KR102174278B1 - Resin composition - Google Patents

Abstract

[Task] In the case of curing and forming an insulating layer, not only the arithmetic mean roughness of the surface of the insulating layer is small in the wet roughening process, but also the value of the root mean square roughness is small, and it is possible to form a plated conductor layer having sufficient peel strength. And the coefficient of linear thermal expansion is also small.
[Solution means] A resin composition containing an epoxy resin, a curing agent, and an inorganic filler, wherein the inorganic filler is surface-treated with an aminoalkylsilane, and the nonvolatile component in the resin composition is 100% by mass, the content of the inorganic filler The resin composition characterized in that it is 55-90 mass %.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition. It also relates to a sheet-like laminate material containing the resin composition, a multilayer printed wiring board, and a semiconductor device.

In recent years, miniaturization and high performance of electronic devices have progressed, and build-up layers are multilayered in multilayer printed wiring boards, and miniaturization and high density of wiring are required.

Various actions have been taken against this. For example, Patent Document 1 discloses an epoxy resin composition comprising an epoxy resin, a curing agent, a filler, and a silane coupling agent. However, the surface roughness and peel strength were not directed at all.

Patent Document 1: Japanese Patent Application Laid-Open No. 2002-97258

The problem to be solved by the present invention is that not only the arithmetic average roughness of the surface of the insulating layer is low in the wet roughening process, the surface of the insulating layer has a low root-average square roughness, and a plated conductor layer having sufficient peel strength is formed on the insulating layer. It is possible to provide a resin composition having a low coefficient of linear thermal expansion.

The present inventors, as a result of earnest study in order to solve the above problems, as a result of a resin composition containing an epoxy resin, a curing agent, and an inorganic filler, wherein the inorganic filler is surface-treated with aminoalkylsilane, and the nonvolatile component in the resin composition is 100 In the case of mass%, the present invention was completed with a resin composition characterized in that the content of the inorganic filler is 55 to 90 mass%.

That is, the present invention includes the following contents.

(1) A resin composition containing an epoxy resin, a curing agent, and an inorganic filler, wherein the inorganic filler is surface-treated with an aminoalkylsilane, and when the nonvolatile component in the resin composition is 100% by mass, the content of the inorganic filler is A resin composition comprising 55 to 90% by mass.

[2] The resin composition according to [1], wherein the aminoalkylsilane contains at least one selected from an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminoisopropyl group, and an aminocyclopropyl group.

[3] The resin composition according to [1] or [2], wherein the aminoalkylsilane is 3-aminopropylsilane.

[4] The resin composition according to any one of [1] to [3], wherein the aminoalkylsilane has a molecular weight of 100 to 2000.

[5] The resin composition according to any one of claims [1] to [4], wherein the inorganic filler has an average particle diameter of 0.01 to 5 µm.

[6] The resin composition according to any one of [1] to [5], wherein the inorganic filler is silica.

[7] The resin composition according to any one of [1] to [6], wherein when the nonvolatile component in the resin composition is 100% by mass, the content of the inorganic filler is 60 to 85% by mass.

[8] The resin composition according to any one of [1] to [7], wherein the aminoalkylsilane is surface-treated with 0.05 to 5 parts by mass per 100 parts by mass of the inorganic filler.

[9] The resin composition according to any one of [1] to [8], wherein the amount of carbon per unit surface area of the inorganic filler is 0.05 to 1 mg/m 2.

(10) The epoxy resin is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, a glycidyl ester type epoxy resin. The resin composition according to any one of [1] to [9], wherein the resin composition is at least one selected from an anthracene type epoxy resin and an epoxy resin having a butadiene structure.

[11] The resin composition 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.

[12] The resin composition according to any one of [1] to [11], wherein the curing agent is at least one selected from an active ester curing agent and a cyanate ester curing agent.

[13] [1], wherein the resin composition is cured to form an insulating layer, and the arithmetic mean roughness after roughening the surface of the insulating layer is 10 to 300 nm, and the root mean square roughness is 20 to 500 nm. The resin composition according to any one of-[12].

[14] Among [1] to [13], characterized in that the peel strength between the insulating layer obtained by curing the resin composition and the conductor layer obtained by roughening and plating the surface of the insulating layer is 0.35 to 1.5 kgf/cm. The resin composition according to any one.

[15] The resin composition according to any one of [1] to [14], which is a resin composition for insulating layers of a multilayer printed wiring board.

[16] The resin composition according to any one of [1] to [15], which is a resin composition for insulating layers of a multilayer printed wiring board in which a conductor layer is formed by plating.

[17] The resin composition according to any one of [1] to [16], which is a resin composition for a build-up 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 from a cured product of the resin composition according to any one of [1] to [17].

[20] A semiconductor device comprising the multilayer printed wiring board according to [19].

A resin composition containing an epoxy resin, a curing agent, and an inorganic filler, wherein when the inorganic filler is surface-treated with aminoalkylsilane and the nonvolatile component in the resin composition is 100% by mass, the content of the inorganic filler is 55 to 90 By using the resin composition characterized by mass%, not only the arithmetic average roughness of the surface of the insulating layer in the wet roughening process is low, but also the value of the root-average square roughness of the surface of the insulating layer is small, and sufficient peel strength is obtained on the insulating layer. It has become possible to form a plated conductor layer, and to provide a resin composition having a low coefficient of linear thermal expansion.

The present invention is a resin composition containing an epoxy resin, a curing agent and an inorganic filler, wherein when the inorganic filler is surface-treated with aminoalkylsilane and the nonvolatile component in the resin composition is 100% by mass, the content of the inorganic filler is It is a resin composition characterized by being 55 to 90 mass %. Hereinafter, the blending components of the resin composition will be described in detail.

<Epoxy resin>

The epoxy resin used in the present invention is not particularly limited, but bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolak type epoxy resin, tert-butyl-cate Cole 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 novolak type epoxy resin, biphenyl type epoxy resin, Anthracene type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, etc. Can be mentioned. These may be used singly or in combination of two or more.

Among these, from the viewpoint of improving heat resistance, improving insulation reliability, and improving peel strength, 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 It is preferable to use at least one selected from 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 (Mitsubishi Chemical Co., Ltd. ``Epicoat 828EL'', ``YL980''), bisphenol F type epoxy resin (Mitsubishi Chemical Co., Ltd. ``jER806H'', ``YL983U''), 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 Shinnitetsu Chemical Co., Ltd.), epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Industries, Ltd.), and an epoxy resin having a biphenyl structure (Nihonkaya Co., Ltd. ``NC3000H'', ``NC3000L'', ``NC3100'', Mitsubishi Chemical Co., Ltd. ``YX4000'', ``YX4000H'', ``YX4000HK'', ``YL6121''), anthracene type epoxy resin (Mitsubishi Chemical Co., Ltd.) Manufacture ``YX8800''), naphthylene ether type epoxy resin (DIC Co., Ltd. ``EXA-7310'', ``EXA-7311'', ``EXA-7311L'', ``EXA7311-G3''), glycidyl ester type epoxy resin (Nagase Chemtex Co., Ltd. "EX711", "EX721", Printtech Co., Ltd. "R540") etc. are mentioned.

It is preferable that the epoxy resin contains an epoxy resin having two or more epoxy groups in one molecule, and among them, it is more preferable to use a liquid epoxy resin and a solid epoxy resin in combination. As the liquid epoxy resin, an aromatic epoxy resin having two or more epoxy groups per molecule and being liquid at a temperature of 20°C is preferable. As the solid epoxy resin, an aromatic epoxy resin having three or more epoxy groups per molecule and which is solid at a temperature of 20°C is preferable. In addition, the aromatic epoxy resin in the present invention means an epoxy resin having an aromatic ring structure in its molecule. As an epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used together, it has adequate flexibility when the resin composition is used in the form of an adhesive film, improves handling properties, and reduces the surface roughness of the cured product of the resin composition. From the point of view, the blending ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.1 to 1:3, more preferably in the range of 1:0.3 to 1:2, and 1:0.6 The range of -1:1.5 is more preferable.

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, glycidyl ester type epoxy resin, or naphthalene type epoxy resin is preferable, and bisphenol A type epoxy resin, bisphenol F type Epoxy resin or naphthalene type epoxy resin is more preferable. These may be used singly or in combination of two or more. As a solid epoxy resin, a tetrafunctional naphthalene type epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a biphenyl type epoxy resin, or a nap A styrene ether type epoxy resin is preferable, and a naphthol type epoxy resin or a biphenyl type epoxy resin is more preferable. These may be used singly or in combination of two or more.

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

<hardener>

The curing agent used in the present invention is not particularly limited, but includes a phenolic curing agent, an active ester curing agent, a cyanate ester curing agent, a benzoxazine curing agent, an acid anhydride curing agent, etc., and the arithmetic average of the cured product of the resin composition From the viewpoint of further reducing the roughness (Ra value) and the root mean square roughness (Rq value), it is preferable to use at least one selected from a phenolic curing agent, an active ester curing agent, and a cyanate ester curing agent, and active ester It is more preferable to use at least one selected from a curing agent and a cyanate ester curing agent. These may be used singly or in combination of two or more.

The phenolic curing agent is not particularly limited, but a biphenyl type curing agent, a naphthalene type curing agent, a phenol novolak type curing agent, a naphthylene ether type curing agent, and a triazine skeleton-containing phenol type curing agent are preferable. Specifically, the biphenyl type curing agent MEH-7700, MEH-7810, MEH-7851 (made by Meiwa Chemical Co., Ltd.), the naphthalene type curing agent NHN, CBN, GPH (manufactured by Nihon Kayaku Corporation), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Shinitetsu Chemical Co., Ltd.), EXB9500 (manufactured by DIC Corporation), TD2090 of phenol novolak type hardener (manufactured by DIC Corporation), naphthylene ether EXB-6000 (manufactured by DIC Corporation) as a type curing agent, LA3018, LA7052, LA7054, and LA1356 (manufactured by DIC Corporation) of a phenolic curing agent containing a triazine skeleton. These may use 1 type or 2 or more types together.

The active ester-based curing agent is not particularly limited, but generally, an ester group having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds is 2 per molecule. Compounds having two or more are preferably used. The active ester curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound 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. As a phenol compound or a naphthol compound, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, trihydroxybenzo Phenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, polycyclopentadiene type diphenol compound (dicyclopentadiene type diphenol compound, tricyclopentadiene type diphenol compound), phenolno And rockfish. One type or two or more types of active ester curing agents may be used. As an active ester curing agent, specifically, an active ester curing agent containing a dicyclopentadiene-type diphenol condensation structure (condensation structure of dicyclopentadiene and phenol), an active ester curing agent containing a naphthalene structure, phenol novolac Active ester-based curing agent, which is an acetylated product of phenol novolak, and an active ester-based curing agent, which is a benzoylated product of phenol novolac, is preferable. Ester curing agents are more preferred. As the active ester curing agent, an active ester curing agent disclosed in Japanese Patent Laid-Open No. 2004-277460 may be used, or a commercially available curing agent may be used. Commercially available products include dicyclopentadiene-type diphenol condensation structures, EXB9451, EXB9460, EXB9460S-65T, HPC-8000-65T (manufactured by DIC Co., Ltd., active group equivalent of about 223), an acetylated product of phenol novolac. DC808 (manufactured by Mitsubishi Chemical Co., Ltd., active group equivalent of about 149) as active ester curing agent, YLH1026 (manufactured by Mitsubishi Chemical Co., Ltd., active group equivalent of about 200), YLH1030 (made by Mitsubishi Chemical Co., Ltd. Chemical Co., Ltd. product, active group equivalent of about 201), YLH1048 (Mitsubishi Chemical Co., Ltd. product, active group equivalent of about 245), etc. are mentioned.

As an active ester curing agent containing a dicyclopentadiene type (or tricyclopentadiene type) diphenol condensed structure, more specifically, a compound represented by the following formula (1) can be mentioned.

(In the formula, R is a phenyl group or a naphthyl group, k represents 0 or 1, and n is an average of 0.05 to 2.5 repeat units.)

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

The cyanate ester curing agent is not particularly limited, but 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 ester type curing agents, and prepolymers in which these are partially triazineized. Although the weight average molecular weight of a cyanate ester type hardening 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- Dimethylphenylcyanate), 4,4′-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4- Cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cya Polyfunctional cyanate resins derived from bifunctional cyanate resins such as natephenyl)thioether and bis(4-cyanatephenyl)ether, phenol novolac, cresol novolac, dicyclopentadiene structure-containing phenol resin, etc. And prepolymers in which a cyanate resin is partially triazineized, etc. These may be used singly or in combination of two or more As a commercially available cyanate ester resin, a phenol novolak type polyvalent represented by the following formula (2) is given. Functional cyanate ester resin (manufactured by Ronza Japan, PT30S, cyanate equivalent 124), a prepolymer in which part or all of the bisphenol A dicyanate represented by the following formula (3) is triazineized to become a trimer (Lonza Japan ( Note) Manufacturing, BA230S, cyanate equivalent 232), cyanate ester resins containing a dicyclopentadiene structure represented by the following formula (4) (manufactured by Ronza Japan, DT-4000, DT-7000), etc. have.

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

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

Although there is no restriction|limiting in particular as a benzoxazine type hardening agent, F-a, P-d (made by Shikoku Chemical Co., Ltd.), HFB2006M (made by Showa Polymer Co., Ltd.) etc. are mentioned as a specific example.

The acid anhydride-based curing agent is not particularly limited, but phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyl Tetrahydrophthalic anhydride, dodecenyl anhydride succinic acid, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimelli anhydride Tic acid, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfontetra Carboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan- And polymeric acid anhydrides such as 1,3-dione, ethylene glycol bis (anhydrotrimelitate), and styrene maleic 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 to the total number of reactive groups of the curing agent is preferably 1:0.2 to 1:2. And 1:0.3-1:1.5 are more preferable, and 1:0.4-1:1 are still more preferable. In addition, the total number of epoxy groups in 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 weight for all epoxy resins, and the total number of reactors of the curing agent is the solid content of each curing agent. It is the sum of all the hardeners obtained by dividing the mass by the reactor equivalent.

<Inorganic filler>

The inorganic filler used in the present invention is not particularly limited, but 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. Among them, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica are preferred, and fused silica and spherical silica are more preferred in view of lowering the surface roughness of the insulating layer. And spherical fused silica is more preferable. These may be used singly or in combination of two or more.

The average particle diameter of the inorganic filler is not particularly limited, but 5 µm or less is preferable, 4 µm or less is more preferable, and 3 µm or less from the viewpoint of the fact that the surface of the insulating layer becomes low in roughness and makes it possible to form fine wiring. The following are more preferable, 2 micrometers or less are more preferable, 1 micrometers or less are especially preferable, 0.8 micrometers or less are especially preferable, and 0.6 micrometers or less are especially preferable. On the other hand, in the case where the resin composition is a resin varnish, the viscosity of the varnish increases, and from the viewpoint of preventing a decrease in handling properties, 0.01 µm or more is preferable, 0.03 µm or more is more preferable, and 0.05 µm or more is More preferably, 0.07 µm or more is still 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, it can be measured by creating a particle size distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle size distribution measuring device, and setting the median diameter to an average particle diameter. As a measurement sample, what made an inorganic filler disperse in water by ultrasonic wave can be used preferably. As a laser diffraction scattering type particle size distribution measuring device, LA-950 manufactured by Horiba Co., Ltd. can be used.

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

The aminoalkylsilane used for the surface treatment of the inorganic filler is not particularly limited, and may be an aminoalkylsilane containing an aminoalkyl group and an alkoxysilyl group, and more specifically, an aminoalkylalkoxysilane is preferable. The aminoalkyl group is excellent in that the compatibility with the resin is improved, and it is excellent in that it contributes to the improvement of the lamination property when the resin composition is formed into a sheet, and contributes to the low illuminance in the present invention. As the aminoalkyl group, at least one selected from an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminoisopropyl group and an aminocyclopropyl group is preferable, and an aminopropyl group is more preferable.

On the other hand, the alkoxysilyl group contributes to the improvement of the peel strength in the present invention. As the alkoxysilyl group, it is preferable to have two to three alkoxy groups per one alkoxysilyl group, and as the alkoxy group, a methoxy group and an ethoxy group are preferable. Further, the alkoxysilyl group may be modified.

Therefore, by surface-treating the inorganic filler with aminoalkylsilane, even when 55 to 90% by mass of the inorganic filler is blended into the resin composition, it is excellent to improve the peel strength while having low roughness.

As a specific aminoalkylsilane, 3-aminopropylsilane is preferable, and it is more preferable to use one or more types selected from 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

The molecular weight of the aminoalkylsilane is preferably 100 or more, more preferably 150 or more, and still more preferably 200 or more, from the viewpoint of inhibiting volatilization during surface treatment or drying. On the other hand, from the viewpoint of appropriate reactivity, 2000 or less is preferable, 1500 or less is more preferable, 1000 or less is still more preferable, and 500 or less is particularly preferable. As a commercial item, Shin-Etsu Chemical Co., Ltd. "KBM903" (3-aminopropyltrimethoxysilane, molecular weight 179), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane, molecular weight 221) And the like.

The amount of the aminoalkylsilane when the inorganic filler is surface-treated with aminoalkylsilane is not particularly limited, but it is preferable to surface-treat the aminoalkylsilane in 0.05 to 5 parts by mass per 100 parts by mass of the inorganic filler, and 0.1 to It is more preferable to surface-treat with 4 mass parts, it is still more preferable to surface-treat with 0.2-3 mass parts, and it is still more preferable to surface-treat with 0.3-2 mass parts.

In addition, in the inorganic filler surface-treated with aminoalkylsilane, the presence of carbon atoms can be confirmed by analyzing the surface composition of the inorganic filler, and the amount of carbon per unit surface area of the inorganic filler can be obtained. Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with aminoalkylsilane, followed by ultrasonic cleaning at 25°C for 5 minutes. After removing the supernatant and drying the solid, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd. can be used.

The amount of carbon per unit surface area of the inorganic filler is preferably 0.05 mg/m2 or more, preferably 0.1 mg/m2, from the viewpoint of improving the dispersibility of the inorganic filler and stabilizing the arithmetic mean roughness and root-average square roughness after the wet roughening process of the cured product. M2 or more is more preferable, 0.15 mg/m2 or more is still more preferable, and 0.2 mg/m2 or more is still more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the melt viscosity in the form of an adhesive film, the amount of carbon per unit surface area of the inorganic filler is preferably 1 mg/m 2 or less, more preferably 0.75 mg/m 2 or less. It is preferable, and 0.5 mg/m 2 or less is more preferable.

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

The surface treatment method in the case of surface treatment of the inorganic filler with aminoalkylsilane is not particularly limited, and a dry method or a wet method may be mentioned. In the dry method, an inorganic filler is placed in a rotary mixer, and an alcohol solution or aqueous solution of an aminoalkylsilane is added dropwise or sprayed while stirring, followed by further stirring and classifying by a sieve. Thereafter, the surface-treated inorganic filler can be obtained by dehydrating and condensing the aminoalkylsilane and the inorganic filler by heating. As a wet method, an aminoalkylsilane is added while stirring the slurry of an inorganic filler and an organic solvent, and after stirring, filtration, drying and classification by sieve are performed. After that, it can be obtained by dehydrating and condensing an aminoalkylsilane and an inorganic filler by heating. In addition, it is possible to perform surface treatment by an integral blending method in which an aminoalkylsilane is added to the resin composition.

<hardening accelerator>

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

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

Although it does not specifically limit as a guanidine-type hardening accelerator, Dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, di Phenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-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 biguanide, 1-(o-tolyl) biguanide, etc. are mentioned. These may be used singly or in combination of two or more.

Although it does not specifically limit as an imidazole-type hardening accelerator, 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 trimellitate, 1-cyanoethyl-2-phenyli Midazolium 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-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2 -a] imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and imidazole compounds and epoxy resin An adduct body (additional body) is mentioned. These may be used singly or in combination of two or more.

The phosphonium-based curing accelerator is not particularly limited, but triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenyl borate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, and the like. These may be used singly or in combination of two or more.

In the case of blending a curing accelerator (excluding a metal curing accelerator) into the resin composition of the present invention, when the total of the epoxy resin and the curing agent is 100 parts by mass, the range is preferably 0.005 to 1 parts by mass, and 0.01 to 0.5 parts by mass. The range is more preferred. When the addition amount of the curing accelerator (excluding the metal curing accelerator) is within this range, thermal curing can be performed more efficiently, and the storage stability of the resin varnish is also improved.

Although it does not specifically limit as a metal-type hardening accelerator, An organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, and 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, organic iron 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 organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like. These may be used singly or in combination of two or more.

In the case of blending a metal-based curing accelerator in the resin composition of the present invention, when the nonvolatile component in the resin composition is 100% by mass, the content of the metal based on the metal-based curing catalyst is preferably in the range of 25 to 500 ppm, and 40 The range of -200 ppm is more preferable. When the amount of the metal-based curing accelerator added is within this range, an excellent conductor layer is formed due to adhesion to the surface of the insulating layer, and the storage stability of the resin varnish is also improved.

<Thermoplastic resin>

By further containing a thermoplastic resin in the resin composition of the present invention, the mechanical strength of the cured product can be improved, and the film forming ability when used in the form of an adhesive film can also be improved. As thermoplastic resins, phenoxy resins, polyvinyl acetal resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketones Resins and polyester resins are mentioned, and phenoxy resins and polyvinyl acetal resins are particularly preferred. These thermoplastic resins may be used individually or in combination of two or more. The weight average molecular weight of the thermoplastic resin is preferably in the range of 8000 to 200000, more preferably in the range of 12000 to 100000. In addition, the weight average molecular weight in this invention is measured by 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 Corporation as a column. -804L can be measured at a column temperature of 40°C using chloroform or the like as a mobile phase, and calculated using a calibration curve of standard polystyrene.

When blending a thermoplastic resin to the resin composition of the present invention, when the nonvolatile component in the resin composition is 100% by mass, 0.1 to 10% by mass is preferable, and 0.5 to 5% by mass is more preferable. When the content of the thermoplastic resin in the resin composition is within this range, the effect of improving the film formability and mechanical strength can be exhibited, and the melt viscosity can be increased and the roughness of the surface of the insulating layer after the wet roughening process can be reduced.

<Rubber particle>

By further containing rubber particles in the resin composition of the present invention, the peel strength can be improved, and the drill workability of the cured product of the resin composition can be improved, the dielectric loss tangent can be reduced, and the stress relaxation effect can also be obtained. The rubber particles that can be used in the present invention are, for example, those that are not soluble in an organic solvent used when preparing the varnish of the resin composition, and are not compatible with an epoxy resin or the like. Accordingly, the rubber particles are present in a dispersed state in the varnish of the resin composition of the present invention. In general, such rubber particles are prepared by increasing the molecular weight of the rubber component to a level in which it is not dissolved in an organic solvent or resin, and making it a particle shape.

Preferable examples of the rubber particles include core-shell rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell rubber particles are rubber particles having a core layer and a shell layer.For example, a two-layer structure in which the shell layer of the outer layer is composed of a glassy polymer, and the core layer of the inner layer is composed of a rubbery polymer, or the shell layer of the outer layer is glassy polymer. And a three-layer structure in which the intermediate layer is composed of a rubber-like polymer and the core layer is composed of a glass-like polymer. The glassy polymer layer is composed of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is composed of, for example, a butyl acrylate polymer (butyl rubber) or the like. The rubber particles may be used in combination of two or more. Specific examples of the core-shell rubber particles include Starphylloid AC3832, AC3816N, AC3401N, IM-401 7-17 (trade name, manufactured by Kantsu Chemical Co., Ltd.), Metabreen KW-4426 (trade name, Mitsubishi Rayon Co., Ltd. ) Manufacturing). As a specific example of the crosslinked acrylonitrile butadiene rubber (NBR) particle, XER-91 (average particle diameter 0.5 µm, manufactured by JSR Corporation), etc. are mentioned. As a specific example of the crosslinked styrene butadiene rubber (SBR) particle, XSK-500 (average particle diameter 0.5 µm, manufactured by JSR Corporation), etc. are mentioned. As a specific example of the acrylic rubber particle, metabrene W300A (average particle diameter 0.1 µm) and W450A (average particle diameter 0.2 µm) (manufactured by Mitsubishi Rayon Co., Ltd.) can be mentioned.

The average particle diameter of the rubber particles 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 a suitable organic solvent by ultrasonic or the like, and the particle size distribution of the rubber particles is prepared on a mass basis using a thick particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). It can be measured by making the median diameter an average particle diameter.

In the case of blending rubber particles in the resin composition of the present invention, the content of the rubber particles is preferably 0.05 to 10% by mass, more preferably 0.5 to 5% by mass, based on 100% by mass of the nonvolatile component in the resin composition. %to be.

<Flame retardant>

Flame retardance 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 silicon flame retardant, and a metal hydroxide. As organic phosphorus-based flame retardants, phenanthrene-type phosphorus compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Corporation, phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd., and ajinomotopine Reoforce 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, manufactured by Techno Co., Ltd., TPPO, PPQ, manufactured by Hoko Chemical Industries, Ltd. Phosphoric acid ester compounds such as OP930 manufactured by Clariant Co., Ltd., PX200 manufactured by Ohachi Chemical Co., Ltd., phosphorus-containing epoxy resin such as FX289, FX305, TX0712 manufactured by Shin Nitetsu Chemical Co., Ltd., manufactured by Shin Nitetsu Chemical Co., Ltd. Phosphorus-containing phenoxy resins such as ERF001 and phosphorus-containing epoxy resins such as YL7613 manufactured by Mitsubishi Chemical Corporation. Examples of organic nitrogen-containing phosphorus compounds include phosphate esteramide compounds such as SP670 and SP703 manufactured by Shikoku Chemical Industries, Ltd., SPB100 and SPE100 manufactured by Otsuka Chemicals, and FP-series manufactured by Fushimi Pharmaceutical Co., Ltd. Phagen compounds, etc. are mentioned. Examples of metal hydroxides include magnesium hydroxide such as UD65, UD650, UD653 manufactured by Ube Mathereals Co., Ltd., B-30, B-325, B-315, B-308, B-303 manufactured by Tomoe Industrial Co., Ltd. And aluminum hydroxide such as UFH-20.

When a flame retardant is blended into the resin composition of the present invention, it is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, based on 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 that does not impair the effects of the present invention. Other components include vinylbenzyl compounds, acrylic compounds, maleimide compounds, thermosetting resins such as block isocyanate compounds, organic fillers such as silicone powder, nylon powder, and fluorine powder, thickeners such as orbene and bentone, silicone-based, fluorine-based, and polymer-based Antifoaming agent or leveling agent, imidazole-based, thiazole-based, triazole-based, silane coupling agent, and other adhesion imparting agents, phthalocyanine-blue, phthalocyanine-green, iodine-green, disazo yellow, carbon black, and other coloring agents, silane couple And surface treatment agents such as ring agents, titanate coupling agents, and silazane compounds. In addition, when this surface treatment agent is used, the aminoalkylsilane may be covalently bonded to the surface of the inorganic filler through the surface treatment agent.

In the resin composition of the present invention, the above components are appropriately mixed, and, if necessary, kneaded by a kneading means such as three rolls, a ball mill, a bead mill, or a sand mill, or a stirring means such as a super mixer or a planetary mixer. Or it can be prepared by mixing. Moreover, it can also be prepared as a resin varnish by adding an organic solvent further.

In the resin composition of the present invention, not only the arithmetic mean roughness of the surface of the insulating layer is low in the wet roughening process, the surface of the insulating layer has a small root-average square roughness, and a plated conductor layer having sufficient peel strength can be formed on the insulating layer. In addition, since the coefficient of linear thermal expansion can also be lowered, the resin composition of the present invention can be preferably used as a resin composition for forming an insulating layer (a resin composition for an insulating layer of a multilayer printed wiring board) in the manufacture of a multilayer printed wiring board. , It can be more preferably used as a resin composition for forming a conductor layer by plating (a resin composition for an insulating layer of a multilayer printed wiring board forming a conductor layer by plating), and as a resin composition for a build-up layer of a multilayer printed wiring board Do.

After curing the resin composition of the present invention to form an insulating layer, and roughening the surface of the insulating layer, the arithmetic mean roughness (Ra value) and the root mean square roughness (Rq value) of the surface of the insulating layer, which will be described later, are described below. It can be grasped by the measurement method described in [Measurement of arithmetic mean roughness (Ra value) and root mean square roughness (Rq value)].

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

Since the root mean square roughness (Rq value) reflects the local state of the surface of the insulating layer, it was confirmed that the surface of the insulating layer became dense and smooth by grasping the Rq value, and the peel strength was stabilized. The upper limit of the root mean square roughness (Rq value) is preferably 500 nm or less, more preferably 450 nm or less, even more preferably 400 nm or less, and 350 nm or less in order to obtain a dense and smooth insulating layer surface. It is even more preferable. From the viewpoint of stabilizing the peel strength, the lower limit of the root mean square roughness (Rq value) is preferably 20 nm or more, more preferably 100 nm or more, and even more preferably 150 nm or more.

The peel strength of the insulating layer obtained by curing the resin composition of the present invention and the conductor layer obtained by roughening the surface of the insulating layer and plating is described in [Measurement of the peel strength (peel strength) of the plated conductor layer] described later. It can be grasped by a measurement method.

The peel strength is preferably 0.35 kgf/cm or more, more preferably 0.4 kgf/cm or more, and even more preferably 0.45 kgf/cm or more in order to sufficiently close the insulating layer and the conductor layer. The higher the upper limit of the peel strength, the better, and there is no particular limitation, but it is generally 1.5 kgf/cm or less, 1.2 kgf/cm or less, 1.0 kgf/cm or less, 0.8 kgf/cm or less.

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

From the viewpoint of reducing the warpage of the substrate, the coefficient of linear thermal expansion is preferably 25 ppm or less, more preferably 23 ppm or less, still more preferably 21 ppm or less, and even more preferably 19 ppm or less. The smaller the coefficient of linear thermal expansion is, the better, and there is no particular lower limit, but it is generally 4 ppm or more, 6 ppm or more, and 8 ppm or more.

The use of the resin composition of the present invention is not particularly limited, but sheet-like laminated materials such as adhesive films and prepregs, circuit boards (laminated boards, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials, semiconductor sealing materials It can be widely used in applications requiring a resin composition, such as hole-filling resin and part-filling resin. Although the resin composition of the present invention may be applied to a circuit board in a varnish state to form an insulating layer, industrially, it is generally preferable to use it 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 lamination property of the sheet-like laminated material.

<Sheet-type laminated material>

(Adhesive film)

In the adhesive film of the present invention, a method known to a person skilled in the art, for example, a resin varnish obtained by dissolving a resin composition in an organic solvent, is prepared, and the resin varnish is applied to a support using a die coater or the like, and further heated or sprayed with hot air. It can be manufactured by a method of forming a resin composition layer by drying an organic solvent by means of or the like.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and acetic acid esters such as carbitol acetate, cellosolve, and butylcar Carbitols such as bitol, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. As an organic solvent, you may use them in combination of 2 or more types of these.

Drying conditions are not particularly limited. For example, it is dried 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. Although it also differs depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer can be formed by drying a varnish containing 30 to 60 mass% of an organic solvent at 50 to 150°C for about 3 to 10 minutes. have.

It is preferable that the thickness of the resin composition layer formed in the adhesive film is not less 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, the thickness of the resin composition layer is more preferably 15 to 80 µm.

As a support, a film of polyolefin such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as ``PET''), polyester film such as polyethylene naphthalate, polycarbonate film, polyimide film Various plastic films, such as are mentioned. Further, as a support, a release paper, a metal foil such as copper foil or aluminum foil may be used. Among these, the support is preferably a plastic film, and a polyethylene terephthalate film is more preferable from the viewpoint of versatility. Surface treatments such as mad treatment and corona treatment may be applied to the support and the protective film described later. Further, the support and the protective film described later may be subjected to a release treatment with a release agent such as a silicone resin release agent, an alkyd resin release agent, and a fluororesin release agent.

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

On the surface of the resin composition layer to which the support is not in close contact, a protective film according to the support can be further laminated. The thickness of the protective film is not particularly limited, but is, for example, 1 to 40 µm. By laminating the protective film on the resin composition layer, it is possible to prevent adhesion or damage of dust or the like on the surface of the resin composition layer.

The adhesive film formed as described above can also be wound and stored in a roll shape.

(Prepreg)

The prepreg of the present invention can be produced by impregnating a sheet-like reinforcing substrate with the resin composition of the present invention by a hot-melt method or a solvent method, followed by heating and semi-curing. That is, a prepreg in which the resin composition of the present invention is impregnated in a sheet-like reinforcing substrate can be obtained. As the sheet-like reinforcing base material, for example, a glass cloth, aramid fiber, or other fiber made of a fiber commonly used as a prepreg fiber can be used. A configuration in which this prepreg is provided on a support is preferable.

In the hot-melt method, the resin composition is not dissolved in an organic solvent, and the resin composition is coated on a support once and laminated on a sheet-shaped reinforcing substrate, or a resin composition is directly coated on a sheet-shaped reinforcing substrate with a die coater to form a prepreg. It is a method of manufacturing. The solvent method is a method of dissolving a resin in an organic solvent in the same manner as an adhesive film to prepare a resin varnish, immersing the sheet-shaped reinforcing substrate in the varnish, impregnating the sheet-shaped reinforcing substrate with the resin varnish, and then drying it. Further, the prepreg can also be prepared by continuously thermally laminating an adhesive film on both surfaces of a sheet-like reinforcing substrate under heating and pressing conditions. A support body, a protective film, etc. can also be used like an adhesive film.

<Multilayer printed wiring board using sheet-type laminated material>

Next, an example of a method of manufacturing a multilayer printed wiring board using the sheet-like laminate material manufactured as described above will be described.

First, a sheet-like laminated material is laminated (laminated) on one or both sides of a circuit board using a vacuum laminator (laminating step). Examples of the substrate used for the circuit board 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, the circuit board here refers to a patterned conductor layer (circuit) formed on one or both sides of the above-described substrate. Further, in a multilayer printed wiring board formed by alternately stacking a conductor layer and an insulating layer, the circuit board referred to herein includes a conductor layer (circuit) in which one or both surfaces of the outermost layer of the multilayer printed wiring board are patterned. Further, the surface of the conductor layer may be previously subjected to roughening treatment such as blackening treatment and copper etching.

In the laminating process, 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 needed, and the sheet-like laminate material is laminated on the circuit board while pressing and heating. . In the sheet-like laminated material of the present invention, a method of laminating a circuit board under reduced pressure by a vacuum lamination method is preferably used. The conditions of the lamination are not particularly limited, for example, the pressing temperature (lamination temperature) is preferably 70 to 140°C, and the pressing pressure (lamination pressure) is preferably 1 to 11 kgf/cm 2 (9.8×10 ⁴ to). 107.9×10 ⁴ N/m 2 ), the pressing time (lamination time) is preferably 5 to 180 seconds, and the lamination is preferably performed under reduced pressure of 20 mmHg (26.7 hPa) or less in air pressure. Further, the method of laminating may be a batch type or a continuous type using a roll. 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, a vacuum pressurized laminator manufactured by Meiki Manufacturing, a roll-type dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi Aishi Inc. And the like.

In the case of peeling the support after laminating the sheet-like laminated material on the circuit board, cooling to around room temperature, and then peeling the support, the support is peeled off, and the resin composition is thermally cured to form a cured product, thereby forming an insulating layer on the circuit board. I can. The conditions for thermal curing may be appropriately selected depending on the type and content of the resin component in the resin composition, but preferably at 150°C to 220°C for 20 to 180 minutes, more preferably at 160°C to 210°C for 30 to Choose from a range of 120 minutes. In the case where the support is not peeled before curing after forming the insulating layer, it may be peeled after curing, if necessary.

In addition, the sheet-like laminated material may be laminated on one or both sides of a circuit board using a vacuum press. The lamination process of heating and pressurizing under reduced pressure can be performed using a general vacuum hot press. For example, the lamination process can be performed by pressing a metal plate such as a heated SUS plate from the side of the support layer. Pressing conditions are the pressure reduction degree of usually 1 × 10 ^-2 MPa or less, preferably 1 × 10 ^-3 MPa or less. The heating and pressurization may be performed in one step, but from the viewpoint of controlling the bleeding of the resin, it is preferable to divide the conditions into two or more steps. For example, the first step press is performed at a temperature of 70 to 150°C and a pressure in the range of 1 to 15 kgf/cm 2, and then the second press is performed at a temperature of 150 to 200°C, and pressure Is preferably carried out in the range of 1 to 40 kgf/cm 2. The time for each step is preferably 30 to 120 minutes. By thermosetting the resin composition layer in this way, an insulating layer can be formed on a circuit board. As a commercially available vacuum hot press machine, MNPC-V-750-5-200 (made by Meiki Co., Ltd.), VH1-1603 (made by Kitagawa Seiki Co., Ltd.), etc. are mentioned, for example.

Subsequently, the insulating layer formed on the circuit board is drilled to form via holes and through holes. The drilling process can be performed by known means such as a drill, laser, plasma, or a combination of them as necessary, but the drilling process using a laser such as a carbon dioxide laser or a YAG laser is the most common method. When the support is not peeled before drilling, it can be peeled after drilling.

Next, roughening treatment is performed on the surface of the insulating layer. Plasma treatment etc. are mentioned as a dry roughening treatment method, and a method of performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order is mentioned as a wet roughening treatment method. 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 for 5 to 20 minutes at 50 to 80°C (preferably at 55 to 70°C for 8 to 15 minutes). Examples of the swelling liquid include an alkali solution, a surfactant solution, and the like, preferably an alkali solution, and examples of the alkali solution include sodium hydroxide solution and potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securiganth P (Swelling Dip Securiganth P), Swelling Dip Securiganth SBU (Swelling Dip Securiganth SBU) manufactured by Atotech Japan, etc. have. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer at 60 to 80°C for 10 to 30 minutes (preferably at 70 to 80°C for 15 to 25 minutes) in an oxidizing agent solution. Examples of the oxidizing agent include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and the like. Further, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrated Compact CP manufactured by Atotech Japan Co., Ltd., and Dosing Solution Security P. The neutralization treatment with the neutralizing liquid is performed by immersing in the neutralizing liquid for 3 to 10 minutes at 30 to 50°C (preferably 3 to 8 minutes at 35 to 45°C). As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercial item, Atotech Japan Co., Ltd. Reduction Solution Securities P is mentioned.

Subsequently, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, known methods such as vapor deposition, sputtering, and ion plating can be used. Examples of the wet plating include a method of forming a conductor layer by combining electroless plating and electrolytic plating, a method of forming a plating resist having an inverse pattern from the conductor layer, and forming a conductor layer only by electroless plating. As a method of subsequent pattern formation, for example, a subtractive method, a semi-additive method, etc. known to those skilled in the art can be used, and a multilayer printed wiring board in which the build-up layers are stacked in multiple stages by repeating the above series of steps a plurality of times Can be formed. The resin composition of the present invention can be preferably used as a build-up layer of a multilayer printed wiring board since the roughness is low and the peel strength is high after curing and roughening treatment.

<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 at a conductive location of the multilayer printed wiring board of the present invention. The "conducting point" is "a place that transmits an electric signal in a multilayer printed wiring board", and the place may be a surface or a buried place. Further, 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 a bumpless build-up layer (BBUL ), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

Example

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

<Measurement method and evaluation method>

First, a measurement method and an evaluation method will be described.

(Preparation of samples for measuring peel strength, arithmetic mean roughness (Ra value), root mean square roughness (Rq value))

(1) substrate treatment of inner circuit board

Epoxy resin double-sided copper-clad laminate (copper foil thickness 18 µm, substrate thickness 0.3 mm, Matsushita Electric Co., Ltd. R5715ES) on which the inner layer circuit was formed was etched by 1 um with CZ8100 manufactured by MAC Co., Ltd. Harmonization treatment was performed.

(2) Laminating process of adhesive film

The adhesive films prepared in Examples and Comparative Examples were laminated on both sides of an inner circuit board using a batch-type vacuum pressurized laminator MVLP-500 (trade name manufactured by Meiki Co., Ltd.). The lamination process was performed by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, followed by compression bonding at 100°C and pressure of 0.74 MPa for 30 seconds.

(3) curing of resin composition

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

(4) Harmonization treatment

The inner circuit board on which the insulating layer was formed was placed in a swelling solution of Atotech Japan Co., Ltd. diethylene glycol monobutyl ether containing Swelling Dip Securigans P (glycol ethers, aqueous solution of sodium hydroxide) at 80°C for 10 Soaked for a minute. Next, as a roughening liquid, it was immersed in Atotech Japan Co., Ltd. concentrate compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) at 80 degreeC for 20 minutes. Finally, as a neutralizing liquid, it was immersed in Reduction Solutions Security P (aqueous solution of sulfuric acid) of Atotech Japan Co., Ltd. at 40 degreeC for 5 minutes. After drying at 80°C for 30 minutes, about the surface of the insulating layer after the roughening treatment, the arithmetic mean roughness (Ra value) and the root mean square roughness (Rq value) were measured.

(5) Plating process by semi-additive method

In order to form a circuit on the surface of the insulating layer, the inner circuit board 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 performing an annealing treatment by heating at 150° C. for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electroplating was performed to form a conductor layer with a thickness of 30 μm. Next, an annealing treatment was performed at 200°C for 60 minutes. With respect to this circuit board, the peel strength (peel strength) of the plated conductor layer was measured.

(Measurement of arithmetic mean roughness (Ra value) and root square mean square roughness (Rq value) after harmonization)

Using a non-contact type surface roughness machine (WYKO NT3300 manufactured by Bcoin Instruments), the Ra value and Rq value were determined by numerical values obtained by using a VSI contact mode and a 50-fold lens with a measurement range of 121 µm×92 µm. And it measured by obtaining the average value of each 10 points.

[Measurement of peel strength (peel strength) of the plated conductor layer]

The conductor layer of the circuit board is partially cut with a width of 10 mm and a length of 100 mm, and this end is peeled off and picked up with tongs (T.S.E. Co., Ltd., Autocom type tester AC-50C-SL), and 50 mm at room temperature. The load (kgf/cm) when 35 mm was peeled off in the vertical direction at a speed of /min was measured.

[Measurement of Coefficient of Linear Thermal Expansion (CTE)]

The adhesive films prepared in Examples and Comparative Examples were heat-cured at 190° C. for 60 minutes, and the support was peeled to obtain a sheet-shaped cured product. The cured body was cut into a test piece having a width of 5 mm and a length of 15 mm, and a thermomechanical analysis was performed by a tensile weighting method using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Corporation). After attaching the test piece to the apparatus, it was continuously measured twice under the conditions of a load of 1 g and a temperature increase rate of 5°C/min. The average coefficient of linear thermal expansion (ppm/°C) from 25°C to 150°C in the second measurement was calculated.

〔Used inorganic filler〕

Inorganic filler 1: For 100 parts of spherical silica ("SFP-130MC" manufactured by Denki Chemical Industries, Ltd., average particle diameter 0.6 µm, specific surface area 6.2 ㎡/g), 3-aminopropylsilane (manufactured by Shin-Etsu Chemical Industries, Ltd.) , "KBM903", molecular weight 179) surface-treated with 0.3 parts, carbon amount per unit surface area 0.13 mg/m 2.

Inorganic filler 2: 3-aminopropylsilane (Shin-Etsu Chemical Co., Ltd.) per 100 parts of spherical silica ("SO-C2" manufactured by Adomatex Co., Ltd., average particle diameter 0.5 µm, specific surface area 5.5 ㎡/g) , "KBE903", molecular weight 221) surface-treated with 0.4 parts, and the amount of carbon per unit surface area is 0.15 mg/m 2.

Inorganic filler 3: Spherical silica ("SFP-130MC" manufactured by Denki Chemical Industries, Ltd., average particle diameter 0.6 µm, specific surface area 6.2 m 2 /g) without surface treatment.

Inorganic filler 4: For 100 parts of spherical silica ("SFP-130MC" manufactured by Denki Chemical Industries, Ltd., average particle diameter 0.6 µm, specific surface area 6.2 m 2 /g), phenylaminosilane (manufactured by Shin-Etsu Chemical Industries, Ltd.), " KBM573", molecular weight 255) surface-treated with 0.5 part, carbon amount per unit surface area 0.30 mg/m 2.

Inorganic filler 5: For 100 parts of spherical silica ("SFP-130MC" manufactured by Denki Chemical Industries, Ltd., average particle diameter 0.6 µm, specific surface area 6.2 m 2 /g), epoxysilane (manufactured by Shin-Etsu Chemical Industries, Ltd.), "KBM403 ", molecular weight 236) surface-treated with 0.5 part, carbon amount per unit surface area 0.19 mg/m 2.

<Example 1>

Naphthalene-type epoxy resin ("HP4032SS" manufactured by DIC Corporation) 10 parts, liquid bisphenol-type epoxy resin (``ZX1059" manufactured by Shinitetsu Chemical Corporation, 1:1 mixture of bisphenol A type and bisphenol F type) 5 parts , Naphthol type epoxy resin (Shinitetsu Chemical Co., Ltd. ``ESN-475V'') 20 parts, phenoxy resin (weight average molecular weight 35000, Mitsubishi Chemical Co., Ltd. ``YL7553BH30''), non-volatile component 30 mass% MEK and A 1:1 solution of cyclohexanone) 5 parts was dissolved by heating while stirring in 50 parts of solvent naphtha, and then cooled to room temperature. Next, 10 parts of an active ester compound ("HPC8000-65T" manufactured by DIC Corporation, an active ester equivalent of 223, a toluene solution of 65% solid content), a prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by Ronza Japan, Ltd.), Cyanate equivalent of about 232, non-volatile content of 75 mass% MEK solution) 20 parts, phenol novolak type polyfunctional cyanate ester resin (Lonza Japan Co., Ltd. ``PT30S'', cyanate equivalent of about 133, non-volatile content 85 mass% MEK solution) 10 parts, rubber particles (manufactured by Kantsu Chemical Co., Ltd., Starphiloid AC3816N) 4 parts swelled in 16 parts of solvent naphtha at room temperature for 12 hours, flame retardant ("HCA-HQ" manufactured by Sanko Corporation) , 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 1 μm) 3 parts, curing accelerator (4-dimethylaminopyridine, 0.5 parts of solid content 4 mass% MEK solution), 4.5 parts of hardening accelerator (manufactured by Tokyo Chemical Co., Ltd., cobalt(III) acetylacetonate, solid content 1 mass% MEK solution) 4.5 parts are added, and 150 parts of inorganic filler 1 are further mixed And uniformly dispersed in a rotary mixer to prepare a resin varnish. Next, on the release surface of a polyethylene terephthalate film (“AL5” manufactured by Lintec Co., Ltd., thickness 38 μm) obtained by subjecting this resin varnish to an alkyd release treatment, a die coater so that the thickness of the resin composition layer after drying is 40 μm. And uniformly applied at 80 to 110°C (average 95°C) for 5 minutes to obtain an adhesive film.

<Example 2>

150 parts of inorganic filler 1 are changed to 175 parts of inorganic filler 2, and 5 parts of liquid bisphenol type epoxy resin (``ZX1059'' manufactured by Shinitetsu Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type) is biphenyl -Type epoxy resin (``YX4000HK'' manufactured by Mitsubishi Chemical Co., Ltd.) was changed to 5 parts, and a prepolymer of bisphenol A dicyanate (``BA230S75'' manufactured by Ronza Japan Co., Ltd. Solution) 20 parts are changed to 25 parts, and 10 parts are changed to 6 parts of a phenol novolak type polyfunctional cyanate ester resin ("PT30S" manufactured by Ronza Japan, a cyanate equivalent of about 133, a MEK solution of 85% by mass of non-volatile content) And, except having changed 4 parts of rubber particles into 3 parts, it carried out completely similarly to Example 1, and produced the resin varnish. Next, it carried out completely similarly to Example 1, and obtained the adhesive film.

<Comparative Example 1>

A resin varnish was produced in exactly the same manner as in Example 1 except that the inorganic filler 1 was changed to the inorganic filler 3. Next, it carried out completely similarly to Example 1, and obtained the adhesive film.

<Comparative Example 2>

A resin varnish was produced in exactly the same manner as in Example 1 except that the inorganic filler 1 was changed to the inorganic filler 4. Next, it carried out completely similarly to Example 1, and obtained the adhesive film.

<Comparative Example 3>

A resin varnish was produced in exactly the same manner as in Example 1 except that the inorganic filler 1 was changed to the inorganic filler 5. Next, it carried out completely similarly to Example 1, and obtained the adhesive film.

Table 1 shows the results. In addition, in the ``inorganic filler content'' shown below, since the ratio derived from aminoalkoxysilane or the like is negligible, the content of ``inorganic filler surface-treated with aminoalkoxysilane, etc.'' It can be identified with the content of ".

From the results of Table 1, it can be seen that the resin composition of the example has a small arithmetic mean roughness value and a square mean square root roughness value, a sufficient peel strength value can be obtained, and a small linear thermal expansion coefficient. On the other hand, in the comparative example, the value of the arithmetic mean roughness and the value of the square mean square roughness became large, and the peeling strength also became a small value.

In the case of curing and forming an insulating layer, not only the arithmetic mean roughness of the surface of the insulating layer is small in the wet roughening process, but also the value of the root mean square roughness is small, and a plated conductor layer having sufficient peel strength can be formed. It has become possible to provide a resin composition with a small coefficient of linear thermal expansion. Further, it became possible to provide a sheet-like laminate material, a multilayer printed wiring board, and a semiconductor device using the same. In addition, electric appliances such as computers, mobile phones, digital cameras, and televisions equipped with them, and vehicles such as motorcycles, automobiles, tanks, ships, and aircraft can be provided.

Claims (20)

As a resin composition containing an epoxy resin, a curing agent and an inorganic filler,
The inorganic filler is surface-treated with aminoalkylsilane,
The aminoalkylsilane includes at least one selected from an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminoisopropyl group, and an aminocyclopropyl group,
The epoxy resin comprises a biphenyl type epoxy resin,
The epoxy resin is a liquid epoxy resin and a solid epoxy resin are used in combination, the mass ratio of the liquid epoxy resin and the solid epoxy resin is 1:0.1 to 1:3,
The curing agent is a cyanate ester resin and an active ester curing agent represented by the following formula (2) or formula (3),
When the nonvolatile component in the resin composition is 100% by mass, the content of the inorganic filler is 55 to 90% by mass,
A resin composition, characterized in that the coefficient of linear thermal expansion of the cured product of the resin composition is 25 ppm or less:

[In formula, n represents 0-20.]

. delete The resin composition according to claim 1, wherein the aminoalkylsilane is 3-aminopropylsilane. The resin composition according to claim 1, wherein the aminoalkylsilane has a molecular weight of 100 to 2000. The resin composition according to claim 1, wherein the inorganic filler has an average particle diameter of 0.01 to 5 µm. The resin composition according to claim 1, wherein the inorganic filler is silica. The resin composition according to claim 1, wherein when the nonvolatile component in the resin composition is 100% by mass, the content of the inorganic filler is 60 to 85% by mass. The resin composition according to claim 1, wherein the aminoalkylsilane is surface-treated in an amount of 0.05 to 5 parts by mass per 100 parts by mass of the inorganic filler. The resin composition according to claim 1, wherein the amount of carbon per unit surface area of the inorganic filler is 0.05 to 1 mg/m 2. delete delete delete The method according to claim 1, wherein the resin composition is cured to form an insulating layer, and the arithmetic mean roughness after roughening the surface of the insulating layer is 10 to 300 nm, and the root mean square roughness is 20 to 500 nm. Resin composition. The resin composition according to claim 1, wherein the peel strength between the insulating layer obtained by curing the resin composition and the conductor layer obtained by roughening and plating the surface of the insulating layer is 0.35 to 1.5 kgf/cm. The resin composition according to any one of claims 1, 3 to 9, 13 and 14, which is a resin composition for insulating layers of a multilayer printed wiring board. The resin composition according to any one of claims 1, 3 to 9, 13, and 14, which is a resin composition for insulating layers of a multilayer printed wiring board in which a conductor layer is formed by plating. The resin composition according to any one of claims 1, 3 to 9, 13, and 14, which is a resin composition for a build-up layer of a multilayer printed wiring board. A sheet-like laminated material comprising the resin composition according to any one of claims 1, 3 to 9, 13, and 14. A multilayer printed wiring board in which an insulating layer is formed by a cured product of the resin composition according to any one of claims 1, 3 to 9, 13, and 14. A semiconductor device comprising the multilayer printed wiring board according to claim 19.