JP2018100421A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which obtains a printed wiring board exhibiting good reflow behavior in a component mounting process.SOLUTION: The resin composition contains (A) an epoxy resin, (B) an active ester curing agent, (C) an inorganic filler, and (D) an epoxy group-containing silicone compound having an epoxy equivalent of 300 or less and having an alkoxy group content of 30 mass% or less based on the mass of the whole molecule. When a nonvolatile component in the resin composition is 100 mass%, the content of the component (C) is 40 mass% or more, and the content of the component (D) is 0.3 to 10 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 manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked on an inner substrate is known. 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 discloses a technology for forming an insulating layer having good heat resistance by curing a resin composition containing an epoxy group-containing silicone compound and a phenolic curing agent and / or a cyanate ester curing agent. It is disclosed.

International Publication No. 2014/61812

  With the recent replacement from lead-containing solder to lead-free solder, the solder reflow temperature in the component mounting process is increasing. In recent years, in order to achieve miniaturization of electronic devices, the printed wiring board has been further reduced in thickness, and the thickness of the inner layer substrate and the insulating layer tends to be gradually reduced.

  As the printed wiring board becomes thinner, it tends to be difficult to stabilize the reflow behavior in the component mounting process by solder reflow. The present inventors have warped the printed wiring board in the component mounting process when the printed wiring board is thin even with the technique described in Patent Document 1 that can form an insulating layer with good heat resistance. It has been found that this may result in poor reflow behavior. If the reflow behavior is poor, problems such as poor contact of parts occur, and the mountability deteriorates.

  The subject of this invention is providing the resin composition which brings about the printed wiring board which shows the favorable reflow behavior in the mounting process of components.

  As a result of intensive studies on the above problems, the present inventors have found that the above-mentioned problems can be solved by the following specific resin composition, and have completed the present invention.

（式中、Ｒ^１はエポキシ基を有する有機基を表し、Ｒ^２は水素原子、炭化水素基、又はアルコキシ基を表し、＊は結合手を表す。）
［３］ （Ｄ）成分が、式（１）で表される構造単位を１分子中に２〜１０個有する、［２］に記載の樹脂組成物。
［４］ （Ｄ）成分が、環状のシロキサン構造を有する、［１］〜［３］のいずれかに記載の樹脂組成物。
［５］ Ｒ^１が、式：Ｘ−（Ｌ）_ｐ−で表される１価の基（式中、Ｘはエポキシアルキル基、エポキシシクロアルキル基又はエポキシアリール基を表し、Ｌはアルキレン基、シクロアルキレン基、アリーレン基、オキシアルキレン基、オキシシクロアルキレン基又はオキシアリーレン基を表し、ｐは０又は１を表す。）である、［２］〜［４］のいずれかに記載の樹脂組成物。
［６］ Ｘが、炭素原子数４〜１０のエポキシシクロアルキル基である、［５］に記載の樹脂組成物。
［７］ （Ｄ）成分が、式（２−１）で表される化合物を含む、［１］〜［６］のいずれかに記載の樹脂組成物。

［８］ （Ｃ）成分がシリカである、［１］〜［７］のいずれかに記載の樹脂組成物。
［９］ （Ｃ）成分の平均粒径が０．０１〜４μｍである、［１］〜［８］のいずれかに記載の樹脂組成物。
［１０］ プリント配線板の絶縁層形成用又は部品埋め込み用である、［１］〜［９］のいずれかに記載の樹脂組成物。
［１１］ 樹脂組成物の硬化物の１５０〜２５０℃の範囲における平均線熱膨張係数（α_２）が４７〜６０ｐｐｍ／℃である、［１］〜［１０］のいずれかに記載の樹脂組成物。
［１２］ ［１］〜［１１］のいずれかに記載の樹脂組成物の層を含む、シート状積層材料。
［１３］ ［１］〜［１１］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層を含むプリント配線板。
［１４］ ［１３］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) Epoxy resin, (B) Active ester curing agent, (C) Inorganic filler, and (D) Epoxy equivalent is 300 or less, and the content of alkoxy groups is the mass of the whole molecule. Including an epoxy group-containing silicone compound of 30% by mass or less as a reference,
Resin composition in which the content of component (C) is 40% by mass or more and the content of component (D) is 0.3 to 10% by mass when the nonvolatile component in the resin composition is 100% by mass object.
[2] The resin composition according to [1], wherein the component (D) includes a structural unit represented by the formula (1).

(In the formula, R ¹ represents an organic group having an epoxy group, R ² represents a hydrogen atom, a hydrocarbon group, or an alkoxy group, and * represents a bond.)
[3] The resin composition according to [2], wherein the component (D) has 2 to 10 structural units represented by the formula (1) in one molecule.
[4] The resin composition according to any one of [1] to [3], wherein the component (D) has a cyclic siloxane structure.
[5] R ¹ is a monovalent group represented by the formula: X- (L) _p- (wherein X represents an epoxyalkyl group, an epoxycycloalkyl group or an epoxyaryl group, L represents an alkylene group, The resin composition according to any one of [2] to [4], which represents a cycloalkylene group, an arylene group, an oxyalkylene group, an oxycycloalkylene group or an oxyarylene group, and p represents 0 or 1. .
[6] The resin composition according to [5], wherein X is an epoxycycloalkyl group having 4 to 10 carbon atoms.
[7] The resin composition according to any one of [1] to [6], wherein the component (D) includes a compound represented by the formula (2-1).

[8] The resin composition according to any one of [1] to [7], wherein the component (C) is silica.
[9] The resin composition according to any one of [1] to [8], wherein the (C) component has an average particle size of 0.01 to 4 μm.
[10] The resin composition according to any one of [1] to [9], which is used for forming an insulating layer of a printed wiring board or for embedding a component.
[11] The resin composition according to any one of [1] to [10], wherein the cured product of the resin composition has an average coefficient of linear thermal expansion (α ₂ ) in the range of 150 to 250 ° C. of 47 to 60 ppm / ° C. object.
[12] A sheet-like laminated material comprising a layer of the resin composition according to any one of [1] to [11].
[13] A printed wiring board including a layer formed of a cured product of the resin composition according to any one of [1] to [11].
[14] A semiconductor device including the printed wiring board according to [13].

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which brings about the printed wiring board which shows the favorable reflow behavior in the component mounting process can be provided.

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

[Resin composition]
The resin composition of the present invention has (A) an epoxy resin, (B) an active ester curing agent, (C) an inorganic filler, and (D) an epoxy equivalent of 300 or less, and an alkoxy group content. When the epoxy group-containing silicone compound is 30% by mass or less based on the mass of the whole molecule and the nonvolatile component in the resin composition is 100% by mass, the content of the component (C) is 40% by mass or more. The content of the component (D) is 0.3 to 10% by mass.

<(A) Epoxy resin>
The resin composition of the present invention contains an epoxy resin as the component (A).

  Examples of the epoxy resin include bisphenol 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-containing ester Carboxymethyl 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 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. Alternatively, the epoxy resin may include only the above-described solid epoxy resin.

  The liquid epoxy resin has a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, and a butadiene structure. Epoxy resins are preferable, and bisphenol A type epoxy resins, bisphenol F type epoxy resins, and naphthalene type epoxy resins are more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032H”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “jER828US”, “jER828EL” manufactured by Mitsubishi Chemical Corporation. (Bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "ZX1059" (bisphenol A type epoxy resin and bisphenol manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) F-type epoxy resin mixture), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, “Celoxide 2021P” (manufactured by Daicel Corporation) (alicyclic epoxy resin having an ester skeleton) ), "PB-3600" Epoxy resin) having an butadiene structure. 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 “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” (cresol novolac type epoxy resin) manufactured by DIC Corporation, “ N-695 "(cresol novolac type epoxy resin)," HP-7200 "," HP-7200H "(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 ”,“ NC 100 ”(biphenyl type epoxy resin),“ ESN475V ”(naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.,“ ESN485 ”(naphthol novolac type epoxy resin),“ YX4000H ”manufactured by Mitsubishi Chemical Corporation,“ YL6121 (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd. “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), etc. Can be mentioned.

  When the liquid epoxy resin and the solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 8 in terms of mass ratio. preferable. By setting the quantitative ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a sheet-like laminated material, ii) the form of the sheet-like laminated material When used in the above, sufficient flexibility is obtained, handling properties are improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.3 to 1: 7 by mass ratio. Is more preferable, and the range of 1: 0.6 to 1: 6 is even more preferable.

The content of the epoxy resin in the resin composition is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 35% by mass, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. More preferably, they are 10 mass%-35 mass% or 10 mass%-30 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.

<(B) Active ester curing agent>
The resin composition of the present invention contains an active ester curing agent as the component (B).

  The active ester curing agent is an active ester compound having one or more active ester groups in one molecule. The present inventors can stabilize the reflow behavior in the component mounting process even in a thin printed wiring board by using a combination of an active ester curing agent and a component (D) described later. I found.

  As the active ester curing agent, an active ester compound having two or more active ester groups in one molecule is preferable. For example, phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound An active ester compound having two or more ester groups having a high reaction activity such as a class is preferably used. An active ester hardening agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  From the viewpoint of improving heat resistance, an active ester compound 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 is preferable. 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. Moreover, 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 the resin composition can be increased, and if it is a compound having an aromatic ring. Heat resistance can be increased.

  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 these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable from the viewpoint of heat resistance, and isophthalic acid and terephthalic acid are more preferable.

  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 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 novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are preferred, catechol, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydride Roxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 , 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferred, 1,5-dihydroxynaphthalene, 1,6 -Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene diphenol, phenol More preferred are phosphorus, phosphorus atom-containing oligomers having phenolic hydroxyl groups, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenols, phosphorus having phenolic hydroxyl groups Atom-containing oligomers are particularly preferred, and dicyclopentadiene type diphenols are particularly preferred.

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

  Preferable specific examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac. Active ester compounds containing an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group. Among them, an active ester compound containing a dicyclopentadiene type diphenol structure, a naphthalene structure 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.

  More specifically, examples of the active ester compound containing a dicyclopentadiene type diphenol structure include compounds of the following formula (i).

（式中、Ｒはフェニル基又はナフチル基であり、ｋは０又は１を表し、ｎは繰り返し単位の平均数で０．０５〜２．５である。）

(In the formula, R is a phenyl group or a naphthyl group, k represents 0 or 1, and n is an average number of repeating units of 0.05 to 2.5.)

  From the viewpoint of reducing the dielectric loss tangent and improving the heat resistance, R is preferably a naphthyl group, k is preferably 0, and n is preferably 0.25 to 1.5.

  As the active ester curing agent, 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 active ester compounds include EXB9451, EXB9460, EXB9460S, HPC-8000-65T (manufactured by DIC Corporation), and naphthalene structures as active ester compounds containing a dicyclopentadiene type diphenol structure. EXB9416-70BK (manufactured by DIC Corporation) as an ester compound, DC808 (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolak, YLH1026 (Mitsubishi Chemical) as an active ester compound containing a benzoylated phenol novolac EXB9050L-62M (manufactured by DIC Corporation) as a phosphorus atom-containing active ester compound.

  In combination with the component (D) described later, from the viewpoint of stabilizing the reflow behavior in the component mounting process, the content of the active ester curing agent in the resin composition is preferably 1% by mass or more, and 2% by mass. The above is more preferable, and 3% by mass or more is more preferable. The upper limit of the content of the active ester curing agent is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.

  When the number of epoxy groups in (A) the epoxy resin is 1, from the viewpoint of obtaining an insulating layer with good mechanical strength, the number of reactive groups in the (B) active ester curing agent is preferably 0.2 to 2, .3 to 1.5 is more preferable, and 0.35 to 1 is more preferable. Here, “the number of epoxy groups of the epoxy resin” is a value obtained by totaling the values obtained by dividing the solid mass of each epoxy resin present in the resin composition by the epoxy equivalent for all epoxy resins. The “reactive group” means a functional group capable of reacting with an epoxy group, and the “reactive group number of the active ester compound” means the solid content mass of the active ester compound present in the resin composition. This is the sum of all values divided by reactive group equivalents.

<(C) Inorganic filler>
The resin composition of the present invention contains an inorganic filler as the component (C).

  From the viewpoint of stabilizing the reflow behavior in the component mounting process and obtaining a cured product having a low coefficient of thermal expansion, the content of the inorganic filler in the resin composition layer is 40% by mass or more, preferably 45% by mass. % Or more, more preferably 50 mass% or more, still more preferably 55 mass% or more, or 60 mass% or more. Increasing the content of the inorganic filler in the resin composition may increase the melt viscosity of the resin composition and may result in a resin composition having poor lamination properties in the production of a printed wiring board. According to the present invention, which is used in combination with the component (D), the content of the inorganic filler can be further increased without excessive increase in melt viscosity. For example, the content of the inorganic filler in the resin composition may be increased to 62% by mass or more, 64% by mass or more, 66% by mass or more, 68% 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 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less, from the viewpoint of mechanical strength of the obtained cured product. .

  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 fused silica include “SO-C2” and “SO-C1” manufactured by Admatechs.

  The average particle diameter of the inorganic filler is not particularly limited, but is preferably 4 μm or less, more preferably 3 μm or less, further preferably 2 μm or less, and more preferably 1 μm or less from the viewpoint of obtaining an insulating layer on which fine wiring can be formed. 0.7 μm or less, 0.5 μm or less, 0.4 μm or less, or 0.3 μm or less is even more preferable. 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 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 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 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, 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.

<(D) Epoxy group-containing silicone compound>
The resin composition of the present invention includes, as component (D), an epoxy group-containing silicone compound having an epoxy equivalent of 300 or less and an alkoxy group content of 30% by mass or less based on the mass of the entire molecule. .

  In combination with the component (B), from the viewpoint of stabilizing the reflow behavior in the component mounting process, the epoxy equivalent of the component (D) is 300 or less, preferably 280 or less, more preferably 260 or less, even more preferably. Is 240 or less, more preferably 220 or less, 210 or less, or 200 or less. Although the minimum of the epoxy equivalent of (D) component is not specifically limited, Preferably it is 100 or more, More preferably, it is 120 or more. The epoxy equivalent of the component (D) can be measured according to JIS K7236 in the same manner as the component (A).

  From the viewpoint of stabilizing the reflow behavior in the component mounting process in combination with the component (B) and obtaining a resin composition exhibiting an appropriate melt viscosity, the alkoxy group content in the component (D) 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less, and 8% by mass or less based on the total mass. 6 mass% or less, 4 mass% or less, 2 mass% or less, or 1 mass% or less. The minimum of content of this alkoxy group is not specifically limited, 0 mass% may be sufficient. The content of the alkoxy group is a value of the content of the alkoxy group when the molecular weight of the component (D) is 100% by mass.

  The weight average molecular weight of the component (D) is not particularly limited as long as the epoxy equivalent and the content of the alkoxy group are in the desired ranges, but from the viewpoint of reducing volatility and improving handleability, and from the viewpoint of improving dispersibility Therefore, 300 to 5000 is preferable, 400 to 4000 is more preferable, and 500 to 3000 is more preferable. In the present invention, the weight average molecular weight is measured by a gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K- manufactured by Showa Denko KK as a column. 804 L 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.

  In combination with the component (B), from the viewpoint of stabilizing the reflow behavior in the component mounting process, the content of the component (D) in the resin composition is 0.3% by mass or more, preferably 0.8%. 5 mass% or more, More preferably, it is 1.0 mass% or more, More preferably, it is 1.5 mass% or more, or 2.0 mass% or more. The upper limit of the content of the component (D) is 10% by mass or less, preferably 9.5% by mass or less, from the viewpoint of promoting the curing of the resin composition and achieving good reflow behavior in the component mounting process. More preferably, it is 9.0 mass% or less, More preferably, it is 8.5 mass% or less, 8.0 mass% or less, 7.5 mass% or less, or 7.0 mass% or less.

  In one embodiment, the component (D) includes a structural unit represented by the formula (1).

（式中、Ｒ^１はエポキシ基を有する有機基を表し、Ｒ^２は水素原子、炭化水素基、又はアルコキシ基を表し、＊は結合手を表す。）

(In the formula, R ¹ represents an organic group having an epoxy group, R ² represents a hydrogen atom, a hydrocarbon group, or an alkoxy group, and * represents a bond.)

The organic group having an epoxy group represented by R ¹ is not particularly limited as long as it has an epoxy group. The number of epoxy groups contained in the organic group is not particularly limited, but is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.

In one embodiment, R ¹ is a monovalent group represented by the formula: X- (L) _p- . In the formula, X represents an epoxyalkyl group, an epoxycycloalkyl group or an epoxyaryl group, L represents an alkylene group, a cycloalkylene group, an arylene group, an oxyalkylene group, an oxycycloalkylene group or an oxyarylene group, and p is 0. Or 1 is represented.

  The number of carbon atoms of the epoxyalkyl group represented by X is preferably 3-20, more preferably 3-10, and even more preferably 3-6.

  The number of carbon atoms of the epoxycycloalkyl group represented by X is preferably 4 to 10, more preferably 4 to 6.

  The number of carbon atoms of the epoxy aryl group represented by X is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10.

  In combination with the component (B), X is preferably an epoxy cycloalkyl group, more preferably an epoxy cycloalkyl group having 4 to 10 carbon atoms, from the viewpoint of further stabilizing the reflow behavior in the component mounting process. . Among these, X is preferably an epoxycyclohexyl group.

  The number of carbon atoms of the alkylene group and oxyalkylene group represented by L is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 6 or 1 to 4.

  The number of carbon atoms of the cycloalkylene group or oxycycloalkylene group represented by L is preferably 3 to 10, more preferably 3 to 10, and still more preferably 3 to 6.

  The number of carbon atoms of the arylene group and oxyarylene group represented by L is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10.

  In combination with the component (B), L is preferably an alkylene group, more preferably an alkylene group having 1 to 6 carbon atoms, from the viewpoint of further stabilizing the reflow behavior in the component mounting process.

  In combination with the component (B), p is preferably 1 from the viewpoint of further stabilizing the reflow behavior in the component mounting process.

In the formula (1), examples of the hydrocarbon group represented by R ² include an alkyl group, a cycloalkyl group, an aryl group, and a monovalent group formed by combining two or more thereof. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 5, 1 to 4, or 1 to 3. The number of carbon atoms of the cycloalkyl group is preferably 3 to 10, more preferably 3 to 6 or 4 to 6. The number of carbon atoms of the aryl group is preferably 6-10. Examples of the monovalent group formed by bonding two or more of an alkyl group, a cycloalkyl group, and an aryl group include a cycloalkylalkyl group and an arylalkyl group.

In the formula (1), the number of carbon atoms of the alkoxy group represented by R ² is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 5, 1 to 4, or 1 to 3.

In combination with the component (B), R ² is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, more preferably methyl, from the viewpoint of further stabilizing the reflow behavior in the component mounting process. Group, ethyl group, propyl group or butyl group.

  The component (D) preferably has 2 to 10 structural units, more preferably 2 to 8, more preferably 2 to 6 and 3 to 6 structural units represented by the above formula (1) in one molecule. Have 3 or 3 pieces.

  The component (D) may have a chain siloxane structure or a cyclic siloxane structure. In combination with the component (B), the component (D) preferably has a cyclic siloxane structure from the viewpoint of further stabilizing the reflow behavior in the component mounting process.

  In a preferred embodiment, the component (D) is a compound represented by the formula (2).

（式中、
Ｒ^１及びＲ^２は上記と同じ意味を表し、
Ｒ^３は、Ｒ^１又はＲ^２を表し、
Ｒ^４は、水素原子、炭化水素基、又は式：−Ｓｉ（Ｒ’）_３で表される１価の基を表し、ここでＲ’はＲ^１又はＲ^２を表す。
Ｒ^３とＲ^４はどちらも単結合であって互いに結合して環状のシロキサン構造を形成していてもよい。
ｎは２〜１０の整数を表し、
ｍは０〜１０の整数を表す。複数存在するＲ^１は同一でも相異なっていてもよく、複数存在するＲ^２は同一でも相異なっていてもよい。）

(Where
R ¹ and R ² have the same meaning as above,
R ³ represents R ¹ or R ² ,
R ⁴ represents a hydrogen atom, a hydrocarbon group, or a monovalent group represented by the formula: —Si (R ′) ₃ , where R ′ represents R ¹ or R ² .
R ³ and R ⁴ are both a single bond and may be bonded to each other to form a cyclic siloxane structure.
n represents an integer of 2 to 10,
m represents an integer of 0 to 10. A plurality of R ¹ may be the same or different, and a plurality of R ² may be the same or different. )

In formula (2), the definition and preferred examples of R ¹ and R ² are as described above.

In the formula (2), the hydrocarbon group represented by R ⁴ is the same as the hydrocarbon group described for R ² in the formula (1). R ³ and R ⁴ may be appropriately determined from the above options as long as the epoxy equivalent and the alkoxy group content are within the desired range. In particular, in combination with component (B), R ³ and R ⁴ are both single bonds and form a cyclic siloxane structure from the viewpoint of further stabilizing the reflow behavior in the component mounting process. It is preferable.

  In formula (2), n is preferably an integer of 2 to 8, more preferably an integer of 2 to 6, still more preferably an integer of 3 to 6 or an integer of 3 to 5.

  In formula (2), m is preferably an integer of 0 to 8, more preferably an integer of 0 to 6, still more preferably an integer of 0 to 4 or an integer of 0 to 2. In the formula (2), the structural unit represented by the subscript n and the structural unit represented by the subscript m may be included randomly or in a block shape.

  In a particularly preferred embodiment, the component (D) includes a compound represented by the formula (2-1).

  (D) A component may be used individually by 1 type or may be used in combination of 2 or more type.

  The manufacturing method of (D) component is not specifically limited, For example, it can obtain by reaction which partially hydrolyzes the alkoxy group of the silane compound which is a monomer, and carries out polycondensation. As the component (D), a commercially available product may be used. Examples of commercially available products include “X-40-2670” manufactured by Shin-Etsu Chemical Co., Ltd. (epoxy equivalent 200, alkoxy group content 0% by mass), “Composeran SQ502-8” manufactured by Arakawa Chemical Industries, Ltd. ( Epoxy equivalent 276, alkoxy group content of about 12% by mass) and the like.

<(E) Thermoplastic resin>
The resin composition of the present invention may further contain (E) 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.

  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., “YL7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Corporation, “YL7290”, “YL7482” and the like can be mentioned.

  Specific examples of the polyvinyl acetal resin include: Electric Butyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., S-Lec BH Series, BX Series manufactured by Sekisui Chemical Co., Ltd. KS series, BL series, BM series, etc. are mentioned.

  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.

  The content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass. .

<(F) Curing accelerator>
The resin composition of the present invention may further contain (F) 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. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type. Although content of the hardening accelerator in a resin composition is not specifically limited, Preferably it is 0.005-1 mass%, More preferably, it is 0.01-0.5 mass%.

<(G) Curing agent>
The resin composition of the present invention may further contain (G) a curing agent (excluding the component (B)).

  Although it does not specifically limit as a hardening | curing agent, For example, a phenol type hardening | curing agent, a naphthol type hardening | curing agent, a cyanate ester type hardening | curing agent, a benzoxazine type hardening | curing agent etc. can be mentioned. A hardening | curing agent may be used individually by 1 type, or may be used in combination of 2 or more type. Among these, in combination with the above components (A) to (D), from the viewpoint of further stabilizing the reflow behavior in the component mounting process, a phenolic curing agent, a naphthol curing agent, and a cyanate ester curing agent are used. preferable.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion strength (peel strength) with the conductor layer, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. . Among these, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength with the conductor layer. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, 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. Commercial products of cyanate ester curing agents include “PT30”, “PT30S” and “PT60” (all of which are phenol novolac polyfunctional cyanate ester resins) and “BA230” (of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. For example, a prepolymer partially or wholly converted into a trimer).

  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.

  Although content of (G) component in a resin composition is not specifically limited, From a viewpoint of the mechanical strength of the insulating layer obtained, 0.5-15 mass% is preferable and 1-10 mass% is more preferable.

  In the resin composition of the present invention, the mass ratio of the (G) component to the total amount of the (B) component and the (G) component [(G) component / ((B) component + (G) component)] is preferably It is 0.1 or more, more preferably 0.2 or more, 0.3 or more, 0.4 or more, or 0.5 or more. The upper limit of the mass ratio is not particularly limited, and may be 1.

<(H) Flame retardant>
The resin composition of the present invention may further contain (H) 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. Although content of the flame retardant in a resin composition is not specifically limited, Preferably it is 0.5 mass%-10 mass%, More preferably, it is 1 mass%-9 mass%.

<(I) Organic filler>
The resin composition of the present invention may further contain (I) an organic filler.

  As the organic filler, any organic filler that can be used in the production of a printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles, and rubber particles are preferable.

  The rubber 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 the 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 (above, 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 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. The content of the organic filler in the resin composition is preferably 1% by mass to 10% by mass, more preferably 2% by mass to 5% by mass.

  The resin composition of the present invention may further contain other components as necessary. Such other components include, for example, organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds, as well as thickeners, antifoaming agents, leveling agents, adhesion imparting agents, colorants, and curable resins. And the like, 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 having a low coefficient of 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, by performing thermomechanical analysis by the tensile load method, the average linear thermal expansion coefficient (α ₁ ; ppm / ° C.) in the plane direction in the range of 25 to 150 ° C., and the range from 150 ° C. to 250 ° C. The average linear thermal expansion coefficient (α ₂ ; ppm / ° C.) in the plane direction can be measured.

The α ₁ of the cured product of the resin composition is preferably as low as possible from the viewpoint of suppressing the occurrence of cracks and circuit distortion in the printed wiring board. α ₁ is preferably 40 ppm / ° C. or less, more preferably 35 ppm / ° C. or less, still more preferably 30 ppm / ° C. or less, and even more preferably 25 ppm / ° C. or less. Although the minimum of (alpha) ₁ is not specifically limited, Usually, it is 1 ppm / degrees C or more. The resin composition of the present invention can exhibit such a low alpha _1.

The α ₂ of the cured product of the resin composition is preferably low from the viewpoint of suppressing the occurrence of cracks and circuit distortion. However, if α ₂ is too low, it may be difficult to achieve good reflow behavior in the component mounting process. We have found that. From the viewpoint of stabilizing the reflow behavior in the component mounting process, α ₂ of the cured product of the resin composition is preferably 47 ppm / ° C. or more, more preferably 48 ppm / ° C. or more, further preferably 50 ppm / ° C. or more, and even more. Preferably, it is 52 ppm / ° C. or higher, or 54 ppm / ° C. or higher. The upper limit of the alpha ₂ is preferably 60 ppm / ° C. or less.

  The resin composition of the present invention can be suitably used as a resin composition (resin composition for forming an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board. By forming the insulating layer of the printed wiring board using the resin composition of the present invention, good reflow behavior can be achieved in the component mounting process even in a thin printed wiring board. In addition, since the resin composition of the present invention exhibits an appropriate melt viscosity and is excellent in component embedding properties, it can be suitably used even when the printed wiring board is a component built-in circuit board. That is, the resin composition of the present invention can be suitably used as a resin composition for embedding components on a component-embedded circuit board (resin composition for embedding components). By using the resin composition of the present invention as a resin composition for embedding components, good reflow behavior can be achieved in the component surface mounting process even in a thin component-embedded circuit board.

  When used as a resin composition for forming an insulating layer of a printed wiring board, the resin composition of the present invention is a resin composition for forming an interlayer insulating layer of a printed wiring board (a resin composition for an interlayer insulating layer of a printed wiring board). Product), and a resin composition for forming a solder resist for printed wiring boards (resin composition for solder resists for printed wiring boards). The resin composition of the present invention is also used in a wide range of applications where a resin composition is required, such as sheet-like laminated materials such as adhesive films and prepregs, underfill materials, die bonding materials, semiconductor sealing materials, and hole-filling resins. it can.

[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 laminated material including a layer of the resin composition.

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

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

  The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and even more preferably 50 μm or less or 40 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, 1 micrometer or more, 5 micrometers or more, 10 micrometers or more etc. can be used.

  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 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 5-75 micrometers is preferable and the range of 10-60 micrometers is more preferable. In addition, when a support body is a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  For the adhesive film, for example, a resin varnish 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 a resin varnish containing 30% by mass to 60% by mass of the organic solvent is used, the resin composition layer is dried at 50 to 150 ° C. for 3 to 10 minutes. 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 sheet-like laminated material, the minimum melt viscosity of the resin composition layer is preferably 15000 poises or less, more preferably 14000 poises or less, from the viewpoint of achieving good lamination properties (circuit embedding properties) in the production of a printed wiring board. More preferably, it is 12000 poise or less, and still more preferably 10,000 poise or less, 9000 poise or less, 8000 poise or less, 7000 poise or less, 6000 poise or less, 5000 poise or less, or 4000 poise or less. The lower limit of the minimum melt viscosity is preferably 300 poise or more, more preferably 500 poise or more, still more preferably 700 poise or more, 900 poise or more, or 1000, from the viewpoint of suppressing the seepage of the resin in the production of a printed wiring board. More than a poise. Here, the “minimum melt viscosity” of the resin composition layer refers to the lowest viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. Specifically, when the resin composition layer is heated at a constant temperature increase rate to melt the resin, the initial stage of the melt viscosity decreases with increasing temperature, and then, when the temperature exceeds a certain temperature, the melt viscosity decreases with increasing temperature. To rise. “Minimum melt viscosity” refers to the melt viscosity at such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelastic method, and can be measured, for example, according to the method described in <Measurement of minimum melt viscosity> described later.

  In sheet-shaped laminated materials, the minimum melt viscosity of the resin composition layer is the specific design of the printed wiring board (circuit thickness of the inner layer substrate, line / space ratio, etc.), and the specific design of the printed wiring board manufacturing method. The optimum value for achieving good stackability (component embeddability) varies depending on (the stacking temperature of the sheet-shaped stacking material and the inner layer substrate, etc.). Therefore, when manufacturing a sheet-like laminated material, it designs so that a resin composition layer may show desired minimum melt viscosity. In this regard, with regard to sheet-like laminated materials using conventional resin compositions, the viscosity of the resin composition layer may gradually increase during storage, and when used for the production of printed wiring boards, May exhibit a significantly higher minimum melt viscosity.

On the other hand, in the present invention in which the (B) component and the (D) component are used in combination, an increase in the viscosity of the resin composition layer during storage is suppressed, and the desired minimum melt viscosity is advantageously achieved. Can keep. In one embodiment, the sheet-shaped laminated material of the present invention has a resin composition after being stored for 72 hours at 23 ° C. and 60% humidity, with the minimum melt viscosity of the resin composition layer immediately after production being V ₁ (poise). When the minimum melt viscosity of the physical layer is V ₂ (poise), the ratio of V ₂ / V ₁ (hereinafter also referred to as “thickening ratio”) is preferably 1.8 or less, more preferably 1.6. Hereinafter, it is 1.5 or less, 1.4 or less, or 1.3 or less more preferably.

  The sheet-like laminated material of the present invention is preferably used for forming an insulating layer of a printed wiring board (for forming an insulating layer of a printed wiring board) and for embedding a component of a component built-in circuit board (for embedding a component). Can do. When used for forming an insulating layer of a printed wiring board, the sheet-like laminated material of the present invention is used to form an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board). In order to form a solder resist (for a solder resist of a printed wiring board), it can be used more suitably.

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

  In one embodiment, the printed wiring board of the present invention includes a layer formed of a cured product of the resin composition of the present invention as an insulating layer. In another embodiment, the printed wiring board of the present invention includes a layer formed of a cured product of the resin composition of the present invention as a solder resist. In the printed wiring board of the present invention, the layer formed of the cured product of the resin composition of the present invention is included as an appropriate member depending on the specific application.

  Hereinafter, an embodiment of a printed wiring board including a layer formed of a cured product of the resin composition of the present invention as an insulating layer will be described.

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.

  The thickness of the inner layer substrate is preferably 800 μm or less, more preferably 400 μm or less, and even more preferably 200 μm or less, from the viewpoint of reducing the thickness of the printed wiring board. According to the present invention, even when a thinner inner layer substrate is used, the reflow behavior in the mounting process can be stabilized. For example, even in the case of using an inner substrate having a thickness of 190 μm or less, 180 μm or less, 170 μm or less, 160 μm or less, 150 μm or less, 140 μm or less, 130 μm or less, 120 μm or less, 110 μm or less, or 100 μm or less, good in the mounting process Reflow behavior can be achieved. The lower limit of the thickness of the inner layer substrate is not particularly limited, but is preferably 10 μm or more, more preferably 20 μm or more from the viewpoint of improving the handleability during the production of the printed wiring board.

  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 may be performed using 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 to 240 ° C (preferably in the range of 150 to 220 ° C, more preferably in the range of 170 to 200 ° C. Range), curing time can be in the range of 5 to 120 minutes (preferably 10 to 100 minutes, more preferably 15 to 90 minutes).

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

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

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

[Semiconductor device]
A semiconductor device can be manufactured using the printed wiring board of the present invention. Even if the printed wiring board of the present invention is thin, it can achieve a good reflow behavior in a component mounting process that employs a high solder reflow temperature, and can realize a good mounting property.

  The reflow behavior in the component mounting process can be evaluated using the warpage of the printed wiring board in the component mounting process as an index. The smaller the warpage, the better (stable) the reflow behavior in the component mounting process. In one embodiment, the printed wiring board of the present invention has a warpage of the printed wiring board of less than 35 μm (preferably not more than 34 μm, more preferably not more than 33 μm) in a mounting process employing a solder reflow temperature having a peak temperature as high as 260 ° C. Even more preferably, it can be suppressed to 32 μm or less, 31 μm or less, or 30 μm or less. The warpage of the printed wiring board is the difference between the maximum height and the minimum height of the displacement data when the warping behavior of the 10 mm square portion at the center of the printed wiring board is observed with a shadow moire device. In the measurement, a reflow temperature profile described in IPC / JEDEC J-STD-020C (“Moisture / Reflow Sensitivity Classification For Nonhermetic Solid State Surface Devices”, July 2002, Reflow Profile Temperature) The printed wiring board is passed once through a reflow apparatus that reproduces the temperature of [° C.], and then one side of the printed wiring board is heat-treated with a reflow temperature profile in accordance with the IPC / JEDEC J-STD-020C. Displacement data is obtained for the grid lines provided on the other surface. An example of the reflow apparatus is “HAS-6116” manufactured by Nippon Antom Co., Ltd., and an example of the shadow moire apparatus is “Thermoire AXP” manufactured by Akrometrix. Even if the printed wiring board including the layer formed of the cured product of the resin composition of the present invention is thin, warpage in the mounting process is suppressed, and good mountability is realized.

  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) at a conduction point of the printed wiring board of the present invention. 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, “part” means “part by mass”.

[Measurement and evaluation methods]
First, various measurement methods and evaluation methods will be described.

<Measurement of minimum melt viscosity>
About the resin composition layer of the adhesive film produced in the Example and the comparative example, the melt viscosity was measured using the dynamic viscoelasticity measuring apparatus ("Rhesol-G3000" by UBM). About 1 g of the sample resin composition, using a parallel plate with a diameter of 18 mm, the temperature was increased from a starting temperature of 60 ° C. to 200 ° C. at a rate of temperature increase of 5 ° C./min. The dynamic viscoelastic modulus was measured under a measurement condition of 1 deg, and the minimum melt viscosity (poise) was measured. For each resin composition layer, the initial minimum melt viscosity V ₁ (poise) immediately after the production of the adhesive film and the minimum melt viscosity V ₂ (poise) after storage at 23 ° C. and 60% humidity for 72 hours were measured. The minimum melt viscosity was evaluated according to the following evaluation criteria.
Evaluation criteria:
○: Both V ₁ and V ₂ are less than 15000 poises X: At least one of V ₁ and V ₂ is 15000 poises or more

<Measurement of linear thermal expansion coefficient>
The adhesive film (200 mm square) produced in the Examples and Comparative Examples was prepared by using a batch-type vacuum press laminator (Nichigo-Morton Co., Ltd., 2-stage buildup laminator CVP700), and the resin composition layer was a polyimide film (Ube). Lamination was performed on the center of one side of the polyimide film so as to be in contact with the smooth surface of “Iupilex 25S” manufactured by Kosan Co., Ltd., thickness 25 μm, 240 mm square. The laminating process was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing the film at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

  The obtained laminated film is so that the polyimide film surface of the laminated film is in contact with a glass cloth base epoxy resin double-sided copper-clad laminate (“R5715ES” manufactured by Matsushita Electric Works Co., Ltd., thickness 0.7 mm, 255 mm square). And it installed on the glass cloth base-material epoxy resin double-sided copper clad laminated board, and fixed the four sides of this laminated film with the polyimide adhesive tape (width 10mm). Subsequently, it heated at 190 degreeC for 90 minute (s), and the resin composition layer was thermosetted.

  After thermosetting, the polyimide adhesive tape was peeled off, and the laminated film was removed from the glass cloth base epoxy resin double-sided copper-clad laminate. Furthermore, the polyimide film and the support were peeled from the laminated film to obtain a sheet-like cured product. The obtained cured product was cut into a test piece having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). It was. Specifically, after the test piece was mounted on the thermomechanical analyzer, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. In the second measurement, the average linear thermal expansion coefficient in the plane direction (α1; ppm / ° C.) in the range from 25 ° C. to 150 ° C. and the average linear thermal expansion coefficient in the plane direction in the range from 150 ° C. to 250 ° C. (Α2; ppm / ° C.) was calculated.

<Preparation of substrate for evaluation of reflow behavior>
(1) Preparation of inner layer substrate As inner layer substrate, glass cloth base epoxy resin laminate (unclad plate with copper foil removed by etching, thickness 0.10 mm, “HL832NSF-LCA” manufactured by Mitsubishi Gas Chemical Co., Ltd.) Prepared.

(2) Lamination of Adhesive Film Using the batch-type vacuum pressure laminator (manufactured by Nichigo Morton Co., Ltd., two-stage buildup laminator CVP700), the resin composition layer is the inner layer. The inner layer substrate was laminated on both sides so as to be in contact with the substrate. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing the film at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Thermosetting of resin composition layer After lamination, the support was peeled from both sides of the substrate. Next, the resin composition layer was thermally cured at 190 ° C. for 90 minutes to form the insulating layer. The obtained substrate is referred to as “substrate 1”.

<Evaluation of reflow behavior>
After the substrate 1 was cut into 45 mm square pieces (n = 5), the substrate 1 was passed once through a reflow apparatus (“HAS-6116” manufactured by Nippon Antom Co., Ltd.) that reproduces the solder reflow temperature with a peak temperature of 260 ° C. Reflow temperature profile is based on IPC / JEDEC J-STD-020C). Next, the lower surface of the substrate was heated with a reflow temperature profile conforming to IPC / JEDEC J-STD-020C (peak temperature 260 ° C.) using a shadow moire device (“Thermoire AXP” manufactured by Akrometrix) and arranged on the upper surface of the substrate. Based on the grid lines, the displacement of the 10 mm square portion at the center of the substrate was measured. The reflow behavior was evaluated according to the following evaluation criteria.
Evaluation criteria:
○: For all five samples, the difference between the maximum height and the minimum height of the displacement data in the entire temperature range is less than 35 μm. ×: For at least one sample, the difference between the maximum height and the minimum height of the displacement data in the entire temperature range is 35 μm or more

<Example 1>
12 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation "jER828EL", epoxy equivalent of about 185), 3 parts of naphthalene type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent of about 144), bixylenol type epoxy 6 parts of resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 25 parts of biphenyl type epoxy resin (“NC3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 288), phenoxy resin (Mitsubishi Chemical ( 10 parts of “YL7553BH30” (MEK / cyclohexanone = 1/1 solution having a solid content of 30% by mass) was dissolved in 20 parts of solvent naphtha with stirring. After cooling to room temperature, 10 parts of an epoxy group-containing silicone compound (“X-40-2670” manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent 200, alkoxy group amount 0% by mass), triazine skeleton-containing phenol novolak Type hardener ("LA-7054" manufactured by DIC Corporation, MEK solution having a hydroxyl equivalent weight of 125 and a solid content of 60% by mass), active ester hardener ("HPC8000-65T" manufactured by DIC Corporation), active group Equivalent weight 223, non-volatile component 65 mass% toluene solution 16 parts, curing accelerator (4-dimethylaminopyridine (DMAP), solid content 5 mass% MEK solution) 2 parts, flame retardant (manufactured by Sanko Co., Ltd.) HCA-HQ ", 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, Spherical silica (average particle size 0.5 μm, manufactured by Admatechs Co., Ltd.) “SO-C2” surface-treated with 3 parts of an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with carbon content 0.39mg ^/ m 2) 135 parts per unit surface area, are uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish.
Next, on the release layer side of the PET film with an alkyd resin release layer (“AL5” manufactured by Lintec Corporation, thickness 38 μm), the resin varnish is so formed that the thickness of the resin composition layer after drying is 40 μm. Was uniformly applied and dried at 80 to 120 ° C. (average 100 ° C.) for 5 minutes to prepare an adhesive film.

<Example 2>
25 parts of biphenyl type epoxy resin (“NC3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 288), 8 parts of phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., MEK solution having a solid content of 30% by mass) The solution was dissolved in 15 parts of solvent naphtha with stirring. After cooling to room temperature, 15 parts of an epoxy group-containing silicone compound (“X-40-2670” manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent 200, amount of alkoxy group 0% by mass), pretreatment of bisphenol A dicyanate 35 parts of polymer ("BA230S75" manufactured by Lonza Japan Co., Ltd., cyanate equivalent of about 232, MEK solution with 75% non-volatile component), active ester curing agent ("HPC8000-65T" manufactured by DIC Co., Ltd.), active group equivalent of about 223 non-volatile component 65 mass% toluene solution) 12 parts, curing accelerator (DMAP, MEK solution with a solid content of 5 mass%) 0.5 part, curing accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt (III) acetyl) 4 parts of acetonate, MEK solution having a solid content of 1% by mass, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd.), 10- (2,5-dihydro Siphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, 3 parts average particle size, surface with aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 145 parts of treated spherical silica (average particle size 0.5 μm, “SO-C2” manufactured by Admatechs Co., Ltd., carbon amount 0.39 mg / m ² per unit surface area) are mixed and uniformly mixed with a high-speed rotary mixer A resin varnish was prepared by dispersing.
Subsequently, the adhesive film 2 was produced in the same procedure as Example 1 using the obtained resin varnish 2.

<Example 3>
Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent of about 169), 5 parts biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation “ YX4000HK ", epoxy equivalent of about 185) 12 parts, dicyclopentadiene type epoxy resin (DIC Corporation" HP-7200H ", epoxy equivalent of about 275) 9 parts, phenoxy resin (Mitsubishi Chemical Corporation" YL7553BH30 "), 15 parts of MEK / cyclohexanone = 1/1 solution having a solid content of 30% by mass was dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, there are 4 parts of an epoxy group-containing silicone compound (“X-40-2670” manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent 200, alkoxy group amount 0 mass%), active ester curing agent. (“HPC8000-65T” manufactured by DIC Corporation, active group equivalent of about 223, toluene solution with 65% by mass of nonvolatile components) 40 parts, curing accelerator (DMAP, MEK solution with a solid content of 5% by mass), 3 parts, aminosilane system Spherical silica surface treated with a coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.25 μm, “SO-C1” manufactured by Admatechs Co., Ltd.), carbon amount per unit surface area 36 parts of 36 mg / m ² ) were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 3.
Subsequently, the adhesive film 3 was produced in the same procedure as Example 1 using the resin varnish 3.

<Comparative Example 1>
(I) The content of the triazine skeleton-containing phenol novolac-based curing agent (“LA-7054” manufactured by DIC Corporation, hydroxyl group equivalent 125, MEK solution having a solid content of 60% by mass) was changed to 18 parts, (ii) Instead of 16 parts of active ester type curing agent (“HPC8000-65T” manufactured by DIC Corporation, active group equivalent of about 223, 65% by mass of non-volatile component in toluene), naphthol type curing agent (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) 12 parts of “SN485”, MEK solution having a hydroxyl group equivalent of 215 and a solid content of 60% by mass), (iii) 1.2 parts of the amount of curing accelerator (DMAP, MEK solution having a solid content of 5% by mass) A resin varnish and an adhesive film were obtained in the same manner as in Example 1 except for changing to.

<Comparative example 2>
(I) The compounding amount of bisphenol A type epoxy resin (“jER828EL” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) was changed to 20 parts, (ii) epoxy group-containing silicone compound (Shin-Etsu Chemical Co., Ltd.) A resin varnish and an adhesive film were obtained in the same manner as in Example 1 except that “X-40-2670”, epoxy equivalent 200, and alkoxy group amount 0% by mass) were not used.

<Comparative Example 3>
(I) The point of not using a naphthalene type epoxy resin (“HP4032SS” manufactured by DIC Corporation, epoxy equivalent of about 144), (ii) a bisphenol A type epoxy resin (“jER828EL” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent) (Iii) The point of not using the xylenol-type epoxy resin (“YX4000HK”, epoxy equivalent of about 185 by Mitsubishi Chemical Corporation), (iv) epoxy group Except that the blending amount of the containing silicone compound (“X-40-2670” manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent 200, alkoxy group amount 0 mass%) was changed to 24 parts, it was the same as in Example 1. A resin varnish and an adhesive film were obtained.

<Comparative example 4>
Instead of 10 parts of epoxy group-containing silicone compound (“X-40-2670” manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent 200, alkoxy group amount 0 mass%), epoxy group-containing silicone compound (Shin-Etsu Chemical Co., Ltd.) A resin varnish and an adhesive film were obtained in the same manner as in Example 1 except that 10 parts of “X-41-1059A” (epoxy equivalent 350, alkoxy group amount 42% by mass) were used.

<Comparative Example 5>
Instead of 10 parts of an epoxy group-containing silicone compound (“X-40-2670” manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent 200, alkoxy group amount 0 mass%), an epoxy group-free silicone compound (Shin-Etsu Chemical ( A resin varnish and an adhesive film were obtained in the same manner as in Example 1 except that 10 parts of “X-40-9227” (amount of alkoxy group: 15% by mass) were used.

<Comparative Example 6>
Instead of 10 parts of an epoxy group-containing silicone compound (“X-40-2670” manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent 200, alkoxy group amount 0 mass%), an epoxy group-free silicone compound (Shin-Etsu Chemical ( Resin varnish and adhesive film were obtained in the same manner as in Example 1 except that 10 parts of “X-40-2651” manufactured by Co., Ltd., amino group-containing, alkoxy group content 7% by mass) were used.

<Comparative Example 7>
Instead of 12 parts of an active ester type curing agent (“HPC8000-65T” manufactured by DIC Corporation, a toluene solution of 65% by mass of a non-volatile component having an active group equivalent of about 223), a phenol novolac type polyfunctional cyanate ester resin (Lonza Japan ( Resin varnish and adhesive film were obtained in the same manner as in Example 2 except that 8 parts of “PT30S” manufactured by META Co., Ltd., a MEK solution having a cyanate equivalent of about 133 and a non-volatile component of 85% by mass were used.

Claims (11)

(A) an epoxy resin (except for the component (D) described later), (B) an active ester curing agent, (C) an inorganic filler, and (D) an epoxy equivalent of 300 or less, and an alkoxy group Containing an epoxy group-containing silicone compound whose content is 30% by mass or less based on the mass of the whole molecule,
When the nonvolatile component in the resin composition is 100% by mass, the content of the component (C) is 40% by mass or more, the content of the component (D) is 0.3 to 10% by mass, and (D The resin composition in which the component has a cyclic siloxane structure. (D) The resin composition of Claim 1 in which a component contains the structural unit represented by Formula (1).

(In the formula, R ¹ represents an organic group having an epoxy group, R ² represents a hydrogen atom, a hydrocarbon group, or an alkoxy group, and * represents a bond.)   (D) The resin composition of Claim 2 in which a component has 3-10 structural units represented by Formula (1) in 1 molecule. R ¹ is a monovalent group represented by the formula: X- (L) _p- (wherein X represents an epoxyalkyl group, an epoxycycloalkyl group or an epoxyaryl group, and L represents an alkylene group or a cycloalkylene group. Represents an arylene group, an oxyalkylene group, an oxycycloalkylene group or an oxyarylene group, and p represents 0 or 1.) The resin composition according to claim 2 or 3.   The resin composition according to claim 4, wherein X is an epoxycycloalkyl group having 4 to 10 carbon atoms. (D) The resin composition of any one of Claims 1-5 in which a component contains the compound represented by Formula (2-1).

  (C) The resin composition of any one of Claims 1-6 whose component is a silica.   (C) The resin composition of any one of Claims 1-7 whose average particle diameter of a component is 0.01-4 micrometers.   The resin composition according to any one of claims 1 to 8, which is used for a semiconductor sealing material. The resin composition of any one of Claims 1-9 whose average linear thermal expansion coefficient ((alpha) ₂ ) in the range of 150-250 degreeC of the hardened | cured material of a resin composition is 47-60 ppm / degreeC.   The sheet-like laminated material containing the layer of the resin composition of any one of Claims 1-10.