KR20210127680A - Resin composition - Google Patents

Abstract

Provided is a resin composition forming an insulating layer capable of suppressing bending in a component mounting process. The present invention relates to a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein the component (C) is surface-treated with a silane coupling agent and an alkoxysilane compound, the mass ratio of the silane coupling agent to the alkoxysilane compound (the silane coupling agent : the alkoxysilane compound) is 1 : 9 to 9 : 1, and the content of the component (C) is 40 mass% or more when the nonvolatile component in the resin composition is 100 mass%.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition.

As a manufacturing technique of a printed wiring board, the manufacturing method by the buildup system which laminates|stacks an insulating layer and a conductor layer alternately is known. In the manufacturing method by a build-up system, an insulating layer is generally formed by hardening a resin composition. For example, Patent Document 1 discloses a technique for forming an insulating layer by curing a resin composition containing an inorganic filler surface-treated with an alkoxysilane compound.

Patent Document 1: Japanese Patent Laid-Open No. 2014-12763

With the recent replacement from solder-containing solder to lead-free solder, the solder reflow temperature in the component mounting process is rising. Moreover, in recent years, in order to achieve size reduction of an electronic device, further thinning of a printed wiring board is advancing.

The inventors of the present invention discovered that, as the thickness of the printed wiring board progressed, warpage occurred in the printed wiring board in the component mounting process, resulting in problems such as circuit deformation and poor contact of components.

The subject of this invention is providing the resin composition which forms the insulating layer which can suppress the curvature in the mounting process of a component.

As a result of earnestly examining the above subject, the present inventors solve the above problem by using a predetermined amount of an inorganic filler surface-treated with a silane coupling agent and an alkoxysilane compound so that the mass ratio of the silane coupling agent and the alkoxysilane compound is in a specific range. It has been found that it can be solved, and the present invention has been completed.

That is, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,

(C) component is surface-treated with a silane coupling agent and an alkoxysilane compound, the mass ratio of the silane coupling agent and the alkoxysilane compound (silane coupling agent: alkoxysilane compound) is 1:9 to 9:1,

When the nonvolatile component in a resin composition is 100 mass %, content of (C)component is 40 mass % or more, The resin composition.

[2] The resin composition according to [1], wherein the amount of carbon per unit surface area of the component (C) is 0.05 mg/m 2 to 1 mg/m 2 .

[3] The resin composition according to [1] or [2], wherein the amount of carbon derived from the silane coupling agent per unit surface area of the component (C) is 0.03 mg/m 2 to 0.8 mg/m 2 .

[4] The component (C) according to any one of [1] to [3], comprising (C1) an inorganic filler surface-treated with a silane coupling agent, and (C2) an inorganic filler surface-treated with an alkoxysilane compound. which is a resin composition.

[5] The resin composition according to any one of [1] to [4], wherein the component (C) contains an inorganic filler surface-treated with both (C3) a silane coupling agent and an alkoxysilane compound. .

[6] The resin composition according to [5], wherein the component (C3) is obtained by simultaneously surface-treating the inorganic filler with a silane coupling agent and an alkoxysilane compound.

[7] The resin composition according to any one of [1] to [6], wherein the inorganic filler has an average particle diameter of 0.01 µm to 5 µm.

[8] The resin composition according to any one of [1] to [7], wherein the content of the component (C) is 60% by mass to 90% by mass, when the nonvolatile component in the resin composition is 100% by mass.

[9] The resin composition according to any one of [1] to [8], wherein the inorganic filler is silica.

[10] The silane coupling agent according to any one of [1] to [9], wherein the silane coupling agent is one selected from the group consisting of an amino group, an epoxy group, a mercapto group, a (meth)acrylic group, a vinyl group, an isocyanate group, and an imidazolyl group. A resin composition having the above functional groups.

[11] The alkoxysilane compound according to any one of [1] to [10], wherein the alkoxysilane compound is monoaryltrialkoxysilane, diaryldialkoxysilane, monoalkyltrialkoxysilane, dialkyldialkoxysilane, or monoalkylmonoaryldialkoxy. At least one selected from the group consisting of silane, diarylmonoalkylmonoalkoxysilane, and dialkylmonoarylmonoalkoxysilane, the resin composition.

[12] The component (A) according to any one of [1] to [11], wherein the component (A) is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, At least one selected from the group consisting of a naphthylene ether type epoxy resin, a glycidyl ester type epoxy resin, an anthracene type epoxy resin, and an epoxy resin having a butadiene structure, a resin composition.

[13] The resin composition according to any one of [1] to [12], wherein the component (B) is at least one selected from the group consisting of a phenol-based curing agent, an active ester-based curing agent, and a cyanate ester-based curing agent.

[14] The resin composition according to any one of [1] to [13], which is a resin composition for an insulating layer of a multilayer printed wiring board.

[15] A sheet-like laminated material comprising the layer of the resin composition according to any one of [1] to [14].

[16] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [14].

[17] A semiconductor device comprising the printed wiring board according to [16].

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which forms the insulating layer which can suppress the curvature in the mounting process of a component can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on suitable embodiment.

[resin composition]

The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent and (C) an inorganic filler, the component (C) is surface-treated with a silane coupling agent and an alkoxysilane compound, and a silane coupling agent and When the mass ratio of the alkoxysilane compound (silane coupling agent: alkoxysilane compound) is 1:9 to 9:1 and the nonvolatile component in the resin composition is 100 mass%, the content of the component (C) is 40 mass% or more do.

<(A) Epoxy resin>

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, naphthylene. Ether type epoxy resin, glycidyl ester type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, Anthracene type epoxy resin, glycidyl amine type epoxy resin, cresol novolak type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane A dimethanol-type epoxy resin, a trimethylol-type epoxy resin, a tetraphenylethane-type epoxy resin, etc. are mentioned. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

Among these, from the viewpoint that a resin composition exhibiting a suitable melt viscosity can be obtained, and from the viewpoint that an insulating layer excellent in heat resistance and peel strength (peel strength) with the conductor layer can be obtained, as an epoxy resin, a bisphenol A type epoxy resin , Bisphenol F-type epoxy resin, naphthol-type epoxy resin, naphthalene-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, glycidyl ester-type epoxy resin, anthracene-type epoxy resin, and epoxy resin having a butadiene structure At least one selected from the group consisting of is preferable.

It is preferable that an epoxy resin contains the epoxy resin which has two or more epoxy groups in 1 molecule. When the nonvolatile component of an epoxy resin is 100 mass %, it is preferable that at least 50 mass % or more is an epoxy resin which has two or more epoxy groups in 1 molecule. Among them, an epoxy resin having two or more epoxy groups in one molecule and liquid at a temperature of 20°C (hereinafter referred to as “liquid epoxy resin”), and three or more epoxy groups in one molecule, and solid epoxy at a temperature of 20°C It is preferable to contain resin (henceforth "solid epoxy resin"). As the epoxy resin, a resin composition having excellent flexibility can be obtained by using a liquid epoxy resin and a solid epoxy resin together. Moreover, the breaking strength of the hardened|cured material of a resin composition also improves.

As the liquid epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin having an ester skeleton, and butadiene structure The epoxy resin which has is preferable, and a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a naphthalene type epoxy resin are more preferable. As a specific example of a liquid epoxy resin, "HP4032", "HP4032H", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, "jER828EL" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol A type) Epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "ZX1059" (bisphenol A type epoxy resin and bisphenol F by Shin-Nittetsu Sumikin Chemical Co., Ltd.) Mixed product of type epoxy resin), "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemutex Co., Ltd., "Seroki Saido 2021P" manufactured by Daiseru Co., Ltd. (having an ester skeleton) alicyclic epoxy resin) and "PB-3600" (epoxy resin which has a butadiene structure) is mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid-state epoxy resin include naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, Anthracene-type epoxy resins, bisphenol A-type epoxy resins, and tetraphenylethane-type epoxy resins are preferable, and naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, and anthracene-type epoxy resins are more preferable. As a specific example of a solid-state epoxy resin, "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation, "N-690" (cresol novolac type epoxy resin), "N- 695" (cresol novolak type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" "(naphthylene ether type epoxy resin), "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000" , "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolak type epoxy resin) manufactured by Shin-Nittetsu Chemical Co., Ltd., Mitsubishi "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin (biphenyl type epoxy resin)), "YX8800" (anthracene type epoxy resin) manufactured by Chemical Industry Co., Ltd. "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" (fluorene-type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "jER1010" manufactured by Mitsubishi Chemical Co., Ltd. ' (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), etc. are mentioned.

As an epoxy resin, when using a liquid epoxy resin and a solid epoxy resin together, these ratio (liquid epoxy resin:solid epoxy resin) is mass ratio, and the range of 1:0.1 - 1:6 is preferable. By setting the ratio of the liquid epoxy resin to the solid epoxy resin within this range, i) can bring about proper adhesion when used in the form of a sheet-like laminated material, and ii) sufficient flexibility when used in the form of a sheet-like laminated material properties can be obtained, handling properties are improved, iii) a cured product having sufficient breaking strength can be obtained, and the like. From the viewpoint of the effects of i) to iii) above, the amount ratio of the liquid epoxy resin and the solid epoxy resin (liquid epoxy resin:solid epoxy resin) is, in terms of mass ratio, more preferably in the range of 1:0.3 to 1:5, 1 The range of :0.6 to 1:4 is more preferable.

When content of the epoxy resin in a resin composition makes the non-volatile component in a resin composition 100 mass %, Preferably it is 3 mass % - 40 mass %, More preferably, it is 5 mass % - 35 mass %, More preferably It is 7 mass % - 30 mass %.

The epoxy equivalent of an epoxy resin becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. By being in this range, the crosslinking density of hardened|cured material becomes enough, and the insulating layer with small surface roughness can be formed. In addition, an epoxy equivalent can be measured according to JISK7236, It is the mass of resin containing 1 equivalent of an epoxy group.

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

<(B) curing agent>

The curing agent (A) is not particularly limited as long as it has a function of curing the epoxy resin, for example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, and an acid and anhydride systems. A hardening|curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

Among these, at least one selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a cyanate ester-based curing agent is preferable from the viewpoint of obtaining an insulating layer having excellent heat resistance, and a phenol-based curing agent is preferable. At least one selected from the group consisting of a curing agent, an active ester curing agent, and a cyanate ester curing agent is more preferable.

As the phenol-based curing agent and the naphthol-based curing agent, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable. Moreover, from a viewpoint of the peeling strength with a conductor layer, a nitrogen-containing phenol-type hardening|curing agent or a nitrogen-containing naphthol-type hardening|curing agent is preferable, and a triazine skeleton containing phenolic hardening|curing agent or triazine skeleton containing naphthol-type hardening|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 peel strength with a conductor layer. These may be used individually by 1 type, and may be used in combination of 2 or more type.

As a specific example of a phenol type hardening|curing agent and a naphthol type hardening|curing agent, For example, Meiwa Chemical Co., Ltd. product "MEH-7700", "MEH-7810", "MEH-7851", Nippon Kayaku Co., Ltd. product " NHN", "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485" manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd. ', "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-1356" manufactured by DIC Corporation, "TD2090" etc. are mentioned.

Although there is no restriction|limiting in particular as an active ester type hardening|curing agent, Generally, ester groups with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters, are 2 in 1 molecule. Compounds having at least one compound are preferably used. It is preferable that the said active ester type hardening|curing agent is obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound, and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol to one molecule of dicyclopentadiene.

Examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoyl product of phenol novolac. The active ester compound containing is preferable, and among these, the active ester compound containing the naphthalene structure and the active ester compound containing the dicyclopentadiene type diphenol structure are more preferable. These may be used individually by 1 type, and may be used in combination of 2 or more type. In addition, "dicyclopentadiene type diphenol structure" represents the divalent structural unit which consists of phenylene-dicyclopentylene-phenyl.

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

As a specific example of a benzoxazine type hardening|curing agent, "HFB2006M" by Showa Kobunshi Co., Ltd., "P-d" by Shikoku Kasei Kogyo Co., Ltd. product, and "F-a" are mentioned.

Although it does not specifically limit as a cyanate ester type hardening|curing agent, For example, a novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening|curing agent, a dicyclopentadiene type cyanate ester type hardening|curing agent, bisphenol Type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate ester type hardening|curing agent, the prepolymer etc. which triazined these in part are mentioned. Specific examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis (2,6-dimethylphenyl cyanate), 4 ,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and Bifunctional cyanate resins, such as bis (4-cyanate phenyl) ether, polyfunctional cyanate resin derived from phenol novolak, cresol novolak, etc., the prepolymer etc. which these cyanate resin were triazine-ized in part are mentioned. As a commercial item of a cyanate ester type hardening|curing agent, "PT30" and "PT60" (all are phenol novolak-type polyfunctional cyanate ester resin) manufactured by Ronza Japan Co., Ltd., "BA230" (part or all of bisphenol A dicyanate) prepolymer) etc. which were triazine-formed and became a trimer are mentioned.

Although it does not specifically limit as an acid anhydride type hardening|curing agent, For example, For example, phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, methyl tetrahydro phthalic anhydride, methyl hexahydro phthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride , trialkyl tetrahydro phthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, anhydride Trimellitic acid, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl)-naphth [1,2-C] furan-1, and polymeric acid anhydrides such as 3-dione, ethylene glycol bis(anhydro trimellitate), and styrene/maleic acid resin copolymerized with styrene and maleic acid.

The amount ratio of the epoxy resin and the curing agent is from the viewpoint of improving the mechanical strength and water resistance of the obtained insulating layer, [the total number of epoxy groups of the epoxy resin]: [the total number of reactive groups of the curing agent] in a ratio of 1:0.2 to 1 The range of :2 is preferable, the range of 1:0.3 to 1:1.5 is more preferable, and the range of 1:0.4 to 1:1 is still more preferable. Here, a reactive group of a hardening|curing agent is an active hydroxyl group, an active ester group, etc., and it changes with the kind of hardening|curing agent. In addition, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is the solid content mass of each curing agent equal to the reactor equivalent. The value divided by , is the sum of all curing agents.

<(C) Inorganic filler>

The material of the inorganic filler is not particularly limited, and for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotal. Site, boehmite, aluminum hydroxide, 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 zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as a silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. As a commercial item of spherical silica, "SO-C1", "SO-C2", "SC1500SQ", "SC2050SQ" etc. manufactured by Adomatex Corporation are mentioned, for example.

Although the average particle diameter of an inorganic filler is not specifically limited, From a viewpoint of obtaining the insulating layer on which fine wiring can be formed, 5 micrometers or less are preferable, 3 micrometers or less are more preferable, 2 micrometers or less, 1 ㎛ or less, 0.7 mu m or less, 0.5 mu m or less, 0.4 mu m or less, or 0.3 mu m or less is more preferable. On the other hand, from the viewpoint of obtaining a resin varnish having a suitable viscosity and good handleability when forming a resin varnish using the resin composition, the average particle diameter of the inorganic filler is preferably 0.01 µm or more, and more preferably 0.03 µm or more. and more preferably 0.05 µm or more, 0.07 µm or more, or 0.1 µm or more. The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle size distribution of an inorganic filler on a volume basis with a laser diffraction type particle size distribution measuring apparatus, and making this median diameter into an average particle diameter. As a measurement sample, what disperse|distributed the inorganic filler in water by ultrasonic wave can be used preferably. As a laser diffraction type particle size distribution measuring apparatus, "LA-500", "LA-750", "LA-950" manufactured by Horiba Corporation, "LA-950", etc. can be used.

In the resin composition of the present invention, the inorganic filler is surface-treated with a silane coupling agent and an alkoxysilane compound, and the mass ratio of the silane coupling agent and the alkoxysilane compound (silane coupling agent:alkoxysilane compound) is 1:9 to 9: It is characterized as 1.

In the production of a printed wiring board, a resin composition containing an inorganic filler surface-treated with an alkoxysilane compound has a low surface roughness after roughening treatment and forms an insulating layer excellent in adhesion strength (peel strength) with the conductor layer It is known (Japanese Patent Laid-Open No. 2014-12763). However, it has not been examined in relation to the warpage in the component mounting process. The present inventors discovered that, in a thin printed wiring board, it may be difficult to suppress the curvature in the mounting process of a component even if it used such a resin composition. In addition, although a silane coupling agent is known as a surface treatment agent for an inorganic filler, a resin composition containing an inorganic filler surface-treated with a silane coupling agent is also a thin printed wiring board. It is difficult to suppress warpage in the component mounting process The present inventors have confirmed that there are cases. In addition, regarding the resin composition containing the inorganic filler surface-treated with the silane coupling agent in a fixed amount or more, it tends to result in high melt viscosity, and may cause lamination|stacking defect at the time of manufacture of a printed wiring board.

The present inventors suppress warpage in the mounting process of components even in a thin printed wiring board by using an inorganic filler surface-treated with a silane coupling agent and an alkoxysilane compound so that the mass ratio of the silane coupling agent and the alkoxysilane compound is within a specific range. found that it can be done. The inorganic filler surface-treated with such a silane coupling agent and an alkoxysilane compound also has a melt viscosity in an appropriate range, even when content in a resin composition is raised, and can form the resin composition which shows favorable lamination|stacking property.

-Silane coupling agent-

In the present invention, the silane coupling agent refers to a silane compound having a functional group contributing to bonding with an inorganic filler and a functional group contributing to bonding with an organic component such as an epoxy resin.

As a functional group contributing to bonding with an inorganic filler, a hydroxyl group and an alkoxy group are mentioned, for example. These may be contained individually by 1 type, and may be contained in combination of 2 or more type. Especially, an alkoxy group is preferable from a viewpoint that an inorganic filler can be surface-treated efficiently. The alkoxy group may be linear, branched, or cyclic. The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, still more preferably 1 or 2. The silane coupling agent has preferably 1 to 3, more preferably 2 or 3 functional groups contributing to bonding with the inorganic filler in one molecule.

Examples of the functional group contributing to bonding with the organic component include an amino group, an epoxy group, a mercapto group, a (meth)acryl group, a vinyl group, an isocyanate group, an imidazolyl group, a ureido group, a sulfide group, and an isocyanurate group. can be lifted These may be contained individually by 1 type, and may be contained in combination of 2 or more type. Among them, amino group, epoxy group, mercapto group, (meth)acryl group, vinyl group, isocyanate group and imida from the viewpoint that warpage in the component mounting process can be further suppressed in combination with the alkoxysilane compound described later. At least one selected from the group consisting of a jolyl group is preferable. The silane coupling agent has, in one molecule, a functional group that contributes to bonding with an organic component, preferably 1 to 3, more preferably 1 or 2 groups.

The molecular weight of the silane coupling agent is preferably 100 or more, more preferably 120 or more, still more preferably 140 or more, 160 or more, 180 or more, or 200 or more from the viewpoint of suppressing volatilization during surface treatment or drying. . From the viewpoint of appropriate reactivity, the upper limit of the molecular weight is preferably 800 or less, more preferably 750 or less, still more preferably 700 or less, 650 or less, 600 or less, 550 or less, 500 or less, 450 or less, or 400 or less. am.

In one embodiment, the silane coupling agent is a silane compound represented by the following formula (1).

[ Formula 1 ]

Si(X) _m1 (R ¹ ) _m2 (R ² ) _4-m1-m2

[of formula 1,

X is an amino group, an epoxy group, a mercapto group, a (meth) acryl group, a vinyl group, an isocyanate group, an imidazolyl group, a ureido group, a sulfide group, and a monovalent containing a functional group selected from the group consisting of an isocyanurate group represents the flag,

R ¹ represents a hydroxyl group or an alkoxy group,

R ² represents a hydrogen atom, an alkyl group or an aryl group,

m1 and m2 represent the integers of 1-3, respectively, on the conditional condition that the sum of m1 and m2 is 4 or less. When two or more X's exist, these may be the same or different, when two or more R<^1> exists, these may be same or different, and when ^{two or more R<2>} exist, these may be same or different]

The number of carbon atoms in the monovalent group represented by X is preferably 20 or less, more preferably 14 or less, still more preferably 12 or less, 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less. The lower limit of the number of carbon atoms varies depending on the functional group contained in the monovalent group represented by X, but is preferably 1 or more, more preferably 2 or more or 3 or more. From the viewpoint that warpage in the component mounting process can be further suppressed in combination with an alkoxysilane compound described later, as the monovalent group represented by X, an amino group, an epoxy group, a mercapto group, a (meth)acryl group, a vinyl group , a monovalent group containing at least one functional group selected from the group consisting of an isocyanate group and an imidazolyl group is preferable.

Specific examples of the monovalent group represented by X include N-(aminoC _1-10 alkyl) _{-aminoC 1-10} alkyl group, N-(phenyl) _{-aminoC 1-10} alkyl group, N-(C _1-10 alkylidene). )-Amino C _1-10 alkyl group, (epoxy C _3-10 cycloalkyl) C _1-10 alkyl group, glycidoxy C _1-10 alkyl group, glycidyl C _1-10 alkyl group, mercapto C _1-10 alkyl group, Acryloxy C _1-10 alkyl group, methacryloxy C _1-10 alkyl group, vinyl group, styryl group, isocyanate C _1-10 alkyl group, imidazolyl C _1-10 alkyl group, ureido C _1-10 alkyl group, tri (C _1-10 alkoxy)silyl C _1-10 alkyltetrasulfide C _1-10 alkyl group, and di[tri(C _1-10 alkoxy)silyl C _1-10 alkyl] isocyanurate C _1-10 alkyl group. . Among them, N-(aminoC _1-10 alkyl) _{-aminoC 1-10} alkyl group, N-(phenyl) _{-aminoC 1-10} alkyl group, N-(C _1-10 alkylidene) _{-aminoC 1-10} alkyl group , (epoxy C _3-10 cycloalkyl) C _1-10 alkyl group, glycidoxy C _1-10 alkyl group, glycidyl C _1-10 alkyl group, mercapto C _1-10 alkyl group, acryloxy C _1-10 alkyl group, Methacryloxy C _1-10 alkyl group, vinyl group, styryl group, and isocyanate C _1-10 alkyl group, imidazolyl C _1-10 alkyl group is preferable, N-(2-aminoethyl)-3-aminopropyl group; N-(phenyl)-3-aminopropyl group, N-(1,3-dimethyl-butylidene)aminopropyl group, (3,4-epoxycyclohexyl)ethyl group, glycidoxypropyl group, glycidylpropyl group A group, a mercaptopropyl group, an acryloxypropyl group, a methacryloxypropyl group, a vinyl group, a styryl group, and an isocyanatepropyl group are particularly preferable.

The term “C _pq ” (p and q are positive integers, satisfying p < q) indicates that the number of carbon atoms in the organic group described immediately after this term is p to q. For example, "C _1-10 alkyl group" represents an alkyl group having 1 to 10 carbon atoms.

The ^{alkoxy group represented by R 1} may be linear, branched or cyclic. The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, still more preferably 1 or 2.

As R<^1> , an alkoxy group is preferable from a viewpoint that an inorganic filler can be surface-treated efficiently.

The ^{alkyl group represented by R 2} may be linear, branched or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4.

The ^{number of carbon atoms in the aryl group represented by R 2} is preferably 6 to 20, more preferably 6 to 14, still more preferably 6 to 10.

As R ^{2 , an} alkyl group is preferable.

In the formula (1), m1 and m2 each represent an integer of 1 to 3 on condition that the sum of m1 and m2 is 4 or less. m1 is preferably 1 or 2, and m2 is preferably 2 or 3.

Examples of suitable silane coupling agents include N-(phenyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltri Methoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3- Acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, [3-(1-imidazolyl)propyl] trimethoxysilane, 3-ureidopropyltriethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and tris(trimethoxysilylpropyl)isocyanurate are mentioned.

As a commercial item of a silane coupling agent, "KBM573" (N-phenyl-3-aminopropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) is, for example, ), "KBM403" (3-glycidoxypropyl trimethoxysilane), "KBM803" (3-mercaptopropyl trimethoxysilane), etc. are mentioned.

A silane coupling agent may be used individually by 1 type, and may be used in combination of 2 or more type.

-Alkoxysilane compound-

In this invention, an alkoxysilane compound is different from a silane coupling agent at the point which does not have the functional group which says the silane compound which has an alkoxy group, and contributes to bonding with organic components, such as an epoxy resin, at least.

The alkoxy group which the alkoxysilane compound has may be linear, branched, or cyclic any. The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, still more preferably 1 or 2. An alkoxysilane compound has an alkoxy group in 1 molecule, Preferably it is 1-3 pieces, More preferably, it has 2 or 3 pieces.

It is preferable that the alkoxysilane compound also has an alkyl group or an aryl group. The alkyl group may be linear, branched or cyclic, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, 1 to 6, 1 to 4, or 1-3. . The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 14, still more preferably 6 to 10. An alkoxysilane compound has an alkyl group or an aryl group in 1 molecule, Preferably it is 1-3 pieces, More preferably, it has 1 or 2 pieces.

The molecular weight of the alkoxysilane compound is preferably 100 or more, more preferably 110 or more, still more preferably 120 or more from the viewpoint of suppressing volatilization at the time of surface treatment or drying. From the viewpoint of appropriate reactivity, the upper limit of the molecular weight is preferably 1000 or less, more preferably 700 or less, still more preferably 400 or less, still more preferably 300 or less, 280 or less, 260 or less, 240 or less, 220 or less. or less or 200 or less.

In one embodiment, the alkoxysilane compound is a silane compound represented by the formula (2).

[ Formula 2 ]

Si(R ³ ) _n (R ⁴ ) _4-n

[Formula 2,

R ³ represents an alkoxy group,

R ⁴ represents a hydrogen atom, an alkyl group or an aryl group,

n represents the integer of 1-3. When two or more R ³ exist, these may be the same or different, and when two or more R ⁴ exists, these may be same or different]

The ^{alkoxy group represented by R 3} may be linear, branched or cyclic. The number of carbon atoms in the alkoxy group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, still more preferably 1 or 2.

The ^{alkyl group represented by R 4} may be linear, branched or cyclic, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, 1 to 6, 1 to 4, or 1 to 3

The ^{number of carbon atoms in the aryl group represented by R 4} is preferably 6 to 20, more preferably 6 to 14, still more preferably 6 to 10.

R ⁴ is preferably an alkyl group or an aryl group.

n represents the integer of 1-3, Preferably it is 1 or 2.

Examples of the alkoxysilane compound include monoaryltrialkoxysilane, diaryldialkoxysilane, monoalkyltrialkoxysilane, dialkyldialkoxysilane, monoalkylmonoaryldialkoxysilane, diarylmonoalkylmonoalkoxysilane and dialkyl. Monoaryl monoalkoxy silane is mentioned. The number of carbon atoms in the alkyl moiety, aryl moiety, and alkoxy moiety is as described above.

Suitable alkoxysilane compounds include, for example, phenyltrialkoxysilane, dimethylalkoxysilane, methyltrialkoxysilane, diethyldialkoxysilane, ethyltrialkoxysilane, diphenyldialkoxysilane, methylphenyldialkoxysilane, and diphenylmethyl. Monoalkoxysilane is mentioned. The number of carbon atoms in the alkoxy moiety is as described above.

As a commercial item of an alkoxysilane compound, "KBM103" (phenyltrimethoxysilane), "KBE103" (phenyltriethoxysilane), "KBM22" (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. are, for example, ), "KBM3103" (decyltrimethoxysilane), etc. are mentioned.

An alkoxysilane compound may be used individually by 1 type, and may be used in combination of 2 or more type.

The mass ratio of the silane coupling agent and the alkoxysilane compound used for surface treatment (silane coupling agent: alkoxysilane compound) is 1:9 to 9:1 from the viewpoint of suppressing warpage in the component mounting process, preferably 2:8 to 8:2, more preferably 3:7 to 7:3.

In one embodiment, the resin composition of the present invention contains, as component (C), (C1) an inorganic filler surface-treated with a silane coupling agent, and (C2) an inorganic filler surface-treated with an alkoxysilane compound (hereinafter referred to as alkoxysilane compound). , also referred to as "the first embodiment").

In component (C1), the amount of the silane coupling agent used for the surface treatment of the inorganic filler is not particularly limited as long as the amount of carbon per unit surface area of the inorganic filler is in the desired range described later, but with respect to 100 parts by mass of the inorganic filler , Preferably it is 0.001 mass part, More preferably, it is 0.01 mass part or more, More preferably, it is 0.05 mass part or more, More preferably, it is 0.1 mass part or more. Preferably the upper limit of the quantity of the said silane coupling agent is 5 mass parts or less with respect to 100 mass parts of inorganic fillers, More preferably, it is 4 mass parts or less, More preferably, it is 3 mass parts or less.

(C1) Component WHEREIN: The method of surface treatment is not specifically limited, For example, a dry method and a wet method are mentioned. You may perform surface treatment by a dry method in the following procedure. First, an inorganic filler is poured into a rotary mixer, and a silane coupling agent is dripped or sprayed, stirring. Then, it heats, further stirring, and dehydration-condensation of a silane coupling agent and an inorganic filler is carried out. You may perform surface treatment by a wet method in the following procedure. First, a silane coupling agent is added and stirred while stirring a slurry containing an inorganic filler and a solvent/dispersion medium. Then, the obtained mixture is filtered and dried. Then, the silane coupling agent and the inorganic filler are dehydrated and condensed by heating.

(C2) component WHEREIN: Although the quantity of the alkoxysilane compound used for surface treatment of an inorganic filler is not specifically limited as long as the amount of carbon per unit surface area of an inorganic filler becomes the desired range mentioned later, With respect to 100 mass parts of inorganic fillers , Preferably it is 0.001 mass part, More preferably, it is 0.01 mass part or more, More preferably, it is 0.05 mass part or more, More preferably, it is 0.1 mass part or more. Preferably the upper limit of the quantity of the said alkoxysilane compound is 5 mass parts or less with respect to 100 mass parts of inorganic fillers, More preferably, it is 4 mass parts or less, More preferably, it is 3 mass parts or less.

(C2) Component WHEREIN: The method of surface treatment is not specifically limited, You may make it similar to the method demonstrated for (C1) component except the point using an alkoxysilane compound.

In the first embodiment, the mass ratio of the component (C1) and the component (C2) may be appropriately determined so that the mass ratio of the silane coupling agent to the alkoxysilane compound is within the desired range. As long as the mass ratio of a silane coupling agent and an alkoxysilane compound becomes the said desired range, 2 or more types of (C1) components may be used and 2 or more types of (C2) components may be used. In addition, as long as the mass ratio of a silane coupling agent and an alkoxysilane compound becomes the said desired range, the resin composition of 1st Embodiment of this invention adds to (C1) component and (C2) component, (C3) mentioned later You may contain an ingredient.

In another embodiment, the resin composition of this invention contains the inorganic filler surface-treated with both (C3) a silane coupling agent and an alkoxysilane compound as (C)component (henceforth "2nd embodiment") box).

(C3) Component WHEREIN: The total amount of the silane coupling agent and alkoxysilane compound used for surface treatment of an inorganic filler is not specifically limited as long as the amount of carbon per unit surface area of an inorganic filler becomes the desired range mentioned later, Inorganic filler To 100 mass parts, Preferably it is 0.001 mass part, More preferably, it is 0.01 mass part or more, More preferably, it is 0.05 mass part or more, More preferably, it is 0.1 mass part or more. To [ the upper limit of the said total amount / 100 mass parts of inorganic fillers ], Preferably it is 5 mass parts or less, More preferably, it is 4 mass parts or less, More preferably, it is 3 mass parts or less.

(C3) Component WHEREIN: The method of surface treatment is not specifically limited, You may make it similar to the method demonstrated for (C1) component except the point using both a silane coupling agent and an alkoxysilane compound. The procedure of the surface treatment is not particularly limited as long as an inorganic filler surface-treated with both a silane coupling agent and an alkoxysilane compound is obtained, for example, i) a surface treatment with a silane coupling agent and an alkoxysilane compound may be performed simultaneously, ii) After surface treatment with a silane coupling agent, the surface may be treated with an alkoxysilane compound, and iii) after surface treatment with an alkoxysilane compound, the surface may be surface treated with a silane coupling agent.

From the viewpoint of being able to further suppress the warpage in the component mounting process, the second embodiment is preferable, and among them, since the warpage in the component mounting step can be remarkably reduced, the component (C3) is an inorganic filler with a silane coupling agent. It is particularly preferably obtained by simultaneously surface-treating with a ring agent and an alkoxysilane compound.

In 2nd Embodiment, as long as the mass ratio of a silane coupling agent and an alkoxysilane compound becomes the said desired range, you may use 2 or more types of (C3) components.

From the viewpoint of sufficiently suppressing warpage in the component mounting process without distinguishing between the first embodiment and the second embodiment, the amount of carbon per unit surface area of component (C) is preferably 0.05 mg/m 2 or more, and 0.1 mg/m 2 or more is more preferable, and 0.2 mg/m 2 or more is still more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or melt viscosity in the sheet form, 1 mg/m 2 or less is preferable, 0.8 mg/m 2 or less is more preferable, and 0.5 mg/m 2 or less is still more preferable.

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

When component (C) contains a plurality of types of inorganic fillers, the amount of carbon per unit surface area of component (C) is measured by measuring the amount of carbon per unit surface area for each inorganic filler used for component (C), , what is necessary is just to calculate|require the said measured value by weighting average by the mass of each inorganic filler. For example, when using a 1st inorganic filler and a 2nd inorganic filler for (C) component, the amount of carbon per unit surface area of (C) component is the amount of carbon per unit surface area of a 1st inorganic filler, and What is necessary is just to calculate|require the amount of carbon per unit surface area of 2 inorganic fillers by weighted average of the surface area of a 1st inorganic filler, and the surface area of a 2nd inorganic filler. Here, the surface area of the inorganic filler may be obtained by multiplying the mass and the specific surface area of the inorganic filler. 1st Embodiment WHEREIN: The component (C1) may be sufficient as the said "1st inorganic filler", and the component (C2) may be sufficient as the said "2nd inorganic filler". In the second embodiment, when two kinds of (C3) components, namely, the first (C3) component and the second (C3) component are included, the “first inorganic filler” is the first (C3) component. ) component may be sufficient, and the 2nd (C3) component may be sufficient as the said "2nd inorganic filler". Also when using 3 or more types of inorganic fillers, the amount of carbon can be calculated|required by a weighted average similarly.

From the viewpoint of being able to further suppress warpage in the component mounting process, the amount of carbon derived from the silane coupling agent per unit surface area of component (C) is preferably 0.03 mg/m 2 or more, and more preferably 0.07 mg/m 2 or more. It is preferable, and 0.15 mg/m<2> or more is more preferable. On the other hand, from the viewpoint of preventing an increase in melt viscosity of the resin varnish or melt viscosity in sheet form, 0.8 mg/m 2 or less is preferable, 0.6 mg/m 2 or less is more preferable, and 0.4 mg/m 2 or less or 0.3 mg/m 2 or less. m2 or less is more preferable. Here, in 1st Embodiment, what is necessary is just to calculate|require the carbon amount derived from a silane coupling agent per unit surface area of (C) component based on the carbon amount per unit surface area of (C1) component. Specifically, the amount of carbon per unit surface area of component (C1) is c1 [mg/m2], the specific surface area of component (C1) is a1 [m2], and the mass of component (C1) is m1 [g], (C2) ) when the carbon content of the component is c2 [mg/m2], the specific surface area of the component (C2) is a2 [m2], and the mass of the component (C2) is m2 [g], (C) per unit surface area of the component , The amount of carbon A _c1 derived from the silane coupling agent is computable by the formula: A _c1 = (c1×a1×m1)/[(a1×m1)+(a2×m2)]. Further, in the second embodiment, (C) the carbon amount of the unit surface area of component A _c [mg / ㎡], the mass of the silane coupling agent m3 [g], per carbon content per unit mass of such a silane coupling agent used When c3 [g/g], the mass of the alkoxysilane compound is m4 [g], and the carbon content per unit mass of the alkoxysilane compound is c4 [g/g], (C) per unit surface area of the component, _{The amount of carbon A c1} derived from the silane coupling agent is computable by the formula: A _c1 = A _c x [(m3 x c3)/{(m3 x c3) + (m4 x c4)}]. The carbon content c3 can be obtained by dividing the amount of carbon per mole of the silane coupling agent by the molecular weight of the silane coupling agent. Similarly, the carbon content c4 can be obtained by dividing the amount of carbon per mole of the alkoxysilane compound by the molecular weight of the alkoxysilane compound. In addition, without distinguishing between a silane coupling agent and an alkoxysilane compound, "amount of carbon per mole" can be calculated|required by multiplying the number of carbon atoms per molecule by a carbon atom weight. In addition, the number of carbon atoms derived from an alkoxy group directly bonded to Si atoms is not included in the number of carbon atoms per molecule. This is because the alkoxy group is dispersed outside the system as an alcohol through a surface treatment process.

Without distinguishing between the first embodiment and the second embodiment, the content of component (C) in the resin composition of the present invention decreases the thermal expansion coefficient of the obtained insulating layer from the viewpoint of suppressing warpage in the component mounting process. From a viewpoint, when the nonvolatile component in a resin composition is 100 mass %, it is 40 mass % or more, Preferably it is 45 mass % or more, More preferably, it is 50 mass % or more, More preferably, it is 55 mass % or more, or 60 mass % or more. In the present invention in which the inorganic filler surface-treated with the silane coupling agent and the alkoxysilane compound is used so that the mass ratio of the silane coupling agent and the alkoxysilane compound falls within a specific range, the content of component (C) is further increased without excessive increase in melt viscosity. can For example, the content of component (C) in the resin composition is 62% by mass or more, 64% by mass or more, 66% by mass or more, 68% by mass or more, 70% by mass or more, 72% by mass or more, or 74% by mass or more. You can raise it up to

The upper limit of the content of component (C) in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less from the viewpoint of mechanical strength of the insulating layer obtained. .

The resin composition of the present invention may further contain at least one additive selected from the group consisting of a thermoplastic resin, a curing accelerator, a flame retardant, and an organic filler, if necessary.

-Thermoplastic resin-

Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamide imide resin, polyether imide resin, polysulfone resin, polyether sulfone resin, poly phenylene ether resin, polycarbonate resin, polyether ether ketone resin, and polyester resin are mentioned. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

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

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene. and phenoxy resins having at least one skeleton selected from the group consisting of skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. Any functional group, such as a phenolic hydroxyl group and an epoxy group, may be sufficient as the terminal of a phenoxy resin. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins) manufactured by Mitsubishi Chemical Co., Ltd., "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" ( bisphenol acetophenone skeleton-containing phenoxy resin), and in addition, "FX280" and "FX293" manufactured by Shin-Nittetsu Chemical Co., Ltd., "YX7553" manufactured by Mitsubishi Chemical Co., Ltd., "YL6794", "YL6794" ', "YL7213", "YL7290", "YL7482", etc. are mentioned.

As a specific example of polyvinyl acetal resin, Denki Chemical Co., Ltd. electric butyral 4000-2, 5000-A, 6000-C, 6000-EP, Sekisui Chemical Co., Ltd. product S The rack BH series, BX series, KS series, BL series, BM series, etc. are mentioned.

As a specific example of polyimide resin, "Ricacoat SN20" and "Ricacoat PN20" by Shin-Nippon Rica Co., Ltd. are mentioned. As specific examples of the polyimide resin, furthermore, a linear polyimide obtained by reacting a difunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (the one described in Japanese Patent Application Laid-Open No. 2006-37083), polysiloxane and modified polyimides such as skeleton-containing polyimides (things described in JP-A-2002-12667 and JP-A-2000-319386).

As a specific example of polyamideimide resin, Toyo Boseki Co., Ltd. product "Viromax HR11NN" and "Viromax HR16NN" are mentioned. As a specific example of polyamideimide resin, modified polyamideimides, such as Hitachi Kasei Kogyo Co., Ltd. product polysiloxane skeleton containing polyamideimide "KS9100" and "KS9300", are further mentioned.

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

As a specific example of polysulfone resin, the polysulfone "P1700", "P3500" of Solvay Advansto Formaz Co., Ltd. product, etc. are mentioned.

When content of the thermoplastic resin in a resin composition makes the nonvolatile component of a resin composition 100 mass %, Preferably it is 0.1 mass % - 20 mass %, More preferably, it is 0.5 mass % - 10 mass %, More preferably It is 1 mass % - 5 mass %.

-curing accelerator-

Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and guanidine-based curing accelerators, and phosphorus-based curing accelerators, amine-based curing accelerators and imidazole-based curing accelerators are preferable. . A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type. When content of a hardening accelerator makes the sum total of an epoxy resin and the nonvolatile component of a hardening|curing agent 100 mass %, it is preferable to use in 0.05 mass % - 3 mass %.

-Flame retardant-

Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may be used in combination of 2 or more type. Although content of the flame retardant in a resin composition is not specifically limited, When the non-volatile component in a resin composition is 100 mass %, Preferably it is 0.5 mass % - 10 mass %, More preferably, it is 0.8 mass % - 9 mass %. .

-Organic Fillings-

As an organic filler, you may use arbitrary organic fillers which can be used when forming the insulating layer of a printed wiring board, For example, a rubber particle, polyamide microparticles|fine-particles, a silicone particle, etc. are mentioned, A rubber particle is preferable.

The rubber particles are not particularly limited as long as they are fine particles of a resin that is chemically crosslinked to a resin exhibiting rubber elasticity and made insoluble and infusible in an organic solvent. For example, acrylonitrile butadiene rubber particles, butadiene rubber particles, Acrylic rubber particle|grains etc. are mentioned. Specifically as rubber particles, XER-91 (manufactured by Nippon Kosei Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (above, manufactured by Aika Kogyo Co., Ltd.) Paraloid EXL2655 , EXL2602 (above, manufactured by Kureha Chemical Industry Co., Ltd.), and the like.

The average particle diameter of the organic filler is preferably in the range of 0.005 µm to 1 µm, more preferably in the range of 0.2 µm to 0.6 µm. The average particle diameter of the organic filler can be measured using a dynamic light scattering method. For example, the organic filler is uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and the particle size distribution of the organic filler is determined by mass using a thick particle size analyzer (“FPAR-1000” manufactured by Otsuka Denshi Co., Ltd.). It can measure by creating and making this median diameter into an average particle diameter. When content of the organic filler in a resin composition makes the non-volatile component in a resin composition 100 mass %, Preferably it is 1 mass % - 10 mass %, More preferably, they are 2 mass % - 5 mass %.

-Other Ingredients-

The resin composition of this invention may contain other components as needed. Examples of such other components include organometallic compounds such as organic copper compounds, organozinc compounds and organocobalt compounds, and resin additives such as thickeners, defoamers, leveling agents, adhesion-imparting agents, colorants and curable resins. can be heard

The preparation method of the resin composition of this invention is not specifically limited, For example, the method of adding a solvent etc. to a compounding component as needed, and mixing and dispersing using a rotary mixer etc. are mentioned.

The resin composition of this invention forms the insulating layer which can suppress the curvature in the mounting process of a component. The resin composition of this invention can also form the resin composition layer which shows moderate melt viscosity. Therefore, the resin composition of this invention can be used suitably as a resin composition for forming the insulating layer of a printed wiring board (resin composition for insulating layers of a printed wiring board), The resin composition for forming the interlayer insulating layer of a printed wiring board (printed wiring board) resin composition for interlayer insulating layer of ) can be more suitably used. The resin composition of the present invention is also widely used in applications requiring a resin composition, such as an adhesive film, a sheet-like laminated material such as a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, a component embedding resin, etc. Can be used.

[Sheet-like laminated material]

Although the resin composition of this invention can be apply|coated and used in a varnish state, it is industrially generally suitable to use it in the form of the sheet-like laminated material containing the resin composition layer formed from the said resin composition.

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

In one embodiment, an adhesive film consists of a support body, and the resin composition layer (adhesive layer) bonded to the said support body, The resin composition layer (adhesive layer) is formed from the resin composition of this invention.

The thickness of the resin composition layer is preferably 100 µm or less, more preferably 80 µm or less, still more preferably 60 µm or less, still more preferably 50 µm or less or 40 µm or less from the viewpoint of reducing the thickness of the printed wiring board. am. Although the lower limit of the thickness of a resin composition layer is not specifically limited, Usually, it can be 1 micrometer or more, 5 micrometers or more, 10 micrometers or more.

As a support body, the film which consists of a plastics material, metal foil, and a release paper are mentioned, for example, The film which consists of a plastics material, and metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material is, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”). ) such as polyester, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), Polyether ketone, polyimide, etc. are 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, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and another metal (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. .

A support body may give a mat treatment and a corona treatment to the surface of the side to join with a resin composition layer. Moreover, as a support body, you may use the support body with a mold release layer which has a mold release layer on the surface of the side joined with a resin composition layer. As a mold release agent used for the mold release layer of a support body with a mold release layer, 1 or more types of mold release agents selected from the group which consists of an alkyd resin, an olefin resin, a urethane resin, and a silicone resin are mentioned, for example. As a commercial item of a mold release agent, "SK-1", "AL-5", "AL-7" etc. which are alkyd resin type mold release agents manufactured by Lintec Co., Ltd. are mentioned, for example.

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

The adhesive film can be produced by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer. .

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

You may perform drying by well-known methods, such as heating and hot-air spraying. Although drying conditions are not specifically limited, Content of the organic solvent in a resin composition layer is 10 mass % or less, Preferably it is made to dry so that it may become 5 mass % or less. Although it changes also with the boiling point of the organic solvent in a resin varnish, for example, when using the resin varnish containing 30 mass % - 60 mass % of an organic solvent, by drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes, the resin A composition layer can be formed.

An adhesive film WHEREIN: The protective film according to a support body can further be laminated|stacked on the surface which is not joined to the support body of a resin composition layer (that is, the surface on the opposite side to a support body). Although the thickness of a protective film is not specifically limited, For example, it is 1 micrometer - 40 micrometers. By laminating|stacking a protective film, adhesion of garbage, etc. to the surface of a resin composition layer, and a flaw can be prevented. The adhesive film can be wound and stored in roll shape. When an adhesive film has a protective film, it becomes usable by peeling off a protective film.

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

The sheet-like fiber base material used for a prepreg is not specifically limited, What is commonly used as a base material for prepregs, such as a glass cloth, an aramid nonwoven fabric, and a liquid crystal polymer nonwoven fabric, can be used. From a viewpoint of thickness reduction of a printed wiring board, Preferably the thickness of a sheet-like fiber base material is 50 micrometers or less, More preferably, it is 40 micrometers or less, More preferably, it is 30 micrometers or less, More preferably, it is 20 micrometers or less. Although the minimum of the thickness of a sheet-like fiber base material is not specifically limited, Usually, it is 10 micrometers or more.

A prepreg can be manufactured by well-known methods, such as a hot melt method and a solvent method.

The thickness of a prepreg can be made into the range similar to the resin composition layer in the adhesive film mentioned above.

In the sheet-like laminated material, the minimum melt viscosity of the resin composition layer is preferably 300 poise or more, more preferably 500 poise or more, still more preferably from the viewpoint of suppressing the resin from oozing out during the production of a printed wiring board. preferably 700 poise or more, 900 poise or more, or 1000 poise or more. The upper limit of the minimum melt viscosity of the resin composition layer is preferably 12,000 poise or less, more preferably 10000 poise or less, further preferably 12,000 poise or less, from the viewpoint of achieving good lamination property (circuit insertability) at the time of manufacturing a printed wiring board. 8000 poise or less, 7000 poise or less, 6000 poise or less, 5000 poise or less, or 4000 poise or less. Here, the "minimum melt viscosity" of a resin composition layer means the minimum viscosity which a resin composition layer shows when resin of a resin composition layer melt|dissolves. Specifically, when the resin composition layer is heated at a constant temperature increase rate to melt the resin, in the initial stage, the melt viscosity decreases as the temperature rises, and then, when it exceeds a certain temperature, the melt viscosity rises with the temperature rise. . "Minimum melt viscosity" means the melt viscosity of such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelasticity method, for example, according to the method described in <Measurement of minimum melt viscosity> mentioned later.

In the present invention in which the inorganic filler surface-treated with the silane coupling agent and the alkoxysilane compound is used so that the mass ratio of the silane coupling agent and the alkoxysilane compound is in a specific range, a resin composition layer exhibiting the lowest melt viscosity in the above suitable range is advantageously formed It is possible to form a sheet-like laminated material exhibiting good lamination properties at the time of manufacturing a printed wiring board.

The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board) ) can be more suitably used, and further suitably used for a resin composition for forming an interlayer insulating layer in which a conductor layer is formed by plating (for an interlayer insulating layer of a printed wiring board in which a conductor layer is formed by plating).

[Printed wiring board]

The printed wiring board of this invention contains the insulating layer formed with the hardened|cured material of the resin composition of this invention.

In one embodiment, the printed wiring board of this invention can be manufactured by the method including the process of following (I) and (II) using the adhesive film mentioned above.

(I) a step of laminating an adhesive film on an inner-layer substrate so that the resin composition layer of the adhesive film is bonded to the inner-layer substrate

(II) Step of thermosetting the resin composition layer to form an insulating layer

The "inner layer substrate" used in step (I) is mainly 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 side of the substrate ( It refers to a circuit board in which a patterned conductor layer (circuit) is formed on both sides or on both sides. Moreover, when manufacturing a printed wiring board, the inner-layer circuit board of the intermediate|middle manufacture on which an insulating layer and/or a conductor layer should further be formed is also included in the "inner-layer board|substrate" referred to in this invention.

From a viewpoint of thickness reduction of a printed wiring board, the thickness of an inner-layer board becomes like this. Preferably it is 800 micrometers or less, More preferably, it is 400 micrometers or less, More preferably, it is 200 micrometers or less. ADVANTAGE OF THE INVENTION According to this invention, even when using a thin inner-layer board|substrate, the curvature of the printed wiring board in a mounting process can be suppressed. For example, use an inner-layer substrate with 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. Even in this case, the curvature in the mounting process can be suppressed. Although the lower limit of the thickness of an inner-layer substrate is not specifically limited, From a viewpoint of the handleability improvement at the time of printed wiring board manufacture, Preferably it is 10 micrometers or more, More preferably, it is 20 micrometers or more.

Lamination of the inner layer substrate and the adhesive film can be performed, for example, by heat-bonding the adhesive film to the inner layer substrate from the support side. As a member (hereinafter also referred to as "thermal compression member") which heat-compresses an adhesive film to an inner-layer board|substrate, a heated metal plate (SUS hard plate etc.), a metal roll (SUS roll), etc. are mentioned, for example. In addition, it is preferable not to press the thermocompression-compression-bonding member directly to the adhesive film, but to press through an elastic material, such as a heat-resistant rubber, so that the adhesive film may fully harvest the surface unevenness|corrugation of an inner-layer board|substrate.

The inner layer substrate and the adhesive film may be laminated by a vacuum lamination method. In the vacuum laminating method, the thermocompression compression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the thermocompression compression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa, and the heat compression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, the vacuum pressurization type laminator by the Meki Sesakusho Co., Ltd. product, the vacuum applicator by the Nichigo Morton Co., Ltd. product, etc. are mentioned, for example.

After lamination, you may perform the smoothing process of the laminated|stacked adhesive film by normal pressure (under atmospheric pressure), for example, pressing a thermocompression-bonding member from the support body side. The press conditions of the smoothing process can be made into the same conditions as the thermocompression-bonding conditions of the said lamination|stacking. A smoothing process can be implemented with a commercially available laminator. In addition, you may perform lamination|stacking and a smoothing process continuously using said commercially available vacuum laminator.

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

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

The thermosetting conditions of a resin composition layer are not specifically limited, When forming the insulating layer of a printed wiring board, you may use the conditions normally employ|adopted.

For example, although the thermosetting conditions of the resin composition layer also differ depending on the kind of resin composition, the curing temperature is in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably 170°C). to 200°C), the curing time may be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before thermosetting a resin composition layer, you may preheat a resin composition layer at temperature lower than hardening temperature. For example, prior to thermosetting the resin composition layer, at a temperature of 50 ° C or more and less than 120 ° C (preferably 60 ° C or more and 110 ° C or less, more preferably 70 ° C or more and 100 ° C or less), the resin composition layer is You may preheat for 5 minutes or more (preferably 5 minutes - 150 minutes, More preferably, 15 minutes - 120 minutes).

When manufacturing a printed wiring board, you may further implement the process of (III) drilling in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer in the insulating layer surface. You may implement these processes (III) - (V) according to various methods well-known to those skilled in the art used for manufacture of a printed wiring board. In the case where the support is removed after the step (II), the removal of the support is performed between the steps (II) and (III), between the steps (III) and (IV), or between the steps (IV) and the step (V). ) may be performed between

In another embodiment, the printed wiring board of this invention can be manufactured using the prepreg mentioned above. 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 this invention. Although the printed wiring board of the present invention is thin, it can suppress warpage even in a component mounting process employing a high solder reflow temperature, and can advantageously reduce problems such as circuit deformation and component contact failure.

In one embodiment, in the printed wiring board of the present invention, in a mounting step employing a solder reflow temperature as high as 260°C, the printed wiring board has a warpage of less than 40 µm (preferably 35 µm or less, more preferably preferably 30 µm or less, more preferably 25 µm or less). In the present invention, the warpage of the printed wiring board is the value of the difference between the maximum height and the minimum height of the displacement data when the warpage behavior of a 10 mm square portion in the center of the printed wiring board is observed with a shadow moiré apparatus. During measurement, the reflow temperature profile (profile for lead-free assembly; peak temperature of 260°C) described in IPC/JEDEC J-STD-020C (“Moisture/Reflow Sensitivity Classification For Nonhermetic Solid State Surface Mount Devies”, July 2004) ), after passing the printed wiring board once through a reflow device that reproduces the Displacement data were obtained for the formed grid lines. Moreover, as a reflow apparatus, "HAS-6116" manufactured by Nippon Antomu Co., Ltd. is mentioned, for example, As a shadow moire apparatus, "TherMoire AXP" by Akrometrix is mentioned, for example. Even if the printed wiring board containing the insulating layer formed with the hardened|cured material of the resin composition of this invention is thin, it can suppress the curvature in a mounting process advantageously.

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

The semiconductor device of this invention can be manufactured by mounting a component (semiconductor chip) in the conduction|electrical_connection location of the printed wiring board of this invention. A "conduction location" is "a location through which an electric signal is transmitted in a printed wiring board", and the location may be a surface, an inserted location, or any. In addition, a semiconductor chip will not be specifically limited if it is an electric circuit element which uses a semiconductor as a material.

The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, and specifically, the wire bonding mounting method, flip chip mounting method, bumpless buildup layer ( BBUL), the mounting method by an anisotropic conductive film (ACF), the mounting method by a non-conductive film (NCF), etc. are mentioned. Here, the "mounting method using a bumpless buildup layer (BBUL)" is "a mounting method in which a semiconductor chip is directly inserted into a recess of a printed wiring board, and the semiconductor chip and wiring on the printed wiring board are connected".

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, "part" in the following description means a "mass part."

First, the measuring method and evaluation method in the physical property evaluation in this specification are demonstrated.

<Measurement of Carbon Amount>

The amount of carbon per unit surface area of the inorganic filler was measured according to the following procedure. MEK in a sufficient amount as a solvent was added to the inorganic filler prepared in the preparation example, and ultrasonic cleaning was carried out at 25 degreeC for 5 minutes. The supernatant was then removed and the solid was dried. For the obtained solid, the amount of carbon was measured using a carbon analyzer ("EMIA-320V" manufactured by Horiba Sesakusho Co., Ltd.). Based on the measured value of the amount of carbon and the mass and specific surface area of the inorganic filler used, the amount of carbon per unit surface area of the inorganic filler was calculated.

<Measurement of Minimum Melt Viscosity>

About the resin composition layer of the adhesive film produced in the Example and the comparative example, melt viscosity was measured using the dynamic viscoelasticity measuring apparatus ("Rheosol-G3000" manufactured by U.B.M Co., Ltd.). For 1 g of the sample resin composition, using a parallel plate with a diameter of 18 mm, the temperature was raised from the starting temperature of 60°C to 200°C at a temperature increase rate of 5°C/min, and dynamic under the measurement conditions of a measurement temperature interval of 2.5°C, a vibration of 1 Hz, and a deformation of 1deg. The viscoelastic modulus was measured and the lowest melt viscosity (poise) was measured.

<Preparation of substrate for evaluation>

(1-1) Preparation of Inner Layer Substrate

As the inner layer substrate, an unclad plate (100 μm thick, “HL832NSF-LCA” manufactured by Mitsubishi Gas Chemical Co., Ltd.) from which the double-sided copper foil of the glass cloth base epoxy resin double-sided copper clad laminate was removed was used.

(1-2) Lamination of the adhesive film

For the adhesive films produced in Examples and Comparative Examples, using a batch vacuum pressurized laminator (Nichigo Morton Co., Ltd. 2-stage build-up laminator CVP700), the resin composition layer was in contact with the inner-layer substrate. laminated on both sides. Lamination|stacking was performed by pressure-reducing for 30 second and making atmospheric|air pressure 13 hPa or less, and then crimping|bonding at 110 degreeC and a pressure of 0.74 MPa for 30 second. Then, it hot-pressed for 60 second at 110 degreeC and the pressure of 0.5 MPa.

(1-3) Thermosetting of the resin composition layer

After lamination, the support body was peeled from both surfaces of the board|substrate. Next, the resin composition layer was thermosetted under curing conditions at 190°C for 90 minutes to form an insulating layer. The obtained board|substrate is called "substrate 1".

<Evaluation of warpage>

After cutting the substrate 1 into 45 mm square pieces (n = 5), a reflow device that reproduces the solder reflow temperature with a peak temperature of 260°C (“HAS-6116” manufactured by Nippon Antomu Co., Ltd.) ') once (reflow temperature profile conforms to IPC/JEDEC J-STD-020C). Next, using a shadow moire device (“TherMoire AXP” manufactured by Akrometrix), the lower surface of the substrate is heated with a reflow temperature profile conforming to IPC/JEDEC J-STD-020C (peak temperature 260° C.), and a grid placed on the upper surface of the substrate. Based on the line, the displacement of a 10 mm square portion in the center of the substrate was measured. Warpage was evaluated according to the following evaluation criteria.

Evaluation standard:

○: For all five samples, the difference between the maximum height and the minimum height of the displacement data in the entire temperature range is less than 40 μm

×: For at least one sample, the difference between the maximum height and the minimum height of the displacement data in the entire temperature range is 40 µm or more

The inorganic filler used in the Example and the comparative example was prepared according to the following preparation example.

<Preparation Example 1: Preparation of inorganic filler 1>

100 parts of spherical silica (“SC1500SQ” manufactured by Adomatex Co., Ltd., average particle diameter of 0.3 μm, specific surface area of 11 m 2 /g) was put into a Henschel-type mixer, and N-phenyl-3 -Spherical silica was stirred for 10 minutes while spraying 2 parts of aminopropyltrimethoxysilane ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 255.4), and further stirred at 75 ° C. for 10 minutes, then the volatile components were removed It distilled off to prepare the inorganic filler 1. The amount of carbon per unit surface area of the inorganic filler 1 was 0.36 mg/m 2 . In addition, the inorganic filler 1 corresponds to (C1) component.

<Preparation Example 2: Preparation of inorganic filler 2>

In place of 2 parts of N-phenyl-3-aminopropyltrimethoxysilane (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 255.4), 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) Co., Ltd. product "KBM-403", molecular weight 236.3) Except having used 1.8 parts, it carried out similarly to Preparation Example 1, and the inorganic filler 2 was prepared. The amount of carbon per unit surface area of the inorganic filler 2 was 0.26 mg/m<2>. In addition, the inorganic filler 2 corresponds to (C1) component.

<Preparation Example 3: Preparation of inorganic filler 3>

In place of 2 parts of N-phenyl-3-aminopropyltrimethoxysilane ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 255.4), phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. " KBM-103", molecular weight 198.3) Except having used 1.5 parts, it carried out similarly to Preparation Example 1, and prepared the inorganic filler 3. The amount of carbon per unit surface area of the inorganic filler 3 was 0.35 mg/m<2>. In addition, the inorganic filler 3 corresponds to (C2) component.

<Preparation Example 4: Preparation of inorganic filler 4>

In place of 2 parts of N-phenyl-3-aminopropyltrimethoxysilane (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 255.4), dimethyldimethoxysilane (“KBM” manufactured by Shin-Etsu Chemical Co., Ltd.) -22", molecular weight 120.2) Except having used 1 part, it carried out similarly to the preparation example 1, and prepared the inorganic filler 4. The amount of carbon per unit surface area of the inorganic filler 4 was 0.20 mg/m 2 . In addition, the inorganic filler 4 corresponds to (C2) component.

<Preparation Example 5: Preparation of inorganic filler 5>

In place of 2 parts of N-phenyl-3-aminopropyltrimethoxysilane ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 255.4), phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. " KBM-103", molecular weight 198.3) and 1 part of N-phenyl-3-aminopropyltrimethoxysilane ("KBM-573", molecular weight 255.4 manufactured by Shin-Etsu Chemical Co., Ltd.) Preparation example except that 1 part was used It carried out similarly to 1, and the inorganic filler 5 was prepared. The amount of carbon per unit surface area of the inorganic filler 5 was 0.38 mg/m 2 . In addition, the inorganic filler 5 corresponds to (C3) component.

<Example 1>

8 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent of about 169) 8 parts, bixylenol type epoxy resin (Mitsubishi Chemical) Co., Ltd. "YX4000HK", epoxy equivalent about 185) 12 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000H", epoxy equivalent about 288) 15 parts, phenoxy resin (Mitsubishi Chemical Co., Ltd.) ) 15 parts of manufacture "YL7553BH30", MEK/cyclohexanone = 1/1 solution) of 30 mass % solid content) were heat-dissolved, stirring 30 parts of solvent naphtha. After cooling to room temperature, 5 parts of a phenol novolac curing agent containing a triazine skeleton (“LA-7054” manufactured by DIC Corporation, a MEK solution having a hydroxyl equivalent of 125 and a solid content of 60%), an active ester curing agent ( DIC Co., Ltd. "HPC8000-65T", active group equivalent about 223, toluene solution of 65 mass % of nonvolatile component) 26 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), MEK solution of 5 mass % of solid content) 2 Part, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 2 μm), 100 parts of inorganic filler 1, and 50 parts of inorganic filler 3 were mixed, uniformly dispersed with a high-speed rotary mixer, and filtered through a cartridge filter (“SHP050” manufactured by ROKITECNO) to prepare a resin varnish.

Next, the obtained resin varnish was applied to the release surface of a PET film with an alkyd resin-based release layer (“AL5” manufactured by Lintec Co., Ltd., 38 µm thick), uniformly with a die coater so that the thickness of the resin composition layer after drying was 40 µm. After coating, the adhesive film was prepared by drying at 80° C. to 120° C. (average 100° C.) for 5 minutes.

In Example 1, component (C) consists of 100 parts of inorganic filler 1 and 50 parts of inorganic filler 3, and the amount of carbon per unit surface area of component (C) (hereinafter referred to as "carbon amount 1") is 0.357 mg/m 2 and the amount of carbon derived from the silane coupling agent per unit surface area of component (C) (hereinafter referred to as "carbon amount 2") were 0.24 mg/m 2 .

<Example 2>

A resin varnish and an adhesive film were obtained in the same manner as in Example 1 except that instead of 100 parts of the inorganic filler 1 and 50 parts of the inorganic filler 3, 25 parts of the inorganic filler 1 and 125 parts of the inorganic filler 4 were used.

In Example 2, component (C) consisted of the inorganic filler 1 of 25 parts and the inorganic filler 4 of 125 parts, the carbon amount 1 was 0.239 mg/m<2>, and the carbon amount 2 was 0.072 mg/m<2>.

<Example 3>

In the same manner as in Example 1 except that instead of 100 parts of inorganic filler 1 and 50 parts of inorganic filler 3, 30 parts of inorganic filler 1, 30 parts of inorganic filler 2 and 90 parts of inorganic filler 3 were used, a resin varnish and adhesive film were obtained. did.

In Example 3, component (C) consisted of 30 parts of inorganic filler 1, 30 parts of inorganic filler 2, and 90 parts of inorganic filler 3, the carbon amount 1 was 0.334 mg/m 2 and the carbon amount 2 was 0.124 mg/m 2 .

<Example 4>

A resin varnish and an adhesive film were obtained in the same manner as in Example 1 except that 150 parts of inorganic filler 5 was used instead of 100 parts of inorganic filler 1 and 50 parts of inorganic filler 3 .

In Example 4, (C) component consisted of 150 parts of inorganic fillers 5, the carbon amount 1 was 0.38 mg/m<2>, and the carbon amount 2 was 0.18 mg/m<2>.

<Comparative Example 1>

A resin varnish and an adhesive film were obtained in the same manner as in Example 1 except that 150 parts of inorganic filler 1 was used instead of 100 parts of inorganic filler 1 and 50 parts of inorganic filler 3 .

In Comparative Example 1, component (C) consisted of 150 parts of inorganic filler 1, the carbon amount 1 was 0.36 mg/m2, and the carbon amount 2 was 0.36 mg/m2.

<Comparative Example 2>

A resin varnish and an adhesive film were obtained in the same manner as in Example 1 except that 150 parts of inorganic filler 2 was used instead of 100 parts of inorganic filler 1 and 50 parts of inorganic filler 3 .

In the comparative example 2, (C) component consisted of 150 parts of inorganic fillers 2, the carbon amount 1 was 0.26 mg/m<2>, and the carbon amount 2 was 0.26 mg/m<2>.

<Comparative Example 3>

A resin varnish and an adhesive film were obtained in the same manner as in Example 1 except that 150 parts of the inorganic filler 3 was used instead of the inorganic filler 1 of 100 parts and the inorganic filler 3 of 50 parts of 50 parts.

In Comparative Example 3, component (C) consisted of 150 parts of inorganic filler 3, the carbon amount 1 was 0.35 mg/m2, and the carbon amount 2 was 0 mg/m2.

<Comparative Example 4>

A resin varnish and an adhesive film were obtained in the same manner as in Example 1 except that 150 parts of inorganic filler 4 was used instead of 100 parts of inorganic filler 1 and 50 parts of inorganic filler 3 .

In the comparative example 4, (C) component consisted of 150 parts of inorganic fillers 4, the carbon amount 1 was 0.20 mg/m<2>, and the carbon amount 2 was 0 mg/m<2>.

The results are shown in Table 1.

Claims (16)

A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,
(C) component contains the inorganic filler surface-treated with both (C3) a silane coupling agent and an alkoxysilane compound,
The mass ratio of the silane coupling agent and the alkoxysilane compound (silane coupling agent: alkoxysilane compound) is 1:9 to 9:1,
When the nonvolatile component in a resin composition is 100 mass %, content of (C)component is 40 mass % or more, The resin composition. The resin composition according to claim 1, wherein the amount of carbon per unit surface area of component (C) is 0.05 mg/m 2 to 1 mg/m 2 . The resin composition according to claim 1, wherein the amount of carbon derived from the silane coupling agent per unit surface area of the component (C) is 0.03 mg/m 2 to 0.8 mg/m 2 . The resin composition according to claim 1, wherein the component (C3) is an inorganic filler surface-treated with both a silane coupling agent having an aryl group and an alkoxysilane compound having an aryl group. The resin composition according to claim 1, wherein the component (C3) is obtained by simultaneously surface-treating an inorganic filler with a silane coupling agent and an alkoxysilane compound. The resin composition according to claim 1, wherein the inorganic filler has an average particle diameter of 0.01 µm to 5 µm. The resin composition of Claim 1 whose content of (C)component is 60 mass % - 90 mass % when the non-volatile component in a resin composition is 100 mass %. The resin composition according to claim 1, wherein the inorganic filler is silica. The resin composition according to claim 1, wherein the silane coupling agent has at least one functional group selected from the group consisting of an amino group, an epoxy group, a mercapto group, a (meth)acrylic group, a vinyl group, an isocyanate group, and an imidazolyl group. The alkoxysilane compound according to claim 1, wherein the alkoxysilane compound is monoaryltrialkoxysilane, diaryldialkoxysilane, monoalkyltrialkoxysilane, dialkyldialkoxysilane, monoalkylmonoaryldialkoxysilane, diarylmonoalkylmonoalkoxysilane and At least one selected from the group consisting of dialkylmonoarylmonoalkoxysilanes, the resin composition. The component (A) according to claim 1, wherein the component (A) is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, glycidyl At least one selected from the group consisting of an ester-type epoxy resin, an anthracene-type epoxy resin, and an epoxy resin having a butadiene structure, the resin composition. The resin composition according to claim 1, wherein the component (B) is at least one selected from the group consisting of a phenol-based curing agent, an active ester-based curing agent, and a cyanate ester-based curing agent. The resin composition of Claim 1 which is a resin composition for insulating layers of a multilayer printed wiring board. A sheet-like laminated material comprising the layer of the resin composition according to any one of claims 1 to 13. The printed wiring board containing the insulating layer formed with the hardened|cured material of the resin composition in any one of Claims 1-13. A semiconductor device comprising the printed wiring board according to claim 15 .