JP6534986B2 - Resin composition - Google Patents

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, although the epoxy resin composition which consists of an epoxy resin, a hardening | curing agent, a filler, and a silane coupling agent is disclosed by patent document 1, it was not directed at all about surface roughness or peel strength.

JP 2002-97258 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 low in the wet roughening step, and a plated conductor layer having sufficient peel strength is formed thereon It is possible to provide a resin composition which can be done and has a low coefficient of linear thermal expansion.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly examining that the present inventors should solve the said subject, it is a resin composition containing an epoxy resin, a hardening | curing agent, and an inorganic filler, Comprising: This inorganic filler is surface-treated with aminoalkylsilane. When the content of the non-volatile component in the resin composition is 100% by mass, the present invention is completed in a resin composition characterized in that the content of the inorganic filler is 55 to 90% by mass.

That is, the present invention includes the following contents.
[1] A resin composition containing an epoxy resin, a curing agent and an inorganic filler, wherein the inorganic filler is surface-treated with an aminoalkylsilane, and the nonvolatile component in the resin composition is 100% by mass. In this case, the content of the inorganic filler is 55 to 90% by mass.
[2] The resin composition according to [1], wherein the aminoalkylsilane contains one or more selected from aminomethyl group, aminoethyl group, aminopropyl group, aminoisopropyl group and aminocyclopropyl group. object.
[3] The resin composition according to [1] or [2], wherein the aminoalkylsilane is 3-aminopropylsilane.
[4] The resin composition according to any one of [1] to [3], wherein the molecular weight of the aminoalkylsilane is 100 to 2000.
[5] The resin composition according to any one of [1] to [4], wherein an average particle size of the inorganic filler is 0.01 to 5 μm.
[6] The resin composition according to any one of [1] to [5], wherein the inorganic filler is silica.
[7] The content of the inorganic filler is 60 to 85% by mass, where the nonvolatile component in the resin composition is 100% by mass, according to any one of [1] to [6]. Resin composition.
[8] The resin composition according to any one of [1] to [7], wherein the aminoalkylsilane is surface-treated with 0.05 to 5 parts by mass with respect to 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 0.05 to 1 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, naphthalene 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 according to any one of [1] to [10], wherein the curing agent is one or more selected from a phenolic curing agent, an active ester curing agent and a cyanate ester curing agent. Resin composition.
[12] The resin composition according to any one of [1] to [11], wherein the curing agent is at least one selected from an active ester curing agent and a cyanate ester curing agent.
[13] 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 300 nm and a root mean square roughness of 20 to 500 nm The resin composition in any one of [1]-[12] characterized by these.
[14] 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 0.35 to 1.5 kgf / cm. The resin composition according to any one of [1] to [13], which is characterized in that
[15] The resin composition according to any one of [1] to [14], which is a resin composition for an insulating layer of a multilayer printed wiring board.
[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 in which a conductor layer is formed by plating.
[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].
[19] A multilayer printed wiring board in which an insulating layer is formed of a cured product of the resin composition according to any one of [1] to [17].
[20] A semiconductor device using the multilayer printed wiring board according to [19].

  A resin composition containing an epoxy resin, a curing agent and an inorganic filler, wherein the inorganic filler is surface-treated with an aminoalkylsilane, and the nonvolatile component in the resin composition is 100% by mass, By using a resin composition characterized in that the content of the inorganic filler is 55 to 90% by mass, 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 rough It is possible to form a plated conductor layer having a low peel strength and a sufficient peel strength thereon, and to provide a resin composition having a low linear thermal expansion coefficient.

  The present invention is a resin composition containing an epoxy resin, a curing agent and an inorganic filler, wherein the inorganic filler is surface-treated with an aminoalkylsilane, and the non-volatile component in the resin composition is 100% by mass. In the case of the resin composition, the content of the inorganic filler is 55 to 90% by mass. Hereinafter, the compounding components of 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 viewpoints of heat resistance improvement, insulation reliability improvement and peel strength improvement, bisphenol A epoxy resin, bisphenol F epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, naphthalene ether It is preferable to use one or more selected from an epoxy resin having an epoxy structure, a glycidyl ester epoxy resin, an anthracene 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 handling 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: 3 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: 2 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 It is preferable to use at least one selected from an active ester-based curing agent and a cyanate ester-based curing agent. 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. Specifically, as the active ester curing agent, an active ester curing agent containing a dicyclopentadienyl diphenol structure, an active ester curing agent containing a naphthalene structure, an active ester curing agent which is an acetylated product of phenol novolac, An active ester-based curing agent which is a benzoyl compound of phenol novolac is preferable, and in particular, an active ester-based curing agent containing a dicyclopentadienyl diphenol structure is more preferable in that the improvement of the peel strength is excellent. 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 products include EXB9451, EXB 9460, EXB 9460S-65T, HPC-8000-65T (manufactured by DIC Corporation, having an active group equivalent weight of about 223), and acetyl derivatives of phenol novolac as those containing a dicyclopentadienyldiphenol structure. DC 808 (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) as an active ester-based curing agent which is a benzyl novolac phenol phenol And YLH1030 (manufactured by Mitsubishi Chemical Co., Ltd., an active group equivalent of about 201), YLH1048 (manufactured by Mitsubishi Chemical Co., Ltd., an active group equivalent of about 245), and the like.

  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 novolac type polyfunctional cyanate ester resin represented by the following formula (2) (Lonza Japan Co., Ltd. product PT30S, cyanate equivalent 124), the following formula (3) Prepolymer in which part or all of the bisphenol A dicyanate represented is triazineated to form a trimer (BA 230S, cyanate equivalent 232, manufactured by Lonza Japan Ltd., dicyclopentadiene represented by the following formula (4) Structure-containing cyanate ester resin (Lonza Japan Co., Ltd.) , It includes the DT-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>
The inorganic filler used in the present invention is not particularly limited, and, for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, nitrided Boron, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like 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 it is preferably 5 μm or less, more preferably 4 μm or less, from the viewpoint that the surface of the insulating layer has low roughness and enables fine wiring formation. Is more preferably 2 μm or less, still more preferably 1 μm or less, particularly preferably 0.8 μm or less, and particularly preferably 0.6 μm or less. On the other hand, in the case where the resin composition is a resin varnish, the viscosity is preferably 0.01 μm or more, more preferably 0.03 μm or more, from the viewpoint of preventing the viscosity of the varnish from increasing and the handling property being reduced. The thickness is more preferably 05 μm or more, still more preferably 0.07 μm or more, and particularly preferably 0.1 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 a laser diffraction scattering type particle size distribution measuring apparatus, LA-950 or the like manufactured by Horiba, Ltd. can be used.

  The content of the inorganic filler is 55 to 90% by mass when the non-volatile component in the resin composition is 100% by mass from the viewpoint of lowering the linear thermal expansion coefficient and preventing cracking of the multilayer printed wiring board I assume. From the viewpoint of preventing the cured product from becoming brittle and preventing the decrease in peel strength, the content is preferably 85% by mass or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less. On the other hand, 60 mass% or more is more preferable, and 65 mass% or more is still more preferable from the point of further reducing the linear thermal expansion coefficient of hardened | cured material.

The aminoalkylsilane used in the present invention is not particularly limited as long as it is an aminoalkylsilane containing an aminoalkyl group and an alkoxysilyl group, and more specifically an aminoalkylalkoxysilane is preferable. The aminoalkyl group is excellent in that the compatibility with the resin is improved, and is further excellent in that it contributes to the improvement of the laminating property when the resin composition is formed into a sheet form, and the low roughness in the present invention Contribute to The aminoalkyl group is preferably one or more selected from an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminoisopropyl group and an aminocyclopropyl group, and more preferably an aminopropyl group.
On the other hand, the alkoxysilyl group contributes to the improvement of the peel strength in the present invention. As an alkoxy silyl group, what has 2-3 alkoxy groups per one alkoxy silyl group is preferable, and a methoxy group and an ethoxy group are preferable as an alkoxy group. The alkoxysilyl group may be modified.
Therefore, surface treatment of the inorganic filler with aminoalkylsilane improves the peel strength with low roughness even when 55 to 90% by mass of the inorganic filler is blended in the resin composition. It will be excellent.
As a specific aminoalkylsilane, 3-aminopropylsilane is preferable, and it is more preferable to use one or more selected from 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

  The molecular weight of the aminoalkylsilane is preferably 100 or more, more preferably 150 or more, and still more preferably 200 or more from the viewpoint of suppressing volatilization during surface treatment or drying. On the other hand, from the viewpoint of appropriate reactivity, 2000 or less is preferable, 1500 or less is more preferable, 1000 or less is more preferable, and 500 or less is particularly preferable. Commercially available products include “KBM 903” (3-aminopropyltrimethoxysilane, molecular weight 179) manufactured by Shin-Etsu Chemical Co., Ltd., “KBE 903” (3-aminopropyltriethoxysilane, molecular weight 221) manufactured by Shin-Etsu Chemical Co., Ltd. Etc.

  The amount of the aminoalkylsilane in the surface treatment of the inorganic filler with the aminoalkylsilane is not particularly limited, but 0.05 to 5 parts by mass of the aminoalkylsilane with respect to 100 parts by mass of the inorganic filler. It is preferable to treat, surface treatment with 0.1 to 4 parts by mass is more preferable, surface treatment with 0.2 to 3 parts by mass is further preferable, and surface treatment is performed with 0.3 to 2 parts by mass Is even more preferred.

  In addition, in the case of an inorganic filler surface-treated with an aminoalkylsilane, the presence of carbon atoms is confirmed by analyzing the surface composition of the inorganic filler, and the amount of carbon per unit surface area of the inorganic filler is determined. be able to. Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with aminoalkylsilane, 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 inorganic filler is 0.05 mg / in that it improves the dispersibility of the inorganic filler, and stabilizes the arithmetic mean roughness and the root mean square roughness after the wet roughening step of the cured product. m ² or more is preferable, 0.1 mg / m ² or more is more preferable, 0.15 mg / m ² or more is more preferable, and 0.2 mg / m ² or more is still more preferable. On the other hand, 1 mg / m ² or less is preferable, 0.75 mg / m ² or less is more preferable, and 0.5 mg / m ² or less from the viewpoint of preventing the melt viscosity of the resin varnish and the melt viscosity increase in the adhesive film form. Is more preferred.

  The inorganic filler surface-treated with an aminoalkylsilane is preferably added to the resin composition after the inorganic filler is surface-treated with an aminoalkylsilane. 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 aminoalkylsilane is not particularly limited, a dry method and a wet method may be mentioned. As a dry method, the inorganic filler is charged into a rotary mixer, and after dropping or spraying an alcohol solution or an aqueous solution of aminoalkylsilane while stirring, the mixture is further stirred and classified by a sieve. Thereafter, it can be obtained by dehydration condensation of an aminoalkylsilane and an inorganic filler by heating. As a wet method, aminoalkylsilane 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 an aminoalkylsilane and an inorganic filler by heating. Furthermore, the integral blend method which adds an aminoalkylsilane in a resin composition is also possible.

<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.

  When a curing accelerator (excluding a metal-based curing accelerator) is added to the resin composition of the present invention, the total amount of the epoxy resin and the curing agent is 100 parts by mass, the range of 0.005 to 1 part by mass Is preferable, and the range of 0.01 to 0.5 parts 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.

  When the metal-based curing accelerator is blended to the resin composition of the present invention, the content of the metal based on the metal-based curing catalyst is in the range of 25 to 500 ppm when the nonvolatile component in the resin composition is 100% by mass. Is preferable, and 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 8,000 to 200,000, and more preferably in the range of 1,200 to 100,000. 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 added to the resin composition of the present invention, the amount is preferably 0.1 to 10% by mass, and 0.5 to 5% by mass, when the nonvolatile component in the resin composition is 100% by mass. 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 include core-shell 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 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.

  In the case of incorporating rubber particles into the resin composition of the present invention, it is preferably 0.05 to 10% by mass, more preferably 0.5 to 5% by mass with respect to 100% by mass of non-volatile components 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.

  When a flame retardant is mixed with the resin composition of the present invention, it is preferably 0.5 to 10% by mass, and more preferably 1 to 5% by mass, with respect to 100% by mass of non-volatile components in the resin composition. is there.

<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, silane coupling agents, titanate coupling agents, and surface treatment agents such as silazane compounds. When this surface treatment agent is used, the aminoalkylsilane may be covalently bonded to the surface of the inorganic filler via the surface treatment agent.

  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 low in the wet roughening step, and a plated conductor layer having sufficient peel strength is formed thereon. And the coefficient of linear thermal expansion can also be lowered, so that they 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 Can be used more suitably as a resin composition for forming a conductor layer by plating (resin composition for insulating layer of a multilayer printed wiring board which forms a conductor layer by plating), and further a multilayer printed wiring board It is suitable as a resin composition for buildup layers of

  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 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)] can be grasped by the measurement method described in the above.

  The upper limit value of the arithmetic average roughness (Ra value) is preferably 300 nm or less, more preferably 250 nm or less, and still more preferably 230 nm or less, from the viewpoint of fine wiring formation. The lower limit of the arithmetic average roughness (Ra value) is not particularly limited, and is 10 nm or more, 50 nm or more, 100 nm or more, or the like.

  Since the root mean square roughness (Rq value) reflects the local state of the insulating layer surface, it is possible to confirm that the insulating layer surface is dense and smooth by grasping the Rq value, and the peel strength is stabilized. I found it to be. 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. The lower limit value of the root mean square roughness (Rq value) is preferably 20 nm or more, more preferably 100 nm or more, and still more preferably 150 nm or more, from the viewpoint of stabilizing the peel strength.

  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 described later. Measurement of peel strength (peel strength)] can be grasped by the measurement method described in the following.

  The peel strength is preferably 0.35 kgf / cm or more, more preferably 0.4 kgf / cm or more, and still more preferably 0.45 kgf / cm or more, in order to keep the insulating layer and the conductor layer in close contact with each other. The upper limit of the peel strength is preferably as high as possible, and is not particularly limited, but generally 1.5 kgf / cm or less, 1.2 kgf / cm or less, 1.0 kgf / cm or less, 0.8 kgf / cm or less, and the like.

The linear thermal expansion coefficient of the cured product of the resin composition of the present invention can be grasped by the measurement method described in [Measurement of linear thermal expansion coefficient (CTE)] described later.

  The linear thermal expansion coefficient is preferably 25 ppm or less, more preferably 23 ppm or less, still more preferably 21 ppm or less, and still more preferably 19 ppm or less from the viewpoint of reducing the warpage of the substrate. The linear thermal expansion coefficient is preferably as low as possible, and there is no lower limit in particular, but it is generally 4 ppm or more, 6 ppm or more, 8 ppm or more, and the like.

  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 80 ° 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.

[Measurement of linear thermal expansion coefficient (CTE)]
The adhesive films prepared in Examples and Comparative Examples were thermally cured at 190 ° C. for 60 minutes, and the support was peeled to obtain a sheet-like cured product. The cured product was cut into a test piece having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer Thermo Plus TMA 8310 (manufactured by Rigaku Corporation). After the test piece was attached to the apparatus, measurement was performed twice continuously under the measurement conditions of a load of 1 g and a temperature rising rate of 5 ° C./min. The average linear thermal expansion coefficient (ppm / ° C) from 25 ° C to 150 ° C in the second measurement was calculated.

[Inorganic filler used]
Inorganic filler 1: 3-aminopropylsilane (Shin-Etsu Chemical Co., Ltd.) per 100 parts of spherical silica ("SFP-130MC" manufactured by Denki Kagaku Kogyo Co., Ltd., average particle diameter 0.6 μm, specific surface area 6.2 m 2 / g) Industrial Co., Ltd. product "KBM 903" (molecular weight: 179) surface-treated with 0.3 parts, carbon amount per unit surface area 0.13 mg / m ² .

Inorganic filler 2: Spherical silica ("SO-C2" manufactured by Admatex Co., Ltd., average particle diameter 0.5 μm, specific surface area 5.5 m 2 / g) per 100 parts of 3-aminopropylsilane (Shin-Etsu Chemical Co., Ltd.) Co., Ltd. product, "KBE 903" (molecular weight: 221) surface-treated with 0.4 parts, carbon amount per unit surface area of 0.15 mg / m ² .

Inorganic filler 3: Spherical silica (SFP-130MC manufactured by Denki Kagaku Kogyo Co., Ltd., average particle diameter 0.6 μm, specific surface area 6.2 m 2 / g) not subjected to surface treatment.

Inorganic filler 4: Spherical silica ("SFP-130 MC" manufactured by Denki Kagaku Kogyo Co., Ltd., average particle diameter 0.6 μm, specific surface area 6.2 m 2 / g) relative to 100 parts of phenylaminosilane (Shin-Etsu Chemical Co., Ltd. Manufactured by "KBM 573", molecular weight 255) surface-treated with 0.5 parts, 0.30 mg / m ² of carbon per unit surface area.

Inorganic filler 5: Epoxysilane (Shin-Etsu Chemical Co., Ltd.) relative to 100 parts of spherical silica ("SFP-130 MC" manufactured by Denki Kagaku Kogyo Co., Ltd., average particle diameter 0.6 μm, specific surface area 6.2 m 2 / g) Manufactured by "KBM 403", molecular weight: 236) surface-treated with 0.5 parts, carbon amount: 0.19 mg / m ² per unit surface area.
mg / m ² .

Example 1
10 parts of naphthalene type epoxy resin ("HP 4032 SS" manufactured by DIC Corporation), liquid bisphenol type epoxy resin ("ZX 1059" 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- 475V" manufactured by Nippon Steel Chemical Co., Ltd.), phenoxy resin (weight average molecular weight 35000, "YL7553BH30" manufactured by Mitsubishi Chemical Co., Ltd.) 5 parts of a 1: 1 solution of cyclohexanone was dissolved by heating in 50 parts of solvent naphtha with 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 (Gantz Chemical Industries, Ltd., Staphyloid 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-phosphaphenanth 10 parts-oxide, average particle diameter 1 μm 3 parts, curing accelerator (4-dimethylaminopyridine, MEK solution with solid content 4% by mass) 0.5 parts, curing accelerator (manufactured by Tokyo Kasei Co., Ltd., cobalt) (III) 4.5 parts of acetylacetonate (MEK solution with solid content of 1% by mass) was added, 150 parts of the inorganic filler 1 was further mixed, and 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
150 parts of the inorganic filler 1 was changed to 175 parts of the inorganic filler 2 and a liquid bisphenol epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., a 1: 1 mixture of bisphenol A and bisphenol F) ) 5 parts of biphenyl type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK") is changed to 5 parts and bisphenol A dicyanate prepolymer (Lonza Japan Co., Ltd. product "BA230S75", cyanate equivalent weight about 232, nonvolatile matter 75) 20 parts by mass of MEK solution was changed to 25 parts, and 10 parts of phenol novolac type polyfunctional cyanate ester resin ("Lonza Japan Co., Ltd. product" PT30S ", cyanate equivalent about 133, MEK solution with 85 mass% of non volatile matter) Resin was changed to 6 parts, and 4 parts of the rubber particles was changed to 3 parts, in the same manner as in Example 1 except that The scan was made. 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 3. Then, in the same manner as in Example 1, an adhesive film was obtained.

Comparative 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 4. Then, in the same manner as in Example 1, an adhesive film was obtained.

Comparative Example 3
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 5. 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 low linear thermal expansion coefficients. On the other hand, in the comparative example, the arithmetic mean roughness and the root mean square roughness became large, and the peel strength also became small.

  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 low, and a plated conductor layer having sufficient peel strength can be formed thereon, and the linear thermal expansion coefficient is also It became possible to provide a low 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 (18)

A resin composition comprising an epoxy resin, a curing agent and an inorganic filler,
The inorganic filler is surface treated with an aminoalkylsilane,
The aminoalkylsilane comprises one or more selected from aminomethyl group, aminoethyl group, aminopropyl group, aminoisopropyl group and aminocyclopropyl group,
The epoxy resin comprises a biphenyl type epoxy resin,
The linear thermal expansion coefficient of the cured product of the resin composition is 25 ppm or less,
When the nonvolatile component in the resin composition is 100% by mass, the content of the inorganic filler is 55 to 90% by mass,
The epoxy resin uses a liquid epoxy resin and a solid epoxy resin in combination, and the mass ratio of the liquid epoxy resin to the solid epoxy resin is 1: 0.1 to 1: 3,
A resin composition characterized in that the curing agent is a cyanate ester curing agent and an active ester curing agent .   The resin composition according to claim 1, wherein the aminoalkylsilane is 3-aminopropylsilane.   The resin composition according to claim 1 or 2, wherein the molecular weight of the aminoalkylsilane is 100 to 2000.   The resin composition according to any one of claims 1 to 3, wherein an average particle diameter of the inorganic filler is 0.01 to 5 m.   The resin composition according to any one of claims 1 to 4, wherein the inorganic filler is silica.   The resin composition according to any one of claims 1 to 5, wherein the content of the inorganic filler is 65 to 90% by mass when the nonvolatile component in the resin composition is 100% by mass. .   The resin composition according to any one of claims 1 to 6, wherein the content of the inorganic filler is 65 to 85% by mass when the nonvolatile component in the resin composition is 100% by mass. .   The resin composition according to any one of claims 1 to 7, wherein the aminoalkylsilane is surface-treated with 0.05 to 5 parts by mass with respect to 100 parts by mass of the inorganic filler. Carbon content per unit surface area of the inorganic filler, any one resin composition as claimed in claim 8, characterized in that a 0.05 to 1 mg / m ^2. The resin composition according to any one of claims 1 to 9, wherein the cyanate ester-based curing agent is a cyanate ester-based curing agent represented by the following formula (2) or the following formula (3). .

[In formula (2), n represents 0-20. ]

  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 300 nm and a root mean square roughness of 20 to 500 nm. The resin composition according to any one of claims 1 to 10.   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 0.35 to 1.5 kgf / cm. The resin composition according to any one of claims 1 to 11, characterized in that   It is a resin composition for insulating layers of a multilayer printed wiring board, The resin composition of any one of the Claims 1-12 characterized by the above-mentioned.   It is a resin composition for insulating layers of the multilayer printed wiring board which forms a conductor layer by plating, The resin composition of any one of the Claims 1-13 characterized by the above-mentioned.   The resin composition according to any one of claims 1 to 14, which is a resin composition for a buildup layer of a multilayer printed wiring board.   A sheet-like laminate material comprising the resin composition according to any one of claims 1 to 15.   The multilayer printed wiring board in which the insulating layer was formed of the hardened | cured material of the resin composition of any one of Claims 1-15.   A semiconductor device using the multilayer printed wiring board according to claim 17.