer (a resin composition for an interlayer insulating layer of a printed wiring board). The resin composition of the present invention also requires a resin composition such as an adhesive film, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole-filling resin, and a component-filling resin. Can be used in a wide range of applications.

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

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

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

  The thickness of the resin composition layer is preferably 180 μm or less, more preferably 160 μm or less, and still more preferably 140 μm or less, from the viewpoint of reducing the thickness of the printed wiring board. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it can be set as 1 micrometer or more, 5 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 polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA). , Cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. 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 a mat treatment or a corona treatment on the surface to be joined to the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resins, olefin resins, urethane resins, and silicone resins. . Examples of commercially available release agents include “SK-1”, “AL-5”, and “AL-7” manufactured by Lintec Corporation, which are alkyd resin release agents.

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

  For the adhesive film, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied on 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.

  In the adhesive film, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). 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.

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

  The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fiber 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.

  In the present invention using the resin composition containing the specific component (A) and the component (B) in combination, and the content of the component (A) is within a predetermined range, it has good flexibility and low tack when uncured. It is possible to realize a sheet-like laminated material that is extremely useful in the production of a printed wiring board, exhibiting the properties and having a cured product with a low linear thermal expansion coefficient and dielectric loss tangent and good adhesion to the conductor layer.

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

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

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

  The “inner layer substrate” used in step (I) is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one or both surfaces of the substrate. A circuit board on which a patterned conductor layer (circuit) is formed. 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 Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., 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 to 150 minutes, more preferably 15 to 120 minutes).

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

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

  Step (III) is a step of making a hole in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, 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.

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

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

  The conductor layer may have a single layer structure or 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.

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

  In other embodiments, the conductor layer may be formed using a metal foil. When forming a conductor layer using metal foil, it is suitable to implement process (V) between process (I) and process (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. Lamination of the resin composition layer and the metal foil may be performed by a vacuum laminating method. The conditions for stacking may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method.

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

  When a printed wiring board is produced using the resin composition of the present invention containing a specific component (A) and a component (B) in combination and the content of the component (A) is within a predetermined range, Regardless of whether it is formed by plating or using a metal foil, the adhesion (peel strength) between the conductor layer and the insulating layer can be remarkably improved.

[Semiconductor device]
The semiconductor device of the present invention includes the printed wiring board of the present invention.

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

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

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, 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.

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

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

<Measurement of viscosity of epoxy compound>
The viscosity (25 ° C.) of the epoxy compound was measured using an E-type viscometer (“RE-25U” manufactured by Toki Sangyo Co., Ltd., using a 1 ° 34 ′ × R24 cone rotor) at 25 ° C. and 20 rpm. .

<Measurement of adhesion (peel strength) with conductor layer>
(1) Substrate treatment of circuit board A glass cloth base epoxy resin double-sided copper-clad laminate with a circuit (copper foil thickness 18 μm, substrate thickness 0.8 mm, “E700GR” manufactured by Hitachi Chemical Co., Ltd.) The copper surface was roughened by etching 1 μm with a microetching agent (“CZ8101” manufactured by MEC Co., Ltd.).

(2) Lamination of adhesive film The adhesive film produced in the examples and comparative examples was obtained by using a batch type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.), and the resin composition layer was a circuit board. And laminated on both sides of the circuit board. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. After laminating the adhesive film, the support was peeled off to expose the resin composition layer. The obtained substrate is referred to as “substrate a”.

(3) Lamination of copper foil 1 μm of the glossy surface of copper foil (thickness 35 μm, “3EC-III” manufactured by Mitsui Mining & Smelting Co., Ltd.) is etched with a microetching agent (“CZ8101” manufactured by Mec Co., Ltd.) to rough The treatment was performed. The copper foil was laminated on the substrate a under the same conditions as in the above (2) so that the glossy surface was bonded to the resin composition layer. Thereafter, the resin composition layer was thermally cured under conditions of 100 ° C. for 30 minutes, 170 ° C. for 30 minutes, and 200 ° C. for 60 minutes to form an insulating layer. The obtained substrate is referred to as “evaluation substrate A”.

(4) Measurement of peel strength In the conductor layer of the evaluation board A, cut a portion of width 10 mm and length 100 mm, peel off one end and hold it with a gripping tool, and at room temperature (25 ° C.), 50 mm / min. The peel strength was determined by measuring the load (kgf / cm (N / cm)) when 35 mm was peeled in the vertical direction at a speed of. For the measurement, a tensile testing machine (“AC-50C-SL” manufactured by TSE Co., Ltd.) was used.

<Measurement of linear thermal expansion coefficient>
(1) Preparation of evaluation cured product The adhesive films prepared in Examples and Comparative Examples were heated at 200 ° C. for 90 minutes to thermally cure the resin composition layer. Subsequently, the support was peeled off to obtain a sheet-like cured product. The cured product is referred to as “evaluated cured product B”.

(2) Measurement of linear thermal expansion coefficient The cured product B for evaluation was cut into a test piece having a width of 5 mm and a length of 15 mm, and a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation) was used. Thermomechanical analysis was performed by the tensile load method. Specifically, after the test piece was mounted on the apparatus, the measurement was continuously performed twice under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. In the second measurement, the average linear thermal expansion coefficient (ppm / ° C.) in the plane direction (XY direction) in the range from 25 ° C. to 150 ° C. was calculated.

<Measurement of dielectric loss tangent>
The evaluation cured product B was cut into a test piece having a width of 2 mm and a length of 80 mm. With respect to the test piece, dielectric loss tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies. Two test pieces were measured, and the average value was calculated.

<Evaluation of flexibility and tackiness>
The adhesive films produced in Examples and Comparative Examples were bent at an angle of 180 degrees in a state where the support was on the inside and the resin composition layer was on the outside, and the flexibility was confirmed. The case where the resin composition layer was not cracked was rated as “◯”, and the cracked one as “×”. For the adhesive films prepared in Examples and Comparative Examples, the tackiness is confirmed by pressing the resin composition layer with a finger, and the adhesive film remains attached to the finger. It was assumed that it was not possible.

  In the following description, unless otherwise specified, “MEK” indicates methyl ethyl ketone, and “PET” indicates polyethylene terephthalate.

[Example 1]
50 parts of a naphthalene type epoxy resin (Nippon Kayaku Co., Ltd. “ESN475V”, epoxy equivalent of about 332), cyclohexanedimethanol type epoxy resin (“ZX1658GS” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) as an epoxy compound, about epoxy equivalent 135 parts, viscosity of 34 mPa · s at 25 ° C.) was dissolved in 20 parts of cyclohexanone and 20 parts of MEK with stirring, and then cooled to room temperature to obtain a mixed solution. There, 190 parts of spherical silica (average particle size 0.5 μm, “SO-C2” manufactured by Admatechs Co., Ltd.) surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), Active ester compound (DIC Corporation "HPC-8000-65T", active group equivalent of about 223, non-volatile component 65% by weight toluene solution) 16 parts, phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", solid content 5 parts of 30% by mass MEK and cyclohexanone mixed solution), 11 parts of phenolic curing agent (“LA3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution having a solid content of 50% by mass) and a curing accelerator (1 -5 parts of benzyl-2-phenylimidazole (1B2PZ) and a MEK solution having a solid content of 10% by mass were mixed and mixed with a high-speed rotary mixer. Dispersed in to prepare a resin varnish.

  As a support, a PET film with a release layer (“AL5” manufactured by Lintec Corporation, thickness 38 μm) was prepared. On the release layer of this support, a resin varnish was uniformly applied so that the thickness of the resin composition layer after drying was 40 μm. Then, it was made to dry at 80 to 120 degreeC (average 100 degreeC) for 5 minutes, the resin composition layer was formed on the support body, and the adhesive film was obtained.

[Example 2]
5 parts of cyclohexanedimethanol type epoxy resin “ZX1658GS” in 5 parts of 1,6-hexanediol type epoxy resin (“Denacol EX212L” manufactured by Nagase ChemteX Corp., epoxy equivalent 135, viscosity at 25 ° C. 10 mPa · s) Except having changed, it carried out similarly to Example 1, and obtained the resin varnish and the adhesive film.

[Example 3]
Except for changing 5 parts of cyclohexanedimethanol type epoxy resin “ZX1658GS” to 5 parts of trimethylolpropane type epoxy resin (“ZX1542” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 120, viscosity at 25 ° C. 109 mPa · s) In the same manner as in Example 1, a resin varnish and an adhesive film were obtained.

[Example 4]
Except for changing 5 parts of cyclohexanedimethanol type epoxy resin “ZX1658GS” to 5 parts of “EP-3980S” (viscosity 31 mPa · s at 25 ° C., epoxy equivalent 115, o-toluidine type epoxy resin) manufactured by ADEKA Corporation. Obtained a resin varnish and an adhesive film in the same manner as in Example 1.

[Example 5]
Change 5 parts of cyclohexanedimethanol type epoxy resin “ZX1658GS” to 5 parts of “EP-4088S” (viscosity 213 mPa · s at 25 ° C., epoxy equivalent 170, dicyclopentadiene dimethanol type epoxy resin) manufactured by ADEKA Corporation. A resin varnish and an adhesive film were obtained in the same manner as in Example 1 except that.

[Example 6]
Example 1 except that (i) the amount of cyclohexanedimethanol type epoxy resin “ZX1658GS” was changed from 5 parts to 15 parts, and (ii) the amount of spherical silica was changed from 190 parts to 210 parts. In the same manner as above, a resin varnish and an adhesive film were obtained.

[Comparative Example 1]
Except for changing 5 parts of cyclohexanedimethanol type epoxy resin “ZX1658GS” to 5 parts of bisphenol A type epoxy resin (“828 US” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 189, viscosity 2000 mPa · s at 25 ° C.) In the same manner as in Example 1, a resin varnish and an adhesive film were obtained.

[Comparative Example 2]
(I) The amount of the naphthalene type epoxy resin “ESN475V” was changed from 50 parts to 30 parts, (ii) the cyclohexane dimethanol type epoxy resin “ZX1658GS” was changed from 5 parts to 30 parts, (Iii) The amount of spherical silica was changed from 190 parts to 210 parts, (iv) The active ester compound “HPC-8000-65T” was changed from 16 parts to 17 parts, (v) phenol A resin varnish and an adhesive film were obtained in the same manner as in Example 1 except that the amount of the system curing agent “LA3018-50P” was changed from 11 parts to 12 parts.

[Comparative Example 3]
Example 1 except that (i) the amount of cyclohexanedimethanol type epoxy resin “ZX1658GS” was changed from 5 parts to 1 part, and (ii) the amount of spherical silica was changed from 190 parts to 180 parts. In the same manner as above, a resin varnish and an adhesive film were obtained.

[Comparative Example 4]
(I) The amount of the naphthalene type epoxy resin “ESN475V” was changed from 50 parts to 35 parts, (ii) the amount of the bisphenol A type epoxy resin “828US” was changed from 5 parts to 15 parts, ( iii) The amount of spherical silica compounded from 190 parts to 180 parts, (iv) The active ester compound “HPC-8000-65T” compounded from 16 parts to 15 parts, (v) phenolic A resin varnish and an adhesive film were obtained in the same manner as in Comparative Example 1, except that the blending amount of the curing agent “LA3018-50P” was changed from 11 parts to 10 parts.

[Comparative Example 5]
Except for changing 5 parts of cyclohexanedimethanol type epoxy resin “ZX1658GS” to 5 parts of alicyclic epoxy resin (“Celoxide 2021P” manufactured by Daicel Corporation, epoxy equivalent 120, viscosity 47 mPa · s at 25 ° C.) In the same manner as in Example 1, a resin varnish and an adhesive film were obtained.

  The evaluation results of the above-described examples and comparative examples are shown in the following table.

  Even when the phenoxy resin “YX7553BH30” is not blended, the curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ)) is not blended, and the phenolic curing agent “LA3018-50P” is not blended, the degree varies. However, it has been confirmed that the result is the same as that of the above example.

Claims (11)

(A) A bifunctional or higher functional epoxy compound containing a monovalent group represented by the following formula (1) having a viscosity at 25 ° C. of 500 mPa · s or less:

(In the formula, X represents a methylene group or a single bond, Y represents an oxygen atom, a nitrogen atom, a carbon atom or an oxycarbonyl group, m represents an integer of 1 to 3. When there are a plurality of X, they are They may be the same or different.
And (B) an active ester compound,
(A) The resin composition whose content of a component is 0.5 mass%-8 mass% when the non-volatile component in a resin composition is 100 mass%.   The resin composition of Claim 1 in which X represents a methylene group and Y represents an oxygen atom, a nitrogen atom, or an oxycarbonyl group in Formula (1).   Component (A) is a cyclohexanedimethanol type epoxy resin, trimethylolpropane type epoxy resin, 1,6-hexanediol type epoxy resin, 1,4-butanediol type epoxy resin, benzenedimethanol type epoxy resin, biphenyldimethanol The resin composition of Claim 1 or 2 selected from the group which consists of a type epoxy resin, a dicyclopentadiene dimethanol type epoxy resin, a diethylene glycol type epoxy resin, and an o-toluidine type epoxy resin.   The component (A) is selected from the group consisting of cyclohexanedimethanol type epoxy resin, trimethylolpropane type epoxy resin, 1,6-hexanediol type epoxy resin, and o-toluidine type epoxy resin. The resin composition according to any one of the above.   (A) The resin composition of any one of Claims 1-4 whose epoxy equivalent of a component is 80-250.   Furthermore, the resin composition of any one of Claims 1-5 containing (C) inorganic filler.   The resin composition according to claim 6, wherein the content of the component (C) is 40% 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 7, which is used for an insulating layer of a printed wiring board.   The sheet-like laminated material containing the resin composition of any one of Claims 1-8.   The printed wiring board containing the insulating layer obtained by thermosetting the resin composition of any one of Claims 1-8, or the sheet-like laminated material of Claim 9.   A semiconductor device comprising the printed wiring board according to claim 10.