KR102132771B1 - Resin composition - Google Patents

Abstract

The problem to be solved by the present invention is to provide a resin composition capable of achieving low-dielectric tangentization of a cured product of a resin composition, and suppressing smear in a via hole after roughening treatment of the cured product.
A specific resin composition containing an epoxy resin, an active ester compound, and a smear inhibiting component.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition. Furthermore, it relates to a sheet-like laminated material, a multilayer printed wiring board, and a semiconductor device.

In recent years, miniaturization and high performance of electronic devices have progressed, and in a multilayer printed wiring board, a build-up layer is multi-layered, so that the wiring is required to be miniaturized and high-density, and an insulating material with a low dielectric tangent is required to reduce transmission loss.

Patent Document 1 discloses an epoxy resin composition for sealing containing an epoxy resin, a curing agent, and carbon black, and describes aggregation prevention of carbon black. However, the concept of smear or low-dielectric tangent was not disclosed or oriented.

Patent Document 1: Japanese Patent Publication No. 2008-121010

When perforating the insulating layer of the multilayer printed wiring board, smear (resin residue) occurs in the via hole, and it is necessary to remove the smear in the roughening process. However, according to the findings of the present inventors, since a multilayer printed wiring board was produced using a resin composition of a low-dielectric tangent containing an active ester compound, smear (resin) in the via-holes even if the via-holes are roughly treated after the insulating layer is drilled. A new problem has arisen that it is difficult to remove the residue).

Accordingly, a problem to be solved by the present invention is to provide a resin composition capable of achieving low-dielectric tangentization of a cured product of a resin composition, and suppressing smear in a via hole after roughening treatment of a cured product. will be.

As a result of earnest research to solve the above problems, the present inventors have accomplished the present invention in a specific resin composition containing an epoxy resin, an active ester compound, and a smear suppressing component.

That is, the present invention includes the following contents.

[1] (A) It is a resin composition containing an epoxy resin, (B) an active ester compound, and (C) a smear suppressing component, and when the nonvolatile component of the resin composition is 100 mass%, (C) smear suppressing The resin composition characterized in that the component is 0.001 to 10% by mass.

[2] The resin composition according to the above [1], wherein the content of the active ester compound is 1 to 30 mass% when the nonvolatile component in the resin composition is 100 mass%.

[3] The resin composition according to the above [1] or [2], wherein (C) the smear suppressing component is an organic smear suppressing component.

[4] The resin composition according to [3], wherein the organic smear suppressing component is at least one selected from the group consisting of pigments, dyes, rubber particles, antioxidants, and infrared absorbers.

[5] The resin composition according to the above [3], wherein the organic smear suppressing component is a pigment and/or rubber particles.

[6] The resin composition according to the above [3], wherein the organic smear suppressing component is a pigment.

[7] The resin composition according to [3], wherein the organic smear suppressing component is at least one selected from the group consisting of blue pigments, yellow pigments, red pigments, and green pigments.

[8] The resin composition according to the above [3], wherein the organic smear suppressing component is a mixed pigment formed by mixing a blue pigment, a yellow pigment and a red pigment.

[9] The resin composition according to any one of [1] to [8], further comprising (D) an inorganic filler.

[10] The resin composition according to the above [9], wherein the average particle diameter of the (D) inorganic filler is 0.01 to 5 µm.

[11] The resin composition according to [9] or [10] above, wherein the content of the inorganic filler is 40 to 85 mass% when the nonvolatile component in the resin composition is 100 mass%.

[12] The resin composition according to any one of [9] to [11], wherein the amount of carbon per unit weight of the inorganic filler is 0.02 to 3%.

[13] A conductive layer obtained by curing a resin composition to form an insulating layer, and after roughening the surface of the insulating layer, the square average roughness Rq of the surface of the insulating layer is 500 nm or less, and is plated on the surface of the insulating layer. The resin composition according to any one of [1] to [12], wherein the peel strength with the insulating layer is 0.3 kgf/cm or more and the dielectric tangent of the cured product of the resin composition is 0.05 or less.

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

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

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

[17] A semiconductor device, characterized in that the multilayer printed wiring board described in [16] is used.

[18] The sheet-like laminated material described in [15] is laminated on a circuit board, and the resin composition is thermally cured to form an insulating layer, and an insulating layer formed on the circuit board is punched from a support to form a via hole. Method of manufacturing a multilayer printed wiring board, characterized in that.

By using a specific resin composition containing an epoxy resin, an active ester compound, and a smear inhibiting component, a low-k dielectric of the cured product of the resin composition can be achieved, and the smear in the via-hole after roughening treatment of the cured product is suppressed. It became possible to provide a resin composition capable of being made.

The present invention is a resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) a smear inhibiting component, and when the nonvolatile component of the resin composition is 100 mass%, (C) smear It is a resin composition characterized in that the inhibitory component is 0.001 to 10% by mass.

<(A) Epoxy resin>

Although it does not specifically limit as (A) epoxy resin used for this invention, It is preferable to contain the epoxy resin which has 2 or more epoxy groups in 1 molecule. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene Type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin , Epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, trimethylol type epoxy resins, halogenated epoxy resins, and the like. These may be used alone or in combination of two or more.

Among these, bisphenol A-type epoxy resin, naphthol-type epoxy resin, naphthalene-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, and glycie from the viewpoints of improving heat resistance, improving insulation reliability, and improving adhesion to a metal foil. Dill ester type epoxy resins, anthracene type epoxy resins, and epoxy resins having a butadiene structure are preferred. Specifically, for example, bisphenol A-type epoxy resin (Mitsubishi Chemical Co., Ltd. "Epicoat 828EL", "YL980"), bisphenol F-type epoxy resin (Mitsubishi Chemical Co., Ltd. "jER806H", "YL983U" ), naphthalene type bifunctional epoxy resin ("HP4032", "HP4032D", "HP4032SS", "EXA4032SS" manufactured by DIC Corporation), naphthalene type four functional epoxy resin ("HP4700", "HP4710" by DIC Corporation) ), naphthol type epoxy resin ("ESN-475V" manufactured by Toto Kasei Co., Ltd.), epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Industries, Ltd.), biphenyl type epoxy resin (Nihon Kayaku Co., Ltd. "NC3000H", "NC3000L", "NC3100", Mitsubishi Chemical Co., Ltd. "YX4000", "YX4000H", "YX4000HK", "YL6121"), anthracene type epoxy resin (Mitsubishi Chemical Co., Ltd.) ``YX8800'' manufactured by Co., Ltd., naphthylene ether type epoxy resin (``EXA-7310'' manufactured by DIC Corporation, ``EXA-7311'', ``EXA-7311L'', ``EXA7311-G3''), glycidyl ester Type epoxy resins ("EX711", "EX721" manufactured by Nagase Chemtex Co., Ltd., "R540" manufactured by Printtech Co., Ltd.) and the like.

Especially, it is preferable to use together a liquid epoxy resin and a solid-state epoxy resin, it has two or more epoxy groups in 1 molecule, and liquid aromatic epoxy resin at a temperature of 20 °C (hereinafter referred to as "liquid epoxy resin"), It is more preferable to have three or more epoxy groups in one molecule and contain a solid aromatic epoxy resin (hereinafter referred to as "solid epoxy resin") at a temperature of 20°C. In addition, the aromatic epoxy resin referred to in the present invention means an epoxy resin having an aromatic ring structure in its molecule. As an epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, the composition has the appropriate flexibility when the resin composition is used in the form of an adhesive film, or the cured product of the resin composition has an appropriate breaking strength. The ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.1 to 1:4 by mass ratio, more preferably in the range of 1:0.1 to 1:2, and in the range of 1:0.3 to 1:1.8. More preferably, the range of 1:0.6 to 1:1.5 is even more preferable.

In the resin composition of the present invention, when the non-volatile component in the resin composition is 100 mass% from the viewpoint of improving the mechanical strength and insulation reliability of the cured product of the resin composition, the content of the epoxy resin (A) is 3 to 40 It is preferable that it is a mass %, it is more preferable that it is 5 to 35 mass %, and it is still more preferable that it is 10 to 30 mass %.

<(B) Active ester compound>

The active ester compound (B) in the present invention is a compound having one or more active ester groups in one molecule, and the dielectric tangent of the resin composition can be made low to make the square mean square root roughness Rq small. (B) The active ester compound can react with an epoxy resin or the like, and a compound having two or more active ester groups in one molecule is preferable. Generally, compounds having two or more ester groups in one molecule having high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferably used. .

From the viewpoint of improving heat resistance, an active ester compound obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound is more preferable. Further, an active ester compound obtained by reacting a carboxylic acid compound with one or two or more selected from phenol compounds, naphthol compounds and thiol compounds is more preferable. Further, an aromatic compound having two or more active ester groups in one molecule, which is obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group, is more preferable. And, an aromatic compound obtained by reacting a carboxylic acid compound having at least two or more carboxyl groups in one molecule and an aromatic compound having a phenolic hydroxyl group, and an aromatic compound having two or more active ester groups in one molecule of the aromatic compound This is particularly preferred. Moreover, it may be linear or multi-branched. Moreover, if the carboxylic acid compound having at least two or more carboxyl groups in one molecule is a compound containing an aliphatic chain, compatibility with the resin composition can be increased, and if it is a compound having an aromatic ring, heat resistance can be increased.

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred from the viewpoint of heat resistance, and isophthalic acid and terephthalic acid are more preferable. As a thiocarboxylic acid compound, thioacetic acid, thiobenzoic acid, etc. are specifically, mentioned.

As a phenol compound or a naphthol compound, specifically, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, 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, tri And hydroxybenzophenone, tetrahydroxybenzophenone, phloroglusine, benzenetriol, dicyclopentadienyldiphenol, and phenol novolac. Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxy from the viewpoint of improving heat resistance and solubility. Naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglusin, benzenetriol, dicyclopenta Dienyl diphenol and phenol novolak are preferred, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, and trihydroxy Benzophenone, tetrahydroxybenzophenone, phloroglusin, benzenetriol, dicyclopentadienyldiphenol, phenol novolak are more preferable, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene , 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, phenol novolak, more preferably, 1,5-dihydroxy Naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienyldiphenol, and phenol novolak are more preferred, and 1,5-dihydroxynaphthalene, 1,6-di Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienyldiphenol is particularly preferred, and dicyclopentadienyldiphenol is particularly preferred. As a thiol compound, specifically, benzene dithiol, triazine dithiol, etc. are mentioned. The active ester compound may be used alone or in combination of two or more.

As an active ester compound containing a dicyclopentadienyldiphenol structure, the compound of the following formula (1) is mentioned more specifically.

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

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

(B) As the active ester compound, an active ester compound disclosed in Japanese Patent Laid-Open No. 2004-277460 may be used, or a commercially available active ester compound may be used. As a commercially available active ester compound, specifically, an active ester-based hardener containing a dicyclopentadienyl structure, an active ester-based curing agent containing a naphthalene structure, and an active ester-based curing agent containing an acetylate of phenol novolac, Active ester-based curing agents containing phenol novolac benzoylates are preferred, and among them, active ester-based curing agents containing a naphthalene structure and active ester-based curing agents containing a dicyclopentadienyldiphenol structure are more preferred. As an active ester-based curing agent containing a dicyclopentadienyldiphenol structure, EXB9451, EXB9460, EXB9460S, HPC-8000-65T (manufactured by DIC Corporation), and an active ester-based curing agent containing a naphthalene structure EXB9416-70BK (DIC (Co., Ltd.), DC808 (Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent containing phenol novolac acetylates, and YLH1026 (Mitsubishi Chemical) as an active ester-based curing agent containing phenol novolac benzoylates. And manufactured by Co., Ltd.).

(B) The content of the active ester compound is 30 mass% or less, preferably 20 mass% or less, when the nonvolatile component in the resin composition is 100 mass% from the viewpoint of improving heat resistance and further suppressing smear. Is more preferable, and 10% by mass or less is even more preferable. On the other hand, from the viewpoint of improving the peel strength, when the nonvolatile component in the resin composition is 100 mass%, 1 mass% or more is preferable, 3 mass% or more is more preferable, and 5 mass% or more is more preferable.

Moreover, when the number of epoxy groups (A) of the epoxy resin is 1, from the viewpoint of improving the mechanical properties of the resin composition, the reactor number of the active ester compound (B) is preferably 0.2 to 2, more preferably 0.3 to 1.5. It is preferable, and 0.4 to 1 is more preferable. Here, the "epoxy group number of the epoxy resin" is a value obtained by dividing the solid content mass of each epoxy resin present in the resin composition by the epoxy equivalent amount for all epoxy resins. In addition, "reactor" means a functional group capable of reacting with an epoxy group, and "reactor number of active ester compound" is a total value obtained by dividing the solid content mass of the active ester compound present in the resin composition by the reactor equivalent weight. to be.

<(C) Smear inhibitory component>

The smear suppressing component used in the present invention is a component capable of suppressing smear of via-holes after roughening treatment by drilling a cured product of the resin composition. Here, the smear suppression includes both the meaning of reducing the amount of smear generated during drilling and making it easier to remove the smear during roughening treatment. Examples of the smear suppressing component include an organic smear suppressing component and an inorganic smear suppressing component, and an organic smear suppressing component is preferred from the viewpoint of improving insulation reliability. Specifically, examples of the organic smear suppressing component include pigments, dyes, rubber particles, antioxidants, and infrared absorbers, and examples of the inorganic smear suppressing component include metal compound powder and metal powder. (C) As a smear suppressing component, it is preferable to use at least one selected from the group consisting of pigments, dyes, rubber particles, antioxidants and infrared absorbers. Of these, pigments and/or rubber particles are more preferable, and pigments are more preferable from the viewpoint of excellent smear suppression ability and excellent peel strength. These may be used alone or in combination of two or more.

As a pigment, blue pigment, yellow pigment, red pigment, black pigment, green pigment, etc. are mentioned. As a blue pigment, pigments, such as a phthalocyanine system, an anthraquinone system, and a dioxazine system, are mentioned. Examples of the yellow pigment include pigments such as monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based. Examples of the red pigment include pigments such as monoazo, disazo, azolake, benzimidazole, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Carbon black, graphite, etc. are mentioned as a black pigment. As a green pigment, a pigment, such as a phthalocyanine system, is mentioned. The pigment may be used alone or in combination of two or more, and one or more selected from the group consisting of blue pigments, yellow pigments, red pigments, black pigments, and green pigments can be suitably blended. Among them, it is preferable to use at least one selected from the group consisting of blue pigments, yellow pigments, red pigments, and green pigments, from the viewpoint of further improving insulation reliability, and blue pigments, yellow pigments, and red pigments are used. It is more preferable to use a mixed pigment formed by mixing. In addition, when preparing a mixed pigment formed by mixing a blue pigment, a yellow pigment, and a red pigment, a blue pigment, a yellow pigment, and a red color are obtained from the viewpoint of efficiently absorbing the laser during drilling and further suppressing smear generation. As for the mass ratio of a pigment, 2-6:5-9:6-10 are preferable and 3-5:6-8:7-9 are more preferable.

As the dye, azo (mono azo, disazo, etc.) dyes, azo-methine dyes, anthraquinone dyes, quinoline dyes, ketoneimine dyes, fluorone dyes, nitro dyes, xanthene dyes, acenaphthene dyes, quinophthalone dyes, Aminoketone dyes, methine dyes, perylene dyes, coumarin dyes, perinone dyes, triphenyl dyes, triallylmethane dyes, phthalocyanine dyes, ink phenol dyes, azine dyes, or mixtures thereof.

Examples of the rubber particles include core shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell-type rubber particles are rubber particles having a core layer and a shell layer, for example, a two-layer structure in which the shell layer of the outer layer is made of a glass-like polymer, and the core layer of the inner layer is made of a rubber-like polymer, or the shell layer of the outer layer is glass. And a three-layer structure composed of a shape polymer, a middle layer composed of a rubber-like polymer, and a core layer composed of a glass-like polymer.

Examples of the antioxidants include hindered phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. As a commercial item, pentaerythritol tetraquis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate ("IRGANOX 1010" by Chiba Japan Co., Ltd.), 2,2-thio-di Ethylene bis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] ("IRGANOX 1035" manufactured by Chiba Japan Co., Ltd.), 1,3,5-tris [[3, 5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Chiba Japan Co., Ltd. ) Manufacturing "IRGANOX 3114") and the like.

Examples of the infrared absorber include phthalocyanine compounds, anthraquinone compounds, and nickel complexes. As a commercial item, IR-14 (made by Nihon Shokubai Co., Ltd.), TX-HA-1 (made by Nihon Shokubai Co., Ltd.), etc. are mentioned.

As the metal compound powder, titanias such as titanium oxide, magnesia such as magnesium oxide, iron oxides such as iron oxide, nickel oxides such as nickel oxide, zinc oxides such as manganese dioxide and zinc oxide, silicon dioxide, aluminum oxide, rare earth oxides, Cobalt oxide such as cobalt oxide, tin oxide such as tin oxide, tungsten oxide such as tungsten oxide, silicon carbide, tungsten carbide, boron nitride, silicon nitride, titanium nitride, aluminum nitride, barium sulfate, rare earth sulfide, or mixtures thereof And powders.

Examples of the metal powder include silver, aluminum, bismuth, cobalt, copper, iron, magnesium, manganese, molybdenum, nickel, palladium, antimony, silicon, tin, titanium, vanadium, tungsten, zinc, or powders of alloys or mixtures thereof. Can be lifted.

(C) The content of the smear suppressing component is preferably 10% by mass or less, more preferably 5% by mass or less, with respect to 100% by mass of the nonvolatile component in the resin composition, from the viewpoint of preventing deterioration of the cured properties. 4 mass% or less is more preferable, 3 mass% or less is more preferable, and 2 mass% or less is particularly preferable. Moreover, from the viewpoint of improving the smear suppressing ability, 0.001 mass% or more is preferable, 0.01 mass% or more is more preferable, 0.02 mass% or more is more preferable, and 0.05 mass or more is preferable with respect to 100 mass% of nonvolatile components in the resin composition. % Or more is more preferable, 0.08 mass% or more is particularly preferable, and 0.1 mass% or more is particularly preferable.

<(D) Inorganic filler>

The resin composition of the present invention may contain (D) an inorganic filler for the purpose of lowering the linear thermal expansion rate and for improving the smear removal property during roughening treatment. (D) As an inorganic filler, for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, And calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among them, silica is preferred. As silica, amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like are preferable, and fused silica is more preferable. Moreover, spherical silica is preferable as silica. These may be used alone or in combination of two or more. As commercially available spherical fused silica, "SO-C2" and "SO-C1" manufactured by Admatex Co., Ltd. are mentioned.

(D) The average particle diameter of the inorganic filler is not particularly limited, but the upper limit of the average particle diameter of the inorganic filler is a viewpoint of forming fine wiring on the insulating layer, and smear during drilling by increasing the total surface area of the inorganic filler. From the viewpoint of suppressing the occurrence, 5 µm or less is preferable, 3 µm or less is more preferable, 1 µm or less is more preferable, 0.7 µm or less is even more preferable, 0.5 µm or less is particularly preferable, and 0.4 µm or less Is particularly preferred, and 0.3 µm or less is particularly preferred. On the other hand, the lower limit of the average particle diameter of the inorganic filler is preferably 0.01 µm or more, and more preferably 0.03 µm or more, from the viewpoint of preventing the viscosity of the varnish from rising and handling deterioration when the resin composition is a varnish. It is preferable, 0.05 µm or more is more preferable, 0.07 µm or more is particularly preferable, and 0.1 µm or more is particularly preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction scattering type particle size distribution measuring device, and the median diameter can be measured by making it an average particle size. As the measurement sample, one in which an inorganic filler is dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-500, 750, 950 manufactured by Horiba Seisakusho Co., Ltd. can be used.

(D) The content of the inorganic filler is not particularly limited, but is 85 mass when the nonvolatile component in the resin composition is 100 mass% from the viewpoint of preventing the decrease in flexibility when the resin composition is in the form of a film. % Or less is preferable, 80 mass% or less is more preferable, and 75 mass% or less is more preferable. In addition, from the viewpoint of lowering the thermal expansion coefficient of the insulating layer, and increasing the total surface area of the inorganic filler, suppressing the occurrence of smear during perforation processing, and easily removing the smear during roughening treatment, non-volatile components in the resin composition When 100 mass %, 40 mass% or more is preferable, 50 mass% or more is more preferable, 60 mass% or more is more preferable, and 70 mass% or more is more preferable.

(D) Inorganic fillers, from the viewpoint of improving moisture resistance and dispersibility, aminosilane-based coupling agent, ureidsilane-based coupling agent, epoxysilane-based coupling agent, mercaptosilane-based coupling agent, silane-based coupling agent, vinylsilane Surface treatment with surface treatment agents such as system coupling agent, styrylsilane coupling agent, acrylate silane coupling agent, isocyanate silane coupling agent, sulfidesilane coupling agent, organosilazane compound, titanate coupling agent, etc. It is desirable. Among them, the inorganic filler is further improved in moisture resistance and dispersibility by surface-treating the inorganic filler with an organosilazane compound, followed by surface treatment with a silane coupling agent. These may be used alone or in combination of two or more.

Specifically, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltri Aminosilane-based coupling agents such as methoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, 3-woo Uradesilane-based coupling agents such as raidpropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 3-glycidyloxypropylmethyldiethoxysilane , Epoxy silane coupling agents such as 3-glycidyloxypropyl (dimethoxy)methylsilane, glycidylbutyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- Mercaptosilane-based coupling agents such as mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 11-mercaptoundecyltrimethoxysilane, methyltrimethoxy Silane coupling agents such as silane, octadecyltrimethoxysilane, phenyltrimethoxysilane, metahydroxypropyltrimethoxysilane, imidazolesilane, triazinesilane, and tert-butyltrimethoxysilane, vinyltrimethoxysilane , Vinyl silane-based coupling agents such as vinyl triethoxysilane and vinyl methyl diethoxysilane, styrylsilane-based coupling agents such as p-styryl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-meta Acrylate silane coupling agents such as krilloxypropyl trimethoxysilane, 3-methacryloxypropyl dimethoxysilane, 3-methacryloxypropyl triethoxysilane, and 3-methacryloxypropyl diethoxysilane, 3-isocyanate Isocyanate silane coupling agents such as propyl trimethoxysilane, sulfide silane coupling agents such as bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexaphenyldisilazane, trisilazane, cyclotrisilazane, 2,2,4,4,6,6-hexamethyl Cyclotrisilazane, octamethylcyclotetrasilazane, hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane , 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltete Laphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, Organosilazane compounds such as hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, tetramethyldisilazane, tetra-n-butyl titanate dimer, titanium-i-propoxyoctylene glycolate, tetra-n- Butyl titanate, titanium octylene glycolate, diisopropoxy titanbis (triethanol aminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene Titanate, bis(dioctylpyrophosphate)oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra(2-ethylhexyl) titanate, tetraisopropylbis( Dioctylphosphite) titanate, tetraoctylbis(ditridecylphosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, isopropyltri Octanoyl titanate, isopropyl cumylphenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tree ( Titanate systems such as dioctyl phosphate) titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, and isopropyl tri (N-amideethyl aminoamino) titanate And coupling agents. Among them, the aminosilane-based coupling agent is preferred because of its excellent moisture resistance, dispersibility, and properties of a cured product, and the organosilazane compound is preferred because of its excellent improvement in dispersibility of the resin varnish. As a commercial product of the surface treatment agent, "KBM403" (3-glycidoxypropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyl trimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), ``KBE903'' manufactured by Shin-Etsu Chemical Co., Ltd. (3-aminopropyl triethoxysilane), ``KBM573'' manufactured by Shin-Etsu Chemical Co., Ltd. (N-phenyl-3-aminopropyl trimethoxysilane) And the like.

In addition, the inorganic filler surface-treated with the surface treatment agent can measure the carbon amount per unit weight of the inorganic filler after washing treatment with a solvent (for example, methyl ethyl ketone). Here, the term "amount of carbon per unit weight of the inorganic filler" refers to the amount of carbon (g) bound to 1 g of the inorganic filler as a percentage. Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment material, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solids, the carbon content per unit weight of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Seisakusho, etc. can be used.

The amount of carbon per unit weight of the inorganic filler is preferably 0.02% or more, more preferably 0.05% or more, and more preferably 0.1% or more from the viewpoint of improving the dispersibility of the inorganic filler or stabilizing the roughness of the square-average square root after roughening of the cured product. This is more preferred. On the other hand, 3% or less is preferable, 2% or less is more preferable, and 1% or less is more preferable from the viewpoint of preventing the increase of the melt viscosity of the resin varnish or the melt viscosity in the form of an adhesive film.

<(E) Curing accelerator>

The resin composition of the present invention may further contain (E) a curing accelerator for the purpose of adjusting the curing time and curing temperature. (E) The curing accelerator is not particularly limited, and examples thereof include imidazole-based curing accelerators, amine-based curing accelerators, organophosphine compounds, and organophosphonium salt compounds. These may be used alone or in combination of two or more.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl( 1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2, 4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adduct, 2-phenyl-4 ,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1 And imidazole compounds such as dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins. . These may be used alone or in combination of two or more.

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-tris(dimethylaminomethyl)phenol, and 1,8-diazabi And amine compounds such as cyclo(5,4,0)-undecene (hereinafter abbreviated as DBU). These may be used alone or in combination of two or more.

Examples of the organophosphine compound and the organophosphonium salt compound include TPP, TPP-K, TPP-S, TPTP-S, TBP-DA, TPP-SCN, and TPTP-SCN (trade names of Tokyo Chemical Industries, Ltd.). Can. These may be used alone or in combination of two or more.

(E) The content of the curing accelerator is preferably 0.01 to 3% by mass, more preferably 0.1 to 2% by mass, relative to 100% by mass of the nonvolatile component in the resin composition, from the viewpoint of storage stability of the resin varnish and efficiency of curing. desirable.

<(F) Thermoplastic resin>

By containing (F) a thermoplastic resin in the resin composition of the invention, the viscosity of the resin varnish obtained from the resin composition can be adjusted to a suitable range, and flexibility of the cured product can be increased. The thermoplastic resin is not particularly limited, and examples thereof include phenoxy resins, polyvinyl acetal resins, polyimide resins, polyamideimide resins, polyamide resins, polyethersulfone resins, polysulfone resins, polybutadiene resins, and ABS resins. have. Among them, phenoxy resin and polyvinyl acetal resin are preferred, and phenoxy resin is more preferred from the viewpoint of increasing the flexibility of the cured product and contributing to adhesion. These may be used alone or in combination of two or more. It is preferable that the thermoplastic resin has a glass transition temperature of 80°C or higher.

The weight average molecular weight of the thermoplastic resin is preferably in the range of 5000 to 800000, more preferably in the range of 10000 to 200000, more preferably in the range of 15000 to 150000, and even more preferably in the range of 20000 to 100,000. . By being in the range, the effect of improving the film forming ability and mechanical strength is sufficiently exhibited, and compatibility with the epoxy resin can also be improved. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by GPC method 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. 804L/K-804L can be calculated by using a chloroform or the like as a mobile phase, measuring at a column temperature of 40°C, and using a calibration curve of standard polystyrene.

As the phenoxy resin, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, And those having one or more skeletons selected from adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The phenoxy resin may be used by mixing two or more kinds. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. As a commercial item, Mitsubishi Chemical Co., Ltd. product 1256, 4250 (bisphenol A skeleton containing phenoxy resin), Mitsubishi Chemical Corporation YX8100 (bisphenol S skeleton containing phenoxy resin), Mitsubishi Chemical Corporation And YX6954 (bisphenol acetophenone skeleton-containing phenoxy resin). As commercial products, Shinnittetsu Chemical Co., Ltd. FX280, FX293, Mitsubishi Chemical Co., Ltd. YL7553, YL6954, YL6794, YL7213, YL7290, YL7482 etc. are mentioned.

As specific examples of the polyvinyl acetal resin, manufactured by Denki Chemical Industry Co., Ltd., Denkabutrial 4000-2, 5000-A, 6000-C, 6000-EP, Sekisui Chemical Industry Co., Ltd. Srek BH series, And BX series, KS series, BL series, and BM series. As a specific example of a polyimide resin, the polyimide "Rika coat SN20" and "Rika coat PN20" manufactured by Shin Nippon Rika Co., Ltd. are mentioned. In addition, a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetrabasic anhydride (described in Japanese Patent Laid-Open No. 2006-37083), a polysiloxane skeleton-containing polyimide (Japan And modified polyimides such as those described in Patent Publication No. 2002-12667, Japanese Patent Publication No. 2000-319386, etc.). As a specific example of a polyamide imide resin, the polyamide imide "Biromax HR11NN" and "Biromax HR16NN" by Toyobo Seki Co., Ltd. are mentioned. Moreover, modified polyamideimides, such as polyamide imide "KS9100" and "KS9300", which are polysiloxane skeletons manufactured by Hitachi Chemical Industries, Ltd., are exemplified. As a specific example of a polyether sulfone resin, Sumitomo Chemical Co., Ltd. polyether sulfone "PES5003P" etc. are mentioned. As a specific example of a polysulfone resin, polysulfone "P1700", "P3500", etc. by Solvent Advanced Polymers Co., Ltd. are mentioned.

Although content of a thermoplastic resin is not specifically limited, 0.5-30 mass% is preferable with respect to 100 mass% of nonvolatile components in a resin composition from a viewpoint of adjustment of melt viscosity of a sheet-like laminated material or adjustment of a resin varnish viscosity. And 1 to 20% by mass is more preferable.

<(G) Curing agent>

The resin composition of the present invention may further contain (G) a curing agent. Accordingly, the insulation reliability, peel strength, and mechanical properties of the cured product of the resin composition can be improved. (G) The curing agent is not particularly limited, and examples thereof include phenolic curing agents, cyanate ester-based curing agents, benzoxazine-based curing agents, and acid anhydride-based curing agents. These can use 1 type(s) or 2 or more types. Among these, phenol-based curing agents and cyanate-based curing agents are preferred from the viewpoints of improving smear removal properties and improving dielectric properties.

The phenolic curing agent is not particularly limited, but includes phenol novolak resins, triazine skeleton-containing phenol novolak resins, naphthol novolak resins, naphthol aralkyl resins, triazine skeleton-containing naphthol resins, biphenyl aralkyl type phenol resins, and the like. Can. For example, as a biphenyl aralkyl type phenol resin, "MEH-7700", "MEH-7810", "MEH-7851" (manufactured by Meiwa Chemical Co., Ltd.), "NHN", "CBN", "GPH" ( Nihon Kayaku Co., Ltd.), as a naphthol aralkyl resin, "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", and "SN395" (Totosei (Manufactured by Co., Ltd.), ``TD2090'' as a phenol novolak resin (manufactured by DIC Corporation), ``LA3018'', ``LA7052'', ``LA7054'', ``LA1356'' as a triazine skeleton-containing phenol novolak resin (DIC (Note) ) Manufacturing). The phenolic curing agent may be used alone or in combination of two or more.

Although there is no restriction|limiting in particular as a cyanate ester type hardener, A novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardener, dicyclopentadiene type cyanate ester type hardener, bisphenol type (bisphenol A Molds, bisphenol F-type, bisphenol S-type, etc.) cyanate ester-based curing agents, and prepolymers in which they are partially triazineized. Although the weight average molecular weight of a cyanate ester-type hardener is not specifically limited, 500-4500 are preferable and 600-3000 are more preferable. As specific examples of the cyanate ester-based curing agent, for example, bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylene bis (2,6- Dimethylphenylcyanate), 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-sia Polyfunctional cyanate resins derived from bifunctional cyanate resins such as natephenyl)thioether and bis(4-cyanatephenyl)ether, phenol novolac, cresol novolac, phenol resin containing dicyclopentadiene structure, etc. And prepolymers in which the cyanate resin is partially triazineized, etc. These may be used alone or in combination of two or more.As a commercially available cyanate ester resin, a phenol novolac-type polyfunctional cyanate ester resin (Londer Japan) Prepolymer, PT30, cyanate equivalent 124), a prepolymer in which a part or all of bisphenol A dicyanate is triazineized to become a trimer (manufactured by Lauder Japan Co., Ltd., BA230, cyanate equivalent 232), dicyclopentadiene Structure-containing cyanate ester resin (manufactured by Lauder Japan Co., Ltd., DT-4000, DT-7000) and the like.

Although there is no restriction|limiting in particular as a benzoxazine type hardener, Specifically, F-a, P-d (made by Shikoku Chemical Co., Ltd.), HFB2006M (made by Showa Kobunshi Co., Ltd.), etc. are mentioned.

The content of the (G) curing agent in the resin composition is not particularly limited, but from the viewpoint of preventing the cured product of the resin composition from becoming brittle, 0.5 to 10 mass% is preferable with respect to 100 mass% of the nonvolatile component in the resin composition. , 1 to 6% by mass is more preferable.

<Other ingredients>

In addition, the resin composition of the present invention, if necessary, in a range that does not impair the effects of the present invention, heat-curing components such as maleimide compound, bisallyl nadiimide compound, vinylbenzyl resin, vinylbenzyl ether resin, silicone powder, nylon Organic fillers such as powders and fluorine powders, thickeners such as Olben and Benton, antifoaming agents or leveling agents of silicone-based, fluorine-based, and polymeric-based adhesives, imidazole-based, thiazole-based, triazole-based, silane coupling agents, etc. Flame retardants, such as metal hydroxides, and the like.

In the resin composition of the present invention, the above components are appropriately mixed, and if necessary, kneading means such as three rolls, a ball mill, a bead mill, or a sand mill, or a stirring means such as a super mixer or planetary mixer. It can be manufactured as a resin varnish by kneading or mixing. In addition, the cured product of the resin composition of the present invention can achieve low dielectric tangentization, and can suppress smear in the via hole after roughening the cured product by drilling.

The dielectric tangent of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of dielectric tangent> described later. Specifically, it can be measured at a frequency of 5.8 GHz and a measurement temperature of 23°C by the cavity resonator perturbation method. From the viewpoint of preventing heat generation at high frequencies, and reducing signal delay and signal noise, the dielectric tangent is preferably 0.05 or less, more preferably 0.04 or less, more preferably 0.03 or less, even more preferably 0.02 or less, and less than 0.01 Is particularly preferred. On the other hand, the lower limit of the dielectric tangent is not particularly limited, but is preferably 0.001 or more.

The square mean square root roughness Rq of hardened|cured material of the resin composition of this invention can be grasped|required by the measuring method described in <Measurement of square mean square root roughness (Rq)> mentioned later. The surface of the insulating layer after the roughening treatment is required to have fine irregularities from the viewpoint of reducing the loss of electrical signals. It shows the density of the unevenness of the surface of the insulating layer, and has an average square root roughness Rq. From this index, it can be seen that the surface of the insulating layer has a dense uneven shape, not a simple average value of the unevenness of the surface of the insulating layer. Specifically, the square average roughness Rq of the surface of the insulating layer after curing the resin composition to form an insulating layer and roughly treating the surface of the insulating layer is preferably 500 nm or less, more preferably 400 nm or less. , 300 nm or less is more preferable, 200 nm or less is even more preferable, and 100 nm or less is particularly preferable. Moreover, 5 nm or more is preferable, 10 nm or more is more preferable, and 20 nm or more is still more preferable at the point which obtains favorable adhesiveness with a plating conductor layer.

The peel strength of the cured product of the resin composition of the present invention can be grasped by a measuring method described in <Measurement of Peel Strength (Peel Strength) of Plating Conductor Layer> described later. Specifically, the peel strength of the conductor layer obtained by curing the resin composition to form an insulating layer, and plating the surface of the insulating layer after roughening treatment, and the insulating layer is preferably 0.3 kgf/cm or more, and 0.5 kgf More than /cm is more preferable, and more than 0.6 kgf/cm is more preferable. On the other hand, the upper limit is not particularly limited, but is generally 1.2 kgf/cm or less.

The use of the resin composition of the present invention is not particularly limited, but sheet-like laminated materials such as adhesive films and prepregs, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductors It can be used for a wide range of applications in which a resin composition is required, such as sealing materials, hole-filling resins, and component embedded resins. Among them, in the resin composition of the present invention, since smear in the via hole after the hardening of the cured product can be suppressed, the adhesion of plating in the via hole is improved, thereby preventing voids in the via hole and forming in multiple stages. The conduction reliability between the insulating layers of a multilayer printed wiring board can be ensured. That is, in the manufacture of a multilayer printed wiring board, it can be suitably used as a resin composition for forming an insulating layer (a resin composition for an insulating layer of a multi-layer printed wiring board), and a resin composition for forming a conductor layer by plating (by plating) It can be used more suitably as a resin composition for insulating layers of the multilayer printed wiring board which forms a conductor layer. The resin composition of the present invention may be applied to a circuit board in a varnish state to form an insulating layer, but industrially, it is generally preferred to use it in the form of a sheet-like laminated material such as an adhesive film or prepreg. The softening point of the resin composition is preferably 40 to 150°C from the viewpoint of lamination of the sheet-like laminated material.

<Sheet-shaped laminated material>

(Adhesive film)

In one embodiment, the sheet-like laminated material of the present invention is an adhesive film. The adhesive film is a resin composition layer formed on a support. The adhesive film is prepared by a method known to those skilled in the art, for example, a resin varnish in which a resin composition is dissolved in an organic solvent, and the resin varnish is applied to a support using a die coater or the like, and further heated or hot air sprayed. It can be manufactured by drying the organic solvent to form a resin composition layer.

Examples of the organic solvent include acetone, methyl ethyl ketone, and ketones such as cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and acetic acid esters such as carbitol acetate, cellosolve, and butylcar. And carbitols such as bitol, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Organic solvents may be used in combination of two or more.

Drying conditions are not particularly limited, and the content of the organic solvent in the resin composition layer is dried so as to be 10% by mass or less, preferably 5% by mass or less. Depending on the amount of the organic solvent in the varnish and the boiling point of the organic solvent, the resin composition layer can be formed by drying the varnish containing, for example, 30 to 60% by mass of the organic solvent at 50 to 150°C for about 3 to 10 minutes. have.

It is preferable that the thickness of the resin composition layer formed in the adhesive film is greater than or equal to the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, it is preferable that the resin composition layer has a thickness of 10 to 100 μm. From the viewpoint of thinning, 15 to 80 µm is more preferable.

Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films. And various plastic films. Moreover, you may use release paper, metal foil, such as copper foil and aluminum foil. Especially, from a versatility point, a plastic film is preferable and a polyethylene terephthalate film is more preferable. The support and the protective film to be described later may be subjected to surface treatments such as mad (MAD) treatment or corona treatment. Further, the release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluorine resin release agent.

Although the thickness of the support is not particularly limited, 10 μm or more is preferable in the case of performing a drilling process from the support, even when the energy of laser irradiation is large, the resin residue is hard to remain and the generation of smear can be suppressed. , 20 µm or more is more preferable, and 30 µm or more is more preferable. In addition, 150 µm or less is preferable, 100 µm or less is more preferable, and 50 µm or less is more preferable from the viewpoint of improving cost performance and efficient puncturing when performing puncture from the support.

A protective film conforming to the support can be further laminated on the surface on the opposite side to the surface of the resin composition layer where the support is in close contact. In this case, the adhesive film includes a support, a resin composition layer formed on the support, and a protective film formed on the resin composition layer. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, adhesion or damage to the surface of the resin composition layer or the like can be prevented. The adhesive film can also be wound up in a roll shape and stored.

(Prepreg)

In one embodiment, the sheet-like laminated material of the present invention is a prepreg. The prepreg can be produced by impregnating the sheet-shaped reinforcing substrate with a sheet-shaped reinforcing substrate by a hot-melt method or a solvent method, and heating and semi-curing it. That is, it can be set as a prepreg in which the resin composition of the present invention is impregnated into the sheet-shaped reinforcing substrate. As the sheet-shaped reinforcing base material, for example, those made of fibers commonly used as prepreg fibers such as glass cross and aramid fibers can be used. And it is suitable that the prepreg is formed on the support.

The hot-melt method produces a prepreg by dissolving the resin composition in an organic solvent, coating it once on a support, laminating it on a sheet-shaped reinforcing substrate, or directly coating the sheet-shaped reinforcing substrate by a die coater. Is how to do it. In the solvent method, a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as an adhesive film, and the sheet-shaped reinforcing substrate is immersed in the varnish, and the resin varnish is impregnated into the sheet-shaped reinforcing substrate, and then dried. It is a way. Moreover, it can also be prepared by heating and laminating an adhesive film continuously on both sides of a sheet-shaped reinforcing substrate under pressure and pressure conditions. A support or a protective film can also be used similarly to the adhesive film.

<Multilayer printed wiring board using sheet-shaped laminated material>

Next, an example of a method for manufacturing a multilayer printed wiring board using the sheet-like laminated material produced as described above will be described.

First, a sheet-like laminated material is laminated (laminated) on one or both sides of a circuit board using a vacuum laminator. As a board|substrate used for a circuit board, a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, a thermosetting polyphenylene ether board etc. are mentioned, for example. In addition, a circuit board here means that the conductor layer (circuit) by which pattern processing was carried out is formed in one side or both surfaces of the said board|substrate. Further, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits). do. In addition, roughening treatment may be previously performed on the surface of the conductor layer by blackening treatment, copper etching, or the like.

When the sheet-like laminated material has a protective film, after removing the protective film, the sheet-like laminated material and the circuit board are preheated as necessary, and the sheet-like laminated material is laminated to the circuit board while pressing and heating. In one suitable embodiment, the sheet-like laminated material of the present invention is laminated to a circuit board under reduced pressure by a vacuum lamination method. The conditions of the lamination are not particularly limited, but, for example, the crimp temperature (laminate temperature) is preferably 70 to 140°C, and the crimp pressure (laminate pressure) is preferably 1 to 11 kgf/cm 2 (9.8×10 ⁴ to 107.9×104 N/m 2 ), and the compression time (laminate time) is preferably 5 to 180 seconds, and it is preferable to laminate under reduced pressure of 20 mmHg (26.7 hPa) or less of air pressure. Moreover, the method of lamination may be a batch type or a continuous type in a roll. Vacuum lamination can be performed using a commercially available vacuum laminator. As commercially available vacuum laminators, for example, Nichigo-Morton Co., Ltd. vacuum applicator, Meiki Seisakusho vacuum pressurized laminator, Hitachi Industries Co., Ltd. roll type dry coater, Hitachi ACC Co., Ltd. The manufacturing vacuum laminator etc. are mentioned.

When the sheet-like laminated material is laminated to a circuit board, and then cooled to near room temperature, when the support is peeled, the peeling is performed and the resin composition is thermally cured to form an insulating layer. Thus, an insulating layer can be formed on the circuit board. The conditions of the thermosetting may be appropriately selected depending on the type, content, etc. of the resin component in the resin composition, but preferably 20 to 180 minutes at 150°C to 220°C, more preferably 30 to 120°C at 160°C to 210°C. It is selected in the range of minutes. After forming the insulating layer, if the support is not peeled off before curing, it may be peeled off as necessary.

Further, the sheet-like laminated material may be laminated on one or both sides of the circuit board using a vacuum press machine. The lamination process of heating and pressurizing under reduced pressure can be performed using a general vacuum hot press machine. For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side. The press conditions are such that the degree of decompression is usually 1×10 ^-2 MPa or less, preferably 1×10 ^-3 MPa or less. Although heating and pressing may be performed in one step, it is preferable to divide the conditions into two or more steps from the viewpoint of controlling the staining of the resin. For example, the first-stage press is performed in a range of 70 to 150°C and the pressure is 1 to 15 kgf/cm 2, and the second-stage press is 150 to 200°C and the pressure is 1 to 40 kgf/ It is preferable to perform in the range of cm2. It is preferable that the time of each step is 30 to 120 minutes. In this way, the insulating layer can be formed on the circuit board by thermally curing the resin composition layer. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

Subsequently, a through hole is formed in the insulating layer formed on the circuit board to form via holes and through holes. The drilling process can be performed by a known method such as drilling, laser, plasma, or the like, and combining these methods as necessary. Among them, perforation processing with a laser such as a carbon dioxide gas laser or a YAG laser is the most common method. In addition, a multilayer printed wiring board is formed by laminating the sheet-like laminated material of the present invention on a circuit board, thermally curing the resin composition layer to form an insulating layer, and forming a via hole by punching the insulating layer formed on the circuit board from the support. It is preferable to manufacture, and it is preferable to peel the support after drilling. As described above, by forming a via hole by drilling from the support, generation of smear can be suppressed. Moreover, in order to cope with thinning of a multilayer printed wiring board, the top diameter (diameter) of the via hole is preferably 15 to 70 m, more preferably 20 to 65 m, and even more preferably 25 to 60 m.

Subsequently, the roughening treatment of the surface of the insulating layer is performed. Plasma treatment etc. are mentioned as a dry roughening process, As a wet roughening process, the method of performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order is mentioned. Either dry or wet roughening treatment may be employed, but the wet roughening treatment is preferable in that it is possible to remove smear in the via hole while forming an uneven anchor on the surface of the insulating layer. The swelling treatment with the swelling solution is performed by immersing the insulating layer in the swelling solution at 50 to 80°C for 5 to 20 minutes (preferably at 55 to 70°C for 8 to 15 minutes). An alkali solution, a surfactant solution, etc. are mentioned as a swelling liquid, Preferably it is an alkali solution. Examples of the alkali solution include sodium hydroxide solution and potassium hydroxide solution. Examples of commercially available swelling solutions include Swelling Dip Securiganth P (Swelling Dip Securiganth P) manufactured by Atotech Japan Co., Ltd., and Swelling Dip Securiganth SBU (SBU). Can. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer at 60 to 80°C for 10 to 30 minutes (preferably at 15 to 25 minutes at 70 to 80°C) and immersing in the oxidizing agent solution. Examples of the oxidizing agent include alkali and manganese acid solutions in which sodium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, bichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and the like. Further, the concentration of the permanganate salt in the alkaline and manganese acid solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline and manganic acid solutions such as Concentrate Compact CP manufactured by Atotech Japan Co., Ltd., and Dosing Solution Security P. The neutralization treatment with the neutralization liquid is performed by immersing the insulating layer in the neutralization liquid at 30 to 50°C for 3 to 10 minutes (preferably at 3 to 8 minutes at 35 to 45°C). As the neutralizing solution, an acidic aqueous solution is preferable, and commercially available products include Reduction Solutions Security P, manufactured by Atotech Japan Co., Ltd.

Subsequently, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, known methods such as vapor deposition, sputtering, and ion plating can be used. Examples of the wet plating include a method of forming a conductor layer by combining electroless plating and electrolytic plating, a method of forming a plating resist having an inverse pattern with the conductor layer, and forming a conductor layer only by electroless plating. As a method of forming a pattern thereafter, for example, a subtractive method, a semiadditive method, or the like known to those skilled in the art can be used. And the multilayer printed wiring board which laminated|stacked the buildup layer in multiple stages can be manufactured by repeating the above-mentioned series of process several times. In the present invention, since the occurrence of smear is suppressed, the reliability of conduction between layers can be ensured. Therefore, the sheet-like laminated material of the present invention can be suitably used to form a build-up layer of a multilayer printed wiring board.

<Semiconductor device>

A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor chip at a conduction point of the multilayer printed wiring board of the present invention. The "conduction point" is "a place for transmitting an electric signal in a multi-layer printed wiring board", and the place may be either a surface or a buried place. Moreover, the semiconductor chip is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

The method of mounting a semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and a bump press build-up layer The mounting method by (BBUL), the mounting method by anisotropic conductive film (ACF), the mounting method by non-conductive film (NCF), etc. are mentioned.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but they do not limit the present invention in any sense. In addition, in the following description, "parts" means "parts by mass".

<Measurement method, evaluation method>

First, various measurement methods and evaluation methods will be described.

<Smear evaluation>

About the adhesive film composition sheet obtained in each Example and each comparative example, the smear (resin residue) was evaluated according to the following.

(1) Fabrication of circuit board

A circuit pattern was formed by etching on both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness of 18 µm, substrate thickness of 0.8 mm, manufactured by Matsushita Denko Co., Ltd.), and also a microetching agent (Mack Co., Ltd. ) Preparation CZ8100) was performed to prepare a circuit board.

(2) Lamination of adhesive film

The adhesive film composition sheet produced in each of the Examples and Comparative Examples was placed on both sides of the circuit board produced in (1) above using a batch-type vacuum pressure laminator MVLP-500 (trade name, manufactured by Makey Co., Ltd.). It was laminated. The laminate was decompressed for 30 seconds to set the atmospheric pressure to 13 hPa or less, and then, by pressing at 100°C for 30 seconds at a pressure of 0.74 MPa.

(3) curing of the resin composition layer

In Example 1-8 and Comparative Example 1, the PET film was peeled from the laminated adhesive film, and the resin composition layer was cured at 170°C for 30 minutes to form an insulating layer. In Example 9, without exfoliating the PET film, the resin composition layer was cured under a curing condition of 170° C. for 30 minutes to form an insulating layer.

(4) Via hole formation

Using a CO ₂ laser processing machine (YB-HCS03T04) manufactured by Matsushita Yosetsu Systems Co., Ltd., perforated the insulating layer at a frequency of 1000 Hz with a pulse width of 13 μs and a number of shots 3, and via hole formation on the surface of the insulating layer A via hole having a top diameter (diameter) of 60 µm was formed. In Example 9, the PET film was peeled after that.

(5) Harmony treatment

The circuit board was immersed in Swelling Deep Security P of Atotech Japan Co., Ltd., which is a swelling solution, at 60°C for 10 minutes. Subsequently, it was immersed in a concentrate compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) of Atotech Japan Co., Ltd., which is a conditioning solution (oxidizing agent), at 80°C for 20 minutes. Finally, it was immersed in a reduction solution and security P of Atotech Japan Co., Ltd., a neutralizing solution, at 40°C for 5 minutes.

(6) Evaluation of the residue at the bottom of the via hole

The periphery of the via hole bottom was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the via hole bottom was measured from the obtained image. ◎○ has a maximum smear length of less than 2 µm, ◎ has a maximum smear length of 2 µm or more and less than 3.5 µm, ○ has a maximum smear length of 3.5 µm or more and less than 5 µm, and × represents a maximum smear length of 5 µm or more.

<Measurement of peeling strength (peel strength) of the plated conductor layer, measurement of square mean square root roughness (Rq) and evaluation of insulation reliability>

(1) Basic treatment of laminated board

On both sides of the glass cloth-based epoxy resin double-sided copper-clad laminate of the inner layer circuit (copper foil thickness 18 µm, cupping rate 60%, substrate thickness 0.3 mm, Matsushita Denko Co., Ltd. R5715ES), manufactured by Mack CZ8100 The copper surface was roughened by immersion.

(2) Lamination of adhesive film

The adhesive film produced in each Example and each comparative example was laminated on both surfaces of a laminated board using the batch-type vacuum pressure laminator MVLP-500 (made by the company Meiki Seisakusho, a brand name). The laminate was decompressed for 30 seconds, the atmospheric pressure was 13 hPa or less, and then, by pressing for 30 seconds at 100°C and a pressure of 0.74 MPa.

(3) curing of the resin composition

The PET film was peeled from the laminated adhesive film, and the resin composition was cured at 170°C for 30 minutes.

(4) Harmony treatment

The laminated plate was immersed in a swelling solution, diethylene glycol monobutyl ether-containing swelling dip security P of Atotech Japan Co., Ltd. for 10 minutes at 60°C, and then, as a coordinating solution, Atotech Japan Co., Ltd. Concentrate compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) immersed at 80°C for 20 minutes, and finally as a neutralization solution, at Atotech Japan's reduction solution and security P Soaked at 40°C for 5 minutes. The laminate after this roughening treatment was used as Sample A.

(5) Plating formation by semi-additive construction method

In order to form a circuit on the surface of the insulating layer, the laminated plate was immersed in a solution for electroless plating containing PdCl ₂ and then immersed in an electroless copper plating solution. After heating at 150° C. for 30 minutes to perform annealing treatment, an etching resistor was formed, and after pattern formation by etching, copper sulfate electroplating was performed to form a conductor layer with a thickness of 30 μm. Next, an annealing treatment was performed at 180°C for 60 minutes. This laminated board was used as Sample B.

(6) Measurement of square mean square root roughness (Rq value)

About sample A, the Rq value was calculated|required by the value obtained by making the measurement range into 121 micrometers x 92 micrometers with a VSI contact mode and a 50-times lens using a non-contact surface roughness machine (WYKO NT3300 by Bco Instruments). . And the average value of 10 points was calculated|required, and it was set as the measured value.

(7) Measurement of peeling strength (peel strength) of the plating conductor layer

In the conductor layer of Sample B, a notch of a portion having a width of 10 mm and a length of 100 mm was placed, and one end was peeled off and held with forceps (Kabushiki Kasiya T.S., Autocomm Tester AC-50C-SL), The load (kgf/cm) when peeling 35 mm in the vertical direction at 50 mm/min at room temperature was measured.

(8) Evaluation of insulation reliability

A resist tape cut out in a circular shape (manufactured by Nitto Denko Co., Ltd., Erep masking tape N380) was applied on the conductor layer of Sample B, and immersed in an aqueous ferric chloride solution for 30 minutes. The conductor layer of the portion to which the resist tape was not adhered was removed, and an evaluation substrate was formed in which a circular conductor layer was formed on the insulating layer. Thereafter, a portion of the insulating layer was cut to expose the underlying copper foil. Then, the exposed copper foil and the circular conductor layer were connected by wiring (wire). A DC power supply (manufactured by Takasago Seisakusho Co., Ltd., TP018-3D) was connected to the wiring of the evaluation board, and a voltage of 3.3 V was applied for 200 hours under conditions of 130°C and 85% RH. After 200 hours, the resistance value is measured, and the resistance value is 1.0×10 ⁸ Ω or more, and “○”, and 1.0×10 ⁷ Ω or more and 1.0×10 ⁸ Ω or less, and “△”, and 1.0×10 ⁷ Ω or less. Let it be "x".

<Measurement of dielectric tangent>

The adhesive films obtained in each of the Examples and Comparative Examples were thermally cured at 190°C for 90 minutes, and the PET film was peeled off to obtain a cured sheet. The cured product was cut into a test piece having a width of 2 mm and a length of 80 mm, and the cavity was measured using a cavity resonator perturbation method dielectric constant measuring device CP521 manufactured by Kanto Denshiyo Yoga Instruments Co., Ltd. and a network analyzer E8362B manufactured by Agilent Technology Co., Ltd. The dielectric tangent (tanδ) was measured at a measurement frequency of 5.8 GHz by the resonator perturbation method. Measurement was performed on two test pieces, and an average value was calculated.

(Example 1)

10 parts of liquid bisphenol A-type epoxy resin (epoxy equivalent 180, Mitsubishi Chemical Co., Ltd. "828US"), and 20 parts biphenyl-type epoxy resin (epoxy equivalent 291, Nihon Kayaku Co., Ltd. "NC3000H") methyl 15 parts of ethyl ketone (hereinafter abbreviated as "MEK") and 15 parts of cyclohexanone were dissolved while stirring. There, 28 parts of an active ester compound ("HPC8000-65T" manufactured by DIC Corporation, an active ester equivalent of 223, a toluene solution having a solid content of 65%), creazine novolak resin containing triazine ("LA3018-50P manufactured by DIC Corporation" , Phenol equivalent 151, 2-methoxypropanol solution with solid content of 50%) 7 parts, curing accelerator (manufactured by Koe Kagaku Kogyo Co., Ltd., "4-dimethylaminopyridine") 0.1 parts, spherical silica (average particle size 0.5 Μm, aminosilane treatment part “SO-C2”, Admatex Co., Ltd., carbon part per unit weight 0.18%) 140 parts, phenoxy resin (YL7553BH30, solid content 30% by mass of MEK and cyclohexanone 1:1 Solution, weight average molecular weight 40000) 7 parts, blue pigment (manufactured by Dainichi Seika Co., Cyanine Blue 4920) 0.04 parts, yellow pigment (manufactured by BASF Co., Pariso Trol Yellow K1841) 0.07 parts, red pigment (client) 0.08 parts manufactured by Japan Co., Ltd., PV Fast Pink E01) was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. Next, this resin varnish is coated on a polyethylene terephthalate film (38 µm thick, hereinafter referred to as “PET film”) with a die coater so that the resin thickness after drying becomes 40 µm, and 80 to 120° C. (average 100) It dried at 6 degreeC for 6 minutes, and the sheet-shaped adhesive film was obtained.

(Example 2)

A resin varnish was prepared in exactly the same manner as in Example 1, except that 0.04 parts of the blue pigment of Example 1, 0.07 parts of the yellow pigment, 0.08 parts of the red pigment, 0.4 parts of the blue pigment, 0.66 parts of the yellow pigment, and 0.84 parts of the red pigment were changed. Did. Next, an adhesive film was obtained in the same manner as in Example 1.

(Example 3)

A resin varnish was prepared in exactly the same manner as in Example 1, except that 0.04 parts of the blue pigment of Example 1, 0.07 parts of the yellow pigment, 0.08 parts of the red pigment, 0.9 parts of the blue pigment, 1.4 parts of the yellow pigment, and 1.6 parts of the red pigment were changed. Did. Next, an adhesive film was obtained in the same manner as in Example 1.

(Example 4)

A resin varnish was produced in exactly the same manner as in Example 1, except that 0.04 parts of the blue pigment of Example 1, 0.07 parts of the yellow pigment, and 0.08 parts of the red pigment were changed to 3 parts of carbon black. Next, an adhesive film was obtained in the same manner as in Example 1.

(Example 5)

The resin varnish was carried out in exactly the same manner as in Example 1, except that 0.04 parts of the blue pigment of Example 1, 0.07 parts of the yellow pigment, and 0.08 parts of the red pigment were changed to 3.5 parts of rubber particles ("AC3816N" manufactured by Gantz Chemical Co., Ltd.). Was produced. Next, an adhesive film was obtained in the same manner as in Example 1.

(Example 6)

A resin varnish was prepared in exactly the same manner as in Example 1, except that 0.04 parts of the blue pigment of Example 1, 0.07 parts of the yellow pigment, and 0.08 parts of the red pigment were changed to 3.5 parts of an antioxidant ("IRGANOX 1010" manufactured by BASF Corporation). It was produced. Next, an adhesive film was obtained in the same manner as in Example 1.

(Example 7)

Completely the same as in Example 1 except that 0.04 parts of the blue pigment of Example 1, 0.07 parts of the yellow pigment, and 0.08 parts of the red pigment were changed to 3.5 parts of an infrared absorber ("IR-14" manufactured by Nihon Shokubai Co., Ltd.). A resin varnish was produced. Next, an adhesive film was obtained in the same manner as in Example 1.

(Example 8)

140 parts of spherical silica of Example 2 (average particle size 0.5 µm, aminosilane treatment given "SO-C2", Admatex Co., Ltd., carbon amount 0.18% per unit weight), spherical silica (average particle size 0.25 µm, amino A resin varnish was produced in exactly the same manner as in Example 2, except that the amount of the silane treatment was given to 100 parts of "SO-C1", manufactured by Admatex Co., Ltd., and 0.8% carbon per unit weight). Next, an adhesive film was obtained in the same manner as in Example 1.

(Example 9)

The same adhesive film as in Example 2 was used.

(Comparative Example 1)

A resin varnish was produced in exactly the same manner as in Example 1, except that 0.04 parts of the blue pigment of Example 1, 0.07 parts of the yellow pigment, and 0.08 parts of the red pigment were not added. Next, an adhesive film was obtained in the same manner as in Example 1.

Table 1 shows the results.

As can be seen from Table 1, it can be seen that, in the Examples, it is a low-k dielectric and excellent in smear suppression in the via hole. In addition, in Examples 1 to 3 and 5 to 9, insulation reliability was particularly excellent, and in Examples 3, 8 and 9, smear was further suppressed. On the other hand, in Comparative Example 1, although the dielectric tangent was low, it resulted in smear remaining.

Industrial availability

Provided is a resin composition, a sheet-like laminated material, a multilayer printed wiring board, and a semiconductor device capable of achieving low-k dielectricization of a cured product of a resin composition, and suppressing smear in a via hole after roughening treatment of the cured product. I can do it. In addition, it is possible to provide electric products such as computers, mobile phones, digital cameras, and televisions equipped with them, and vehicles such as automobiles, electric vehicles, ships, aircraft, and the like.

Claims (13)

A resin composition containing (A) an epoxy resin, (B) an active ester compound, (C) a smear suppressing component, and (D) an inorganic filler,
When the non-volatile component of the resin composition is 100 mass%, the content of the active ester compound (B) is 5 mass% or more,
When the non-volatile component of the resin composition is 100 mass%, (C) the smear suppressing component is 0.001 to 10 mass%,
When the non-volatile component of the resin composition is 100 mass%, (D) the inorganic filler is 70 mass% or more,
(C) The resin composition characterized in that the smear suppressing component is rubber particles. The resin composition according to claim 1, wherein the content of the active ester compound is 5 to 30 mass% when the nonvolatile component in the resin composition is 100 mass%. The resin composition according to claim 1, wherein the content of the active ester compound is 5 to 10 mass% when the nonvolatile component in the resin composition is 100 mass%. The resin composition according to claim 1, wherein the content of the inorganic filler is 70 to 85 mass% when the nonvolatile component in the resin composition is 100 mass%. The resin composition according to claim 1, wherein the amount of carbon per unit weight of the inorganic filler is 0.02 to 3%. The method of claim 1, wherein the resin composition is cured to form an insulating layer, and the surface of the insulating layer after roughening the insulating layer has an average square root roughness Rq of 500 nm or less, and is obtained by plating on the insulating layer surface. A resin composition, wherein the peel strength between the conductor layer and the insulating layer is 0.3 kgf/cm or more, and the dielectric tangent of the cured product of the resin composition is 0.05 or less. The resin composition according to claim 1, which is a resin composition for an insulating layer of a multilayer printed wiring board. A sheet-like laminated material comprising the resin composition according to any one of claims 1 to 7. A multilayer printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 7. A semiconductor device comprising the multilayer printed wiring board according to claim 9. A multilayer printed wiring board, characterized in that the sheet-like laminated material according to claim 8 is laminated on a circuit board, the resin composition is thermally cured to form an insulating layer, and a via hole is formed by drilling into the insulating layer formed on the circuit board. Method of manufacturing. 12. The method of claim 11, wherein the via hole has a top diameter (diameter) of 60 µm or less. 12. The method of claim 11, wherein the maximum smear length from the wall surface of the bottom of the via hole is less than 5 µm.