TW201412862A - Resin composition - Google Patents

Abstract

The topic of the present invention is to form a plated conductor layer having an adequate peeling strength and with an excellent lamination property on an insulation layer, which is formed by curing in a wet roughening step, having not only a small arithmetic-mean roughness value of the insulation layer surface but also a small root-mean-square roughness value of the insulation layer surface. The solution of the present invention is to provide a resin composition, which is characterized by containing an inorganic filler with surface treatment carried out by epoxy resin, a curing agent, and an alkoxysilane compound.

Description

Resin composition

The present invention relates to a resin composition. Further, the resin composition, the sheet-like laminate, the multilayer printed wiring board, and the semiconductor device are contained.

In recent years, the miniaturization and high performance of electronic devices have been progressing, and Build-up Layer delamination in multilayer printed wiring boards has been sought, and wiring has been made finer and higher in density.

Look for a variety of methods for this. For example, Patent Document 1 discloses that a film is surface-treated with a decane-based or titanium-based coupling agent. However, the alkoxydecane compound is completely free of charge. Further, Patent Document 2 has a description of an alkoxydecane compound, but has not been described in detail, and it is not possible to know the contents of the present invention.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-224644

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-74668

The object of the present invention is to provide a resin composition characterized in that in the wet roughening step, not only the arithmetic mean roughness of the surface of the insulating layer is low, but also the root mean square roughness of the surface of the insulating layer is low. A plated conductor layer having sufficient peel strength is formed thereon, and the laminate property is also excellent.

The inventors of the present invention have carefully studied the above-mentioned problems, and have a resin composition characterized by containing an inorganic filler which has been surface-treated with an epoxy resin, a curing agent, and an alkoxysilane compound. The invention is achieved.

That is, the present invention is intended to contain the following contents.

[1] A resin composition comprising a resin composition which is an inorganic filler which is surface-treated with an epoxy resin, a curing agent and an alkoxydecane compound, wherein the inorganic filler has an average particle diameter of 0.01 to 5 μm. When the nonvolatile content in the resin composition is 100% by mass, the content of the inorganic filler is 30 to 90% by mass.

[2] The resin composition according to [1], wherein the alkoxydecane compound contains an alkyl group and/or an aryl group.

[3] The resin composition according to [1] or [2], wherein the alkoxydecane compound comprises an alkyl group having 1 to 10 carbon atoms, a phenyl group, a benzyl group, a tolyl group, and a xylene group. One or more of the group and the naphthyl group are selected.

[4] The resin composition according to any one of [1] to [3] wherein the alkoxydecane compound comprises methyl, ethyl, propyl, isopropyl, cyclopropyl, phenyl, One or more selected from the group consisting of a benzyl group, a tolyl group, a xylyl group and a naphthyl group.

[5] The resin composition according to any one of [1] to [4] wherein the alkoxydecane compound is derived from phenyltrialkoxydecane, dimethyldialkoxydecane, methyltrioxane Oxy decane, diethyl dialkoxy decane, ethyl trialkoxy decane, diphenyl dialkoxy decane, methyl phenyl dialkoxy decane and diphenylmethyl monoalkoxy decane One or more of them are selected.

[6] The resin composition according to any one of [1] to [5] wherein the alkoxydecane compound has a molecular weight of from 100 to 1,000.

[7] The resin composition according to any one of [1] to [6] wherein the inorganic filler is cerium oxide.

[8] The resin composition according to any one of [1] to [7], wherein the alkoxydecane compound is surface-treated at 0.05 to 4 parts by mass based on 100 parts by mass of the inorganic filler.

[9] The resin composition according to any one of [1] to [8] wherein the inorganic filler has a carbon amount per unit surface area of 0.01 to 0.8 mg/m ² .

[10] The resin composition according to any one of [1] to [9] wherein the epoxy resin is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthol type epoxy resin, One or more selected from the group consisting of a naphthalene type epoxy resin, a biphenyl type epoxy resin, a naphthyl ether type epoxy resin, a glycidyl ester type epoxy resin, a fluorene type epoxy resin, and a butadiene structure epoxy resin .

[11] The resin composition according to any one of [1] to [10] wherein the hardener is One or more kinds are selected from the group consisting of a phenolic curing agent, an active ester curing agent, and a cyanate curing agent.

[12] The resin composition according to any one of [1] to [11] wherein the hardener is from a biphenyl type hardener, a naphthalene type hardener, a phenol novolak type hardener, a naphthyl ether type type hardening. Agent, triterpene phenolic curing agent, active ester curing agent containing dicyclopentadiene type diphenol condensation structure, phenolic cyanate curing agent, dicyclopentadiene type cyanate curing agent One or more selected from the group consisting of bisphenol type cyanate curing agents.

[13] The resin composition according to any one of [1] to [12] wherein the hardened resin composition forms an insulating layer, and the arithmetic mean roughness after roughening the surface of the insulating layer is 400 nm or less, rms The roughness is 500 nm or less.

[14] The resin composition according to any one of [1] to [13], wherein the hardened resin composition forms an insulating layer, and the arithmetic mean roughness after roughening the surface of the insulating layer is 10 to 400 nm, mean square Root roughness is 30~500nm.

[15] The resin composition according to any one of [1] to [14] wherein the hardened resin composition forms an insulating layer, the surface of the insulating layer is roughened, and the conductor layer and the insulating layer are obtained after plating. The peel strength between 0.3 and 1.2 kgf/cm or more.

[16] The resin composition according to any one of [1] to [15] which is a resin composition for an insulating layer of a multilayer printed wiring board.

[17] The resin composition according to any one of [1] to [16] which is a resin composition for a build-up layer of a multilayer printed wiring board.

[18] A sheet-like laminate comprising the resin composition according to any one of [1] to [17].

[19] A multilayer printed wiring board characterized in that the insulating layer is formed by a cured product of the resin composition according to any one of [1] to [17].

[20] A semiconductor device characterized by using the multilayer printed wiring board of [19].

The present invention provides a resin composition comprising a resin composition containing an inorganic filler after surface treatment with an epoxy resin, a hardener and an alkoxydecane compound, and not only the surface of the insulating layer in the wet roughening step The arithmetic mean roughness is low, and the value of the root mean square roughness of the surface of the insulating layer is also low, and a plated conductor layer having sufficient peeling strength can be formed on the insulating layer, and the laminate property is also excellent.

The present invention provides a resin composition characterized by comprising an epoxy resin, a curing agent, and an alkoxydecane compound, and then containing an inorganic filler. The resin composition is described in detail below.

<Epoxy resin>

The epoxy resin used in the present invention is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and phenol novolac type ring. Oxygen resin, tert-butyl-catechol epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, naphthyl ether epoxy resin, glycidylamine epoxy resin, glycidyl ester type ring Oxygen resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, linear aliphatic epoxy resin, butadiene-structured epoxy resin, alicyclic epoxy resin, complex Ring epoxy resin, including spiro epoxy resin, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, and the like. One type or two or more types can be used in combination.

Even from the viewpoints of improving heat resistance, improving laminate properties, and improving peel strength, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type are used. One or more selected from the group consisting of epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, glycidyl ester type epoxy resin, fluorene type epoxy resin, and epoxy resin having butadiene structure good. Specifically, for example, bisphenol A type epoxy resin ("Epikote 828EL" manufactured by Mitsubishi Chemical Corporation, "YL980"), bisphenol F type epoxy resin ("JER806H" manufactured by Mitsubishi Chemical Corporation, "YL983U"), Naphthalene type 2-functional epoxy resin ("HP4032", "HP4032D", "HP4032SS", "EXA4032SS", manufactured by DIC), naphthalene type 4-functional epoxy resin (HP4700, "HP4710" manufactured by DIC Corporation ), a naphthol type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Co., Ltd.), an epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Industry Co., Ltd.), having two Epoxy resin of phenyl structure ("NC3000H", "NC3000L", "NC3100" made by Nippon Kayaku Co., Ltd., "YX4000", "YX4000H", "YX4000HK", "YL6121" by Mitsubishi Chemical Corporation)蒽-type epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Co., Ltd.), naphthyl ether epoxy resin (EXA-7310, "EXA-7311", "EXA-7311L"," EXA7311-G3"), glycidyl ester epoxy resin (Nagase chemteX) "EX711", "EX721", "shares" ("540" made by Printec).

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule, and a liquid epoxy resin and a solid epoxy resin are preferably used in combination. The liquid epoxy resin is preferably one having two or more epoxy groups in one molecule and a liquid aromatic epoxy resin at a temperature of 20 ° C. The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule and a solid temperature at 20 ° C. Further, the term "aromatic epoxy resin" as used in the present invention means an epoxy resin having an aromatic ring structure in the molecule. When the epoxy resin is used together with the liquid epoxy resin and the solid epoxy resin, the resin composition has moderate flexibility, improves the laminate property when used in the form of a film, or reduces the surface roughness of the cured product of the resin composition. From the viewpoint of the degree, the mixing ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of mass ratio 1:0.1 to 1:2, and preferably in the range of 1:0.3 to 1:1.8, 1 : The range of 0.6~1:1.5 is better.

Liquid epoxy resin such as bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, glycidyl ester epoxy resin or naphthalene epoxy resin is preferred, bisphenol A ring An oxy resin, a bisphenol F type epoxy resin or a naphthalene type epoxy resin is preferred. One type or two or more types may be used in combination. The solid epoxy resin is a 4-functional naphthalene epoxy resin, a cresol novolac epoxy resin, a dicyclopentadiene epoxy resin, a phenol epoxy resin, a naphthol epoxy resin, and a fluorene epoxy resin. A biphenyl type epoxy resin or a naphthyl ether type epoxy resin is preferred, a naphthol type epoxy resin, or a biphenyl type epoxy resin is preferred. One type or two or more types may be used in combination.

In the resin composition of the present invention, from the viewpoint of improving the mechanical strength or water resistance of the cured product of the resin composition, when the nonvolatile content in the resin composition is 100% by mass, the content of the epoxy resin is 3 to 40% by mass. Preferably, 5 to 30% by mass is preferred, and 10 to 20% by mass is more preferred.

<hardener>

The curing agent used in the present invention is not particularly limited, and examples thereof include a phenolic curing agent, an active ester curing agent, a cyanate curing agent, and benzo. From the viewpoint of reducing the arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) of the cured product of the resin composition, the curing agent and the acid anhydride-based curing agent are used. One or more of the ester-based curing agent and the cyanate-based curing agent are preferably selected. One type or two or more types can be used in combination.

The phenolic curing agent is not particularly limited, and is preferably a biphenyl type hardener, a naphthalene type hardener, a phenol novolak type hardener, a stretch naphthyl ether type hardener, or a triterpene skeleton phenol type hardener. Specifically, such as biphenyl type hardener, MEH-7700, MEH-7810, MEH-7851 (made by Minghe Chemical Co., Ltd.), naphthalene type hardener NHN, CBN, GPH (Nippon Chemical Co., Ltd.), SN170 , SN180, SN190, SN475, SN485, SN495, SN375, SN395 (Nippon Steel Chemical Co., Ltd.), EXB9500 (DIC system), phenolic phenolic type hardener TD2090 (DIC system), extension EXB-6000 (manufactured by DIC) of a naphthyl ether type curing agent, LA3018, LA7052, LA7054, LA1356 (manufactured by DIC Co., Ltd.) containing a triterpene skeleton phenolic curing agent. One type or two or more types can be used in combination.

The active ester-based hardener is not particularly limited, and phenol is generally used. The ester of the ester, the thiophenolate, the N-hydroxylamine, and the complex cyclic hydroxy compound is preferably a compound having two or more highly reactive ester groups in one molecule. The active ester-based curing agent is preferably obtained by a condensation reaction of a carbonic acid compound and/or a thiocarbonate compound with a hydroxy compound and/or a thiol compound. Particularly, from the viewpoint of improvement, heat resistance is preferably an active ester-based curing agent obtained from a carbonic acid compound and a hydroxy compound, and a carbonate compound, a phenol compound and/or a naphthol compound and the obtained active ester-based curing agent are preferred. Carbonic acid compounds such as benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, p-phthalic acid, pyromellitic dianhydride, and the like. Phenolic compounds or naphthol compounds such as hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, 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, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, 1,3,5-benzenetriol, benzenetriol, polycyclopentadiene diphenol A compound (dicyclopentadiene type diphenol compound, tricyclopentadiene type diphenol compound), phenol novolac, and the like. One or two or more kinds of the active ester-based curing agents can be used. As the active ester-based curing agent, an active ester-based curing agent disclosed in JP-A-2004-277460 can be used, and a commercially available one can also be used. A commercially available active ester-based curing agent, such as an active ester-based curing agent containing a dicyclopentadiene-type diphenol condensation structure (a condensation structure of a dicyclopentadiene type and a phenol), and an active ester-based curing agent containing a naphthalene structure. An active ester-based hardener of phenol phenolic acetal, an active ester-based hardener of phenol phenolic benzoyl amide, and the like, wherein the improvement in peel strength is excellent. An active ester-based curing agent containing a dicyclopentadiene-type diphenol condensation structure is preferred. Specifically, a dicyclopentadiene-type diphenol condensation structure such as EXB9451, EXB9460, EXB9460S-65T, HPC-8000-65T (manufactured by DIC, having an active base equivalent of about 223), and a bisphenol phenolic acetal compound The active ester-based hardener is DC808 (manufactured by Mitsubishi Chemical Corporation, having an active base equivalent of about 149), and the active ester-based hardener of the benzophenone of phenol novolac is YLH1026 (manufactured by Mitsubishi Chemical Corporation). 200), YLH1030 (manufactured by Mitsubishi Chemical Corporation, active base equivalent: about 201), YLH1048 (manufactured by Mitsubishi Chemical Corporation, active base equivalent: about 245), and the like.

The active ester-based curing agent having a dicyclopentadiene type (or tricyclopentadiene type) containing a diphenol condensation structure is more specifically a compound of the following formula (1).

(wherein R is a phenyl group or a naphthyl group, k is 0 or 1 and n is an average of 0.05 to 2.5 in terms of repeating units).

From the viewpoint of lowering the dielectric loss of the cured product of the resin composition and improving the heat resistance, R is preferably a naphthyl group. On the one hand, k is preferably 0, and n is preferably 0.25 to 1.5.

The cyanate-based curing agent is not particularly limited, and is, for example, a phenolic type (phenol novolic type, an alkylphenol novolak type, etc.) cyanate type hardener, a dicyclopentadiene type cyanate type hardener, and a bisphenol type (double Cyanate-based hardeners such as phenol A type, bisphenol F type, and bisphenol S type, and the pretreatment of these three parts Polymers, etc. The weight average molecular weight of the cyanate-based curing agent is not particularly limited, and is preferably 500 to 4,500, more preferably 600 to 3,000. Specific examples of the cyanate-based curing agent, such as bisphenol A dicyanate, polyphenol cyanate (oligomer (3-methyl-1,5-phenylene), 4,4 '-Methyl bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2 - bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1 , 3-bis(4-cyanate phenyl-1-(methylethylidene)) benzene, bis(4-cyanate phenyl) sulfide, bis(4-cyanate phenyl) ether, etc. a polyfunctional cyanate resin induced by a bifunctional cyanate resin, a phenol novolac, a cresol novolak, a phenol resin having a dicyclopentadiene structure, or the like, and a part of the cyanate resin is triterpene A prepolymer or the like may be used in combination of one or more of them. The commercially available cyanate resin is a phenol novolac type polyfunctional cyanate resin represented by the following formula (2) (manufactured by Lonza Japan Co., Ltd.). PT30, cyanate ester equivalent 124), a prepolymer of a part or all of a trimerized trimer of bisphenol A dicyanate represented by the following formula (3) (manufactured by Lonza Japan Co., Ltd., BA230, Cyanide Ester 232 equiv), the formula (4) represented by the structure comprising dicyclopentadiene-type cyanate resin (Lonza Japan (shares) manufactured, DT-4000, DT-7000) and the like.

[wherein n is an average value expressed as an arbitrary number (preferably 0 to 20)].

(where n is a number with an average value of 0 to 5).

Benzo The curing agent is not particularly limited, and specific examples thereof include Fa, Pd (manufactured by Shikoku Chemical Co., Ltd.), and HFB2006M (manufactured by Showa Polymer Co., Ltd.).

The acid anhydride-based hardener is not particularly limited, and examples thereof include phthalic anhydride, tetrahydrogen phthalic anhydride, hexahydrophthalic anhydride, and methyl group. Phthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic acid Anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarbonic anhydride, partial benzene Tricarboxylic anhydride, pyrogallite anhydride dianhydride, diphenyl ketone tetracarbonic dianhydride, diphenyltetracarbonic dianhydride, naphthalene tetracarbonic dianhydride, oxydiphthalic phthalic anhydride, 3,3 '-4,4'-diphenylphosphonium tetracarbonate dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3 -furyl)-naphthalene [1,2-C]furan-1,3-dione, ethylene glycol bis(dehydrated trimellitate), styrene copolymerized with maleic acid and styrene. A polymer type acid anhydride such as maleic acid resin.

The resin composition of the present invention has a ratio of the total number of epoxy groups of the epoxy resin to the total number of reactive groups of the hardener from the viewpoint of improving the mechanical strength or water resistance of the cured product of the resin composition: 1:0.2 1:2 is better, 1:0.3~1:1.5 is better, and 1:0.4~1:1 is better. Further, the total number of epoxy groups of the epoxy resin present in the resin composition is the total value of all the epoxy resins obtained by dividing the mass of the solid content of each epoxy resin by the epoxy equivalent, and the hardener The total number of the reactive groups is the total value of all the hardeners after dividing the mass of the solid content of each hardener by the equivalent of the reactive base.

<Inorganic filler after surface treatment with alkoxydecane compound>

The alkoxydecane compound using the inorganic filler after surface treatment with an alkoxydecane compound is not particularly limited, and is composed of a resin. From the viewpoint of improving the lamination property in the form of a flaky form, the alkoxydecane compound preferably contains an alkyl group and/or an aryl group, and is grouped from an alkyl group, an aryl group and an alkoxyalkyl group. It is preferred to select one or more of them in combination with a ruthenium atom. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 6 carbon atoms is preferred. From the viewpoint of preventing an increase in viscosity of the varnish resin, an alkyl group having 1 to 4 carbon atoms is more preferable. It is more preferable to select one or more of a group, an ethyl group, a propyl group, an isopropyl group and a cyclopropyl group. The aryl group is preferably one or more selected from the group consisting of a phenyl group, a benzyl group, a tolyl group, a xylyl group, and a naphthyl group. Specifically, the alkoxydecane compound is derived from phenyltrialkoxydecane, dimethyldialkoxydecane, methyltrialkoxydecane, diethyldialkoxydecane, ethyltrialkoxy One or more selected from the group consisting of decane, diphenyl dialkoxy decane, methylphenyl dialkoxy decane, and diphenylmethyl monoalkoxy decane are preferred. From the viewpoint of improving the peel strength, it is preferred that each alkoxyalkylene group has 2 to 3 alkoxy groups, and the alkoxy group is preferably a methoxy group or an ethoxy group. Further, the alkoxyalkyl group can also be modified. These alkoxydecane compounds do not have a toxic gas or the like during surface treatment, and are excellent in productivity and environmental surface. Further, the alkoxydecane compound is different from the coupling agent having an organic functional group, and is excellent from the viewpoint of improving hydrophobicity and compatibility with a resin. Further, the alkoxydecane compound is different from the coupling agent having an organic functional group, and is excellent in that it is not agglomerated during surface treatment and is easily surface-treated. Therefore, the surface treatment with the alkoxydecane compound is followed by the use of an inorganic filler to improve the laminate property or the low thickness while improving the peel strength.

Molecular weight of alkoxydecane compound from inhibition surface treatment From the viewpoint of volatilization at the time of drying or drying, it is preferably 100 or more, more preferably 110 or more, and still more preferably 120 or more. On the other hand, from the viewpoint of appropriate reactivity, the alkoxydecane compound preferably has a molecular weight of 1,000 or less, more preferably 700 or less, and still more preferably 400 or less. Commercial products of alkoxydecane compounds such as "KBM103" (phenyltrimethoxydecane), "KBE-22" (dimethyldiethoxydecane), "KBM-13" manufactured by Shin-Etsu Chemical Co., Ltd. (methyltrimethyldecane), "KBM-22" (dimethyldimethoxydecane), "KBM-3063" (hexyltrimethoxydecane), "KBE-3063" (hexyltriethoxydecane) ), "KBM-3103" (tridecamethoxydecane), "LS-2400" (diethyldiethoxydecane), "LS-890" (ethyltrimethyldecane), "LS-5300" (Diphenyldimethoxydecane), "LS-2720" methylphenyldimethoxydecane, "LS-5610" (diphenylmethylmethoxydecane), and the like.

The inorganic filler of the inorganic filler after surface treatment with an alkoxydecane compound is not particularly limited, and examples thereof include cerium oxide, aluminum, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, and the like. Calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Among them, amorphous cerium oxide, pulverized cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, hollow cerium oxide, spherical cerium oxide, etc., preferably in order to reduce insulation From the viewpoint of surface roughness of the layer, molten cerium oxide, spherical cerium oxide is preferred, and spherical molten cerium oxide is more preferable. One type or two or more types may be used in combination.

The average particle diameter of the inorganic filler is not particularly limited, and the upper limit of the average particle diameter of the inorganic filler is preferably 5 μm or less from the viewpoint of forming a low roughness on the surface of the insulating layer and forming fine wiring, and 4 μm or less. Preferably, it is more preferably 3 μm or less, more preferably 2 μm or less, particularly preferably 1 μm or less, particularly preferably 0.8 μm or less, and particularly preferably 0.6 μm or less. On the other hand, when the resin composition is used to form a varnish resin, the lower limit of the average particle diameter of the inorganic filler is preferably 0.01 μm or more, and preferably 0.05 μm or more from the viewpoint of preventing the operability from lowering the viscosity of the varnish. More preferably, it is 0.1 μm or more, particularly preferably 0.2 μm or more, and particularly preferably 0.3 μm or more. The average particle size of the above inorganic filler is based on the Mie scattering theory by laser diffraction. The scattering method was used for the measurement. Specifically, it is produced by a laser diffraction scattering type particle size distribution measuring apparatus, and the particle size distribution of the inorganic filler is used as a volume basis to determine the average particle diameter. It is preferred that the sample is prepared by dispersing the inorganic filler material in water by ultrasonic waves. The laser diffraction scattering type particle size distribution measuring apparatus uses a LA-750 manufactured by Horiba, Ltd., and the like.

The content of the inorganic filler is not particularly limited, and when the non-volatile component in the resin composition is 100% by mass, 90% by mass or less is preferable from the viewpoint of preventing the cured material from becoming brittle or the peel strength is prevented from being lowered, and 85 mass is preferable. % or less is preferable, 80% by mass or less is more preferable, and 75% by mass or less is more preferable. On the other hand, the content of the inorganic filler is preferably 30% by mass or more, more preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more, from the viewpoint of reducing the thermal expansion ratio of the cured product.

An inorganic filler after surface treatment with an alkoxydecane compound, alkoxydecane compound which is surface-treated with the inorganic filler The amount of the material is not particularly limited, and the alkoxydecane compound is preferably surface-treated with 0.05 to 4 parts by mass, more preferably 0.1 to 3 parts by mass, and 0.2 to 3 parts by mass, based on 100 parts by mass of the inorganic filler. It is more preferable to perform surface treatment for 2 parts by mass, and it is more preferable to perform surface treatment with 0.3 to 1 part by mass.

Further, the inorganic filler obtained by surface treatment with an alkoxydecane compound was examined for the presence of carbon atoms by analyzing the surface composition of the inorganic filler, and the amount of carbon per unit surface area of the inorganic filler was sought. For the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. is used.

Specifically, a sufficient amount of MEK as a solvent was added to an inorganic filler which was surface-treated with an alkoxydecane compound, and ultrasonically washed at 25 ° C for 5 minutes. After the supernatant liquid was removed to dry the solid content, the amount of carbon per unit surface area of the inorganic filler was measured using a carbon analyzer. For the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. is used.

The amount of carbon per unit surface area of the above inorganic filler is 0.01 mg / from the viewpoint of improving the dispersibility of the inorganic filler or the arithmetic mean roughness and root mean square roughness after the wet roughening step of the cured product. More preferably, m ² or more, more preferably 0.05 mg/m ² or more, still more preferably 0.1 mg/m ² or more. On the other hand, from the viewpoint of preventing the melt viscosity of the varnish resin or the increase in the melt viscosity in the form of the film, the amount of carbon per unit surface area of the above inorganic filler is preferably 0.8 mg/m ² or less, and 0.5 mg/ It is preferably m ² or less, more preferably 0.3 mg/m ² or less.

An inorganic filler which has been surface-treated with an alkoxydecane compound, and the inorganic filler is surface-treated with an alkoxydecane compound After the treatment, it is preferably added to the resin composition. At this time, the dispersibility of the inorganic filler is further improved.

The surface treatment method in the case where the inorganic filler is surface-treated with an alkoxydecane compound is not particularly limited, and is, for example, a dry method or a wet method. In the dry method, an inorganic filler is added to a rotary mixer, and an alcohol solution or an aqueous solution of an alkoxydecane compound is dropped or sprayed while stirring, and further stirred, and classified by a sieve. Thereafter, the alkoxydecane compound and the inorganic filler are dehydrated and condensed by heating to obtain an inorganic filler after surface treatment. In the wet method, an alkoxysilane compound is added while stirring the slurry of the inorganic filler and the organic solvent, and after stirring, it is filtered, dried, and classified by a sieve. Thereafter, the alkoxysilane compound and the inorganic filler are heated and dehydrated and condensed, and an inorganic filler is obtained by surface treatment. Further, the alkoxydecane compound may be added to the resin composition to be surface-treated by an overall blending method.

<hardening accelerator>

The resin composition of the present invention further efficiently hardens the epoxy resin and the curing agent by containing a curing accelerator. The hardening accelerator is not particularly limited, and examples thereof include an amine-based hardening accelerator, a lanthanum-based hardening accelerator, an imidazole-based hardening accelerator, an oxime-based hardening accelerator, and a metal-based hardening accelerator. One type or two or more types can be used in combination.

The amine-based hardening accelerator is not particularly limited, and is, for example, trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-gin. (dimethylaminomethyl)phenol, 1,8-dioxinbicyclo An amine compound such as (5,4,0)-undecene (hereinafter abbreviated as DBU.). One type or two or more types can be used in combination.

The lanthanide hardening accelerator is not particularly limited, and is, for example, dicyandiamide, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl hydrazine, 1-phenyl fluorene, 1-(o-phenyl) fluorene, Dimethyl hydrazine, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazine bicyclo [4.4.0] tens-5-ene, 7-methyl- 1,5,7-triazine bicyclo[4.4.0]deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylindole, 1, 1-Dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-tolyl biguanide, 1-(o-methylphenyl)biguanide, and the like. One type or two or more types can be used in combination.

The imidazole-based hardening accelerator is not particularly limited, and is, for example, 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- Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole benzene Triformate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triterpene, 2,4-diamino-6-[2' -undecyl imidazolyl-(1')]-ethyl-s-triterpene, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1') ]-ethyl-s-triterpene, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triterpene isocyanuric acid, 2-Phenyl imidazole iso-cyanuric acid addition, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-di Hydrogen-1H-pyrrolo[1,2-a] Imidazole compound of benzimidazole, 1-dodecyl-2-methyl-3-chlorobenzylimidazole, 2-methylimidazoline, 2-phenylimidazoline, etc., and adduct of imidazole compound and epoxy resin . One type or two or more types can be used in combination.

The lanthanide hardening accelerator is not particularly limited, and examples thereof include triphenylphosphine, bismuth borate compound, tetraphenylphosphonium tetraphenyl borate, n-butyl fluorene tetraphenyl borate, and tetrabutyl decane. An acid salt, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. One type or two or more types can be used in combination.

In the resin composition of the present invention, the content of the curing accelerator (excluding the metal-based hardening accelerator) is preferably in the range of 0.005 to 1% by mass, and 0.01 to 0.5 in the case where the nonvolatile content in the resin composition is 100% by mass. The range of mass % is preferred. The content of the hardening accelerator (excluding the metal-based hardening accelerator) is such that the heat hardening is more efficient and the storage stability of the varnish resin can be improved.

The metal-based hardening accelerator is not particularly limited, and is an organometallic complex or an organic metal salt of a metal such as cobalt, copper, zinc, iron, nickel, manganese or tin. Specific examples of the organometallic complex include an organic cobalt complex such as cobalt (II) acetoacetate, cobalt (III) acetoacetate, or an organic copper complex such as copper (II) acetoacetate, zinc. (II) an organic zinc complex such as acetoacetate, an organic iron complex such as iron (III) acetoacetate, an organic nickel complex such as nickel (II) acetoacetate, or manganese (II) An organic manganese complex such as acetoacetate or the like. Organometallic salts such as zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like. One type or two or more types can be used in combination.

When the amount of the metal-based hardening accelerator in the resin composition is 100% by mass, the content of the metal based on the metal-based curing catalyst is preferably in the range of 25 to 500 ppm, 40~ A range of 200 ppm is preferred. The addition amount of the metal-based hardening accelerator is such that an excellent conductor layer is formed by the adhesion of the surface of the insulating layer in this range, and the storage stability of the varnish resin is improved.

<Thermoplastic resin>

Further, the resin composition of the present invention further improves the mechanical strength of the cured product by containing a thermoplastic resin, and further improves the film forming ability when used in the form of a film. Thermoplastic resin such as phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamidamine resin, polyether oxime resin, polyfluorene resin, polyether oxime resin, polyphenylene ether A resin, a polycarbonate resin, a polyether ether ketone resin, a polyester resin or the like, particularly a phenoxy resin or a polyvinyl acetal resin is preferred. These thermoplastic resins may be used singly or in combination of two or more. The weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000. Further, the weight average molecular weight of the present invention is measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). For the weight average molecular weight of the GPC method, LC-9A/RID-6A manufactured by Shimadzu Corporation was used as a measuring device, and Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd. was used as a column. Trichloromethane was used as the mobile phase and was measured at a column temperature of 40 ° C, using a calibration curve of standard polystyrene.

When the resin composition of the present invention is combined with a thermoplastic resin, The content of the thermoplastic resin in the resin composition is not particularly limited, and is preferably 0.1 to 10% by mass, and preferably 0.5 to 5% by mass based on 100% by mass of the nonvolatile component in the resin composition. When the content of the thermoplastic resin in the resin composition is within this range, the film forming ability or the mechanical strength is improved, and the increase in the melt viscosity or the roughness of the surface of the insulating layer after the wet roughening step is further reduced.

<Rubber Particles>

Further, the resin composition of the present invention further improves the peeling strength by containing the rubber particles, and also improves the drilling processability of the cured product of the resin composition, reduces the dielectric loss, and obtains a stress relieving effect. When the obtained rubber particles are used in the present invention, such as a varnish for preparing the resin composition, they are not dissolved in the organic solvent to be used, and are not compatible with an epoxy resin or the like. Therefore, the rubber particles are present in a dispersed state in the varnish of the resin composition of the present invention. As described above, the rubber particles generally have a molecular weight of the rubber component increased to such an extent that they are not dissolved in the organic solvent or the resin.

Preferred examples of the rubber particles obtained by the present invention are core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, propylene rubber particles and the like. The core-shell type rubber particles are a two-layer structure in which a core layer and a shell layer and rubber particles are used, for example, a shell layer of an outer layer is aggregated by a glassy polymer, and a core layer of an inner layer is a rubbery polymer, or an outer layer. The shell layer is composed of a glassy polymer, the intermediate layer is composed of a rubbery polymer, and the core layer is a three-layer structure composed of a glassy polymer. a glassy polymer layer such as a polymer of methyl methacrylate The rubbery polymer layer is composed of, for example, a butyl acrylate polymer (butyl rubber). Two or more types of rubber particles can be used in combination. Specific examples of the core-shell type rubber particles are, for example, STAFILLOYD AC3822, AC3816N, AC3401N, IM-401, 7-17 (trade name, GANTSU Chemical Co., Ltd.), METABLEN KW-4426 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle diameter: 0.5 μm, manufactured by JSR Co., Ltd.). A specific example of the crosslinked styrene butadiene rubber (SBR) particles is XSK-500 (average particle diameter: 0.5 μm, manufactured by JSR Co., Ltd.). Specific examples of the acrylic rubber particles are METABLEN W300A (average particle diameter: 0.1 μm) and W450A (average particle diameter: 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.).

The average particle diameter of the rubber particles to be blended is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of the rubber particles used in the present invention was measured by using kinetic dispersion. For example, the rubber particles are more uniformly dispersed by ultrasonic waves in a suitable organic solvent, and a particle size distribution of rubber particles is used as a quality standard by using a thick particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). The average particle diameter was measured as an average particle diameter.

The content of the rubber particles is preferably from 0.05 to 10% by mass, more preferably from 0.5 to 5% by mass, based on 100% by mass of the nonvolatile matter in the resin composition.

<flammable agent>

The resin composition of the present invention further imparts flame retardancy by containing a flame retardant. The flame retardant is, for example, an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polyoxygenated flame retardant, a metal hydroxide or the like. Organophosphorus-based flame retardants such as HCA, HCA-HQ, HCA-NQ and other phenanthrene-type phosphorus compounds manufactured by Sanguang Co., Ltd., and HFB-2006M manufactured by Showa Polymer Co., Ltd. Compound, Ajinomoto Fine-Techno (stock) made by Leofos 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, Beixing Chemical Industry Co., Ltd. TPPO, PPQ, Clariant (OP) OP930, Da Ba Chemical (share) PX200 phosphate compound, Nippon Steel Chemical Co., Ltd. FX289, FX305, TX0712, etc. containing phosphorus epoxy resin, Nippon Chemical Co., Ltd., such as ERF001, contains a phosphorus phenoxy resin, and YL7613 manufactured by Mitsubishi Chemical Co., Ltd. contains a phosphorus epoxy resin. Organic nitrogen-containing phosphorus compounds such as SP670, SP703 and other phosphate ester guanamine compounds manufactured by Shikoku Chemicals Co., Ltd., SPB100, SPE100 manufactured by Otsuka Chemical Co., Ltd., FP-series manufactured by Fushi Pharmaceutical Co., Ltd., etc. Phosphazene compounds and the like. Metal hydroxides such as UD65, UD650, UD653, etc. made by Ube Materials, B-30, B-325, B-315, B-308, B-303, manufactured by Ba Industrial Co., Ltd. , such as UFH-20 and other aluminum hydroxide.

The content of the flame retardant is preferably from 0.5 to 10% by mass, and more preferably from 1 to 5% by mass, based on 100% by mass of the nonvolatile component in the resin composition.

<Other ingredients>

The resin composition of the present invention does not hinder the effect of the present invention. Inside, you need to match other ingredients as appropriate. Other ingredients such as ethylene benzyl compounds, acrylic compounds, maleic imine compounds, thermosetting resins such as blocked isocyanate compounds, organic fillers such as barium powder, nylon powder, and fluorine powder, and tackifiers such as ORBEN and BENTON , polyoxane type, fluorine type, polymer type antifoaming agent or leveling agent, imidazole type, thiazole type, triazole type, decane coupling agent and other adhesion imparting agent, anthraquinone. Blue, phthalocyanine. Green, iodine. A coloring agent such as green, disazo yellow, carbon black, a decane coupling agent, a surface treatment agent such as a titanate coupling agent, or the like.

The resin composition of the present invention suitably mixes the above components, and if necessary, by a mixing method of three rolls, a ball mill, a bead mill, a sand mixer, or a high-speed flow type mixing and kneading machine, a planetary mixer The stirring method is performed by mixing or mixing. Further, a varnish resin is further prepared by adding an organic solvent.

In the wet refining step of the resin composition of the present invention, not only the arithmetic mean roughness of the surface of the insulating layer is low, but also the root mean square roughness of the surface of the insulating layer is low, and a plating conductor layer having sufficient peeling strength is formed on the insulating layer. The resin composition of the present invention is suitably used for forming a resin composition of an insulating layer (a resin composition for an insulating layer of a multilayer printed wiring board) when a multilayer printed wiring board is manufactured, and is more suitably used for forming a conductor layer by plating. Resin composition (resin composition for insulating layer of a multilayer printed wiring board in which a conductor layer is formed by plating). In general, the resin composition of the present invention is suitable as a resin composition for layering of a multilayer printed wiring board.

The resin composition of the present invention is hardened to form an insulating layer, and the arithmetic mean thickness of the surface of the insulating layer after roughening the surface of the insulating layer Roughness (Ra value) and root mean square roughness (Rq value), which are measured by <measurement of arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) after roughening described later> Come to master.

The upper limit of the arithmetic mean roughness (Ra value) is to reduce the transmission loss of the electric signal, preferably 400 nm or less, preferably 350 nm or less, more preferably 300 nm or less, more preferably 250 nm or less, and particularly preferably 200 nm or less, and particularly preferably 180 nm or less. The lower the lower limit of the arithmetic mean roughness (Ra value), the better the stability is, preferably 10 nm or more, more preferably 50 nm or more, and still more preferably 100 nm or more from the viewpoint of stable peel strength.

Since the root mean square roughness (Rq value) reflects the local state of the surface of the insulating layer, the surface of the insulating layer is found to be dense and smooth by grasping the Rq value. The upper limit of the root mean square roughness (Rq value) is preferably 500 nm or less because of the dense and smooth insulating layer surface, preferably 450 nm or less, more preferably 400 nm or less, more preferably 350 nm or less, and particularly preferably 300 nm or less, 250 nm. The following is especially good, especially below 200nm. The lower the lower limit of the root mean square roughness (Rq value), the better. From the viewpoint of the stability of the peeling strength, 30 nm or more is preferable, 70 nm or more is preferable, and 120 nm or more is more preferable.

The resin composition of the present invention is cured to form an insulating layer, and the surface of the insulating layer is roughened, and the peeling strength between the conductor layer and the insulating layer obtained after plating is determined by the measurement of the peeling strength of the plated conductor layer described later. The measurement method is used to grasp.

The peeling strength is sufficiently adhered to the insulating layer and the conductor layer, preferably 0.3 kgf/cm or more, more preferably 0.35 kgf/cm or more, more preferably 0.4 kgf/cm or more, and even more preferably 0.45 kgf/cm or more. The higher the upper limit of the peel strength It is not particularly limited, and is generally 1.2 kgf/cm or less, 1.0 kgf/cm or less, and 0.8 kgf/cm or less.

The use of the resin composition of the present invention is not particularly limited, and it can be used for a sheet-like laminate such as a film or a prepreg, a circuit board (for laminate use, multilayer printed wiring board use, etc.), a solder resist, a filler, and a crystal. A grain-forming material, a semiconductor sealing material, a hole-filling resin, a component-embedded resin, and the like are widely used for applications requiring a resin composition. The resin composition of the present invention is applied to a circuit board in a varnish state to form an insulating layer. Industrially, it is generally preferred to use a sheet-like laminate such as a film or a prepreg. The softening point of the resin composition is preferably from 40 to 150 ° C from the viewpoint of the lamination property of the sheet-like laminate.

<Sheet laminate] (following the film)

The adhesive film of the present invention is a method known to a person skilled in the art. For example, a resin composition is dissolved in an organic solvent to prepare a varnish resin, and the varnish resin is applied to a support by a die coater, and then dried by heating or hot air blowing. A method in which an organic solvent forms a resin composition layer is produced by a manufacturer.

Organic solvents such as ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc., acetates such as ethyl acetate, butyl acetate, celecoxib acetate, propylene glycol monomethyl ether acetate, carbitol acetic acid, etc. Carbitol such as Lucu or butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. A guanamine solvent or the like. The organic solvent may be used in combination of two or more of them.

The drying conditions are not particularly limited. For example, the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less, and is dried. The amount of the organic solvent in the varnish varies depending on the boiling point of the organic solvent. For example, the resin composition layer is dried by drying at 50 to 150 ° C for 3 to 10 minutes by using a varnish containing 30 to 60% by mass of an organic solvent.

It is preferable that the thickness of the resin composition layer formed on the film is equal to or greater than the thickness of the conductor layer. The thickness of the circuit board having the conductor layer is usually in the range of 5 to 70 μm, and the resin composition layer is preferably 10 to 100 μm. The thickness of the resin composition layer is preferably from 15 to 80 μm from the viewpoint of film formation.

A film of a polyolefin such as polyethylene, polypolypropylene or polyvinyl chloride, or a polyethylene terephthalate (hereinafter abbreviated as "PET"). Polyester such as polyethylene naphthalate Film, polycarbonate film, polyimide film and other plastic film. Further, as the support, a release paper, a copper foil, a metal foil such as an aluminum foil, or the like can be used. Among them, from the broad point of view, the support is preferably a plastic film, and a polyethylene terephthalate film is preferred. The support and the protective film described later may be subjected to surface treatment such as dry cracking or corona treatment. Further, the support and the protective film to be described later may be subjected to a release treatment by a release agent such as a polyoxymethylene resin release agent, an alkyd resin release agent or a fluororesin release agent.

The thickness of the support is not particularly limited, and is preferably 10 to 150 μm, and more preferably 25 to 50 μm.

The support of the resin composition layer has no dense surface to support The protective film is further laminated on the basis of the holder. The thickness of the protective film is not particularly limited, and is, for example, 1 to 40 μm. By laminating the protective film to the resin composition layer, it is possible to prevent dust from adhering to the surface of the resin composition layer or to prevent ruthenium.

The adhesive film formed as described above can be crimped into a roll shape for collection.

(prepreg)

The prepreg of the present invention is produced by immersing the resin composition of the present invention in a sheet-like reinforcing substrate by a hot melt method or a solvent method, and semi-curing by heating. That is, the resin composition of the present invention is a prepreg formed in a state of being immersed in a sheet-like reinforcing substrate. For the sheet-like reinforcing substrate, for example, a fiber commonly used for a prepreg is composed of a fiber such as a glass cloth or an aromatic polyamide fiber. This prepreg is suitable for the composition carried on the support.

The resin composition of the hot melt method is not dissolved in the organic solvent, and once applied to the support, the laminate is laminated to the flaky reinforcing substrate or the resin composition is directly applied to the flaky reinforcing substrate by a die coater. Materials and the like are methods for manufacturing prepregs. In the solvent method, a resin is dissolved in an organic solvent-prepared varnish resin in the same manner as the film, and the flaky reinforcing substrate is immersed in a varnish, and the varnish resin is impregnated into a sheet-like reinforcing substrate, followed by drying. Further, the prepreg is prepared by continuously laminating the adhesive film on both sides of the sheet-like reinforcing substrate under heating and lamination conditions. A support or a protective film or the like can also be used in the same manner as the adhesive film.

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

Next, the use of the flaky laminate after the manufacture is described as described above. An example of a method of manufacturing a multilayer printed wiring board.

First, the sheet-like laminate is laminated on one side or both sides (lamination) of the circuit board using a vacuum laminator (laminating step). The substrate used for the circuit board is, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or the like. Further, the circuit board here is a patterning process for forming a conductor layer (circuit) on one side or both sides of the substrate as described above. Further, the conductor layer and the insulating layer are laminated to form a multilayer printed wiring board, and the outermost layer of the multilayer printed wiring board is patterned on one side or both sides to form a conductor layer (circuit). The circuit board here is also included. Further, a roughening treatment such as blackening treatment or copper etching may be applied to the surface of the conductor layer.

In the laminating step, when the sheet-like laminate has a protective film, after removing the protective film, it is necessary to preheat the sheet-like laminate and the circuit substrate as necessary, and laminating and laminating the laminar laminate while laminating Circuit board. The sheet-like laminate of the present invention is suitably used in a method of laminating a circuit substrate under reduced pressure by vacuum lamination. The conditions for lamination are not particularly limited. For example, the pressing temperature (laminating temperature) is preferably 70 to 140 ° C, and the pressing pressure (laminating pressure) is preferably 1 to 11 kgf/cm ² (9.8 × 10 ⁴ to 107.9). ×10 ⁴ N/m ² ), the pressing time (lamination time) is preferably 5 to 180 seconds, and it is preferred that the atmospheric pressure is laminated under a reduced pressure of 20 mmHg (26.7 hPa) or less. Further, the lamination method may be a batch type or a continuous type of rolls. Vacuum lamination can be carried out using a commercially available vacuum laminator. Commercially available vacuum laminating machines such as Nichigo. A vacuum laminating machine manufactured by Morton Co., Ltd., a vacuum laminating laminating machine manufactured by Nihon Seiki Co., Ltd., a dry coating of a Hitachi Industries, and a vacuum laminating machine made of Hitachi AIC.

After the sheet-like laminate is laminated on the circuit board, when the support is cooled and peeled off at room temperature, the support is peeled off, and the thermosetting resin composition forms a cured product, whereby an insulating layer can be formed on the circuit board. The conditions for the heat curing are preferably selected depending on the type and content of the resin component in the resin composition, and preferably from 150 ° C to 220 ° C for 20 minutes to 180 minutes, more preferably from 160 ° C to 210 ° C. Choose from 30 to 120 points. After the formation of the insulating layer, it is necessary to peel off the support after hardening as necessary without peeling off the support before curing.

Further, the sheet-like laminate was laminated on one side or both sides of the circuit board using a vacuum press. The lamination step of heating and laminating under reduced pressure is carried out using a general vacuum hot press. For example, the laminating step is performed by pressing the metal plate of the heated SUS plate or the like from the side of the support layer. The lamination conditions are usually such that the degree of pressure reduction is 1 × 10 ^-2 MPa or less, preferably 1 × 10 ^-3 MPa or less. Heating and lamination can be carried out in one stage, and it is preferable to distinguish them in two or more stages from the viewpoint of suppressing the occurrence of bleeding of the resin. For example, the lamination in the first stage is carried out in a range of 70 to 150 ° C and a pressure of 1 to 15 kgf/cm ² , and the second step is to form a temperature of 150 to 200 ° C and the pressure becomes A range of 1 to 40 kgf/cm ² is preferred. The time of each stage is preferably 30 to 120 points. The insulating layer is formed on the circuit substrate by thermally hardening the resin composition layer. Commercially available vacuum hot presses, for example, MNPC-V-750-5-200 (manufactured by Nihon Seiki Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

Secondly, the insulating layer formed on the circuit substrate is opened. Hole machining forms through holes and through holes. The punching process is performed by a well-known method such as drilling, laser, plasma, etc., and may be combined as occasion demands, and the laser drilling of a carbon dioxide gas laser or a YAG laser is performed. The most general method. When the support is not peeled off before the punching, it can be peeled off after punching.

Next, the roughening treatment is performed with respect to the surface of the insulating layer. The dry roughening treatment method is plasma treatment, etc., and the wet roughening treatment method is carried out by swelling treatment of the swelling liquid, roughening treatment by oxidizing agent, neutralization treatment by neutralizing liquid, and the like. By. The method of roughening the wet type is to form a convex and concave fixing on the surface of the insulating layer, and it is preferable to remove the slag in the through hole. The swelling treatment is carried out by swelling the swelling liquid at 50 to 80 ° C for 5 to 20 minutes (preferably at 55 to 70 ° C for 8 to 15 minutes), and immersed in the swelling liquid. The swelling liquid is, for example, an alkaline solution, a surfactant solution or the like, preferably an alkaline solution such as a sodium hydroxide solution, a calcium hydroxide solution or the like. Commercially available swelling liquids such as Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, etc., manufactured by ATOTECH JAPAN Co., Ltd., and the like. The oxidizing agent is immersed in an oxidizing agent solution at 60 to 80 ° C for 10 to 30 minutes (preferably at 70 to 80 ° C for 15 to 25 minutes). The oxidizing agent dissolves, for example, an alkaline permanganic acid solution of permanganate or sodium permanganate in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid or the like. Further, it is preferred that the concentration of the permanganate in the alkaline permanganic acid solution is 5 to 10% by weight. Commercially available oxidants such as Concentrate by ATOTECH JAPAN. Basicity of Compact CP, Dozing Solution Securigance P, etc. Manganic acid solution. The neutralization solution is immersed in the neutralizing solution for 3 to 10 minutes at 30 to 50 ° C (preferably 3 to 8 minutes at 35 to 45 ° C). The neutralizing solution is preferably an acidic aqueous solution, and a commercial product such as ATOTECH JAPAN (Research Solution). Securiganth P.

Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. For dry plating, a well-known method such as steaming, sputtering, ion evaporation, or the like is used. The wet plating is a method in which a conductor layer is formed by combining electroless plating and electrolytic plating, and the conductor layer is a plating resist which forms an inverse pattern, and a conductor layer is formed only by electroless plating. Thereafter, a method of forming a pattern is carried out, for example, by using a subtractive method, a semi-additive method, or the like which is well known to the practitioner, to repeatedly operate the above-described series of steps to form a multi-layer laminated multilayer printed wiring board. The resin composition of the present invention is suitably used as a buildup layer of a multilayer printed wiring board because it is hardened and subjected to a roughening treatment, and has a low roughness and a high peel strength.

<semiconductor device>

A semiconductor device is manufactured using the multilayer printed wiring board of the present invention. A semiconductor device is fabricated by mounting a semiconductor wafer at a conductive portion of the multilayer printed wiring board of the present invention. The "conduction portion" is "the portion where the electrical signal is transmitted through the multilayer printed wiring board", and the portion may be located on the surface or in the buried portion. Further, the semiconductor wafer is not particularly limited as long as it is an electronic circuit element forming a material of the semiconductor.

There is no particular limitation on the method of mounting the semiconductor wafer in the manufacture of the semiconductor device of the present invention in order to impart effective functions to the semiconductor wafer. Specifically, the wire bonding method, the flip chip mounting method, the mounting method via the bumpless build-up layer (BBUL), the mounting method by the anisotropic conductive film (ACF), and the non-conductivity The mounting method of the film (NCF), and the like.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. Also, "parts" means parts by mass.

<Measurement method. Evaluation method>

First, explain the method of measurement. Evaluation method.

[Peeling strength, arithmetic mean roughness (Ra value), root mean square roughness (Rq value) measurement sample preparation] (1) Matrix processing of the inner layer circuit substrate

The double-sided copper sheet laminate (the thickness of the copper foil is 18 μm, the thickness of the substrate is 0.3 mm, and the R5715ES made by Matsushita Electric Co., Ltd.) of the glass cloth substrate after the formation of the inner layer circuit is performed on the CZ8100 manufactured by MEC Co., Ltd. The 1 um etching forms a roughening treatment of the surface of the copper foil.

(2) subsequent lamination step of the film

The adhesive film produced in the examples and the comparative examples was laminated on both sides of the inner layer circuit board using a batch type vacuum laminating laminator MVLP-500 (manufactured by a famous machine). The laminating step is a decompression for 30 seconds and the gas pressure becomes 13 Below hPa, lamination was carried out at 100 ° C and a pressure of 0.74 MPa for 30 seconds thereafter.

(3) Hardening of resin composition

After the lamination, the film was cured at 100 ° C for 30 minutes, and the resin composition was cured at 180 ° C for 30 minutes to form an insulating layer, and then the PET film was peeled off.

(4) roughening treatment

The inner layer circuit substrate after forming the insulating layer is immersed in the swelling liquid, ATOTECH JAPAN (s), Swelling Dip containing diethylene glycol monobutyl ether. Securigantte P (glycol ether, aqueous solution of sodium hydroxide) at 60 ° C for 10 minutes. Next, the roughening liquid is impregnated with Concentrate of ATOTECH JAPAN. CompactP (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) at 80 ° C for 20 minutes. Finally, the neutralizing solution is immersed in the Reduction Solution of ATOTECH JAPAN. Securigantte P (aqueous solution of sulfuric acid) at 40 ° C for 5 minutes. After drying at 80 ° C for 30 minutes, the arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) of the surface of the insulating layer after the roughening treatment were measured.

(5) Plating step by semi-processing method

In order to form a circuit on the surface of the insulating layer, the inner layer circuit board was immersed in a solution for electroless plating containing PdCl ₂ at 40 ° C for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C for 20 minutes. After annealing at 150 ° C for 30 minutes, an etching resist was formed, and a pattern was formed by etching, followed by electrolytic plating of copper sulfate to form a conductor layer having a thickness of 30 μm. Next, annealing treatment was carried out at 200 ° C for 60 minutes. The circuit board was used to measure the peel strength of the plated conductor layer.

[Measurement of arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) after roughening]

The Ra value and the Rq value were determined using a non-contact surface roughness meter (WYKO NT3300, manufactured by VEECO Instruments Co., Ltd.) from a VSI Contact Mode and a 50-fold lens to obtain a measurement range of 121 μm × 92 μm. Next, an average of 10 points was obtained to measure the average.

[Measurement of peel strength of plated conductor layer]

On the conductor layer of the circuit board, cut into a section of 10 mm wide and 100 mm in length, and peel off the end and catch it with a gripper (Autocom type tester AC-50C-SL of T.S.E.) at room temperature. The weight (kgf/cm) at 35 mm peeling was measured in the vertical direction at a speed of 50 mm/min.

[Evaluation of lamination]

The film after the preparation of the examples and the comparative examples was a batch type vacuum laminating laminating machine MVLP-500 (manufactured by a famous machine), with a conductor thickness of 35 μmL (line: wiring width) / S (space). : Spacer width = 160/160 μm laminated on a conductor pattern of a comb-like shape. The lamination was carried out by a pressure of 30 seconds under reduced pressure to 13 hPa or less, and thereafter laminated by 100 ° C and 0.74 MPa for 30 seconds. Slave layer The film was peeled off and the PET film was peeled off, and the resin composition was cured at 180 ° C for 30 minutes to form an insulating layer. A non-contact type surface roughness meter (WYKO NT3300 manufactured by VEECO Instruments Co., Ltd.) was used for the difference in the unevenness (Rt: maximum peak-to-valley) of the conductor on the insulating layer and the other portion, by VSI Contact Mode, The 10x lens obtained a value of the measurement range of 1.2 mm x 0.91 mm. In addition, there is no void after lamination, and when the difference between the unevenness of the conductor and the other portion is less than 5 μm, it is ○, and when the difference between the unevenness of the conductor on the conductor and the other portion after the lamination is 5 μm or more It is △, and when the void occurs after lamination, it is ×.

[Inorganic filler after use]

In the case of the inorganic filler 1 : spherical cerium oxide ("SO-C2" manufactured by ADMATECHS, average particle diameter: 0.5 μm), 100 parts, phenyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103", molecular weight 198.3 When the surface treatment was carried out in 0.3 parts, the amount of carbon per unit surface area was 0.126 mg/m ² .

With respect to the inorganic filler 2: spherical cerium oxide ("SO-C2" manufactured by ADMATECHS, average particle diameter: 0.5 μm) 100 parts, dimethyldiethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBE-22" The molecular weight of 148.3) was 0.3 part by weight, and the amount of carbon per unit surface area was 0.063 mg/m ² .

With respect to the inorganic filler 3: 100 parts of spherical cerium oxide ("SO-C1" manufactured by ADMATECHS, average particle diameter: 0.25 μm), phenyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103", molecular weight 198.3 The surface amount of the surface treatment was 0.583 mg/m ² per unit surface area.

With respect to the inorganic filler 4: 100 parts of spherical cerium oxide ("SO-C2" manufactured by ADMATECHS, average particle diameter: 0.5 μm), epoxy decane ("KBM403", molecular weight 236, manufactured by Shin-Etsu Chemical Co., Ltd.) For 0.5 parts of the surface treatment, the amount of carbon per unit surface area is 0.19 mg/m ²

Inorganic filler 5: Spherical cerium oxide ("SO-C2" manufactured by ADMATECHS, average particle diameter: 0.5 μm) was not subjected to surface treatment.

Inorganic filler 6: Spherical cerium oxide ("SO-C1" manufactured by ADMATECHS, average particle diameter: 0.25 μm) was not subjected to surface treatment.

<Example 1>

8 parts of naphthalene type epoxy resin (epoxy equivalent 144, "EXA4032SS" manufactured by DIC Co., Ltd.) and 11 parts of Bixylenol type epoxy resin (epoxy equivalent 190, "YX4000HK" manufactured by Mitsubishi Chemical Corporation) 9 parts of a naphthalene type epoxy resin (Ethyl Ethyl Ethylene Co., Ltd., "ESN 475V") was stirred and dissolved in 32 parts of a solvent oil to be heated and dissolved, and then cooled at room temperature. In the mixed solution, 1.5 parts of rubber particles (manufactured by GANTSU Co., Ltd., AC3816N) were statically swelled in 6 ml of solvent oil for 12 hours, and further mixed with 140 parts of inorganic filler 1 at 20 ° C, and kneaded by three rolls and uniformly Disperse it. Here, 45 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Co., Ltd., a toluene solution having a nonvolatile content of 65% by mass of an active base of about 223) was mixed, and a phenoxy resin (weight average) Molecular weight: 35,000, "YL7553" manufactured by Mitsubishi Chemical Co., Ltd. has a non-volatile content of 30% by mass of a 1:1 solution of MEK and cyclohexanone), and the hardening accelerator is 10% by mass of 4-dimethylaminopyridine. One part of the MEK solution and 7 parts of methyl ethyl ketone (MEK) were uniformly dispersed in a rotary mixer to prepare a varnish resin. Next, the varnish resin was dried on the release surface of a polyethylene terephthalate film ("AL5" manufactured by LINTECH Co., Ltd., thickness: 38 μm) having an Alkyd release treatment, and the resin composition layer after drying. The thickness was 40 μm and uniformly applied to a die coater, and dried at 80 to 110 ° C (average 95 ° C) for 5 minutes to obtain a film.

<Example 2>

A varnish resin was produced in the same manner as in Example 1 except that the inorganic filler 1 was changed to the inorganic filler 2. Next, an adhesive film identical to that of Example 1 was obtained.

<Example 3>

A varnish resin was produced in the same manner as in Example 1 except that the inorganic filler 1 was changed to the inorganic filler 3. Next, an adhesive film identical to that of Example 1 was obtained.

<Example 4>

5 parts of naphthalene type epoxy resin (epoxy equivalent 144, "HP4700" made by DIC), liquid bisphenol type epoxy resin (ZX1059, manufactured by Nippon Steel Chemical Co., Ltd., bisphenol A type) 1:1 mixture with bisphenol F) 14 In a portion, 14 parts of a biphenyl type epoxy resin (epoxy equivalent 269, manufactured by Nippon Kayaku Co., Ltd.) was stirred and dissolved in 30 parts of a solvent oil to be heated and dissolved, and then cooled to room temperature. In the mixed solution, 1.5 parts of rubber particles (manufactured by GANTSU Co., Ltd., AC3816N) were allowed to stand for 6 hours in a solvent oil for 6 hours, and further, 140 parts of an inorganic filler was added at 20 ° C, and a flame retardant (three light) was further added. (H)-HQ-HQ, 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxy-10-phosphaphenanthrene-10-oxide, average particle size 1 μm) 5 parts The mixture was mixed by 3 rolls. Here, 10 parts of a phenol novolak-curing agent ("LA-7054" manufactured by DIC Co., Ltd., a MEK solution having a nonvolatile content of 60% by mass of a phenolic hydroxyl equivalent of 124), and a naphthalene phenol resin (phenolic hydroxyl equivalent 215) were mixed. , Nippon Steel Chemical Co., Ltd. "SN485", non-volatile content of 60% by mass of MEK solution) 10 parts by mass, phenoxy resin (weight average molecular weight 35000, Mitsubishi Chemical Corporation "YL7553" non-volatiles 30 7 parts by mass of MEK and cyclohexanone in 1:1 solution, 2 parts of MEK solution of 5% by mass of 4-dimethylaminopyridine, 4 parts of MEK, and uniformly dispersed by a rotary mixer Make varnish resin. Next, an adhesive film identical to that of Example 1 was obtained.

<Example 5>

10 parts of naphthalene type epoxy resin ("EXA4032SS" manufactured by DIC Co., Ltd.), liquid bisphenol type epoxy resin (ZX1059 manufactured by Nippon Steel Chemical Co., Ltd.), bisphenol A type and bisphenol F type 1:1 mixed product) 5 parts, 20 parts of naphthol type epoxy resin ("ESN475V" manufactured by Nippon Steel Chemical Co., Ltd.), phenoxy resin (weight average molecular weight 35000, "YL7553" manufactured by Mitsubishi Chemical Corporation) Non-volatile 7 parts by mass of a mixture of MEK and cyclohexanone in a 1:1 solution) was stirred and dissolved in 50 parts of a solvent oil to be heated and dissolved, and then cooled to room temperature. Next, an active ester compound ("HPC8000-65T" manufactured by DIC), an active ester equivalent of 223, a toluene solution having a solid content of 65%, and 10 parts of a prepolymer of bisphenol A dicyanate (Lonza Japan) 20 parts of "BA230S75", MEK solution having a cyanate ester equivalent of about 232 and a nonvolatile content of 75% by mass), phenol novolac type polyfunctional cyanate resin ("3030S" manufactured by Lonza Japan Co., Ltd., cyanate equivalent) About 133, a non-volatile 85 mass% MEK solution) 10 parts, 4 parts of rubber particles (GANTSU Chemicals Co., Ltd., AC3816N) 4 parts of solvent oil was swelled at room temperature for 12 hours, and a flame retardant was added (three light ( "HCA-HQ", 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxy-10-phosphaphenanthrene-10-oxide, average particle size 1 μm), 3 parts, Hardening accelerator (4-dimethylaminopyridine, MEK solution with a solid content of 10% by mass) 0.1 part, hardening accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt (III) acetoacetate, solid content 1% by mass The MEK solution was 4.5 parts, and further 140 parts of the inorganic filler 1 was mixed, and uniformly dispersed in a rotary mixer to prepare a varnish resin. Next, an adhesive film identical to that of Example 1 was obtained.

<Comparative Example 1>

A varnish resin which was completely the same as that of Example 1 was produced except that the inorganic filler 1 was changed to the inorganic filler 4. Next, an adhesive film identical to that of Example 1 was obtained.

<Comparative Example 2>

A varnish resin which was completely the same as that of Example 1 was produced except that the inorganic filler 1 was changed to the inorganic filler 5. Next, an adhesive film identical to that of Example 1 was obtained.

<Comparative Example 3>

A varnish resin which was completely the same as that of Example 1 was produced except that the inorganic filler 1 was changed to the inorganic filler 6. Next, an adhesive film identical to that of Example 1 was obtained.

The results are shown in Table 1.

From the results of Table 1, it is understood that the resin composition of the example is hardened to form an insulating layer, and the value of the arithmetic mean roughness and the root mean square thickness are obtained. The value of the roughness is small, the value of the sufficient peel strength, and the laminate property are also good. Further, since the Rq value reflects the local state of the surface of the insulating layer, a dense rough surface is formed by the decrease in the Rq value. On the other hand, when the arithmetic mean roughness and the root mean square roughness of the comparative example were increased, the peel strength was small and the laminate property was not good.

[Industry use possibility]

In the wet roughening step, in the wet roughening step, not only the arithmetic mean roughness value of the surface of the insulating layer is small, but also the root mean square roughness value of the surface of the insulating layer is small, and sufficient peeling is formed on the insulating layer. A plated conductor layer of strength and a resin composition excellent in lamination property. Further, a sheet-like laminate, a multilayer printed wiring board, and a semiconductor device using the same can be provided. Furthermore, it is also possible to provide electronic products such as such computers, mobile phones, digital cameras, televisions, and the like, locomotives, automobiles, electric cars, ships, airplanes, and the like.

Claims (20)

A resin composition comprising a resin composition of an inorganic filler which is surface-treated with an epoxy resin, a curing agent and an alkoxydecane compound, characterized in that the inorganic filler has an average particle diameter of 0.01 to 5 μm, and the resin When the nonvolatile content in the composition is 100% by mass, the content of the inorganic filler is 30 to 90% by mass. The resin composition of claim 1, wherein the alkoxydecane compound comprises an alkyl group and/or an aryl group. The resin composition of claim 1, wherein the alkoxydecane compound comprises one or more selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a phenyl group, a benzyl group, a tolyl group, a xylyl group, and a naphthyl group. The resin composition of claim 1, wherein the alkoxydecane compound comprises methyl, ethyl, propyl, isopropyl, cyclopropyl, phenyl, benzyl, tolyl, xylyl and naphthalene. One or more of the bases are selected. The resin composition of claim 1, wherein the alkoxydecane compound is derived from phenyltrialkoxydecane, dimethyldisilazane, methyltrialkoxydecane, diethyldialkoxy One or more selected from the group consisting of decane, ethyl trialkoxy decane, diphenyl dialkoxy decane, methylphenyl dialkoxy decane, and diphenylmethyl monoalkoxy decane. The resin composition of claim 1, wherein the alkoxydecane compound has a molecular weight of from 100 to 1,000. The resin composition of claim 1, wherein the inorganic filler is cerium oxide. The resin composition of claim 1, wherein the inorganic filler is relative to the inorganic filler 100 parts by mass of the material, the alkoxydecane compound was surface-treated at 0.05 to 4 parts by mass. The resin composition of claim 1, wherein the inorganic filler has a carbon amount per unit surface area of 0.01 to 0.8 mg/m ² . The resin composition of claim 1, wherein the epoxy resin is from a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a biphenyl type ring One or more selected from the group consisting of an oxygen resin, a naphthyl ether type epoxy resin, a glycidyl ester type epoxy resin, a fluorene type epoxy resin, and an epoxy resin having a butadiene structure. The resin composition of claim 1, wherein the curing agent is one or more selected from the group consisting of a phenolic curing agent, an active ester curing agent, and a cyanate curing agent. The resin composition of claim 1, wherein the hardener is a biphenyl type hardener, a naphthalene type hardener, a phenol novolak type hardener, a naphthyl ether type hardener, a triterpene skeleton phenol type hardener, An active ester-based curing agent comprising a dicyclopentadiene-type diphenol condensation structure, a phenolic-type cyanate-based curing agent, a dicyclopentadiene-type cyanate-based curing agent, and a bisphenol-type cyanate-based curing agent One or more kinds are selected. The resin composition of claim 1, which is obtained by curing the resin composition to form an insulating layer, and roughening the surface of the insulating layer to have an arithmetic mean roughness of 400 nm or less and a root mean square roughness of 500 nm or less. The resin composition of claim 1, which is obtained by curing the resin composition to form an insulating layer, and roughening the surface of the insulating layer to have an arithmetic mean roughness of 10 to 400 nm and a root mean square roughness of 30 to 500 nm. The resin composition of claim 1, wherein the hardened resin composition forms an insulating layer, the surface of the insulating layer is roughened, and the peeling strength between the conductor layer and the insulating layer obtained after plating is 0.3 to 1.2 kgf/cm. the above. The resin composition of claim 1, which is a resin composition for an insulating layer of a multilayer printed wiring board. The resin composition of claim 1, which is a resin composition for a build-up layer of a multilayer printed wiring board. A sheet-like laminate material comprising the resin composition according to any one of claims 1 to 17. A multilayer printed wiring board characterized by forming an insulating layer by a cured product of the resin composition according to any one of claims 1 to 17. A semiconductor device characterized by using the multilayer printed wiring board of claim 19.