JP2016084413A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which can provide a hardened material which is superior in curvature suppression and smear removal and can form a conductor layer with high peel strength to a surface.SOLUTION: A resin composition contains (A) epoxy resin and (B) curing agent. The (A) epoxy resin contains (A1) epoxy resin having a biphenyl skeleton and a diglycidyl oxy-benzene skeleton. The (B) curing agent contains one or more selected from a phenolic curing agent, a cyanate ester curing agent and an active ester curing agent.SELECTED DRAWING: None

Description

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

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

  Various efforts were made against this. For example, Patent Document 1 discloses that a resin composition containing a biphenyl aralkyl epoxy resin, a specific curing agent, a specific inorganic filler, and a specific phenoxy resin is cured while maintaining a low coefficient of thermal expansion. Disclosure that the surface roughness of the obtained insulating layer is stable and low, enables formation of a conductor layer having high peel strength, and is excellent in soldering heat resistance and can be suitably used for forming an insulating layer of a circuit board. Has been. However, there is no description of a resin composition that can provide a cured product that has sufficient warpage suppression and smear removal properties and can form a high peel strength conductor layer on the surface.

JP 2011-89038 A

  The problem to be solved by the present invention is to provide a resin composition capable of obtaining a cured product that is excellent in warpage suppression and smear removability and capable of forming a conductor layer having high peel strength on the surface.

  As a result of intensive studies, the present inventors have (A) an epoxy resin and (B) a resin composition containing a curing agent, wherein (A) the epoxy resin has (A1) a biphenyl skeleton and a diglycidyloxybenzene skeleton. The above-mentioned problem can be solved by a resin composition comprising an epoxy resin having (B) one or more selected from a phenol-based curing agent, a cyanate ester-based curing agent and an active ester-based curing agent. As a result, the present invention has been completed.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin and (B) a curing agent,
(A) The epoxy resin includes (A1) an epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton,
(B) The resin composition in which a hardening | curing agent contains 1 or more types selected from a phenol type hardening | curing agent, a cyanate ester hardening | curing agent, and an active ester hardening agent.
[2] The above [1] description, wherein the content of the epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton is 3 to 20% by mass when the nonvolatile component in the resin composition is 100% by mass. Resin composition.
[3] (A1) The resin composition according to the above [1] or [2], wherein the epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton is an epoxy resin having a biphenyldimethylene skeleton and a diglycidyloxybenzene skeleton. .
[4] (A1) The epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton is an epoxy resin having a structural unit of the following general formula (1), and is described in any one of the above [1] to [3] Resin composition.

(In the formula, R is a glycidyloxy group, and m is 2.)
[5] The resin composition according to any one of [1] to [4], wherein (A) the epoxy resin further includes (A2) another epoxy resin.
[6] The resin composition according to any one of [1] to [5], wherein (B) the curing agent is an active ester curing agent.
[7] When the nonvolatile component in the resin composition is 100% by mass, the content of (B) the curing agent is 3 to 20% by mass, and any one of the above [1] to [6] Resin composition.
[8] The resin composition according to any one of [1] to [7], further including (C) an inorganic filler.
[9] The resin composition according to the above [8], wherein the content of the inorganic filler (C) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass.
[10] The resin composition according to [8] or [9], wherein (C) the inorganic filler has an average particle diameter of 0.01 to 5 μm.
[11] The resin composition according to any one of [1] to [10], which is a resin composition for forming an insulating layer of a multilayer printed wiring board.
[12] A sheet-shaped laminate material using the resin composition according to any one of [1] to [11].
[13] A cured product obtained by thermally curing the resin composition according to any one of [1] to [11].
[14] The cured product according to the above [13], wherein a conductor layer is formed on the surface of the cured product by plating, and a plating peel strength between the surface of the cured product and the conductor layer is 0.25 to 1.0 kgf / cm.
[15] The surface of the cured product is a surface after the roughening treatment, the arithmetic average roughness of the surface after the roughening treatment is 10 to 250 nm, and the root mean square roughness is 20 to 350 nm. The cured product according to [13] or [14].
[16] A multilayer printed wiring board in which an insulating layer is formed from the cured product according to any one of [13] to [15].
[17] A semiconductor device using the multilayer printed wiring board according to [16].

  ADVANTAGE OF THE INVENTION According to this invention, it came to be able to provide the resin composition from which the hardened | cured material which is excellent in curvature suppression property and smear removal property, and in which a conductor layer of high peel strength is formed on the surface is obtained.

  The resin composition of the present invention is a resin composition containing (A) an epoxy resin and (B) a curing agent, wherein (A) the epoxy resin has (A1) a biphenyl skeleton and a diglycidyloxybenzene skeleton. And (B) the curing agent contains at least one selected from a phenolic curing agent, a cyanate ester curing agent and an active ester curing agent.

In the present specification, unless otherwise specified, “cured product” means a cured product obtained by thermosetting the resin composition of the present invention, and “cured product” forms an insulating layer. Typically, an insulating layer in a circuit board (laminated board, multilayer printed wiring board, etc.) is formed.
Further, in the present invention, “cured product warp” refers to warping of an insulating layer formed of a cured product or a circuit board (laminated board, multilayer printed wiring board, etc.) including an insulating layer formed of a cured product. It is a concept that includes warping.

Hereinafter, the compounding component of the resin composition of this invention is explained in full detail.
<(A) Epoxy resin>
The (A) epoxy resin used in the present invention includes (A1) an epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton. Having a biphenyl skeleton is effective in improving the adhesion of the cured product to the conductor layer, and having a diglycidyloxybenzene skeleton prevents warpage of the cured product (particularly in the solder reflow process applied to the cured product). (Warp suppression property) and smear removability improvement in the cured product.

  (A1) The epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton is preferably an epoxy resin having a biphenyldimethylene skeleton and a diglycidyloxybenzene skeleton, and an epoxy having a structural unit of the following general formula (1) More preferably, it is a resin.

(In the formula, R is a glycidyloxy group, and m is 2.)

  (A1) As the epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton, commercially available products can be used. For example, as an epoxy resin having the structural unit of the general formula (1), for example, the following formula (2 ) Can be mentioned. Such an epoxy resin is commercially available from Nippon Kayaku Co., Ltd. under the name “NC3500”.

  In the formula (2), the number of repeating units n and l is an average value of 1 to 15 (preferably 1 to 7, more preferably 1 to 4), and l is an average value of 0 to 15 ( The number is preferably 0 to 7, more preferably 0 to 4). Moreover, the ratio (l / n) of n and l is 0-15, Preferably it is 0.5-5. The sum of n and l is 30 or less (preferably 14 or less, more preferably 8 or less).

  (A1) The epoxy equivalent of the epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton is not particularly limited, but is preferably 100 to 2000, more preferably 100 to 1000, still more preferably 130 to 500, and particularly preferably 150 to 270. preferable. When the epoxy equivalent is in such a preferable range, the crosslink density of the cured product can be improved, and the desmear property and warpage suppressing property of the cured product are improved. In addition, epoxy equivalent (g / eq) is the mass of resin containing 1 equivalent of epoxy groups, and can be measured according to JIS K7236: 2001.

  (A1) The ICI melt viscosity at 150 ° C. of the epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton is not particularly limited, but is preferably 0.1 to 0.5 Pa · s. Thereby, there exists an advantage that an inorganic filler can be mix | blended highly in a resin composition. The ICI melt viscosity is measured with an ICI cone plate viscometer (for high temperature).

  The content of the (A1) epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton in the resin composition of the present invention is not particularly limited, but the adhesion of the cured product to the conductor layer is improved, and curing in the solder reflow process From the viewpoint of warpage suppression of the product, when the nonvolatile component in the resin composition is 100% by mass, 3% by mass or more is preferable, and 6% by mass or more is more preferable. On the other hand, from the viewpoint of flexibility of the resin composition (in particular, improvement in flexibility of an adhesive film formed using the resin composition), the content is preferably 20% by mass or less, and more preferably 15% by mass or less.

  In the resin composition of the present invention, (A1) an epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton and (A2) another epoxy resin are used in combination within the range where the effects of the present invention are exhibited. be able to. That is, the (A) epoxy resin in the present invention includes (A1) an embodiment of an epoxy resin alone having a biphenyl skeleton and a diglycidyloxybenzene skeleton, and (A1) an epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton and ( A2) A combination mode of other epoxy resins is included.

  (A2) Examples of other epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, phenol novolac type epoxy resins, and tert-butyl-catechol type epoxy resins. , Naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type Epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane Sanji methanol epoxy resin, trimethylol type epoxy resins, and halogenated epoxy resins. These can use 1 type (s) or 2 or more types, Especially, a bisphenol A type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and a dicyclopentadiene type epoxy resin are preferable.

  When (A1) an epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton and (A2) another epoxy resin are used in combination, the adhesion of the cured product to the conductor layer is improved and the warpage of the cured product in the solder reflow process is suppressed. From the viewpoint of the above, the content of the (A) epoxy resin in the resin composition is preferably 10 to 40% by mass, and 13 to 30% by mass when the nonvolatile component in the resin composition is 100% by mass. It is more preferable that In the content of the (A) epoxy resin, the ratio ((A1) :( A2)) of (A1) an epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton to (A2) another epoxy resin is 1: 0. 3 to 1: 3 (mass ratio) is preferable, and 1: 0.5 to 1: 2 (mass ratio) is more preferable.

<(B) Curing agent>
The (B) curing agent used in the present invention contains one or more selected from phenolic curing agents, cyanate ester curing agents and active ester curing agents. From the viewpoint of suppressing warpage of the cured product and contributing to low roughness of the cured product after the roughening treatment, an active ester curing agent is preferred. In addition, when an active ester curing agent is used as the curing agent for the epoxy resin composition, generally, the cured product of the epoxy resin composition tends to have smears after processing, but in the resin composition of the present invention, The smear removability after processing of the cured product is also improved.

  Although there is no restriction | limiting in particular as a phenol type hardening | curing agent, One or more types selected from a biphenyl type hardening | curing agent, a naphthalene type hardening | curing agent, a phenol novolak type hardening | curing agent, a naphthylene ether type hardening | curing agent, and a triazine skeleton containing phenol type hardening | curing agent. Is preferably used. Specifically, biphenyl type curing agents MEH-7700, MEH-7810, MEH-7785 (Maywa Kasei Co., Ltd.), naphthalene type curing agents NHN, CBN, GPH (Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by NS Examples include naphthylene ether type curing agents EXB-6000 (manufactured by DIC Corporation), triazine skeleton-containing phenolic curing agents LA3018, LA7052, LA7054, LA1356 (manufactured by DIC Corporation), and the like. These can use 1 type (s) or 2 or more types.

  Although there is no restriction | limiting in particular as cyanate ester type hardening | curing agent, Novolac type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening agent, dicyclopentadiene type cyanate ester type hardening agent, bisphenol type (bisphenol A type, bisphenol) Fate, bisphenol S type, etc.) cyanate ester curing agents, and prepolymers in which these are partially triazines. Although the weight average molecular weight of a cyanate ester hardening | curing agent is not specifically limited, 500-4500 are preferable and 600-3000 are more preferable. Specific examples of the cyanate ester curing agent include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3, Bifunctional cyanate resins such as 5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether , Phenol novolac, Examples thereof include polyfunctional cyanate resins derived from resole novolac, dicyclopentadiene structure-containing phenol resins, prepolymers in which these cyanate resins are partially triazines, etc. These can be used alone or in combination. As the cyanate ester resin, a phenol novolak type polyfunctional cyanate ester resin (manufactured by Lonza Japan Co., Ltd., PT30S, cyanate equivalent 124), a part or all of bisphenol A dicyanate was triazine to form a trimer. Prepolymer (Lonza Japan Co., Ltd. product, BA230S, cyanate equivalent 232), dicyclopentadiene structure containing cyanate ester resin (Lonza Japan Co., Ltd. product, DT-4000, DT-7000) etc. are mentioned.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like. 1 type (s) or 2 or more types can be used for an active ester type hardening | curing agent. As the active ester curing agent, specifically, an active ester curing agent having a dicyclopentadienyl diphenol structure, an active ester curing agent having a naphthalene structure, an active ester curing agent which is an acetylated product of phenol novolac, An active ester curing agent that is a benzoylated product of phenol novolac is preferable, and among them, an active ester curing agent containing a dicyclopentadienyl diphenol structure is more preferable in terms of excellent peel strength. As the active ester curing agent, an active ester curing agent disclosed in JP-A-2004-277460 may be used, or a commercially available one may be used. Commercially available products containing dicyclopentadienyl diphenol structure EXB9451, EXB9460, EXB9460S-65T, HPC8000-65T (manufactured by DIC Corporation, active group equivalent of about 223), an active ester which is an acetylated product of phenol novolak DC808 (manufactured by Mitsubishi Chemical Corporation, active group equivalent of about 149) as a system hardener, YLH1026 (manufactured by Mitsubishi Chemical Corporation, active group equivalent of about 200), YLH1030 as an active ester type hardener that is a benzoylated phenol novolak (Mitsubishi Chemical Corporation, active group equivalent of about 201), YLH1048 (Mitsubishi Chemical Corporation, active group equivalent of about 245) and the like.

  More specifically, examples of the active ester curing agent containing a dicyclopentadienyl diphenol structure include a compound represented by the following formula (3).

(In the formula, R is an aryl group, k represents 0 or 1, and n is 0.05 to 2.5 on the average of repeating units.)

  Examples of the aryl group of R include a phenyl group and a naphthyl group. From the viewpoint of reducing the dielectric loss tangent of the cured product and improving the heat resistance, R is preferably a naphthyl group, while k is preferably 0, , N is preferably 0.25 to 1.5.

  (B) The curing agent can be used alone or in combination of two or more, and the content of the (B) curing agent is the viewpoint of curling of the cured product and the low roughness of the cured product after the roughening treatment. Therefore, when the non-volatile component in the resin composition is 100% by mass, 3 to 20% by mass is preferable, and 5 to 15% by mass is more preferable.

  In the resin composition of the present invention, the ratio of (A) the total number of epoxy groups in the epoxy resin and (B) the total number of reactive groups in the curing agent is preferably 1: 0.2 to 1: 2. : 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1 is more preferable. The total number of epoxy groups in the epoxy resin is a value obtained by dividing the solid content mass of each epoxy resin present in the resin composition by the epoxy equivalent for all epoxy resins, and the reactive group of the curing agent. The total number of is a value obtained by totaling the values obtained by dividing the solid content mass of each curing agent present in the resin composition by the reactive group equivalent for all curing agents.

<(C) Inorganic filler>
By further containing (C) an inorganic filler in the resin composition of the present invention, it is possible to improve warpage suppression. The inorganic filler is not particularly limited. For example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, Examples include barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica is preferable. In particular, fused silica and spherical silica are more preferable in terms of reducing the surface roughness of the insulating layer. Preferably, spherical fused silica is more preferable. You may use these 1 type or in combination of 2 or more types. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs Co., Ltd.

  (C) The average particle diameter of the inorganic filler is not particularly limited, but is preferably 5 μm or less from the viewpoint that the surface of the cured product after the roughening treatment has low roughness and enables fine wiring formation. 3 μm or less is more preferable, 2 μm or less is further preferable, 1 μm or less is even more preferable, 0.8 μm or less is particularly preferable, and 0.6 μm or less is particularly preferable. On the other hand, when the resin composition is a resin varnish, it is preferably 0.01 μm or more, more preferably 0.03 μm or more, from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from decreasing. 05 μm or more is more preferable, 0.07 μm or more is further more preferable, and 0.1 μm or more is particularly preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-950 manufactured by Horiba, Ltd. or the like can be used.

  (C) The content of the inorganic filler is preferably 40% by mass or more, more preferably 50% by mass or more, when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of enhancing the effect of suppressing warpage of the cured product. Is more preferable, 60 mass% or more is still more preferable, and 70 mass% or more is still more preferable. On the other hand, 90 mass% or less is preferable, 85 mass% or less is more preferable, and 80 mass% or less is preferable from the point which prevents that hardened | cured material becomes weak, and the point which prevents the fall of the peel strength of the conductor layer formed in the cured | curing material surface. % Or less is more preferable. In particular, in the cured product of the resin composition containing 50% by mass or more of the inorganic filler, in general, the peel strength of the conductor layer formed on the surface is likely to be reduced. However, in the resin composition of the present invention, the cured product It is possible to achieve both the warp suppressing effect and the peel strength of the conductor layer formed on the surface of the cured product.

  (C) It is preferable that the inorganic filler is surface-treated with a surface treatment agent. Specifically, as the surface treatment agent, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, Styryl silane coupling agent, acrylate silane coupling agent, isocyanate silane coupling agent, sulfide silane coupling agent, vinyl silane coupling agent, silane coupling agent, organosilazane compound, titanate coupling agent, etc. Is mentioned. Of these, aminosilane coupling agents, epoxysilane coupling agents, silane coupling agents, and organosilazane compounds are preferred. Commercially available products include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ" manufactured by Shin-Etsu Chemical Co., Ltd. -31 "(hexamethyldisilazane) and the like. One or more surface treatment agents can be used. By using the inorganic filler surface-treated with such a surface treating agent, the dispersibility of the inorganic filler (C) in the resin composition and the moisture resistance of the resin composition can be improved.

  Although the method of surface-treating an inorganic filler with a surface treating agent is not specifically limited, A dry method and a wet method are mentioned. As a dry method, for example, an inorganic filler is charged in a rotary mixer, and an alcohol solution or an aqueous solution of a surface treatment agent is dropped or sprayed while stirring, followed by further stirring, classification with a sieve, and then surface treatment by heating. And a method of dehydrating and condensing the agent and the inorganic filler. As the wet method, for example, a surface treatment agent is added to the slurry while stirring the slurry containing an inorganic filler and an organic solvent, and after stirring, classification is performed by filtration, drying and sieving, and then the surface is heated by heating. The method of dehydrating and condensing a processing agent and an inorganic filler is mentioned. It is also possible to perform surface treatment by an integral blend method in which a surface treatment agent is added to a resin composition containing an inorganic filler.

  In addition, it is preferable to add the surface-treated inorganic filler (namely, the inorganic filler surface-treated already with the surface treatment agent) to the resin composition. By doing in this way, the dispersibility in the resin composition of (C) inorganic filler can be improved further.

<(D) polymer resin>
The resin composition of the present invention may further contain (D) a polymer resin. By containing the polymer resin, the mechanical strength of the cured product can be improved, and the film molding ability when the resin composition is used in the form of an adhesive film can be improved. Examples of the polymer resin (D) include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, A polyester resin can be mentioned, and among these, a phenoxy resin and a polyvinyl acetal resin are preferable, and a phenoxy resin is more preferable. (D) 1 type (s) or 2 or more types can be used for polymer resin.

  (D) The weight average molecular weight of the polymer resin is preferably in the range of 8000 to 200000, more preferably in the range of 12000 to 100,000, and still more preferably in the range of 20000 to 60000. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  When the (D) polymer resin is blended in the resin composition of the present invention, 0.1 to 10% by mass is preferable when the nonvolatile component in the resin composition is 100% by mass, preferably 0.5 to 5%. The mass% is more preferable. Within this range, the film forming ability of the resin composition and the effect of improving the mechanical strength of the cured product are exhibited, and further the increase in the melt viscosity of the resin composition and the roughness of the insulating layer surface after the wet roughening step. The effect of lowering is exhibited.

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

  The amine curing accelerator is not particularly limited, but trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl). And amine compounds such as phenol and 1,8-diazabicyclo [5,4,0] -undecene (hereinafter abbreviated as DBU). You may use these 1 type or in combination of 2 or more types.

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

The imidazole curing accelerator is not particularly limited, but 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1- Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium tri Meritate 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2 '-Undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethyl Imidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl- - methyl-3-benzyl-imidazolium chloride, 2-methyl-imidazoline, adduct of 2-phenyl-imidazo imidazole compounds such as phosphorus and imidazole compound and an epoxy resin. You may use these 1 type or in combination of 2 or more types.

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

  When blending a curing accelerator (excluding a metal-based curing accelerator) in the resin composition of the present invention, a range of 0.005 to 1 part by mass with respect to 100 parts by mass of the total amount of the epoxy resin and the curing agent. Is preferable, and the range of 0.01 to 0.5 parts by mass is more preferable. Within this range, thermosetting can be performed more efficiently, and the storage stability of the resin varnish is improved.

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

  When 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 metal content based on the metal-based curing catalyst is in the range of 25 to 500 ppm. Is preferable, and the range of 40 to 200 ppm is more preferable. Within this range, a conductor layer having superior adhesion to the surface of the insulating layer is formed, and the storage stability of the resin varnish is also improved.

<(F) Other ingredients>
In the resin composition of the present invention, other components can be blended as necessary within a range not inhibiting the effects of the present invention. Other components include vinyl benzyl compounds, acrylic compounds, maleimide compounds, thermosetting resins such as blocked isocyanate compounds, silicone powder, nylon powder, fluororesin powder, organic fillers such as rubber particles, Orben, Benton, etc. Thickeners, silicone-based, fluorine-based, polymer-based antifoaming or leveling agents, phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, carbon black and other colorants, phosphorus compounds, metal hydroxides Flame retardants such as products.

  The resin composition of the present invention is appropriately mixed with the above components and, if necessary, kneaded or mixed by a kneading means such as a three-roll, ball mill, bead mill, or sand mill, or a stirring means such as a super mixer or a planetary mixer. To be prepared. In addition, the resin composition of the present invention can be prepared as a resin varnish by dissolving or dispersing the above components in an organic solvent. Further, an organic solvent is further added to the resin composition prepared without adding an organic solvent. Can be prepared as a resin varnish.

  In the resin composition of the present invention, the cured product is excellent in warpage suppression and smear removal, and can form a high peel strength conductor layer on the surface. It can be suitably used as a resin composition. Also, it can be suitably used as a resin composition for forming a conductor layer by plating (particularly, a resin composition for forming an insulating layer of a multilayer printed wiring board on which a conductor layer is formed by plating). It is also suitable as a resin composition for embedding a circuit on a board, a resin composition for forming a buildup layer of a multilayer printed wiring board, and the like.

  The resin composition of the present invention can be used as a cured product obtained by thermosetting. The conditions for thermosetting may be appropriately selected according to the type and content of the resin component in the resin composition, but are preferably 90 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 150 ° C. to 210 ° C. It is selected in the range of 30 to 120 minutes at ° C. Moreover, you may perform thermosetting in 2 steps or more.

<Sheet laminated material>
Although the resin composition of the present invention can be used for forming an insulating layer by applying it to a circuit board in a varnish state, it is industrially used for forming an insulating layer in the form of a sheet-like material such as an adhesive film or a prepreg. Is preferred. That is, it is preferable to produce an insulating film by preparing an adhesive film, a prepreg, or the like using the resin composition of the present invention, and laminating (laminating) the adhesive film, the prepreg, or the like on a circuit board. In addition, since sheet-like materials such as adhesive films and prepregs using the resin composition of the present invention are laminated (laminated) on a circuit board, they are referred to as “sheet-like laminated materials”. The softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminate property of the sheet-like laminated material.

(Adhesive film)
The adhesive film of the present invention is obtained by forming a resin composition layer of the resin composition of the present invention on a support, and a method known to those skilled in the art, for example, a resin composition dissolved or dispersed in an organic solvent. The resin varnish can be produced by applying the resin varnish to a support using a die coater or the like, and further drying the organic solvent by heating or blowing hot air to form a resin composition layer on the support. .

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. And aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

  The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. can do.

  Although the thickness of the resin composition layer formed in an adhesive film is not specifically limited, It is preferable to set it as more than the thickness of the conductor layer which a circuit board has. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm. From the viewpoint of thinning, 15 to 80 μm is more preferable, and 20 to 50 μm is still more preferable.

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

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

  A protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can also be stored in a roll.

(Prepreg)
The prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing base material by a hot melt method or a solvent method, and heating and semi-curing it. That is, the prepreg of the present invention is a prepreg formed by impregnating the sheet-shaped reinforcing base material with the resin composition of the present invention. As a sheet-like reinforcement base material, what consists of a fiber currently used as prepreg fibers, such as glass cloth and an aramid fiber, can be used, for example.

  In the hot melt method, the resin composition is once coated on a support without being dissolved in an organic solvent, and then laminated on a sheet-like reinforcing substrate, or directly applied to a sheet-like reinforcing substrate by a die coater. Thus, a prepreg is manufactured. In the solvent method, a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as the adhesive film, and a sheet-like reinforcing base material is immersed in the varnish, and then the resin-like varnish is impregnated into the sheet-like reinforcing base material. It is a method of drying. Moreover, a prepreg can also be prepared by heating and laminating the adhesive film continuously from both sides of the sheet-like reinforcing base material under heat and pressure. A support, a protective film, and the like can be used in the same manner as the adhesive film. That is, the prepreg of the present invention includes a prepreg with a support (a support / prepreg laminate), a support and a prepreg with a protective film (a support / prepreg / protection film laminate). An attached prepreg, a support, and a prepreg with a protective film are preferred.

<Multilayer printed wiring board using sheet-like laminated material>
Next, an example of a method for producing a multilayer printed wiring board using the sheet-like laminated material produced as described above will be described.

  First, a sheet-like laminated material is laminated (laminated) on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. Here, the “circuit board” means that a conductor layer (circuit) patterned on one or both sides of the board as described above is formed. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

In the above laminate, when the sheet-like laminate material has a protective film, after removing the protective film, the sheet-like laminate material and the circuit board are preheated as necessary, and the sheet-like laminate material is pressurized and Laminate to circuit board while heating. In the sheet-like laminated material of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure (laminating pressure) is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), the pressure bonding time (laminating time) is preferably 5 to 180 seconds, and the lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll. The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.

  After laminating the sheet-like laminated material on the circuit board, after cooling to near room temperature, if the support is peeled off, it is peeled off, and the resin composition in the sheet-like laminated material is thermally cured to form a cured product An insulating layer can be formed on the circuit board. The conditions for thermosetting are as described above. After the insulating layer is formed, if the support is not peeled before curing, it can be peeled off here if necessary.

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

  The insulating layer formed on the circuit board is a cured product obtained by thermosetting the resin composition layer when the sheet-shaped laminated material is an adhesive film, and the sheet is formed when the sheet-shaped laminated material is a prepreg. It is a composite of a reinforced reinforcing substrate and a cured product obtained by thermosetting a resin composition impregnated in a sheet reinforcing substrate. When the insulating layer is the composite, the surface of the insulating layer is formed by a cured product of the resin composition.

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

  Next, a roughening process is performed on the surface of the insulating layer. In the case of dry-type roughening treatment, plasma treatment or the like can be mentioned. It is done. The wet roughening treatment is preferable in that smear in the via hole can be removed while forming an uneven anchor on the surface of the insulating layer. The swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 5 to 20 minutes (preferably at 55 to 70 ° C. for 8 to 15 minutes). Examples of the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of the commercially available swelling liquid include Swelling Dip Securiganth P (Swelling Dip Securiganth P) and Swelling Dip Securiganth SBU (ABUTEC Japan). be able to. The roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 85 ° C. for 10 to 30 minutes (preferably at 70 to 80 ° C. for 15 to 25 minutes). Examples of the oxidizing agent include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is performed by immersing in a neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes (preferably at 35 to 45 ° C. for 3 to 8 minutes). As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.

  Here, the surface of the insulating layer after the roughening treatment, that is, the arithmetic average roughness (Ra value) of the cured product surface is preferably 250 nm or less, more preferably 200 nm or less, and more preferably 150 nm or less from the viewpoint of fine wiring formation. Further preferred. Further, the lower limit value of the arithmetic average roughness (Ra value) is not particularly limited, and is usually 10 nm or more or 30 nm or more. Furthermore, since the root mean square roughness (Rq value) of the cured product surface reflects the local state of the cured product surface, it can be confirmed that the cured product surface is dense and smooth by grasping the Rq value. . The root mean square roughness (Rq value) is preferably 350 nm or less, more preferably 280 nm or less, and even more preferably 200 nm or less in order to obtain a dense and smooth cured product surface. Further, the lower limit of the root mean square roughness (Rq value) is preferably 20 nm or more, and more preferably 40 nm or more, from the viewpoint of stabilizing the peel strength. Arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) are described in “Measurement of arithmetic mean roughness (Ra value) and root mean square roughness (Rq value)” described later. Further, using a non-contact type surface roughness meter (WYKONT 3300 manufactured by Becoins Instruments Co., Ltd.), the measurement range can be measured as 121 μm × 92 μm with a VSI contact mode and a 50 × lens.

  Next, a conductor layer is formed on the insulating layer after the roughening treatment by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. Examples of wet plating include a method in which a conductive layer is formed by combining electroless plating and electrolytic plating, a method in which a plating resist having a pattern opposite to that of the conductive layer is formed, and a conductive layer is formed only by electroless plating. It is done. After the conductor layer is formed on the insulating layer after the roughening treatment, it is preferable to perform an annealing treatment to improve the adhesion of the conductor layer. The annealing treatment is preferably performed at 140 to 200 ° C. for 30 to 90 minutes, more preferably at 150 to 200 ° C. for 30 to 60 minutes.

  The plating peel strength is preferably 0.25 kgf / cm or more, more preferably 0.30 kgf / cm or more, and 0.40 kgf / cm or more in order to sufficiently adhere the cured product (insulating layer) and the conductor layer. Further preferred. The upper limit of the plating peel strength is preferably as high as possible and is not particularly limited, but is generally 1.0 kgf / cm or less, 0.8 kgf / cm or less, 0.6 kgf / cm or less, or the like.

  As a pattern formation method thereafter, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. By repeating the above-described series of steps a plurality of times, a multilayer in which build-up layers are stacked in multiple stages It can be a printed wiring board.

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

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

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

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

<Semiconductor device>
A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor chip in a conductive portion of the multilayer printed wiring board of the present invention. The “conduction location” is a “location where an electrical signal is transmitted in a multilayer printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to these Examples. In the following description, “part” and “%” mean “part by mass” and “% by mass”, respectively, unless otherwise specified.

<Measurement and evaluation method>
First, the measurement / evaluation method in the physical property evaluation in this specification will be described.

[Preparation of substrate for measurement and evaluation of surface roughness]
(1) Substrate treatment of a circuit board Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic Corporation “R1515A”) on which a circuit is formed Was etched by 1 μm with a microetching agent (“CZ8100” manufactured by MEC Co., Ltd.) to roughen the copper surface.

(2) Lamination | stacking of adhesive film The protective film was peeled from the adhesive film produced in the Example and the comparative example. Using the batch type vacuum pressure laminator (Nichigo Morton 2-stage buildup laminator “CVP700”), the resin composition layer is bonded to the circuit board using the exposed adhesive film of the resin composition layer. And laminated on both sides of the circuit board. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 110 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, the laminated adhesive film was smoothed by hot pressing at 110 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure.

(3) Curing of resin composition layer After laminating the adhesive film, the resin composition layer was thermally cured to form cured bodies on both sides of the circuit board. At that time, for Examples 1 and 3 and Comparative Examples 1 and 3, the resin composition layer was thermally cured with a PET film as a support attached thereto. Regarding Example 2 and Comparative Example 2, the resin composition layer was thermally cured after peeling off the PET film as the support.

The thermosetting of the resin composition layer was performed by the following thermosetting treatment.
Thermal curing was carried out at 100 ° C. for 30 minutes (after being placed in a 100 ° C. oven) and then at 175 ° C. (after being transferred to a 175 ° C. oven) for 30 minutes. Thereafter, the substrate was taken out in a room temperature atmosphere.

(4) Formation of via hole In the case of Examples 1 and 3 and Comparative Examples 1 and 3, with a support attached, a CO ₂ laser processing machine (“LC-2E21B / 1C” manufactured by Hitachi Via Mechanics Co., Ltd.) Was used to drill the insulating layer under the conditions of a mask diameter of 1.60 mm, a focus offset value of 0.050, a pulse width of 25 μs, a power of 0.66 W, an aperture of 13, a shot number of 2, and a burst mode to form a via hole. The top diameter (diameter) of the via hole on the surface of the insulating layer was 50 μm. After the shape of the via hole, the support (PET film) was peeled off.
In the case of Example 2 and Comparative Example 2, a CO ₂ laser processing machine (“LC-2E21B / 1C” manufactured by Hitachi Via Mechanics Co., Ltd.) was used on the exposed insulating layer surface, the mask diameter was 1.40 mm, and the focus offset. The insulating layer was drilled under the conditions of value 0.075, pulse width 7 μs, power 0.08 W, aperture 14, number of shots 5 and cycle mode to form a via hole. The top diameter (diameter) of the via hole on the surface of the insulating layer was also 50 μm.

(5) Roughening treatment The substrate on which the via hole was formed was placed in a swelling liquid (an aqueous solution containing “Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd., diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes ( Example 3 and Comparative Example 3) or 10 minutes (Examples 1, 2 and Comparative Examples 1 and 2), oxidizing agent ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd.), KMnO4: 60 g / L, NaOH: (40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally immersed in a neutralizing solution (“Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd., sulfuric acid aqueous solution) at 40 ° C. for 5 minutes, then at 80 ° C. It dried for 30 minutes and formed the roughening hardening body on both surfaces of the circuit board. The obtained substrate is referred to as “evaluation substrate A”.

(6) Formation of conductor layer by semi-additive method In accordance with the following procedure, a conductor layer having a desired circuit pattern was formed on the surface of the insulating layer.
The evaluation substrate A was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then in an electroless copper plating solution at 25 ° C. for 20 minutes. The obtained substrate was heated at 150 ° C. for 30 minutes for annealing treatment, and then a pattern forming photosensitive dry film was formed. After patterning the dry film by exposure and development, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 μm. After peeling off the dry film, unnecessary electroless copper plating was removed by flash etching, and the substrate on which the conductor pattern was formed was heated at 190 ° C. for 60 minutes for annealing. The obtained substrate was designated as “evaluation substrate B”.

[Measurement of arithmetic mean roughness (Ra) and root mean square roughness (Rq)]
For the evaluation substrate A, Ra value and Rq value are obtained by using a non-contact type surface roughness meter ("WYKO NT3300" manufactured by Bee Coins Instruments Co., Ltd.) and a VSI contact mode, a numerical value obtained by a 50 × lens with a measurement range of 121 μm × 92 μm. Asked. The measured values were obtained by calculating the average value of 10 points selected at random.

[Measurement of peel strength (peel strength) of plated conductor layer]
The conductor layer of the evaluation board B is cut with a 10 mm width and 100 mm length, and one end is peeled off to grasp the grip (TSE Co., Ltd., Autocom type tester “AC-50C-SL”) And the load (kgf / cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min at room temperature was measured.

[Evaluation of smear at bottom of via hole]
The bottom of the via hole of the evaluation substrate A was observed with a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, S-4800), and the maximum smear length from the wall surface of the bottom of the via hole was measured from the obtained image. The evaluation criteria are shown below.

Evaluation criteria:
○: Maximum smear length is less than 3 μm ×: Maximum smear length is 3 μm or more

[Preparation of substrate for warpage evaluation]
(1) Preparation of inner layer substrate As an inner layer substrate, an unclad plate (thickness 100 μm, manufactured by Mitsubishi Gas Chemical Co., Ltd. “HL832NSF-LCA”) from which all the double-sided copper foils of the glass cloth base epoxy resin double-sided copper clad laminate were removed ) Was prepared.

(2) Lamination of Adhesive Film Using the batch-type vacuum pressure laminator (manufactured by Nichigo Morton Co., Ltd., two-stage buildup laminator CVP700), the resin composition layer is the inner layer. The inner layer substrate was laminated on both sides so as to be in contact with the substrate. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 110 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, the laminated adhesive film was smoothed by hot pressing at 110 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure.

(3) Curing of resin composition layer After laminating the adhesive film, the support was peeled from both sides of the substrate. Next, the resin composition layer was thermally cured at 190 ° C. for 90 minutes to form an insulating layer. The obtained substrate was designated as “evaluation substrate C”.

[Evaluation of warpage]
The evaluation substrate C was cut into 45 mm square pieces (n = 5), and then passed once through a reflow apparatus (“HAS-6116” manufactured by Nippon Antom Co., Ltd.) that reproduces the solder reflow temperature at a peak temperature of 260 ° C. (The reflow temperature profile conforms to IPC / JEDEC J-STD-020C). Next, the lower surface of the substrate was heated with a reflow temperature profile conforming to IPC / JEDEC J-STD-020C (peak temperature 260 ° C.) using a shadow moire device (“Thermoire AXP” manufactured by Akrometrix) and arranged on the upper surface of the substrate. Based on the grid lines, the displacement of the 10 mm square portion at the center of the substrate was measured. The warpage was evaluated according to the following evaluation criteria.
Evaluation criteria:
A: The difference between the maximum height and the minimum height of the displacement data in all temperature ranges is less than 30 μm for all 5 samples. ○: The difference in the maximum height and the minimum height of the displacement data in all temperature ranges is 30 to about 5 samples. Less than 50 μm ×: For at least one sample, the difference between the maximum height and the minimum height of displacement data in the entire temperature range is 50 μm or more

<Example 1>
Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169, 1: 1 mixture of bisphenol A type and bisphenol F type) 5 parts, naphthalene type epoxy resin (“HP4032SS” manufactured by DIC Corporation) ”, Epoxy equivalent (about 144) 5 parts, bixylenol type epoxy resin (Mitsubishi Chemical Corporation“ YX4000HK ”, epoxy equivalent about 185) 5 parts, epoxy resin (Nippon Kayaku Co., Ltd.“ NC-3500 ”, Epoxy equivalent 206, 20 parts of ICI melt viscosity 0.37 Pa · s at 150 ° C., and phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation), cyclohexanone: methyl ethyl ketone (MEK) 1: 1 with a solid content of 30% by mass Solution) 10 parts are stirred into 30 parts of solvent naphtha and 5 parts of cyclohexanone. It was heated and dissolved. After cooling to room temperature, there are 8 parts of a triazine skeleton-containing cresol novolac-based curing agent (hydroxyl equivalent 151, “LA-3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution with a solid content of 50%), Active ester-based curing agent (“HPC8000-65T” manufactured by DIC Corporation, active group equivalent of about 223, non-volatile component 65% by weight toluene solution) 20 parts, amine-based curing accelerator (4-dimethylaminopyridine (DMAP), 1.5 parts of MEK solution having a solid content of 5% by mass, 1 part of an imidazole curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), MEK solution having a solid content of 5% by mass), flame retardant (Sanko Co., Ltd.) ) “HCA-HQ”, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-1 2 parts of oxide, average particle diameter 2 μm, spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd.), average particle surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle 180 parts of carbon having a diameter of 0.5 μm and a carbon amount per unit surface area of 0.38 mg / m ² ) are mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP050” manufactured by ROKITECNO) to obtain a resin varnish 1 was prepared.

  As a support, a PET film (“Lumirror T6AM” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C.) subjected to release treatment with an alkyd resin mold release agent (“AL-5” manufactured by Lintec Corporation) Prepared. The resin varnish 1 was applied to the release surface of the support with a die coater and dried at 80 ° C. to 110 ° C. (average 100 ° C.) for 4.5 minutes to form a resin composition layer. The thickness of the resin composition layer was 35 μm. Next, a polypropylene film (“Alphan MA-411” manufactured by Oji Specialty Paper Co., Ltd., thickness 15 μm) is used as a protective film on the surface of the resin composition layer not bonded to the support, and the rough surface of the protective film. Were laminated so as to be bonded to the resin composition layer, whereby an adhesive film 1 was obtained.

<Example 2>
Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169, 1: 1 mixture of bisphenol A type and bisphenol F type) 5 parts, naphthalene type epoxy resin (“HP4032SS” manufactured by DIC Corporation) ”, Epoxy equivalent (about 144) 5 parts, bixylenol type epoxy resin (Mitsubishi Chemical Corporation“ YX4000HK ”, epoxy equivalent about 185) 5 parts, epoxy resin (Nippon Kayaku Co., Ltd.“ NC-3500 ”, 15 parts of epoxy equivalent 206) and 10 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass), 20 parts of solvent naphtha and 5 parts of cyclohexanone The mixture was heated and dissolved with stirring. After cooling to room temperature, 15 parts of an active ester curing agent (“HPC8000-65T” manufactured by DIC Corporation, a toluene solution having an active group equivalent of about 223 and a non-volatile component of 65% by mass), a pre-form of bisphenol A dicyanate Polymer ("BA230S75" manufactured by Lonza Japan Ltd., cyanate equivalent of about 232, MEK solution with non-volatile content of 75% by mass), amine-based curing accelerator (4-dimethylaminopyridine (DMAP), solid content of 5% by mass MEK solution) 0.6 parts, curing accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt (III) acetylacetonate, MEK solution having a solid content of 1% by mass), rubber particles (manufactured by Ganz Kasei Co., Ltd., AC3816N) ) 2 parts swollen in 10 parts of solvent naphtha at room temperature for 12 hours, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10 2 parts of (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm, aminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) 150 parts of spherical silica surface treated with “KBM573” (“SO-C1” manufactured by Admatechs Co., Ltd., average particle size of 0.25 μm, carbon amount per unit surface area of 0.36 mg / m 2) is mixed. After uniformly dispersing with a rotary mixer, the resin varnish 2 was prepared by filtering with a cartridge filter ("SHP030" manufactured by ROKITECNO).

  An adhesive film 2 was produced in the same manner as in Example 1 except that the resin varnish 1 of Example 1 was changed to the resin varnish 2.

<Example 3>
10 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 238), 5 parts of naphthylene ether type epoxy resin ("EXA-731-G4S" manufactured by DIC Corporation, epoxy equivalent 186), 5 parts of bixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185), 15 parts of epoxy resin (Nippon Kayaku "NC-3500", epoxy equivalent 206), and phenoxy resin (YX7553BH30 manufactured by Mitsubishi Chemical Corporation, 10 parts of a cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution having a solid content of 30% by mass) was dissolved in 20 parts of solvent naphtha and 5 parts of cyclohexanone with stirring. After cooling to room temperature, 5 parts of a triazine skeleton-containing phenol novolac curing agent (hydroxyl equivalent 125, “LA-7054” manufactured by DIC Corporation, MEK solution with a solid content of 60%), naphthol curing agent ( “SN-485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 24 parts of a MEK solution having a hydroxyl equivalent weight of 215 and a solid content of 60%, polyvinyl butyral resin (glass transition temperature of 105 ° C., “KS-1” manufactured by Sekisui Chemical Co., Ltd.) ) 10 parts of a 1: 1 mixed solution of ethanol and toluene with a solid content of 15%, 1 part of an amine curing accelerator (DMAP, MEK solution with a solid content of 5% by weight), an imidazole curing accelerator (1-benzyl- 0.5 parts of 2-phenylimidazole (1B2PZ), MEK solution having a solid content of 5% by mass, and 2 parts of rubber particles (manufactured by Ganz Kasei Co., Ltd., AC3816N) were dissolved in solvent naphtho. Spherical silica surface-treated with phenyltrimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.), which had been swollen at room temperature for 12 hours at 10 parts, “UFP-30 manufactured by Electrochemical Industry Co., Ltd.” ”, 60 parts of an average particle size of 0.1 μm and carbon amount per unit surface area of 0.22 mg / m 2) were mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered with a cartridge filter (“ SHP030 ”manufactured by ROKITECNO). Resin varnish 3 was prepared.

  An adhesive film 3 was produced in the same manner as in Example 1 except that the resin varnish 1 of Example 1 was changed to the resin varnish 3.

<Comparative Example 1>
20 parts of the epoxy resin of the present invention (“NC-3500” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 206, ICI melt viscosity 0.37 Pa · s at 150 ° C.) was added to biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. ) “NC3000H”, epoxy equivalent 288, ICI melt viscosity at 150 ° C. 0.32 Pa · s) Resin varnish 4 was prepared in the same manner as in Example 1 except for changing to 20 parts.

  An adhesive film 4 was produced in the same manner as in Example 1 except that the resin varnish 1 of Example 1 was changed to the resin varnish 4.

<Comparative Example 2>
Other than changing 15 parts of epoxy resin (Nippon Kayaku Co., Ltd. “NC-3500”, epoxy equivalent 206) to 15 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000H”, epoxy equivalent 288) In the same manner as in Example 2, a resin varnish 5 was prepared.

  An adhesive film 5 was produced in the same manner as in Example 1 except that the resin varnish 1 of Example 1 was changed to the resin varnish 5.

<Comparative Example 3>
Other than changing 15 parts of epoxy resin (Nippon Kayaku Co., Ltd. “NC-3500”, epoxy equivalent 206) to 15 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000H”, epoxy equivalent 288) In the same manner as in Example 3, a resin varnish 6 was prepared.

  An adhesive film 6 was produced in the same manner as in Example 1 except that the resin varnish 1 of Example 1 was changed to the resin varnish 6.

  The evaluation results are shown in Table 1 below.

Claims (17)

A resin composition containing (A) an epoxy resin and (B) a curing agent,
(A) The epoxy resin includes (A1) an epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton,
(B) The resin composition in which a hardening | curing agent contains 1 or more types selected from a phenol type hardening | curing agent, a cyanate ester hardening | curing agent, and an active ester hardening agent.   The resin composition according to claim 1, wherein the content of the epoxy resin having (A1) biphenyl skeleton and diglycidyloxybenzene skeleton is 3 to 20% by mass when the nonvolatile component in the resin composition is 100% by mass. .   (A1) The resin composition according to claim 1 or 2, wherein the epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton is an epoxy resin having a biphenyldimethylene skeleton and a diglycidyloxybenzene skeleton. (A1) The resin composition according to any one of claims 1 to 3, wherein the epoxy resin having a biphenyl skeleton and a diglycidyloxybenzene skeleton is an epoxy resin having a structural unit represented by the following general formula (1).

(In the formula, R is a glycidyloxy group, and m is 2.)   The resin composition according to any one of claims 1 to 4, wherein the (A) epoxy resin further comprises (A2) another epoxy resin.   (B) The resin composition of any one of Claims 1-5 whose hardening agent is an active ester type hardening | curing agent.   The resin composition of any one of Claims 1-6 whose content of (B) hardening | curing agent is 3-20 mass% when the non-volatile component in a resin composition is 100 mass%.   Furthermore, the resin composition of any one of Claims 1-7 containing (C) inorganic filler.   The resin composition of Claim 8 whose content of (C) inorganic filler is 50 mass% or more when the non-volatile component in a resin composition is 100 mass%.   (C) The resin composition of Claim 8 or 9 whose average particle diameter of an inorganic filler is 0.01-5 micrometers.   The resin composition according to any one of claims 1 to 10, which is a resin composition for forming an insulating layer of a multilayer printed wiring board.   The sheet-like laminated material formed using the resin composition of any one of Claims 1-11.   Hardened | cured material formed by thermosetting the resin composition of any one of Claims 1-11.   The hardened | cured material of Claim 13 whose conductor layer is formed by plating on the hardened | cured material surface, and the plating peel strength of this hardened | cured material surface and this conductor layer is 0.25-1.0 kgf / cm.   The cured product surface is a surface after the roughening treatment, the arithmetic average roughness of the surface after the roughening treatment is 10 to 250 nm, and the root mean square roughness is 20 to 350 nm. 14. Hardened | cured material of 14.   The multilayer printed wiring board by which the insulating layer was formed with the hardened | cured material of any one of Claims 13-15.   A semiconductor device using the multilayer printed wiring board according to claim 16.