KR20190104287A - Resin composition - Google Patents

Abstract

The purpose of the present invention is to provide a resin composition capable of achieving low dielectric tangentization of a cured product of the resin composition and inhibiting smears in a via hole after perforating and roughening the cured product. The resin composition contains 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 is related with 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. In a multilayer printed wiring board, build-up layers are multilayered, wiring is required to be finer and denser, and an insulating material having a low dielectric tangent is required to reduce transmission loss.

In patent document 1, the epoxy resin composition for sealing containing an epoxy resin, a hardening | curing agent, and carbon black is disclosed, and it describes about the prevention of aggregation of carbon black. However, the concepts of smear and low dielectric tangent were not disclosed or directed at all.

Patent Document 1: Japanese Patent Application Laid-Open No. 2008-121010

When drilling the insulating layer of a multilayer printed wiring board, smear (resin residue) arises in a via hole, and it is necessary to remove smear in a roughening process process. However, according to the findings of the present inventors, a multilayer printed wiring board was produced using a resin composition of a low dielectric tangent containing an active ester compound. Even though the inside of the via hole was roughened after drilling the insulating layer, the smear (resin) in the via hole was used. A new problem arises that it is difficult to remove the residue).

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

MEANS TO SOLVE THE PROBLEM This inventor came to complete this invention in the specific resin composition containing an epoxy resin, an active ester compound, and a smear suppression component as a result of earnestly researching in order to solve the said subject.

That is, this invention includes the following content.

[1] A resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) a smear suppression component, wherein (C) smear suppression when the nonvolatile component of the resin composition is 100 mass% The component is 0.001-10 mass%, The resin composition characterized by the above-mentioned.

[2] When the nonvolatile component in the resin composition is 100 mass%, the content of the active ester compound (B) is 1 to 30 mass%, the resin composition according to the above [1].

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

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

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

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

[9] The resin composition according to any one of the above [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 inorganic filler (D) is 0.01 to 5 µm.

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

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

[13] a conductor layer obtained by curing the resin composition to form an insulating layer and roughening the surface of the insulating layer, wherein the root mean square 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 peeling strength with the said insulating layer is 0.3 kgf / cm or more, and the dielectric tangent of the hardened | cured material of a resin composition is 0.05 or less, The resin composition in any one of said [1]-[12] characterized by the above-mentioned.

[14] The resin composition according to any one of the above [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 resin composition according to any one of the above [1] to [14].

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

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

[18] The sheet-like lamination material according to the above [15] is laminated on a circuit board, the resin composition is thermoset to form an insulating layer, and a via hole is formed on the insulating layer formed on the circuit board by drilling through a support. The manufacturing method of the multilayer printed wiring board characterized by the above-mentioned.

By the specific resin composition containing an epoxy resin, an active ester compound, and a smear suppression component, the low dielectric tangent of the hardened | cured material of the said resin composition can be achieved, and the smear in a via hole after a roughening process by carrying out hardening processing of hardened | cured material is suppressed. It became possible to provide the resin composition which can be done.

This invention is a resin composition containing (A) epoxy resin, (B) active ester compound, and (C) smear suppression component, (C) smear when the non-volatile component of the said resin composition is 100 mass% An inhibitory component is 0.001-10 mass%, It is a resin composition characterized by the above-mentioned.

<(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 two 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 Epoxy resin, naphthylene ether epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, anthracene epoxy resin, linear aliphatic epoxy resin And 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. You may use these 1 type or in combination or 2 or more types.

Among these, bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, glycy from a viewpoint of heat resistance improvement, insulation reliability improvement, and adhesiveness improvement with metal foil. The epoxy resin which has a diester type epoxy resin, an anthracene type epoxy resin, and a butadiene structure is preferable. Specifically, for example, bisphenol A type epoxy resin ("Epitcoat 828EL", "YL980" by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin ("jER806H" and "YL983U" by Mitsubishi Chemical Corporation) ), Naphthalene type bifunctional epoxy resin (DIC Corporation make "HP4032", "HP4032D", "HP4032SS", "EXA4032SS"), naphthalene type tetrafunctional epoxy resin (DIC make "HP4700", "HP4710" ), Naphthol type epoxy resin (DOTGAsei Co., Ltd. product "ESN-475V"), epoxy resin (but Daisen Chemical Co., Ltd. product "PB-3600") having a butadiene structure, 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) (Manufactured by "YX8800"), naphthylene ether type epoxy resin (DIC Corporation make "EXA-7310", "EXA-7311", "EXA-7311L) And "EXA7311-G3"), glycidyl ester type epoxy resin ("EX711" by Nagase ChemteX Corp., "EX721", "R540" by Printech Co., Ltd.), etc. are mentioned.

Especially, it is preferable to use together a liquid epoxy resin and a solid epoxy resin, It has two or more epoxy groups in 1 molecule, A liquid aromatic epoxy resin (henceforth "liquid epoxy resin") at a temperature of 20 degreeC, The aspect which has three or more epoxy groups in 1 molecule, and contains a solid aromatic epoxy resin (henceforth "solid epoxy resin") at the temperature of 20 degreeC is more preferable. In addition, the aromatic epoxy resin in this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator. As an epoxy resin, when using a liquid epoxy resin and a solid epoxy resin together, when mix | blending a resin composition in the form of an adhesive film, since it has the suitable flexibility, and the hardened | cured material of a resin composition has the suitable breaking strength, it mix | blends it 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: 0.6-1: 1.5 is still more preferable.

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

<(B) Active Ester Compounds>

The (B) active ester compound in this invention is a compound which has one or more active ester groups in 1 molecule, can lower the dielectric tangent of a resin composition, and can also make square average square root roughness Rq small. The active ester compound (B) 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, the compound which has 2 or more of ester groups with high reaction activity in 1 molecule, such as phenol ester, thiophenol ester, N-hydroxyamine ester, and ester of a heterocyclic hydroxy compound, is used preferably. .

From the viewpoint of heat resistance improvement, 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. And the active ester compound obtained by making 1 type (s) or 2 or more types chosen from a carboxylic acid compound, a phenol compound, a naphthol compound, and a thiol compound react is more preferable. And the aromatic compound which has two or more active ester groups in 1 molecule obtained by making a carboxylic acid compound and the aromatic compound which has a phenolic hydroxyl group react 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 with 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. In addition, a linear or multi-branch shape may be used. Moreover, if the carboxylic acid compound which has at least 2 or more carboxyl groups in 1 molecule is a compound containing an aliphatic chain, compatibility with a resin composition can be made high, and if it is a compound which has an aromatic ring, heat resistance can be made high.

Specific 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 preferable, and isophthalic acid and terephthalic acid are more preferable. Specific examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid.

Specific examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, and m-cresol. , p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, tri Hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadienyldiphenol, phenol novolac and the like. Among them, from the viewpoint of improving heat resistance and solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxy Naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucin, benzenetriol, dicyclopenta Dienyldiphenol and phenol novolak are preferable, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone and trihydroxy Benzophenone, tetrahydroxy benzophenone, fluoroglucin, benzene triol, dicyclopentadienyl diphenol, and phenol novolak are more preferable, and 1, 5- dihydroxy naphthalene, 1, 6- dihydroxy naphthalene , 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihi More preferred are hydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, phenol novolac, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxy Naphthalene, dicyclopentadienyldiphenol, phenol novolak are more preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienyl Diphenol is particularly preferred, and dicyclopentadienyldiphenol is particularly preferred. Specific examples of the thiol compound include benzenedithiol, triazinedithiol and the like. An active ester compound may use together 1 type (s) or 2 or more types.

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

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

From the viewpoint of lowering the dielectric 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 an active ester compound, the active ester compound disclosed by Unexamined-Japanese-Patent No. 2004-277460 may be used, and a commercially available active ester compound can also be used. Specific examples of commercially available active ester compounds include an active ester curing agent containing a dicyclopentadienyl structure, an active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylate of phenol novolac, The active ester type hardening | curing agent containing the benzoylidene of a phenol novolak is preferable, and the active ester type hardening | curing agent containing a diphthalpentadienyl diphenol structure is especially preferable especially the naphthalene structure. As an active ester curing agent containing a dicyclopentadienyl diphenol structure, EXB9451, EXB9460, EXB9460S, HPC-8000-65T (manufactured by DIC Corporation), an active ester curing agent containing a naphthalene structure EXB9416-70BK (DIC Co., Ltd.), an active ester curing agent containing an acetylate of phenol novolac, DC808 (manufactured by Mitsubishi Chemical Co., Ltd.), and an YLH1026 (Mitsubishi Chemical Co., Ltd.) as an active ester curing agent containing a benzoylate of phenol novolac Co., Ltd.) etc. are mentioned.

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

Moreover, when the epoxy group number of (A) epoxy resin is set to 1, since the mechanical characteristic of a resin composition is improved, 0.2-2 are preferable and, as for the reactor water of (B) active ester compound, 0.3-1.5 are more preferable. It is preferable and 0.4-1 are more preferable. Here, "the epoxy group number of an epoxy resin" is the value which totaled the value which divided | segmented the solid content mass of each epoxy resin which exists in a resin composition by epoxy equivalent, about all the epoxy resins. In addition, "reactor" means the functional group which can react with an epoxy group, and "reactor number of an active ester compound" means the value which totaled the value which divided | segmented the value which divided | segmented the solid content mass of the active ester compound which exists in a resin composition by reactor equivalent. to be.

<(C) smear suppression component>

The smear suppression component used in this invention is a component which can suppress the smear of the via hole after carrying out a roughening process by hardening the hardened | cured material of a resin composition. Here, smear suppression also includes both the meaning of reducing the amount of smear generated at the time of drilling and making it easier to remove the smear at the time of roughening. As a smear suppression component, an organic smear suppression component and an inorganic smear suppression component are mentioned, An organic smear suppression component is preferable at the point of insulation insulation improvement. Specifically, examples of the organic smear suppression component include pigments, dyes, rubber particles, antioxidants, infrared absorbers, and the like. Examples of the inorganic smear suppression component include metal compound powder and metal powder. (C) As a smear suppression component, it is preferable to use 1 or more types chosen from the group which consists of a pigment, dye, a rubber particle, antioxidant, and an infrared absorber. Among these, a pigment and / or rubber particle are more preferable and a pigment is more preferable at the point which is excellent in smear suppression ability and also excellent in peel strength. You may use these 1 type or in combination or 2 or more types.

As a pigment, a blue pigment, a yellow pigment, a red pigment, a black pigment, a green pigment, etc. are mentioned. As a blue pigment, pigments, such as a phthalocyanine series, anthraquinone series, a dioxazine system, are mentioned. Examples of the yellow pigment include pigments such as monoazo, disazo, condensed azo, benzimidazolone, isoindolinone and anthraquinone. As a red pigment, pigments, such as a monoazo system, a disazo system, an azo lake system, a benzimidazolone system, a perylene system, a diketopyrrolopyrrole system, a condensation azo system, an anthraquinone system, a quinacridone system, are mentioned. Carbon black, graphite, etc. are mentioned as a black pigment. As a green pigment, pigments, such as a phthalocyanine system, are mentioned. A pigment may use together 1 type (s) or 2 or more types, and can mix suitably 1 or more types chosen from the group which consists of a blue pigment, a yellow pigment, a red pigment, a black pigment, and a green pigment. Especially, since it can improve insulation reliability further, it is preferable to use 1 or more types chosen from the group which consists of a blue pigment, a yellow pigment, a red pigment, and a green pigment, and a blue pigment, a yellow pigment, and a red pigment are used. It is more preferable to use the mixed pigment which mixes. Moreover, when preparing the mixed pigment which mixes a blue pigment, a yellow pigment, and a red pigment, a blue pigment, a yellow pigment, and a red from a viewpoint which can absorb the laser at the time of a drilling process efficiently, and can suppress smear generation more. 2-6: 5-9: 6-10 are preferable and, as for the mass ratio of a pigment, 3-5: 6-8: 7-9 are more preferable.

Examples of the dyes include azo (monoazo, disazo, etc.) dyes, azo-methine dyes, anthraquinone dyes, quinoline dyes, ketoneimine dyes, fluoron dyes, nitro dyes, xanthene dyes, acenaphthene dyes, quinophthalone dyes, Amino ketone dyes, methine dyes, perylene dyes, coumarin dyes, perinone dyes, triphenyl dyes, triallyl methane dyes, phthalocyanine dyes, inklophenol dyes, azine dyes, or mixtures thereof.

Examples of the rubber particles include core-shell rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles and acrylic rubber particles. The core-shell rubber particles are rubber particles having a core layer and a shell layer. For example, the shell layer of the outer layer is made of glass polymer, and the inner layer core layer is made of rubber polymer, or the shell layer of the outer layer is glass. The three-layer structure etc. which consist of a shape polymer, an intermediate | middle layer consist of a rubber polymer, and a core layer consist of a glass polymer are mentioned.

As antioxidant, a hindered phenolic antioxidant, phosphorus antioxidant, sulfur-type antioxidant, etc. are mentioned. As a commercial item, pentaerythritol tetraquis [3- (3,5-di-tert- butyl- 4-hydroxyphenyl) propionate (Ciba Japan Co., Ltd. product "IRGANOX 1010"), 2, 2-thio-di Ethylenebis [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.) ) "IRGANOX 3114") etc. are mentioned.

As an infrared absorber, a phthalocyanine type compound, an anthraquinone compound, a nickel complex, etc. are mentioned. As a commercial item, IR-14 (made by Nihon Shokubai Co., Ltd.), TX-HA-1 (made by Nihon Shokubai Co., Ltd.), etc. are mentioned.

Examples of the metal compound powder include titania such as titanium oxide, magnesia such as magnesium oxide, iron oxide such as iron oxide, nickel oxide such as nickel oxide, zinc oxide such as manganese dioxide and zinc oxide, silicon dioxide, aluminum oxide and rare earth oxide, Cobalt oxides such as cobalt oxide, tin oxides such as tin oxide, tungsten oxides such as tungsten oxide, silicon carbide, tungsten carbide, boron nitride, silicon nitride, titanium nitride, aluminum nitride, barium sulfate, rare earth sulfides, or mixtures thereof Powder and the like.

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 mentioned.

(C) 10 mass% or less is preferable with respect to 100 mass% of non volatile components in a resin composition, and, as for content of a smear suppression component, from a viewpoint of preventing the fall of hardening physical property, 5 mass% or less is more preferable, 4 mass% or less is more preferable, 3 mass% or less is more preferable, and 2 mass% or less is especially preferable. Moreover, from a viewpoint of improving smear suppression ability, 0.001 mass% or more is preferable with respect to 100 mass% of non volatile components in a resin composition, 0.01 mass% or more is more preferable, 0.02 mass% or more is more preferable, 0.05 mass % Or more is even more preferable, 0.08 mass% or more is especially preferable, and 0.1 mass% or more is especially preferable.

<(D) inorganic filler>

The resin composition of this invention can also contain (D) inorganic filler for the purpose of reducing linear thermal expansion rate, and the objective of improving smear removal property at the time of a roughening process. Examples of the inorganic filler (D) include 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, Calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Especially, silica is preferable. As silica, amorphous silica, crushed silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. are preferable, and fused silica is more preferable. Moreover, as silica, spherical silica is preferable. You may use these 1 type or in combination or 2 or more types. Examples of commercially available spherical fused silica include "SO-C2" and "SO-C1" manufactured by ADMATEX.

(D) Although the average particle diameter of an inorganic filler is not specifically limited, The upper limit of the average particle diameter of an inorganic filler is a smear at the time of a drilling process by increasing the total surface area of an inorganic filler from a viewpoint of forming fine wiring on an insulating layer. 5 micrometers or less are preferable, 3 micrometers or less are more preferable, 1 micrometer or less is still more preferable, 0.7 micrometers or less are still more preferable, 0.5 micrometers or less are especially preferable from a viewpoint of suppressing generation | occurrence | production, and 0.4 micrometers or less Is especially preferable, and 0.3 micrometer or less is especially preferable. On the other hand, the lower limit of the average particle diameter of the inorganic filler is preferably 0.01 µm or more, more preferably 0.03 µm or more, from the viewpoint of preventing the viscosity of the varnish from rising and handling loss when the resin composition is used as a varnish. It is preferable, 0.05 micrometer or more is more preferable, 0.07 micrometer or more is especially preferable, and 0.1 micrometer or more is especially preferable. The average particle diameter of the said inorganic filler can be measured by the laser diffraction and the scattering method based on the Mie scattering theory. Specifically, it can measure by making a particle size distribution of an inorganic filler by volume basis with a laser diffraction scattering type particle size distribution measuring device, and making the median diameter into an average particle diameter. The measurement sample can use preferably what disperse | distributed the inorganic filler in water according to the ultrasonic wave. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-500, 750, 950, etc. made by Horiba Seisakusho can be used.

Although content of the (D) inorganic filler is not specifically limited, From the viewpoint of preventing the flexibility at the time of making a resin composition into the film form, when it sets the non volatile component in a resin composition to 100 mass%, it is 85 mass % Or less is preferable, 80 mass% or less is more preferable, and 75 mass% or less is further more preferable. In addition, in view of lowering the coefficient of thermal expansion of the insulating layer and increasing the total surface area of the inorganic filler, it is possible to suppress smear generation at the time of drilling, and to easily remove the smear during roughening treatment. When it is 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 still more preferable.

(D) The inorganic filler is an aminosilane coupling agent, a ureide silane coupling agent, an epoxy silane coupling agent, a mercapto silane coupling agent, a silane coupling agent, a vinyl silane from a viewpoint of improving moisture resistance and dispersibility. It is surface-treated with a surface treatment agent such as a system coupling agent, a styryl silane coupling agent, an acrylate silane coupling agent, an isocyanate silane coupling agent, a sulfide silane coupling agent, an organosilazane compound, a titanate coupling agent, etc. It is desirable to have. Especially, after surface-treating an inorganic filler with an organosilazane compound and then surface-treating with a silane coupling agent, moisture resistance and dispersibility of an inorganic filler further improve. You may use these 1 type or in combination or 2 or more types.

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, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, and 3-right Ureasilane-based coupling agents such as raidpropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, and 3-glycidyloxypropylmethyldiethoxysilane Epoxysilane-based coupling agents such as 3-glycidyloxypropyl (dimethoxy) methylsilane, glycidylbutyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3- Mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 11 -Mercaptosilane-based coupling agents such as mercaptodecyltrimethoxysilane, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methoxypropyltrimethoxysilane, imidazolesilane, and tria Silane coupling agent such as true truth, tert-butyltrimethoxysilane, vinyl silane coupling agent such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, p-styryltrimethoxysilane, etc. Styryl silane coupling agent, 3-acryloxypropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, Acrylate silane coupling agents, such as 3-methacryloxypropyl diethoxysilane, Isocyanate silane coupling agents, such as 3-isocyanate propyl trimethoxysilane, bis (triethoxy silylpropyl) disulfide, bis (triethoxy room Sulfidesilane-based coupling agents such as arylpropyl) tetrasulfide, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexaphenyldisilazane, trisila Glass, cyclotrisilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexabutyldisilazane, hexaoctyldisilazane, 1,3-di Ethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-di Ethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsila Organosilazane compounds such as a glass and tetramethyldisilazane, tetra-n-butyl titanate dimer, titanium-i-propoxyoctylene glycolate, tetra-n-butyl titanate, titanium octylene glycolate, di Isopro Cititan bis (triethanol aluminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate Titanate, tri-n-butoxy titanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (di Tridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyltrioctanoyl titanate, isopropyl cumylphenyl titanate, iso Propyl Triisostearoyl Titanate, Isopropyl Isostearoyl Diacrylic Titanate, Isopropyl Dimethacrylic Iso Stearoyl Titanate, Isopropyltri (dioctylphosphate) tee Titanate coupling agents such as nate, isopropyltridodecylbenzenesulfonyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, and isopropyl tri (N-amide ethyl aminoethyl) titanate Can be. Among these, the aminosilane-based coupling agent is preferred because of its excellent moisture resistance, dispersibility, properties of the cured product, and the organosilazane compound is preferred because it is excellent in dispersibility improvement of the resin varnish. As a commercial item of a surface treating agent, Shin-Etsu Chemical Co., Ltd. product "KBM403" (3-glycidoxy propyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. product "KBM803" (3-mercaptopropyl trimethoxy) Silane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyl triethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyl trimethoxysilane) Etc. can be mentioned.

In addition, the inorganic filler surface-treated with the surface treating agent can measure the carbon amount per unit weight of the inorganic filler after wash | cleaning process with a solvent (for example, methyl ethyl ketone). Here, the "carbon amount per unit weight of an inorganic filler" shows the carbon amount (g) couple | bonded with 1 g of inorganic fillers by 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 solid content, the carbon amount per unit weight of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, Horiba Seisakusho "EMIA-320V" 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 in terms of improving the dispersibility of the inorganic filler and stabilizing the root mean square roughness after the roughening treatment of the cured product. This is more preferable. On the other hand, 3% or less is preferable, 2% or less is more preferable, and 1% or less is more preferable at the point which prevents the raise of the melt viscosity of a resin varnish and the melt viscosity in the form of an adhesive film.

<(E) Curing Accelerator>

The resin composition of this invention can also contain (E) hardening accelerator for the purpose of adjusting hardening time and hardening temperature. Although it does not specifically limit as (E) hardening accelerator, An imidazole series hardening accelerator, an amine hardening accelerator, an organic phosphine compound, an organic phosphonium salt compound, etc. are mentioned. You may use these 1 type or in combination or 2 or more types.

As imidazole series hardening accelerator, 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 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-phenyl Dazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo Imidazole compounds and imidazole compounds such as [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazole, 2-phenylimidazolin And an adduct of an epoxy resin. You may use these 1 type or in combination or 2 or more types.

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-diazabile. And amine compounds such as cyclo (5,4,0) -undecene (hereinafter abbreviated as DBU). You may use these 1 type or in combination or 2 or more types.

Examples of the organic phosphine compound and the organic phosphonium salt compound include TPP, TPP-K, TPP-S, TPTP-S, TBP-DA, TPP-SCN, and TPTP-SCN (trademark of Hokyo Chemical Industries, Ltd.). Can be. You may use these 1 type or in combination or 2 or more types.

(E) As for content of a hardening accelerator, 0.01-3 mass% is preferable with respect to 100 mass% of non volatile components in a resin composition from the point of the storage stability of a resin varnish, and efficiency of hardening, and 0.1-2 mass% is more desirable.

<(F) Thermoplastic Resin>

By containing (F) thermoplastic resin in the resin composition of this invention, the viscosity of the resin varnish obtained from the said resin composition can be adjusted to a suitable range, and the flexibility of hardened | cured material can be improved. Although it does not specifically limit as a thermoplastic resin, A phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyamide resin, polyether sulfone resin, polysulfone resin, polybutadiene resin, ABS resin etc. are mentioned. have. Especially, a phenoxy resin and a polyvinyl acetal resin are preferable from a viewpoint of improving the flexibility of hardened | cured material and contributing to adhesiveness, and a phenoxy resin is more preferable. You may use these 1 type or in combination or 2 or more types. It is preferable that a thermoplastic resin has a glass transition temperature of 80 degreeC or more.

It is preferable that the weight average molecular weight of a thermoplastic resin is the range of 5000-80000000, It is more preferable that it is the range of 10000-200000, It is still more preferable that it is the range of 15000-150000, It is still more preferable that it is the range of 20000-100000. . By being in a range, the effect of film forming capability and mechanical strength improvement are fully exhibited, and compatibility with an 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). As for the weight average molecular weight by GPC method, Shodex K-800P / K- made by Showa Denko Co., Ltd. as LC as the measuring apparatus by LC-9A / RID-6A made by Shimadzu Corporation 804L / K-804L can be measured at the column temperature of 40 degreeC using chloroform etc. as a mobile phase, and can be computed using the analytical curve of standard polystyrene.

Examples of the phenoxy resin include 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, The thing which has 1 or more types of frame | skeleton chosen from an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton is mentioned. You may use phenoxy resin in mixture of 2 or more types. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. As a commercial item, Mitsubishi Chemical Corporation 1256, 4250 (bisphenol A skeleton containing phenoxy resin), Mitsubishi Chemical Corporation YX8100 (bisphenol S skeleton containing phenoxy resin), Mitsubishi Chemical Corporation make YX6954 (bisphenol acetophenone frame | skeleton containing phenoxy resin) is mentioned. As a commercial item, Shinnitetsu Chemical Co., Ltd. product FX280, FX293, Mitsubishi Chemical Co., Ltd. product YL7553, YL6954, YL6794, YL7213, YL7290, YL7482 etc. are mentioned.

As a specific example of polyvinyl acetal resin, Denki Chemical Co., Ltd. product, Denka Butyral 4000-2, 5000-A, 6000-C, 6000-EP, Sekisui Chemical Co., Ltd. product Esrek BH series, BX series, KS series, BL series, BM series, etc. are mentioned. As a specific example of polyimide resin, the polyimide "Rica coat SN20" and "Rica coat PN20" by Shin-Nippon Rica Co., Ltd. are mentioned. Moreover, linear polyimide obtained by making bifunctional hydroxyl-group-end polybutadiene, a diisocyanate compound, and tetrabasic anhydride react (thing of Unexamined-Japanese-Patent No. 2006-37083), polysiloxane skeleton containing polyimide (Japan Modified polyimides such as those described in Japanese Patent Application Laid-Open No. 2002-12667, Japanese Patent Laid-Open No. 2000-319386, and the like. As a specific example of polyamide-imide resin, the polyamide-imide "Biromax HR11NN" and "Biromax HR16NN" by Toyo Boseki Co., Ltd. are mentioned. Moreover, modified polyamideimide, such as polysiloxane frame | skeleton containing polyamideimide "KS9100" and "KS9300" by Hitachi Chemical Co., Ltd., is mentioned. As a specific example of polyether sulfone resin, Sumitomo Chemical Co., Ltd. polyether sulfone "PES5003P" etc. are mentioned. As a specific example of polysulfone resin, polysulfone "P1700", "P3500", etc. made 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 non volatile components in a resin composition from the point of adjustment of melt viscosity of a sheet-like laminated material, or adjustment of resin varnish viscosity. 1-20 mass% is more preferable.

<(G) Curing Agent>

The resin composition of this invention can be made to contain (G) hardening | curing agent further. Thereby, insulation reliability, peeling strength, and mechanical characteristics of the hardened | cured material of a resin composition can be improved. Although it does not specifically limit as (G) hardening | curing agent, For example, a phenol type hardening | curing agent, a cyanate ester type hardening | curing agent, a benzoxazine type hardening | curing agent, an acid anhydride type hardening | curing agent, etc. are mentioned. These can use 1 type (s) or 2 or more types. Among these, a phenol type hardening | curing agent and a cyanate ester type hardening | curing agent are preferable from a viewpoint of the improvement of smear removal property and the improvement of dielectric properties.

Although there is no restriction | limiting in particular as a phenolic hardening | curing agent, A phenol novolak resin, a triazine skeleton containing phenol novolak resin, a naphthol novolak resin, a naphthol aralkyl type resin, a triazine skeleton containing naphthol resin, a biphenyl aralkyl type phenol resin etc. are mentioned. Can be. For example, as a biphenyl aralkyl type phenol resin, "MEH-7700", "MEH-7810", "MEH-7851" (made by Meiwa Kasei Co., Ltd.), "NHN", "CBN", "GPH" ( Nihon Kayaku Co., Ltd.), a naphthol aralkyl type resin, "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" (Dotogasei) As a phenol novolak resin, "TD2090" (manufactured by DIC Corporation), a triazine skeleton-containing phenol novolak resin as "LA3018", "LA7052", "LA7054", "LA1356" (DIC (Ltd.) ) Production). A phenolic hardening | curing agent may use together 1 type (s) or 2 or more types.

Although there is no restriction | limiting in particular as a cyanate ester type hardening | curing agent, 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 these were triazine-ized, etc. are mentioned. Although the weight average molecular weight of a cyanate ester type hardening | curing agent is not specifically limited, 500-4500 are preferable and 600-3000 are more preferable. As a specific example of a cyanate ester type hardening | curing agent, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylenecyanate), 4,4'-methylenebis (2,6-, for example) 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, dicyclopentadiene structure-containing phenol resins, and the like. And prepolymers obtained by partially triazine cyanate resin, etc. These may be used alone or in combination of two or more thereof. As a cyanate ester resin marketed, one part or all part of a phenol novolak-type polyfunctional cyanate ester resin (London Japan Co., Ltd. product, PT30, cyanate equivalent 124), bisphenol A dicyanate is triazine-ized, and a trimer Prepolymer (London Japan Co., Ltd. product, BA230, cyanate equivalent weight 232), dicyclopentadiene structure containing cyanate ester resin (London Japan Co., Ltd. product, DT-4000, DT-7000), etc. are mentioned.

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

Although content of the (G) hardening | curing agent in a resin composition is not specifically limited, 0.5-10 mass% is preferable with respect to 100 mass% of non volatile components in a resin composition from a viewpoint of preventing the hardened | cured material of a resin composition from becoming weak. , 1-6 mass% is more preferable.

<Other ingredients>

As for the resin composition of this invention, thermosetting components, such as a maleimide compound, bisallyl naimide compound, a vinyl benzyl resin, and a vinyl benzyl ether resin, silicone powder, nylon as needed, in the range which does not impair the effect of this invention. Adhesives such as organic fillers such as powders and fluorine powders, thickeners such as olben and benton, silicone-based, fluorine-based, anti-foaming agents or leveling agents, imidazole-based, thiazole-based, triazole-based and silane coupling agents, phosphorus-based compounds, Flame retardants, such as a metal hydroxide, etc. are mentioned, for example.

The resin composition of this invention mixes the said component suitably, Moreover, if necessary, it mixes with kneading means, such as three rolls, a ball mill, a bead mill, a sand mill, or stirring means, such as a super mixer and a planetary mixer. It can be manufactured as a resin varnish by kneading or mixing by the mixture. And the hardened | cured material of the resin composition of this invention can achieve low dielectric tangentization, and can suppress the smear in the via hole after carrying out roughening process by hardening a hardened | cured material.

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 measure by the cavity resonator perturbation method at frequency 5.8GHz and measurement temperature 23 degreeC. The dielectric tangent is preferably 0.05 or less, more preferably 0.04 or less, still more preferably 0.03 or less, even more preferably 0.02 or less, and 0.01 or less from the viewpoint of preventing heat generation at high frequencies, and reducing signal delay and signal noise. 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 average square root roughness Rq of the hardened | cured material of the resin composition of this invention can be grasped | ascertained by the measuring method as described in <measurement of square average square root roughness (Rq) mentioned later. The surface of the insulating layer after the roughening treatment is required to have fine concavo-convex in terms of reducing the loss of the electrical signal. As showing the density of irregularities on the surface of the insulating layer, there is a root mean square roughness Rq. This index shows that the surface of the insulating layer has a dense uneven shape rather than a simple average value of the unevenness of the insulating layer surface. Specifically, 500 nm or less is preferable and, as for the square root mean square roughness Rq of the said insulating layer surface after hardening a resin composition and forming an insulating layer and roughening the said insulating layer surface, 400 nm or less is more preferable, 300 nm or less is more preferable, 200 nm or less is more preferable, and 100 nm or less is especially preferable. In addition, the lower limit is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 20 nm or more, from the viewpoint of obtaining good adhesion to the plating conductor layer.

The peeling strength of the hardened | cured material of the resin composition of this invention can be grasped | ascertained by the measuring method as described in <measurement of peeling strength (filling strength) of the plating conductor layer> mentioned later. Specifically, the peel strength of the conductor layer and the insulating layer obtained by curing the resin composition to form an insulating layer and plating the surface of the insulating layer after the roughening treatment is preferably 0.3 kgf / cm or more, and 0.5 kgf. / Cm or more is more preferable, and 0.6 kgf / cm or more is more preferable. On the other hand, there is no restriction | limiting in particular in an upper limit, Usually, it is 1.2 kgf / cm or less.

Although the use of the resin composition of this invention is not specifically limited, Sheet-like laminated materials, such as an adhesive film and a prepreg, a circuit board (for laminated board use, a multilayer printed wiring board use, etc.), a soldering resist, an underfill material, a die bonding material, a semiconductor It can use for the wide range of uses which resin composition, such as a sealing material, hole filling resin, and a part embedding resin, are required. Especially, in the resin composition of this invention, since the smear in a via hole after drilling and hardening hardened | cured material can be suppressed, plating adhesion force in a via hole improves, and the void generation in a via hole is prevented, and it is formed in multiple stages. The conduction reliability between the insulating layers of a multilayer printed wiring board can be ensured. That is, in manufacture of a multilayer printed wiring board, it can be used suitably as a resin composition (resin composition for insulating layers of a multilayer printed wiring board) for forming an insulating layer, and the resin composition for forming a conductor layer by plating (by plating It can be used more suitably as the resin composition for insulating layers of the multilayer printed wiring board which forms a conductor layer. Although the resin composition of this invention can be apply | coated to a circuit board in a varnish state, and can form an insulation layer, it is industrially generally used in the form of sheet-like laminated materials, such as an adhesive film and a prepreg. As for the softening point of a resin composition, 40-150 degreeC is preferable from a lamination property of a sheet-like laminated material.

<Sheet-like laminated material>

(Adhesive film)

In one embodiment, the sheet-like laminated material of the present invention is an adhesive film. The said adhesive film is a thing in which the resin composition layer was formed on the support body. The said adhesive film prepares the resin varnish which melt | dissolved the resin composition in the organic solvent, the method known to a person skilled in the art, for example, apply | coats this resin varnish to a support body using a die coater, etc., and heats or hot-air spray etc. It can manufacture by drying an organic solvent and forming a resin composition layer.

As the organic solvent, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbotolv acetate, acetate esters such as carbitol acetate, Examples thereof include carbitols such as bitol, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. You may use the organic solvent in combination of 2 or more type.

Although drying conditions are not specifically limited, It drys so that content of the organic solvent in a resin composition layer may be 10 mass% or less, Preferably it is 5 mass% or less. The amount of the organic solvent in the varnish and the boiling point of the organic solvent are different, but for example, the resin composition layer can be formed by drying the varnish containing 30 to 60 mass% of the organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. have.

It is preferable to make the thickness of the resin composition layer formed in an adhesive film more than the thickness of a conductor layer. Since the thickness of the conductor layer which a circuit board has is normally 5-70 micrometers, it is preferable that a resin composition layer has a thickness of 10-100 micrometers. From a viewpoint of thinning, 15-80 micrometers is more preferable.

Examples of the support include a film of polyolefin such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), a film of polyester such as polyethylene naphthalate, polycarbonate film, polyimide film Various plastic films, such as these, are mentioned. Moreover, you may use metal foil, such as a release paper, copper foil, and aluminum foil. Especially, a plastic film is preferable and a polyethylene terephthalate film is more preferable at the point of general use. Surface treatments, such as a mad treatment and a corona treatment, may be given to the support body and the protective film mentioned later. Moreover, the mold release process may be performed with mold release agents, such as a silicone resin mold release agent, an alkyd resin mold release agent, and a fluororesin mold release agent.

Although the thickness of a support body is not specifically limited, When performing a punching process from a support body, 10 micrometers or more are preferable at the point that resin residue hardly remains and generation | occurrence | production of smear can be suppressed even when the energy of laser irradiation is large. 20 micrometers or more are more preferable, and 30 micrometers or more are more preferable. Moreover, 150 micrometers or less are preferable, 100 micrometers or less are more preferable, and 50 micrometers or less are more preferable from a viewpoint of cost performance improvement and efficient punching, when punching from a support body.

The protective film based on a support body can be further laminated | stacked on the surface on the opposite side to the surface which the support body of a resin composition layer adjoins. In this case, an adhesive film contains a support body, the resin composition layer formed on the said support body, and the protective film formed on the said resin composition layer. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating | stacking a protective film, adhesion | attachment of a dust etc. to a surface of a resin composition layer, and a wound can be prevented. An adhesive film can also be wound up and stored in roll shape.

(Prepreg)

In one embodiment, the sheet-like laminated material of the present invention is a prepreg. The said prepreg can be manufactured by impregnating the resin composition of this invention by the hot-melt method or the solvent method to a sheet-like reinforcement base material, and heating and semi-hardening. That is, it can be set as the prepreg which becomes the state which the resin composition of this invention is impregnated to the sheet-like reinforcement base material. As a sheet-like reinforcement base material, what consists of fibers commonly used as prepreg fiber, such as glass cross and aramid fiber, can be used. And it is suitable that the prepreg was formed on the support body.

In the hot-melt method, a prepreg is produced by coating a resin composition on a support without first dissolving it in an organic solvent, laminating it on a sheet-like reinforcing substrate, or coating it directly on a sheet-like reinforcing substrate by a die coater. That's how. In the solvent method, the resin is dissolved in an organic solvent in the same manner as the adhesive film to prepare a resin varnish, the sheet-like reinforcement base material is immersed in the varnish, the resin varnish is impregnated into the sheet-like reinforcement base material, and then dried. It is a way. Moreover, an adhesive film can also be prepared by thermally laminating from both surfaces of a sheet-like reinforcement base material continuously under heating and pressurization conditions. A support body, a protective film, etc. can also be used similarly to an adhesive film.

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

Next, an example of the method of manufacturing a multilayer printed wiring board using the sheet-like laminated material manufactured as mentioned above is demonstrated.

First, a sheet-like laminated material is laminated (laminated) on one side 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 | substrate, a polyester board | substrate, a polyimide board | substrate, a BT resin board | substrate, a thermosetting polyphenylene ether board | substrate, etc. are mentioned, for example. In addition, a circuit board means here that the conductor layer (circuit) pattern-processed was formed in one side or both surfaces of the above board | substrates. Moreover, in the multilayer printed wiring board which alternately laminates a conductor layer and an insulating layer, it is also included in the circuit board mentioned here that one side or both sides of the outermost layer of the said multilayer printed wiring board is a patterned conductor layer (circuit). do. Moreover, the roughening process may be previously given to the conductor layer surface by blackening process, copper etching, etc.

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 on the circuit board while pressing and heating. In one suitable embodiment, the sheet-like laminated material of the present invention is laminated on a circuit board under reduced pressure by a vacuum lamination method. The conditions of the laminate are not particularly limited, but for example, the crimping temperature (lamination temperature) is preferably 70 to 140 ° C and the crimping pressure (lamination pressure) is preferably 1 to 11 kgf / cm 2 (9.8 × 10 ⁴ to). 107.9 x 10 &lt; 4 &gt; N / m &lt; 2 &gt;), the pressing time (lamination time) is preferably 5 to 180 seconds, and lamination under reduced pressure of 20 mm Hg (26.7 hPa) or less is preferable. Moreover, the lamination method may be a batch type or a continuous type in a roll. Vacuum lamination can be performed using a commercially available vacuum laminator. As a commercial vacuum laminator, Nichigo Morton Co., Ltd. pressure applicator, the Meiki Seisakusho Co., Ltd. vacuum press type laminator, Hitachi Industries Co., Ltd. roll type dry coater, Hitachi AIC Co., Ltd. A manufacturing vacuum laminator etc. are mentioned, for example.

After laminating a sheet-like laminated material to a circuit board, and cooling to around room temperature, when peeling a support body, it peels and thermosets a resin composition and forms an insulating layer. Thereby, an insulating layer can be formed on a circuit board. Although the conditions of thermosetting may be selected suitably according to the kind, content, etc. of the resin component in a resin composition, Preferably it is 20 to 180 minutes at 150 degreeC-220 degreeC, More preferably, it is 30 to 120 degreeC at 160 degreeC-210 degreeC It is selected in the range of minutes. After forming an insulating layer, when a support body is not peeled off before hardening, you may peel here as needed.

In addition, the sheet-like lamination material may be laminated on one side or both sides of the circuit board using a vacuum press. The lamination | stacking process which heats and pressurizes under reduced pressure can be performed using a general vacuum hot press machine. For example, it can carry out by pressing metal plates, such as a heated SUS board, from a support body layer side. The press conditions are such that the reduced pressure is usually 1 × 10 ⁻² MPa or less, preferably 1 × 10 ⁻³ MPa or less. Although heating and pressurization may be performed in one step, it is preferable to divide conditions into two or more steps from a viewpoint of controlling the unevenness of resin. For example, the press of the 1st stage is performed in the range of the temperature of 70-150 degreeC, and the pressure of 1-15 kgf / cm <2>, and the press of the 2nd step of temperature of 150-200 degreeC and the pressure of 1-40 kgf / It is preferable to carry out in the range which is cm <2>. It is preferable to perform the time of each step in 30 to 120 minutes. Thus, an insulating layer can be formed on a circuit board by thermosetting a resin composition layer. Commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

Subsequently, a perforation process is performed to the insulating layer formed on a circuit board, and a via hole and a through hole are formed. Drilling can be performed by well-known methods, such as a drill, a laser, and a plasma, for example, combining these methods as needed. Among them, drilling is performed by lasers such as carbon dioxide lasers and YAG lasers. In addition, the sheet-like laminated material of the present invention is laminated on a circuit board, the resin composition layer is thermally cured to form an insulating layer, and a via hole is formed by forming a via hole in the insulating layer formed on the circuit board from the support to form a multilayer printed wiring board It is preferable to prepare the product, and it is preferable to peel off the support after drilling. Thus, generation | occurrence | production of a smear can be suppressed by drilling through a support body and forming a via hole. Moreover, in order to respond to the thinning of a multilayer printed wiring board, 15-70 micrometers is preferable, as for the top diameter (diameter) of a via hole, 20-65 micrometers is more preferable, 25-60 micrometers is still more preferable.

Then, the roughening process of the surface of an insulating layer is performed. As a dry roughening process, a plasma process etc. are mentioned, As a wet roughening process, the swelling process with a swelling liquid, the roughening process with an oxidizing agent, and the neutralization process with a neutralizing liquid are mentioned in this order. Although the roughening process of either dry or wet may be employ | adopted, a wet roughening process is preferable at the point which can remove the smear in a via hole, forming an uneven anchor on the surface of an insulating layer. The swelling treatment by the swelling liquid is performed by immersing the insulating layer in the swelling liquid for 5 to 20 minutes (preferably 8 to 15 minutes at 55 to 70 ° C) at 50 to 80 ° C. Examples of the swelling liquid include an alkaline solution, a surfactant solution, and the like, and preferably an alkaline solution. As said alkaline solution, a sodium hydroxide solution, a potassium hydroxide solution, etc. are mentioned, for example. Examples of commercially available swelling liquids include, for example, Swelling Dip Securiganth P (Swelling Dip Securiganth P) manufactured by Atotech Japan Co., Ltd., and Swelling Dip Securiganth SBU (SBU). Can be. The roughening treatment by the oxidizing agent is performed by immersing the insulating layer in the oxidizing agent solution for 10 to 30 minutes (preferably 15 to 25 minutes at 70 to 80 ° C) at 60 to 80 ° C. Examples of the oxidizing agent include alkaline and manganese solutions in which gallium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, and nitric acid. In addition, the concentration of permanganate in the alkaline and manganese acid solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline and manganese acid solutions such as Concentrate Compact CP manufactured by Atotech Japan Co., Ltd. and Dosing Solution Security P. The neutralization treatment by the neutralizing liquid is performed by immersing the insulating layer in the neutralizing liquid for 3 to 10 minutes (preferably 3 to 8 minutes at 35 to 45 ° C) at 30 to 50 ° C. As a neutralization liquid, an acidic aqueous solution is preferable, and as a commercial item, reduction solution security P of the Atotech Japan Co., Ltd. product is mentioned.

Subsequently, a conductor layer is formed on an insulating layer by dry plating or wet plating. As dry plating, well-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 pattern formation after that, the subtractive method, the semiadditive method, etc. which are well-known to a person skilled in the art can be used, for example. And a multilayer printed wiring board which laminated | stacked the buildup layer in multiple stages can be manufactured by repeating the above-mentioned series of process in multiple times. In this invention, since generation | occurrence | production of smear is suppressed, the conduction | electrical_connection reliability between layers can be ensured. Therefore, the sheet-like laminated material of this invention can be used suitably in order to form the buildup layer of a multilayer printed wiring board.

<Semiconductor Device>

A semiconductor device can be manufactured by using the multilayer printed wiring board of this invention. A semiconductor device can be manufactured by mounting a semiconductor chip in the conduction part of the multilayer printed wiring board of this invention. A "conduction point" is a "point which transmits an electric signal in a multilayer printed wiring board", and the place may be a surface or a buried point anywhere. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method for mounting a semiconductor chip in 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 method, a flip chip mounting method, and a bump press build up layer The mounting method by (BBUL), the mounting method by an anisotropic conductive film (ACF), the mounting method by a nonelectroconductive film (NCF), etc. are mentioned.

Example

Hereinafter, although an Example and a comparative example demonstrate this invention in detail, these do not limit this invention in any meaning. In addition, in the following description, "part" means a "mass part."

<Measurement method and evaluation method>

First, various measurement methods and evaluation methods are described.

<Smear evaluation>

About the adhesive film composition sheet obtained by each Example and each comparative example, the smear (resin residue) was evaluated as follows.

(1) Manufacture of circuit board

A circuit pattern is formed on both surfaces of the glass cloth base material epoxy resin double-sided copper clad laminated board (18 micrometers of copper foil, 0.8 mm of substrate thickness, R5715ES by Matsushita Denko Co., Ltd.) by an etching, and a microetching agent (Mac (Note) ) CZ8100) was subjected to a roughening process to produce a circuit board.

(2) Lamination of Adhesive Film

The adhesive film composition sheet produced by each Example and each comparative example was used on both surfaces of the circuit board produced by said (1) using batch type vacuum pressurization laminator MVLP-500 (brand name, the product made by Meiki Corporation). Laminated. Lamination was performed by depressurizing for 30 second, making atmospheric pressure 13 hPa or less, and then crimping | bonding at 100 degreeC and 30 second and the 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 under curing conditions at 170 ° C. for 30 minutes to form an insulating layer. In Example 9, the resin composition layer was cured under curing conditions at 170 ° C. for 30 minutes without peeling off the PET film to form an insulating layer.

(4) Via hole formation

Matsushita yaw Massachusetts System Co. produced CO ₂ laser beam machine (YB-HCS03T04) by using, in the via-hole in the pulse width 13 μ sec at the frequency 1000 Hz, isolated drilling an insulating layer under the conditions of a shot number 3, and the floor surface Via holes having a column diameter (diameter) of 60 µm were formed. In Example 9, the PET film was peeled after that.

(5) coordination treatment

The circuit board was immersed for 10 minutes at 60 degreeC in the swelling dip security gun P of Atotech Japan Co., Ltd. which is a swelling liquid. Next, the blend solution (an oxidizing agent) of Ato Tech Japan Co., Concentrate of compact P was immersed for 20 minutes at 80 ℃ to (KMnO _4: aqueous solution of 40 g / L: 60 g / L, NaOH). Finally, it was immersed for 5 minutes in 40 degreeC reduction solution security P of Atotech Japan Co., Ltd. which is neutralization liquid.

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

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

<Measurement of Peel Strength (Peel Strength), Plating Average Square Root Roughness (Rq) of Plating Conductor Layer, and Evaluation of Insulation Reliability>

(1) Basic treatment of laminated board

Both sides of the glass cloth base material epoxy resin double-sided copper clad laminated board (18 micrometers of copper foil, 60% of copper foils, board | substrate thickness 0.3mm, Matsushita Denko Co., Ltd. product R5715ES) of the inner layer circuit which were formed were made to Mack Corporation CZ8100. It immersed and performed the roughening process of the copper surface.

(2) Lamination of Adhesive Film

The adhesive film produced by each Example and each comparative example was laminated on both surfaces of the laminated board using the batch type vacuum pressurizer laminator MVLP-500 (made by Meiki Seisakusho, brand name). Lamination was performed by depressurizing for 30 second and making atmospheric pressure 13 hPa or less, and then crimping | bonding at 100 degreeC and pressure 0.74 MPa for 30 second.

(3) curing of the resin composition

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

(4) coordination treatment

The laminated board was immersed in Atotech Japan Co., Ltd. diethylene glycol monobutyl ether containing swelling dip security gun P which is a swelling liquid at 60 degreeC for 10 minutes, and next as a roughening liquid of Atotech Japan Co., Ltd. It is immersed in concentrate compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) for 20 minutes at 80 degreeC, and finally, as neutralization liquid, to Atotech Japan Co., Ltd. reduction solution security guns P It was immersed at 40 degreeC for 5 minutes. The laminated board after this roughening process was made into sample A.

(5) Plating formation by semiadditive process

The insulating layer to form a circuit, immersing the laminate in an electroless plating solution comprising a PdCl _2, which was immersed in an electroless copper plating solution of the following: After performing annealing treatment by heating at 150 degreeC for 30 minutes, an etching resistor was formed, and after pattern formation by etching, copper sulfate electroplating was performed and the conductor layer was formed in the thickness of 30 micrometers. Next, annealing treatment was performed at 180 degreeC for 60 minutes. This laminated sheet was referred to as Sample B.

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

Regarding Sample A, using a non-contact surface roughness machine (WYKO NT3300, manufactured by Noncoinstrument Co., Ltd.), an Rq value was obtained from a value obtained by setting the measurement range to 121 μm × 92 μm using a VSI contact mode and a 50x lens. . And the average value of 10 points | pieces was calculated | required, respectively.

(7) Measurement of Peel Strength (Peel Strength) of Plating Conductor Layer

Into the conductor layer of Sample B, a notch of a part having a width of 10 mm and a length of 100 mm was placed, and this end was peeled off and held by a forceps (clamped with T-S E, autocommercial tester AC-50C-SL), In room temperature, the load (kgf / cm) at the time of peeling 35 mm in the vertical direction at the speed of 50 mm / min was measured.

(8) evaluation of insulation reliability

The resist tape cut out in a circular shape (Nepto Denko Co., Ltd. make, Erep masking tape N380) was stuck on the conductor layer of Sample B, and it was immersed for 30 minutes in the ferric chloride aqueous solution. The conductor layer of the part to which the resist tape did not adhere was removed, and the evaluation board | substrate with which the circular conductor layer was formed on the insulating layer was produced. Then, the base copper foil was exposed by shaving a part of insulating layer. And the exposed copper foil and the circular conductor layer were connected by wiring (wire). A DC power supply (TP018-3D, manufactured by Takasago Seisakusho Co., Ltd.) 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 that the resistance value is equal to or greater than 1.0 × 10 ⁸ Ω as "○" in, and 1.0 × 10 ⁷ Ω or more 1.0 × 10 ⁸ Ω "△" is less than, 1.0 × 10 ⁷ Ω under Was made into "x".

Measurement of Dielectric Tangent

The adhesive film obtained by each Example and each comparative example was thermosetted at 190 degreeC for 90 minutes, the PET film was peeled off, and the sheet-like hardened | cured material was obtained. The hardened | cured material is cut into the test piece of width 2mm and 80mm in length, and it uses the cavity resonator perturbation dielectric constant measuring apparatus CP521 and the Agilent Technology Co., Ltd. network analyzer E8362B manufactured by Kanto Toshio-Yogahaitsu Co., Ltd. The dielectric tangent (tan δ) was measured by the resonator perturbation method at a measurement frequency of 5.8 GHz. Two test pieces were measured and the average value was computed.

(Example 1)

10 parts of liquid bisphenol A type epoxy resins (Epoxy equivalent 180, Mitsubishi Chemical Corporation make "828US") and 20 parts of biphenyl type epoxy resins (Epoxy equivalent 291, Nihon Kayaku Co., Ltd. make "NC3000H") It melt | dissolved by stirring, stirring 15 parts of ethyl ketones (it abbreviates as "MEK" hereafter), and 15 parts of cyclohexanone. There, 28 parts of active ester compounds (DIC Corporation make "HPC8000-65T", active ester equivalent weight 223, toluene solution of 65% of solid content), triazine containing cresol novolak resin (DIC Corporation make "LA3018-50P") Phenol, equivalent to 151, 7 parts of 2-methoxypropanol solution of 50% solid content), 0.1 parts of a curing accelerator (manufactured by Koega Chemical Industries, Ltd., "4-dimethylaminopyridine"), spherical silica (average particle size 0.5) Μm, aminosilane-treated part "SO-C2", manufactured by Admatex Co., Ltd., 140 parts of carbon amount per unit weight, 140 parts of phenoxy resin (YL7553BH30, solid content of 30% by mass of MEK and cyclohexanone 1: 1) 7 parts of a solution, a weight average molecular weight 40000), 0.04 parts of blue pigments (made by Daiichi Seika Co., Ltd., cyanine blue 4920), 0.07 parts of yellow pigments (BASF Co., Ltd., Paris Otrol Yellow K1841), red pigment (client Japan Co., Ltd., PV Fast Pink E01) 0.08 parts are mixed and uniformly dispersed with a high-speed rotary mixer to produce a resin varnish It was. Next, this resin varnish is applied onto a polyethylene terephthalate film (thickness 38 mu m, hereinafter abbreviated as "PET film") with a die coater so that the resin thickness after drying is 40 mu m, and 80 to 120 ° C (average 100 Drying at 6 ° C. for 6 minutes to obtain a sheet-like adhesive film.

(Example 2)

A resin varnish was produced in exactly the same manner as in Example 1 except that 0.04 parts of blue pigment, 0.07 parts of yellow pigment, 0.08 parts of red pigment, and 0.44 parts of blue pigment, 0.66 parts of yellow pigment, and 0.84 parts of red pigment of Example 1 were changed. It was. Next, it carried out similarly to Example 1, and obtained the adhesive film.

(Example 3)

A resin varnish was produced in exactly the same manner as in Example 1 except that 0.04 part of blue pigment, 0.07 part of yellow pigment, 0.08 part of red pigment of Example 1 were changed to 0.9 part of blue pigment, 1.4 part of yellow pigment, and 1.6 part of red pigment. It was. Next, it carried out similarly to Example 1, and obtained the adhesive film.

(Example 4)

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

(Example 5)

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

(Example 6)

The resin varnish was made exactly the same as in Example 1 except that 0.04 parts of blue pigment, 0.07 parts of yellow pigment and 0.08 parts of red pigment of Example 1 were changed to 3.5 parts of antioxidant (BASF Co., Ltd. product "IRGANOX 1010"). Produced. Next, it carried out similarly to Example 1, and obtained the adhesive film.

(Example 7)

Except for changing the blue pigment 0.04 part, the yellow pigment 0.07 part, and the red pigment 0.08 part of Example 1 to 3.5 parts of infrared absorbers ("IR-14" by Nihon Shokubai Co., Ltd.) A resin varnish was produced. Next, it carried out similarly to Example 1, and obtained the adhesive film.

(Example 8)

140 parts of spherical silica (average particle diameter: 0.5 micrometer, aminosilane treatment provision "SO-C2", the admatex make, 0.18% of carbon amount per unit weight) 140 parts of spherical silica (average particle diameter: 0.25 micrometer, amino Except having changed into 100 parts of silane treatment provision "SO-C1", the product made by ADMATEX, and carbon amount per unit weight) 100 parts, it carried out similarly to Example 2, and produced the resin varnish. Next, it carried out similarly to Example 1, and obtained the adhesive film.

(Example 9)

The same adhesive film as in Example 2 was used.

(Comparative Example 1)

Except not adding 0.04 part of blue pigments of Example 1, 0.07 part of yellow pigments, and 0.08 part of red pigments, the resin varnish was produced like Example 1 completely. Next, it carried out similarly to Example 1, and obtained the adhesive film.

The results are shown in Table 1.

As is clear from Table 1, it can be seen that in the examples, it is a low dielectric tangent and has excellent smear suppression in the via holes. Moreover, in Examples 1-3, 5-9, the insulation reliability was also especially excellent, and in Examples 3, 8, 9, smear was further suppressed. On the other hand, in Comparative Example 1, although the dielectric tangent was low, smear remained.

Industrial availability

Provides a resin composition, a sheet-like laminated material, a multilayer printed wiring board, and a semiconductor device capable of achieving low dielectric tangent of the cured product of the resin composition and suppressing smear in the via hole after the cured product is bored and roughened. I can do it. In addition, electric appliances such as computers, mobile phones, digital cameras, televisions, and the like, and vehicles such as motorcycles, automobiles, trams, ships, and aircrafts can be provided.

Claims (13)

As a resin composition containing (A) epoxy resin, (B) active ester compound, (C) smear suppression component, and (D) inorganic filler,
In the case where the nonvolatile component of the resin composition is 100 mass%, the content of the (B) active ester compound is 5 mass% or more,
(C) smear suppression component is 0.001-10 mass% when the non volatile component of the said resin composition is 100 mass%,
When the non-volatile component of the resin composition is 100% by mass, the inorganic filler (D) is 70% by mass or more,
(C) Smear suppression component is a rubber particle, The resin composition characterized by the above-mentioned. The content of the (B) active ester compound is 5-30 mass%, when the non-volatile component in a resin composition is 100 mass%, The resin composition of Claim 1 characterized by the above-mentioned. The content of the (B) active ester compound is 5-10 mass%, when the non-volatile component in a resin composition is 100 mass%, The resin composition of Claim 1 characterized by the above-mentioned. The content of the (D) inorganic filler is 70-85 mass%, when the non-volatile component in a resin composition is 100 mass%, The resin composition of Claim 1 characterized by the above-mentioned. The resin composition according to claim 1, wherein the carbon amount per unit weight of the inorganic filler is 0.02 to 3%. The square root mean square roughness Rq of the said insulating layer surface after hardening a resin composition and forming an insulating layer, and roughening the said insulating layer surface is 500 nm or less, and is obtained by plating on the said insulating layer surface. The peel strength of a conductor layer and the said insulating layer is 0.3 kgf / cm or more, and the dielectric tangent of the hardened | cured material of a resin composition is 0.05 or less, The resin composition characterized by the above-mentioned. The resin composition of Claim 1 which is a resin composition for insulating layers of a multilayer printed wiring board. The resin composition as described in any one of Claims 1-7 is contained, The sheet-like laminated material characterized by the above-mentioned. An insulating layer is formed of the hardened | cured material of the resin composition of any one of Claims 1-7, The multilayer printed wiring board characterized by the above-mentioned. The multilayer printed wiring board of Claim 9 is used, The semiconductor device characterized by the above-mentioned. The multilayer printed wiring board of claim 8, wherein the sheet-like laminate material is laminated on a circuit board, the resin composition is thermally cured to form an insulating layer, and a via hole is formed by punching through the insulating layer formed on the circuit board. Manufacturing method. The method of manufacturing a multilayer printed wiring board according to claim 11, wherein the top diameter (diameter) of the via holes is 60 µm or less. The method of manufacturing a multilayer printed wiring board according to claim 11, wherein the maximum smear length from the wall surface of the via hole bottom portion is less than 5 m.