JP6028587B2 - 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.

  In recent years, miniaturization and high performance of electronic devices have progressed, and in a semiconductor package substrate, a build-up layer has been formed into multiple layers, and miniaturization and high density of wiring have been demanded.

  Various efforts were made against this. For example, Patent Document 1 discloses an epoxy resin, an active ester compound, an inorganic filler, and a triazine-based adhesion imparting agent as compounding components of a resin composition, and an insulating layer formed by these resin compositions However, it is described that the peel strength and the linear expansion coefficient can be compatible. However, no long-term insulation reliability has been studied.

JP 2010-90238 A

  According to the knowledge of the present inventors, a multilayer printed wiring board was produced using a low dielectric loss tangent resin composition containing an active ester curing agent and a cyanate ester curing agent. When long-term insulation reliability was confirmed by an environmental test, the problem was found that the adhesion strength between the cured product of the resin composition and the conductor layer formed on the cured product would be extremely low.

  Accordingly, an object of the present invention is to provide a resin composition having a low dielectric loss tangent of a cured product of the resin composition and excellent long-term insulation reliability.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition containing (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, and (D) an amine stabilizer. The resin composition in which the (B) curing agent includes an active ester curing agent and / or a cyanate ester curing agent, and the content of the amine stabilizer is in a specific range, and the present invention is completed. It came to do.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, and (D) an amine stabilizer, wherein the (B) curing agent is an active ester type Including a curing agent and / or a cyanate ester curing agent, and when the nonvolatile component in the resin composition is 100% by mass, the content of the (D) amine stabilizer is 0.01 to 0.5% by mass. A resin composition.
[2] The resin composition according to [1], wherein the amine stabilizer is a triazole compound or a triazine compound.
[3] The resin composition according to [1] or [2], wherein the amine stabilizer has a number average molecular weight of 50 to 1,000.
[4] The resin according to any one of [1] to [3], wherein the ratio of the total number of epoxy groups of the epoxy resin to the total number of reactive groups of the curing agent is 1: 0.2 to 1: 2. Composition.
[5] The resin composition according to any one of [1] to [4], wherein the content of the inorganic filler is 30 to 90% by mass when the nonvolatile component in the resin composition is 100% by mass.
[6] The resin composition according to any one of [1] to [5], wherein the inorganic filler has an average particle size of 0.01 to 5 μm.
[7] The epoxy resin has at least one selected from bisphenol A type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, and dicyclopentadiene type epoxy resin, and the active ester type curing agent as the curing agent The resin composition according to any one of [1] to [6], having silica as the inorganic filler.
[8] The resin composition according to any one of [1] to [7], further comprising (E) a polymer resin.
[9] The resin composition according to any one of [1] to [8], which is a resin composition for forming an insulating layer of a multilayer printed wiring board.
[10] The resin composition according to any one of [1] to [9], which is a resin composition for forming a buildup layer of a multilayer printed wiring board.
[11] A sheet-like laminate material using the resin composition according to any one of [1] to [10].
[12] A cured product obtained by thermosetting the resin composition according to any one of [1] to [11].
[13] The cured product according to [12], wherein the dielectric loss tangent is 0.001 to 0.01.
[14] The cured product according to [12] or [13], wherein the surface of the cured product after the roughening treatment has an arithmetic average roughness of 10 to 200 nm and a root mean square roughness of 20 to 300 nm.
[15] A conductor layer is formed by plating on the surface of the cured product after the roughening treatment, and the plating peel strength after an environmental test between the surface of the cured product and the conductor layer is 0.25 to 0.8 kgf / cm. [12] A cured product as set forth in any one of [14].
[16] A multilayer printed wiring board in which an insulating layer is formed from the cured product of any one of [12] to [15].
[17] A semiconductor device using the multilayer printed wiring board according to [16].

  ADVANTAGE OF THE INVENTION According to this invention, the dielectric loss tangent of the hardened | cured material of the resin composition can be made low, and the resin composition excellent in long-term insulation reliability can be provided now.

  The present invention is a resin composition containing (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, and (D) an amine stabilizer, wherein the (B) curing agent is an active ester. When a non-volatile component in the resin composition is 100% by mass including a system hardener and / or a cyanate ester hardener, the content of the amine stabilizer is 0.01 to 0.5% by weight. It is a resin composition. Hereinafter, the compounding components of the resin composition will be described in detail.

<(A) 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 butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, dicyclopentadiene type epoxy Fat, cyclohexanedimethanol type epoxy resins, 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 epoxy resin from the viewpoint of improving heat resistance and maintaining peel strength for a long period of time. It is preferable to use one or more selected from glycidyl ester type epoxy resin, anthracene type epoxy resin and dicyclopentadiene type epoxy resin, and bisphenol A type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, and dicyclo It is more preferable to use one or more selected from pentadiene type epoxy resins. 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 together as an epoxy resin, when the resin composition is used in the form of an adhesive film, it has moderate flexibility and improved handling properties and curing of the resin composition 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: 3 by mass ratio, and 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.

  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.

<(B) Curing agent>
The curing agent used in the present invention can reduce the dielectric loss tangent by including an active ester curing agent and / or a cyanate ester curing agent. Furthermore, it is preferable to use an active ester curing agent from the viewpoint of reducing the roughness of the surface of the cured product and advantageous for forming fine wiring. These may be used alone or in combination of two or more.

  The active ester curing agent is not particularly limited, and is a compound having one or more active ester groups in one molecule. The active ester curing agent can react with an epoxy resin or the like, and a compound having two or more active ester groups in one molecule is preferable. In general, compounds having two or more ester groups with high reaction activity in one molecule such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are 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, specifically, an active ester curing agent having a dicyclopentadienyl diphenol structure, an active ester curing agent having a naphthalene structure, an active ester curing agent which is an acetylated product of phenol novolac, Active ester hardeners, which are benzoylated phenol novolacs, are preferred. Among them, active ester hardeners containing dicyclopentadienyl diphenol structure and active esters containing naphthalene structure are particularly excellent in improving peel strength. A system hardening agent is more preferable. 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 containing dicyclopentadienyl diphenol structure EXB9451, EXB9460, EXB9460S-65T, HPC8000-65T (manufactured by DIC Corporation, active group equivalent of about 223), an active ester which is an acetylated product of phenol novolak DC808 (manufactured by Mitsubishi Chemical Corporation, active group equivalent of about 149) as a system hardener, YLH1026 (manufactured by Mitsubishi Chemical Corporation, active group equivalent of about 200), YLH1030 as an active ester type hardener that is a benzoylated phenol novolak (Mitsubishi Chemical Corporation, active group equivalent of about 201), YLH1048 (Mitsubishi Chemical Corporation, active group equivalent of about 245) and the like.

  More specifically, examples of the active ester curing agent containing a dicyclopentadienyl diphenol structure include compounds represented by the following general 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 a cyanate ester hardening | curing agent, It is a compound which has one or more cyanato groups in 1 molecule. The cyanate ester curing agent can react with an epoxy resin and the like, and a compound having two or more cyanato groups in one molecule is preferable. Specifically, novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester curing agent, dicyclopentadiene type cyanate ester curing agent, bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate Examples thereof include ester-based curing agents and prepolymers in which these are partially triazine. 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) (manufactured by Lonza Japan Co., Ltd., PT30S, cyanate equivalent 124), and the following formula (3): Prepolymer (part Lona Japan Co., Ltd., BA230S, cyanate equivalent 232), a dicyclopentadiene represented by the following formula (4): Structure-containing cyanate ester resin (Lonza Japan 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 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.)

  The content of the active ester curing agent and / or cyanate ester curing agent in the resin composition is not particularly limited, but in the wet roughening step, the surface roughness of the insulating layer is reduced and the plating conductor layer From the viewpoint of achieving both high peel strength and 1% by mass of the nonvolatile component in the resin composition, 1 to 30% by mass is preferable, 5 to 25% by mass is more preferable, and 10 to 20% by mass is even more. preferable.

  In the resin composition of the present invention, an active ester-based curing agent and / or a cyanate ester-based curing agent may be used in combination with another curing agent as necessary within the range where the effects of the present invention are exhibited. . Examples of such other curing agents include phenol-based curing agents and benzoxazine-based curing agents. These may be used alone or in combination of two or more.

  When using an active ester-based curing agent and / or cyanate ester-based curing agent in combination with another curing agent as the curing agent, lowering the roughness of the insulating layer surface and high peel strength of the plated conductor layer in the wet-roughening process From the viewpoint of achieving both of the above, when the solid content of the entire curing agent is 100 parts by mass, the active ester curing agent and / or the cyanate ester curing agent is preferably 30 to 100 parts by mass, and 40 to 95 It is more preferable that it is a mass part, and it is still more preferable that it is 50-90 mass parts.

  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 between the total number of epoxy groups of the epoxy resin and the total number of reactive groups of the curing agent. Is preferably 1: 0.2 to 1: 2, more preferably 1: 0.3 to 1: 1.5, and still more preferably 1: 0.4 to 1: 1. 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.

<(C) Inorganic filler>
The resin composition of this invention can reduce a dielectric loss tangent and a thermal expansion coefficient by containing an inorganic filler. The inorganic filler is not particularly limited. For example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate , Barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like. 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. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs Co., Ltd.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 3 μm or less, and more preferably 2 μm or less from the viewpoint that the surface of the insulating layer has low roughness and enables fine wiring formation. Is more preferably 1 μm or less, still more preferably 0.8 μm or less, and particularly preferably 0.6 μm or less. On the other hand, when the resin composition is a resin varnish, it 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 handling properties from decreasing. 05 μm or more is more preferable, 0.07 μm or more is further more preferable, and 0.1 μm or more is particularly preferable. 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 type particle size distribution measuring apparatus, LA-950 manufactured by Horiba, Ltd. or the like can be used.

  The content of the inorganic filler is preferably 30% by mass or more when the nonvolatile component in the resin composition is 100% by mass in terms of reducing the dielectric loss tangent and preventing cracks in the multilayer printed wiring board. 40 mass% or more is more preferable, 50 mass% or more is still more preferable, and 60 mass% or more is still more preferable. On the other hand, 90 mass% or less is preferable, 85 mass% or less is more preferable, and 80 mass% or less is still more preferable from the point which prevents hardened | cured material from becoming weak and the point which prevents a peeling strength fall.

  The inorganic filler is preferably surface-treated with a surface treatment agent. Specifically, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a styrylsilane coupling agent, and an acrylate silane. One or more surface treatments selected from a series coupling agent, an isocyanate silane coupling agent, a sulfide silane coupling agent, a vinyl silane coupling agent, a silane coupling agent, an organosilazane compound and a titanate coupling agent More preferably, the surface treatment is performed with an agent. Thereby, the dispersibility and moisture resistance of an inorganic filler can be improved.

  Specifically, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane Aminosilane coupling agents such as N-2 (-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, 3-glycidyloxypropyltrimethoxysilane , 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, glycidylbutyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Epoxysilane coupling agents such as ethyltrimethoxysilane, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 11-mercaptoundecyltrimethoxysilane Coupling agents, styrylsilane coupling agents such as p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyl Acrylate silane coupling agents such as triethoxysilane and 3-methacryloxypropyldiethoxysilane, and isocyanates such as 3-isocyanatopropyltrimethoxysilane Silane coupling agents, sulfide silane coupling agents such as bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacloxy Silane coupling agents such as propyltrimethoxysilane, imidazolesilane, triazinesilane, t-butyltrimethoxysilane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexa Phenyldisilazane, trisilazane, cyclotrisilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexabutyldisilazane, hexaoctyldisilazane, 1 3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldi Organos such as silazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, tetramethyldisilazane Silazane compound, tetra-n-butyl titanate dimer, titanium-i-propoxy octylene glycolate, tetra-n-butyl titanate, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy Cis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate Tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyltrioctanoyl titanate, Isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, Titanate coupling agents such as propyldimethacrylisostearoyl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-amidoethyl / aminoethyl) titanate, etc. Is mentioned. Of these, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, and organosilazane compounds are preferred. Commercially available products include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ" manufactured by Shin-Etsu Chemical Co., Ltd. -31 "(hexamethyldisilazane) and the like.

  Moreover, in the inorganic filler surface-treated with the surface treatment agent, the amount of carbon per unit surface area of the inorganic filler can be determined by analyzing the surface composition of the inorganic filler. Specifically, an inorganic filler surface-treated with a surface treatment agent is added to MEK, and after ultrasonic cleaning at 25 ° C. for 5 minutes, the supernatant is removed and the solid content is dried. Thereafter, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. Examples of the carbon analyzer include “EMIA-320V” manufactured by HORIBA, Ltd.

The amount of carbon per unit surface area of the inorganic filler is preferably 0.05 mg / m ² or more in terms of improving the dispersibility of the inorganic filler and stabilizing the root mean square roughness after the wet roughening step of the cured product. 0.1 mg / m ² or more is more preferable, 0.15 mg / m ² or more is further preferable, and 0.2 mg / m ² or more is even more preferable. On the other hand, in terms of preventing an increase in the melt viscosity at the melt viscosity and the adhesive film forms of the resin varnish is preferably 1 mg / ^{m 2} or less, more preferably 0.75 mg / ^{m 2} or less, 0.5 mg / ^{m 2} or less Is more preferable.

  The inorganic filler surface-treated with the surface treatment agent is preferably added to the resin composition after the inorganic filler is surface-treated with the surface treatment agent. 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 surface treatment agent 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 a surface treatment agent is dropped or sprayed while stirring, followed by further stirring and classification with a sieve. Thereafter, the surface treatment agent and the inorganic filler can be dehydrated and condensed by heating. As a wet method, a surface treatment agent 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, the surface treatment agent and the inorganic filler can be dehydrated and condensed by heating. Furthermore, an integral blend method in which a surface treating agent is added to the resin composition is also possible.

<(D) Amine-based stabilizer>
The amine stabilizer used in the present invention is not particularly limited as long as it can prevent deterioration of the resin composition and improve long-term insulation reliability, but a triazole compound or a triazine compound is preferable. More preferred are benzotriazole compounds or triazine compounds, and even more preferred are benzotriazole compounds.

  The number average molecular weight of the amine stabilizer is preferably 50 to 1000, more preferably 80 to 700, and still more preferably 100 to 500, from the viewpoint of reducing volatility and improving handleability. The number average molecular weight in the present invention is measured by a gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number 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.

  Specific examples of the amine stabilizer include IRGANOX 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6). (1H, 3H, 5H) -trione), IRGANOX 3790 (1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2 , 4,6 (1H, 3H, 5H) -trione), IRGANOX5057 (reaction product of N-phenylbenzenamine and 2,4,4-trimethylpentene), IRGANOX565 (2,6-di-tert-butyl- 4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol), TINUVIN P (2- (2H-benzotri) Sol-2-yl) -p-cresol), TINUVIN 234 (2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol), TINUVIN 326 (2 -[5-Chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol), TINUVIN 328 (2- (2H-benzotriazol-2-yl) -4,6 -Di-tert-pentylphenol), TINUVIN 329 (2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol), TINUVIN 360 (2, 2 ' -Methyllenbis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) Enol]), TINUVIN 213 (reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol 300), TINUVIN 571 (2 -(2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol), TINUVIN 1577ED (2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[( (Hexyl) oxy] -phenol), BT-120SG (benzotriazole), BT-LX (1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole), CBT-1 (carboxybenzotriazole), TT -LX (1- [N, N-bis (2-ethylhexyl) aminomethyl L] methylbenzotriazole), TT-LYK (2,2 '-[[(methyl-1H-benzotriazol-1-yl) methyl] imino] bisethanol), BT-M (1- (1', 2 ' -Dicarboxyethyl) benzotriazole), BT-250 (1- (2,3-dicarboxypropyl) benzotriazole), BT-260 (1- (2-ethylhexylaminomethyl) benzotriazole), BT-3700 (2,6-bis [(1H-benzotriazol-1-yl) methyl] -4-methylphenol), 5M-BTA (5-methylbenzotriazole) and the like.

  From the point which improves long-term insulation reliability, content of the amine stabilizer in a resin composition will be 0.01-0.5 mass% when the non-volatile component in a resin composition is 100 mass%. . Preferably it is 0.01-0.45 mass%, More preferably, it is 0.02-0.45 mass%.

  One preferred embodiment of the resin composition of the present invention is a bisphenol A type epoxy resin or naphthalene as an epoxy resin from the viewpoint of providing a resin composition having a low dielectric loss tangent of a cured product and excellent long-term insulation reliability. Type epoxy resin, biphenyl type epoxy resin, and dicyclopentadiene type epoxy resin, at least one active ester type curing agent as a curing agent, silica as an inorganic filler, and amine An embodiment of a resin composition having a system stabilizer is preferred.

<(E) polymer resin>
By adding a polymer 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 polymer 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 polymer resins may be used alone or in combination of two or more. The weight average molecular weight of the polymer resin is preferably in the range of 8,000 to 200,000, and more preferably in the range of 12,000 to 100,000. 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 polymer resin is blended in the resin composition of the present invention, 0.1 to 10% by mass is preferable and 0.5 to 5% by mass is preferable when the nonvolatile component in the resin composition is 100% by mass. More preferred. 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.

<(F) 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, an imidazole hardening accelerator, a phosphonium 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.

  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.

  When mix | blending a hardening accelerator with the resin composition of this invention, the range of 0.005-1 mass part is preferable when the sum total of an epoxy resin and a hardening | curing agent is 100 mass parts, 0.01-0. The range of 5 parts by mass is more preferable. Within this range, thermosetting can be performed more efficiently, and the storage stability of the resin varnish is improved.

<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 thermosetting resins such as vinyl benzyl compounds, acrylic compounds, maleimide compounds, and blocked isocyanate compounds, organic fillers such as silicon powder, nylon powder, fluorine powder, and rubber particles; Adhesives, silicone-based, fluorine-based, polymer-based antifoaming or leveling agents, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, carbon black and other colorants, phosphorus compounds, metal hydroxides And flame retardants.

  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, the said component may be melt | dissolved in the organic solvent and you may add in a resin composition, and it can also adjust as a resin varnish by adding an organic solvent further in a resin composition.

  Furthermore, since the cured product of the resin composition of the present invention can achieve a low dielectric loss tangent and can provide a resin composition that achieves long-term insulation reliability, it can be used as a resin composition for forming an insulating layer of a multilayer printed wiring board. It can be preferably used. Further, it can be suitably used as a resin composition for forming a conductor layer by plating (resin composition for forming an insulating layer of a multilayer printed wiring board on which a conductor layer is formed by plating). It is suitable as a resin composition for forming a buildup layer.

  The resin composition of the present invention can be used as a cured product obtained by thermosetting. 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.

  Although it does not specifically limit as a form of the resin composition of this invention, It can apply to sheet-like laminated materials, such as an adhesive film and a prepreg, and a circuit board (a laminated board use, a multilayer printed wiring board use, etc.). 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 has a resin composition layer formed on a support, and is prepared by a method known to those skilled in the art, for example, a resin varnish in which a resin composition is dissolved in an organic solvent. Can be produced by applying the composition to a support using a die coater or the like, and further drying the organic solvent by heating or blowing hot air to form a 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. Moreover, a prepreg can also be prepared by heating and laminating the adhesive film continuously from both sides of the sheet-like reinforcing base material under heat and pressure. 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 around room temperature, if the support is peeled off, it is peeled off to form a cured product obtained by thermosetting the resin composition. An insulating layer can be formed. The conditions for thermosetting are as described above. 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 It is preferred to do so. 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.

  Here, the dielectric loss tangent of the cured product is preferably 0.01 or less, more preferably 0.008 or less, and still more preferably 0.006 or less, from the viewpoint of reducing electric signal loss. The lower the dielectric loss tangent, the better. There is no particular lower limit, but generally it is 0.001 or more, 0.002 or more, and the like. Specifically, as described later in <Evaluation of dielectric loss tangent>, a sheet-like cured product obtained by thermosetting at 190 ° C. for 90 minutes is subjected to cavity resonance perturbation using an HP 8362B apparatus manufactured by Agilent Technologies. The dielectric loss tangent can be measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by the method.

  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 or the like can be mentioned. 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 commercially available swelling liquids include Swelling Dip Securiganth P (Swelling Dip Securiganth S) 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.

  Here, the arithmetic average roughness (Ra value) of the surface of the cured product after the roughening treatment is preferably 200 nm or less, more preferably 150 nm or less, and still more preferably 100 nm or less, from the viewpoint of fine wiring formation. Further, the lower limit value of the arithmetic average roughness (Ra value) is not particularly limited, and is 10 nm or more. Furthermore, since the root mean square roughness (Rq value) of the cured product surface reflects the local state of the cured product surface, it can be confirmed that the cured product surface is dense and smooth by grasping the Rq value. . The root mean square roughness (Rq value) is preferably 300 nm or less, more preferably 250 nm or less, even more preferably 200 nm or less, and even more preferably 150 nm or less in order to obtain a dense and smooth cured product surface. Further, the lower limit of the root mean square roughness (Rq value) is preferably 20 nm or more, more preferably 30 nm or more, from the viewpoint of stabilizing the peel strength. Specifically, as described later in “Measurement of Arithmetic Average Roughness (Ra Value) and Root Mean Square Roughness (Rq Value)”, a non-contact type surface roughness meter (WYKO manufactured by Beec Instruments Inc.) NT3300) can be measured with a VSI contact mode and a 50 × lens with a measurement range of 121 μm × 92 μm.

  Next, a conductor layer is formed on the insulating layer after the roughening treatment 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.

  Here, in the present invention, long-term insulation reliability can be confirmed by performing an environmental test under high temperature and high humidity on a circuit board and measuring the plating peel strength after the environmental test. Highly accelerated life test apparatus PM422 (manufactured by Enomoto Kasei Co., Ltd.) can be used. Specifically, a conductor layer is formed by plating on the surface of the cured product after the roughening treatment, and the plating peel strength after an environmental test between the surface of the cured product and the conductor layer is measured. Examples of the environmental test conditions include 130 ° C., 85% RH, and a condition of standing for 100 hours.

  The plating peel strength after the environmental test is preferably 0.25 kgf / cm or more and more preferably 0.27 kgf / cm or more in order to sufficiently adhere the cured product (insulating layer) and the conductor layer. The upper limit of the plating peel strength after the environmental test is preferably as high as possible and is not particularly limited, but is generally 0.8 kgf / cm or less, 0.7 kgf / cm or less, 0.6 kgf / cm or less, and the like.

  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. By repeating the above-described series of steps a plurality of times, a multilayer in which build-up layers are stacked in multiple stages It can be a printed wiring board.

  Another example of a method for producing a multilayer printed wiring board using the sheet-like laminated material produced as described above will be described.

  In the same manner as described above, after laminating the sheet-like laminated material on one or both sides of the circuit board using a vacuum laminator, after cooling to near room temperature, the support is peeled off, and a copper foil is further laminated. Lamination is the same as described above.

  Next, in the same manner as described above, an insulating layer is formed on the circuit board by forming a cured product obtained by thermosetting the resin composition. Thereby, copper foil was laminated | stacked on the hardened | cured material surface. The conditions for thermosetting are the same as those described above.

  Here, the long-term insulation reliability in the present invention can also be confirmed by measuring the copper foil peel strength after the environmental test. Specifically, the copper foil peel strength after the environmental test between the cured product surface and the copper foil is measured. Examples of the environmental test conditions include 130 ° C., 85% RH, and a condition of standing for 100 hours.

  The copper foil peel strength after the environmental test is preferably 0.3 kgf / cm or more, and more preferably 0.35 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 copper foil peel strength after the environmental test is preferably as high as possible and is not particularly limited, but is generally 0.9 kgf / cm or less, 0.8 kgf / cm or less, 0.7 kgf / cm or less, and the like.

  Then, a multilayer printed wiring board in which a hole patterning process is appropriately performed, a wiring pattern is formed by a subtractive method or the like, and build-up layers are laminated in multiple stages can be obtained.

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

<Long-term reliability evaluation by plating test>
(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 substrate was cured at 100 ° C. for 30 minutes and then cured at 180 ° C. for 30 minutes to form an insulating layer. Thereafter, the polyethylene terephthalate (PET) support film was peeled from the adhesive film.

(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, this substrate was designated as evaluation substrate A.

(5) Plating by semi-additive method Evaluation board A was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. After annealing 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 treatment was performed at 190 ° C. for 60 minutes. This substrate was designated as evaluation substrate B.

(6) Measurement of arithmetic average roughness (Ra value) and root mean square roughness (Rq value) Evaluation substrate A was measured using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Beeco Instruments Corp.) in the VSI contact mode. The Ra value and the Rq value were obtained from numerical values obtained with a measurement range of 121 μm × 92 μm using a 50 × lens. Each was measured by obtaining an average value of 10 points.

(7) Measurement of Peeling Strength of Plating Conductor Layer (Plating Peel Strength) In the conductor layer of the evaluation board B, a notch of 10 mm width and 100 mm length is cut, and one end is peeled off to grasp・ S / E, Autocom type testing machine AC-50C-SL) and using Instron universal testing machine, the load when peeling 35mm vertically at a speed of 50mm / min at room temperature (Kgf / cm) was measured and used as the plating peel strength before the environmental test. The plating peel strength before the environmental test is as follows. Example 1: 0.51 kgf / cm, Example 2: 0.48 kgf / cm, Example 3: 0.5 kgf / cm, Example 4: 0.55 kgf / cm Comparative Example 1: 0.5 kgf / cm, Comparative Example 2: 0.38 kgf / cm, Comparative Example 3: 0.47 kgf / cm, Comparative Example 4: 0.54 kgf / cm, Comparative Example 5: 0.48 kgf / cm Met.
Furthermore, the same sample was subjected to a 100-hour accelerated environment test at 130 ° C. and 85% RH using a highly accelerated life test apparatus PM422 (manufactured by Enomoto Kasei Co., Ltd.), and the peel strength was measured in the same manner. The plating peel strength after the environmental test was determined. Those having a plating peel strength after the environmental test of 0.25 kgf / cm or more were evaluated as “◯”, and those having a plating peel strength of less than 0.25 kgf / cm were evaluated as “x”.

<Long-term reliability evaluation by copper foil test>
(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 films prepared in Examples and Comparative Examples were laminated on both sides of a laminate 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) Surface treatment of copper foil The glossy surface of 3EC-III (electrolytic copper foil, 35 μm) manufactured by Mitsui Mining Co., Ltd. is immersed in Mec Etch Bond CZ-8100 manufactured by Mec Co., Ltd., and roughened on the copper surface. (1 um etching) was performed.

(4) Lamination of copper foil and formation of insulating layer The PET film is peeled from the adhesive film laminated in (2) above, and the glossy surface of the copper foil treated in (3) above is set to the resin composition layer side. Under the same conditions as in 2), the copper foil was laminated on the resin composition layer formed on both surfaces of the circuit board. A sample was produced by curing the resin composition under the curing conditions of 100 ° C. for 30 minutes, 180 ° C. for 30 minutes, and further 190 ° C. for 60 minutes to form an insulating layer.

(5) Measurement of peel strength (copper foil peel strength) of copper foil conductor layer>
The substrate prepared in the above (4) was cut into small pieces of 150 × 30 mm. Cut the copper foil part of the small piece with a width of 10mm and a length of 100mm, peel off one end of the copper foil and use a gripping tool (TSE Co., Ltd., Autocom type testing machine AC-50C-SL) Using a Instron universal testing machine, the load when peeling 35 mm in the vertical direction at a speed of 50 mm / min was measured at room temperature to obtain the copper foil peel strength before the environmental test. The copper foil peel strength before the environmental test is as follows: Example 1: 0.66 kgf / cm, Example 2: 0.59 kgf / cm, Example 3: 0.64 kgf / cm, Example 4: 0.68 kgf / cm cm, Comparative Example 1: 0.65 kgf / cm, Comparative Example 2: 0.5 kgf / cm, Comparative Example 3: 0.63 kgf / cm, Comparative Example 4: 0.69 kgf / cm, Comparative Example 5: 0.64 kgf / cm cm.
Furthermore, the same sample was subjected to a 100-hour accelerated environment test at 130 ° C. and 85% RH using a highly accelerated life test apparatus PM422 (manufactured by Enomoto Kasei Co., Ltd.), and the peel strength was measured in the same manner. The copper foil peel strength after the environmental test was determined. A copper foil peel strength after the environmental test of 0.3 kgf / cm or more was evaluated as “◯”, and a copper foil peel strength of less than 0.3 kgf / cm was evaluated as “x”.

<Evaluation of dielectric loss tangent>
In Examples and Comparative Examples, the same resin composition layers as those in Examples and Comparative Examples are used except that PET ("PET501010" manufactured by Lintec Co., Ltd.) having a thickness of 50 m is used. An adhesive film was obtained, and the obtained adhesive film was thermally cured at 190 ° C. for 90 minutes, and a support was peeled off to obtain a sheet-like cured product, which was cut into a length of 80 mm and a width of 2 mm for evaluation. A dielectric loss tangent of this evaluation sample was measured by a cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. using an HP 8362B apparatus manufactured by Agilent Technologies.

<Example 1>
3 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent of about 169), naphthalene type epoxy resin (manufactured by DIC Corporation “ "HP4032SS", epoxy equivalent of about 144) 3 parts, crystalline bifunctional epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) 12 parts, dicyclopentadiene type epoxy resin (made by DIC "HP7200H" ”, 9 parts of an epoxy equivalent of about 275) and 10 parts of phenoxy resin (“ YL7553BH30 ”manufactured by Mitsubishi Chemical Corporation, MEK solution with a solid content of 30% by mass) were dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 40 parts of an active ester compound (“HPC8000-65T” manufactured by DIC Corporation, a toluene solution having a nonvolatile content of 65% by mass with an active group equivalent of about 223), a curing accelerator (4-dimethylamino) 3 parts of pyridine, MEK solution having a solid content of 5% by mass, 0.2 part of benzotriazole (“BT-120SG” manufactured by Johoku Chemical Industry Co., Ltd., methyl ethyl ketone solution having a solid content of 20% by mass), phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd., “KBM573”) surface-treated spherical silica (average particle size 0.25 μm, Admatechs Co., Ltd. “SOC1”, carbon amount per unit surface area 0.36 mg / m ² 140 parts) was mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.
Next, the resin varnish is uniformly applied on the release surface of a polyethylene terephthalate film with a release treatment (“AL5” manufactured by Lintec Corporation, thickness 38 μm) so that the thickness of the resin composition layer after drying is 30 μm. It apply | coated and dried at 80-120 degreeC (average 100 degreeC) for 4 minutes, and produced the adhesive film.

<Example 2>
Except for changing 0.2 parts of benzotriazole of Example 1 (“BT-120SG” manufactured by Johoku Chemical Industry Co., Ltd., methyl ethyl ketone solution having a solid content of 20% by mass) to 4 parts, the same procedure as in Example 1 was performed. An adhesive film was prepared.

<Example 3>
0.2 parts of the benzotriazole of Example 1 (“BT-120SG” manufactured by Johoku Chemical Industry Co., Ltd., methyl ethyl ketone solution having a solid content of 20% by mass) was added to a triazine compound (“TINUVIN 1577ED” manufactured by BASF, 2- (4 , 6-Diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 1: 1 solution of methyl ethyl ketone and cyclohexanone having a solid content of 5% by mass, except for changing to 2 parts Produced an adhesive film in the same manner as in Example 1.

<Example 4>
5 parts of naphthalene type epoxy resin (“HP4032SS” manufactured by DIC Corporation, epoxy equivalent of about 144), 5 parts of crystalline bifunctional epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, about 185 of epoxy equivalent), biphenyl type epoxy 12 parts of resin (Nippon Kayaku Co., Ltd. “NC3000H”, epoxy equivalent of about 288), 10 parts of phenoxy resin (Mitsubishi Chemical Co., Ltd. “YL7553BH30”, MEK solution with a solid content of 30% by mass), solvent naphtha 30 The mixture was heated and dissolved with stirring. After cooling to room temperature, 20 parts of a prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan Co., Ltd., MEK solution having a cyanate equivalent of about 232 and a non-volatile content of 75% by mass), a phenol novolac type polyfunctional cyanate ester Resin ("PT30S" manufactured by Lonza Japan Co., Ltd., cyanate equivalent of about 133, MEK solution having a nonvolatile content of 85% by mass), 6 parts, curing accelerator (4-dimethylaminopyridine, MEK solution having a solid content of 5% by mass) 4 parts, 3 parts of curing accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt (III) acetylacetonate, MEK solution having a solid content of 1% by mass), benzotriazole-based compound ("TINUVIN 234" manufactured by BASF, 2- (2H) -Benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) fe Nord, 5 parts by weight of methyl ethyl ketone and cyclohexanone (1: 1 solution) 1.2 parts, spherical silica surface-treated with phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average) A resin varnish is prepared by mixing 100 parts of particle size 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd., carbon amount 0.39 mg / m ² per unit surface area, and uniformly dispersing with a high-speed rotary mixer. did. Next, an adhesive film was produced in the same manner as in Example 1.

<Comparative Example 1>
An adhesive film was produced in exactly the same manner as in Example 1 except that the benzotriazole of Example 1 was not added.

<Comparative example 2>
Except for changing 0.2 parts of benzotriazole of Example 1 (“BT-120SG” manufactured by Johoku Chemical Industry Co., Ltd., methyl ethyl ketone solution having a solid content of 20% by mass) to 6 parts, the same procedure as in Example 1 was performed. An adhesive film was prepared.

<Comparative Example 3>
0.2 part of the benzotriazole of Example 1 (“BT-120SG” manufactured by Johoku Chemical Industry Co., Ltd., methyl ethyl ketone solution with a solid content of 20% by mass) was used as a hindered phenol antioxidant (“IRGANOX 1010” manufactured by BASF), Except for changing to 1 part of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], a 1: 1 solution of methyl ethyl ketone and cyclohexanone having a solid content of 5 mass%) An adhesive film was prepared in exactly the same manner as in Example 1.

<Comparative example 4>
An adhesive film was produced in exactly the same manner as in Example 4 except that the benzotriazole-based compound of Example 4 was not added.

<Comparative Example 5>
1.2 parts of the benzotriazole compound of Example 4 was added to a benzoate light stabilizer (“TINUVIN 120” manufactured by BASF, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4- An adhesive film was produced in exactly the same manner as in Example 4 except that the content was changed to 1.2 parts (hydroxybenzoate, 1: 1 solution of methyl ethyl ketone and cyclohexanone having a solid content of 5% by mass).

  The results are shown in Table 1.

  As shown in Table 1, it can be seen that the examples have a low dielectric loss tangent and excellent long-term adhesion reliability. On the other hand, in Comparative Examples 1, 3, 4, and 5, no amine stabilizer was added, and long-term adhesion reliability was poor. Moreover, since the comparative example 2 has too many amine stabilizers, a balance with hardened | cured material is impaired and long-term adhesion reliability is inferior.

  It has become possible to provide a resin composition having a low dielectric loss tangent of a cured product of the resin composition and excellent long-term insulation reliability. 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 (17)

A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, and (D) an amine stabilizer,
The (B) curing agent contains an active ester curing agent and / or a cyanate ester curing agent,
The resin composition whose content of the said (D) amine stabilizer is 0.01-0.5 mass% when the non-volatile component in the said resin composition is 100 mass%.   The resin composition according to claim 1, wherein the amine stabilizer is a triazole compound or a triazine compound.   The resin composition according to claim 1 or 2, wherein the amine stabilizer has a number average molecular weight of 50 to 1,000.   The resin composition according to any one of claims 1 to 3, wherein the ratio of the total number of epoxy groups of the epoxy resin to the total number of reactive groups of the curing agent is 1: 0.2 to 1: 2.   The resin composition according to any one of claims 1 to 4, wherein the content of the inorganic filler is 30 to 90 mass% when the nonvolatile component in the resin composition is 100 mass%.   The resin composition according to any one of claims 1 to 5, wherein the inorganic filler has an average particle size of 0.01 to 5 µm.   The epoxy resin has at least one selected from bisphenol A type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, and dicyclopentadiene type epoxy resin, and has an active ester type curing agent as the curing agent. The resin composition according to claim 1, wherein silica is used as the inorganic filler.   The resin composition according to any one of claims 1 to 7, further comprising (E) a polymer resin.   The resin composition according to any one of claims 1 to 8, which is a resin composition for forming an insulating layer of a multilayer printed wiring board.   The resin composition according to any one of claims 1 to 9, which is a resin composition for forming a buildup layer of a multilayer printed wiring board.   The sheet-like laminated material formed using the resin composition of any one of Claims 1-10. Any one cured product of the resin composition obtained by heat curing according to claim 1-10.   The hardened | cured material of Claim 12 whose dielectric loss tangent is 0.001-0.01.   The hardened | cured material of Claim 12 or 13 whose arithmetic mean roughness of the hardened | cured material surface after a roughening process is 10-200 nm, and whose root mean square roughness is 20-300 nm. Plating by forming a conductive layer on the cured product surface after roughening treatment, 130 ° C., the main Kkipiru strength between the cured product surface and the conductor layer after environmental test for 100 hours at 85% RH, 0. It is 25-0.8kgf / cm, Hardened | cured material of any one of Claims 12-14.   A multilayer printed wiring board having an insulating layer formed of the cured product according to any one of claims 12 to 15.   A semiconductor device comprising the multilayer printed wiring board according to claim 16.