JP2019116630A - Resin composition - Google Patents

Abstract

To provide a resin composition that has not only a low arithmetic average roughness but also a small root-mean-square roughness on an insulating layer surface in a wet roughening step, is capable of forming a plated conductor layer having sufficient peel strength thereon and is excellent in laminate properties.SOLUTION: The resin composition contains an epoxy resin, a curing agent and an inorganic filler surface-treated with an alkoxysilane compound. The inorganic filler has an average particle size of 0.01 to 5 μm and when a nonvolatile component in the resin composition is 100 mass%, the content of the inorganic filler is 30 to 90 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition. Furthermore, the present invention relates to a sheet-like laminate material, a multilayer printed wiring board, and a semiconductor device, which contain the resin composition.

  In recent years, miniaturization and high performance of electronic devices have progressed, and in multilayer printed wiring boards, buildup layers are multilayered, and miniaturization and densification of wiring are required.

  Various efforts have been made to this. For example, Patent Document 1 discloses that the filler is surface-treated with a silane or titanium coupling agent. However, no mention is made of alkoxysilane compounds at all. Patent Document 2 also describes an alkoxysilane compound, but there is no specific description, and it is not intended to be directed to the present invention.

Unexamined-Japanese-Patent No. 2006-224644 JP 2008-74668 A

  The problem to be solved by the present invention is that not only the arithmetic mean roughness of the surface of the insulating layer is low but also the root mean square roughness is small in the wet roughening step, and a plated conductor layer having sufficient peel strength is formed thereon It is an object of the present invention to provide a resin composition which is excellent in laminating property.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly examining that the present inventors should solve the said subject, in the resin composition characterized by including the inorganic filler surface-treated by the epoxy resin, the hardening | curing agent, and the alkoxysilane compound, It came to complete.

That is, the present invention includes the following contents.
[1] A resin composition containing an epoxy resin, a curing agent, and an inorganic filler surface-treated with an alkoxysilane compound, wherein the average particle diameter of the inorganic filler is 0.01 to 5 μm, and the resin composition The resin composition characterized by content of this inorganic filler being 30-90 mass%, when the non-volatile component in it is 100 mass%.
[2] The resin composition according to [1], wherein the alkoxysilane compound contains an alkyl group and / or an aryl group.
[3] The alkoxysilane compound contains one or more selected from 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 [1] or The resin composition as described in [2].
[4] The alkoxysilane compound contains one or more selected from methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, phenyl group, benzyl group, tolyl group, xylyl group and naphthyl group The resin composition in any one of [1]-[3] characterized by the above-mentioned.
[5] The alkoxysilane compound is phenyltrialkoxysilane, dimethyldialkoxysilane, methyltrialkoxysilane, diethyldialkoxysilane, ethyltrialkoxysilane, diphenyldialkoxysilane, methylphenyldialkoxysilane and diphenylmethylmonoalkoxysilane The resin composition according to any one of [1] to [4], which is at least one selected from the group consisting of
[6] The resin composition according to any one of [1] to [5], wherein the molecular weight of the alkoxysilane compound is 100 to 1000.
[7] The resin composition according to any one of [1] to [6], wherein the inorganic filler is silica.
[8] The resin composition according to any one of [1] to [7], which is surface-treated with 0.05 to 5 parts by mass of the alkoxysilane compound based on 100 parts by mass of the inorganic filler. .
[9] The resin composition according to any one of [1] to [8], wherein the amount of carbon per unit surface area of the inorganic filler is 0.01 to 0.8 mg / m ² .
[10] The epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, naphthylene ether epoxy resin, glycidyl ester epoxy resin, anthracene epoxy resin It is 1 or more types selected from the epoxy resin and the epoxy resin which has a butadiene structure, The resin composition in any one of [1]-[9] characterized by the above-mentioned.
[11] The curing agent is one or more selected from a phenolic curing agent, an active ester curing agent and a cyanate ester curing agent, according to any one of [1] to [10]. Resin composition.
[12] An activity in which the curing agent contains a biphenyl type curing agent, a naphthalene type curing agent, a phenol novolac type curing agent, a naphthylene ether type curing agent, a triazine skeleton-containing phenolic curing agent, and a dicyclopentadienyl diphenol structure. At least one selected from ester-based curing agents, novolac-type cyanate ester-based curing agents, dicyclopentadiene-type cyanate ester-based curing agents, and bisphenol-type cyanate ester-based curing agents [1] to [11] ] The resin composition in any one of-.
[13] The resin composition is cured to form an insulating layer, and the surface of the insulating layer is roughened 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 according to any one of [1] to [12].
[14] The resin composition is cured to form an insulating layer, and the surface of the insulating layer is roughened to have an arithmetic average roughness of 10 to 400 nm and a root mean square roughness of 30 to 500 nm The resin composition according to any one of [1] to [13], which is characterized in that
[15] The resin composition is cured to form an insulating layer, the surface of the insulating layer is roughened, and the peel strength between the conductive layer and the insulating layer obtained by plating is 0.3 to 1.2 kgf / cm. It is the above, The resin composition in any one of [1]-[14] characterized by the above-mentioned.
[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 buildup layer of a multilayer printed wiring board.
[18] A sheet-like laminate material comprising the resin composition according to any one of [1] to [17].
The multilayer printed wiring board in which the insulating layer was formed of the hardened | cured material of the resin composition in any one of [19] [1]-[17].
[20] A semiconductor device using the multilayer printed wiring board according to [19].

  By using a resin composition containing an inorganic resin surface-treated with an epoxy resin, a curing agent and an alkoxysilane compound, not only the arithmetic mean roughness of the surface of the insulating layer is low in the wet roughening step, but also the root mean square The roughness was also small, and the plating conductor layer which has sufficient peel strength on it can be formed, and it came to be able to provide the resin composition which is excellent also in lamination nature.

  The present invention is a resin composition comprising an epoxy resin, a curing agent, and an inorganic filler surface-treated with an alkoxysilane compound. Hereinafter, the resin composition will be described in detail.

<Epoxy resin>
The epoxy resin used in the present invention is not particularly limited, but bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol resin Type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthalene ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, wire Aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane dimethanol type Carboxymethyl resin, trimethylol type epoxy resins, and halogenated epoxy resins. These may be used alone or in combination of two or more.

  Among these, from the viewpoint of heat resistance improvement, lamination property improvement and peel strength improvement, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthalene ether type It is preferable to use one or more selected from an epoxy resin, a glycidyl ester type epoxy resin, an anthracene type epoxy resin, and an epoxy resin having a butadiene structure. Specifically, for example, bisphenol A type epoxy resin ("Epikote 828EL", "YL 980", manufactured by Mitsubishi Chemical Corp.), bisphenol F epoxy resin ("jER806H," YL 983 U ", manufactured by Mitsubishi Chemical Corp.), Naphthalene type bifunctional epoxy resin (“HP4032”, “HP4032D”, “HP4032SS”, “EXA4032SS” manufactured by DIC Corporation), naphthalene type tetrafunctional epoxy resin (“HP4700”, “HP4710” manufactured by DIC Corporation), Naphthol type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Co., Ltd.), epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Industries, Ltd.), epoxy resin having a biphenyl structure (Nipponization) Medicine Co., Ltd. "NC3000H", "NC3000L", "NC31 00 ”, Mitsubishi Chemical Corporation“ YX4000 ”,“ YX4000H ”,“ YX4000HK ”,“ YL6121 ”, anthracene epoxy resin (Mitsubishi Chemical Corporation“ YX8800 ”), napthalene ether epoxy resin (DIC) Ltd. “EXA-7310”, “EXA-7311”, “EXA-7311L”, “EXA7311-G3”, glycidyl ester type epoxy resin (Nagase Chemtex Co., Ltd. “EX711”, “EX721”, Examples include "R540" manufactured by PRINTEC CO., LTD.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule, and it is more preferable to use a liquid epoxy resin and a solid epoxy resin in combination. The liquid epoxy resin is preferably an aromatic epoxy resin having two or more epoxy groups in one molecule and liquid at a temperature of 20 ° C., and the solid epoxy resin may have three or more epoxy groups in one molecule. It is preferable to use an aromatic epoxy resin which is solid at a temperature of 20 ° C. In addition, the aromatic epoxy resin as used in the field of this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator. When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the resin composition has appropriate flexibility when used in the form of an adhesive film, and the lamination property is improved, and the curing of the resin composition The compounding ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 1: 2 in terms of mass ratio from the viewpoint that the surface roughness of the product can be lowered, 1: 0.3 The range of 1: 1.8 is more preferable, and the range of 1: 0.6 to 1: 1.5 is more preferable.

  As the liquid epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, glycidyl ester epoxy resin, or naphthalene epoxy resin is preferable, and bisphenol A epoxy resin, bisphenol F epoxy resin, Or a naphthalene type epoxy resin is more preferable. These may be used alone or in combination of two or more. As a solid epoxy resin, tetrafunctional naphthalene type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, or naphtylene Ether type epoxy resins are preferable, and naphthol type epoxy resins or biphenyl type epoxy resins are more preferable. These may be used alone or in combination of two or more.

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

<Hardening agent>
The curing agent used in the present invention is not particularly limited, and examples thereof include phenol-based curing agents, active ester-based curing agents, cyanate ester-based curing agents, benzoxazine-based curing agents, acid anhydride-based curing agents, etc. From the viewpoint of further lowering the average roughness (Ra value) and the root mean square roughness (Rq value), one or more selected from a phenolic curing agent, an active ester curing agent and a cyanate ester curing agent are used Is preferred. These may be used alone or in combination of two or more.

  The phenol-based curing agent is not particularly limited, but is preferably a biphenyl-type curing agent, a naphthalene-type curing agent, a phenol novolac-type curing agent, a naphthylene ether-type curing agent, or a triazine skeleton-containing phenol-based curing agent. Specifically, biphenyl type curing agents MEH-7700, MEH-7810, MEH-7851 (manufactured by Meiwa Kasei Co., Ltd.), naphthalene type curing agents NHN, CBN, GPH (manufactured by Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN395, SN395 (manufactured by Nippon Steel Chemical Co., Ltd.), EXB 9500 (manufactured by DIC Corporation), TD 2090 (manufactured by DIC Corporation), a phenol novolac curing agent, Examples thereof include EXB-6000 (manufactured by DIC Corporation), a naphthylene ether-type curing agent, LA3018, LA7052, LA7054, LA1356 (manufactured by DIC Corporation), and the like, and a triazine skeleton-containing phenol-based curing agent. One or more of these may be used in combination.

  The active ester curing agent is not particularly limited, but generally an ester group having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters and esters of heterocyclic hydroxy compounds is contained in one molecule. Compounds having two or more of them are preferably used. The active ester curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. As a phenol compound or naphthol compound, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenol phthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxy benzophenone, trihydroxy benzophenone, tetrahydroxy benzophenone, phloroglucin, benzenetriol And dicyclopentadienyl diphenol, phenol novolac and the like. The active ester curing agent can be used alone or in combination of two or more. As the active ester curing agent, an active ester curing agent disclosed in JP-A-2004-277460 may be used, or a commercially available one may be used. Commercially available active ester-based curing agents include active ester-based curing agents containing dicyclopentadienyl diphenol structure, active ester-based curing agents containing naphthalene structure, and active ester-based curing agents that are acetylated products of phenol novolac And an active ester-based curing agent which is a benzoyl compound of a phenol novolak, etc., among which an active ester-based curing agent having a dicyclopentadienyl diphenol structure is more preferable in that the improvement of the peel strength is excellent. Specifically, EXB9451, EXB 9460, EXB 9460S-65T, HPC-8000-65T (manufactured by DIC Corporation, having an active group equivalent weight of about 223) as acetylated products of phenol novolac as those containing a dicyclopentadienyldiphenol structure. DC808 (Mitsubishi Chemical Co., Ltd., active group equivalent about 149) as an active ester-based curing agent, YLH1026 (Mitsubishi Chemical Co., Ltd., active group equivalent: about 200) And YLH1030 (manufactured by Mitsubishi Chemical Co., Ltd., an active group equivalent of about 201), and YLH1048 (manufactured by Mitsubishi Chemical Co., Ltd., an active group equivalent of about 245).

  More specifically, examples of the active ester-based curing agent containing a dicyclopentadienyl diphenol structure include a compound of the following formula (1).

（式中、Ｒはフェニル基、ナフチル基であり、ｋは０又は１を表し、ｎは繰り返し単位の平均で０．０５〜２．５である。）

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

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

  The cyanate ester-based curing agent is not particularly limited, but novolak type (phenol novolac type, alkylphenol novolac type, etc.) cyanate ester type curing agent, dicyclopentadiene type cyanate ester type curing agent, bisphenol type (bisphenol A type, bisphenol Examples thereof include F-type and bisphenol S-type) cyanate ester-based curing agents, and prepolymers in which these are partially triazineated. The weight-average molecular weight of the cyanate ester-based curing agent is not particularly limited, but is preferably 500 to 4,500, and more preferably 600 to 3,000. Specific examples of cyanate ester-based curing agents include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylene bis (2,6-dimethylphenyl cyanate), 4,4'-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatophenylmethane), bis (4-cyanate-3, Bifunctional cyanate resins such as 5-dimethylphenyl) methane, 1,3-bis (4-cyanatophenyl-1- (methylethylidene)) benzene, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) ether and the like , Phenol novolak, Resol novolac, polyfunctional cyanate resins derived from dicyclopentadiene structure-containing phenolic resins, etc., prepolymers in which these cyanate resins are partially triazineated, etc. These may be used alone or in combination of two or more. As a commercially available cyanate ester resin, a phenol novolak type polyfunctional cyanate ester resin represented by the following formula (2) (Lonza Japan Co., Ltd. product PT30, cyanate equivalent 124), the following formula (3) Prepolymer in which a part or all of bisphenol A dicyanate represented is triazinated to form a trimer (manufactured by Lonza Japan Ltd., BA 230, cyanate equivalent 232), dicyclopentadiene represented by the following formula (4) Structure-containing cyanate ester resin (manufactured by Lonza Japan Co., Ltd., T-4000, DT-7000), and the like.

［式中、ｎは平均値として任意の数（好ましくは０〜２０）を示す。］

[In the formula, n represents an arbitrary number (preferably 0 to 20) as an average value. ]

（式中、ｎは平均値として０〜５の数を表す。）

(In the formula, n represents the number of 0 to 5 as an average value.)

  The benzoxazine-based curing agent is not particularly limited, and specific examples include Fa, P-d (manufactured by Shikoku Kasei Co., Ltd.), HFB2006M (manufactured by Showa Highpolymer Co., Ltd.), and the like.

  The acid anhydride curing agent is not particularly limited, but is phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride Hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Acid anhydride, trimellitic anhydride, pyromellitic anhydride, bensophenone tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3 ' -4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 1,3,3 4,5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione, ethylene glycol bis (anhydrotrimelitate) And polymer type acid anhydrides such as styrene-maleic acid resins obtained by copolymerizing styrene and maleic acid.

  In the resin composition of the present invention, the ratio of the total number of epoxy groups of the epoxy resin and the total number of reactive groups of the curing agent is, from the viewpoint of improving the mechanical strength and water resistance of the cured product of the resin composition. 1: 0.2 to 1: 2 are preferable, 1: 0.3 to 1: 1.5 are more preferable, and 1: 0.4 to 1: 1 are more preferable. The total number of epoxy groups of the epoxy resin present in the resin composition is a value obtained by dividing the mass of the solid content of each epoxy resin by the epoxy equivalent, for all epoxy resins, and the reactive group of the curing agent The total number of is the value obtained by dividing the mass of the solid content of each curing agent by the equivalent weight of the reactive group for all the curing agents.

<Inorganic filler surface-treated with alkoxysilane compound>
The alkoxysilane compound of the inorganic filler surface-treated with the alkoxysilane compound used in the present invention is not particularly limited, but from the viewpoint of improving the laminateability when the resin composition is formed into a sheet, an alkyl group and / or It is preferable to contain an aryl group, and one having one or more selected from the group consisting of an alkyl group, an aryl group and an alkoxysilyl group bonded to a silicon atom is more preferable. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms from the viewpoint of preventing viscosity increase of the resin varnish One or more selected from ethyl group, propyl group, isopropyl group and cyclopropyl group is still more preferable. The aryl group is preferably at least one selected from a phenyl group, a benzyl group, a tolyl group, a xylyl group and a naphthyl group. Specific alkoxysilane compounds include phenyltrialkoxysilane, dimethyldialkoxysilane, methyltrialkoxysilane, diethyldialkoxysilane, ethyltrialkoxysilane, diphenyldialkoxysilane, methylphenyldialkoxysilane and diphenylmethyl monoalkoxysilane It is preferable to use one or more selected from From the viewpoint of improving the peel strength, it is preferable to have 2 to 3 alkoxy groups per alkoxysilyl group, and as the alkoxy group, a methoxy group or an ethoxy group is preferable. Also, the alkoxysilyl group may be modified. These alkoxysilane compounds are excellent in productivity and environment without generation of toxic gas at the time of surface treatment. In addition, unlike the coupling agent having an organic functional group, the alkoxysilane compound is excellent in that the hydrophobicity is improved and the compatibility with the resin is improved. Furthermore, unlike the coupling agent having an organic functional group, the alkoxysilane compound is excellent in that it is easy to perform surface treatment without self-aggregation at the time of surface treatment. Therefore, by using an inorganic filler surface-treated with an alkoxysilane compound, it is possible to improve peel strength while improving the lamination property and low roughness.

  The molecular weight of the alkoxysilane compound is preferably 100 or more, more preferably 110 or more, and still more preferably 120 or more from the viewpoint of suppressing volatilization during surface treatment or drying. On the other hand, from the viewpoint of appropriate reactivity, 1000 or less is preferable, 700 or less is more preferable, and 400 or less is more preferable. Commercially available products include "KBM103" (phenyltrimethoxysilane), "KBE-22" (dimethyldiethoxysilane), "KBM-13" (methyltrimethylsilane), "KBM-22" manufactured by Shin-Etsu Chemical Co., Ltd. (Dimethyldimethoxysilane), "KBM-3063" (hexyltrimethoxysilane), "KBE-3063" (hexyltriethoxysilane), "KBM-3103" (decyltrimethoxysilane), "LS-2400" (diethyldisilane) Ethoxysilane), “LS-890” (ethyltrimethylsilane), “LS-5300” (diphenyldimethoxysilane), “LS-2720” methylphenyldimethoxysilane, “LS-5610” (diphenylmethylmethoxysilane), etc. Be

  The inorganic filler of the inorganic filler surface-treated with an alkoxysilane compound used in the present invention is not particularly limited, and examples thereof include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, and hydroxide Magnesium, 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, etc. It can be mentioned. Among them, silicas such as amorphous silica, crushed silica, fused silica, crystalline silica, synthetic silica, hollow silica, spherical silica and the like are preferable, and fused silica and spherical silica are more preferable in that they reduce the surface roughness of the insulating layer. Preferably, spherical fused silica is more preferred. These may be used alone or in combination of two or more.

  The average particle size of the inorganic filler is not particularly limited, but the upper limit of the average particle size of the inorganic filler is 5 μm from the viewpoint that the surface of the insulating layer has low roughness and enables fine wiring to be formed. The following are preferable, 4 μm or less is more preferable, 3 μm or less is further preferable, 2 μm or less is still more preferable, 1 μm or less is particularly preferable, 0.8 μm or less is particularly preferable, and 0.6 μm or less is particularly preferable. On the other hand, the lower limit value of the average particle diameter of the inorganic filler is 0.01 μm or more from the viewpoint of preventing the viscosity of the varnish from rising and the handling property from decreasing when the resin composition is a resin varnish. The thickness is preferably 0.05 μm or more, more preferably 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 inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering type particle size distribution measuring device, and the median diameter can be measured as an average particle size. As a measurement sample, one in which an inorganic filler is dispersed in water by ultrasonic waves can be preferably used. As laser diffraction scattering type particle size distribution measuring apparatus, LA-750 grade | etc., By Horiba, Ltd. can be used.

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

  In the inorganic filler surface-treated with the alkoxysilane compound, the amount of the alkoxysilane compound which is surface-treated the inorganic filler is not particularly limited, but the amount of the alkoxysilane compound is 0 based on 100 parts by mass of the inorganic filler. It is preferable to surface-treat with 0.5 to 4 parts by mass, more preferably 0.1 to 3 parts by mass, and further preferably 0.2 to 2 parts by mass, 0.3 to It is even more preferable to surface treat at 1 part by mass.

  In the inorganic filler surface-treated with an alkoxysilane compound, the presence of carbon atoms is confirmed by analyzing the surface composition of the inorganic filler, and the carbon amount per unit surface area of the inorganic filler is determined. Can. As a carbon analyzer, Horiba "EMIA-320V" etc. can be used.

  Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with an alkoxysilane compound, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, Horiba "EMIA-320V" etc. can be used.

The amount of carbon per unit surface area of the above-mentioned inorganic filler, in terms of stabilizing the arithmetic mean roughness and the root mean square roughness after the improvement of the dispersibility of the inorganic filler and the wet roughening process of the cured product, is 0. 01mg / ^{m 2} or more preferably, 0.05 mg / ^{m 2} or more preferably, 0.1 mg / ^{m 2} or more is more preferable. On the other hand, it is preferably 0.8 mg / m ² or less, more preferably 0.5 mg / m ² or less, and 0.3 mg / m ² in view of preventing the melt viscosity of the resin varnish and the increase in the melt viscosity in the adhesive film form. ² or less is more preferable.

  The inorganic filler surface-treated with the alkoxysilane compound is preferably added to the resin composition after the inorganic filler is surface-treated with the alkoxysilane compound. In this case, the dispersibility of the inorganic filler can be further enhanced.

  Although the surface treatment method to the inorganic filler surface-treated with the alkoxysilane compound is not specifically limited, A dry method and a wet method are mentioned. As a dry method, an inorganic filler is charged into a rotary mixer, and after an alcohol solution or an aqueous solution of an alkoxysilane compound is dropped or sprayed while stirring, it is further stirred and classified by a sieve. Thereafter, it can be obtained by dehydration condensation of the alkoxysilane compound and the inorganic filler by heating. As a wet method, an alkoxysilane compound is added while stirring a slurry of an inorganic filler and an organic solvent, and after stirring, filtration, drying and classification by sieving are performed. Thereafter, it can be obtained by dehydration condensation of the alkoxysilane compound and the inorganic filler by heating. Furthermore, it is also possible to use an integral blending method in which an alkoxysilane compound is added to the resin composition.

<Hardening accelerator>
The epoxy resin and the curing agent can be efficiently cured by further incorporating a curing accelerator into the resin composition of the present invention. The curing accelerator is not particularly limited, and examples thereof include an amine curing accelerator, a guanidine curing accelerator, an imidazole curing accelerator, a phosphonium curing accelerator, a metal curing accelerator and the like. These may be used alone or in combination of two or more.

  The amine-based curing accelerator is not particularly limited, but includes triethylamine, trialkylamine such as tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) And amine compounds such as phenol and 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU). These may be used alone or in combination of two or more.

  The guanidine curing accelerator is not particularly limited, but dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, dimethyl guanidine , Diphenyl guanidine, trimethyl guanidine, tetramethyl guanidine, pentamethyl guanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide 1-cyclohexyl biguanide, 1-allyl biguanide, 1-fe Rubiguanido, 1-(o-tolyl) biguanide, and the like. These may be used alone or in combination of two or more.

  The imidazole-based curing accelerator is not particularly limited, but 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-undecylimidazolium tri Meritate 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-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethyl Imidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1 Dodecyl-2-methyl-3-benzyl-imidazolium chloride, 2-methyl-imidazoline, adduct of 2-phenyl-imidazo imidazole compounds such as phosphorus and imidazole compound and an epoxy resin. These may be used alone or in combination of two or more.

  The phosphonium curing accelerator is not particularly limited, but triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- Examples include methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like. These may be used alone or in combination of two or more.

  In the resin composition of the present invention, the content of the curing accelerator (excluding the metal-based curing accelerator) is in the range of 0.005 to 1% by mass, assuming that the nonvolatile component in the resin composition is 100% by mass. Preferably, the range of 0.01 to 0.5% by mass is more preferable. Within this range, heat curing can be performed more efficiently, and the storage stability of the resin varnish is also improved.

  The metal-based curing accelerator is not particularly limited, and examples thereof include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, zinc (II) acetylacetonate Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, organic manganese complexes such as manganese (II) acetylacetonate, and the like. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like. These may be used alone or in combination of two or more.

  In the resin composition of the present invention, the amount of the metal-based curing accelerator added is such that the content of the metal based on the metal-based curing catalyst is in the range of 25 to 500 ppm based on 100% by mass of the non-volatile component in the resin composition. Preferably, the range of 40 to 200 ppm is more preferable. The conductor layer which is excellent in the adhesiveness to the insulating layer surface as it is in this range is formed, and the storage stability of resin varnish is also improved.

<Thermoplastic resin>
By further incorporating a thermoplastic resin into the resin composition of the present invention, the mechanical strength of the cured product can be improved, and the film moldability when used in the form of an adhesive film can also be improved. . Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamide imide resin, polyether imide resin, polysulfone resin, polyether sulfone resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin and polyester resin. In particular, phenoxy resin and polyvinyl acetal resin are preferable. These thermoplastic resins may be used alone 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. The weight average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (in terms of polystyrene). Specifically, the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. It can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and calculated using a calibration curve of standard polystyrene.

  When a thermoplastic resin is blended to the resin composition of the present invention, the content of the thermoplastic resin in the resin composition is not particularly limited, but 100% by mass of non-volatile components in the resin composition On the other hand, 0.1-10 mass% is preferable, and 0.5-5 mass% is more preferable. Within this range, the effect of improving the film moldability and mechanical strength is exhibited, and the increase in the melt viscosity and the roughness of the surface of the insulating layer after the wet roughening step can be further reduced.

<Rubber particles>
By further including rubber particles in the resin composition of the present invention, the plating peel strength can be improved, and the drill processability can be improved, the dielectric loss tangent can be lowered, and the stress relaxation effect can be obtained. The rubber particles that can be used in the present invention are, for example, those that do not dissolve in the organic solvent used when preparing the varnish of the resin composition and are not compatible with the 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. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which the rubber component does not dissolve in an organic solvent or resin, and forming it into particles.

  Preferred examples of the rubber particles that can be used in the present invention include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles and the like. The core-shell rubber particles are rubber particles having a core layer and a shell layer, and for example, a two-layer structure in which the shell layer of the outer layer is composed of a glassy polymer and the core layer of the inner layer is composed of a rubbery polymer, The shell layer of the outer layer is composed of a glassy polymer, the middle layer is composed of a rubbery polymer, and the core layer is composed of a glassy polymer. The glassy polymer layer is made of, for example, a polymer of methyl methacrylate and the like, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber) and the like. The rubber particles may be used in combination of two or more. Specific examples of the core-shell type rubber particles include staphyroids AC3832, AC3816N, AC3401N, IM-401 revision 7-17 (trade name, manufactured by Ganz Chemical Co., Ltd.), metabrene KW-4426 (trade name, Mitsubishi Rayon Co., Ltd.) Manufactured by Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle diameter 0.5 μm, manufactured by JSR Corporation). Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle diameter 0.5 μm, manufactured by JSR Corporation) and the like. As a specific example of an acrylic rubber particle, metabrene W300A (average particle diameter 0.1 micrometer), W450A (average particle diameter 0.2 micrometer) (Mitsubishi Rayon Co., Ltd. product) can be mentioned.

  The average particle diameter of the rubber particles to be blended is preferably in the range of 0.005 to 1 μm, and more preferably in the range of 0.2 to 0.6 μm. The average particle size of the rubber particles used in the present invention can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and the particle size distribution of rubber particles is made based on mass using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.) It can measure by making the median diameter into an average particle diameter.

  The content of the rubber particles is preferably 0.05 to 10% by mass, and more preferably 0.5 to 5% by mass, with respect to 100% by mass of the non-volatile component in the resin composition.

<Flame retardant>
Flame retardancy can be imparted to the resin composition of the present invention by further containing a flame retardant. Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides and the like. As organophosphorus flame retardants, phenanthrene type phosphorus compounds such as HCA, HCA-HQ and HCA-NQ manufactured by Sanko Co., Ltd., phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Highpolymer Co., Ltd., Ajinomoto Leofos 30, 50, 65, 90, 110 manufactured by Fine Techno Co., Ltd., TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP 140, TIBP, TPPO, PPQ manufactured by Hokuko Chemical Co., Ltd., Phosphoric acid ester compounds such as OP 930 manufactured by Clariant Co., Ltd., PX 200 manufactured by Daihachi Chemical Co., Ltd., phosphorus-containing epoxy resins such as FX 289, FX 305, TX 0712 manufactured by Nippon Steel Chemical Co., Ltd. Phosphorus-containing phenoxy resin such as ERF 001 manufactured by Co., Ltd. Phosphorus-containing epoxy resin such as YL 7613 manufactured by Mitsubishi Chemical Corporation And the like. Examples of organic nitrogen-containing phosphorus compounds include phosphoric acid ester amide compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd. SPB100 manufactured by Otsuka Chemical Co., Ltd., SPE100 manufactured by Fushimi Pharmaceutical Co., Ltd. FP-series manufactured by Fushimi Pharmaceutical Co., Ltd. And phosphazene compounds and the like. As metal hydroxide, magnesium hydroxide such as UD 65, UD 650, UD 653 manufactured by Ube Materials Co., Ltd., B-30 manufactured by Sakai Industry Co., Ltd., B-325, B-315, B-308, Aluminum hydroxides, such as B-303 and UFH-20, etc. are mentioned.

  The content of the flame retardant is preferably 0.5 to 10% by mass, and more preferably 1 to 5% by mass, with respect to 100% by mass of the non-volatile component in the resin composition.

<Other ingredients>
If necessary, other components can be blended into the resin composition of the present invention as long as the effects of the present invention are not impaired. Other components include vinyl benzyl compounds, acrylic compounds, maleimide compounds, thermosetting resins such as blocked isocyanate compounds, organic fillers such as silicon powders, nylon powders and fluorine powders, thickeners such as olben and bentone, Silicone type, fluorine type, polymer type antifoaming agent or leveling agent, imidazole type, thiazole type, triazole type, adhesion imparting agent such as silane coupling agent, phthalocyanine blue, phthalocyanine green, iodine green, disazo Examples thereof include colorants such as yellow and carbon black, surface coupling agents such as silane coupling agents and titanate coupling agents.

  In the resin composition of the present invention, the above-mentioned components are appropriately mixed, and if necessary, kneading or mixing is carried out by kneading means such as a triple roll, ball mill, bead mill or sand mill, or stirring means such as a super mixer or planetary mixer. It can be adjusted by doing. Moreover, it can also be adjusted as a resin varnish by adding an organic solvent.

  In 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 is small in the wet roughening step, and a plated conductor layer having sufficient peel strength is formed thereon. Can be suitably used as a resin composition for forming an insulating layer (resin composition for insulating layer of multilayer printed wiring board) in the production of a multilayer printed wiring board, and the conductor layer is formed by plating. It can use more suitably as a resin composition for forming (resin composition for insulating layers of the multilayer printed wiring board which forms a conductor layer by plating). That is, it is suitable as a resin composition for buildup layers of a multilayer printed wiring board.

  After the resin composition of the present invention is cured to form an insulating layer, and the surface of the insulating layer is roughened, the arithmetic mean roughness (Ra value) and the root mean square roughness (Rq value) will be described later. Measurement of Arithmetic Average Roughness (Ra Value) after Roughening, Measurement of Root-Mean-Square Roughness (Rq Value)> The measurement method can be grasped by the following method.

  The upper limit of the arithmetic average roughness (Ra value) is preferably 400 nm or less, more preferably 350 nm or less, still more preferably 300 nm or less, still more preferably 250 nm or less, in order to reduce the transmission loss of the electric signal. Is particularly preferable, and 180 nm or less is particularly preferable. The lower limit of the arithmetic average roughness (Ra value) is preferably as low as possible, but from the viewpoint of stabilizing the peel strength, 10 nm or more is preferable, 50 nm or more is more preferable, and 100 nm or more is still more preferable.

  Since the root mean square roughness (Rq value) reflects the local state of the surface of the insulating layer, it was found that the dense and smooth surface of the insulating layer can be confirmed by grasping the Rq value. The upper limit of the root mean square roughness (Rq value) is preferably 500 nm or less, more preferably 450 nm or less, still more preferably 400 nm or less, and still more preferably 350 nm or less, in order to obtain a dense and smooth insulating layer surface. 300 nm or less is particularly preferable, 250 nm or less is particularly preferable, and 200 nm or less is particularly preferable. The lower limit of the root mean square roughness (Rq value) is preferably as low as possible, but from the viewpoint of stabilizing the peel strength, 30 nm or more is preferable, 70 nm or more is more preferable, and 120 nm or more is still more preferable.

  The resin composition of the present invention is cured to form an insulating layer, the surface of the insulating layer is roughened, and the peel strength of the conductive layer obtained by plating is as described below. Measurement of peel strength (peel strength)> It can be grasped by the measurement method described in the above.

  The peel strength is preferably 0.3 kgf / cm or more, more preferably 0.35 kgf / cm or more, still more preferably 0.4 kgf / cm or more, in order to keep the insulating layer and the conductor layer in close contact with each other. 45 kgf / cm or more is still more preferable. The upper limit value of the peel strength is preferably as high as possible, and is not particularly limited, but generally it is 1.2 kgf / cm or less, 1.0 kgf / cm or less, 0.8 kgf / cm or less.

  The application of the resin composition of the present invention is not particularly limited, and sheet-like laminate materials such as adhesive films and prepregs, circuit boards (laminate board applications, multilayer printed wiring board applications etc), solder resists, under-fill materials, dies It can be used in a wide range of applications where a resin composition is required, such as a bonding material, a semiconductor sealing material, a hole filling resin, and a component embedding resin. The resin composition of the present invention can be applied to a circuit board in the form of a varnish to form an insulating layer, but industrially, it is generally preferable to use a sheet-like laminate material such as an adhesive film or a prepreg. . The softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminateability of the sheet-like laminate material.

<Sheet-like laminated material>
(Adhesive film)
The adhesive film of the present invention is prepared by a method known to those skilled in the art. For example, a resin varnish prepared by dissolving a resin composition in an organic solvent is prepared, and the resin varnish is applied to a support using a die coater or the like. It can manufacture by making an organic solvent dry by heating or hot-air blowing etc., and forming a resin composition layer.

  Examples of organic solvents include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, acetates such as propylene glycol monomethyl ether acetate and carbitol acetate, carbitols such as cellosolve and butyl carbitol And aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Two or more organic solvents may be used in combination.

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

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

  As the support, films of polyolefins such as polyethylene, polypropylene and polyvinyl chloride, films of polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), films of polyesters such as polyethylene naphthalate, polycarbonate films, polyimide films, etc. Various plastic films are mentioned. Further, release paper, copper foil, metal foil such as aluminum foil, or the like may be used. Among them, plastic films are preferable and polyethylene terephthalate films are more preferable from the viewpoint of versatility. The support and a protective film to be described later may be subjected to surface treatment such as mud treatment and corona treatment. Further, the release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluorine resin release agent.

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

  The protective film according to the support can be further laminated on the surface of the resin composition layer to which the support is not adhered. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, it is possible to prevent adhesion of dust and the like to the surface of the resin composition layer and scratches. The adhesive film can also be wound and stored in a roll.

(Prepreg)
The prepreg of the present invention can be produced by impregnating a sheet-like reinforcing substrate with the resin composition of the present invention by a hot melt method or a solvent method, and heating and semi-curing it. That is, it can be set as the prepreg which will be in the state which the resin composition of this invention impregnated in the sheet-like reinforcement base material. As a sheet-like reinforcement base material, what consists of fibers usually used as fibers for prepregs, such as glass cloth and an aramid fiber, can be used, for example. And it is preferable that a prepreg is formed on a support.

  In the hot melt method, the resin composition is once coated on a support without dissolving it in an organic solvent, and then it is laminated on a sheet-like reinforcing substrate, or directly coated on a sheet-like reinforcing substrate by a die coater. And so on, to produce a prepreg. In the solvent method, the resin is dissolved in an organic solvent to prepare a resin varnish in the same manner as in the adhesive film, and the sheet-like reinforcing substrate is immersed in the varnish to impregnate the resin varnish into the sheet-like reinforcing substrate. It is a method of drying. The adhesive film can also be prepared by continuously heat laminating from both sides of the sheet-like reinforcing substrate under heating and pressure conditions. A support, a protective film and the like can also be used in the same manner as the adhesive film.

<Multilayer Printed Wiring Board Using Sheet-like Laminated Material>
Next, an example of a method for producing a multilayer printed wiring board using the sheet-like laminate material produced as described above will be described.

  First, a sheet-like laminate material is laminated (laminated) on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means that by which the conductor layer (circuit) by which pattern processing was carried out was carried out on the single side | surface or both surfaces of the above board | substrates here. In addition, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately stacked, a conductor layer (circuit) in which one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned is also used here. Included in the circuit board. The surface of the conductor layer may be roughened in advance by blackening treatment, copper etching or the like.

In the above laminate, when the sheet-like laminate material has a protective film, after removing the protective film, the sheet-like laminate material and the circuit board are preheated if necessary, and the sheet-like laminate material is pressurized and Laminate on a circuit board while heating. In the sheet-like laminate material of the present invention, a method of laminating on a circuit board under reduced pressure by vacuum lamination is suitably used. The conditions of the laminate are not particularly limited, but, 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 × It is preferable to use 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), a pressure bonding time (lamination time) of preferably 5 to 180 seconds, and laminating under a reduced pressure of 20 mm Hg (26.7 hPa) or less. In addition, the method of laminating may be a batch system or a continuous system with a roll. Vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, Vacuum Applicator manufactured by Nichigo Morton Co., Ltd., vacuum pressure type laminator manufactured by Meiki Co., Ltd., roll type dry coater manufactured by Hitachi Industries, Ltd., Hitachi AC Co., Ltd. A vacuum laminator etc. can be mentioned.

  After laminating the sheet-like laminate material on the circuit board, it is cooled to around room temperature, and then the support is peeled off if peeled off, and the resin composition is thermally cured to form a cured product on the circuit board. An insulating layer can be formed. The conditions for heat curing may be appropriately selected according to the type, content, etc. of the resin component in the resin composition, but preferably 20 minutes to 180 minutes at 150 ° C. to 220 ° C., more preferably 160 ° C. to 210 ° C. The temperature is selected in the range of 30 to 120 minutes. After the formation of the insulating layer, if the support is not peeled off before curing, it can be peeled off here if necessary.

The sheet-like laminate material can also be laminated on one side or both sides of the circuit board using a vacuum press. The lamination process of heating and pressurizing under reduced pressure can be performed using a general vacuum hot press. For example, it can be carried out by pressing a heated metal plate such as a SUS plate from the support layer side. The pressing conditions are such that the degree of reduced pressure is usually 1 × 10 ⁻² MPa or less, preferably 1 × 10 ⁻³ MPa or less. Although heating and pressurization can be performed in one step, it is preferable to divide the conditions into two or more steps in order to control the bleeding of the resin. For example, the temperature of the first stage press is 70 to 150 ° C., the pressure is 1 to 15 kgf / cm 2, and the second stage press is 150 to 200 ° C., the pressure is 1 to 40 kgf / cm 2 It is preferred to do. The time of each step is preferably 30 to 120 minutes. By thermally curing the resin composition layer in this manner, an insulating layer can be formed on the circuit board. As a vacuum hot press marketed commercially, MNPC-V-750-5-200 (made by Meiki Seisakusho KK), VH1-1603 (made by Kitagawa Seiki Co., Ltd.) etc. are mentioned, for example.

  Next, the insulating layer formed on the circuit board is subjected to a drilling process to form a via hole and a through hole. For example, drilling can be performed by a known method such as a drill, laser, plasma or the like and, if necessary, a combination of these methods, but laser drilling such as a carbon dioxide gas laser or a YAG laser is most common. It is a method. If the support is not peeled off before drilling, it will be peeled off here.

  Next, the surface of the insulating layer is roughened. In the case of dry roughening treatment, plasma treatment etc. may be mentioned, and in the case of wet roughening treatment, swelling treatment by swelling liquid, roughening treatment by oxidizing agent and neutralization treatment by neutralization solution may be mentioned in this order Be The wet roughening treatment is preferable in that the smear in the via hole can be removed while forming an uneven anchor on the surface of the insulating layer. The swelling treatment with the swelling solution is performed by immersing the insulating layer in the swelling solution at 50 to 80 ° C. for 5 to 20 minutes (preferably 8 to 15 minutes at 55 to 70 ° C.). The swelling solution includes an alkaline solution, a surfactant solution and the like, preferably an alkaline solution, and examples of the alkaline solution include sodium hydroxide solution, potassium hydroxide solution and the like. Examples of commercially available swelling solutions include Swelling Dip Securiganth P manufactured by Atotech Japan Co., Ltd., Swelling Dip Securiganth SBU, and the like. be able to. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer at 60 to 80 ° C. for 10 to 30 minutes (preferably, at 70 to 80 ° C. for 15 to 25 minutes) in an oxidizing agent solution. As the oxidizing agent, for example, alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, etc. may be mentioned. it can. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as concentrate compact CP manufactured by Atotech Japan Co., Ltd. and dosing solution Security G. The neutralization treatment with the neutralization solution is carried out by immersing in the neutralization solution for 3 to 10 minutes at 30 to 50 ° C. (preferably 3 to 8 minutes at 35 to 45 ° C.). As the neutralization solution, an acidic aqueous solution is preferable, and as a commercial product, reduction solution thin security G made by Atotech Japan Co., Ltd. can be mentioned.

  Then, a conductor layer is formed on the insulating layer by dry plating or wet plating. As dry plating, known methods such as vapor deposition, sputtering, ion plating and the like can be used. As wet plating, a method of forming a conductor layer by combining electroless plating and electrolytic plating, a method of forming a plating resist having a pattern reverse to that of the conductor layer, and forming a conductor layer only by electroless plating, etc. may be mentioned. Be As a subsequent pattern formation method, for example, a subtractive method, a semi-additive method or the like known to those skilled in the art can be used, and a multilayer formed by stacking buildup layers in multiple stages by repeating the above-described series of steps multiple times It becomes a printed wiring board. In the present invention, since it has low roughness and high peel, it can be suitably used as a buildup layer of a multilayer printed wiring board.

<Semiconductor device>
A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor chip in the conduction part of the multilayer printed wiring board of the present invention. The "conductive location" is a "location for transmitting an electrical signal in a multilayer printed wiring board", and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method in the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, the wire bonding mounting method, flip chip mounting method, no bump A mounting method using a buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a nonconductive film (NCF), and the like can be given.

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

<Measurement method and evaluation method>
First, various measurement methods and evaluation methods will be described.

[Preparation of sample for measurement of peel strength, arithmetic mean roughness (Ra value), root mean square roughness (Rq value)]
(1) Base treatment of inner layer circuit board Both sides of glass cloth base material epoxy resin double-sided copper-clad laminate (18 μm copper foil, 0.3 mm board thickness, R5715 ES made by Matsushita Electric Works Co., Ltd.) with inner layer circuit formed. The copper surface was roughened by etching 1 um with CZ 8100 manufactured by MEC CORPORATION.

(2) Lamination of adhesive film The adhesive films prepared in Examples and Comparative Examples were laminated on both sides of the inner layer circuit board using a batch-type vacuum pressure laminator MVLP-500 (trade name of Meishin Co., Ltd.). . Lamination was performed by reducing the pressure for 30 seconds to make the pressure 13 hPa or less, and then press-bonding at 100 ° C. under a pressure of 0.74 MPa for 30 seconds.

(3) Curing of the resin composition The laminated adhesive film was cured at 100 ° C. for 30 minutes continuously and cured at 180 ° C. for 30 minutes to form the insulating layer, and then the PET film was peeled off. .

(4) Roughening treatment The inner layer circuit board on which the insulating layer is formed is made into swelling liquid, swelling dip security gullet P containing diethylene glycol monobutyl ether of Atotech Japan Ltd. (glycolether, aqueous solution of sodium hydroxide) Soaked at 60 ° C. for 10 minutes. Next, it was immersed for 20 minutes at 80 ° C. in a concentrate compact P (KMnO 4: 60 g / L, NaOH: 40 g / L aqueous solution) as a roughening solution. Finally, as a neutralization solution, it was immersed for 5 minutes at 40 ° C. in a reduction solution Suliganth P (aqueous solution of sulfuric acid) of Atotech Japan Co., Ltd. After drying at 80 ° C. for 30 minutes, measurements of arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) were performed on the surface of the insulating layer after the roughening treatment.

(5) Plating by the semi-additive method In order to form a circuit on the surface of the insulating layer, the inner layer circuit board is immersed in a solution for electroless plating containing PdCl ₂ for 5 minutes at 40 ° C., and then in an electroless copper plating solution. Soaked at 25 ° C. for 20 minutes. After annealing for heating at 150 ° C. for 30 minutes, an etching resist was formed, and after forming a pattern by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing was performed at 200 ° C. for 60 minutes. The peel strength (peel strength) of the plated conductor layer was measured on this circuit board.

[Measurement of arithmetic mean roughness (Ra value), root mean square roughness (Rq value) after roughening]
The Ra value and the Rq value were determined from the values obtained using a non-contact surface roughness meter (WYKO NT3300 manufactured by Becoin Instruments, Inc.) and a measurement range of 121 μm × 92 μm with a VSI contact mode, 50 × lens. And it measured by calculating | requiring the average value of 10 points | pieces, respectively.

[Measurement of peel strength (peel strength) of plated conductor layer]
Insert a cut of 10 mm in width and 100 mm in length in the conductor layer of the circuit board, peel off one end, and hold it with a clamp (TCS Corporation, auto-com type tester AC-50C-SL), The load (kgf / cm) when 35 mm was peeled off vertically at a speed of 50 mm / min was measured at room temperature.

[Evaluation of laminating property]
The adhesive film produced in the example and the comparative example was subjected to L (line: wiring width) / S (space) with a conductor thickness of 35 μm using a batch-type vacuum pressure laminator MVLP-500 (trade name of Meishin Co., Ltd.). : Lamination width: A comb-like conductor pattern of 160/160 μm was laminated. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing for 30 seconds at 100 ° C. under a pressure of 0.74 MPa. The PET film was peeled off from the laminated adhesive film, and the resin composition was cured under curing conditions of 180 ° C. for 30 minutes to form an insulating layer. The value of unevenness difference (Rt: maximum peak-to-valley) on the conductor and the other part in the insulating layer is VSI contact mode, using a non-contact surface roughness meter (WYKO NT3300 manufactured by Becoin Instruments), It was determined by a numerical value obtained with a 10 × lens as a measurement range of 1.2 mm × 0.91 mm. There is no generation of voids after lamination, and a difference of less than 5 μm between the conductor and the other parts is ○, no void is generated after lamination, but the difference between the conductor and the other parts is 5 μm The above case was evaluated as Δ, and the case where a void occurred after lamination was evaluated as x.

[Inorganic filler used]
Inorganic filler 1: 100 parts of spherical silica ("SO-C2" manufactured by Admatex, average particle size 0.5 μm), phenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., "KBM103", molecular weight 198. 3) Surface-treated with 0.3 part, carbon amount per unit surface area 0.126 mg / m 2.

Inorganic filler 2: Spherical silica ("SO-C2" manufactured by Admatex, average particle diameter 0.5 μm) 100 parts, dimethyldiethoxysilane (Shin-Etsu Chemical Co., Ltd., "KBE-22", molecular weight 148.3) Surface-treated with 0.3 part, carbon content per unit surface area 0.063 mg / m 2.

Inorganic filler 3: 100 parts of spherical silica (“SO-C1” manufactured by Admatex, average particle size 0.25 μm), phenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., “KBM103”, molecular weight 198. 3) Surface-treated with 0.5 part, carbon content per unit surface area 0.083 mg / m 2.

Inorganic filler 4: Epoxysilane (Shin-Etsu Chemical Co., Ltd., "KBM 403", molecular weight 236) 0 to 100 parts of spherical silica ("SO-C2" manufactured by Admatex, average particle diameter 0.5 μm) 0. Surface-treated with 5 parts, 0.19 mg / m 2 of carbon per unit surface area

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

Inorganic filler 6: Spherical silica ("SO-C1" manufactured by Admatex, average particle diameter 0.25 μm) without surface treatment.

Example 1
8 parts of naphthalene type epoxy resin (epoxy equivalent 144, DIC Corporation "EXA 4032 SS") and 11 parts of bixylenol type epoxy resin (epoxy equivalent 190, Mitsubishi Chemical Corporation "YX4000HK"), modified naphthalene type epoxy resin 9 parts of (Epoxy equivalent weight: about 330, "ESN 475V" manufactured by Nippon Steel Chemical Co., Ltd.) was heated and dissolved in 32 parts of solvent naphtha while stirring, and then cooled to room temperature. The mixed solution was mixed with 1.5 parts of rubber particles (manufactured by Ganz Chemical Co., Ltd., AC3816N) in 6 parts of solvent naphtha for 12 hours at 20 ° C., and 140 parts of the inorganic filler 1 were mixed It knead | mixed and disperse | distributed uniformly by 3 rolls. Thereto, 45 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC, a toluene solution having a non-volatile content of 65% by weight of about 223 active groups equivalent), phenoxy resin (weight average molecular weight 35000, Mitsubishi Chemical 5 parts of MEK and cyclohexanone in 30% by mass non volatile matter "YL7553", 1 part of a 10% by mass MEK solution of 4-dimethylaminopyridine as a curing accelerator, 7 parts of methyl ethyl ketone (MEK) Were uniformly dispersed by a rotary mixer to prepare a resin varnish. Next, the thickness of the resin composition layer after drying is 40 μm on the release surface of the resin varnish with a release surface of an alkyd-based release-treated polyethylene terephthalate film (“AL5” manufactured by Lintec Co., Ltd., thickness 38 μm). As described above, it was uniformly applied by a die coater and dried at 80 to 110 ° C. (average 95 ° C.) for 5 minutes to obtain an adhesive film.

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

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

Example 4
Naphthalene type epoxy resin (epoxy equivalent 144, DIC Corporation "HP 4700") 5 parts, liquid bisphenol type epoxy resin (Nippon Chemical Co., Ltd. "ZX1059", 1: 1 of bisphenol A type and bisphenol F type Mixed product: 14 parts of biphenyl type epoxy resin (epoxy equivalent 269, “NC3000H” manufactured by Nippon Kayaku Co., Ltd.) and 30 parts of solvent naphtha were heated and dissolved while stirring, and then cooled to room temperature. Into the mixed solution, 1.5 parts of rubber particles (manufactured by Ganz Kasei Co., Ltd., AC3816N) was subjected to static swelling at 20 ° C. for 12 hours in 6 parts of solvent naphtha, and 140 parts of inorganic filler 1 was further added Furthermore, a flame retardant (Sanko Co., Ltd. “HCA-HQ”, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 1 μm 5 parts were added, and it knead | mixed and disperse | distributed with 3 rolls. There, 10 parts of a phenol novolac curing agent ("LA-7054" manufactured by DIC, a MEK solution with 60% by mass of a nonvolatile content of phenolic hydroxyl equivalent 124), a naphthalene based phenolic resin (phenolic hydroxyl equivalent 215, new 10 parts by weight of "SN 485" manufactured by Nippon Steel Chemical Co., Ltd., MEK solution having a nonvolatile content of 60% by mass, phenoxy resin (weight-average molecular weight 35000, "YL7553" manufactured by Mitsubishi Chemical Corp.) 7 parts of a 1: 1 solution, 2 parts of a 5% by weight MEK solution of 4-dimethylaminopyridine as a curing accelerator, and 4 parts of MEK were mixed and uniformly dispersed by a rotary mixer to prepare a resin varnish. Then, in the same manner as in Example 1, an adhesive film was obtained.

Example 5
10 parts of naphthalene type epoxy resin (“EXA 4032 SS” manufactured by DIC Corporation), liquid bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type) 5 Parts, 20 parts of naphthol type epoxy resin ("ESN 475 V" manufactured by Nippon Steel Chemical Co., Ltd.), phenoxy resin (weight average molecular weight 35000, "YL 7553" manufactured by Mitsubishi Chemical Co., Ltd., 30 mass% of nonvolatile components MEK and cyclohexanone 7 parts of a 1: 1 solution was dissolved by heating in 50 parts of solvent naphtha while stirring, and then cooled to room temperature. Next, 10 parts of an active ester compound ("HPC8000-65T" manufactured by DIC Corporation, active ester equivalent 223, 65% solid solution in toluene), a prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan Co., Ltd.) 20 parts of cyanate equivalent about 232, MEK solution of non volatile matter 75% by mass, phenol novolak type polyfunctional cyanate ester resin ("Lonza Japan Ltd. product" PT30S ", cyanate equivalent of about 133, MEK solution of non volatile matter 85 mass%) 10 parts, 4 parts of rubber particles (Gants Chemical Co., Ltd., AC3816N) swollen in 16 parts of solvent naphtha at room temperature for 12 hours, flame retardant (Sanko Co., Ltd. “HCA-HQ”, 10- (2,5-Dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxai 3 parts of average particle diameter 1 μm, 0.1 part of hardening accelerator (4-dimethylaminopyridine, 10% by mass of solid MEK solution), hardening accelerator (manufactured by Tokyo Kasei Kogyo Co., Ltd., cobalt (III) acetylaceto) 4.5 parts of MEK solution having a solid content of 1% by mass was added, and 140 parts of the inorganic filler 1 were further mixed, and uniformly dispersed by a rotary mixer to prepare a resin varnish. Then, in the same manner as in Example 1, an adhesive film was obtained.

Comparative Example 1
A resin varnish was produced in exactly the same manner as in Example 1 except that the inorganic filler 1 was changed to the inorganic filler 4. Then, in the same manner as in Example 1, an adhesive film was obtained.

Comparative Example 2
A resin varnish was produced in the same manner as in Example 1 except that the inorganic filler 1 was changed to the inorganic filler 5. Then, in the same manner as in Example 1, an adhesive film was obtained.

Comparative Example 3
A resin varnish was produced in the same manner as in Example 1 except that the inorganic filler 1 was changed to the inorganic filler 6. Then, in the same manner as in Example 1, an adhesive film was obtained.

  The results are shown in Table 1.

  From the results of Table 1, it can be seen that the resin compositions of Examples give low peel strengths and low root mean square roughness values with sufficient peel strength and good laminateability. Note that, since the Rq value reflects the local state of the surface of the insulating layer, it can be seen that the dense rough surface is obtained as the Rq value decreases. On the other hand, in the comparative example, the arithmetic mean roughness and the root mean square roughness were large, the peel strength was small, and the laminateability was poor.

  In the wet roughening process, not only the arithmetic mean roughness of the surface of the insulating layer is low, but also the root mean square roughness is small, and a plated conductor layer having sufficient peel strength can be formed thereon, and the laminateability is also excellent. It became possible to provide a resin composition. Furthermore, it has become possible to provide a sheet-like laminate material, a multilayer printed wiring board and a semiconductor device using the same. Furthermore, it has become possible to provide electronic products such as computers, mobile phones, digital cameras, TVs, etc., and vehicles such as motorcycles, automobiles, trains, ships, aircrafts, etc. equipped with these.

Claims (1)

A resin composition comprising an epoxy resin, a curing agent and an inorganic filler surface-treated with an alkoxysilane compound,
The average particle size of the inorganic filler is 0.01 to 5 μm,
The resin composition, wherein the content of the inorganic filler is 30 to 90% by mass, when the nonvolatile component in the resin composition is 100% by mass.