JP6512328B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition. Furthermore, the present invention relates to a sheet-like laminate material, a printed wiring board, and a semiconductor device using the 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 layer substrate is known. In the build-up method, the insulating layer is generally formed by curing the resin composition. For example, Patent Document 1 discloses a technique for curing a resin composition containing an epoxy group-containing silicone compound and a phenol-based curing agent and / or a cyanate ester-based curing agent to form a heat-resistant insulating layer. It is disclosed.

International Publication No. 2014/61812

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

  As thinning of printed wiring boards progresses, it tends to be difficult to stabilize the reflow behavior in the process of mounting components by solder reflow. The present inventors warp the printed wiring board in the component mounting process if the printed wiring board is thin even with the technology described in Patent Document 1 that can form an insulating layer with good heat resistance. It has been found that in some cases, it may result in defects in reflow behavior such as If the reflow behavior is not good, problems such as contact failure of parts will occur, and the mountability will deteriorate.

  An object of the present invention is to provide a resin composition that provides a printed wiring board that exhibits good reflow behavior in the component mounting process.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly examining about said subject, the present inventors discover that said subject can be solved according to the following specific resin composition, and came to complete this 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 weight are 300 or less, and the content of alkoxy group is the mass of the whole molecule Containing an epoxy group-containing silicone compound which is 30% by mass or less as a standard,
The resin composition, wherein the content of the component (C) is 40% by mass or more and the content of the 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) contains a structural unit represented by the formula (1).

(Wherein, 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 epoxy alkyl group, an epoxy cycloalkyl group or an epoxy aryl 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 epoxy cycloalkyl group having 4 to 10 carbon atoms.
[7] The resin composition according to any one of [1] to [6], wherein the component (D) contains 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 average particle size of the component (C) is 0.01 to 4 μm.
[10] The resin composition according to any one of [1] to [9], which is 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 average linear thermal expansion coefficient (α ₂ ) in the range of 150 to 250 ° C. of the cured product of the resin composition is 47 to 60 ppm / ° C. object.
[12] A sheet-like laminate 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 comprising 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 favorable reflow behavior in the mounting process of components can be provided.

  Hereinafter, the present invention will be described in detail in line with the preferred embodiments.

[Resin composition]
The resin composition of the present invention has (A) an epoxy resin, (B) an active ester-based curing agent, (C) an inorganic filler, and (D) an epoxy equivalent of 300 or less, and an alkoxy group content The content of the component (C) is 40% by mass or more when the epoxy group-containing silicone compound containing 30% by mass or less based on the mass of the whole molecule is included and the nonvolatile component in the resin composition is 100% by mass. 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 novolac type epoxy resin, Phenolic novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, biphenyl type Epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing resin Carboxymethyl resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. The epoxy resins may be used alone or in combination of two or more.

  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, it is preferable that at least 50% by mass or more is an epoxy resin having two or more epoxy groups in one molecule. Among them, an epoxy resin having two or more epoxy groups in one molecule, a liquid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “liquid epoxy resin”), and three or more epoxy groups in one molecule, It is preferable to contain a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, a resin composition having excellent flexibility can be obtained. In addition, the breaking strength of the cured product of the resin composition is also improved. Alternatively, the epoxy resin may contain only the solid epoxy resin described above.

  As liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, and butadiene structure An epoxy resin is preferable, and a bisphenol A epoxy resin, a bisphenol F epoxy resin, and a naphthalene epoxy resin are more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032H”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “jER828US” manufactured by Mitsubishi Chemical Corporation, “jER828EL”. (Bisphenol A type epoxy resin), “jER 807” (bisphenol F type epoxy resin), “jER 152” (phenol novolac type epoxy resin), “ZX1059” (bisphenol A type epoxy resin and bisphenol manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Mixed product of F type epoxy resin), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., Ltd., “Ceroxide 2021P” (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Co., Ltd. ), "PB-3600" Epoxy resin) having an butadiene structure. These may be used singly or in combination of two or more.

  Examples of 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, naphthalene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, 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 epoxy resin), manufactured by DIC Corporation. N-695 "(cresol novolac epoxy resin)," HP-7200 "," HP-7200H "(dicyclopentadiene type epoxy resin)," EXA7311 "," EXA7311-G3 "," EXA7311-G4 "," EXA7311 -G4S, "HP 6000" (naphthylene ether type epoxy resin), "EPPN-502H" (Trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC 7000 L" (naphthol novolac type epoxy resin), "NC 3000 H , "NC3000", "NC3000L", "NC 100 "(biphenyl type epoxy resin)," ESN 475 V "(naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.," ESN 485 "(naphthol novolac type epoxy resin)," YX4000H "manufactured by Mitsubishi Chemical Corporation," YL 6121 "(biphenyl type epoxy resin)," YX 4000 HK "(bixylenol type epoxy resin)," YX 8800 "(anthracene type epoxy resin)," PG-100 "or" CG-500 "manufactured by Osaka Gas Chemicals Co., Ltd. Mitsubishi Chemical's "YL 7800" (fluorene-type epoxy resin), Mitsubishi Chemical's "jER 1010" (solid bisphenol A-type epoxy resin), "jER 1031 S" (tetraphenylethane-type epoxy resin), etc. It can be mentioned.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the mass ratio (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 8 in mass ratio. preferable. By setting the ratio of the liquid epoxy resin to the solid epoxy resin in such a range, i) suitable adhesiveness is provided when used in the form of a sheet-like laminate material, ii) the form of a sheet-like laminate material Sufficient flexibility is obtained when used in the above, and the effect of improving the handleability and iii) being able to obtain a cured product having sufficient breaking strength is obtained. From the viewpoint of the effects of i) to iii), the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.3 to 1: 7 in mass ratio Is more preferable, and the range of 1: 0.6 to 1: 6 is 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, it is 10% by mass to 35% by mass or 10% by mass to 30% by mass.
In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass unless otherwise specified.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and still more preferably 110 to 1000. By being in this range, the crosslink density of the cured product is sufficient, and an insulating layer with a small surface roughness can be provided. In addition, an epoxy equivalent can be measured according to JISK7236, and is a mass of resin containing an epoxy group of 1 equivalent.

<(B) Active ester curing agent>
The resin composition of the present invention contains an active ester-based 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 mounting process of components even in a thin printed wiring board by using an active ester curing agent in combination with the component (D) described later. Found out.

  The active ester-based curing agent is preferably an active ester compound having two or more active ester groups in one molecule, and examples thereof include phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. An active ester compound having two or more ester groups having high reaction activity such as those in one molecule is preferably used. The active ester curing agent may be used singly or in combination of two or more.

  From the viewpoint of improving heat resistance, active ester compounds obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound are preferable. Among them, an active ester compound obtained by reacting a carboxylic acid compound and 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 Is more preferably an aromatic compound having two or more active ester groups in one molecule, and a carboxylic acid compound having at least two or more carboxy groups in one molecule, and a phenolic hydroxyl group. An aromatic compound obtained by reacting an aromatic compound, which is an aromatic compound having two or more active ester groups in one molecule is still more preferable. The active ester compound may be linear or branched. Moreover, if the carboxylic acid compound having at least two or more carboxy groups in one molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be enhanced, and if it is a compound having an aromatic ring Heat resistance can be increased.

  Examples of the carboxylic acid compounds include aliphatic carboxylic acids having 1 to 20 (preferably 2 to 10, more preferably 2 to 8) carbon atoms, and aromatics having 7 to 20 carbon atoms (preferably 7 to 10) Carboxylic acid is mentioned. Examples of aliphatic carboxylic acids 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 and pyromellitic acid. Among them, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferable, 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 (preferably 6 to 30, more preferably 6 to 23, more preferably 6 to 22) carbon atoms, and preferable specific examples include hydroquinone, Resorcinol, 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 include hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol and the like. Moreover, as a phenol compound, you may use the phenol novolak and the phosphorus atom containing oligomer which has a phenolic hydroxyl group of Unexamined-Japanese-Patent No. 2013-40270.

  Examples of naphthol compounds include naphthol compounds having 10 to 40 carbon atoms (preferably 10 to 30, more preferably 10 to 20), and preferred specific examples include α-naphthol, β-naphthol, 1 Examples include 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. 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-Dihydroxy naphthalene, dihydroxy benzophenone, trihydroxy benzophenone, tetrahydroxy benzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol, phenol novolac, phosphorus atom containing oligomer having phenolic hydroxyl group is preferable, catechol 1,5 -Dihydroxy naphthalene, 1, 6- dihydroxy naphthalene, 2, 6- dihydroxy naphthalene, dihydroxy benzophenone, trihydric Roxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol, phenol novolak, phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 , 6-dihydroxy naphthalene, dihydroxy benzophenone, trihydroxy benzophenone, tetrahydroxy benzophenone, dicyclopentadiene type diphenol, phenol novolac, phosphorus atom-containing oligomers having a phenolic hydroxyl group are more preferable, 1, 5-dihydroxy naphthalene, 1, 6 -Dihydroxy naphthalene, 2, 6- dihydroxy naphthalene, dicyclopentadiene type diphenol, phenol Lac, a phosphorus atom-containing oligomer having a phenolic hydroxyl group is further more preferable, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenol, phosphorus having a phenolic hydroxyl group 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, triazine dithiol and the like.

  Preferred specific examples of the active ester-based curing agent include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated compound of phenol novolac, and a benzoyl compound of phenol novolac And active ester compounds obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group, among which active ester compounds containing a dicyclopentadiene type diphenol structure, a naphthalene structure More preferred are active ester compounds containing the following, and active ester compounds obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group. In the present invention, "dicyclopentadiene type diphenol structure" represents a bivalent structural unit consisting of phenylene-dicyclopentalene-phenylene.

  More specifically, examples of the active ester compound containing a dicyclopentadiene type diphenol structure include a compound 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 0.05 to 2.5 in the average number of repeating units.)

  From the viewpoint of lowering 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-based curing agent, active ester compounds disclosed in JP-A-2004-277460 and JP-A-2013-40270 may be used, and commercially available active ester compounds can 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 acetylated compound of phenol novolac, YLH1026 (Mitsubishi Chemical Co., Ltd.) as an active ester compound containing benzoyl compound of phenol novolac EXB9050L-62M (made by DIC Corporation) as a phosphorus atom containing active ester compound.

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

  When the number of epoxy groups of the (A) epoxy resin is one, the number of reactive groups of the (B) active ester-based curing agent is preferably 0.2 to 2 from the viewpoint of obtaining an insulating layer with good mechanical strength. .3 to 1.5 is more preferable, and 0.35 to 1 is more preferable. Here, "the epoxy group number of epoxy resin" is a value which totaled the value which remove | divided the solid content mass of each epoxy resin which exists in a resin composition by the epoxy equivalent, about all the epoxy resins. Further, "reactive group" means a functional group capable of reacting with an epoxy group, and "the number of reactive groups of the active ester compound" means the solid content mass of the active ester compound present in the resin composition. It is the value which totaled all the values divided by the reaction group equivalent.

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

  The content of the inorganic filler in the resin composition layer is 40% by mass or more, and preferably 45% by mass, from the viewpoint of stabilizing the reflow behavior in the mounting process of parts and from the viewpoint of obtaining a cured product having a low coefficient of thermal expansion. % Or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, or 60% by mass or more. When the content of the inorganic filler in the resin composition is increased, the melt viscosity of the resin composition may be increased, which may result in the resin composition having poor laminateability in the production of the 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 an excessive increase in the melt viscosity. For example, the content of the inorganic filler in the resin composition may be increased to 62 mass% or more, 64 mass% or more, 66 mass% or more, 68 mass% or more, or 70 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, still more preferably 85% by mass or less from the viewpoint of the mechanical strength of the cured product obtained .

  Although 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 And zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc., with silica being particularly preferred. That. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Moreover, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more. Examples of commercially available spherical fused silica include "SO-C2" and "SO-C1" manufactured by Admatex Co., Ltd.

  The average particle size of the inorganic filler is not particularly limited, but it is preferably 4 μm or less, more preferably 3 μm or less, still more preferably 2 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, the average particle diameter of the inorganic filler is preferably 0.01 μm or more from the viewpoint of obtaining a resin varnish having an appropriate viscosity and good handling when forming a resin varnish using a resin composition, 0.03 micrometer or more is more preferable, and 0.05 micrometer or more, 0.07 micrometer or more, or 0.1 micrometer or more is further more preferable. The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction type particle size distribution measuring apparatus, and the median diameter can be measured as an average particle size. As a measurement sample, one in which an inorganic filler is dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, "LA-500", "LA-750", "LA-950" etc. by Horiba, Ltd. can be used.

  The inorganic filler is an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, and a titanate coupling agent from the viewpoint of enhancing the moisture resistance and dispersibility. It is preferable to be treated with one or more surface treatment agents such as. As a commercial item of a surface treatment agent, Shin-Etsu Chemical Co., Ltd. product "KBM403" (3-glycidoxypropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. product "KBM 803" (3-mercapto propyl trimethoxy) is mentioned, for example. Silane), Shin-Etsu Chemical Co., Ltd. “KBE 903” (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. “KBM 573” (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyl disilazane) etc. are mentioned.

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

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

<(D) Epoxy Group-Containing Silicone Compound>
The resin composition of the present invention contains, as the 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. .

  The epoxy equivalent of component (D) is 300 or less, preferably 280 or less, more preferably 260 or less, and more preferably, from the viewpoint of stabilizing the reflow behavior in the component mounting step in combination with component (B). Is 240 or less, still 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 in accordance with JIS K 7236 as in the case of the component (A).

  From the viewpoint of stabilizing the reflow behavior in the mounting step of the component in combination with the component (B) and from the viewpoint of obtaining a resin composition exhibiting an appropriate melt viscosity, the content of alkoxy group in the component (D) It is 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, still more preferably 10% by mass or less, 8% by mass or less based on the total mass. 6% by mass or less, 4% by mass or less, 2% by mass or less, or 1% by mass or less. The lower limit of the content of the alkoxy group is not particularly limited, and may be 0% by mass. The content of the alkoxy group is the 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 above-mentioned desired range, but the viewpoint of improving the handleability by reducing the volatility and the viewpoint of improving the dispersibility Therefore, 300 to 5000 are preferable, 400 to 4000 are more preferable, and 500 to 3000 are more preferable. In the present invention, the weight average molecular weight is measured by gel permeation chromatography (GPC) method (in terms of polystyrene). Specifically, the weight average molecular weight according to 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 calculated using a calibration curve of standard polystyrene.

  From the viewpoint of stabilizing the reflow behavior in the mounting process of the component in combination with the component (B), the content of the component (D) in the resin composition is 0.3% by mass or more, preferably 0. It is 5% by mass or more, more preferably 1.0% by mass or more, and further preferably 1.5% by mass or more, or 2.0% by 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 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 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) contains a structural unit represented by 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。）

(Wherein, 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 epoxy alkyl group, an epoxy cycloalkyl group or an epoxy aryl 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 carbon atom number of the epoxy alkyl group represented by X is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 6.

  The carbon atom number of the epoxy cycloalkyl group represented by X is preferably 4 to 10, more preferably 4 to 6.

  The carbon atom number 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.

  From the viewpoint of being able to further stabilize the reflow behavior in the component mounting process 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. . Among them, X is preferably an epoxycyclohexyl group.

  The carbon atom number of the alkylene group represented by L and the oxyalkylene group is preferably 1 to 20, more preferably 1 to 10, and still more 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 or oxyarylene group represented by L is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10.

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

  It is preferable that p is 1 from a viewpoint of being able to stabilize the reflow behavior in the mounting process of components in combination with (B) component.

Examples of the hydrocarbon group represented by R ² in the formula (1) include an alkyl group, a cycloalkyl group, an aryl group, and a monovalent group formed by combining two or more of these. The carbon atom number of an alkyl group becomes like this. Preferably it is 1-10, More preferably, it is 1-6, More preferably, it is 1-5, 1-4, or 1-3. The carbon atom number of the cycloalkyl group is preferably 3 to 10, more preferably 3 to 6 or 4 to 6. The carbon atom number of the aryl group is preferably 6 to 10. Examples of the monovalent group formed by combining two or more of an alkyl group, a cycloalkyl group and an aryl group include a cycloalkylalkyl group and an arylalkyl group.

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

R ² is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably methyl, from the viewpoint of being able to further stabilize the reflow behavior in the component mounting step in combination with the component (B). It is a group, an ethyl group, a propyl group or a butyl group.

  The component (D) is preferably 2 to 10, more preferably 2 to 8, still more preferably 2 to 6, 3 to 6, per molecule, as the structural unit represented by the above formula (1). There are three or three or five.

  The component (D) may have a linear siloxane structure or may have a cyclic siloxane structure. The component (D) preferably has a cyclic siloxane structure from the viewpoint of being able to further stabilize the reflow behavior in the mounting process of the component in combination with the component (B).

  In a preferred embodiment, the component (D) is a compound represented by 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。）

(In the formula,
R ¹ and R ² have the same meaning as described 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 , wherein R ′ represents R ¹ or R ² .
R ³ and R ⁴ may both be a single bond and 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; Plural R ^{1 s} may be the same or different, and plural R ^{2 s} may be the same or different. )

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

The hydrocarbon group represented by R ⁴ in Formula (2) is the same as the hydrocarbon group described for R ² in Formula (1). R ³ and R ⁴ may be appropriately determined from the above options as long as the epoxy equivalent and the content of the alkoxy group fall within the above-described desired range. Among them, in combination with the component (B), R ³ and R ⁴ are both single bonds and are bonded to each other to form a cyclic siloxane structure, from the viewpoint of being able to further stabilize the reflow behavior in the component mounting step. Is preferred.

  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 randomly included or may be included in a block form.

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

  As the component (D), one type may be used alone, or two or more types may be used in combination.

  The method for producing the component (D) is not particularly limited. For example, the component (D) can be obtained by a reaction of partially hydrolyzing and polycondensing an alkoxy group of a silane compound which is a monomer. The component (D) may also be a commercially available product. As a commercial item, for example, Shin-Etsu Chemical Co., Ltd. product “X-40-2670” (epoxy equivalent 200, content of alkoxy group 0 mass%), Arakawa Chemical Industry Co., Ltd. product “Compoceran SQ 502-8” ( Epoxy equivalent 276, content of alkoxy group about 12% by mass) and the like.

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

  As a thermoplastic resin, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamide imide resin, polyether imide resin, polysulfone resin, polyether sulfone resin, polyphenylene ether resin, polycarbonate resin, polyether resin Ether ketone resin and polyester resin are mentioned. The thermoplastic resin may be used alone or in combination of two or more.

  The range of 8,000 to 70,000 is preferable, the range of 10,000 to 60,000 is more preferable, and the range of 20,000 to 60,000 is more preferable.

  As the phenoxy resin, for example, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene The phenoxy resin which has 1 or more types of frame | skeleton selected from frame | skeleton, and the group which consists of trimethyl cyclohexane frame | skeleton is mentioned. The terminal of the phenoxy resin may be any functional group such as phenolic hydroxyl group and epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include “1256” and “4250” (both of which are bisphenol A skeleton-containing phenoxy resins), “YX8100” (bisphenol S skeleton-containing phenoxy resins), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). Bisphenol acetophenone skeleton-containing phenoxy resin may be mentioned, and in addition, “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YL7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Co., Ltd. Examples include "YL7290" and "YL7482".

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

  As a specific example of a polyimide resin, Shin-Nika Chemical Co., Ltd. "Rika coat SN20" and "Rika coat PN20" are mentioned. Specific examples of the polyimide resin also include a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A-2006-37083), and a polysiloxane skeleton Modified polyimides such as contained polyimides (described in JP-A-2002-12667 and JP-A-2000-319386) may, for example, be mentioned.

  As a specific example of a polyamide imide resin, Toyobo Co., Ltd. product "Viromax HR11NN" and "Viromax HR16NN" are mentioned. Specific examples of the polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimide "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd.

  As a specific example of polyether sulfone resin, Sumitomo Chemical Co., Ltd. "PES5003P" etc. are mentioned.

  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, still more preferably 1% by mass to 5% by mass .

<(F) Hardening 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, metal-based curing accelerators, and the like. The curing accelerator may be used alone or in combination of two or more. 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) Hardening agent>
The resin composition of the present invention may further comprise (G) a curing agent (but excluding the (B) component).

  Although it does not specifically limit as a hardening agent, For example, a phenol type hardening agent, a naphthol type hardening agent, a cyanate ester type hardening agent, a benzoxazine type hardening agent etc. can be mentioned. The curing agent may be used alone or in combination of two or more. Among these, from the viewpoint of being able to further stabilize the reflow behavior in the mounting step of the component in combination with the components (A) to (D), a phenol-based curing agent, a naphthol-based curing agent, and a cyanate ester-based curing agent preferable.

  From the viewpoints of heat resistance and water resistance, as the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure is preferable. Further, from the viewpoint of adhesion strength (peel strength) to the conductor layer, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferable. . Among them, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength with a conductor layer. Specific examples of the phenolic curing agent and naphthol curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485” manufactured by Nippon Steel Sumikin Chemical Co., Ltd., “SN-495”, “SN-375”, “SN-395”, “LA-7052”, “LA-7054”, “LA-3018”, “LA-1356”, “TD 2090” manufactured by DIC Corporation Etc. are mentioned.

  The cyanate ester-based curing agent is not particularly limited. For example, novolak type (phenol novolac type, alkylphenol novolac type, etc.) cyanate ester type curing agent, dicyclopentadiene type cyanate ester type curing agent, bisphenol type (bisphenol A type, Examples thereof include bisphenol F type, bisphenol S type, etc.) cyanate ester-based curing agents, and prepolymers in which these are partially triazineated. Specific examples thereof include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylene bis (2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl Dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatophenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, Difunctional cyanate resins such as 1,3-bis (4-cyanatophenyl-1- (methylethylidene)) benzene, bis (4-cyanatophenyl) thioether, and bis (4-cyanatophenyl) ether, phenol novolak and cresol novolac Invitation from Polyfunctional cyanate resin is, these cyanate resins and partially triazine of prepolymer. Commercially available cyanate ester-based curing agents include “PT30”, “PT30S” and “PT60” (all are phenol novolac type polyfunctional cyanate ester resins) and “BA230” (bisphenol A dicyanate) manufactured by Ronza Japan Ltd. And the like) and the like.

  Specific examples of the benzoxazine-based curing agent include “HFB 2006 M” manufactured by Showa Highpolymer 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 organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides and the like. The flame retardants may be used alone or in combination of two or more. 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 comprise (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, silicone particles and the like, and rubber particles are preferable.

  The rubber particles are not particularly limited as long as they are fine particles of resin insoluble and insoluble in an organic solvent by subjecting a resin exhibiting rubber elasticity to chemical crosslinking treatment, for example, acrylonitrile butadiene rubber particles, butadiene rubber particles, Acrylic rubber particles and the like can be mentioned. Specific examples of rubber particles include XER-91 (manufactured by Japan Synthetic Rubber Co., Ltd.), staphyroid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (all manufactured by Aika Kogyo Co., Ltd.), paraloid Examples include EXL 2655 and EXL 2602 (all manufactured by Toha Chemical Industry Co., Ltd.).

  The average particle size of the organic filler is preferably in the range of 0.005 μm to 1 μm, and more preferably in the range of 0.2 μm to 0.6 μm. The average particle size of the organic filler can be measured using a dynamic light scattering method. For example, the organic filler is uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and the particle size distribution of the organic filler is determined using a concentrated particle size analyzer ("FPAR-1000" manufactured by Otsuka Electronics Co., Ltd.) It can be prepared on the basis of the standard, and can be measured by using its 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. As such other components, for example, organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds, and thickeners, antifoaming agents, leveling agents, adhesion imparting agents, colorants and curable resins Resin additives and the like.

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

The resin composition of the present invention can provide a cured product with 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, the average linear thermal expansion coefficient (α ₁ ; ppm / ° C.) in the planar direction in the range of 25 to 150 ° C., and the range from 150 ° C. to 250 ° C. by performing thermomechanical analysis by a tensile loading method The average linear thermal expansion coefficient (α ₂ ; ppm / ° C.) in the planar direction at can be measured.

The lower α ₁ of the cured product of the resin composition is preferable from the viewpoint of suppressing the occurrence of cracks and circuit distortion in the printed wiring board. alpha ₁ is preferably 40 ppm / ° C. or less, more preferably 35 ppm / ° C. or less, more preferably 30 ppm / ° C. or less, even more preferably at most 25 ppm / ° C.. The lower limit of the alpha ₁ is not particularly limited, but usually, 1 ppm / ° C. or higher. 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, but if α ₂ is too low, it may be difficult to achieve good reflow behavior in the component mounting process. The present inventors have found that there is. The α ₂ of the cured product of the resin composition is preferably 47 ppm / ° C. or more, more preferably 48 ppm / ° C. or more, still more preferably 50 ppm / ° C. or more, from the viewpoint of stabilizing the reflow behavior in the mounting process of parts. Preferably, it is 52 ppm / ° C. or more, or 54 ppm / ° C. or more. The upper limit of α ₂ is preferably 60 ppm / ° C. or less.

  The resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for 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, even in a thin printed wiring board, good reflow behavior can be achieved in the component mounting process. In addition, since the resin composition of the present invention exhibits appropriate melt viscosity and is excellent in component embedding property, 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 (resin composition for component embedding) for embedding a component of a component-embedded circuit board. By using the resin composition of the present invention as a component embedding resin composition, good reflow behavior can be achieved in the surface mounting step of components 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 And a resin composition for forming a solder resist of a printed wiring board (resin composition for a solder resist of a printed wiring board). The resin composition of the present invention is also used in a wide range of applications where a resin composition is required, such as adhesive films, sheet-like laminate materials such as prepregs, underfill materials, die bonding materials, semiconductor sealing materials, hole filling resins, etc. it can.

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

  As a sheet-like lamination material, the adhesive film shown below and a prepreg are preferable.

  In one embodiment, the adhesive film comprises a support and a resin composition layer (adhesive layer) joined to the support, and the resin composition layer (adhesive layer) is the resin composition of the present invention. It is 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 still more preferably 50 μm or less or 40 μm or less from the viewpoint of thinning the printed wiring board. The lower limit of the thickness of the resin composition layer is not particularly limited, but may usually be 1 μm or more, 5 μm or more, 10 μm or more.

  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"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Ketone, polyimide and the like can be mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, copper foil, aluminum foil etc. are mentioned as metal foil, 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.) You may use.

  In the support, the surface on the side to be bonded to the resin composition layer may be subjected to a matting treatment and a corona treatment. Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface of the side joined to a resin composition layer. As a release agent used for the release layer of the support with release layer, for example, one or more release agents selected from the group consisting of alkyd resin, olefin resin, urethane resin, and silicone resin can be mentioned. . As a commercial item of a mold release agent, "SK-1", "AL-5", "AL-7" etc. which are the alkyd resin type mold release agents and are manufactured by Lintec Co., Ltd. are mentioned, for example.

  The thickness of the support is not particularly limited, but a range of 5 to 75 μm is preferable, and a range of 10 to 60 μm 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 support body with a release layer is the said range.

  The adhesive film is prepared, for example, by dissolving a resin composition in an organic solvent, preparing a resin varnish, applying the resin varnish on a support using a die coater or the like, and drying it to form a resin composition layer. Can be manufactured by

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

  Drying may be carried out by known methods such as heating and 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. Although it changes also with the boiling points of the organic solvent in a resin varnish, when using the resin varnish containing 30 mass%-60 mass% organic solvent, for example, it is resin composition layer by making it dry at 50-150 degreeC 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 not bonded 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 adhesion of dust and the like to the surface of the resin composition layer and scratches. The adhesive film can be wound and stored in a roll. When the adhesive film has a protective film, it can be used by peeling off the protective film.

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

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

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

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

  In the sheet-like laminate material, the minimum melt viscosity of the resin composition layer is preferably 15000 poise or less, more preferably 14000 poise or less, from the viewpoint of achieving good laminateability (circuit embeddability) when producing a printed wiring board. More preferably, it is 12000 poise or less, still more preferably 10000 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 poise or more, from the viewpoint of suppressing bleeding of resin during production of a printed wiring board. It is more than poise. Here, the "minimum melt viscosity" of the resin composition layer refers to the minimum 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 rising rate to melt the resin, the melt viscosity decreases with the temperature rise in the initial stage, and then the melt viscosity increases with the temperature rise when exceeding a certain temperature To rise. The "minimum melt viscosity" refers to the melt viscosity of such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by the dynamic viscoelasticity method, and can be measured, for example, according to the method described in <Measurement of minimum melt viscosity> described later.

  In the sheet-like laminate material, 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 lamination (part embedding) is different depending on (the lamination temperature of the sheet-like laminated material and the inner layer substrate, etc.). Therefore, in producing a sheet-like laminate material, the resin composition layer is designed to exhibit the desired minimum melt viscosity. In this respect, in the case of a sheet-like laminate material using a conventional resin composition, the viscosity of the resin composition layer may gradually increase during storage, and from the desired value when used for the production of a printed wiring board May also exhibit a significantly higher minimum melt viscosity.

On the other hand, in the present invention using the combination of the components (B) and (D), the increase in viscosity of the resin composition layer during storage is suppressed, and the desired minimum melt viscosity is advantageously obtained. You can keep it. In one embodiment, the sheet-like laminate material of the present invention is a resin composition after the minimum melt viscosity of the resin composition layer immediately after the production thereof is V ₁ (poise) and stored for 72 hours at 23 ° C. and 60% humidity. When the minimum melt viscosity of the product layer is V ₂ (poise), the ratio V ₂ / V ₁ (hereinafter also referred to as “thickening ratio”) is preferably 1.8 or less, more preferably 1.6. Or less, more preferably 1.5 or less, 1.4 or less, or 1.3 or less.

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

[Printed wiring board]
The printed wiring board of the present invention includes a layer formed by the 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, as a solder resist, a layer formed of a cured product of the resin composition of the present invention. 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 a suitable member depending on the specific use.

  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 the present invention can be manufactured by the method including the following steps (I) and (II) using the above-mentioned adhesive film.
(I) Step of laminating an adhesive film on the inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate (II) Step of thermally curing the resin composition layer to form an insulating layer

  The "inner layer substrate" used in step (I) mainly refers to a substrate such as 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 sides of the substrate. A circuit board on which a patterned conductor layer (circuit) is formed. Further, when manufacturing a printed wiring board, an inner layer circuit board of an intermediate product on which an insulating layer and / or a conductor layer is to be 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 substrate incorporating components may be used.

  The thickness of the inner layer substrate is preferably 800 μm or less, more preferably 400 μm or less, and still more preferably 200 μm or less from the viewpoint of thinning 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 layer 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 Reflow behavior can be achieved. Although the lower limit of the thickness of the inner layer substrate is not particularly limited, it is preferably 10 μm or more, more preferably 20 μm or more from the viewpoint of improving the handleability at the time of printed wiring board production.

  The lamination of the inner layer substrate and the adhesive film can be performed, for example, by heat-pressing the adhesive film from the support side to the inner layer substrate. Examples of the member (hereinafter, also referred to as “heat-pressing member”) for heat-pressing the adhesive film to the inner layer substrate include a heated metal plate (SUS mirror plate or the like) or a metal roll (SUS roll). In addition, it is preferable to press via elastic materials, such as heat resistant rubber, so that an adhesive film may fully follow the surface asperity of an inner-layer board | substrate instead of pressing a thermocompression-bonding member directly to an adhesive film.

  The lamination of the inner layer substrate and the adhesive film may be carried out by a vacuum lamination 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 heat compression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

  Lamination may be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressure type laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nichigo Morton Co., Ltd., etc. may be mentioned.

  After lamination, the laminated adhesive film may be subjected to a smoothing treatment by normal pressure (atmospheric pressure), for example, by pressing the heat pressure-bonding member from the support side. The pressing conditions for the smoothing treatment can be the same as the heating and pressing conditions for the above-mentioned lamination. The smoothing treatment can be performed by a commercially available laminator. In addition, you may perform lamination | stacking and smoothing processing continuously using said commercially available vacuum laminator.

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

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

  The heat curing conditions of the resin composition layer are not particularly limited, and conditions generally employed for forming an insulating layer of a printed wiring board may be used.

  For example, the heat curing conditions of the resin composition layer vary depending on the type of resin composition and the like, but the curing temperature is in the range of 120 to 240 ° C. (preferably 150 to 220 ° C., more preferably 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 thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to heat curing the resin composition layer, the resin composition layer is heated at a temperature of 50.degree. C. or more and less than 120.degree. C. (preferably 60.degree. C. or more and 110.degree. C. or less, more preferably 70.degree. C. or more and 100.degree. C. or less). It may be preheated for 5 minutes or more (preferably 5 to 150 minutes, more preferably 15 to 120 minutes).

  In the case of producing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming the 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 for producing a printed wiring board. When the support is removed after the step (II), the removal of the support may be performed between the step (II) and the step (III), between the step (III) and the step (IV), or 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 above-mentioned prepreg. The manufacturing method is basically the same as in the case of using an adhesive film.

[Semiconductor device]
A semiconductor device can be manufactured using the printed wiring board of the present invention. The printed wiring board of the present invention can achieve good reflow behavior in the mounting process of parts adopting high solder reflow temperature even if it is thin, and can realize good mountability.

  The reflow behavior in the component mounting process can be evaluated using the warp of the printed wiring board in the component mounting process as an index, and the smaller the warp, the better (stable) the reflow behavior in the component mounting process. In one embodiment, the printed wiring board of the present invention has a warp of less than 35 μm (preferably 34 μm or less, more preferably 33 μm or less) in a mounting process that employs a high solder reflow temperature with a peak temperature of 260 ° C. And still more preferably 32 μm or less, 31 μm or less, or 30 μm or less. The warpage of the printed wiring board is the value of the difference between the maximum height and the minimum height of displacement data when the warpage behavior of a 10 mm square portion at the center of the printed wiring board is observed with a shadow moire apparatus. At the time of measurement, the reflow temperature profile (profile for lead-free assembly; peak temperature 260) described in IPC / JEDEC J-STD-020C ("Moisture / Reflow Sensitivity Classification For Nonhermetic Solid State Surface Devices", July 2004). The printed wiring board is passed once through a reflow apparatus that reproduces C), and one side of the printed wiring board is then heat treated with the reflow temperature profile in accordance with the above IPC / JEDEC J-STD-020C. Displacement data is obtained for grid lines provided on the other surface. In addition, as a reflow apparatus, Japanese Anttom Co., Ltd. product "HAS-6116" is mentioned, for example, As a shadow moire apparatus, Akrometrix make "TherMoire AXP" is mentioned, for example. 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 step can be suppressed and good mountability can be realized.

  Examples of the semiconductor device include various semiconductor devices provided for electric products (for example, computers, mobile phones, digital cameras, televisions and the like) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft and the like) and the like.

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) at the conduction portion of the printed wiring board of the present invention. The "conductive location" is a "location for transmitting an electrical signal in 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 in the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, the wire bonding mounting method, flip chip mounting method, no bump A mounting method using a buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a nonconductive film (NCF), and the like can be given. Here, "the mounting method using a bumpless build-up layer (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board to connect the semiconductor chip and the wiring on the printed wiring board". It is.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In the following description, "parts" means "parts by mass".

[Measurement method, evaluation method]
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 by the Example and the comparative example, melt viscosity was measured using the dynamic-viscoelasticity measuring apparatus ("Rheosol-G3000" made from Corporation | KK bM). For 1 g of the sample resin composition, using a parallel plate with a diameter of 18 mm, raise the temperature from start point 60 ° C to 200 ° C at a heating rate of 5 ° C / min, measure temperature interval 2.5 ° C, vibration 1Hz, strain 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 formation of the adhesive film and the minimum melt viscosity V ₂ (Poise) after storage for 72 hours at 23 ° C. and 60% humidity were measured. The lowest melt viscosity was evaluated according to the following evaluation criteria.
Evaluation criteria:
○: Both V ₁ and V ₂ are less than 15000 poise ×: At least one of V ₁ and V ₂ is 15000 poise or more

<Measurement of linear thermal expansion coefficient>
A resin composition layer is a polyimide film (Ube) using the batch type vacuum-pressure laminator (2 stage build-up laminator CVP 700 manufactured by Nichigo-Morton Co., Ltd.) using the adhesive film (200 mm square) prepared in Examples and Comparative Examples. The polyimide film was laminated at the center on one side so as to be in contact with the smooth surface of Kousei Co., Ltd. “UPILEX 25S, thickness 25 μm, 240 mm square). The lamination treatment was carried out by pressure-reducing for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

  The resulting laminated film is in contact with the glass film base epoxy resin double-sided copper-clad laminated sheet ("R5715 ES" manufactured by Matsushita Electric Works Co., Ltd., 0.7 mm thickness, 255 mm square) with the laminated film of the laminated film A glass cloth-based epoxy resin was placed on a double-sided copper-clad laminate, and the four sides of the laminated film were fixed with a polyimide adhesive tape (width 10 mm). Next, the resin composition layer was thermally cured by heating at 190 ° C. for 90 minutes.

  After heat curing, the polyimide adhesive tape was peeled off, and the laminated film was removed from the glass cloth-based epoxy resin double-sided copper-clad laminate. Further, the polyimide film and the support were peeled off from the laminated film to obtain a sheet-like cured product. The obtained cured product is cut into test pieces of 5 mm in width and 15 mm in length, and thermomechanical analysis is performed by a tensile load method using a thermomechanical analyzer ("Thermo Plus TMA 8310" manufactured by RIGAKU Co., Ltd.) The Specifically, after the test piece was attached to the thermomechanical analyzer, measurement was performed twice under a measurement condition of a load of 1 g and a temperature rising rate of 5 ° C./min. And in the second measurement, the average linear thermal expansion coefficient (α1; ppm / ° C) in the planar direction in the range of 25 ° C. to 150 ° C., and the average linear thermal expansion coefficient in the planar direction in the range of 150 ° C. to 250 ° C. (Α2; ppm / ° C.) was calculated.

<Preparation of a substrate for reflow behavior evaluation>
(1) Preparation of inner layer substrate As an inner layer substrate, a glass cloth-based epoxy resin laminate (unclad plate with a copper foil removed by etching, thickness 0.10 mm, "HL 832 NSF-LCA" manufactured by Mitsubishi Gas Chemical Co., Ltd.) Prepared.

(2) Lamination of adhesive film Using the batch-type vacuum pressure laminator (2 stage build-up laminator CVP 700 manufactured by Nichigo-Morton Co., Ltd.), the adhesive film prepared in the example and the comparative example was used as a resin composition layer as an inner layer. It laminated | stacked on both surfaces of the inner layer board | substrate so that a board | substrate might be touched. The lamination was performed by reducing the pressure for 30 seconds to make the air pressure 13 hPa or less, and then press-bonding at 100 ° C. under a pressure of 0.74 MPa for 30 seconds. Next, heat 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 under the curing conditions of 190 ° C. for 90 minutes to form an 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), it was passed once through a reflow apparatus ("HAS-6116" manufactured by Nippon Antom Co., Ltd.) that reproduces a solder reflow temperature with a peak temperature of 260 ° C Reflow temperature profile conforms to 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 The displacement of a 10 mm square portion at the center of the substrate was measured based on the grid lines. The reflow behavior was evaluated according to the following evaluation criteria.
Evaluation criteria:
○: The difference between the maximum height and the minimum height of displacement data in all temperature ranges is less than 35 μm for all five samples. ×: The difference between the maximum height and the minimum height of displacement data in all temperature ranges is at least 35 μm for at least one sample.

Example 1
12 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. “jER 828 EL”, epoxy equivalent weight about 185), 3 parts of naphthalene type epoxy resin (DIC Co., Ltd. “HP 4032 SS”, epoxy equivalent weight about 144), bixylenol type epoxy Resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent about 185) 6 parts, Biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC 3000H", epoxy equivalent about 288) 25 parts, phenoxy resin (Mitsubishi Chemical ( 10 parts of "YL7553BH30", MEK / cyclohexanone = 1/1 solution having a solid content of 30% by mass, was heated and dissolved in 20 parts of solvent naphtha while stirring. After cooling to room temperature, 10 parts of epoxy group-containing silicone compound ("X-40-2670" manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent 200, alkoxy group weight 0 mass%), triazine skeleton-containing phenol novolac 10 parts of a curing agent based on DIC (“LA-7054” manufactured by DIC Corporation, a MEK solution having a hydroxyl content of 125 and a solid content of 60 mass%), a curing agent based on active ester (“HPC8000-65T” manufactured by DIC), an active group Equivalent amount about 223, 16 parts of toluene solution of non-volatile component 65% by mass, 2 parts of curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution of solid content 5% by mass), flame retardant (manufactured by Sanko Co., Ltd.) HCA-HQ ", 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, plain Spherical silica (average particle diameter 0.5 μm, surface-treated with an aminosilane coupling agent (“KBM 573” manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts of particle diameter 2 μm) “SO-C2” manufactured by Admatex Co., Ltd. Then, 135 parts of a carbon amount of 0.39 mg / m ² ) per unit surface area were mixed and uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish.
Next, a resin varnish is applied so that the thickness of the resin composition layer after drying becomes 40 μm on the release layer side of an alkyd resin-based release layer-attached PET film (“AL5” manufactured by Lintec Co., Ltd., “AL 5”, thickness 38 μm). Were uniformly applied and dried at 80 to 120 ° C. (average 100 ° C.) for 5 minutes to produce an adhesive film.

Example 2
25 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000H", epoxy equivalent weight about 288), 8 parts of phenoxy resin (Mitsubishi Chemical Co., Ltd. "YL7553BH30", MEK solution having a solid content of 30% by mass) The mixture was heated and dissolved in 15 parts of solvent naphtha while stirring. After cooling to room temperature, 15 parts of epoxy group-containing silicone compound ("X-40-2670" manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent 200, alkoxy group content 0 mass%), bisphenol A dicyanate 35 parts of polymer (Lonza Japan Co., Ltd. "BA 230 S 75", cyanate equivalent about 232, MEK solution of non-volatile component 75 mass%), active ester curing agent (DIC Co. "HPC 8000-65T", active group equivalent about Non-volatile component 65 mass% of toluene solution 12 parts 12 parts, hardening accelerator (DMAP, MEK solution of solid content 5 mass%) 0.5 parts, hardening accelerator (manufactured by Tokyo Kasei Co., Ltd., cobalt (III) acetyl) Acetonato, 4 parts of MEK solution having a solid content of 1% by mass, a flame retardant (manufactured by Sanko Co., Ltd. “HCA-HQ”, 10- (2,5-dihydro) 3 parts of Siphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (average particle size 2 μm), surface with aminosilane coupling agent ("KBM 573" manufactured by Shin-Etsu Chemical Co., Ltd.) Mix 145 parts of treated spherical silica (average particle size 0.5 μm, "SO-C2", 0.39 mg / m ² of carbon per unit surface area, made by Admatex Co., Ltd.) and mix uniformly with a high-speed rotary mixer After dispersion, a resin varnish was prepared.
Subsequently, the adhesive film 2 was produced in the same procedure as Example 1 using the obtained resin varnish 2.

Example 3
Bisphenol 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 (Mitsubishi Chemical Co., Ltd.) "YX 4000 HK", epoxy equivalent weight about 185) 12 parts, dicyclopentadiene type epoxy resin (DIC Corporation "HP-7200H", epoxy equivalent weight about 275) 9 parts, phenoxy resin (Mitsubishi Chemical Co., Ltd. product "YL7553BH30", A solution of 30 parts by mass of MEK / cyclohexanone (1/1 solution) 15 parts was dissolved in 30 parts of solvent naphtha while heating and stirring. After cooling to room temperature, 4 parts of epoxy group-containing silicone compound ("X-40-2670" manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent 200, alkoxy group content 0 mass%), active ester curing agent ("HPC 8000-65T" manufactured by DIC Corporation, 40 equivalent active group equivalents of about 223, non-volatile component 65 mass% toluene solution), 3 parts curing accelerator (DMAP, 5 mass% MEK solution), aminosilane Spherical silica (average particle diameter 0.25 μm, surface-treated with a coupling agent (Shin-Etsu Chemical Co., Ltd. “KBM 573”), average particle diameter 0.25 μm, “SO-C1” manufactured by Admatechs Co., Ltd.) The resin varnish 3 was prepared by mixing 150 parts of 36 mg / m ² ) and uniformly dispersing with a high-speed rotary mixer.
Subsequently, using the resin varnish 3, an adhesive film 3 was produced in the same manner as in Example 1.

Comparative Example 1
(I) The content of the triazine skeleton-containing phenol novolac curing agent (“LA-7054” manufactured by DIC Corporation, a MEK solution having a hydroxyl content of 125 and a solid content of 60 mass%) changed to 18 parts, (ii) Active ester-based curing agent (manufactured by DIC Corporation “HPC8000-65T”, active group equivalent weight about 223, non-volatile component 65% by mass in toluene solution) replaced with 16 parts of a naphthol-based curing agent 12 parts of “SN 485”, hydroxyl equivalent 215, solid content 60 mass% MEK solution), (iii) 1.2 parts of curing accelerator (DMAP, solid content 5 mass% MEK solution) A resin varnish and an adhesive film were obtained in the same manner as in Example 1 except that the above was changed to.

Comparative Example 2
(I) The compounding amount of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation "jER 828EL", epoxy equivalent weight 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”, an epoxy equivalent of 200, and an alkoxy group content of 0 mass% were not used.

Comparative Example 3
(I) Not using naphthalene type epoxy resin ("HP4032SS" manufactured by DIC Corporation, epoxy equivalent of about 144), (ii) Bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. manufactured "jER828EL", epoxy equivalent 7) changing the blending amount of about 185) to 7 parts; (iii) not using bixylenol type epoxy resin (“YX 4000 HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), (iv) epoxy group In the same manner as Example 1 except that the blending amount of the silicone compound ("X-40-2670" manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent 200, alkoxy group weight 0 mass%) was changed to 24 parts. A resin varnish and an adhesive film were obtained.

Comparative Example 4
Epoxy group-containing silicone compound (Shin-Etsu Chemical Co., Ltd.) in place of 10 parts of epoxy group-containing silicone compound (Shin-Etsu Chemical Co., Ltd. “X-40-2670”, epoxy equivalent 200, alkoxy group weight 0 mass%) 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 weight 42% by mass were used.

Comparative Example 5
Epoxy group-free silicone compound (Shin-Etsu Chemical Co., Ltd. (Shin-Etsu Chemical Co., Ltd.) instead of 10 parts of epoxy group-containing silicone compound (Shin-Etsu Chemical Co., Ltd. “X-40-2670”, epoxy equivalent 200, alkoxy group weight 0 mass%) 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”, an alkoxy group weight of 15% by mass, was used.

Comparative Example 6
Epoxy group-free silicone compound (Shin-Etsu Chemical Co., Ltd. (Shin-Etsu Chemical Co., Ltd.) instead of 10 parts of epoxy group-containing silicone compound (Shin-Etsu Chemical Co., Ltd. “X-40-2670”, epoxy equivalent 200, alkoxy group weight 0 mass%) A resin varnish and an 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, and alkoxy group weight 7) were used.

Comparative Example 7
Phenolic novolac-type polyfunctional cyanate ester resin (Lonza Japan (Lonza Japan Co., Ltd.) instead of 12 parts of an active ester-based curing agent ("HPC8000-65T" manufactured by DIC Corporation, a toluene solution of 65% by A resin varnish and an adhesive film were obtained in the same manner as in Example 2 except that 8 parts of "PT30S", a cyanate equivalent of about 133, and a non-volatile component (MEK solution of 85% by mass) was used.

Claims (11)

(A) Epoxy resin (however, except for (D) component described later), (B) active ester curing agent, (C) inorganic filler, and (D) epoxy equivalent is 300 or less, and an alkoxy group Containing an epoxy group-containing silicone compound having a content of not more than 30% by mass 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. The resin composition of Claim 1 in which (D) component contains the structural unit represented by Formula (1).

(Wherein, 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 resin composition according to claim 2, wherein the component (D) has 3 to 10 structural units represented by the formula (1) in one molecule. R ¹ has the formula: X- (L) p _- 1 monovalent group represented by (wherein, X is an epoxy alkyl group, an epoxy cycloalkyl group or an epoxy aryl group, L is an alkylene group, a cycloalkylene group The resin composition according to claim 2 or 3, wherein arylene group, oxyalkylene group, oxycycloalkylene group or oxyarylene group is represented, and p represents 0 or 1.   The resin composition according to claim 4, wherein X is an epoxy cycloalkyl group having 4 to 10 carbon atoms. The resin composition of any one of Claims 1-5 in which (D) component contains the compound represented by Formula (2-1).

  The resin composition according to any one of claims 1 to 6, wherein the component (C) is silica.   The resin composition according to any one of claims 1 to 7, wherein the average particle diameter of the component (C) is 0.01 to 4 μm.   The resin composition according to any one of claims 1 to 8, which is 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.