TW201420346A - Resin composition - Google Patents

Abstract

This invention provides a resin composition, which forms, when being subjected to curing, during a wet type roughening process, an insulated layer having a surface with less arithmetic mean roughness and less root mean square roughness, allowing the formation of a conductor layer with sufficient peel strength on the insulated layer by coating, and achieving low dielectric loss tangent of the cured object. The resin composition of this invention is characterized by comprising one or two of epoxy resin having a naphthyl fluorene structure, an active ester-based curing agent, and an isocyanate-based curing agent.

Description

Resin composition

The present invention relates to a resin composition. Further, the present invention relates to a sheet-like laminate including the resin composition, a multilayer printed wiring board, and a semiconductor device.

In recent years, with the advancement of miniaturization and high performance of electronic equipment, multi-layer printed wiring boards are required to be multilayered, and the wiring is made finer and higher in density.

There are various disposals for this. For example, Patent Document 1 discloses that a curable composition containing an epoxy compound having an olefin skeleton has high heat resistance, low linear expansion property, and high refractive index, but its performance is not necessarily sufficient.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2012-102228

The problem to be solved by the present invention is to provide a hardening roughening step after hardening an insulating layer, which not only reduces the value of the arithmetic mean roughness of the surface of the insulating layer but also the root mean square roughness on the insulating layer (root mean square) The value of the surface roughness is also small, and a resin composition having a dielectric tangent of a conductor layer having sufficient peel strength can be formed by plating on the insulating layer.

As a result of the positive review of the above-mentioned problems, the inventors of the present invention have a resin composition having an epoxy resin having a naphthylquinone structure and an active ester-based curing agent and/or a cyanate-based curing agent. The present invention has been completed.

That is, the present invention is intended to include the following.

[1] A resin composition characterized by comprising an epoxy resin having a naphthylfluorene structure of component (A), and an active ester curing agent and a cyanate curing agent of component (B) By.

[2] The resin composition according to the above [1], wherein the content of the component (A) is from 1 to 20% by mass based on 100% by mass of the nonvolatile component in the resin composition.

[3] The resin composition according to [1] or [2], wherein the content of the component (B) is from 1 to 30% by mass based on 100% by mass of the nonvolatile component in the resin composition.

[4] The resin composition according to any one of [1] to [3] wherein the component (B) is an active ester-based curing agent.

[5] The resin composition according to any one of [1] to [4] further comprising an inorganic filler.

[6] The resin composition according to [5], wherein the inorganic filler has an average particle diameter of 0.01 to 5 μm.

[7] The resin composition according to the above [5], wherein the content of the inorganic filler is 30 to 90% by mass based on 100% by mass of the nonvolatile component in the resin composition.

[8] The resin composition according to any one of [5] to [7] wherein the inorganic filler is surface-treated with a surface treatment agent.

[9] The resin composition according to any one of [5] to [8] wherein the inorganic filler is cerium oxide.

[10] The resin composition according to any one of [1] to [9] further comprising a thermoplastic resin.

[11] The resin composition according to any one of [1] to [10] wherein the resin composition is cured to form an insulating layer, and the arithmetic mean of the surface of the insulating layer after the surface of the insulating layer is roughened The roughness is 10 to 350 nm, and the root mean square roughness is 20 to 500 nm.

[12] The resin composition according to any one of [1] to [11] which is a resin composition for an insulating layer of a multilayer printed wiring board.

[13] The resin composition according to any one of [1] to [12] which is a resin composition for an insulating layer of a multilayer printed wiring board, wherein the multilayer printed wiring board-based conductor layer is formed by a plating station Former.

[14] A sheet-like laminate comprising the resin composition according to any one of [1] to [13].

[15] A multilayer printed wiring board comprising the resin composition according to any one of [1] to [13] as an insulating layer.

[16] A semiconductor device comprising the multilayer printed wiring board according to [15].

By using a resin composition characterized by containing an epoxy resin having a naphthylquinone structure and an active ester-based hardener and/or a cyanate-based hardener, a wet roughening step after hardening the insulating layer can be provided In the meantime, not only the value of the arithmetic mean roughness of the surface of the insulating layer is reduced, but also the value of the root mean square roughness of the surface of the insulating layer is small, and the dielectric layer of the conductor layer having sufficient peeling strength can be formed by plating on the insulating layer. Tangerally lower resin composition.

The present invention is a resin composition characterized by comprising an epoxy resin having a naphthylquinone structure, an active ester-based curing agent, and/or a cyanate-based curing agent, that is, an active ester-based curing agent and a cyanate ester-based curing agent. Either or both of the hardeners. Hereinafter, the compounding component of the resin composition will be described in detail.

<Component (A) Epoxy resin having naphthyl fluorene structure>

The epoxy resin having a naphthylquinone structure used in the present invention is not particularly The restriction is as long as it is an epoxy resin having an anthracene skeleton and a naphthalene skeleton. For example, an epoxy resin having a molecular structure in which glycidyl etherification of the phenol resin is carried out by reacting a phenol resin having a naphthylquinone structure obtained by reacting an anthrone with a naphthalene with epichlorohydrin is exemplified. An epoxy resin having a naphthylquinone structure disclosed in JP-A-2012-102228 can also be used. In particular, an epoxy resin having a structure represented by the following formula (1) is preferably used.

In the formula, R ₁ and R ₂ each independently represent a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom. a is 0~3. b is 0~3].

The commercially available epoxy resin having a naphthylfluorene structure is exemplified by CG-500 (manufactured by Osaka Gas Chemical Co., Ltd., having the structure represented by the above formula (1)).

The content of the epoxy resin having a naphthylquinone structure in the resin composition is not particularly limited, but the insulating layer table is considered in the wet roughening step. When the non-volatile content in the resin composition is 100% by mass, the content of the low-roughness of the surface is preferably from 1 to 20% by mass, more preferably from 1 to 20% by mass. 3 to 15% by mass, and more preferably 5 to 10% by mass.

In the resin composition of the present invention, an epoxy resin having a naphthylquinone structure and another epoxy resin may be used in combination as needed within the range in which the effects of the present invention can be exerted. These other epoxy resins are exemplified by, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, phenol novolac hydrogenated epoxy resin, Third butyl catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthalene ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, A Phenolic novolak type epoxy resin, biphenyl type epoxy resin, bismuth type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic ring Oxygen resin, epoxy resin containing a spiro ring, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, and the like. These may be used alone or in combination of two or more kinds as other epoxy resins.

When an epoxy resin having a naphthylfluorene structure and another epoxy resin are used as the epoxy resin, the wet roughening step takes into consideration the low thickness of the surface of the insulating layer and the high peel strength of the conductor layer formed by plating. When the solid content of the entire epoxy resin is 100 parts by mass, the epoxy resin having a naphthylquinone structure is preferably 30 to 90 parts by mass, more preferably 35 to 80 parts by mass, and still more preferably 40. ~70 parts by mass.

<Component (B) Active ester-based curing agent and/or cyanate-based curing agent>

The active ester-based curing agent and/or the cyanate-based curing agent used in the resin composition of the present invention are not particularly limited, but an active ester-based curing agent is preferably used from the viewpoint of achieving low dielectric tangent. The active ester-based curing agent and/or the cyanate-based curing agent may be used alone or in combination of two or more.

The active ester-based curing agent is not particularly limited, and it is generally preferred to use two or more reactive esters in a molecule such as a phenol ester, a thiophene ester, an N-hydroxylamine, or an ester of a heterocyclic hydroxy compound. Base compound. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. Particularly, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Agent. The carboxylic acid compound is exemplified by, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid or the like. The phenol compound or naphthol compound is exemplified by hydroquinone, meta-xyl phenol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, and Bisphenol bisphenol, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-di Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl Diphenol, phenol novolak resin, and the like. Active ester-based hardener in the present invention One type or two or more types can be used. The active ester-based hardener is preferably an active ester-based hardener containing a dicyclopentadienyl-type diphenol condensation structure, an active ester-based hardener containing a naphthalene structure, and an acetylated phenol novolac resin. The active ester-based curing agent, the active ester-based curing agent of the benzoquinone-based phenol novolac resin, and the like, and the dicyclopentadienyl-based diphenol condensation is more preferable from the viewpoint of improving the peel strength. An active ester-based curing agent and an active ester-based curing agent containing a naphthalene structure. As the active ester-based curing agent, an active ester-based curing agent disclosed in JP-A-2004-277460 may be used, and a commercially available one may also be used. As a commercial product, the dicyclopentadienyl type diphenol condensation structure is exemplified as EXB9451, EXB9460, EXB9460S-65T, HPC-8000-65T (made by DIC (shares, active base equivalent: about 223), phenol novolac The active ester-based hardener of the acetal of the resin is exemplified by DC808 (manufactured by Mitsubishi Chemical Corporation, active base equivalent of about 149), and the active ester-based hardener of the benzoic acid phenolic phenolic resin is listed as YLH1026 (Mitsubishi Chemical) (Stock) system, active base equivalent of about 200), YLH1030 (manufactured by Mitsubishi Chemical Corporation, active base equivalent of about 201), YLH1048 (manufactured by Mitsubishi Chemical Corporation, active base equivalent of about 245), and the like.

More specifically, the active ester-based curing agent containing a dicyclopentadienyl diphenol condensation structure is a compound represented by the following formula (2).

Wherein R is a phenyl or naphthyl group, k represents 0 or 1, and n is an average of repeating units, and is 0.05 to 2.5].

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

The cyanate-based curing agent is not particularly limited, and examples thereof include a novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate-based curing agent, a dicyclopentadiene type cyanate-based curing agent, and A bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate type curing agent, and a part of the triazine-based prepolymer. The weight average molecular weight of the cyanate-based curing agent is not particularly limited, but is preferably from 500 to 4,500, more preferably from 600 to 3,000. Specific examples of the cyanate-based curing agent are, for example, bisphenol A dicyanate and polyphenol cyanate (oligo(3-methylene-1,5-phenylene), 4,4 '-Methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2 - bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl) Methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl) sulfide, bis(4-cyanate) A difunctional cyanate resin such as phenyl phenol acetal, a polyfunctional cyanate resin derived from a phenol novolak, a cresol novolak, a phenol resin having a dicyclopentadiene type structure, or the like, and the cyanate resin Triazine Prepolymers and the like. These may be used alone or in combination of two or more. The commercially available cyanate resin is a phenol novolac type polyfunctional cyanate resin (manufactured by LONZA Co., Ltd., PT30S, cyanate equivalent 124) represented by the following formula (3), and is represented by the following formula (4). A part or all of the bisphenol A dicyanate is triazine-formed into a prepolymer of a terpolymer (manufactured by LONZA Co., Ltd., BA230S, cyanate equivalent 232), and the following formula (5) contains a bicyclic ring. Cyanate resin of pentadiene type structure (manufactured by LONZA Co., Ltd., DT-4000, DT-7000).

[In the formula, n is represented by an average value (preferably 0 to 20)].

[where n is represented by an average value of 0 to 5].

The content of the active ester-based curing agent and/or the cyanate-based curing agent in the resin composition is not particularly limited, but the low-thickness of the surface of the insulating layer and the conductor formed by plating are considered in the wet roughening step. When the non-volatile content in the resin composition is 100% by mass, the content is preferably from 1 to 30% by mass, more preferably from 3 to 25% by mass, even more preferably from 5 to 20. quality%.

In the resin composition of the present invention, an active ester-based curing agent and/or a cyanate-based curing agent and other curing agents may be used in combination as needed within the range in which the effects of the present invention can be exerted. The other curing agent is exemplified by, for example, a phenolic curing agent, a benzoxazine-based curing agent, and the like. The phenolic curing agent is not particularly limited, and one selected from the group consisting of a biphenyl type curing agent, a naphthalene type curing agent, a phenol novolac resin type curing agent, a naphthyl ether type curing agent, and a triazine skeleton-containing phenol type curing agent is preferably used. More than one species. The benzoxazine-based curing agent is not particularly limited, and specific examples thereof include F-a, P-d (manufactured by Shikoku Kasei Co., Ltd.), and HFB2006M (manufactured by Showa Polymer Co., Ltd.). These may be used alone or in combination of two or more.

When an active ester-based curing agent and/or a cyanate-based curing agent and other curing agents are used as a curing agent, the insulating layer in the wet roughening step is also considered. From the viewpoint of the low-thickness of the surface and the high peel strength of the conductor layer formed by plating, when the solid content of the entire curing agent is 100 parts by mass, the active ester-based curing agent and/or the cyanate-based curing agent It is preferably from 30 to 100 parts by mass, more preferably from 40 to 95 parts by mass, even more preferably from 50 to 90 parts by mass.

Further, in the resin composition of the present invention, the total number of epoxy groups in the entire epoxy resin and the reactive groups in all the hardeners are from the viewpoint of improving the mechanical strength or water resistance of the cured product of the resin composition. The ratio of the total count is preferably 1:0.2 to 1:2, more preferably 1:0.3 to 1:1.5, and even more preferably 1:0.4 to 1:1. Further, the total number of epoxy groups in all the epoxy resins present in the resin composition is a value obtained by dividing the solid content of each epoxy resin by the total value of the epoxy equivalent for all the epoxy resins, so-called all The total number of the reactive groups in the hardener is a value obtained by dividing the solid content of each hardener by the total value of the reactive base equivalents for all the hardeners.

<Inorganic filler>

The resin composition of the present invention can further reduce the dielectric tangent or thermal expansion coefficient of the cured product of the resin composition by further containing an inorganic filler. The inorganic filler is not particularly limited and is exemplified by, for example, cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, boric acid. Aluminum, barium titanate, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Among them, amorphous cerium oxide, pulverized cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, hollow cerium oxide, etc. The cerium oxide is preferably a molten cerium oxide, a spherical cerium oxide, and more preferably a spherical molten cerium oxide from the viewpoint of further reducing the surface roughness of the insulating layer. These may be used alone or in combination of two or more. Commercially available spherical molten cerium oxide is exemplified by "SOC2" and "SOC1" manufactured by Advantex Co., Ltd.

The average particle diameter of the inorganic filler is not particularly limited, but the surface of the insulating layer may have a low thickness and may be formed by fine wiring on the surface of the insulating layer, preferably 5 μm or less, more preferably 3 μm. Hereinafter, it is more preferably 2 μm or less, still more preferably 1 μm or less, still more preferably 0.8 μm or less, and most preferably 0.6 μm or less. On the other hand, when the resin composition is a resin paint, the average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.03 μm, from the viewpoint of improving the viscosity of the paint and reducing the workability. The above is more preferably 0.05 μm or more, still more preferably 0.07 μm or more, and most preferably 0.1 μm or more. The average particle diameter of the above inorganic filler can be measured by a laser diffraction ‧ scattering method in accordance with the Mie scattering theory. Specifically, the laser diffraction scattering type particle size distribution measuring apparatus can be used to determine the particle size distribution of the inorganic filler on a volume basis, and the median diameter is used as the average particle diameter. The measurement sample can be preferably used by dispersing an inorganic filler in water by ultrasonic waves. As for the laser diffraction scattering type particle size distribution measuring apparatus, LA-950 or the like manufactured by Horiba, Ltd. can be used.

The content of the inorganic filler is preferably 30% by mass in terms of reducing the linear thermal expansion coefficient or suppressing the occurrence of cracks in the multilayer printed wiring board, and when the nonvolatile content in the resin composition is 100% by mass. The above is more preferably 40% by mass or more, still more preferably 50% by mass or more, and still more preferably 60% by mass or more. On the other hand, the content of the inorganic filler is preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less in terms of preventing the cured material from becoming brittle or preventing the peeling strength from being lowered.

The inorganic filler is preferably surface-treated with a surface treatment agent, and more preferably from an amino decane coupling agent, an epoxy decane coupling agent, a mercapto decane coupling agent, a styryl decane coupling agent, or acrylic acid. One or more surfaces selected from an ester decane coupling agent, an isocyanate decane coupling agent, a thioether decane coupling agent, a vinyl decane coupling agent, a decane coupling agent, an organic decazane compound, and a titanate coupling agent The treatment agent is surface treated. Thereby, the dispersibility or moisture resistance of the inorganic filler can be improved.

Specifically, as a surface treatment agent, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-aminopropyldiethoxymethyldecane, and N-benzene are listed. 3-aminopropyltrimethoxydecane, N-methylaminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N- Amino decane coupling agent such as (2-aminoethyl)-3-aminopropyldimethoxymethyl decane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyl Triethoxy decane, 3-glycidoxypropylmethyldiethoxy decane, 3-glycidoxypropyl (dimethoxy)methyl decane, glycidyl butyl trimethoxy decane Epoxy decane coupling agent such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxy A mercapto decane coupling agent such as decane, 3-mercaptopropylmethyldimethoxydecane or 11-decylundecyltrimethoxydecane, or a styryl decane system such as p-styryltrimethoxydecane Coupling agent, 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyldimethoxydecane, 3-methyl An acrylate decane coupling agent such as a propylene methoxy propyl triethoxy decane, a 3-methyl propylene oxy propyl diethoxy decane, or an isocyanate such as 3-isocyanate propyl trimethoxy decane a decane coupling agent, a thioether decane coupling agent such as bis(triethoxydecylpropyl)disulfide or bis(triethoxydecylpropyl)tetrasulfide, methyltrimethoxydecane, a decane system such as octadecyltrimethoxydecane, phenyltrimethoxydecane, methacryloxypropyltrimethoxydecane, imidazolyl decane, triazine decane or tert-butyltrimethoxy decane a coupling agent, hexamethyldioxane, 1,3-divinyl-1,1,3,3-tetramethyldiazepine, hexaphenyldioxane, Indole, cyclotriazane, 2,2,4,4,6,6-hexamethylcyclotriazane, octamethylcyclotetraazane, hexabutyldioxane, hexa Dioxazane, 1,3-diethyltetramethyldiazepine, 1,3-di-n-octyltetramethyldiazepine, 1,3-diphenyltetramethyldiazoxide Alkane, 1,3-dimethyltetraphenyldiazepine, 1,3-diethyltetramethyldiazide, 1,1,3,3-tetraphenyl-1,3-dimethyl Dioxazane, 1,3-dipropyltetramethyldiazepine, hexamethylcyclotriazane, dimethylaminotrimethylguanidine, tetramethyldiazane, etc. Organic decazane compound, tetra-n-butyl titanate dimer, isopropyl isopropoxide octanediol, tetra-n-butyl titanate, titanium octoate, diisopropoxide bis(triethanol aluminate) , dihydroxy titanium dilactate, dihydroxy bis(ammonium lactate) titanium, double (dioctyl pyrophosphate) ethylene titanate, bis(dioctylpyrophosphate)oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, titanium Tetrakis(2-ethylhexyl) acid, tetraisopropylbis(dioctylphosphite) titanate, tetraoctylbis(di-tridecylphosphite) titanate, tetra (2) ,2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphite titanate, isopropyl trioctadecyl titanate, isopropyl tricumylphenyl titanium Acid ester, isopropyl triisostearyl decyl titanate, isopropyl isostearyl decyl diacrylate titanate, isopropyl dimethyl propylene decyl isostearyl decyl titanate, isopropyl Tris(dioctylphosphite) titanate, isopropyltridecylbenzenesulfonate titanate, isopropyl cis (dioctyl pyrophosphate) titanate, isopropyl tri A titanate coupling agent such as N-nonylaminoethylaminoethyl titanate or the like. Among these, an amino decane coupling agent, an epoxy decane coupling agent, a mercapto decane coupling agent, and an organic decazane compound are preferable. Commercially available products are "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd. (N-phenyl-3-amino group) "propyl trimethoxy decane", "SZ-31" (hexamethyldioxane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The amount of the surface treatment agent when the inorganic filler is surface-treated with a surface treatment agent is not particularly limited, but it is preferably surface-treated with 0.05 to 5 parts by mass of the surface treatment agent per 100 parts by mass of the inorganic filler. Surface treatment with 0.1~4 parts by mass, and better 0.2~3 The parts are subjected to surface treatment, and more preferably 0.3 to 2 parts by mass.

Further, the inorganic filler which has been surface-treated with a surface treatment agent can measure the amount of carbon per unit weight of the inorganic filler after washing with a solvent (for example, methyl ethyl ketone: MEK for short). Here, the "carbon amount per unit weight of the inorganic filler" means the amount (g) of carbon bonded to the inorganic filler 1g in percentage. Specifically, a sufficient amount of MEK was added as a solvent to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning was performed at 25 ° C for 5 minutes. After removing the supernatant liquid and drying the solid component, the solid component is analyzed using a carbon analyzer, whereby the amount of carbon per unit weight of the inorganic filler can be measured. As for the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The amount of carbon per unit weight of the inorganic filler is preferably 0.02% or more, more preferably from the viewpoint of improving the dispersibility of the inorganic filler or the root mean square roughness after the wet roughening step of the cured product. It is 0.05% or more, and more preferably 0.1% or more. On the other hand, from the viewpoint of preventing the melt viscosity of the resin paint or the melt viscosity in the film form from increasing, it is preferably 3% or less, more preferably 2% or less, still more preferably 1% or less.

When the resin composition contains an inorganic filler which is surface-treated with a surface treatment agent, it is preferably added to the resin composition after surface treatment of the inorganic filler with a surface treatment agent. In this case, the dispersibility of the inorganic filler can be further improved.

Surface treated with surface treatment agent for inorganic filler The treatment method is not particularly limited and is exemplified by a dry method or a wet method. As for the dry method, the inorganic filler is fed into a rotary kneading machine, and an alcohol solution or an aqueous solution of the surface treatment agent is added dropwise or sprayed with stirring, stirred, and classified by a sieve. Subsequently, heat treatment is performed to dehydrate the surface treatment agent with the inorganic filler, whereby the surface-treated inorganic filler can be obtained. As for the wet method, a surface treatment agent is added while stirring the slurry of the inorganic filler and the organic solvent, and after stirring, it is filtered, dried, and classified by a sieve. Subsequently, heat treatment is performed to dehydrate the surface treatment agent with the inorganic filler, whereby a surface-treated inorganic filler can be obtained. Further, it is also possible to carry out surface treatment by adding a surface treatment agent to the resin composition as a whole.

<hardening accelerator>

In the resin composition of the present invention, the epoxy resin and the curing agent can be effectively cured by further containing a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include an amine-based curing accelerator, an lanthanum-based curing accelerator, an imidazole-based curing accelerator, and an lanthanum-based curing accelerator. These may be used alone or in combination of two or more.

The amine-based hardening accelerator is not particularly limited, and examples thereof include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-gin ( An amine compound such as dimethylaminomethyl)phenol or 1,8-diazabicyclo(5,4,0)-undecene (hereinafter abbreviated as DBU). These may be used alone or in combination of two or more.

The lanthanide hardening accelerator is not particularly limited and is listed, for example, as Dicyanoguanamine, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl hydrazine, 1-phenyl hydrazine, 1-(o-tolyl) fluorene, dimethyl hydrazine, diphenyl hydrazine, Trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0]non-5-ene, 7-methyl-1,5,7-triaza Bicyclo[4.4.0]non-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1 , 1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, and the like. These may be used alone or in combination of two or more.

The imidazole-based hardening accelerator is not particularly limited, but may be exemplified by 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-phenyl Imidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6 -[2'-undecyl imidazolyl-(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-phenylimidazolium isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo[1,2-a]benzimidazole 2-methyl-1-dodecyl benzimidazolium chloride, 2-imidazoline, 2-phenyl imidazole and imidazoline compounds, and An adduct of an imidazole compound and an epoxy resin. These may be used alone or in combination of two or more.

The lanthanum hardening accelerator is not particularly limited, and examples thereof include triphenylphosphine, lanthanum borate, tetraphenylphosphonium tetraphenylborate, n-butyl fluorene tetraphenylborate, tetrabutyl citrate, 4-methylphenyl)triphenylsulfonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. These may be used alone or in combination of two or more.

In the resin composition of the present invention, when the curing accelerator is used in an amount of 100 parts by mass in total of the epoxy resin and the curing agent, the curing accelerator is preferably in the range of 0.005 to 1 part by mass, more preferably 0.01 to 0.5 part by mass. The scope. When the hardening accelerator falls within this range, it can be thermally cured more efficiently, and the storage stability of the resin paint can also be improved.

<Thermoplastic resin>

In the resin composition of the present invention, the mechanical strength of the cured product can be improved by further containing a thermoplastic resin, and the film forming ability of the resin composition when the resin composition is used in the form of a film can be improved. The thermoplastic resin may be exemplified by a phenoxy resin, a polyvinyl acetal resin, a polyimine resin, a polyamidimide resin, a polyether quinone resin, a polyfluorene resin, a polyether oxime resin, and a poly The phenyl ether resin, the polycarbonate resin, the polyether ether ketone resin, and the polyester resin are preferably a phenoxy resin or a polyethylene acetal resin. These thermoplastic resins may be used singly or in combination of two or more. The weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 200,000, more preferably in the range of 12,000 to 100,000. Further invention The weight average molecular weight in the medium is measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). For the weight average molecular weight measured by the GPC method, LC-9A/RID-6A manufactured by Shimadzu Corporation can be used as a measuring device, and Shpdex K-800P/K-804L/K manufactured by Showa Denko Co., Ltd. can be used. -804L was used as a column, and chloroform was used as a mobile phase, and it was measured at a column temperature of 40 ° C, and was calculated using a calibration line of standard polystyrene.

When the thermoplastic resin is blended in the resin composition of the present invention, the blending ratio of the thermoplastic resin is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 5% by mass based on the nonvolatile content of the resin composition. %. When the blending ratio of the thermoplastic resin is within this range, the film forming ability of the resin composition or the mechanical strength of the cured product can be improved, the increase in the melt viscosity can be further suppressed, and the surface of the insulating layer after the wet roughening step can be lowered. Roughness.

<Other ingredients>

The resin composition of the present invention may be blended with other components as needed within the range not impairing the effects of the present invention. The other components may, for example, be a vinyl benzyl compound, an acrylic compound, a maleic imine compound, a thermosetting resin of a blocked isocyanate compound, an organic filler such as a cerium powder, a nylon powder, a fluorine compound powder or a rubber particle. Oluben, Benton and other tackifiers, polyfluorene-based, fluorine-based, polymer-based antifoaming agents or leveling agents, imidazole-based, thiazole-based, triazole-based, decane coupling agents, etc., phthalocyanine ‧ Blue, phthalocyanine ‧ green, iodine ‧ green, disazo yellow, carbon black and other colorants, aluminum hydroxide, phosphorus compounds and other flame retardants

The resin composition of the present invention may be mixed by appropriately mixing the above components, and if necessary, by a mixing means such as a three-roller, a ball mill, a bead mill, a sand mill, or a mixing means such as a super-kneader or a planetary kneader or Mix and modulate. Further, a resin paint may be prepared by further adding an organic solvent to the resin composition.

When the resin composition of the present invention is hardened to form an insulating layer, not only the value of the arithmetic mean roughness of the surface of the insulating layer after the roughening treatment (wet roughening) is made small, but also the root mean square roughness of the surface of the insulating layer is made. The value of the degree is small, and a conductor layer having sufficient peeling strength can be formed on the surface of the insulating layer by plating to reduce the dielectric tangent of the cured product. Therefore, in the manufacture of the multilayer printed wiring board, it can be suitably used as a multilayer printed wiring board. A resin composition for the insulating layer. Further, the resin composition of the present invention can be suitably 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 formed by plating a conductor layer), and is more suitable as a multilayer printing layer. A resin composition for layering of a wiring board.

The resin composition of the present invention is cured to form an insulating layer, and the arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) of the surface of the insulating layer after roughening the surface of the insulating layer can be utilized as described later [ The measurement method described in the measurement of the tear strength (peel strength), the arithmetic mean roughness (Ra value), and the root mean square roughness (Rq value) of the conductor layer formed by plating is grasped.

The upper limit of the arithmetic mean roughness (Ra value) of the surface of the insulating layer is preferably 350 nm or less, more preferably 300 nm or less, still more preferably 250 nm or less, from the viewpoint of forming fine wiring. Below 200 nm, it is more preferably 150 nm or less, and most preferably 100 nm or less. The lower limit of the arithmetic mean roughness (Ra value) of the surface of the insulating layer is not particularly limited, and is set to 10 nm or more.

Since the root mean square roughness (Rq value) of the surface of the insulating layer reflects the local state of the surface of the insulating layer, it is confirmed by the Rq value whether it is a dense and smooth insulating layer surface, and becomes a dense and smooth insulating layer. On the surface, it exhibits a stable peel strength. The upper limit of the root mean square roughness (Rq value) of the surface of the insulating layer is preferably 500 nm or less, more preferably 400 nm or less, still more preferably 300 nm or less, in order to obtain a dense and smooth insulating layer surface. Below 200 nm. The lower limit of the root mean square roughness (Rq value) of the surface of the insulating layer is preferably 20 nm or more, and more preferably 40 nm or more from the viewpoint of stability of the peeling strength.

The resin composition of the present invention is cured to form an insulating layer, and the surface of the insulating layer is roughened, and the peeling strength of the conductor layer and the insulating layer formed by plating can be utilized as described later [Tear strength of the plated conductor layer (peeling off) The measurement method described in the measurement of the strength, the arithmetic mean roughness (Ra value), and the root mean square roughness (Rq value) is grasped.

The peeling strength is such that the insulating layer and the conductor layer are sufficiently adhered, and is preferably 0.37 kgf/cm or more, more preferably 0.4 kgf/cm or more, and still more preferably 0.43 kgf/cm or more. The upper limit of the peel strength is preferably as high as possible, and is not particularly limited, and is generally 1.5 kgf/cm or less, 1.2 kgf/cm or less, 1.0 kgf/cm or less, and 0.8 kgf/cm or less.

The dielectric tangent of the cured product of the resin composition of the present invention can be grasped by the measurement method described in [Measurement of Dielectric Tangent] which will be described later. The dielectric tangent is preferably 0.007 or less, more preferably 0.006 or less, from the viewpoint of reducing the loss of the electric signal. The dielectric tangent is as high as possible, and there is no particular lower limit, but it is generally 0.001 or more, 0.002 or more, and the like.

The form of the resin composition of the present invention is not particularly limited, and can be applied to a sheet-like laminate such as a film or a prepreg, or a circuit board (for laminate use, multilayer printed wiring board use, etc.). The resin composition of the present invention may be applied as a resin paint to a circuit board to form an insulating layer. However, it is generally industrially used in the form of a sheet-like laminate such as a film or a prepreg. The softening point of the resin composition is preferably from 40 to 150 ° C from the viewpoint of the lamination property of the sheet-like laminate.

<Sheet laminate> (following the film)

The adhesive film of the present invention can be prepared by dissolving a resin composition in an organic solvent to prepare a resin paint, and applying the resin paint to a support using a die coater or the like, for example, by a method known to those skilled in the art. It is produced by heating or drying the organic solvent by hot air blowing or the like to form a resin composition layer.

The organic solvent is exemplified by a ketone such as acetone, methyl ethyl ketone or cyclohexanone, ethyl acetate, butyl acetate, fibrin acetate, propylene glycol monomethyl ether acetate, carbitol acetate. Acetate, cellulase, butyl carbitol, etc., aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidine A guanamine-based solvent such as a ketone. The organic solvent may be used in combination of two or more kinds.

The drying conditions are not particularly limited. For example, the resin paint is dried so that the content of the organic solvent to the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although the amount of the organic solvent in the resin paint varies depending on the boiling point of the organic solvent, for example, by drying the resin paint containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C for about 3 to 10 minutes, it can be formed. Resin composition layer.

The thickness of the resin composition layer formed in the film is preferably more than the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, so the resin composition layer preferably has a thickness of 10 to 100 μm. From the viewpoint of film formation, it is preferably from 15 to 80 μm.

The support is exemplified by a film of a polyolefin such as polyethylene, polypropylene or polyvinyl chloride, a polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), or a polyester such as polyethylene naphthalate. Film, polycarbonate film, polyimide film and other plastic film. Further, a metal foil such as release paper, copper foil, or aluminum foil may be used as the support. Among them, the support is preferably a plastic film from the viewpoint of versatility, and more preferably a polyethylene terephthalate film. The support and the protective film described later may be subjected to a surface treatment such as matting treatment or corona treatment. Further, the support and a protective film to be described later may be subjected to a release treatment by a release agent such as a polyoxymethylene resin release agent, an alkyd resin release agent, or a fluororesin release agent.

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

The surface of the resin composition layer which is not adhered to the support may be further laminated with the same protective film as the support. The thickness of the protective film is not special Limit, but can be, for example, 1 to 40 μm. By laminating the protective film, it is possible to prevent dust or scratches from adhering to the surface of the resin composition layer. The film formed as described above may also be wound into a roll for storage.

(prepreg)

The prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing substrate by a hot melt method or a solvent method, and heating and semi-curing. In other words, it can be a prepreg sheet in a state in which the resin composition of the present invention is impregnated into a sheet-like reinforcing substrate. As the sheet-like reinforcing substrate, for example, a glass cloth or an arylamine fiber or the like which is commonly used as a fiber for prepreg sheets can be used. The prepreg is preferably configured to be disposed on a support.

The hot melt method is not applied to the organic solvent in the organic solvent, but is temporarily applied to the support, or laminated on the sheet-like reinforcing substrate, or directly coated on the sheet by the nozzle coating. A method of making a prepreg by reinforcing the substrate. The solvent method dissolves the resin in an organic solvent in the same manner as the adhesive film, prepares a resin paint, immerses the flaky reinforcing substrate in the resin paint, and impregnates the resin paint in the flaky reinforcing substrate, followed by drying. method. Further, it can be prepared by continuously laminating the subsequent film on both sides of the sheet-like reinforcing substrate under heating and pressurization conditions. The support or protective film can also be used in the same manner as the adhesive film.

<Multilayer Printed Wiring Board Using Sheet Laminates>

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

First, a sheet laminate is laminated on one or both sides of a circuit board using a vacuum laminator (laminating step). The substrate used in the circuit board is exemplified by, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or the like. Here, the circuit board refers to a conductor layer (circuit) formed by patterning on one surface or both surfaces of the substrate. In the multilayer printed wiring board in which the conductor layer and the insulating layer are alternately laminated, the one or both sides of the outermost layer of the multilayer printed wiring board are referred to as a patterned conductor layer (circuit). In the circuit board. Further, the surface of the conductor layer may be subjected to a roughening treatment such as blackening treatment or copper etching.

In the laminating step, when the sheet-like laminate material has a protective film, after removing the protective film, the sheet-like laminate material and the circuit substrate are preheated as needed, and the laminate is laminated while pressing and heating the sheet-like laminate material. Circuit board. In the sheet-like laminate of the present invention, a method of laminating on a circuit board under reduced pressure by vacuum lamination is preferably used. The conditions for lamination are not particularly limited, and the pressing temperature (laminating temperature) is preferably 70 to 140 ° C, and the pressing pressure (laminating pressure) is preferably 1 to 11 kgf/cm ² (9.8 ×). 10 ⁴ to 107.9 × 10 ⁴ N/m ² ), the pressing time (lamination time) is preferably 5 to 180 seconds, and the pressure is laminated under a reduced pressure of 20 mmHg (26.7 hPa) or less. In addition, the lamination method may be a batch type or a continuous type using a roll. Vacuum lamination can be carried out using a commercially available vacuum laminator. Commercially available vacuum laminating machines include, for example, a vacuum coating machine manufactured by Nichigo Morton Co., Ltd., a vacuum pressure laminating machine manufactured by a famous machine manufacturer, and a drum type dry coating manufactured by Hitachi Industrial Co., Ltd. Cloth machine, vacuum laminator made by Hitachi AIC (share).

After laminating the sheet-like laminate material on the circuit board, after cooling to room temperature, when the support is peeled off, the support is peeled off, and the resin composition is thermally cured to form a cured product, thereby forming on the circuit board. Insulation. The heat curing condition may be appropriately selected depending on the type and content of the resin component in the resin composition, but it is preferably from 150 ° C to 220 ° C for 20 minutes to 180 minutes, more preferably from 160 ° C to 210 ° C for 30 to 120 minutes. Choose within the range. After the insulating layer is formed, in the case where the support is not peeled off before the hardening, the support may be peeled off after hardening as necessary.

Further, the sheet-like laminate may be laminated on one or both sides of the circuit board using a vacuum press. The laminating step of heating and pressurizing under reduced pressure can be carried out using a general vacuum hot press. For example, it can be performed by pressurizing a metal plate such as a heated SUS plate from the side of the support. The pressurization condition is usually such that the degree of pressure reduction is 1 × 10 ^-2 MPa or less, and preferably under reduced pressure of 1 × 10 ^-3 MPa or less. Heating and pressurization can be carried out in one stage, but it is preferably carried out in two or more stages from the viewpoint of suppressing resin bleeding. For example, it is preferred to carry out the first-stage pressurization in a range of a temperature of 70 to 150 ° C and a pressure of 1 to 15 kgf/cm ² , and the temperature is set to 150 to 200 ° C, and the pressure is set to 1 to 40 kgf / cm ^{2 .} The range is pressurized in the second stage. It is preferable to set the time to 30 to 120 minutes in each stage. The insulating layer can be formed on the circuit substrate by thermally hardening the resin composition in this manner. Commercially available vacuum hot presses are exemplified by, for example, MNPC-V-750-5-200 (manufactured by Nago Seiki Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

Next, the insulating layer formed on the circuit substrate is subjected to a hole drilling process to form a through hole and a through hole. The drilling process can be carried out by conventional means such as drilling machine, laser, plasma, etc., and can be combined as needed, but the most common method is to perform lasers such as carbon dioxide gas laser and YAG laser. Hole processing. In the case where the support is not peeled off before the hole processing, the support may be peeled off after the hole processing.

Next, the surface of the insulating layer is roughened. The method of dry roughening treatment is exemplified by plasma treatment, etc., and the method of wet roughening treatment is exemplified by sequential swelling treatment of swelling liquid, roughening treatment with oxidizing agent, and neutralization treatment in the order of neutralization liquid. method. In the wet roughening treatment, it is preferable to remove the slag in the perforation based on the anchoring which can form irregularities on the surface of the insulating layer. The swelling treatment by the swelling liquid is carried out by immersing the insulating layer in the swelling liquid at 50 to 80 ° C for 5 to 20 minutes (preferably, immersion for 8 to 15 minutes at 55 to 70 ° C). The swelling liquid is exemplified by an alkaline solution, a surfactant solution, etc., and is preferably an alkaline solution, which is exemplified by, for example, a sodium hydroxide solution, a potassium hydroxide solution or the like. Commercially available swellable liquids include, for example, Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, etc., manufactured by ATOTECH Co., Ltd., Japan. The roughening treatment by the oxidizing agent is carried out by immersing the insulating layer in the oxidizing agent solution at 60 to 80 ° C for 10 to 30 minutes (preferably, immersing at 70 to 80 ° C for 15 to 25 minutes). The oxidizing agent may, for example, be an alkaline permanganic acid solution, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid or the like obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Further, the permanganate concentration in the alkaline permanganic acid solution is preferably set to 5 to 10% by weight. Commercial oxygen The chemical agent is exemplified by an alkaline permanganic acid solution such as Concentrate Compact CP or Doesing Solution Securiganth P manufactured by ATOTECH Co., Ltd., Japan. The neutralization solution and the treatment system are immersed in the neutralization solution at 30 to 50 ° C for 3 to 10 minutes (preferably at 35 to 45 ° C for 3 to 8 minutes). The neutralizing liquid is preferably an acidic aqueous solution, and the commercial product is listed as Reduction Solution Securiganth P manufactured by ATOTECH Co., Ltd., Japan.

Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. Dry plating can be carried out by a conventional method such as vapor deposition, sputtering, or ion plating. The wet plating is a method in which a conductor layer is formed by combining electroless plating and electrolytic plating, a plating resist having a pattern opposite to that of the conductor layer is formed, and a conductor layer is formed only by electroless plating. Subsequent methods of forming the pattern may be carried out by repeating the above-described series of steps, for example, by a subtractive method, a semi-additive method, or the like as known to those skilled in the art, and multi-layer lamination is performed to form a multilayer printed wiring board. Since the resin composition of the present invention is subjected to curing and roughening treatment, it has a low thickness and a high peel strength, and thus can be suitably used as a build-up layer of a multilayer printed wiring board.

<semiconductor device>

A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. That is, the semiconductor device comprises the multilayer printed wiring board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor wafer on a conduction portion of the multilayer printed wiring board of the present invention. The "conduction portion" is "a portion where a conductive signal is transmitted in a multilayer printed wiring board", and the position thereof may be a surface or a buried portion. Moreover, the semiconductor wafer is only a semiconductor The electrical circuit component of the material is not particularly limited.

The method of mounting the semiconductor wafer in the manufacture of the semiconductor device of the present invention is not particularly limited as long as the semiconductor wafer can function effectively. Specifically, it is a wire bonding mounting method, a flip chip mounting method, a bumpless Build Up Layer (BBUL) mounting method, an anisotropic conductive film (ACF) mounting method, and a non-conductive method. Installation method of the film (NCF), etc.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but these are not intended to limit the invention. In the following description, "parts" means "parts by mass".

<Measurement method ‧ Evaluation method>

First, the measurement method and evaluation method will be described.

[Measurement of tear strength (peel strength) of conductor layer formed by plating, arithmetic mean roughness (Ra value), root mean square roughness (Rq value)] (1) Underlayer treatment of laminate

The glass cloth substrate on which the inner layer circuit is formed is immersed in the MEC on both sides of the copper-clad laminate (copper foil thickness 18 μm, residual copper ratio 60%, substrate thickness 0.3 mm, Matsushita Electric Co., Ltd. R5715ES) In the CZ8100 manufactured by the method, the surface of the copper foil is roughened.

(2) subsequent lamination step of the film

The adhesive film produced in each of the examples and the comparative examples was laminated on both faces of the laminate using a batch vacuum pressure laminator MVLP-500 (trade name manufactured by Nikko Seisakusho Co., Ltd.). The laminating step was carried out under reduced pressure for 30 seconds to bring the gas pressure to 13 hPa or less, followed by pressing at 100 ° C and a pressure of 0.74 MP for 30 seconds.

(3) Hardening of resin composition

The PET film was peeled off from the laminated film, and the resin composition was cured at 170 ° C for 30 minutes to form an insulating layer.

(4) roughening treatment

The laminate in which the insulating layer was formed was immersed in Swelling Dip Securiganth P containing diethylene glycol monobutyl ether manufactured by Atotech Co., Ltd., Japan, at 60 ° C for 10 minutes, and then immersed at 80 ° C as a coarse layer. Chemical solution of Japan ATOTECH Co., Ltd., CONCENTRATE COMPACT P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) for 20 minutes, and finally immersed in 40 ° C as a neutralizing liquid in Japan ATOTECH (share) system 5 minutes in REDUCTION SOLUTION SECURIGANTH P. The laminate after the roughening treatment was used as the sample A.

(5) Plating using a semi-additive process

Sample A was immersed in a solution for electroless plating containing PdCl ₂ and then immersed in an electroless copper plating solution. After annealing at 150 ° C for 30 minutes, an etching resist was formed, and a pattern was formed by etching, and then copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 μm. Next, annealing treatment was performed at 180 ° C for 60 minutes. The laminate was used as sample B.

(6) Determination of arithmetic mean roughness (Ra value) and root mean square roughness (Rq value)

For the sample A, a non-contact surface roughness meter (WYKO NT3300 manufactured by VEECO Instruments Co., Ltd.) was used, and the Ra value and the Rq value were determined using a VSI contact mode and a 50-fold lens, and the measurement range was set to 121 μm × 92 μm. Next, an average value of 10 points was obtained and used as a measured value.

(7) Determination of tear strength (peel strength) of a conductor layer formed by plating

For the conductor layer of sample B, a slit was cut out at a portion surrounded by a width of 10 mm and a length of 100 mm, and one end thereof was peeled off, and a jig (AUTOCOM type test machine AC-50C-SL of TSI Co., Ltd.) was pinched and measured at room temperature. The load (kgf/cm) when peeling 35 mm in the vertical direction at a speed of 50 mm/min.

[Measurement of dielectric tangent]

The film obtained in each of the examples and the comparative examples was thermally cured at 190 ° C for 90 minutes, and the PET film was peeled off to obtain a flaky cured product. The cured product was cut into test pieces of 2 mm in width and 80 mm in length, and used in Kanto. Sub-development (share) cavity resonator vibrating method dielectric ratio measuring device CP521 and Agilent Technology (share) network analyzer E8362B, using dielectric resonance method to measure dielectric tangent (tan δ) by measuring frequency 5.8HGz . The measurement was performed on two test pieces, and the average value was calculated.

(Example 1)

10 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 165, "ZX1059" manufactured by Nippon Steel Chemical Co., Ltd.), naphthyl fluorene type epoxy resin (epoxy equivalent 300, Osaka Gas Chemistry) 10 parts of "CG-500"), 5 parts of methyl ethyl ketone (hereinafter referred to as "MEK"), and 5 parts of cyclohexanone were heated and dissolved while stirring. Among them, 30 parts of an active ester compound ("HPC8000-65T" manufactured by DIC Co., Ltd., an active ester equivalent of 223, a toluene solution of 65% solid content), and a hardening accelerator ("Golden Chemical Industry Co., Ltd.") were mixed. 4-dimethylaminopyridine" 0.3 parts, spherical cerium oxide (average particle size 0.5 μm, "SO-C2" treated with phenylamino decane, manufactured by Adventex, with a carbon content per unit weight of 0.18 %) 130 parts of phenoxy resin (YL7553BH30, MEK solution of solid content 30% by mass, weight average molecular weight 35000) 5 parts, uniformly dispersed by a high-speed rotary kneading machine to prepare a resin paint. Next, the resin paint was applied onto a PET film (thickness: 38 μm) by a die coater so that the thickness of the resin after drying became 40 μm, and dried at 80 to 120 ° C (average 100 ° C). In minutes, a flaky subsequent film was obtained.

(Example 2)

10 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 165, "ZX1059" manufactured by Nippon Steel Chemical Co., Ltd.), naphthyl fluorene type epoxy resin (epoxy equivalent 300, Osaka Gas Chemistry) 10 parts of "CG-500" manufactured by the method of heating and dissolving in 5 parts of MEK and 5 parts of cyclohexanone while stirring. In this case, an active ester compound ("HPC8000-65T" manufactured by DIC Co., Ltd., an active ester equivalent of 223, and a toluene solution of 65% solid content) was mixed with a phenol compound ("LA3018-50P" manufactured by DIC Corporation). 10 parts of phenol equivalent 151, 50% solid solution of 2-methoxypropanol), hardening accelerator ("4-dimethylaminopyridine" manufactured by Kwong Wing Chemical Industry Co., Ltd.) 0.1 part, spherical Cerium oxide ("SO-C2" having an average particle diameter of 0.5 μm, treated with phenylamino decane, 0.18% by weight of Adventex), and phenoxy resin (YL7553BH30, solid content 30) The mass% of the MEK solution, the weight average molecular weight of 35,000) was 5 parts, and was uniformly dispersed by a high-speed rotary kneading machine to prepare a resin paint. Next, a film was obtained in the same manner as in Example 1.

(Comparative Example 1)

In addition, 10 parts of the naphthyl fluorene type epoxy resin (epoxy equivalent 300, "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.) of Example 2 was changed to a naphthalene type epoxy resin ("DIC") A resin paint was prepared in the same manner as in Example 2 except that HP4710", an epoxy equivalent of 171) was 10 parts. Next, a film was obtained in the same manner as in Example 1.

(Comparative Example 2)

In addition to the addition of the active ester compound of Example 2 ("HPC-800-65T" manufactured by DIC), 15 parts of active ester equivalent 223, 65% solids in toluene solution, phenol compound (DIC) "LA3018-50P", phenol equivalent 151, 50% solid solution of 2-methoxypropanol) was changed to 20 parts, and further spherical cerium oxide (average particle diameter 0.5 μm, treated with phenylamino decane) The resin paint was prepared in the same manner as in Example 2 except that "SO-C2" and "Adventex (share) system, 0.18% by weight of carbon per unit weight) were changed to 115 parts. Next, a film was obtained in the same manner as in Example 1.

The results are shown in Table 1.

As can be seen from the results of Table 1, in Examples 1 and 2, when the insulating layer was hardened, the values of the arithmetic mean roughness and the root mean square roughness were small, and the peel strength was sufficient, and the dielectric tangent was obtained. low. On the other hand, in the resin compositions of Comparative Examples 1 and 2, the values of the arithmetic mean roughness and the root mean square roughness were large, and the peel strength was small and the dielectric tangent was high.

(Example 3)

9 parts of a semi-solid naphthalene type epoxy resin (epoxy equivalent 144, "HP4032" manufactured by DIC Co., Ltd.) and naphthyl fluorene type epoxy resin (epoxy equivalent 300, manufactured by Osaka Gas Chemical Co., Ltd.) CG-500") 10 parts in 5 parts of MEK and 5 parts of cyclohexanone were heated and dissolved while stirring. Among them, 7.65 parts of a cyanate ester compound (cyanate ester equivalent 124, "PT30S" manufactured by LONZA Co., Ltd.), and a hardening accelerator (4-dimethylaminopyridine manufactured by Kwong Wing Chemical Industry Co., Ltd.) ” 0.02 parts of spherical cerium oxide (average particle size 0.5 μm, “SO-C2” treated with phenylamino decane, made by Adventex (stock), 0.18% by weight of carbon) 190 parts, phenoxy 5 parts of a resin (YL7553BH30, a MEK solution having a solid content of 30% by mass, a weight average molecular weight of 35,000) was uniformly dispersed by a high-speed rotary kneader to prepare a resin paint. Next, a film of the following film was obtained in the same manner as in Example 1.

(Comparative Example 3)

In addition, 10 parts of the naphthyl fluorene type epoxy resin (epoxy equivalent 300, "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.) of Example 3 was changed to a biphenyl type epoxy resin (epoxy equivalent 185, Mitsubishi) A resin paint was prepared in the same manner as in Example 3 except for 6 parts of "YX4000H" manufactured by Chemical Co., Ltd.). Next, a film was obtained in the same manner as in Example 1.

The results are shown in Table 2.

As is clear from the results of Table 2, the values of the arithmetic mean roughness and the root mean square roughness of Example 3 were small, and sufficient values were obtained as the peel strength, and the dielectric tangent was low. On the other hand, in Comparative Example 3, the values of the arithmetic mean roughness and the root mean square roughness were both large, the peel strength was small, and the dielectric tangent was high.

[Industrial availability]

When the hardened insulating layer is provided, not only the value of the arithmetic mean roughness of the surface of the insulating layer in the wet roughening step is small, but also the value of the root mean square roughness of the surface of the insulating layer is small, and plating can be applied to the insulating layer. A conductor composition having a sufficient peel strength and a resin composition having a low dielectric tangent of the cured product is formed thereon. In addition, it can provide sheet-like laminates and multi-layer printing Wiring board, semiconductor device. Further, it is also possible to provide a portable tool such as a computer, a mobile phone, a digital camera, a television, or the like, or an electric motor vehicle, a car, a train, a ship, or an airplane.

Claims (16)

A resin composition comprising either or both of the epoxy resin having a naphthylquinone structure of the component (A) and the active ester-based curing agent and the cyanate-based curing agent of the component (B). The resin composition of claim 1, wherein the content of the component (A) is from 1 to 20% by mass based on 100% by mass of the nonvolatile component in the resin composition. The resin composition of claim 1, wherein the content of the component (B) is from 1 to 30% by mass based on 100% by mass of the nonvolatile component in the resin composition. The resin composition of claim 1, wherein the component (B) is an active ester-based hardener. The resin composition of claim 1, which further contains an inorganic filler. The resin composition of claim 5, wherein the inorganic filler has an average particle diameter of 0.01 to 5 μm. The resin composition of claim 5, wherein the content of the inorganic filler is 30 to 90% by mass based on 100% by mass of the nonvolatile component in the resin composition. The resin composition of claim 5, wherein the inorganic filler is surface-treated with a surface treatment agent. The resin composition of claim 5, wherein the inorganic filler is cerium oxide. The resin composition of claim 1, which further contains a thermoplastic resin. The resin composition of claim 1, wherein the resin composition is cured to form an insulating layer, and the surface of the insulating layer is subjected to roughening treatment, and the arithmetic mean roughness of the surface of the insulating layer is 10 to 350 nm, and the root mean square roughness is 20~500nm. The resin composition of claim 1, which is a resin composition for an insulating layer of a multilayer printed wiring board. The resin composition of claim 1, which is a resin composition for an insulating layer of a multilayer printed wiring board, wherein the multilayer printed wiring board-based conductor layer is formed by plating. A sheet-like laminate material comprising the resin composition according to any one of claims 1 to 13. A multilayer printed wiring board characterized by containing a cured product of the resin composition according to any one of claims 1 to 13 as an insulating layer. A semiconductor device characterized by comprising the multilayer printed wiring board of claim 15.