JP6489148B2 - Resin composition - Google Patents

Description

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

  2. Description of the Related Art In recent years, electronic devices have been reduced in size and performance, and in multilayer printed wiring boards, build-up layers have been multilayered, and miniaturization and high density of wiring have been demanded.

  Various approaches have been made against this. For example, Patent Document 1 discloses that the filler is surface-treated with a silane-based or titanium-based coupling agent. However, there is no description about alkoxysilane compounds. Moreover, although patent document 2 has the description of the alkoxysilane compound, there is no specific description and it is not intended for the present invention.

JP 2006-224644 A JP 2008-74668 A

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

  As a result of intensive studies to solve the above problems, the inventors of the present invention provide a resin composition comprising an inorganic filler surface-treated with an epoxy resin, a curing agent, and an alkoxysilane compound. It came to be completed.

That is, the present invention includes the following contents.
[1] A resin composition comprising an inorganic filler surface-treated with an epoxy resin, a curing agent and an alkoxysilane compound, wherein the inorganic filler has an average particle size of 0.01 to 5 μm, and the resin composition A resin composition, wherein the content of the inorganic filler is 30 to 90% by mass when the non-volatile component in the content is 100% by 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 includes 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 [2] The resin composition according to [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 according to any one of [1] to [3].
[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], wherein the resin composition is one or more selected from the group consisting of:
[6] The resin composition according to any one of [1] to [5], wherein the alkoxysilane compound has a molecular weight of 100 to 1000.
[7] The resin composition as described in any one of [1] to [6], wherein the inorganic filler is silica.
[8] The resin composition according to any one of [1] to [7], wherein the alkoxysilane compound 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 inorganic filler has a carbon amount per unit surface area of 0.01 to 0.8 mg / m ² .
[10] The epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, glycidyl ester type epoxy resin, anthracene type The resin composition according to any one of [1] to [9], which is one or more selected from an epoxy resin and an epoxy resin having a butadiene structure.
[11] The curing agent according to any one of [1] to [10], wherein the curing agent is at least one selected from a phenolic curing agent, an active ester curing agent, and a cyanate ester curing agent. Resin composition.
[12] Activity in which the curing agent includes 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, or a dicyclopentadienyl diphenol structure [1] to [11], which are one or more selected from ester-based curing agents, novolak-type cyanate ester-based curing agents, dicyclopentadiene-type cyanate ester-based curing agents, and bisphenol-type cyanate ester-based curing agents. ] The resin composition in any one of these.
[13] The resin composition is cured to form an insulating layer, the arithmetic average roughness after roughening the surface of the insulating layer is 400 nm or less, and the root mean square roughness is 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, the arithmetic average roughness after roughening the surface of the insulating layer is 10 to 400 nm, and the root mean square roughness is 30 to 500 nm. The resin composition according to any one of [1] to [13].
[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 conductor layer and the insulating layer obtained by plating is 0.3 to 1.2 kgf / cm It is above, The resin composition in any one of [1]-[14] characterized by the above-mentioned.
[16] The resin composition as described in 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].
[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].

  By using a resin composition containing an inorganic filler that has been surface-treated with an epoxy resin, a curing agent, and an alkoxysilane compound, the arithmetic average roughness of the surface of the insulating layer in the wet roughening step is not only low, but also the root mean square A plated conductor layer having a small roughness and a sufficient peel strength can be formed thereon, and a resin composition having excellent laminating properties can be provided.

  The present invention is a resin composition comprising an inorganic filler surface-treated with an epoxy resin, a curing agent and 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 is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol. Type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, wire Aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol 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, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type from the viewpoint of improving heat resistance, laminating property, and peel strength. It is preferable to use one or more selected from epoxy resins, glycidyl ester type epoxy resins, anthracene type epoxy resins, and epoxy resins having a butadiene structure. Specifically, for example, bisphenol A type epoxy resin (“Epicoat 828EL”, “YL980” manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (“jER806H”, “YL983U” manufactured by Mitsubishi Chemical Corporation), 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 butadiene structure (“PB-3600” manufactured by Daicel Chemical Industries, Ltd.), epoxy resin having biphenyl structure (Nipponization) “NC3000H”, “NC3000L”, “NC31” manufactured by Yakuhin Co., Ltd. "00", "YX4000", "YX4000H", "YX4000HK", "YL6121") manufactured by Mitsubishi Chemical Corporation, anthracene type epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Corporation), naphthylene ether type epoxy resin (DIC) “EXA-7310”, “EXA-7311”, “EXA-7311L”, “EXA7311-G3”), glycidyl ester type epoxy resin (“EX711”, “EX721” manufactured by Nagase ChemteX Corp.) ("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 a liquid at a temperature of 20 ° C. The solid epoxy resin has three or more epoxy groups in one molecule. And an aromatic epoxy resin that is solid at a temperature of 20 ° C. is preferable. 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 using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, the resin composition has moderate flexibility when used in the form of an adhesive film, and the point that the laminating property is improved and the resin composition is cured. From the point that the surface roughness of the product can be lowered, the blending ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 1: 2 by mass ratio, and 1: 0.3. A range of ˜1: 1.8 is more preferred, and a range of 1: 0.6 to 1: 1.5 is even more preferred.

  As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, glycidyl ester type epoxy resin, or naphthalene type epoxy resin are preferable, bisphenol A type epoxy resin, bisphenol F type epoxy resin, Or a naphthalene type epoxy resin is more preferable. You may use these 1 type or in combination of 2 or more types. As the 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 naphthylene. An ether type epoxy resin is preferable, and a naphthol type epoxy resin or a biphenyl type epoxy resin is more preferable. You may use these 1 type or in combination of 2 or more types.

  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, when the nonvolatile component in the resin composition is 100% by mass, the content of the epoxy resin is 3 to 3. 40 mass% is preferable, 5-30 mass% is more preferable, and 10-20 mass% is still more preferable.

<Curing agent>
The curing agent used in the present invention is not particularly limited, and examples thereof include phenolic curing agents, active ester curing agents, cyanate ester curing agents, benzoxazine curing agents, acid anhydride curing agents, and the like. From the viewpoint of further reducing the average roughness (Ra value) and the root mean square roughness (Rq value), one or more selected from phenolic curing agents, active ester curing agents and cyanate ester curing agents are used. It is preferable. These may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular as a phenol type hardening | curing agent, A biphenyl type hardening | curing agent, a naphthalene type hardening | curing agent, a phenol novolak type hardening | curing agent, a naphthylene ether type hardening | curing agent, and a triazine skeleton containing phenol type hardening | curing agent are preferable. Specifically, biphenyl type curing agents MEH-7700, MEH-7810, MEH-7785 (Maywa Kasei Co., Ltd.), naphthalene type curing agents NHN, CBN, GPH (Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Nippon Steel Chemical Co., Ltd.), EXB9500 (manufactured by DIC Corporation), phenol novolac type curing agent TD2090 (manufactured by DIC Corporation), Examples include naphthylene ether type curing agents EXB-6000 (manufactured by DIC Corporation), triazine skeleton-containing phenolic curing agents LA3018, LA7052, LA7054, LA1356 (manufactured by DIC Corporation), and the like. These may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester 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. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like. 1 type (s) or 2 or more types can be used for an active ester type hardening | curing agent. 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 hardeners include active ester hardeners containing dicyclopentadienyl diphenol structures, active ester hardeners containing naphthalene structures, and active ester hardeners that are acetylated phenol novolacs. An active ester type curing agent that is a benzoylated product of phenol novolac is preferable, and an active ester type curing agent containing a dicyclopentadienyl diphenol structure is more preferable in terms of excellent peel strength. Specifically, EXB9451, EXB9460, EXB9460S-65T, HPC-8000-65T (produced by DIC Corporation, active group equivalent of about 223), an acetylated product of phenol novolak as a dicyclopentadienyl diphenol structure. DC808 (manufactured by Mitsubishi Chemical Corporation, active group equivalent of about 149) as an active ester type curing agent, YLH1026 (manufactured by Mitsubishi Chemical Corporation, active group equivalent of about 200) as an active ester type curing agent that is a benzoylated phenol novolak. ), YLH1030 (Mitsubishi Chemical Corporation, active group equivalent of about 201), YLH1048 (Mitsubishi Chemical Corporation, active group equivalent of about 245) and the like.

  More specifically, the active ester curing agent containing a dicyclopentadienyl diphenol structure includes a compound represented by 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。）

(In the formula, R is 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 reducing 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.

  Although there is no restriction | limiting in particular as cyanate ester type hardening | curing agent, Novolac type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening agent, dicyclopentadiene type cyanate ester type hardening agent, bisphenol type (bisphenol A type, bisphenol) Fate, bisphenol S type, etc.) cyanate ester curing agents, and prepolymers in which these are partially triazines. Although the weight average molecular weight of a cyanate ester hardening | curing agent is not specifically limited, 500-4500 are preferable and 600-3000 are more preferable. Specific examples of the cyanate ester curing agent include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3, Bifunctional cyanate resins such as 5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether , Phenol novolac, Examples thereof include polyfunctional cyanate resins derived from resole novolac, dicyclopentadiene structure-containing phenol resins, prepolymers in which these cyanate resins are partially triazines, and these may be used alone or in combination of two or more. Examples of commercially available cyanate ester resins include phenol novolac polyfunctional cyanate ester resins represented by the following formula (2) (Lonza Japan Co., Ltd., PT30, cyanate equivalent 124), and the following formula (3): Prepolymer (part Lona Japan Co., Ltd., BA230, cyanate equivalent 232), dicyclopentadiene represented by the following formula (4): a part or all of the bisphenol A dicyanate represented by triazine Structure-containing cyanate ester resin (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 formula, n shows arbitrary numbers (preferably 0-20) as an average value. ]

（式中、ｎは平均値として０〜５の数を表す。）

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

  Although there is no restriction | limiting in particular as a benzoxazine type hardening | curing agent, As a specific example, Fa, Pd (made by Shikoku Kasei Co., Ltd.), HFB2006M (made by Showa Polymer Co., Ltd.), etc. are mentioned.

  The acid anhydride curing agent is not particularly limited, but phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid 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, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3 ' -4,4'-diphenylsulfonetetracarboxylic 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 (anhydrotrimellitate) ), And polymer type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized.

  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 ratio of the total number of epoxy groups of the epoxy resin and the total number of reactive groups of the curing agent is: 1: 0.2-1: 2 is preferable, 1: 0.3-1: 1.5 is more preferable, and 1: 0.4-1: 1 is still more preferable. The total number of epoxy groups of the epoxy resin present in the resin composition is a value obtained by dividing the solid content mass 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 a value obtained by adding the values obtained by dividing the solid mass of each curing agent by the reactive group equivalent for all curing agents.

<Inorganic filler surface-treated with alkoxysilane compound>
Although it does not specifically limit as an alkoxysilane compound of the inorganic filler surface-treated with the alkoxysilane compound used for this invention, From the point of the laminating improvement at the time of making a resin composition into a sheet form, an alkyl group and / or It preferably contains an aryl group, more preferably one or more selected from the group consisting of an alkyl group, an aryl group and an alkoxysilyl group bonded to a silicon atom. As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable from the viewpoint of preventing the viscosity increase of the resin varnish, and a methyl group And more preferably one or more selected from ethyl, propyl, isopropyl and cyclopropyl. 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, diphenyl dialkoxysilane, methylphenyl dialkoxysilane, and diphenylmethylmonoalkoxysilane. It is preferable to use 1 or more types selected from. From the viewpoint of improving the peel strength, it is preferable to have 2-3 alkoxy groups per alkoxysilyl group, and the alkoxy group is preferably a methoxy group or an ethoxy group. Moreover, the alkoxysilyl group may be modified. These alkoxysilane compounds are excellent in productivity and environment without generation of toxic gases during surface treatment. Further, unlike a coupling agent having an organic functional group, an alkoxysilane compound is excellent in that hydrophobicity is improved and compatibility with a resin is improved. Furthermore, unlike a coupling agent having an organic functional group, an alkoxysilane compound is superior in that it does not self-aggregate during surface treatment and is easily surface treated. Therefore, by using an inorganic filler surface-treated with an alkoxysilane compound, it is possible to improve the peel strength while improving laminating properties 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 still 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" (diethyldi) Ethoxysilane), “LS-890” (ethyltrimethylsilane), “LS-5300” (diphenyldimethoxysilane), “LS-2720” methylphenyldimethoxysilane, “LS-5610” (diphenylmethylmethoxysilane) and the like. It is done.

  The inorganic filler of the inorganic filler surface-treated with the alkoxysilane compound used in the present invention is not particularly limited. For example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, 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. Can be mentioned. Of these, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica is preferable. In particular, fused silica and spherical silica are more preferable in terms of reducing the surface roughness of the insulating layer. Preferably, spherical fused silica is more preferable. You may use these 1 type or in combination of 2 or more types.

  The average particle size of the inorganic filler is not particularly limited, but the upper limit value 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 formation. Is preferably 4 μm or less, more preferably 3 μm or less, still more preferably 2 μm or less, even 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, the lower limit value of the average particle size of the inorganic filler is 0.01 μm or more from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from being lowered when the resin composition is a resin varnish. Preferably, it is 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 diameter 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 particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction / scattering particle size distribution measuring apparatus, LA-750 manufactured by Horiba, Ltd. or the like 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, it is 90% from the viewpoint of preventing the cured product from becoming brittle and from reducing the peel strength. % Or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, and even more preferably 75% by weight or less. On the other hand, 30 mass% or more is preferable from the point of reducing the thermal expansion coefficient of hardened | cured material, 40 mass% or more is more preferable, 50 mass% or more is further more preferable, and 60 mass% or more is still more preferable.

  In the inorganic filler surface-treated with the alkoxysilane compound, the amount of the alkoxysilane compound surface-treating the inorganic filler is not particularly limited, but the alkoxysilane compound is reduced to 0 with respect to 100 parts by mass of the inorganic filler. The surface treatment is preferably performed at 0.05 to 4 parts by mass, more preferably 0.1 to 3 parts by mass, and even more preferably 0.2 to 2 parts by mass. Even more preferably, the surface treatment is performed at 1 part by mass.

  In addition, 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 amount of carbon per unit surface area of the inorganic filler is obtained. Can do. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.

  Specifically, a sufficient amount of MEK as a solvent is added to an 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 amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.

The amount of carbon per unit surface area of the inorganic filler is 0. in terms of improving the dispersibility of the inorganic filler and stabilizing the arithmetic average roughness and the root mean square roughness after the wet roughening step of the cured product. 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, 0.8 mg / m ² or less is preferable, 0.5 mg / m ² or less is more preferable, and 0.3 mg / m ² or less is preferable in terms of preventing an increase in the melt viscosity of the resin varnish or the adhesive film. 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.

  The surface treatment method for the inorganic filler surface-treated with the alkoxysilane compound is not particularly limited, and examples thereof include a dry method and a wet method. As a dry method, an inorganic filler is charged in a rotary mixer, and an alcohol solution or an aqueous solution of an alkoxysilane compound is dropped or sprayed while stirring, and then further stirred and classified by sieving. Thereafter, it can be obtained by dehydrating 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, classification is performed by filtration, drying, and sieving. Thereafter, it can be obtained by dehydrating condensation of the alkoxysilane compound and the inorganic filler by heating. Furthermore, an integral blend method in which an alkoxysilane compound is added to the resin composition is also possible.

<Curing accelerator>
When the resin composition of the present invention further contains a curing accelerator, the epoxy resin and the curing agent can be efficiently cured. Although it does not specifically limit as a hardening accelerator, An amine hardening accelerator, a guanidine hardening accelerator, an imidazole hardening accelerator, a phosphonium hardening accelerator, a metal hardening accelerator, etc. are mentioned. These may be used alone or in combination of two or more.

  The amine curing accelerator is not particularly limited, but trialkylamines such as triethylamine and 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). You may use these 1 type or in combination of 2 or more types.

  Although it does not specifically limit as a guanidine type hardening accelerator, Dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, dimethyl guanidine , Diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-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-phenyl Rubiguanido, 1-(o-tolyl) biguanide, and the like. You may use these 1 type or in combination of 2 or more types.

  The imidazole 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. You may use these 1 type or in combination of 2 or more types.

  Although it does not specifically limit as a phosphonium type hardening accelerator, Triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. You may use these 1 type or in combination of 2 or more types.

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

  Although it does not specifically limit as a metal type hardening accelerator, The organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.

  In the resin composition of the present invention, the addition amount of the metal-based curing accelerator is such that the content of the metal based on the metal-based curing catalyst is 25 to 500 ppm when the nonvolatile component in the resin composition is 100% by mass. Preferably, the range of 40-200 ppm is more preferable. Within this range, a conductor layer having superior adhesion to the surface of the insulating layer is formed, and the storage stability of the resin varnish is also improved.

<Thermoplastic resin>
By adding a thermoplastic resin to the resin composition of the present invention, the mechanical strength of the cured product can be improved, and the film molding ability 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, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone 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. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by 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. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  When a thermoplastic resin is blended with the resin composition of the present invention, the content of the thermoplastic resin in the resin composition is not particularly limited, but the non-volatile component in the resin composition is 100% by mass. 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 forming ability and mechanical strength can be exhibited, and the melt viscosity can be increased and the roughness of the insulating layer surface after the wet roughening step can be reduced.

<Rubber particles>
When the resin composition of the present invention further contains rubber particles, the plating peel strength can be improved, and drilling workability can be improved, the dielectric loss tangent can be reduced, 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 an organic solvent used when preparing the varnish of the resin composition and are incompatible with an epoxy resin or the like. Accordingly, the rubber particles exist 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 it does not dissolve in an organic solvent or resin and making it into particles.

  Preferable examples of rubber particles that can be used in the present invention include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which an outer shell layer is made of a glassy polymer and an inner core layer is made of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glassy polymer layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). Two or more rubber particles may be used in combination. Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N, AC3401N, IM-401 modified 7-17 (trade name, manufactured by Gantz Kasei Co., Ltd.), Metabrene KW-4426 (trade name, Mitsubishi Rayon Co., Ltd.) Manufactured). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size: 0.5 μm, manufactured by JSR Corporation). Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include Methbrene W300A (average particle size 0.1 μm) and W450A (average particle size 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.).

  The average particle diameter of the rubber particles to be blended is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of the rubber particles used in the present invention can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and a particle size distribution of rubber particles is created on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). And 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 nonvolatile 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 an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. Examples of organic phosphorus flame retardants include 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 Polymer Co., Ltd., and Ajinomoto Reefos 30, 50, 65, 90, 110, Fine Techno Co., TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, TPPO, PPQ, manufactured by Hokuko Chemical Co., Ltd. Phosphoric ester compounds such as OP930 manufactured by Clariant Co., Ltd., PX200 manufactured by Daihachi Chemical Co., Ltd., phosphorus-containing epoxy resins such as FX289, FX305 and TX0712 manufactured by Nippon Steel Chemical Co., Ltd., Nippon Steel Chemical Co., Ltd. Phosphorus-containing phenoxy resins such as ERF001 manufactured by Co., Ltd., phosphorus-containing epoxy resins such as YL7613 manufactured by Mitsubishi Chemical Corporation, etc. And the like. Examples of organic nitrogen-containing phosphorus compounds include phosphoric ester amide compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd., and FP-series manufactured by Fushimi Pharmaceutical Co., Ltd. Phosphazene compounds such as As the metal hydroxide, magnesium hydroxide such as UD65, UD650, UD653 manufactured by Ube Materials Co., Ltd., B-30, B-325, B-315, B-308 manufactured by Sakai Kogyo Co., Ltd. Examples thereof include aluminum hydroxide such as B-303 and UFH-20.

  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 nonvolatile component in the resin composition.

<Other ingredients>
In the resin composition of the present invention, other components can be blended as necessary within a range not inhibiting the effects of the present invention. Other components include vinyl benzyl compounds, acrylic compounds, maleimide compounds, thermosetting resins such as blocked isocyanate compounds, organic fillers such as silicon powder, nylon powder and fluorine powder, thickeners such as Orben and Benton, Silicone-based, fluorine-based, polymer-based antifoaming or leveling agents, imidazole-based, thiazole-based, triazole-based, silane coupling agents, and other adhesion-imparting agents, phthalocyanine blue, phthalocyanine green, iodin green, disazo Examples thereof include colorants such as yellow and carbon black, and surface treatment agents such as silane coupling agents and titanate coupling agents.

  The resin composition of the present invention is appropriately mixed with the above components and, if necessary, kneaded or mixed by a kneading means such as a three-roll, ball mill, bead mill, or sand mill, or a stirring means such as a super mixer or a planetary mixer. It can be adjusted by doing. Moreover, it can adjust also as a resin varnish by adding an organic solvent.

  In the resin composition of the present invention, in the wet roughening step, not only the arithmetic average roughness of the insulating layer surface is low, but also the root mean square roughness is small, and a plated conductor layer having sufficient peel strength is formed thereon. Therefore, in the production of a multilayer printed wiring board, it can be suitably used as a resin composition (resin composition for an insulating layer of a multilayer printed wiring board) for forming an insulating layer. It can be more suitably used as a resin composition for forming (a resin composition for an insulating layer of a multilayer printed wiring board in which a conductor layer is formed by plating). That is, it is suitable as a resin composition for buildup layers of multilayer printed wiring boards.

  The arithmetic average roughness (Ra value) and the root mean square roughness (Rq value) after curing the resin composition of the present invention to form an insulating layer and roughening the surface of the insulating layer will be described later. It can be grasped by the measuring method described in the section “Measurement of arithmetic average roughness (Ra value) and root mean square roughness (Rq value) after roughening>.

  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, even more preferably 250 nm or less, and even more preferably 200 nm or less in order to reduce transmission loss of electric signals. Is more 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 is preferably 10 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more from the viewpoint of stabilizing the peel strength.

  Since the root mean square roughness (Rq value) reflects the local state of the insulating layer surface, it was found that the surface of the insulating layer can be confirmed to be dense and smooth by grasping the Rq value. The upper limit of the root mean square roughness (Rq value) is preferably 500 nm or less, more preferably 450 nm or less, still more preferably 400 nm or less, 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 is preferably 30 nm or more, more preferably 70 nm or more, and still more preferably 120 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 between the conductor layer and the insulating layer obtained by plating is described in <Plating conductor layer pulling> It can be grasped by the measurement method described in Measurement of Peel Strength (Peel Strength)>.

  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. More preferably, it is 45 kgf / cm or more. The upper limit of peel strength is preferably as high as possible, and is not particularly limited, but is generally 1.2 kgf / cm or less, 1.0 kgf / cm or less, 0.8 kgf / cm or less, and the like.

  Although the use of the resin composition of the present invention is not particularly limited, sheet-like laminated materials such as adhesive films and prepregs, circuit boards (for laminated boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, die 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-filling resin. The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but in general, it is preferably used in the form of a sheet-like laminated 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 laminate property of the sheet-like laminated material.

<Sheet 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, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish to a support using a die coater or the like. It can be produced by drying the organic solvent by heating or blowing hot air to form the resin composition layer.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. And aromatic hydrocarbons such as toluene and xylene, 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 resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. 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.

  Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films. Various plastic films are listed. Moreover, you may use release foil, metal foil, such as copper foil and aluminum foil. Among these, from the viewpoint of versatility, a plastic film is preferable, and a polyethylene terephthalate film is more preferable. The support and a protective film described later may be subjected to surface treatment such as mud treatment or corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.

  Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.

  A protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact. 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 dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can also be stored in a roll.

(Prepreg)
The prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing base material 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 impregnated the sheet-like reinforcement base material with the resin composition of this invention. As a sheet-like reinforcement base material, what consists of a fiber currently used as prepreg fibers, such as glass cloth and an aramid fiber, can be used, for example. And what formed the prepreg on the support body is suitable.

  In the hot melt method, the resin composition is once coated on a support without being dissolved in an organic solvent, and then laminated on a sheet-like reinforcing substrate, or directly applied to a sheet-like reinforcing substrate by a die coater. Thus, a prepreg is manufactured. In the solvent method, a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as the adhesive film, and a sheet-like reinforcing base material is immersed in the varnish, and then the resin-like varnish is impregnated into the sheet-like reinforcing base material. It is a method of drying. Alternatively, the adhesive film can be prepared by continuously laminating the adhesive film from both sides of the sheet-like reinforcing substrate under heating and pressure conditions. A support, a protective film, and the like can 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 laminated material produced as described above will be described.

  First, a sheet-like laminated 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 here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, 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 as necessary, and the sheet-like laminate material is pressurized and Laminate to circuit board while heating. In the sheet-like laminated material of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure (laminating pressure) is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), the pressure bonding time (laminating time) is preferably 5 to 180 seconds, and the lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll. The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.

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

Moreover, a sheet-like laminated material can also be laminated | stacked on the single side | surface or both surfaces of a circuit board using a vacuum press machine. The lamination process for heating and pressurizing under reduced pressure can be performed using a general vacuum hot press machine. For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side. The pressing condition is that the degree of vacuum is usually 1 × 10 ⁻² MPa or less, preferably 1 × 10 ⁻³ MPa or less. Although heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the oozing of the resin. For example, the first stage press has a temperature of 70 to 150 ° C. and the pressure is in the range of 1 to 15 kgf / cm 2, and the second stage press has the temperature of 150 to 200 ° C. and the pressure is in the range of 1 to 40 kgf / cm 2 Preferably it is done. The time for each stage is preferably 30 to 120 minutes. Thus, an insulating layer can be formed on a circuit board by thermosetting the resin composition layer. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

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

  Next, a roughening process is performed on the surface of the insulating layer. In the case of dry-type roughening treatment, plasma treatment and the like can be mentioned, and in the case of wet-type roughening treatment, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid are performed in this order. It is done. The wet roughening treatment is preferable in that 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 liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 5 to 20 minutes (preferably at 55 to 70 ° C. for 8 to 15 minutes). Examples of the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of the commercially available swelling liquid include Swelling Dip Securiganth P (Swelling Dip Securiganth P) and Swelling Dip Securiganth SBU (ABUTEC Japan). be able to. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ° C. for 10 to 30 minutes (preferably at 70 to 80 ° C. for 15 to 25 minutes). Examples of the oxidizing agent include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. 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 and Dosing Solution Securigans P manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is performed by immersing in a neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes (preferably at 35 to 45 ° C. for 3 to 8 minutes). As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.

  Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. Examples of wet plating include a method in which a conductive layer is formed by combining electroless plating and electrolytic plating, a method in which a plating resist having a pattern opposite to that of the conductive layer is formed, and a conductive layer is formed only by electroless plating. It is done. As a pattern formation method thereafter, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. 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 build-up layer of a multilayer printed wiring board.

<Semiconductor device>
A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor chip in a conductive portion of the multilayer printed wiring board of the present invention. The “conduction location” is a “location where an electrical signal is transmitted 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 for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. “Part” means part by mass.

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

[Preparation of samples for peel strength, arithmetic average roughness (Ra value), root mean square roughness (Rq value)]
(1) Underlayer treatment of inner layer circuit board Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works R5715ES) on which an inner layer circuit is formed The copper surface was roughened by etching 1 μm with CZ8100 manufactured by MEC Co., Ltd.

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

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

(4) Roughening treatment The inner layer circuit board on which the insulating layer is formed is a swelling liquid, diethylene glycol monobutyl ether-containing swelling dip securigant P (glycol ethers, aqueous solution of sodium hydroxide) of Atotech Japan Co., Ltd. And soaking at 60 ° C. for 10 minutes. Next, as a roughening liquid, it was immersed in the concentrate compact P (KMnO4: 60g / L, NaOH: 40g / L aqueous solution) of Atotech Japan Co., Ltd. for 20 minutes at 80 ° C. Finally, as a neutralizing solution, it was immersed for 5 minutes at 40 ° C. in Reduction Sholysin Securigant P (an aqueous solution of sulfuric acid) of Atotech Japan Co., Ltd. After drying at 80 ° C. for 30 minutes, arithmetic surface roughness (Ra value) and root mean square roughness (Rq value) were measured on the surface of the insulating layer after the roughening treatment.

(5) Plating by semi-additive method In order to form a circuit on the surface of the insulating layer, the inner layer circuit board is immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then in an electroless copper plating solution. It was immersed for 20 minutes at 25 ° C. After annealing for 30 minutes at 150 ° C., an etching resist was formed. After pattern formation 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 circuit board was measured for peel strength (peel strength) of the plated conductor layer.

[Measurement of arithmetic average roughness (Ra value) and root mean square roughness (Rq value) after roughening]
Using a non-contact type surface roughness meter (WYKO NT3300, manufactured by Beeco Instruments), Ra value and Rq value were obtained from numerical values obtained with a measurement range of 121 μm × 92 μm by a VSI contact mode and a 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]
Make a notch of 10mm width and 100mm length in the conductor layer of the circuit board, peel off one end and grasp it with a gripping tool (TSE Co., Ltd., Autocom type testing machine AC-50C-SL), The load (kgf / cm) when peeling 35 mm in the vertical direction at a speed of 50 mm / min at room temperature was measured.

[Evaluation of laminating properties]
The adhesive films produced in the examples and comparative examples were 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, manufactured by Meiki Co., Ltd.). : Interval width) = 160/160 μm was laminated on a comb-like conductor pattern. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. The PET film was peeled from the laminated adhesive film, and the resin composition was cured under curing conditions at 180 ° C. for 30 minutes to form an insulating layer. The value of the unevenness difference (Rt: maximum peak-to-valley) between the conductor and other portions in the insulating layer is determined using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Beeco Instruments Inc.), VSI contact mode, The value was obtained by a numerical value obtained with a 10 × lens with a measurement range of 1.2 mm × 0.91 mm. In addition, there is no generation of voids after lamination, and the difference in unevenness between the conductor and other portions is less than 5 μm, and no void is generated after lamination, but the unevenness difference between the conductor and other portions is 5 μm. The case above was evaluated as Δ, and the case where void occurred after lamination was evaluated as ×.

[Inorganic filler used]
Inorganic filler 1: Phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM103”, molecular weight: 198.100 parts with respect to 100 parts of spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm). 3) Surface treatment with 0.3 part, carbon amount per unit surface area of 0.126 mg / m2.

Inorganic filler 2: dimethyldiethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBE-22”, molecular weight) with respect to 100 parts of spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm) 148.3) Surface treated with 0.3 part, carbon amount per unit surface area 0.063 mg / m2.

Inorganic filler 3: Phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM103”, molecular weight 198.100) with respect to 100 parts of spherical silica (“SO-C1” manufactured by Admatechs, average particle size of 0.25 μm). 3) Surface treated with 0.5 part, carbon amount per unit surface area 0.083 mg / m2.

Inorganic filler 4: Epoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM403”, molecular weight 236) with respect to 100 parts of spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm) Surface treated with 5 parts, carbon amount per unit surface area 0.19 mg / m2

Inorganic filler 5: Spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm) not surface-treated.

Inorganic filler 6: Spherical silica (“SO-C1” manufactured by Admatechs, average particle size of 0.25 μm) not surface-treated.

<Example 1>
8 parts of naphthalene type epoxy resin (epoxy equivalent 144, “EXA4032SS” manufactured by DIC Corporation), 11 parts of bixylenol type epoxy resin (epoxy equivalent 190, “YX4000HK” manufactured by Mitsubishi Chemical Corporation), modified naphthalene type epoxy resin 9 parts (epoxy equivalent: about 330, “ESN475V” manufactured by Nippon Steel Chemical Co., Ltd.) were dissolved in 32 parts of solvent naphtha with stirring and then cooled to room temperature. To the mixed solution, 1.5 parts of rubber particles (manufactured by Gantz Kasei Co., Ltd., AC3816N) were mixed in 6 parts of solvent naphtha for 12 hours at 20 ° C. and further 140 parts of inorganic filler 1 were mixed. It was kneaded with three rolls and dispersed uniformly. Thereto, 45 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution having a non-volatile content of 65 mass% with an active group equivalent of about 223), a phenoxy resin (weight average molecular weight 35000, Mitsubishi Chemical) "YL7553" manufactured by Co., Ltd .: 5 parts of a 30% by mass MEK and cyclohexanone 1: 1 solution), 1 part of a 10% by weight MEK solution of 4-dimethylaminopyridine as a curing accelerator, 7 parts of methyl ethyl ketone (MEK) Were mixed uniformly with a rotary mixer to prepare a resin varnish. Next, the resin composition layer after drying is 40 μm on the release surface of the polyethylene terephthalate film with alkyd release treatment (“AL5” manufactured by Lintec Co., Ltd., thickness 38 μm). As above, it was uniformly coated with 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 the same manner as in Example 1 except that the inorganic filler 1 was changed to the inorganic filler 2. Next, an adhesive film was obtained in exactly the same manner as in Example 1.

<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. Next, an adhesive film was obtained in exactly the same manner as in Example 1.

<Example 4>
5 parts of naphthalene type epoxy resin (epoxy equivalent 144, “HP4700” manufactured by DIC Corporation), liquid bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd.), 1: 1 of bisphenol A type and bisphenol F type 14 parts of a mixed product) and 14 parts of a biphenyl type epoxy resin (epoxy equivalent 269, “NC3000H” manufactured by Nippon Kayaku Co., Ltd.) were dissolved in 30 parts of solvent naphtha with heating and then cooled to room temperature. To the mixed solution, 1.5 parts of rubber particles (manufactured by Ganz Kasei Co., Ltd., AC3816N) were added to 6 parts of solvent naphtha for 12 hours at 20 ° C., and 140 parts of inorganic filler 1 were added. Furthermore, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 1 μm ) 5 parts were added and kneaded with three rolls and dispersed. There, 10 parts of phenol novolac-based curing agent (“LA-7054” manufactured by DIC Corporation, MEK solution having a non-volatile content of 60% by mass of phenolic hydroxyl group equivalent 124), naphthalene-based phenol resin (phenolic hydroxyl group equivalent 215, new) “SN485” manufactured by Nippon Steel Chemical Co., Ltd., 10 parts by mass of MEK solution having a nonvolatile content of 60% by mass, phenoxy resin (weight average molecular weight 35000, “YL7553” manufactured by Mitsubishi Chemical Co., Ltd., 30% by mass of MEK and cyclohexanone 1: 1 solution) 7 parts, 2 parts of a 5% by weight MEK solution of 4-dimethylaminopyridine as a curing accelerator, and 4 parts of MEK were mixed and dispersed uniformly with a rotary mixer to prepare a resin varnish. Next, an adhesive film was obtained in exactly the same manner as in Example 1.

<Example 5>
10 parts of a naphthalene type epoxy resin (“EXA4032SS” 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 (“ESN475V” manufactured by Nippon Steel Chemical Co., Ltd.), phenoxy resin (weight average molecular weight 35000, “YL7553” manufactured by Mitsubishi Chemical Co., Ltd.), MEK having 30% by mass of nonvolatile components and cyclohexanone (1: 1 solution) 7 parts were dissolved 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% solids toluene solution), prepolymer of bisphenol A dicyanate (“BA230S75” manufactured by Lonza Japan Co., Ltd.) 20 parts of cyanate equivalent about 232, MEK solution with non-volatile content of 75% by mass), phenol novolac type polyfunctional cyanate ester resin ("PT30S" manufactured by Lonza Japan Co., Ltd., MEK solution with cyanate equivalent of about 133, non-volatile content of 85% by mass) 10 parts, 4 parts of rubber particles (manufactured by Ganz Kasei Co., Ltd., AC3816N) swollen in 16 parts of solvent naphtha at room temperature for 12 hours, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxai , 3 parts of average particle size 1), 0.1 part of curing accelerator (4-dimethylaminopyridine, MEK solution having a solid content of 10% by mass), curing accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt (III) acetylacetate) 4.5 parts of MET solution with a solid content of 1% by weight, and 140 parts of inorganic filler 1 were further mixed and dispersed uniformly with a rotary mixer to prepare a resin varnish. Next, an adhesive film was obtained in exactly the same manner as in Example 1.

<Comparative Example 1>
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 4. Next, an adhesive film was obtained in exactly the same manner as in Example 1.

<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. Next, an adhesive film was obtained in exactly the same manner as in Example 1.

<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. Next, an adhesive film was obtained in exactly the same manner as in Example 1.

  The results are shown in Table 1.

  From the results in Table 1, it can be seen that the resin compositions of the examples have a low arithmetic average roughness, a low root mean square roughness, a sufficient peel strength, and a good laminating property. Note that the Rq value reflects a local state on the surface of the insulating layer, and thus it can be seen that the Rq value is reduced to a dense rough surface. On the other hand, in the comparative example, the arithmetic average roughness and the root mean square roughness were large, the peel strength was small, and the laminate property was poor.

  In the wet roughening step, not only the arithmetic average roughness of the insulating layer surface is low, but also the root mean square roughness is small, a plated conductor layer having sufficient peel strength can be formed thereon, and the laminate property is also excellent. A resin composition can be provided. Furthermore, sheet-like laminated materials, multilayer printed wiring boards, and semiconductor devices using the same can be provided. Furthermore, electric products such as computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, and airplanes equipped with these can be provided.

Claims (15)

A resin composition for a build-up layer of a multilayer printed wiring board containing an inorganic filler surface-treated with an epoxy resin, a curing agent and an alkoxysilane compound,
The curing agent is a phenolic curing agent;
The alkoxysilane compound is selected from phenyltrialkoxysilane, dimethyldialkoxysilane, methyltrialkoxysilane, diethyldialkoxysilane, ethyltrialkoxysilane, diphenyldialkoxysilane, methylphenyl dialkoxysilane and diphenylmethylmonoalkoxysilane. One or more
The inorganic filler has an average particle size of 0.01 to 5 μm,
When the non-volatile component in a resin composition is 100 mass%, content of this inorganic filler is 50-90 mass%, The resin composition characterized by the above-mentioned.   The resin composition according to claim 1, wherein the alkoxysilane compound has a molecular weight of 100 to 1,000.   The resin composition according to claim 1 or 2, wherein the inorganic filler is silica.   The resin composition according to any one of claims 1 to 3, wherein the alkoxysilane compound is surface-treated with 0.05 to 4 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 1, characterized in that the 0.01~0.8mg / ^{m 2.}   The resin composition according to claim 1, wherein the inorganic filler has an average particle size of 0.1 μm or more.   The resin composition according to any one of claims 1 to 6, wherein the content of the inorganic filler is 60% by mass or more when the nonvolatile component in the resin composition is 100% by mass.   The epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, glycidyl ester type epoxy resin, anthracene type epoxy resin, and The resin composition according to claim 1, wherein the resin composition is at least one selected from epoxy resins having a butadiene structure.   The curing agent is at least one selected from a biphenyl type curing agent, a naphthalene type curing agent, a phenol novolac type curing agent, a naphthylene ether type curing agent, and a triazine skeleton-containing phenol type curing agent. The resin composition of any one of Claims 1-8.   The arithmetic average roughness after curing the resin composition to form an insulating layer and roughening the surface of the insulating layer is 400 nm or less, and the root mean square roughness is 500 nm or less. Item 10. The resin composition according to any one of Items 1 to 9.   The arithmetic average roughness after the resin composition is cured to form an insulating layer and the surface of the insulating layer is roughened is 10 to 400 nm, and the root mean square roughness is 30 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 conductor layer and the insulating layer obtained by plating is 0.3 to 1.2 kgf / cm or more. The resin composition according to any one of claims 1 to 11, wherein: A sheet-like laminated material comprising the resin composition according to any one of claims 1 to 12 . Multilayer printed wiring board having an insulating layer formed by the cured product of the resin composition of any one of claims 1 to 12. A semiconductor device comprising the multilayer printed wiring board according to claim 14 .